Professional Documents
Culture Documents
Objective Chemistry For Jee Main PDF
Objective Chemistry For Jee Main PDF
guru
Objective
CHEMISTRY
for JEE MAIN
with BOARDS SCORE BOOSTER
So
lly
Fu ed
lv
F
F
F
F
F
JEE Main 2014-15 Solved Papers
Key Concepts with Illustrations
4 levels of Exercises
1200+Questions based on NCERT
1500+Past Competitive Exam MCQ's
F 3500+ Practice MCQ's for JEE Main
F Aligned as per Class 11 & 12 NCERT
JEEMAIN.GURU
downloaded from jeemain.guru
• Head Office : B-32, Shivalik Main Road, Malviya Nagar, New Delhi-110017
• Sales Office : B-48, Shivalik Main Road, Malviya Nagar, New Delhi-110017
Tel. : 011-26691021 / 26691713
DISHA PUBLICATION
ALL RIGHTS RESERVED
© Copyright Author
JEEMAIN.GURU
downloaded from jeemain.guru
PREFACE
With the Boards having a weightage (40%) for admission through JEE Main the need of a book that can help students
both in JEE Main and Boards becomes more prominent. The All New “Objective Chemistry for JEE Main with Boards
Score Booster” encapsulates the formula for cracking Boards & JEE Main simultaneously.
Salient features of Disha's “Objective Chemistry for JEE Main with Boards Score Booster” book are:
• Fully Solved 2015 JEE Main Question paper has been added.
• Exhaustive theory, with solved examples, explaining all fundamentals/ concepts to build a strong base.
• Illustrations to master applications of concepts & sharpen problem-solving skills.
• 4 level of graded exercises to ensure sufficient practice.
• 1200+ NCERT based Questions (Boards Score Booster) for Board exams covered in a separate exercise.
• 1500+ past Competitive Exam MCQ’s of JEE Main/ AIEEE and other entrance exams to provide a better exposure
covered in the exercise “Window to Competitive Exams.”
• 3500+ Practice MCQ’s for the JEE Main exam. Finally 2 Practice exercises at the end of each chapter – Basic
and Applied.
• The book covers all variety of questions as per the format of the previous year AIEEE/ JEE Main Papers.
• The book has a very strong focus on Practical Skills as per the syllabus of JEE Main exam and the questions that
have been asked in previous exams. The book covers Volumetric Analysis, Analytical Chemistry and other
practical skills as per the syllabus of JEE Main.
• Covers entire syllabus as per the latest NCERT books and JEE Main syllabus. The complete book has been
aligned as per the chapter flow of NCERT class 11 & 12 books. At places certain chapters have been divided into
sub-chapters. For example - Equilibrium is divided into 2 parts Part A – Chemical Equilibrium; Part B – Ionic
Equilibrium.
More than 25 out of the 30 JEE Main questions were directly or indirectly covered in our book and the readers must
have really benefitted from it.
We are highly thankful to the Disha Publication team who continuously encouraged us to update this book. We are
also thankful to the editorial team and the D.T.P. Team who worked day & night for bringing this work before you.
We would like to give a special thanks to Mr. Kulpreet Singh (Sr. SME - Chemistry) who has really spent a lot of time
in bringing this book to the present shape.
Last but not the least we would request all readers to come up with suggestions so that we can further improve the
book in the next edition.
With best of luck!!
AUTHORS
DR. DALJEET SINGH
Ph.D., Delhi University
Professor of Chemistry (Retd.)
MM PG College, Meerut University,
Modinagar (U.P.)
ER. PRAMIT SINGH
B.Tech. MS
Concordia University, Montreal, Canada
JEEMAIN.GURU
downloaded from jeemain.guru
INDEX
JEE MAIN 2015 Solved Paper (with solutions) 2015-1 – 2015-4
JEE MAIN 2014 Solved Paper (with solutions) 2014-1 – 2014-7
6. Thermodynamics 145-178
Terminology used in thermodynamics; Internal energy and its transfer; Processes and their types; Thermodynamic equilibrium; First law of
thermodynamics; Factros affecting DH; Relation between DH and DE; Applications of first law; Hess’s law of constant heat summation;
Heat capacity of system; Entropy; Criteria for feasibility of a process; Zeroth law of thermodynamics; Third law of thermodynamics;
Clapeyron Clausius equation and its applications; Heat engine and its efficiency; Carnot cycle; Resonance energy; Calorific value; Types
of reactions and corresponding enthalpy changes; Laws of thermochemistry.
JEEMAIN.GURU
downloaded from jeemain.guru
9. Hydrogen 257-270
Preparation and manufacturing of hydrogen and its properties; Different forms of hydrogen; Hydrides; Hydrogen peroxide; Water; Hydrates.
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
1. Which compound would give 5 - keto - 2 - methylhexanal 6. Which of the following compounds is not colored yellow ?
upon ozonolysis ? (a) (NH4)3 [As(Mo3O10)4 ] (b) BaCrO4
(c) Zn2[Fe(CN)6] (d) K3[Co(NO2)6]
CH3
7. Which of the following is the energy of a possible excited
CH3
state of hydrogen ?
H3C (a) –3.4 eV (b) +6.8 eV
(a) (b) (c) +13.6 eV (d) –6.8 eV
CH3 8. Which of the following compounds is not an antacid ?
(a) Phenelzine (b) Ranitidine
CH3 (c) Aluminium hydroxide (d) Cimetidine
CH3 9. The ionic radii (in Å) of N3–, O2– and F– are respectively :
(a) 1.71, 1.40 and 1.36 (b) 1.71, 1.36 and 1.40
(c) CH3 (d) (c) 1.36, 1.40 and 1.71 (d) 1.36, 1.71 and 1.40
10. In the context of the Hall - Heroult process for the extraction
CH3 of Al, which of the following statements is false ?
2. Which of the vitamins given below is water soluble ? (a) Al3+ is reduced at the cathode to form Al
(a) Vitamin E (b) Vitamin K (b) Na3AlF6 serves as the electrolyte
(c) Vitamin C (d) Vitamin D (c) CO and CO2 are produced in this process
3. Which one of the following alkaline earth metal sulphates (d) Al2O3 is mixed with CaF2 which lowers the melting point
has its hydration enthalpy greater than its lattice enthalpy ? of the mixture and brings conductivity
(a) BaSO4 (b) SrSO4 11. In the following sequence of reactions :
(c) CaSO4 (d) BeSO4 KMnO SOCl H / Pd
Toluene ¾¾¾¾
4
® A ¾¾¾
2
® B ¾¾¾®
2
C
4. In the reaction BaSO 4
the product C is :
NH2
(a) C6H5CH2OH (b) C6H5CHO
(c) C6H5COOH (d) C6H5CH3
¾¾¾¾¾
NaNO /HCl
2
® D ¾¾¾¾¾
CuCN/KCN
® E + N2 12. Higher order (>3) reactions are rare due to :
0–5° C D
(a) shifting of equilibrium towards reactants due to elastic
collisions
CH3 (b) loss of active species on collision
(c) low probability of simultaneous collision of all the
the product E is : reacting species
CH3 (d) increase in entropy and activation energy as more
CN
molecules are involved
13. Which of the following compounds will exhibit geometrical
(a) (b) isomerism ?
(a) 2 - Phenyl -1 - butene
(b) 1, 1 - Diphenyl - 1 - propene
CH3
(c) 1 - Phenyl - 2 - butene
COOH (d) 3 - Phenyl -1 - butene
14. Match the catalysts to the correct processes :
Catalyst Process
(c) (d) H3C CH3 (A) TiCl4 (i) Wacker process
(B) PdCl2 (ii) Ziegler - Natta
polymerization
CH3
(C) CuCl2 (iii) Contact process
5. Sodium metal crystallizes in a body centred cubic lattice with (D) V2O5 (iv) Deacon's process
a unit cell edge of 4.29Å. The radius of sodium atom is (a) (A) - (ii), (B) - (iii), (C) - (iv), (D) - (i)
approximately : (b) (A) - (iii), (B) - (i), (C) - (ii), (D) - (iv)
(a) 5.72Å (b) 0.93Å (c) (A) - (iii), (B) - (ii), (C) - (iv), (D) - (i)
(c) 1.86Å (d) 3.22Å (d) (A) - (ii), (B) - (i), (C) - (iv), (D) - (iii)
JEEMAIN.GURU
downloaded from jeemain.guru
2 CHEMISTRY
15. The intermolecular interaction that is dependent on the 24. Which among the following is the most reactive ?
inverse cube of distance between the molecules is : (a) I2 (b) IC1
(a) London force (b) hydrogen bond (c) Cl2 (d) Br2
(c) ion - ion interaction (d) ion - dipole interaction 25. The standard Gibbs energy change at 300 K for the reaction
16. The molecular formula of a commercial resin used for
B + C is 2494.2 J. At a given time, the composition
2A
exchanging ions in water softening is C8H7SO3– Na+ (Mol.
wt. 206. What would be the maximum uptake of Ca2 + ions by
the resin when expressed in mole per gram resin ? 1 1
of the reaction mixture is [A] = , [B] = 2 and [C] = . The
2 2
2 1 reaction proceeds in the : [R = 8.314 J/K/mol, e = 2.718]
(a) (b)
309 412 (a) forward direction because Q < Kc
1 1 (b) reverse direction because Q < Kc
(c) (d) (c) forward direction because Q > Kc
103 206
17. Two Faraday of electricity is passed through a solution of (d) reverse direction because Q > Kc
CuSO4. The mass of copper deposited at the cathode is 26. Assertion: Nitrogen and oxygen are the main components in
(at. mass of Cu = 63.5 amu) the atmosphere but these do not react to form oxides of
nitrogen.
(a) 2g (b) 127 g
Reason: The reaction between nitrogen and oxygen requires
(c) 0 g (d) 63.5 g
high temperature.
18. The number of geometric isomers that can exist for square
(a) The assertion is incorrect, but the reason is correct
planar complex [Pt (Cl) (py) (NH3 ) (NH2 OH)] + is
(py = pyridine) : (b) Both the assertion and reason are incorrect
(a) 4 (b) 6 (c) Both assertion and reason are correct, and the reason is
the correct explanation for the assertion
(c) 2 (d) 3
(d) Both assertion and reason are correct, but the reason is
19. In Carius method of estimation of halogens, 250 mg of an
not the correct explanation for the assertion
organic compound gave 141 mg of AgBr. The percentage of
bromine in the compound is : 27. Which one has the highest boiling point ?
(at. mass Ag =108; Br = 80) (a) Kr (b) Xe
(a) 48 (b) 60 (c) He (d) Ne
(c) 24 (d) 36 28. Which polymer is used in the manufacture of paints and
lacquers ?
20. The color of KMnO4 is due to :
(a) Polypropene (b) Polyvinyl chloride
(a) L ® M charge transfer transition
(c) Bakelite (d) Glyptal
(b) s - s* transition
29. The following reaction is performed at 298 K.
(c) M ® L charge transfer transition
(d) d – d transition 2NO (g)
2NO(g) + O2(g) 2
21. The synthesis of alkyl fluorides is best accomplished by :
The standard free energy of formation of NO(g) is 86.6 kj/mol
(a) Finkelstein reaction (b) Swarts reaction
at 298 K. What is the standard free energy of formation of
(c) Free radical fluorination (d) Sandmeyer's reaction
NO2(g) at 298 K? (Kp = 1.6 × 1012)
22. 3 g of activated charcoal was added to 50 mL of acetic acid
solution (0.06N) in a flask. After an hour it was filtered and ln (1.6 ´ 1012 )
the strength of the filtrate was found to be 0.042 N. The (a) 86600 –
R (298)
amount of acetic acid adsorbed (per gram of charcoal) is :
(b) 0.5[2 × 86,600 – R(298) ln(1.6 × 1012)]
(a) 42 mg (b) 54 mg
(c) R(298) ln(1.6 × 1012) – 86600
(c) 18 mg (d) 36 mg
(d) 86600 + R(298) ln(1.6 × l012)
23. The vapour pressure of acetone at 20°C is 185 torr. When 1.2
g of a non-volatile substance was dissolved in 100 g of 30. From the following statements regarding H2O2, choose the
acetone at 20°C, its vapour pressure was 183 torr. The molar incorrect statement :
mass (g mol–1) of the substance is : (a) It has to be stored in plastic or wax lined glass bottles in
(a) 128 (b) 488 dark
(c) 32 (d) 64 (b) It has to be kept away from dust
(c) It can act only as an oxidizing agent
(d) It decomposes on exposure to light
JEEMAIN.GURU
downloaded from jeemain.guru
SOLUTIONS
1. (d) When 1, 3-dimethylcyclopentene is heated with ozone 10. (b) In the metallurgy of aluminium, purified Al2O3 is mixed
and then with zinc and acetic acid, oxidative cleavage with Na3AlF6 or CaF2 which lowers the melting point
leads to keto - aldehyde. of the mix and brings conductivity.
11. (b)
CH3 CH3
O CH3 COOH COCl CHO
1O - 78° C
¾ ¾ ¾3¾ ¾ ¾ ¾ ® O C–H
2 - Zn- CH 3 COOH KMnO4 SOCl2 H2/Pd
BaSO 4
CH3 CH3
(A) (B) (C)
O O
|| || Rosenmund’s
CH3 — C— CH 2 — CH 2 — CH— C— H reaction
|
CH3 12. (c) Reactions of higher order (>3) are very rare due to very
less chances of many molecules to undergo effective
5- keto – 2 – methylhexanal collisions.
2. (c) Water-soluble vitamins dissolve in water and are not
stored by the body. The water soluble vitamins include H
|
the vitamin B-complex group and vitamin C.
13. (c) H3C — C = CH — CH 2
3. (d) In alkaline earth metals, ionic size increases down the |
group. The lattice energy remains constant because Ph
sulphate ion is so large, so that small change in cationic
size does not make any difference. On moving down 1- Phenyl-2-butene the two groups around each of the
the group the degree of hydration of metal ions doubly bonded carbon
decreases very much leading to decrease in solubility. Because, all are different. This compound can show
cis-and trans-isomerism.
\ BeSO 4 > MgSO 4 > CaSO 4 > SrSO 4 > BaSO 4
14. (d) (A) - (ii), (B) - (i), (C) - (iv), (D) - (iii)
4. (a) 15. (b) Hydrogen bond is a type of strong electrostatic dipole-
+ – dipole interaction and dependent on the inverse cube
NH2 N = NCl CN of distance between the molecular ion-dipole
1
¾ NaNO
¾¾¾ 2 /HCl
¾¾ ® ¾ CuCN/KCN
¾ ¾ ¾ ¾® interaction µ .
0 - 5° C D r3
16. (b) 2 mole of water softner require 1 mole of Ca 2+ ion
CH3 CH3 CH3
1
5. (c) In bcc the atoms touch along body diagonal So, 1 mole of water softner require mole of Ca2+ ion
2
\ 2r + 2r = 3a
1 1
Thus, = mol / g will be maximum uptake
3a 3 ´ 4.29 2 ´ 206 412
\ r= = = 1.857Å
4 4 17. (d) Cu 2+ + 2e – ¾¾ ® Cu
6. (c)
2F i.e. 2 × 96500 C deposit Cu = 1 mol = 63.5 g
–13.6Z2 18. (d) Square planar complexes of type M[ABCD] form three
7. (a) Total energy = eV isomers. Their position may be obtained by fixing the
n2 position of one ligand and placing at the trans position
where n = 2, 3, 4 .... any one of the remaining three ligands one by one.
Putting n = 2
HOH2N Cl HOH2N NH3
-13.6
ET = = -3.4eV
4
8. (a) Phenelzine is an antidepressant, while others are Pt Pt
antacids.
9. (a) For isoelectronic species, size of anion increases as
negative charge increases. Thus the correct order is py NH3 py Cl
trans cis
N 3- > O 2 - > F -
(1.71) (1.40) (1.36)
JEEMAIN.GURU
downloaded from jeemain.guru
4 CHEMISTRY
HOH2N where w1, M1 = mass in g and mol. mass of solvent
NH3 w2, M2 = mass in g and mol. mass of solute
Let M2 = x
Pt p° = 185 torr
ps = 183 torr
CH 3Br + AgF ¾¾
® CH 3 F + AgBr 2494.2 J
Þ log KC = –
2.303 ´ 8.314 J / K / mol ´ 300 K
2CH3CH 2 Cl + Hg 2 F2 ¾¾ ® 2CH 3CH 2 F + Hg 2Cl 2 Þ log KC = – 0.4341
22. (c) Let the weight of acetic acid initially be w1 in 50 ml of KC = 0.37
0.060 N solution. Q > KC.
w 1 ´ 1000 26. (c) Nitrogen and oxgen in air do not react to form oxides of
Let the N = (Normality = 0.06 N) nitrogen in atmosphere because the reaction between
M.wt . ´ 50 nitrogen and oxygen requires high temperature.
w1 ´ 1000 27. (b) Xe. As we move down the group, the melting and boiling
0.06 = points show a regular increase due to corresponding
60 ´ 50
increase in the magnitude of their van der waal forces of
0.06 ´ 60 ´ 50 attraction as the size of the atom increases.
Þ w1 = = 0.18 g = 180 mg.
1000 28. (d) Glyptal is used in the manufacture of paints and
After an hour, the strength of acetic acid = 0.042 N lacquers.
so, let the weight of acetic acid be w2 29. (b) DG°NO(g) = 86.6k J/mol = 86600 J/mol
w ´1000 G° NO2 (g) = x J/mol
N= 2
60 ´ 50 T = 298, KP = 1.6 × 1012
w ´ 1000 DG° = – RT ln KP
0.042 = 2 Given equation,
3000
Þ w2 = 0.126 g = 126 mg 2NO (g)
2NO(g) + O2 (g) 2
So amount of acetic acid adsorbed per 3g
= 180 – 126 mg = 54 mg \ 2DG°NO – 2DG°NO = – R (298) ln (1.6 × 1012)
2
Amount of acetic acid adsorbed per g 2DG°NO – 2 × 86600 = – R (298) ln (1.6 × 1012)
2
2DG°NO = 2 × 86600 – R (298) ln (1.6 × 1012)
54 2
= = 18 mg 1
3 DG°NO = [2 × 86600 – R(298) ln (1.6 × 1012]
23. (d) Using relation, 22
= 0.5 [2 × 86600 – R (298) ln (1.6 × 1012)]
p° - ps w 2 M1
= 30. (c) H 2O2 has oxidizing and reducing properties both.
ps w1M 2
JEEMAIN.GURU
downloaded from jeemain.guru
C2 H5OH ( l ) + 3O2 ( g ) ¾¾
® 2CO2 ( g ) + 3H 2 O ( l ) ,
the amount of heat produced as measured in bomb calorimeter, The rate law for the formation of C is:
is 1364.47 kJ mol–1 at 25ºC. Assuming ideality the enthalpy dc dc
= k [ A][ B ] = k [ A] [ B ]
2
JEEMAIN.GURU
downloaded from jeemain.guru
2014-2 CHEMISTRY
11. Among the following oxoacids, the correct decreasing order 19. Which series of reactions correctly represents chemical
of acid strength is: reactions related to iron and its compound?
(a) HOCl > HClO2 > HClO3 > HClO4 dil. H 2SO 4
(a) Fe ¾¾¾¾¾ H 2SO 4 , O 2
® FeSO 4 ¾¾¾¾¾ ®
(b) HClO4 > HOCl > HClO 2 > HClO3
Fe 2 ( SO4 )3 ¾¾¾
heat
® Fe
(c) HClO4 > HClO3 > HClO2 > HOCl
O2 , heat dil. H2SO4 heat
(d) HClO2 > HClO 4 > HClO3 > HOCl (b) Fe ¾¾¾¾ ® FeO ¾¾¾¾¾ ® FeSO 4 ¾¾¾ ® Fe
12. The metal that cannot be obtained by electrolysis of an Cl2 , heat heat , air Zn
aqueous solution of its salts is: (c) Fe ¾¾¾¾® FeCl3 ¾¾¾¾® FeCl 2 ¾¾® Fe
(a) Ag (b) Ca O 2 , heat CO , 600°C
(c) Cu (d) Cr (d) Fe ¾¾¾¾ ® Fe3O 4 ¾¾¾¾¾ ®
13. The octahedral complex of a metal ion M3+ with four CO , 700°C
FeO ¾¾¾¾¾
® Fe
monodentate ligands L1, L2, L3 and L4 absorb wavelengths
in the region of red, green, yellow and blue, respectively. The 20. The equation which is balanced and represents the correct
increasing order of ligand strength of the four ligands is: product(s) is:
(a) L4 < L3 < L2 < L1 (b) L1 < L3 < L2 < L4 (a) Li 2O + 2KCl ® 2LiCl + K 2 O
( )
2 Mn3+ + e - ® Mn 2+ ; E 0 = +1.51V
(b) K2Cr2O7
(c) CrO3
The E0 for 3Mn 2 + ® Mn + 2Mn 3+ will be: (d) PCC (Pyridinium Chlorochromate)
24. The major organic compound formed by the raction of
(a) –2.69 V; the reaction will not occur
1, 1, 1-trichloroethane with silver powder is:
(b) –2.69 V; the reaction will occur
(a) Acetylene (b) Ethene
(c) –0.33 V; the reaction will not occur
(d) –0.33 V; the reaction will occur (c) 2 - Butyne (d) 2 - Butene
JEEMAIN.GURU
downloaded from jeemain.guru
25. Sodium phenoxide when heated with CO2 under pressure at 27. For which of the following molecule significant m ¹ 0?
125ºC yields a product which on acetylation produces C.
CI CN
ONa 125° H+
+ CO 2 ¾¾¾¾ ®B ¾¾¾® C
5 Atm Ac2 O
(i) (ii)
The major product C would be
OCOCH3 OH CI CN
COOH COCH3
(a) (b) OH SH
OH OCOCH3
OH SH
COOCH3 (a) Only (i) (b) (i) and (ii)
(c) (d)
COOH (c) Only (iii) (d) (iii) and (iv)
28. Which one is classified as a condensation polymer?
26. Considering the basic strength of amines in aqueous solution,
which one has the smallest pKb value? (a) Dacron (b) Neoprene
(a) (CH3)2NH (b) CH3NH2 (c) Teflon (d) Acrylonitrile
(c) (CH3)3N (d) C6H5NH2 29. Which one of the following bases is not present in DNA?
(a) Quinoline (b) Adenine
(c) Cytosine (d) Thymine
30. In the reaction,
LiAH PCl Alc.KOH
CH 3 COOH ¾¾¾¾
4 ® A ¾¾¾
5 ® B ¾¾¾¾® C,
JEEMAIN.GURU
downloaded from jeemain.guru
2014-4 CHEMISTRY
SOLUTIONS
1. (a) The electronic configuration of Rubidium (Rb = 37) is
1.4 ´ meq. of acid
1s 2 2s 2 2 p 6 3s 2 3 p 6 3d 10 4s 2 4 p 6 5s1 4. (b) % of N =
mass of organic compound
Since last electron enters in 5s orbital
1 M
Hence n = 5, l = 0, m = 0, s = ± meq. of H2SO4 = 60´ ´ 2 = 12
2 10
PV M
2. (b) Compressibility factor ( Z ) = meq. of NaOH = 20´ = 2
RT 10
(For one mole of real gas)
van der Waals equation \ meq. of acid consumed = 12 – 2 = 10
a 1.4 ´ 10
(P + )(V - b) = RT \ % of N = = 10%
2 1.4
V
At low pressure, volume is very large and hence 5. (a) Given for 0.2 M solution
correction term b can be neglected in comparison to
R = 50 W
very large volume of V.
i.e. V - b » V k = 1.4 S m–1 = 1.4 × 10–2 S cm–1
æ a ö l 1 l
Now, R = r = ´
çè P + 2 ÷ø V = RT a k a
V
a l
PV + = RT Þ = R ´ k = 50 ´1.4 ´ 10-2
V a
a For 0.5 M solution
PV = RT -
V R = 280 W
PV a k =?
= 1-
RT VRT
l
= 50 ´ 1.4 ´ 10-2
a a
Hence, Z = 1 -
VRT
l 1 l
Þ R=r = ´
3. (c) a k a
Cl – Cl –
1
Cl – Cl Þ k= ´ 50 ´ 1.4 ´ 10 -2
280
Cs+ =
1
´ 70 ´ 10-2 = 2.5 × 10–3 S cm–1
280
JEEMAIN.GURU
downloaded from jeemain.guru
1 O
9. (b) SO3 (g)
SO 2 (g) + O 2 (g)
2
For a given metal ion, weak field ligands create a complex
x with smaller D, which will absorbs light of longer l and
K P = K C ( RT )
thus lower frequency. Conservely, stronger field ligands
create a larger D, absorb light of shorter l and thus
where x = Dng = number of gaseous moles in product
higher v i.e. higher energy.
– number of gaseous moles in reactant
Red < Yellow < Green < Blue
l = 650 nm 570 nm 490 nm 450 nm
æ 1ö 3 1
= 1 - ç1 + ÷ = 1 - = - So order of ligand strength is
è 2 ø 2 2
L1 < L3 < L2 < L4
d [C ] 14. (a) Nitric oxide is paramagnetic in the gaseous state
10. (d) Let rate of reaction = = k[A]x [B]y because of the presence of one unpaired electron in its
t
outermost shell.
Now from the given data
The electronic configuration of NO is
1.2 × 10 – 3 = k [0.1]x[0.1]y .....(i)
1.2 × 10 – 3 = k [0.1]x[0.2]y .....(ii) s12s s1*2s s 22 s s*2 2 2 2 *1
2 s s 2 p p 2 p x = p2 p y p 2 p x
z
2.4 × 10 – 3 = k [0.2]x[0.1]y .....(iii) 15. (d) The reducing agent loses electron during redox
Dividing equation (i) by (ii) reaction i.e. oxidises itself.
-1 -2
1.2 ´10-3 k[0.1]x [0.1] y (a) H 2O 2 + 2H + + 2e - ¾¾
® 2H 2 O (Re d.)
Þ =
1.2 ´10-3 k [0.1]x [0.2] y
-1 0
We find, y = 0
(b) ® O 2 + 2H + + 2e- (Ox.)
H 2O 2 ¾¾
Now dividing equation (i) by (iii)
-1 -2
1.2 ´10-3 k[0.1]x [0.1] y (c) H 2O 2 + 2e - ¾¾
® 2 OH - (Re d.)
Þ =
2.4 ´10 -3 k [0.2] x [0.1] y
We find, x = 1 0
(d) H 2O-2 1 + 2OH - ¾¾
® O 2 + H 2 O + 2e - (Ox.)
d [C ]
Hence = k[ A]1 [ B ]0
dt
JEEMAIN.GURU
downloaded from jeemain.guru
2014-6 CHEMISTRY
16. (b) CsI3 dissociates as
CsI3 ® Cs+ + I3– Cl
|
w 24. (c) 2Cl - C - CH3 + 6Ag
17. (b) Number of moles of O 2 = |
32 Cl
4w w
Number of moles of N 2 = = 1, 1, 1-trichloroethane
28 7
¾¾
® CH 3C º CCH 3 + 6AgCl
\ Ratio = w : w = 7 : 32
32 7 2-butyne
3Mn 2+ ® Mn + + 2Mn 3+ ;
OH
H SO
0
E = EOx. + ERed. = – 1.18 + (– 1.51) = – 2.69 V ¾¾¾¾
2 4®
COOH
(–ve value of EMF (i.e. DG = +ve) shows that the
Salicylic acid
reaction is non-spontaneous)
19. (c) In equation (i) Fe2(SO4)3 and in equation (ii) Fe2(SO4)3
on decomposing will form oxide instead of Fe. (CH 3 CO) 2 O
The correct sequence of reactions is
O ,heat Co,600° C
Fe ¾¾¾¾
2 ® Fe3O 4 ¾¾¾¾¾ ®
O
D ||
Fe 2 (SO 4 )3 ¾¾® Fe O - C - CH3
+ CH3COOH
20. (b) The complex [CoCl(NH3 )5 ]+ decomposes under
COOH
acidic medium, so Aspirin
(Acetyl Salicylate)
[CoCl(NH3 )5 ]+ + 5H + ¾¾
® Co 2+ + 5NH 4 + + Cl -
21. (b) Steric congestion around the carbon atom undergoing 26. (a) Arylamines are less basic than alkyl amines and even
the inversion process will slow down the SN2 reaction, ammonia. This is due to resonance. In aryl amines the
hence less congestion faster will the reaction. So, the lone pair of electrons on N is partly shared with the
order is ring and is thus less available for sharing with a proton.
CH3Cl > (CH3)CH2 – Cl > (CH3)2CH – Cl > (CH3)3CCl In alkylamines, the electron releasing alkyl group
22. (d) R – CH2 – NH2 + CHCl3 + 3KOH (alc) ¾¾
® increases the electron density on nitrogen atom and
Carbyl amine reaction thus also increases the ability of amine for protonation.
R – CH2 – NC + 3KCl + 3H2O Hence more the no. of alkyl groups higher should be
Alkyl isocynide
the basicity of amine. But a slight discrepancy occurs
in case of trimethyl amines due to steric effect. Hence
23. (d) An excellent reagent for oxidation of 1° alcohols to
the correct order is
aldehydes is PCC.
PCC
(CH3 )2 NH > CH3 NH 2 > (CH3 )3 N > C 6 H5 NH 2
R - CH 2 - OH ¾¾¾
® R - CHO
JEEMAIN.GURU
downloaded from jeemain.guru
27. (d)
O O
H
[CO CH 2 - CH 2 - O - ] n
H Dacron (Polyester)
Alc. KOH
HOOC COOH +
CH2 = CH2
(C)
Terephthalic acid
HO – CH2 – CH2 – OH ¾¾
® Hence the product (C) is ethylene.
Ethylene glycol
JEEMAIN.GURU
downloaded from jeemain.guru
1
Some Basic Concepts
of Chemistry
PHYSICAL QUANTITIES AND SI UNITS : Physical Definition SI Unit
The 11th general conference of weights and measures in 1960 Quantity
recommended the use of international system of units. volume length cube m3
Abbreviated as SI Units (after the French expression La System area length square m2
International de units). The SI system has seven basic units of speed distance travelled ms– 1
physical quantities as follows : per unit time
Physical quantity Abbreviation Name of unit Symbol acceleration speed changed ms– 2
per unit time
time t second s
density mass per unit volume kg m–3
mass m kilogram kg
pressure force per unit area kgm–1s–2 or Nm–2
length l metre m (pressure = Pa)
temperature T kelvin K force mass times acceleration kgms–2
of object (Newton N)
electric current I ampere A
energy force times distance kgm2s–2
light intensity Iv candela Cd
travelled (Joule J)
amount of substance n mole mol frequency cycles per second s–1 (hertz = Hz)
JEEMAIN.GURU
downloaded from jeemain.guru
2 Chemistry
pound lb 0.453502 kg
10 –1 deci d 10 1 Deka da
10 –2 centi c 10 2 Hecta h
10 –3 milli m 10 3 kilo k
10 –6 micro m 10 6 Mega M
10 –9 nano n 10 9 Giga G
10 –12 pico p 10 12 Tera T
10 –15 femto f 10 15 Peta P
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
4 Chemistry
(a) 34.72 (has two decimal places) SEPARATION OF MIXTURES :
8.1 (has one decimal place) Mixtures can be separated into constituents by following methods:
------------ (i) Filtration can separate those mixtures whose one component
42.82 is soluble in a particular solvent and other is not.
------------ (ii) Distillation can be used to separate constituents of mixtures
Ans. = 42.82 but it should have only one decimal place so having different boiling points.
answer is 42.8. (iii) Extraction dissolves one out of several components of
(b) 59.273 mixture.
– 24.92 (iv) Crystallisation is a process of separating solids having
------------ different solubilities in a particular solvent.
34.353 (v) Sublimation separates volatile solids which sublime on
------------ heating from non-volatile solids.
Ans. = 34.35 (upto two decimal places) (vi) Chromatography is the technique of separating constituents
(vi) Calculations involving multiplication and division : In this of a mixture which utilises the property of difference of
case the final result should be reported having same number adsorption on a particular adsorbent.
of significant digits as that of the number having least (vii) Gravity separation separates constituents having different
significant digits. densities.
Example : 9.24 × 3.6 = 33.264 Rounded off to 33. (viii) Magnetic separation can separate magnetic components
3.6 is the number with least significant figures (two), hence from non magnetic ones.
final result is limited to two significant digits. Result is 33.
PHYSICAL AND CHEMICAL CHANGES :
5.235 A change which does not affect chemical composition and
In case of division = 0.3996 . Rounded off to 0.400.
13.1 molecular structure is a physical change and the one that involves
13.1 is the number with least (three) significant figures hence alteration of chemical composition and molecular structure is a
the result will be 0.400. chemical change.
MATTER : (i) Chemical Combination is reaction between two or more
Anything which occupies space, possesses mass and can be felt elements or compounds to form a single substance.
is called matter. H2 + I2 2HI
CLASSIFICATION OF MATTER :
(ii) Displacement means replacement of one element of compound
MATTER by another.
Physical Chemical
(iii) Decomposition involves splitting of a compound to form
Classification Classification
two or more substances.
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
6 Chemistry
DETERMINATION OF ATOMIC MASS : (ii) Victor meyer method : This method can determine the
(i) Dulong and petit's rule : It is based on experimental facts. molecular mass as
"At ordinary temperature, product of atomic mass and W
specific heat for solid elements is approximately 6.4 and this Molecular mass = × 22400
V
product is known as atomic heat of the element".
where W is the mass of liquid in gm. occupying a volume V
Atomic mass × specific heat = 6.4 ml at STP.
The law is valid for solid elements except Be, B, Si (iii) Vapour density method : Vapour density is the ratio of
and C. volume of a gas to the mass of same volume of hydrogen
Correct At. mass = Eq. mass × valency under identical conditions.
Cp Mass of V litre of gas
(ii) Specific heat method : This method is for gases. = , V.D. =
Cv Mass of V litre of hydrogen
where C p = specific heat at constant pressure and
Cv = specific heat at constant volume. the ratio g is a constant 1 Weight of volatile substance
or V.D. = ´ 22400
= 1.66 for monoatomic, 1.40 for diatomic, 1.33 for triatomic 2 Volume at STP
gas
Thus molecular mass = 2 × V.D.
and atomic mass of gaseous element
(iv) Colligative properties method : This method can be helpful
Mol. mass Mol. mass in determining molecular mass as
= = .
atomicity g
Kb ´ w ´1000
(iii) Chloride formation method : This method converts the elevation in boiling point ( DTb ) =
W ´ mol. mass
element (whose mass is to be determined) into volatile
chloride whose vapour density is found by Victor Mayer Where DTb is elevation in b.p., Kb is molal elevation constant
method. w is wt. of solute W is wt. of solvent
Molecular mass = 2 × V.D.
Kf ´ w ´1000
(iv) Vapour density method is suitable for elements having volatile Depression in freezing point ( DTf ) =
chlorides. W ´ mol. mass
Atomic mass = Eq. mass of metal × valency. GRAM MOLECULAR MASS OR MOLAR MASS :
(v) Mitscherlich's law of isomorphism : It states that That amount of substance whose mass in grams is equal to its
isomorphous substances have similar chemical constitution. molecular mass or the equivalently molecular mass of a substance
Isomorphous substances form crystals of same shape and expressed in grams is called gram molecular mass. Gram molecular
valencies of elements forming isomorphous salts are also
mass is also called one gram molecule. thus
same. eg: ZnSO4. 7H2O, MgSO4.7H2O and FeSO4.7H2O are
isomorphous. Wt. of substance (gms.)
No. of gm molecules =
GRAM ATOMIC MASS (GAM) GMM of substance
Is the mass of an atom expressed in gms. EQUIVALENT MASS :
Mass of element in grams It is the number of parts by weight of the substance that combines
No. of Gm-atoms of element =
GAM of element or displaces, directly or indirectly, 1.008 parts by mass of hydrogen
or 8 parts by mass of oxygen or 35.5 parts by mass of chlorine.
MOLECULAR MASS :
It can be calculated as
It is the average relative mass of the molecule as compared with
mass of C-12 atom. Atomic mass
(i) Equivalent mass for elements = Valency
Molecular mass = Average relative mass of one molecule
1
´ Mass of C - 12 atom Molecular mass
12 (ii) Equivalent mass for acids =
Basicity of acids
CALCULATION OF MOLECULAR MASS :
(i) Graham's law of diffusion : It states that rate of diffusion of Molecular mass
(iii) Equivalent mass for bases =
two gases is inversely proportional to the square root of Acidity of base
ratio of their molecular weights.
(iv) Equivalent mass for salts
r1 M2
= Formula mass
r2 M1 =
(Valency of cation ) ( No. of cations)
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
8 Chemistry
(xi) Volatile chloride method PARTS PER MILLION (ppm) :
Valency of metal It is the mass of solute present in one million parts by mass of
solution.
2 ´ VD of chloride 2 ´ VD
= = Mass of solute
Eq. mass of metal chloride E + 35.5 ppm = ´ 10 6
Mass of solution
2 ´ VD of chloride NORMALITY :
ÞE= - 35.5 It is the number of gram equivalents of a solute present in one litre
Valency
of solution.
CHEMICAL EQUATION : Gram equivalent s of solute
Normality =
It is the equation representing chemical change in terms of formula Volume of solution in litre
of reactants and products
(i) An equation which has not been equalised in terms of number Mass of solute in gms.
=
of atoms of reactants and products is called a skeleton GEM of solute ´ volume of solution in litre
equation. Normality depends on temperature. Also if strength is given in
(ii) An equation having equal number of atoms of various kinds normalities, N1 of A & N2 of B
on both sides is a balanced equation. Then N1V1 = N2V2.
MOLARITY :
EMPIRICAL FORMULA : It is the number of moles of solute present in one litre of solution.
It is the simplest formula of a compound giving simplest whole
number ratio of atoms present in one molecule. e.g. CH is empirical Moles of solute
M=
formula of benzene. Volume of solution (L)
MOLECULAR FORMULA : Weight of solute
=
It is the actual formula of a compound showing the total number GMM of solute ´ Volume of solution (L)
of atoms of constituent elements e.g. C6H6 is molecular formula of
benzene. Þ Moles = M ´ V(in litre) and millimoles = M × V(in ml).
Molecular formula = n × empirical formula, where n is simple whole Molarity and mass percentage have the relation M
number.
mass percentage ´10 ´ d
= , where d = density
SOLUTION : GMM of solute
It is a homogenous mixture of two or more substances. The If a solution of molarity M1 and volume V1 adds up with a solvent
component of solution having larger proportion is solvent and to a final volume V2, then molarity M2 is given by
others are solute.
M1V1
MOLE FRACTION : M2 =
V2
It is the ratio of moles of a constituent to the total number of moles
in a solution. If two different solutions (M1, V1) and (M2, V2) are mixed then
Let A be solute & B is solvent then mole fraction of solute (xA) molarity of resulting solution is
M1V1 + M 2 V2
nA M=
= , where n is the number of moles. V1 + V2
nA + nB
Also, Molarity × GMM of solute = Normality × GEM of solute
Mole fraction of solution x A + x B = 1 MOLALITY :
It is the number of moles of solute in 1 kg of solvent.
MASS PERCENTAGE :
It is the number of parts by mass of solute per hundred parts by Moles of solute
Molality (m) =
mass of solution. If WA is mass of solute and WB the mass of Weight of solvent (Kg)
solvent, then
Weight of solute ´ 1000
=
WA Mol. wt. of solute ´ Wt. of solvent
Mass percentage of A = ´100 .
WA + WB Molality is independent of temperature.
FORMALITY (F) :
VOLUME PERCENTAGE : It is the number of gram formula mass of ionic solute dissolved in
It is the number of parts by volume of solute per hundred parts by 1 litre of solution.
volume of solution. If VA is volume of solute and VB is the volume
of solvent then Mass of solute (gm)
Formality =
Volume of solution (litre)´ GFM of solute
VA
Volume percentage of A = ´100 LIMITING REAGENT :
VA + VB It is the reactant which is completely consumed during the reaction.
JEEMAIN.GURU
downloaded from jeemain.guru
1. Calculate the weight of Iron which will be converted into its Sol. Since terpentine oil absorbs O3, the volume of O3 absorbed
oxide by the action of 18 g of steam. by terpentine oil is 10 ml.
Sol. The required equation is 3Fe + 4H2O ¾¾ ® Fe3O4 + 4H2 Volume of O2 = 100 – 10 = 90 ml
From gas equation (m)
3 × 56 g 4 × 18 g
3´ 56 WRT
g 18 g PV =
4 M
\ Weight of Fe converted into oxide = 42 g. Mol. wt of ozonised oxygen
2. The vapour density of a mixture containing NO2 and N2O4 is WRT 1.5 ´ 0.0821´ 273
38.3 at 27°C. Calculate the moles of NO2 in 100 g mixture. = = = 33.62
PV 1´1
Sol. Molecular weight of mixture = 2 × 38.3 = 76.6
Let weight of NO2 present in mixture be x g Mol. ratio of O2 and O3 90 : 10.
M. wt. of ozonised oxygen
x 100 - x 100
then + = \ x = 20.10 g
46 92 76.6 90 ´ 32 + 10 ´ a
= = 33.62 Þ a = 48.2 .
100
20.10
Hence moles of NO2 in mixture = = 0.43 Mol. wt. of ozone = 48.2.
46
5. How many millilitre of 0.5M H2SO4 are needed to dissolve
3. A mixture of 20 ml of CO, CH4 and N2 was burnt in excess of
0.5 g of copper (II) carbonate.
O2, resulting in reduction of 13 ml of volume. The residual
gas was then treated with KOH solution to show a Sol. Millimoles of H2SO4 = Millimoles of CuCO3
contraction of 14 ml in Volume. Calculate volume of CO, CH4 0.5 ´1000
and N2 in mixture. All measurements are made at constant T and P. 0.5 ´ V = or V = 8.097 ml.
123.5
Sol. Let a, b and c be the volume of CO, CH4 and N2 in mixture.
(II) CH 4 + 2O 2 ¾
¾® CO 2 + 2 H 2 O 40 ´ 1000
Sol. Normality of NaOH = =1
b 2b b 40 ´ 1000
(III) N 2 + O 2 ¾
¾® No Reaction 39 ´ 1000 39n
Normality of acid = =
Since reduction in volume is 13. This is volume of O2 used 82
then we have ´ 1000 82
n
a n = Basicity of acid
+ 2b = 13 (I)
2 N1V1 = N2V2
Volume of CO2 formed is volume absorbed by KOH
a + b = 14 (II) 39n ´ 100
= 1 ´ 95 n = 1.99 = 2 Basicity is 2 .
\ c = 20 – 14 = 6 ml 82
Solving I & II we get a = 10 ml, b = 4 ml.
\ CO = 10 ml, CH4 = 4 ml and N2 = 6 ml 7. For the reaction N2O5 (g) 2NO2 (g) + 0.5 O2 (g).
Calculate the mole fraction of N2O5 (g) decomposed at a
4. The weight of one litre sample of ozonised oxygen at NTP
was found to be 1.5 g. When 100 ml of this mixture at NTP constant volume and temperature if the initial pressure is 600
were treated with terpentine oil the volume was reduced to mm Hg and the pressure at any time is 960 mm Hg. Assume
90 ml. Hence calculate the molecular weight of Ozone. ideal gas behaviour.
JEEMAIN.GURU
downloaded from jeemain.guru
10 Chemistry
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
12 Chemistry
20. One g of the chloride of an element was found to contain 22. 0.2988g of the silver salt of a dibasic acid on ignition gave
0.835 g of chlorine. It’s vapour density is 85. Find the 0.1944g of Silver. Find the equivalent weight of acid.
molecular formula of chloride. Sol. Equivalent weight of the acid
Sol. Weight of element = (1 – 0.835) = 0.165g æ wt. of silver salt ´ 108 ö
=ç - 107 ÷
è wt. of silver ø
Eq. wt. of element = 0.165 ´ 35.5 = 7.014
0.835
æ 0.2988 ´ 108 ö
=ç - 107 ÷ = 59
Let x be the valency of element è 0 .1944 ø
Atomic wt. of element = 7.014 x 23. 0.298g platinichloride salt of the mono acid base yielded
The Molecular formula of chloride MCl x 0.0975g of platinum. Find the equivalent weight of mono
\ Molecular weight of chloride acid base
= 7.014.x + x.35.3 = V.D ´ 2 Sol. Equivalent weight of the base
or, (42.541)x = 2 × 85 1 æ wt of Pt.salt´195 ö
= ç - 410÷
\ x= 4 2è wt of Pt. ø
Hence Molecular formula of chloride = MCl4
1 æ 0.298 ´ 195 ö
21. Copper sulphide and Metal sulphide are isomorphous. In = ç - 410 ÷ = 93
2 è 0.0975 ø
the first compound sulphur is 20.14% and in the second
compound 12.94%. If the atomic weight of Copper is 63.57. 24. 1.0g of metal on treatment with dilute mineral acid gave
Find the atomic weight of Metal 1242 ml of hydrogen at NTP. Calculate the equivalent
weight, atomic weight and valency of the metal, if its
Sol. Find the fixed (same) amount of sulphur reacting with
specific heat is 0.238
copper and Metal separately.
In the first-compound 1g sulphur combines with wt. of metal
Sol. Equivalent weight of metal = wt. of hydrogen ´ 1.008
(100 - 20.14)
= 3.96 g Copper 1 ml of hydrogen at NTP = 0.00009g
20.14
1
In the second compound 1g sulphur combines with \ Eq. wt of metal = ´ 1.008 = 9 g
0.00009 ´ 1242
By Dulong Petit’s law
(100 - 12.94)
= 6.72 g Metal Atomic mass×sp. heat = 6.4
12.94
6.4
Atomic wt. of Metal wt of Metal Atomic mass = = 26.86
= 0.238
Atomic wt. of Cu wt of Copper 26.86
valency = =3
6.72 9
Atomic wt. of Metal = ´ 63.57 = 107.87
3.96 \ Exact atomic mass = 9×3 = 27
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
14 Chemistry
(a) Results of both the students are neither accurate nor 20. One mole of a gas occupies a volume of 22.4 L. This is
precise. derived from
(b) Results of student A are both precise and accurate. (a) Berzelius’ hypothesis
(c) Results of student B are neither precise nor accurate. (b) Gay-Lussac’s law
(d) Results of student B are both precise and accurate. (c) Avogadro’s law
(d) Dalton’s law
16. A measured temperature on Fahrenheit scale
is 200 °F. What will this reading be on Celsius scale ? 21. Two containers P and Q of equal volume (1 litre each) contain
6 g of O2 and SO2 respectively at 300 K and 1 atmosphere,
(a) 40° C (b) 94° C
then
(c) 93.3 °C (d) 30° C (a) number of molecules in P is less than that in Q
17. Which of the following is an example of a heterogeneous (b) number of molecules in P and Q is same
substance? (c) number of molecules in Q is less than that in P
(a) Bottled water (b) Table salt (d) Either (a) or (b)
(c) Pieces of copper (d) Candle 22. In a chemical reaction
18. Which of the following statements about a compound is K 2 Cr 2 O 7 + xH 2 SO 4 + ySO 2
incorrect ?
¾ ¾® K 2SO 4 + zCr2 (SO 4 ) 3 + H 2 O
(a) A molecule of a compound has atoms of different elements.
(b) A compound cannot be separated into its constituent the values of x, y, z are
(a) 4, 1, 4 (b) 1, 3, 1
elements by physical methods of separation.
(c) 3, 2, 3 (d) 2, 1, 2
(c) A compound retains the physical properties of its
constituent elements. 23. 25.4 g of I 2 and 14.2 g of Cl 2 are made to react completely
(d) The ratio of atoms of different elements in a compound to yield a mixture of ICl and ICl3 . Calculate moles of ICl
is fixed.
and ICl3 formed
19. In compound A, 1.00g of nitrogen unites with 0.57g of
(a) 0.1, 0.1 (b) 0.2, 0.2
oxygen. In compound B, 2.00g of nitrogen combines with
(c) 0.1, 0.2 (d) 0.2, 0.1
2.24g of oxygen. In compound C, 3.00g of nitrogen combines
24. The Statue of Liberty is made of 2.0 × 105 lbs of copper
with 5.11g of oxygen. These results obey the following law sheets bolted to a framework. (1lb = 454 g). How many atoms
(a) law of constant proportion of copper are on the statue?
(b) law of multiple proportion (Atomic weight: Cu = 63.5).
(c) law of reciprocal proportion (a) 2.1 × 1027 (b) 8.6 × 1029
(c) 4.3 × 10 26 (d) 8.6 × 1026
(d) Dalton’s law of partial pressure
1. In the final answer of the expression How would the weight of the sample be reported?
(a) 3.93 g (b) 3g
(29.2 - 20.2)(1.79 ´ 10 )
(c) 3.9 g (d) 3.929 g
1.37 5. Dimension of pressure are same as that of
the number of significant figures is (a) Energy (b) Force
(a) 1 (b) 3 (c) 2 (d) 4 (c) Force per unit volume (d) Energy per unit volume
2. Given the numbers : 161 cm, 0.161 cm, 0.0161 cm. The number 6. The prefix 1018 is
of significant figures for the three numbers are (a) giga (b) kilo
(a) 3, 4 and 5 respectively (b) 3, 3 and 4 respectively (c) exa (d) nano
(c) 3, 3 and 3 respectively (d) 3, 4 and 4 respectively 7. Which of the following halogen can be purified by
3. One fermi is sublimation?
(a) 10–15 cm (b) 10–13 cm (a) I2 (b) Cl2
–10
(c) 10 cm (d) 10–12 cm (c) Br2 (d) F2
4. A sample was weighted using two different balances. The 8. A mixture of sand and iodine can be separated by
results were (a) crystallisation (b) distillation
(i) 3.929 g (ii) 4.0 g (c) sublimation (d) fractionation
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
16 Chemistry
36. For preparing 0.1 N solution of a compound from its impure 46. The volume of water to be added to 100 cm3 of 0.5 N H2SO4 to
sample of which the percentage purity is known, the weight get deci normal concentration is
of the substance required will be (a) 400 cm3 (b) 450 cm3
(a) less than the theoretical weight (c) 500 cm 3 (d) 100 cm3
(b) more than the theoretical weight 47. 250 ml of a sodium carbonate solution contains 2.65 grams
(c) same as the theoretical weight of Na2CO3. If 10 ml of this solution is diluted to one litre,
what is the concentration of the resultant solution?
(d) none of these
(mol. wt. of Na2CO3 = 106)
37. 10 g CaCO3 gives on strong heating CO2. It gives quicklime
(a) 0.1 M (b) 0.01 M
(in grams)
(c) 0.001 M (d) 10–4 M
(a) 5g (b) 4.4 g (c) 5.6 g (d) 4 g
48. 3.92 g of ferrous ammonium sulphate crystals are dissolved in
38. Haemoglobin contains 0.33% of iron by weight. The 100 ml of water. 20 ml of this solution requires 18 ml of potassium
molecular weight of haemoglobin is approximately 67200. permaganate during titration for complete oxidation. The weight
The number of iron atoms (at. wt. of Fe = 56) present in one of KMnO4 present in one litre of the solution of
molecule of haemoglobin is (a) 3.476 g (b) 12.38 g
(a) 6 (b) 1 (c) 2 (d) 4 (c) 1.238 g (d) 34.76 g
39. The number of molecules in 16 g of methane is 49. 30 g of Magnesium and 30 g of oxygen are reacted, then the
residual mixture contains
16
(a) 3.0 × 1023 (b) ´ 10 23 (a) 50 g of Magnesium oxide and 10 g of oxygen
6.02
(b) 40 g of Magnesium oxide and 20 g of oxygen
16 (c) 45 g of Magnesium oxide and 15 g of oxygen
(c) 6.02 × 1023 (d) ´ 10 23 (d) 60 g of Magnesium oxide only
3.0
50. In order to prepare one litre normal solution of KMnO4, how
40. 50 ml 10 N H2SO4, 25 ml 12 N HCl and 40 ml 5 N HNO3 were
many grams of KMnO4 are required if the solution is to be
mixed together and the volume of the mixture was made 1000 ml
used in acid medium for oxidation?
by adding water. The normality of the resultant solution will be
(a) 158 g (b) 62.0 g
(a) 2 N (b) 1 N (c) 3 N (d) 4 N
(c) 31.6 g (d) 790 g
41. A molal solution is one that contains 1 mole of a solute in 51. In a chemical reaction
(a) one litre of the solvent K 2 Cr 2 O 7 + xH 2 SO 4 + ySO 2
(b) 1000 g of the solvent
(c) one litre of the solution ¾
¾® K 2SO 4 + zCr2 (SO 4 ) 3 + H 2 O
(d) 22.4 litres of the solution the values of x, y, z are
42. A 100 ml solution of 0.1 N HCl was titrated with 0.2 N NaOH (a) 4, 1, 4 (b) 1, 3, 1
solution. The titration was discontinued after adding 30 ml (c) 3, 2, 3 (d) 2, 1, 2
of NaOH solution. The remaining titration was completed 52. The maximum amount of BaSO4 precipitated on mixing equal
by adding 0.25 N KOH solution. The volume of KOH required volumes of BaCl2 (0.5 M) with H2SO4 (1 M) will correspond to
for completing the titration is (a) 1.0 M (b) 0.5 M
(a) 16 ml (b) 32 ml (c) 1.5 M (d) 2.0 M
(c) 35 ml (d) 70 ml 53. In the reaction
43. An aqueous solution of 6.3 g of oxalic acid dihydrate is ® 4NO(g) + 6H 2 O(l ) ,when 1 mole
4NH 3 (g) + 5O 2 (g) ¾¾
made up to 250 ml. The volume of 0.1 N NaOH required to of ammonia and 1 mole of O2 are made to react to completion
completely neutralise 10 ml of this solution is (a) 1.0 mole of H2O is produced
(a) 20 ml (b) 40 ml (b) 1.0 mole of NO will be produced
(c) 10 ml (d) 4 ml (c) all the ammonia will be consumed
44. The percentage of nitrogen in urea is about (d) all the oxygen will be consumed
(a) 85 (b) 46 (c) 18 (d) 28 54. The set of numerical coefficients that balances the equation
45. How much of NaOH is required to neutralise 1500 cm3 of 0.1 ¾® K 2 Cr2 O 7 + KCl + H 2 O is
K 2 CrO 4 + HCl ¾
N HCl? (Na = 23) (a) 2, 2, 1, 2, 1 (b) 2, 2, 1, 1, 1
(a) 60 g (b) 4 g (c) 6 g (d) 40 g (c) 2, 1, 1, 2, 1 (d) 1, 1, 2, 2, 1
JEEMAIN.GURU
downloaded from jeemain.guru
1. The mass of carbon anode consumed (giving only 12. With increase of temperature, which of these changes?
carbondioxide) in the production of 270 kg of aluminium (a) molality [AIEEE 2002]
metal from bauxite by the Hall process is (Atomic mass: (b) weight fraction of solute
Al = 27) [CBSE-PMT 2005] (c) fraction of solute present in water
(a) 270 kg (b) 540 kg (c) 90 kg (d) 180 kg (d) mole fraction.
2. The number of moles of KMnO4 reduced by one mole of 13. Number of atoms in 558.5 gram Fe (at. wt. of Fe = 55.85
KI in alkaline medium is: [CBSE-PMT 2005] g mol–1) is [AIEEE 2002]
(a) one (b) two (c) five (d) one fifth (a) twice that in 60 g carbon (b) 6.023 ´ 1022
3. Volume occupied by one molecule of water (c) half that in 8 g He (d) 558.5 ´ 6.023 ´ 1023
(density = 1 g cm–3) is : [CBSE-PMT 2008] 14. One mole of magnesium nitride on the reaction with an
(a) 9.0 × 10–23 cm3 (b) 6.023 × 10– 23 cm3 excess of water gives : [AIEEE 2004]
(a) two moles of ammonia (b) one mole of nitric acid
(c) 3.0 × 10–23 cm3 (d) 5.5 × 10– 23 cm3
- (c) one mole of ammonia (d) two moles of nitric acid
4. Number of moles of MnO4 required to oxidize one mole of
15. If we consider that 1/6, in place of 1/12, mass of carbon atom
ferrous oxalate completely in acidic medium will be : is taken to be the relative atomic mass unit, the mass of one
[CBSE-PMT 2008] mole of the substance will [AIEEE 2005]
(a) 0.6 moles (b) 0.4 moles (a) be a function of the molecular mass of the substance
(c) 7.5 moles (d) 0.2 moles (b) remain unchanged
5. An organic compound contains carbon, hydrogen and (c) increase two fold
oxygen. Its elemental analysis gave C, 38.71% and H, 9.67%. (d) decrease twice
The empirical formula of the compound would be : 16. How many moles of magnesium phosphate, Mg3(PO4)2 will
[CBSE-PMT 2008] contain 0.25 mole of oxygen atoms? [AIEEE 2006]
(a) 1.25 × 10 –2 (b) 2.5 × 10 –2
(a) CH3O (b) CH2O (c) CHO (d) CH4O
6. How many moles of lead (II) chloride will be formed from a (c) 0.02 (d) 3.125 × 10–2
reaction between 6.5 g of PbO and 3.2 g of HCl ? –1
17. The density (in g mL ) of a 3.60 M sulphuric acid solution
[CBSE-PMT 2008] that is 29% H2SO4 (molar mass = 98 g mol–1) by mass will
(a) 0.044 (b) 0.333 (c) 0.011 (d) 0.029 be [AIEEE 2007]
7. 10 g of hydrogen and 64 g of oxygen were filled in a steel (a) 1.45 (b) 1.64
vessel and exploded. Amount of water produced in this (c) 1.88 (d) 1.22
reaction will be: [CBSE-PMT 2009] 18. In the reaction, [AIEEE 2007]
(a) 3 mol (b) 4 mol (c) 1 mol (d) 2 mol 2Al( s ) 6HCl( aq ) 2Al3 (aq) + 6Cl (aq) + 3H2 ( g)
8. The number of atoms in 0.1 mol of a triatomic gas is :(NA = (a) 11.2 L H2(g) at STP is produced for every mole HCl(aq)
6.02 ×1023 mol–1) [CBSE-PMT 2010] consumed
(a) 6.026 × 1022 (b) 1.806 × 1023 (b) 6 L HCl(aq) is consumed for every 3 L H2(g) produced
(c) 3.600 × 1023 (d) 1.800 × 1022 (c) 33.6 L H2(g) is produced regardless of temperature and
9. Which has the maximum number of molecules among the pressure for every mole Al that reacts
following ? [CBSE-PMT 2011 M] (d) 67.2 H2(g) at STP is produced for every mole Al that
reacts.
(a) 44 g CO2 (b) 48 g O3
19. The molality of a urea solution in which 0.0100 g of urea,
(c) 8 g H2 (d) 64 g SO2
[(NH2)2CO] is added to 0.3000 dm3 of water at STP is :
10. How many grams of concentrated nitric acid solution should
[AIEEE 2011 RS]
be used to prepare 250 mL of 2.0M HNO3 ? The concentrated
acid is 70% HNO3 [NEET 2013] (a) 5.55 10 4 m (b) 33.3 m
(a) 90.0 g conc. HNO3 (b) 70.0 g conc. HNO3 (c) 3.33 × 10–2 m (d) 0.555 m
(c) 54.0 g conc. HNO3 (d) 45.0 g conc. HNO3 20. A gaseous hydrocarbon gives upon combustion 0.72 g of
20
11. 6.02 × 10 molecules of urea are present in 100 mL of its water and 3.08 g. of CO2. The empirical formula of the
solution. The concentration of solution is : [NEET 2013] hydrocarbon is : [JEE Main 2013]
(a) C2H4 (b) C3H4 (c) C6H5 (d) C7H8
(a) 0.01 M (b) 0.001 M (c) 0.1 M (d) 0.02 M
JEEMAIN.GURU
downloaded from jeemain.guru
18 Chemistry
21. Experimentally it was found that a metal oxide has formula 22. Consider a titration of potassium dichromate solution with
M0.98O. Metal M, present as M2+ and M3+ in its oxide. acidified Mohr's salt solution using diphenylamine as
Fraction of the metal which exists as M3+ would be : indicator. The number of moles of Mohr's salt required per
[JEE Main 2013] mole of dichromate is [IIT-JEE 2007]
(a) 7.01% (b) 4.08% (c) 6.05% (d) 5.08% (a) 3 (b) 4 (c) 5 (d) 6
1. The correctly reported answer of addition of 29.4406, 3.2 12. A compound made up of two elements A and B is found to
and 2.25 will have significant figures contain 25% A (atomic mass = 12.5) and 75% B (atomic mass
(a) 3 (b) 4 (c) 2 (d) 5 = 37.5). The simplest formula of the compound is
2. On dividing 0.25 by 22.1176 the actual answer is 0.011303. (a) AB (b) AB2 (c) AB3 (d) A3B
The correctly reported answer will be 13. On analysis a certain compound was found to contain iodine
and oxygen in the ratio of 254 gm of iodine (atomic mass
(a) 0.011 (b) 0.01 (c) 0.0113 (d) 0.013
127) and 80 gm oxygen (at mass = 16). What is the formula of
3. In which of the following number all zeros are significant? the compound.
(a) 0.0005 (b) 0.0500 (c) 50.000 (d) 0.0050 (a) IO (b) I2O (c) I5O3 (d) I2O5
4. If law of conservation of mass was to hold true, then 20.8 14. Two oxides of a metal contain 50% and 40% metal (M)
gm of BaCl2 on reaction with 9.8 gm of H2SO4 will produce respectively. If the formula of first oxide is MO2 the formula
7.3 gm of HCl and BaSO4 equal to : of second oxide will be
(a) 11.65 gm (b) 23.3 gm (a) MO2 (b) MO3 (c) M2O (d) M2O5
(c) 25.5 gm (d) 30.6 gm 15. The ratio of the molar amounts of H2S needed to precipitate
5. One of the following combination which illustrates the law the metal ions form 20 ml each of 1 M Ca(NO3)2 and 0.5M
of reciprocal proportions ? CuSO4 is
(a) N2O3, N2O4, N2O5 (b) NaCl, NaBr, NaI (a) 1 : 1 (b) 2 : 1 (c) 1 : 2 (d) indefinite
(c) CS2, CO2, SO2 (d) PH3, P2O3, P2O5 16. 12 gm of Mg (atomic mass 24) will react completely with
hydrochloric acid to give
6. If isotopic distribution of C-12 and C-14 is 98% and 2%
(a) One mol of H2
respectively then the no. of C-14 atoms in 12gm of carbon is
(b) 1/2 mol of H2
(a) 1.032 × 1022 (b) 3.0 × 1022
(c) 2/3 mol of O2
(c) 5.88 ×1023 (d) 6.02 × 1023
(d) both 1/2 mol of H2 and 1/2 mol of O2
7. Which of the following contains maximum number of atom
17. The total number of protons in 10 gm of calcium carbonate
(a) 2.0 mole of S8 (b) 6.0 mole of S is (No = 6.023 × 1023)
(c) 5.5 mole of SO2 (d) 44.8 litre of CO2 of S.T.P. (a) 1.5057 × 1024 (b) 2.0478 × 1024
8. A sample of AlF3 contains 3.0 × 1024 F– ions. The number of (c) 3.0115 × 1024 (d) 14.0956 × 1024
formula unit of this sample are 18. 2.76 gm of silver carbonate (at mass of Ag 108) on being
(a) 9 × 1024 (b) 3 × 1024 heated strongly yield a residue weighing
(c) 0.75 × 10 24 (d) 1.0 × 1024 (a) 2.16 gm (b) 2.48 gm
9. What mass of calcium chloride in grams would be enough (c) 2.32 gm (d) 2.64 gm
to produce 14.35 gm of AgCl ? 19. If 0.5 mol of BaCl2 is mixed with 0.2 mol of Na3PO4 then maximum
(a) 5.55 gm (b) 8.295 gm (c) 16.5 gm (d) 11.19 gm number of moles of Ba 3 (PO 4 ) 2 that can be formed is
10. If potassium chlorate is 80% pure, then 48 gm of oxygen (a) 0.7 (b) 0.5 (c) 0.3 (d) 0.1
would be produced from (atomic mass of K =39) 20. 1.12 ml of a gas is produced at S.T.P. by the action of 4.12 mg
(a) 153.12 gm of KClO3 (b) 122.5 gm of KClO3 of alcohol ROH with methyl magnesium Iodide. The
(c) 245 gm of KClO3 (d) 98 gm of KClO3 molecular mass of alcohol is
11. If 224 ml of a triatomic gas has a mass of 1 gm at 273K and 1 (a) 16.0 (b) 41.2 (c) 82.4 (d) 156.0
atmospheric pressure then the mass of one atom is 21. An unsaturated hydrocarbon weighing 1.68 gm has volume
(a) 8.30 × 10–23 gm (b) 2.08 × 10–23 gm of 488 ml at S.T.P. If it contains 14% of hydrogen, then the
(c) 5.53 × 10–23 gm (d) 6.24 × 10–23 gm family to which the hydrocarbon belongs is
(a) alkane (b) alkene (c) alkyl (d) benzene
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
20 Chemistry
= Force =
Work (energy/di stance)
=
Energy M. Wt = 30.12 Hence gas is NO.
area Area Volume
6. (c) Exa = 1018 (see text.) 1
20. (b) 1 amu = of the mass of C-12.
12
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
22 Chemistry
46. (a) N1V1 = N2V2
270 ´ 10 3
\ 100 × 0.5 = 0.1 × V2 No. of gram equivalent of Al = = 30 × 103
\ V2 = 500 water to be is added 400 ml. 100 ml is already 9
present. Hence,
No. of gram equivalent of C = 30 × 103
Wt ´ 1000 2.65 ´ 1000 Again,
47. (c) Molarity = = = 0.1 M
MW ´ V 106 ´ 250 No. of gram equivalent of C
M1V1 = M2V2 mass in gram mass
\ 10 × 0.1 = 1000 × M2 = 0.001 M = Þ 30 × 103 =
gram equivalent weight 3
48. (a) Normality of ferrous Amm. sulphate
Þ mass = 90 × 10 g = 90 kg
3
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
24 Chemistry
21. (b) For one mole of the oxide 9. (a) The desired equation is
Moles of M = 0.98
CaCl 2 + 2AgNO3 ® 2AgCl + Ca(NO3 ) 2
Moles of O2– = 1 111g 143.5´2g
Let moles of M3+ = x
\ Moles of M2+ = 0.98– x \ 14.35 g of AgCl will be obtained from
on balancing charge 111 ´ 14.35
= 5.55gm
(0.98 – x) × 2 + 3x – 2 = 0 143.5 ´ 2
x = 0.04
heat
10. (a) 2KClO3 ¾¾¾
0.04 ® 2KCl + 3O 2
\ % of M3+ = ´100 = 4.08% 2´122.5g 3´32g
0.98 245 96
22. (d) The following reaction occurs:
48 gm of oxygen will be produced from 122.5 g of KClO3
6Fe 2 + Cr2 O 27 + 14H + 6Fe3+ + 2Cr 3+ + 7H2O
\ Amount of 80% KClO3 needed
From the above equation, we find that Mohr's salt
(FeSO4.(NH4)2SO4.6H2O) and dichromate reacts in 6 : 1 100
= ´ 122.5 = 153.12gm
molar ratio. 80
EXERCISE 4 11. (c) The conditions given are standard conditions
1. (a) Sum of the figures 29.4406, 3.2 and 2.25 is 34.8906. The 224 ml has mass = 1g ;
sum should be reported to the first place of decimal as 3.2 22400 ml will have mass = 100g. This is mol. wt of gas
has only one decimal place. After rounding off the sum is 6.023 × 1023 molecules have 3 × 6.023 × 1023 atoms since
34.9. Hence number of significant figures is three. gas is triatomic
2. (a) 0.25/22.1176 = 0.011303. The least precise term has two \ weight of one atom
significnat figures, hence the result is 0.011.
100
3. (c) If zero is used to locate the decimal point it is considered = = 5.5 ´ 10 - 23 g
a significant figure. In 50.000 all zero are significant. 3 ´ 6.023 ´ 10 23
4. (b) The desired equation is 12. (a) Proceed as follows :
Element % At. wt. RNA Simplest ratio
BaCl 2 + H 2SO 4 ® BaSO 4 + 2HCl
208g 98g 233g 73g
7.3g 25
20.8g 9.8g 23.3g A 25 12.5 =2 1
12.5
5. (c) In law of reciprocal proportions, the two elements
combining with the third element, must combine with each 75
B 75 37.5 =2 1
other in the same ratio or multiple of that Ratio of S and O 37.5
when combine with C is 2 : 1. Ratio of S and O is SO2 is 1 : 1
\ The simplest formula of compound is AB
2 ´ 12
6. (a) 2% of 12 gm of carbon is = = 0.24g which is 254
100 13. (d) Moles of Iodine present = =2
127
C-14
\ The number of atoms in it 80
Moles of oxygen = =5
16
0.24 ´ 6.02 ´10 23
= = 1.03 ´10 22 atoms \ The molecular formula is = I2O5
14
7. (c) Number of atoms in 2.0 mole of S8 14. (b) Let the atomic weight of metal be M then
M = 50% 50/M = 1
= 2 ´ N A ´ 8 = 16 N A
O = 50% 50/16 = 2
number of atoms in 6.0 mole of S = 6 × NA = 16.5 NA
The formula is = MO2
Number of atoms in in 5.5 mole of SO2
= 5.5 × NA × 3 = 16.5 NA 16 1
Number of atoms in 44.8 litre at STP of \ = . Thus atomic weight of metal = 32
M 2
CO2 = 2 × NA × 3 = 6 NA
8. (d) An, AlF3 the number of F is 3 for one AlF3 molecule For second oxide
3F– º 1 formula unit of AlF3 M = 40% 40/32 = 1.25 1
O = 60% 60/16 = 3.75 3
1
3.0 × 1024 F– º ´ 3.0 ´ 10 24 AlF3 units \ Formula is MO3
3
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
26 Chemistry
JEEMAIN.GURU
downloaded from jeemain.guru
2
Structure of Atom
ATOM : (VIII)Atomic mass unit : It is 0.0005486 amu.
John Dalton proposed in 1808 that atom is the smallest indivisible (IX) Mass of one mole of electron : It is 0.55 mg.
particle of matter. CATHODE RAYS :
ATOMIC RADII : Originate from cathode. Electrons were discovered by cathode
Atomic radii are of the order of 10–8 cm (1Å) and radii of nuclei are ray experiment.
JEEMAIN.GURU
downloaded from jeemain.guru
28 Chemistry
(II) It is heavier than proton by 0.18%. (II) Radius of nucleus : It is of the order 1.5 × 10–13 cm to
(III) Density : Its density is 1.5 × 1014 g/cm3. 6.5 × 10–13 cm (1.5 – 6.5 Fermi). In general r n = r0 ´ A1 / 3 cm
(IV) Specific Charge : It is zero. Where r0 is a proportionality constant with value 1.4 × 10–13
cm. and A is mass number.
(V) Stability : It is least stable of all elementary particles present
(III) Volume of nucleus : It is about 10–39 cm3. and that of atom is
in an atom.
10–24 cm3
(VI) Disintegration : Isolated neutron is unstable and (IV) Density of nucleus : It is about 10 14 g/cm 3 .
distintegrates into electron, proton and neutrino.
Mass of nucleus Mass number
(VII) Among all elementary particles neutron is the heaviest and Density = =
Volume of nucleus 6.023 ´ 10 23 ´ 4 pr 3
least stable. 3
OTHER SUBATOMIC PARTICLES : (V) Diameter : It is about 10–15 m or 1 fm (1 fm = 10–15 m)
(I) Positron (Positive electron +1e0). Discovered by Dirac (1930) (VI) Nucleus contains neutrons and protons, collectively known
and C. D. Anderson (1932). They are highly unstable and as nucleons.
produce g-rays on combining with electrons. ATOMIC NUMBER/MOSELEY'S POSTULATES :
The number of protons present in an atom is called the atomic
(II) Neutrino and Antineutrino are particles of small mass and number, denoted by Z. Moseley postulated that the frequency of
no charge as stated by Fermi (1934). Anti-neutrino spin X-rays produced when beam of strong electrons fall on metal
clockwise and neutrino spin anticlockwise. target, called anti-cathode is related to the charge present on the
(III) Meson : They are unstable particles and include pions (p+, nucleus of an atom of the element used as anti cathode.
Mathematically
p– or p0) Kaons (K+, K–, K0, K–0) and eta meson ( h0 ).
n = a(Z - b) ; where n = frequency of X-rays, Z = nuclear charge,
Mass : They have mass intermediate of electron and proton.
a and b = constants
Discovery : By Yukawa (1935) and Kemmer. MASS NUMBER :
(IV) Anti proton (–1p1) : Negative proton produced by Segre and It is sum of number of protons and neutrons present in the nucleus
Weigland (1955) by proton-proton and proton-neutron (nucleons as a whole) and denoted by A. It is always a whole
collisions. number.
(V) v-particles : They may be positive, negative or neutral.
AVERAGE ATOMIC MASS :
It is the average mass of all existing isotopes and not necessarily
Discovered by G. D. Rochester and C C. Butler v– and v0
a whole number.
are 2200 times heavier than electron. Heavier disintegrate
ISOTOPES :
into pions and lighter into mesons.
Isotopes are atoms of the same element having same atomic number
THOMSON'S ATOMIC MODEL : but different mass number. e.g. 8O16, 8O17 and 8O18. They were
Atom is a sphere of positive electricity with a number of electrons discovered by Soddy (1911).
distributed within the sphere. ISOBARS :
Atoms of different elements having same mass number but different
RUTHERFORD'S NUCLEAR MODEL : atomic numbers e.g. 19K40, 20Ca40.
It is based upon a particles scattering experiment. Only a few (one ISOTONES :
in 10,000) a-particles were returned back from the Au-foil (10–4 Atoms of different elements with different atomic and mass
mm thick). numbers but same number of neutrons e.g. 14Si30, 15P31, 16S32.
ISODIAPHERS :
1 Atoms having same Isotopic number.
Scattering of a-particles µ
æqö ISOELECTRONIC SPECIES :
sin 4 ç ÷ Species having same number of electrons e.g. CO and CN– (both
è2ø
contain 14 electrons each) Na+ and Ne (both contain 10 electrons
Conclusion : Atom consists of two parts - (a) Nucleus each).
(b) Extra nuclear part. The ionic size decreases with increasing effective nuclear charge
of iso-electronic species.
Drawbacks - This model fails to explain the stability of the atoms
and line spectrum of hydrogen. P
Ionic size of isoelectronic species depend on (effective nuclear
e
THE NUCLEUS :
charge).
(I) Nucleus - It is small heavy and positively charged material
located in the centre of atom and electrons are distributed in 1
Ionic size µ
extra nuclear part of atom and revolve around the nucleus. Effective nuclear charge
JEEMAIN.GURU
downloaded from jeemain.guru
Structure of Atom 29
P WAVE NUMBER :
(effective 1.1 1.2 1.3 1.4 It is the number of wavelengths per cm. It is equal to the inverse of
e
Nuclear charge) wavelength. Unit is cm–1 and is denoted by n .
Ionic radius (Å) 0.95 0.65 0.50 0.41
1
FAILURE OF RUTHERFORD'S MODEL : n=
l
According to classical theory of electromagnetism whenever a
charge is subjected to an acceleration around an opposite charge, AMPLITUDE :
it emits radiations continuously. Therefore the electron while It is the height of crest or trough. Square of amplitude determines
moving around nucleus in circular path must loose energy, go the amount of energy carried by the wave.
into spiral motion and ultimately fall into the nucleus. Practically it ELECTROMAGNETIC SPECTRUM :
does not happen. Arrangement of all electro-magnetic radiations in the increasing
PLANCK QUANTUM THEORY : order of their wavelengths or decreasing order of frequencies is
According to Max Planck (1901) radiant energy is emitted or called electromagnetic spectrum.
absorbed only in discrete units in form of bundle or packets of
energy called photon (quantum). Photon is not a material body. It Rays Wavelength Frequency
is massless bundle of energy (l in Å) n in Hz
Energy associated with each photon (quantum) Cosmic Rays 3×1021 to ¥
c g Rays 0.01 3×1019 to 3×1020
E = hn = h
l X Rays 1.0 2×1016 to 3×1019
h = Planck's constant = 6.626 × 10 –34 Js in S.I. units
(or 6.6726 × 10–27 ergs in c.g.s. units). n = frequency of radiation UV Rays 150 7.9×1014 to 2×1016
(each photon). Visible Light 3800 3.9×1014 to 7.9×1014
c = velocity of light, l = wavelength of radiation. Infra Red 7600 1×1011 to 3.95×1014
Thus a body can radiate energy in multiples of quantum hn, 2hn, Micro Waves 6×106 1×109 to 5×1011
3hn .... nhn where n is an integer.
Radio Waves 3×109 1×105 to 1×109
INTENSITY OF LIGHT :
ATOMIC SPECTRUM :
It is defined as number of photons falling per unit area per sec.
and depends upon wavelength of photons. Atoms of different elements emit electromagnetic radiations of
definite frequencies when excited by heating, passing current or
or it is defined as amount of energy falling per unit area per sec
electric discharge. Arrangement of these radiations in decreasing
and depends upon wavelength of photons.
order of frequencies is called atomic spectrum.
ELECTROMAGNETIC RADIATION :
Electromagnetic radiation by James maxwell (1870). An electrically DISPERSION :
changed particles moving under acceleration produces alternating Phenomenon of splitting of beam of light into radiations of different
electrical and magnetic fields mutually perpendicular to each other. frequencies after passing through a prism is called dispersion.
These fields are transmitted in the form of waves having same CONTINUOUS SPECTRUM :
wavelengths, frequency, speed and amplitude and are called It is obtained by passing sunlight (white light) through a prism.
electromagnetic waves or electromagnetic radiations. In vaccum The light is dispersed or resolved into continuous spectra of
all types of electromagnetic radiations travel at the same speed colours from Violet to Red. It contains radiations of all the
(3.0 × 108 ms–1) regardless of wavelengths. frequencies.
JEEMAIN.GURU
downloaded from jeemain.guru
30 Chemistry
LINE SPECTRUM : (III) Number of Lines in a Transition : Mathematical formula for
It is an atomic spectrum of an element which consists of a number number of lines is follows as
of bright lines separated by dark bands. Atomic Spectra of most
(n 2 - n1 )(n 2 - n1 + 1)
elements is line spectrum. No. of lines =
2
ABSORPTION SPECTRUM :
BLACK BODY RADIATION :
It is obtained by passing white light through solutions or vapours
of chemical substance and then is analysed by spectroscope. It The radiation emitted by a body when heated is called black body
has few dark lines in otherwise continuous spectrum. radiation. The frequency of radiation increases with temperature.
At a given temperature the intensity of radiation emitted increases
EMISSION SPECTRUM :
with decrease of wavelength, reaches a maximum value and then
It is obtained by passing radiations from the atoms through prism. starts decreasing with further decrease of wavelength. A black
It has few bright lines against a dark back ground. body can emit and absorb all frequencies.
HYDROGEN SPECTRUM : PHOTOELECTRIC EFFECT :
It is obtained by passing light being emitted from discharge tube Phenomenon of ejection of electrons from the surface of a metal
containing hydrogen at low pressure through spectrograph. when light of suitable frequency strikes on it is called photoelectric
Hydrogen Spectrum has five Series effect.
Spectral Line Region n1 n2 (I) Threshold frequency (v0) : The minimum frequency of
Lyman Series U.V. 1 2, 3, 4..... incident radiation to cause the photoelectric effect is called
Balmer Series Visible 2 3, 4, 5..... threshold frequency.
Paschen Series I.R. 3 4, 5, 6..... (II) Work function : A part of the photons energy that is absorbed
Brackett Series I.R. 4 5, 6, 7.... by the metal surface to release the electron is known as work
Pfund Series I.R. 5 6, 7, 8.... function of the surface denoted by f. The remaining part of
the energy of photons goes into the Kinetic energy of the
éIn Balmer Series of hydrogen spectrum ù electron emitted.
ê the first line (3 ® 2) is known as L line ú
ê the second line (4 ® 2) is L line. a ú If n0 is the threshold frequency and n the frequency of incident
ë b û
light then f = hn 0 and E = hn.
Wavelength of line in spectrum is given by the expression
K.E. = E - f = hn - hn 0 = h (n - n 0 )
1 1 1 Note: • K.E. is independent of the intensity of light.
= = R H Z2 ÷
n12 n 22 ÷ • Number of photoelectrons µ Intensity of light
• K.E. is directly proportional to frequency of incident
RH = Rydberg Constant, Z = charge on nucleus, light.
n1, n2 = electronic levels involved in transition, = Wave number • E = K.E. + f is known as Einstein's photoelectric
2 equation.
2 me 4
RH = = 109677.76 cm -1 also for hydrogen • Energy required to stop the ejection of electrons is given
ch 3
by eV0 where e is the electric charge and V0 is stopping
æ 1 potential.
1 ö÷ -1
n = 3.29 ´ 1015 ç - sec where is frequency..
çn 2
è 1 n2 ø
2÷ BOHR’S MODEL OF ATOM :
Proposed by Niel Bohr to overcome the drawbacks of Rutherford’s
(I) For calculation of longest wavelength line use n 2 nearest
model.
and for shortest wavelength line use n 2 infinity e.g. value of
(i) Electrons revolve around nucleus only in certain selected
longest wave length in Balmer Series of hydrogen spectrum
circular orbits. These orbits are associated with definite
use n1 = 2 and n2 = 3.
energies and are called energy shells or levels.
(II) Last line of spectrum is called Series limit. Last line is the line
of shortest wavelength and high energy when n 2 = ¥ we (ii) Electrons can move only in those circular orbits where
get last wavelength angular momentum is a whole number and multiple of h/2p.
nh
1 R H2 n12 i.e. mvr = . or simply an integral number of wavelengths
= l (series limit) = , 2
n12 R H2
should fit in given electron orbit of radius r i.e. n =2 r.
JEEMAIN.GURU
downloaded from jeemain.guru
Structure of Atom 31
(iii) Electrons energy in a particular orbit is constant. (xii) Number of revolutions per second in n th orbit,
(iv) Lowest energy state is called ground state and when electron vn velocity of electron in n th orbit
absorbs energy and jumps to higher state, it is called excited =
2prn circumference of the n th orbit
state v Velocity
(v) Electronic energy is negative because at infinite distance (xiii)Angular velocity = =
r radius
there is no interaction between electron and nucleus thus (xiv) Angular momentum = mvr
energy is zero. While when close to nucleus, attraction takes (xv) Number of spectral lines when electron jumps from the n th
place, energy is released and it becomes negative as it was
n (n - 1)
already zero. The energy of electron increases with the value to ground level = =
of n, but the difference of energy between two successive 2
orbits decreases. Thus (xvi) The electrons energy is generally expressed in kcal or kJ
E2 – E1 > E3 – E2 > E4 – E3 .......... etc. mol–1 or in electron volts eV.
(vi) Energy of electron in nth orbit 1 ergmol–1 = 1.44×1013 kcalmol–1 = 6.022×1013 kJmol–1
1eV = 1.602×10–19J
k2 2 2
me 4 z 2 -13.6Z2 (xvii)Some important values :
En = - = eV atom -1
n 2h 2 n2 In c.g.s. system,
m = 9.109×10–28g
-2.178 ´10-18 Z2 e = 4.803×10–10 esu,
= J atom -1
2
n h = 6.626×10–27 ergs,
where m = Mass of the electron, k= 1
e = Charge on the electron,
2 p 2 me 4
h = Planck's constant RH = cm - 1
ch 3
n = Principal quantum number,
k = A universal constant = 9.0 × 109 J.m/C2 In S I system,
The constant k is inverse of permitivity factor 4p 0 of the m = 9.109×10–31kg
e = 1.602×10–19C,
1
medium k = . The numerical value of permitivity factor h = 6.626×10–34 J.s,
4p 0
is 4p 0 = 1.11264 × 10–10 C2N–1m–2. In C.G.S. system k = 1. k = 9.0 × 109 Jm/C2
(vii) The radius of nth orbit
2 p 2 me 4
RH = = m -1
n2h 2 a0n 2
0.528Ån 2 2
(4 p o ) ch 3
rn = = = Å
2 2 Z Z
4 me Zk
(viii)The velocity of electron in nth orbit, e
In S I system the charge e is replaced by 4p o
nh 2 Ze 2 k 2.19 ´ 108 Z
vn = = = cm/sec. LIMITATIONS OF BOHR’S MODEL ARE :
2 mr nh n
1 (i) Explains the spectrum of elements having only one electron
The velocity of electron in first orbit of hydrogen is of (ii) Does not explain splitting of spectral lines under magnetic
137
the velocity of light. field (Zeeman effect) and electric field (stark effect)
(iii) Does not explain quantisation of angular momentum.
(ix) Kinetic energy of electron in nth orbit, (iv) It goes against the Heisenberg’s uncertainity principle.
2m p 2 e 4 Z 2 k 2 13.6 ´ Z 2 SOMMERFIELD MODEL :
Ek = = eV
n2h2 n2 (i) Motion of electrons is in closed elliptical paths of definite
(x) Potential energy of electron in nth orbit, energy levels having nucleus on either of the focii.
(ii) Angular momentum is quantized
- e2 - 4m p 2 e 4 Z 2 k 2 - 27.2 Z 2
Ep = = = eV n major axis length
r n2h2 n2 (iii) = where k = 1, 2 ---------n.
k minor axis length
(xi) Total energy of electron in nth orbit,
(iv) It does not explain distribution of electrons in extranuclear
part of atom and also does not explain for de Brogalie
k 2 2 2me4 Z2 13.6Z2
En = Ek + Ep = = eV concept.
n 2h 2 n2
JEEMAIN.GURU
downloaded from jeemain.guru
32 Chemistry
QUANTUM MECHANICS : (v) has no physical significance but 2 gives intensity of
It was developed independently by Warner Heisenberg and Erwin electrons and thus gives probability of electron in a particular
Schrodinges and takes into account the dual behaviour (particle region.
and wave nature) of matter proposed by de Broglie. ORBITALS :
Planck’s Quantum theory successfully explains.
Orbitals are the regions in space around nucleus where probability
(i) Photoelectric effect
of finding the electron is maximum.
(ii) Black-body radiation
(iii) Line spectra of H-atom (i) Probability does not become zero even at infinity and is
(iv) Variation of heat capacity of solids with temperature. given by 2.
(ii) Electron orbitals in atoms arecalled atomic orbitals while
de- BROGLIE PRINCIPLE (1924) :
those in molecules are called molecular orbitals.
(i) Proposes that just as radiations have particle nature, the
(iii) Orbitals have definite energy and momentum and are
material particles are also associated with wave nature.
quantized. i.e, En = –E1/n2 thus Bohr’s concept of well
h h defined orbits is ruled out.
(ii) de Broglie wavelength is l = = h = Planck’s constant
mv p QUANTUM NUMBERS :
m = mass of object ; v= velocity and this equation is called
the de Broglie equation. (i) Four quantum numbers (n, l, m, s) help in providing complete
information about an electron in an atom.
DAVISSON AND GERMER’S EXPERIMENT :
(ii) Principal quantum number (n) determines the energy and
Confirms the wave nature of electrons.
average distance of electron. It has whole number values also
SCINTILLATION METHOD AND PHOTOELECTRIC denoted as K, L, M, N. etc. As n increases, distance of electron
EFFECT : from nucleus increases and energy increases.
Confirm the particle nature. (iii) Azimuthal quantum number (l) determines angular momentum
HEISENBERG’S UNCERTAINITY PRINCIPLE : of the electron. It also determines the shape of orbitals and it
may have all possible whole number values from 0 to n–1 for
“It is not possible to determine simultaneously the position and
each principal energy level. The sublevels are:
momentum of small moving sub-atomic e.g.,
Value of l 0 1 2 3
+
1H , He + , 1B, , n particle, such as electron with entire Sub-shell s p d f
certainty”. Magnitude of angular momentum of an electron in orbital,
h
(i) Mathematically ± Dx ´ Dp ³ h mvr = l (l + 1)
4p 2
where, D x = uncertainity in position Angular momentum of an electron in any orbit,
D p = uncertainity in momentum and h = Planck’s constant
(ii) As the mass of particle increases, the uncertainity decreases nh
mvr =
QUANTUM MECHANICAL MODEL OF ATOM : 2p
(i) Based on de Broglie's and Heisenberg’s principle. (iv) Magnetic quantum number (m) defines the orientation of
(ii) Put forward by Schrodinger (1920). Behaviour of electron electrons cloud in a particular sub shell. Values of m are the
was described in terms of equation known as Schrodinger number of orbitals associated with a particular sub shell in
wave equation main shell. Values of m lie from 0 to ± l. Total values of ‘m’
2 2 2 2
for a given n is n 2. Total values of ‘m’ for a given l is 2l +1.
m The table shows a clear relation between quantum numbers.
+ + +
(E - V) = 0 where is
2 2 2 2
x y z h Shell (n) Sub -shells (l) Orbitals (m)
amplitude of electron wave and is also called wave function.
n=1 Þ K shell l= 0 Þ 1s m= 0
x, y, z, are space coordinates, m is mass of electron, h is
Planck’s constant, E is total energy and V is potential energy n=2 Þ L shell l= 0 Þ 2s m= 0
of the electron. l= 1 Þ 2p m = –1,0, +1
(iii) Many solutions for this equation are possible for hydrogen
but only certain solutions are permissible and are called ( 2p x , 2p y , 2pz )
eigen values
n=3 Þ M shell l= 0 Þ 3s m= 0
(iv) The solution must be single valued, should satisfy the
l= 1 Þ 3p m = –1, 0, +1
l= 2 Þ 3d m = –2, –1, 0,+1, +2
relation dr = 0 and must be finite and continuous.
æ 3d , 3d , 3d , 3d 3d ö÷
0 ç xy yz zx x2 - y2 , z2 ø
è
JEEMAIN.GURU
downloaded from jeemain.guru
Structure of Atom 33
(v) Spin quantum number (s) tells the spin of the electron. It Shape of d-orbitals :
+1 -1 y y z
can have two value (clockwise) and (anticlockwise).
2 2
x z x
h
Mathematically S = s(s +1) where s is amplitude of spin
2 dyz
dxy dxz
quantum angular momentum.
SHAPE OF ORBITALS : m = 0 for d
z2
(i) s orbitals are spherically symmetrical.
(ii) p orbitals are dumbell shaped. m = ± 1 for d and d xy
x 2 - y2
(iii) d orbitals have five different orientation. Three of them dxy,
dyz, dxz are identical in shape but have different orientation. m = ± 2 for d and d
x2 y2
(iv) The plane passing through nucleus where probability of
finding the electron is zero is called a nodal plane. Number z
y
of nodal planes in an orbital = l. Number of nodal planes
increases with increasing value of n. e.g. 1s has no nodal
plane. 2s has one nodal plane. For e.g. : s orbitals (l=0) have x x
no nodal plane, p orbital (l=1) have one nodal plane, d
orbitals (l=2) have two nodal planes.
d
Nodal plane = n - l - 1 x 2 - y2 d
z2
(v) Orbitals of a sub shell having same energy are called
degenerated orbitals. PAULI’S EXCLUSION PRINCIPLE :
(vi) Spherical surface within an orbital where probability of No two electrons in an atom can have same values for all the four
finding an electron is zero is called spherical or radial node. quantum numbers.
Number of spherical nodes = (n–l–1). Angular or non (i) It is not possible to accomodate more than two electrons in
spherical nodes = (l). Thus total nodes = (n – 1). an orbital. In other words. s sub shell can have maximum of
Shape of s-orbital : 2 electrons p sub shell can have maximum of 6 electrons.
z Thus max. no. of electrons in a shell can be 2n2.
(ii) Maximum number of electrons in a sub shell can be 2, 6, 10,
14 in s, p, d, f respectively and max. electrons in an atomic
x
orbital can be 2.
y Maximum number of electrons in a sub shell is equal to
4l + 2
s orbital
Shape of p-orbital : where l = 0, 1, 2, 3
px AUFBAU’S RULE :
Electrons are added to orbitals in increasing order of energies.
z The order of energies for orbitals is 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p,
z 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s.
(i) The order of energies can be calculated by (n + l) rule. i.e.
x x orbitals are filled in order of increasing (n+l) values the one
y with lower n value is filled first.
y
py (ii) The energy of atomic orbitals for H-atom depends on the
pz value of n only.
1s < 2s = 2p < 3s = 3p = 3d < 4s = 4p = 4d = 4f
JEEMAIN.GURU
downloaded from jeemain.guru
34 Chemistry
HUND’S RULE OF MAXIMUM MULTIPLICITY : In case of s orbitals the number of peaks is equal to n,
The pairing of electrons in orbitals of a subshell does not take In case of p orbitals the number of peaks is equal to (n–1),
place until all orbitals of sub shell are singly occupied. In case of d, orbitals the number of peaks is equal to (n–2)
(i) This arrangement leads to lower energy level. The point at which the probability of finding the electrons is zero
(ii) Singly occupied orbitals should have same spins giving rise iscalled nodal point.
to lower energies. The distance of maximum probability increases with increase in
the value of n. hence 2s, 2p electrons are greater distance than 1s.
RADIAL PROBABILITY DISTRIBUTION CURVES :
and have greater energy also.
2
The electron density is directly proportional to . The larger ANGULAR PROBABILITY DISTRIBUTION CURVES :
the value of
2
more is the probability of finding the electrons. The total angular ( ). (f) depends only on the direction and
Schrodinger wave equation may be separated into a product of remain independent of the distance electrons from the nucleus
three functions dependent on r, q, f P
P
Q
z
R(r) ( ) ( ) O
( r, q, f ) = { 14243 O
¯ ¯ px
Radial Part Angular part
Note : ® 4 r 2 .dr is the volume of spherical shell having small Angular probability distribution curves for s and p orbitals. The
length of the line OP is proportional to the probability of finding
thickness dr.
the electrons. The length of the line OP is the same in all directions
n=1 for s orbital Hence there are equal chances for finding electrons
n=2
R .4pr .dr
R .4pr .dr
l c çx 2
y 2 ÷ø
è
2
2p
2
3p
RH = Rydberg constant
2
2
®r ®r COMPTON EFFECT :
The decrease in energy (or increase in wavelength) of X-rays
after the scattering from the surface of carbon or light element is
R .4pr .dr
n=3
2
®r
JEEMAIN.GURU
downloaded from jeemain.guru
Structure of Atom 35
1. An electron beam can undergo diffraction by crystals. 4. A bulb emits light of = 4500Å . The bulb is rated as 150
Through what potential a beam of electrons be accelerated
so that its wavelength becomes equal to 1.54Å. (IIT 1997) watt and 8% of the energy is emitted as light. How many
photons are emitted by the bulb per second?
1 h Sol. Energy of one photon
Sol. mv 2 = eV and l =
2 mv
hc 6.6 ´ 10 -34 ´ 3 ´ 10 8
2 = E = hu = = = 4.42 ´ 10 -19 J
1 h l -10
\V = . 4500 ´ 10
2 ml2 e
150 ´ 8
Energy emitted by bulb = J
(6.62 ´10 -34 ) 2 100
=
2 ´ 9.108 ´10 -31 (1.54 ´ 10 -10 ) 2 ´1.6202 ´10 -19
19 150 8
= 63.3 volt. n .42 10 =
100
2. Wavelength of photon having energy 2 eV.
\ n = 27.2 ´1018 photons
-19 -12
Sol. 1 eV = 1.6 ´ 10 J or 1.6 ´ 10 ergs
5. If the critical wavelength for producing photoelectric effect
-34 8 is 2000Å. Then what wavelength of light will be required to
hc 6.62 ´10 ´ 3 ´ 10
l= = = 6.20 ´103 Å produce photoelectrons with double the K.E. of those
E -19
2 ´1.6 ´ 10
produced by light of wavelength of 1500Å.
3. The velocity of electron in a certain Bohr's orbit of
H-atom bears the ratio 1: 275 to the velocity of light. æ hc hc ö
Sol. K.E. with 1500Å = ç - ÷ (I)
(i) What is quantum number n of orbit. è 1500 2000 ø
(ii) Wave number of radiations emitted when electron jumps
from (n + 1) to ground state. æ hc hc ö
KE with xÅ = ç - ÷ (II)
è x 2000 ø
1
Sol. (i) Velocity of electron = ´ Velocity of light
275 According to question 2I = II
æ hc hc ö æ hc hc ö
2.19 ´ 108 ´ Z 2ç - ÷=ç - ÷
Again Vn = cm / sec è 1500 2000 ø è x 2000 ø
n
JEEMAIN.GURU
downloaded from jeemain.guru
36 Chemistry
7. Calculate the momentum of a particle with de-Broglie
Sol. Magnetic moment = n ( n + 2)
wavelength 1Å.
Where n is the number of unpaired electrons.
Sol. 1Å = 10 -10 m
1.73 = n ( n + 2) \n =1
-34
h 6.62 ´ 10 \ Vanadium atom must have one unpaired electron hence its
p= = = 6.62 ´ 10 -24 kgms -1
-10
10 configuration is 23 V 4 + = 1s 2 , 2s 2 p 6 , 3s 2 p 6 3d1
8. The uncertainity in the position of a bullet weighing 20 g is 12. Find the ratio of the radius of the first Bohr orbit for the
± 10–4 m. Calculate the uncertainity in its velocity. electron orbiting the hydrogen nucleus to that of the electron
Sol. 20 g = 0.02 Kg orbiting the deuterium nucleus (mass nearly twice that of the
hydrogen nucleus).
h
± Δx.Δp = a0n 2
4 Sol. rn = ;
Z
h
or Dx.mDv = a 0 ´1 a 0 ´1
4p r1 = for hydrogen; r 2 = for deuterium;
1 1
6.62 ´ 10-34
\± Δv = = 2.63 ´ 10-29 ms-1 r1 1
4 ´ 3.14 ´ 0.02 ´10 -4 = ; 1 :1.
r2 1
9. What transition in the hydrogen spectrum would have the 13. In an atom 2 electrons move round the nucleus in circular
same wavelength as th e Balmer transition n = 4. orbits of radii R and 4R. The ratio of the time taken by them to
(n = 2 of He+ Spectrum). complete one revolution is.
1 æ 1 1 ö Sol. T 2 µ R 3
Sol. For He+ = R H Z 2 çç - ÷÷
l è2 2
42 ø T12 = K(R )3 ; T22 = K(4R ) 3
1 æ 1 1 ö÷ T12 R3 T1 1
For H = RH ç - \ = Þ =
l ç 2 2 ÷
T22 3 T2 8
è n1 n 2 ø 64R
14. Calculate the speed of electron in third orbit of hydrogen
1 ù é 12é 1 ù
1 atom. Also calculate the number of revolutions per second
Since l is the same Z ê 2 - 2 ú = ê 2 - 2 ú that this electron makes around the nucleus. Given
ë2 4 û êë n 1 n 2 úû
4p 0 = 1.112 ´10 -10 C 2 N -1m -2 .
é1 1 ù é 1 1 ù
Since Z = 2 ê 2 - 2 ú = ê 2 - 2 ú 2p(Ze2 / 4p 0 )
ë1 2 û êë n1 n 2 úû Sol. Speed v =
nh
n1 = 1 and n2 = 2
2 ´ 3.14(1.6 ´ 10 -19 C) 2 / 1.112 ´ 10 -10
= = 7.27 ´ 10 5 ms -1
10. Find out the number of waves by a Bohr electron in one 3 ´ 6.626 ´ 10 -34
complete revolution in its 3rd orbit. [IIT 1994]
Sol. Number of waves in an orbit v
Number of revolutions made by the electron =
2 pr
Circumference of orbit 2 r
= =
Wavelength n2 h2
r= 2
4 m( Ze2 / 4 0)
æ nh ö
2 ç ÷ 34
2 r 2 (mvr) 2 9 (6.626 10 )
= = = è ø =n =
h / mv h h 2 31 19 2 10
4(3.14) (9.1 10 kg)(1.6 10 ) / 1.112 10
(Since angular momentum mvr = nh/ 2p) Ans. 3.
= 4.782 ´ 10 -10 m
11. A compound of Vanadium has a magnetic moment of 1.73
BM. Work out the electronic configuration of the vanadium 7.27 ´ 10 5
v= = 2.42 ´ 10 4 s -1
ion in the compound. [IIT 1997] 2 ´ 3.14 ´ 4.782 ´ 10 -10
JEEMAIN.GURU
downloaded from jeemain.guru
Structure of Atom 37
15. Calculate the frequency, energy and wavelength of the - 12
radiation corresponding to the spectral line of lowest D E = E ¥ - E 2 = 5.425 × 10 ergs
frequency in Lyman series in the spectra of H atom. Also
hc 6.626 ´ 10 - 27 ´ 3 ´ 1010
calculate the energy for the corresponding line in the spectra E= = 5.425 × 10 - 12 =
of Li2+ l l
4 4 1 6.626 ´ 10 - 34 ´ 3 ´ 108
l = 3R = × = 1.216 × 10 - 7 m = = 4.417 × 10 - 19 J
H 3 1.09678 ´ 107 m -1 4500 ´ 10 -10
JEEMAIN.GURU
downloaded from jeemain.guru
38 Chemistry
23. Find out the electronic state from which an electron drops to
0.01 ´ 300
Sol. Accurate velocity = = 0.03 ms -1 emit radiation with a wavelength of 926Å and lying in
100 ultraviolet region (Lyman series) in the spectrum of hydrogen
atom.
6.62 ´ 10 - 34
Dx = = 0.0019 m R H = 1.097 × 10 7 m -1
4 ´ 3.14 ´ 0.03 ´ 9.1 ´ 10 - 31
-8
22. A photon of wavelength 4000 Å strikes a metal surface, the Sol. l = 926 Å = 926 × 10 cm = 926 × 10 - 10 m
work function of the metal being 2.13 eV. Calculate
1 æ 1 1 ö÷
(i) the energy of photon in eV = = RH ç -
l ç n2 n2 ÷
(ii) the kinetic energy of the emitted photoelectron and è 1 2ø
(iii) the velocity of the photoelectron Since the radiation is in the U.V region and belongs to Lyman
Sol. (i) Energy of the photon series therefore n1 = 1
hc
E = hu = 1 æ 1 1 ö÷
l \ = - 10
= 1.097 × 10 - 7 m -1 ç -
9.26 ´10 m ç 12 n 2 ÷
è 2ø
6.626 ´ 10 - 34 Js ´ 3 ´ 108 ms -1
E= = 4.97 × 10 - 19 J 1 1
4000 ´ 10 -10 m 1= =
n 22 -10
9.26 ´10 ´ 1.097 ´10 7
- 19
eV = 1.602 × 10 J
On solving , n 2 = 8
- 19
4.97 ´ 10 J 24. The normal human eye responds to visible light of
E= -19 = 3.10 eV
1.602 ´ 10 J wavelength raging from about 390 to 710 nm. Determine the
frequency range of the human eye
(ii) Kinetic energy of emitted photo electron
Sol. Wavelength l and frequency u are related to the velocity
Work function f = 2.13 eV
c
Kinetic energy = hu – f = 3.10 eV – 2.13 V = 0.97 eV by u=
l
Velocity of photoelectron
3.00 ´ 108 ms -1
1 2
K.E. = mv = 0.97 eV = 0.97 × 1.602 × 10 - 19 J = = 7.7 × 10 14 s - 1
2 390 ´ 10 - 9 m
3.00 ´ 108 ms -1
= 1.55 ´10-19 J and u = = 4.2 × 10 14 s - 1
710 ´ 10 - 9 m
1/ 2
é 2 ´ 0.97 ´ 1.602 ´ 10 -19 ù The frequency range of the human eye is 4.2 × 10 14 to
(iii) v = ê ú = 5.85 × 10 5 ms -1
êë 9.109 ´ 10- 31 úû 14
7.7 × 10 Hz.
JEEMAIN.GURU
downloaded from jeemain.guru
Structure of Atom 39
JEEMAIN.GURU
downloaded from jeemain.guru
40 Chemistry
21. Which of the following pairs have identical values of e/m? 26. In a Bohr model of an atom, when an electron jumps from n
(a) A proton and a neutron = 3 to n = 1, how much energy will be emitted?
(b) A proton and deuterium (a) 2.15 × 10–11 ergs (b) 2.389 × 10–12 ergs
(c) Deuterium and an a-particle (c) 0.239 × 10–10 ergs (d) 0.1936 × 10–10 ergs
(d) An electron and g-rays
27. The uncertainty in the momentum of an electron is 1.0 × 10–
22. Chlorine exists in two isotopic forms, Cl-37 and Cl-35 but 5 kg ms–1. The uncertainty in its position will be (h = 6.62 ×
its atomic mass is 35.5. This indicates the ratio of Cl-37 and
Cl-35 is approximately 10–34 kg m2s–1)
(a) 1 : 2 (b) 1 : 1 (a) 1.05 × 10–26 m (b) 1.05 × 10–28 m
(c) 1 : 3 (d) 3 : 1 (c) 5.27 × 10–30 m (d) 5.25 × 10–28 m
23. If E1, E2, and E3 represent respectively the kinetic energies 28. Which one of the following set of quantum numbers is not
of an electron and an alpha particle and a proton each having possible for 4p electron?
same de-broglie wavelength then
(a) E1 > E3 > E2 (b) E2 > E3 > E1 1
(a) n = 4, l = 1, m = –1, ms = +
(c) E1 > E2 > E3 (d) E1 = E2 = E3 2
24. If travelling at same speeds, which of the following matter
waves have the shortest wavelength? 1
(b) n = 4, l = 1, m = 0, ms = +
(a) Electron (b) Alpha particle (He2+) 2
(c) Neutron (d) Proton
25. The third line of the Balmer series, in the emission spectrum 1
(c) n = 4, l = 1, m = 2, ms = +
of the hydrogen atom, is due to the transition from the 2
(a) fourth Bohr orbit to the first Bohr orbit
(b) fifth Bohr orbit to the second Bohr orbit 1
(d) n = 4, l = 1, m = –1, ms = –
(c) sixth Bohr orbit to the third Bohr orbit 2
(d) seventh Bohr orbit to the third Bohr orbit
1. A neutral atom (Atomic No > 1) has 4. Which of the following statements is incorrect?
(a) electron and proton (a) Cathode rays carry negative charge
(b) neutron and electron (b) Frequency of X-rays is higher than that of microwaves
(c) neutron, electron and proton (c) Unit for wave number is m–1
(d) neutron and proton. (d) Threshold frequency is the same for all metals.
2. Which of the following set of quantum numbers belong to 5. Which is not true with respect to cathode rays?
highest energy? (a) A stream of electrons
(b) Charged particles
1
(a) n = 4, l = 0, m = 0, s = + (c) Move with speed same as that of light
2 (d) Can be deflected by magnetic fields
1 6. Rutherford’s a-particle dispersion experiment concludes
(b) n = 3, l = 0, m = 0, s = + (a) all positive ions are deposited at small part
2
(b) all negative ions are deposited at small part
1 (c) proton moves around the electron
(c) n = 3, l = 1, m = 1, s = + (d) neutrons are charged particles.
2
7. Ratio of mass of proton and electron is
1 (a) infinite (b) 1.8 × 103
(d) n = 3, l = 2, m = 1, s = +
2 (c) 1.8 (d) None of these.
1-
8. Which of the following is the main cause of late discovery of
3. The number of electrons in é 19
40 ù
K is neutron?
ë û (a) Neutron is chargeless particle
(a) 20 (b) 40 (b) Neutron is highly unstable particle
(c) 18 (d) 19 (c) Neutron in the nucleus moves very fast
(d) All of these.
JEEMAIN.GURU
downloaded from jeemain.guru
Structure of Atom 41
9. Which of the following does not contain number of neutrons (a) 3 : 1 (b) 2 : 1
40 (c) 1 : 2 (d) 1 : 3
equal to that of 18 Ar ? 20. The energy of a photon is given as DE/atom
(a) 41 (b) 43
19 K 21 Sc 3.03 ´10-19 J atom-1 . Then the wavelength (l) of the
(c) 40 (d) 42 photon is
21 Sc 20 Ca
(a) 65.6 nm (b) 656 nm
10. Rutherford’s experiment which established the nuclear model
of the atom used a beam of (c) 0.656 nm (d) 6.56 nm
(a) b-particles which impinged on a metal foil and got 21. If wavelength of photon is 2.2×10–11 m, h = 6.6 ×10–34 Js,
absorbed then momentum of photon is
(b) g-rays which impinged on a metal foil and ejected (a) 3 × 10–23 kg/s (b) 3.33 × 1022 kg/s
–44
electrons (c) 1.452 × 10 kg/s (d) 6.89 × 1043 kg/s
(c) helium atoms, which impinged on a metal foil and got 22. Which orbital of carbon can absorb photon but not emit it?
scattered (a) 1 s (b) 2 s
(d) helium nuclei, which impinged on a metal foil and got (c) 3 p (d) 2 p.
scattered 23. Brackett series are produced when the electrons from the
11. Number of protons, neutrons and electrons in the element outer orbits jump to
231 (a) 2nd orbit (b) 3rd orbit
89 X is (c) 4th orbit (d) 5th orbit.
(a) 89, 89, 242 (b) 89, 142, 89 24. The first emission line in the atomic spectrum of hydrogen in
(c) 89, 71, 89 (d) 89, 231, 89 the Balmer series appears at
12. An element has atomic number 11 and mass number 24. What
9R 7R
does the nucleus contain? (a) cm -1 (b) cm -1
(a) 11 protons, 13 neutrons 400 144
(b) 11 protons, 13 neutrons, 13 electrons
3R 5R
(c) 13 protons, 11 neutrons (c) cm -1 (d) cm -1
(d) 13 protons, 11 electrons 4 36
13. The number of electrons and neutrons of an element is 18 25. In hydrogen spectrum which of the following lies in the
and 20 respectively. Its mass number is wavelength range 350–700 nm?
(a) 2 (b) 17 (a) Balmer series (b) Lyman series
(c) 37 (d) 38 (c) Brackett series (d) paschen series.
14. The hydride ion is isoelectronic with 26. In Balmer series of hydrogen atom spectrum which electronic
(a) H+ (b) He+ transition causes third line?
(c) He (d) Be. (a) Fifth Bohr orbit to second one
15. Which of the following isoelectronic species has the smallest (b) Fifth Bohr orbit to first one.
atomic radius? (c) Fourth Bohr orbit to second one
(a) N 3- (b) O 2- (d) Fourth Bohr orbit to first one.
27. The spectrum of He is expected to be similar to that of
(c) F - (d) Ne. (a) H (b) Na
16. Among the following groupings which represents the (c) He +
(d) Li+
collection of isoelectronic species? 28. In hydrogen atom, energy of first excited state is –3.4eV.
(a) NO + , C 22 - , O -2 , CO (b) N 2 , C 22 - , CO, NO Then find out the KE of the same orbit of hydrogen atom
(a) + 3.4 eV (b) + 6.8 eV
(c)CO, NO + , CN - , C 22 - (d) NO, CN - , N 2 , O -2 (c) – 13.6 eV (d) + 13.6 eV
17. Which of the following is not iso electronic 29. In the Bohr’s orbit, what is the ratio of total kinetic energy
and total energy of the electron?
+
(a) Na (b) Mg 2+ (a) –1 (b) –2
(c) 1 (d) +2
2-
(c) O (d) Cl - 30. The kinetic energy of an electron accelerated from rest
18. Chloride ion and potassium ion are isoelectronic. Then through a potential difference of 5 V will be
(a) their sizes are same (a) 5 J (b) 5 erg
(b) chloride ion is bigger than potassium ion (c) 5 eV (d) 8 × 10–19eV
(c) potassium ion is relatively bigger 31. The angular momentum of an electron revolving around the
(d) depends upon the other cation or anion nucleus is integral multiple of
19. Ratio of energy of photon of wavelength 3000 Å and 6000Å (a) 2n (b) h
is (c) h / 2p (d) 2pn
JEEMAIN.GURU
downloaded from jeemain.guru
42 Chemistry
32. The orbital angular momentum of an electron in 2 s orbital is 44. The radius of hydrogen atom in the ground state is 0.53Å.
The radius of Li2+ ion (atomic number = 3) in a similar state is
1 h
(a) + . (b) zero (a) 0.17 Å (b) 1.06 Å
2 2p (c) 0.53 Å (d) 0.265 Å
h h 45. The Bohr orbit radius for the H-atom (Z=1) is approximately
(c) (d) 2. 0.53 Å. The radius for the first excited state orbit is
2p 2p
(a) 0.13 Å (b) 1.06Å
33. The energy of an electron in the first Bohr orbit of H atom is
(c) 4.77 Å (d) 2.12 Å
– 13.6 eV. The possible energy value(s) of the excited state
46. The ratio of the radius of the first Bohr orbit for the electron
(s) for electrons in Bohr orbits of hydrogen is (are)
orbiting the hydrogen nucleus to that of the electron orbiting
(a) – 3.4eV (b) – 4.2eV
the deuterium nucleus (mass nearly twice that of the
(c) – 6.8 eV (d) + 6.8eV. hydrogen nucleus) is approximately
34. If the radius of first Bohr orbit be a0, then the radius of the (a) 2 : 1 (b) 1 : 1
third orbit would be (c) 1 : 2 (d) 4 : 1
(a) 3 × a0 (b) 6 × a0 47. The energy of the first electron in helium will be
(c) 9 × a0 (d) 1/9 × a0 (a) –13.6 eV (b) –54.4 eV
35. According to Bohr’s theory of hydrogen atom, which of the (c) –5.44 eV (d) zero
following is quantised for an electron? 48. Who modified Bohr’s theory by introducing eiliptical orbits
(a) Angular momentum (b) Angular acceleration for electron path?
(c) Acceleration (d) Velocity. (a) Hund (b) Thomson
36. According to Bohr’s theory the energy required for the (c) Rutherford (d) Sommerfeld.
transition of H-atom from n = 6 to n = 8 state is 49. Wavelength associated with electron motion
(a) equal to the energy required for the transition from n = (a) increases with increase in speed of electron
5 to n = 6 state (b) remains same irrespective of speed of electron
(b) larger than in (a) (c) decreases with increase of speed of e– (electron)
(c) less than in (a) (d) is zero.
(d) equal to the energy required for the transition from n = 50. If the Planck’s constant h = 6.6×10–34 Js, the de Broglie
7 to n = 9 state. wavelength of a particle having momentum of 3.3 × 10–24
37. The wave number of the light emitted by a certain source is kg ms –1 will be
2 × 106 m . The wavelength of this light is (a) 0.002 Å (b) 0.5Å
(a) 500 m (b) 200 nm (c) 2Å (d) 500Å
(c) 500 nm (d) 5 × 107 m 51. What is the wavelength associated with an electron moving
38. For which of the following species, Bohr’s theory is not with a velocity of 106 m/s?
applicable? (given h = 6.63 × 10–34 Js and m = 9.11 × 10–31 kg)
(a) Be3+ (b) Li2+ (a) 72.7 nm (b) 0.727 nm
2+
(c) He (d) H. (c) 7.27 nm (c) None of these.
39. As the nuclear charge increases from Neon to Calcium, the 52. The wavelength associated with a golf balf weighing 200 g
orbital energies and moving at a speed of 5 m/h is of the order
(a) increase (b) increase very rapidly (a) 10–10 m (b) 10–20m
–30
(c) increase very slowly (d) fall (c) 10 m (d) 10–40m
40. The ratio of ionization energy of H and Be+3 is 53. The uncertainty in the position of an electron
(a) 1 : 1 (b) 1 : 3 (mass = 9.1 × 10–28 g) moving with a velocity of 3.0 × 104
(c) 1 : 9 (d) 1 : 16 cm s–1 accurate upto 0.011% will be
41. In a Bohr model of on atom, when an electron jumps from n = (a) 1.92 cm (b) 7.68 cm
3 to n = 1, how much energy will be emitted? (c) 0.175 cm (d) 3.84 cm.
(a) 2.15 × 10–11 ergs (b) 2.389 × 10 –12 ergs 54. The uncertainty in the momentum of an electron is
(c) 0.239 × 10 ergs–10
(d) 0.1936 × 10 –10 ergs 1.0 × 10–5 kg ms –1. The uncertainty in its position will be (h =
42. In H-atom electron jumps from 3rd to 2nd energy level, the 6.62 × 10–34 kg m2 s–1)
energy released is (a) 1.05 × 10–26 m (b) 1.05 × 10–28 m
–30
(a) 3.03 × 10–19 J/atom (b) 1.03 × 10–19 J/atom (c) 5.27 × 10 m (d) 5.25 × 10–28 m
(c) 3.03 × 10–12 J/atom (d) 6.06 × 10–19 J/atom 55. Azimuthal quantum number determines the
43. The value of the energy for the first excited state of hydrogen (a) size
atom will be (b) spin
(a) –13.6 eV (b) –3.40 eV (c) orientation
(c) –1.51 eV (d) –0.85eV (d) angular momentum of orbitals
JEEMAIN.GURU
downloaded from jeemain.guru
Structure of Atom 43
56. When the value of azimuthal quantum number, l = 2, value of 65. The electrons, identified by quantum numbers n and l (i) n =
‘n’ will be 4, l = 1 (ii) n = 4, l = 0 (iii) n = 3, l = 2 (iv) n = 3,
(a) 3 (b) 4 l = 1 can be placed in order of increasing energy, from the
(c) 5 (d) any one of these. lowest to highest, as
57. The values of quantum numbers n, l and m for the 5th electron (a) (iv) < (ii) < (iii) < (i) (b) (ii) < (iv) < (i) < (iii)
of Boron will be (c) (i) < (iii) < (ii) < (iv) (d) (iii) < (i) < (iv) < (ii)
(a) n = 1, l = 0, m = –1 (b) n = 2, l = 1, m = –1 66. Bohr's model of atom is in conflict with
(c) n = 2, l = 2, m = –1 (d) n = 1, l = 2, m = –1 (a) Pauli's exclusion principle
(b) Heiseinberg's uncertainity principle
58. The total number of orbitals in a shell with principal quantum
(c) Max Planck's quantum theory
number ‘n’ is
(d) All the above three
(a) 2 n (b) 2 n2
2 67. What is the maximum number of electrons that can be
(c) n (d) n.
accomodated in an atom in which the highest principal
59. Which of the following combinations of quantum numbers quantum number value is 4?
is allowed? (a) 10 (b) 18
n l m ms (c) 36 (d) 54.
(a) 3 2 1 0 68. The total number of orbitals possible for principal quantum
1 number n is
(b) 2 0 0 - (a) n (b) n 2
2
(c) 2n (d) 2n2
1 69. Which of the following is not possible ?
(c) 3 –3 –2 + (a) n = 3, l = 0, m = 0
2
(b) n = 3, l = 1, m = –1
1 (c) n = 2, l = 0, m = –1
(d) 1 0 1 +
2 (d) n = 2, l = 1, m = 0.
60. Which one of the following set of quantum numbers is not 70. For how many orbitals, the quantum numbers
possible for 4p electron? n = 3, l =2, m = +2 are possible?
(a) 1 (b) 2
1
(a) n = 4, l = 1, m = –1, mS= + (c) 3 (d) 4
2 71. The correct set of quantum numbers for a 4d electron is
1 1
(b) n = 4, l = 1, m = 0, mS = + (a) 4, 3, 2, + (b) 4, 2, 1, 0
2 2
1 1 1
(c) n = 4, l = 1, m = 2, mS = + (c) 4, 3, - 2, + (d) 4, 2,1, -
2 2 2
1 72. For a, f-orbital, the values of m are
(d) n = 4, l = 1, m = –1, mS = - (a) –2, –1, 0, +1, +2
2
(b) –3, –2, –1, 0, +1, +2, 3
61. The maximum number of electrons in subshell with
(c) –1, 0, +1
l = 2 and n = 3 is
(d) 0, +1, +2, +3
(a) 2 (b) 6
73. The values of Planck's constant is 6.63 × 10–34 Js. The velocity
(c) 12 (d) 10 of light is 3.0 × 108 m s–1. Which value is closest to the
62. An electron has principal quantum number 3. The number of wavelength in nanometres of a quantum of light with
its (i) sub-shells and (ii) orbitals would be respectively frequency of 8 × 1015 s–1?
(a) 3 and 5 (b) 3 and 7 (a) 5 × 10–18 (b) 4 × 101
7
(c) 3 and 9 (d) 2 and 5 (c) 3 × 10 (d) 2 × 10–25
63. An e– has magnetic quantum number as –3, what is its 74. The number of nodal planes ‘d’ orbital has
principal quantum number? (a) 1 (b) 2
(a) 1 (b) 2 (c) 3 (d) 0
(c) 3 (d) 4 75. What do you mean by degenerate orbitals?
64. The four quantum numbers of the valence electron of (a) Orbitals having equal energy
potassium are (b) Oribitals having equal wave function
(a) 4, 1, 1, 1/2 (b) 4, 0, 0, 1/2 (c) Oribitals having equal energy but different wave
(c) 4, 5, 0, 1/2 (d) 4, 4, 0, 1/2 function
(d) Orbitals having equal energy and equal wave function.
JEEMAIN.GURU
downloaded from jeemain.guru
44 Chemistry
76. The number of nodal planes in a px orbital is 90. The number of unpaired electrons in a Nickel atom (ground
(a) one (b) two state) are (Atomic No. of Ni = 28)
(c) three (d) zero. (a) 2 (b) 5 (c) 3 (d) 7
77. A 5f orbital has 91. The element with its electronic configuration of its
(a) one node (b) two nodes atom 1 s2 2 s2 2 p6 3 s2 3 p6 3 d10 4 s1 is
(c) three nodes (d) four nodes. (a) Fe (b) Co (c) Ni (d) Cu.
78. “ No two electrons in an atom can have same set of all the 92. In Cu. (At. No. 29)
four quantum numbers” is known as (a) 13 electrons have spin in one direction and 16 electrons
(a) Hund’s rule in other direction
(b) Aufbau principle (b) 14 electrons have spin one direction and 15 electrons
(c) Uncertainty principle in other direction
(d) Pauli’s exclusion principle. (c) one electron can have spin only in the clockwise
79. Which of the following has maximum number of unpaired direction
electrons ? (d) None of the above is correct.
3+ 93. Which of the following atom has no neutron in its nucleus?
(a) Mg 2+ (b) Ti 3+ (c) V (d) Fe 2 +
(a) Helium (b) Lithium
80. An element M has an atomic mass 19 and atomic number 9, (c) Protium (d) Tritium
its ion is represented by 94. In the ground state, an element has 13 electrons in its M-
(a) M + (b) M 2 + (c) M - (d) M 2 - shell. The element is
2 2 5 1
81. The configuration 1s 2 s 2p 3 s shows (a) zinc (b) chromium
(a) ground state of fluorine (c) nickel (d) iron
(b) excited state of fluorine 95. Which one of the following pairs of ions has the same
(c) excited state of neon atom electronic configuration?
JEEMAIN.GURU
downloaded from jeemain.guru
Structure of Atom 45
1. If uncertainty in position and momentum are equal, then 11. The value of Planck’s constant is 6.63 × 10–34 Js. The speed
uncertainty in velocity is : [CBSE-PMT 2008] of light is 3 × 1017 nm s–1.. Which value is closest to the
wavelength in nanometer of a quantum of light with frequency
1 h h 1 h h of 6 × 1015 s–1? [NEET 2013]
(a) (b) (c) (d)
2m p 2p m p p (a) 25 (b) 50 (c) 75 (d) 10
2. The measurement of the electron position is associated with 12. What is the maximum numbers of electrons that can be
an uncertainty in momentum, which is equal to 1×10–18 g cm s–1. associated with the following set of quantum numbers?
The uncertainty in electron velocity is, [CBSE-PMT 2008] n = 3, l = 1 and m = –1 [NEET 2013]
(mass of an electron is 9 × 10– 28 g) (a) 6 (b) 4 (c) 2 (d) 10
(a) 1 × 109 cm s–1 (b) 1 × 106 cm s–1 æ Z2 ö
5 –1 (d) 1 × 1011 cm s–1
(c) 1 × 10 cm s 13. Based on equation E = – 2.178 × J çç 2 ÷÷ , certain
10-18
3. The energy absorbed by each molecule (A2) of a substance èn ø
is 4.4 × 10–19 J and bond energy per molecule is 4.0 × 10–19 J. conclusions are written. Which of them is not correct ?
The kinetic energy of the molecule per atom will be: [NEET 2013]
[CBSE-PMT 2009] (a) Larger the value of n, the larger is the orbit radius.
(a) 2.2 × 10–19 J (b) 2.0 × 10–19 J (b) Equation can be used to calculate the change in energy
(c) 4.0 × 10–20 J (d) 2.0 × 10–20 J when the electron changes orbit.
4. Maximum number of electrons in a subshell of an atom is (c) For n = 1, the electron has a more negative energy than it
determined by the following: [CBSE-PMT 2009] does for n = 6 which mean that the electron is more loosely
(a) 2 l + 1 (b) 4 l – 2 (c) 2 n2 (d) 4 l + 2 bound in the smallest allowed orbit.
5. Which of the following is not permissible arrangement of (d) The negative sign in equation simply means that the
electrons in an atom? [CBSE-PMT 2009] energy or electron bound to the nucleus is lower than it
(a) n = 5, l = 3, m = 0, s = + 1/2 would be if the electrons were at the infinite distance
(b) n = 3, l = 2, m = – 3, s = – 1/2 from the nucleus.
(c) n = 3, l = 2, m = – 2, s = – 1/2 14. In a hydrogen atom, if energy of an electron in ground state is
(d) n = 4, l = 0, m = 0, s = – 1/2 13.6. eV, then that in the 2nd excited state is [AIEEE 2002]
6. A 0.66 kg ball is moving with a speed of 100 m/s. The associated (a) 1.51 eV (b) 3.4 eV (c) 6.04 eV (d) 13.6 eV.
wavelength will be ( h = 6.6 ´ 10 -34 Js) : [CBSE-PMT 2010] 15. Uncertainty in position of a minute particle of mass 25 g in
(a) 1.0 ´ 10–32m (b) 6.6 ´ 10–32m space is 10–5 m. What is the uncertainty in its velocity (in
(c) 6.6 ´ 10 m–34 (d) 1.0 ´ 10–35m ms–1)? (h = 6.6 ´ 10–34 Js) [AIEEE 2002]
7. The total number of atomic orbitals in fourth energy level of (a) 2.1 ´ 10 –34 (b) 0.5 ´ 10–34
JEEMAIN.GURU
downloaded from jeemain.guru
46 Chemistry
19. Which one of the following groupings represents a collection of 28. Of the following sets which one does NOT contain
isoelectronic species ? [AIEEE 2003] isoelectronic species? [AIEEE 2005]
(At. nos. : Cs : 55, Br : 35)
(a) BO 33 - , CO 32 - , NO 3- (b) SO 32 - , CO 32 - , NO 3-
(a) N3–, F–, Na+ (b) Be, Al3+, Cl–
2+ +
(c) Ca , Cs , Br (d) Na+, Ca2+, Mg2+ (c) CN - , N 2 , C 22 - (d) PO 34 - , SO 24 - , ClO -4
20. In Bohr series of lines of hydrogen spectrum, the third line
29. According to Bohr's theory, the angular momentum of an
from the red end corresponds to which one of the following
electron in 5th orbit is [AIEEE 2006]
inter-orbit jumps of the electron for Bohr orbits in an atom of
hydrogen [AIEEE 2003] (a) 10 h / p (b) 2.5 h / p
(a) 5 ® 2 (b) 4 ® 1 (c) 2 ® 5 (d) 3 ® 2 (c) 25 h / p (d) 1.0 h / p
21. The de Broglie wavelength of a tennis ball of mass 60 g moving 30. Uncertainty in the position of an electron (mass = 9.1 ×
with a velocity of 10 metres per second is approximately 10–31 kg) moving with a velocity 300 ms–1, accurate upto
Planck’s constant, h = 6.63 × 10–34 Js [AIEEE 2003] 0.001% will be (h = 6.63 × 10–34 Js) [AIEEE 2006]
–31
(a) 10 metres –16
(b) 10 metres (a) 1.92 × 10–2 m (b) 3.84 × 10–2 m
(c) 10–25 metres (d) 10–33 metres (c) 19.2 × 10–2 m (d) 5.76 × 10–2 m
22. Which of the following sets of quantum numbers is correct 31. Which one of the following sets of ions represents a collection
for an electron in 4f orbital ? [AIEEE 2004] of isoelectronic species? [AIEEE 2006]
(a) n = 4, l = 3, m = + 1, s = + ½
(a) N3–, O2–, F–, S2– (b) Li+, Na+, Mg2+, Ca2+
(b) n = 4, l = 4, m = – 4, s = – ½
(c) n = 4, l = 3, m = + 4, s = + ½ (c) K+, Cl–, Ca2+, Sc3+ (d) Ba2+, Sr2+, K+, Ca2+
(c) n = 3, l = 2, m = – 2, s = + ½ 32. Which of the following sets of quantum numbers represents
23. Consider the ground state of Cr atom (X = 24). The number of the highest energy of an atom? [AIEEE 2007]
electrons with the azimuthal quantum numbers, l = 1 and 2 (a) n = 3, l = 0, m = 0, s = +1/2
are, respectively [AIEEE 2004] (b) n = 3, l = 1, m = 1, s = +1/2
(a) 16 and 4 (b) 12 and 5 (c) 12 and 4 (d) 16 and 5
(c) n = 3, l = 2, m = 1, s = +1/2
24. The wavelength of the radiation emitted, when in a hydrogen
atom electron falls from infinity to stationary state 1, would be (d) n = 4, l = 0, m = 0, s = +1/2.
(Rydberg constant = 1.097×107 m–1) [AIEEE 2004] 33. The ionization enthalpy of hydrogen atom is
(a) 406 nm (b) 192 nm 1.312 × 106 J mol–1. The energy required to excite the electron
(c) 91 nm (d) 9.1×10–8 nm in the atom from n = 1 to n = 2 is [AIEEE 2008]
25. Which one of the following sets of ions represents the (a) 9.84 × 105 J mol–1 (b) 6.56 × 105 J mol–1
collection of isoelectronic species? [AIEEE 2004] (c) 7.56 × 105 J mol–1 (d) 8.51 × 105 J mol–1
(a) K+, Cl–, Mg2+, Sc3+ (b) Na+, Ca2+, Sc3+, F– 34. Which one of the following constitutes a group of the
(c) K+, Ca2+, Sc3+, Cl– (d) Na+, Mg2+, Al3+, Cl– isoelectronic species? [AIEEE 2008]
(Atomic nos. : F = 9, Cl = 17, Na = 11, Mg = 12, Al = 13, K = 19, (a) C2– –
2 , O2 , CO, NO (b) CN – , N 2 ,O 2– 2–
2 , C2
Ca = 20, Sc = 21)
(c) NO+ , C2– –
2 , CN , N 2 (d) N 2 , O 2– , NO + , CO
26. Of the following outer electronic configurations of atoms, the
highest oxidation state is achieved by which one of them ? 35. Calculate the wavelength (in nanometer) associated with a
[AIEEE 2004] proton moving at 1.0 × 103 ms –1. [AIEEE 2009]
3
(a) (n – 1)d ns 2 (b) (n – 1)d ns1
5 (Mass of proton = 1.67 × 10–27 kg and h = 6.63 × 10–34 Js)
8
(c) (n – 1)d ns 2 (d) (n – 1)d5 ns2 (a) 0.40 nm (b) 2.5 nm (c) 14.0 nm (d) 0.32 nm
27. In a multi-electron atom, which of the following orbitals 36. In an atom, an electron is moving with a speed of 600 m/s with
described by the three quantum members will have the same an accuracy of 0.005%. Certainity with which the position of
energy in the absence of magnetic and electr ic the electron can be located is ( h = 6.6 × 10–34 kg m2s–1, mass
fields ? [AIEEE 2005] of electron, em = 9.1 × 10–31 kg) [AIEEE 2009]
(a) 5.10 × 10 m–3 (b) 1.92 × 10 –3 m
(A) n = 1, l = 0, m = 0 (B) n = 2, l = 0, m = 0
(c) 3.84 × 10 m –3 (d) 1.52 × 10 –4 m
(C) n = 2, l = 1, m = 1 (D) n = 3, l = 2, m = 1
(E) n = 3, l = 2, m = 0 37. The energy required to break one mole of Cl – Cl bonds in Cl 2
Options is 242 kJ mol–1. The longest wavelength of light capable of
breaking a single Cl – Cl bond is [AIEEE 2010]
(a) (D) and (E) (b) (C) and (D)
(c = 3 × 108 ms–1 and NA = 6.02 × 1023 mol–1).
(c) (B) and (C) (d) (A) and (B)
(a) 594 nm (b) 640 nm (c) 700 nm (d) 494 nm
JEEMAIN.GURU
downloaded from jeemain.guru
Structure of Atom 47
38. Ionisation energy of He+ is 19.6 × 10–18 J atom–1. The energy 41. The increasing order of the ionic radii of the given
of the first stationary state (n = 1) of Li2+ is [AIEEE 2010] isoelectronic species is : [AIEEE 2012]
(a) Cl–, Ca2+ , K+, S2– (b) S2–, Cl–, Ca2+ , K+
(a) 4.41 × 10–16 J atom–1 (b) –4.41 × 10–17 J atom–1
(c) Ca2+ , K+, Cl–, S2– (d) K+, S2–, Ca2+, Cl–
(c) –2.2 × 10–15 J atom–1 (d) 8.82 × 10–17 J atom–1
18 Z2
39. The frequency of light emitted for the transition n = 4 to n = 2 42. Energy of an electron is given by E = – 2.178 × 10 J
÷.
n2
of the He+ is equal to the transition in H atom corresponding Wavelength of light required to excite an electron in an
to which of the following ? [AIEEE 2011 RS] hydrogen atom from level n = 1 to n = 2 will be :
(a) n = 2 to n = 1 (b) n = 3 to n = 2 (h = 6.62 × 10 –34 Js and c = 3.0 × 108 ms–1)
[JEE Main 2013]
(c) n = 4 to n = 3 (d) n = 3 to n = 1 (a) 1.214 × 10–7 m (b) 2.816 × 10.–7 m
40. The electrons identified by quantum numbers n and l : (c) 6.500 × 10–7 m (d) 8.500 × 10–7 m
43. The kinetic energy of an electron in the second Bohr orbit of
(A) n = 4, l = 1 (B) n = 4, l = 0 a hydrogen atom is [a0 is Bohr radius] : [IIT-JEE 2009 S]
(C) n = 3, l = 2 (D) n = 3, l = 1 h2 h2 h2 h2
can be placed in order of increasing energy as :[AIEEE 2012] (a) (b) (c) (d)
4 2 ma02 16 2 ma02 32 2 ma02 64 2 ma02
(a) (C) < (D) < (B) < (A) (b) (D) < (B) < (C) < (A) 44. Given that the abundances of isotopes 54Fe, 56Fe and 57 Fe
(c) (B) < (D) < (A) < (C) (d) (A) < (C) < (B) < (D) are 5%, 90% and 5%, respectively, the atomic mass of Fe is
[IIT-JEE 2012]
(a) 55.85 (b) 55.95 (c) 55.75 (d) 56.05
1. Which statement is not correct ? (c) electrons come out of metal with a constant velocity
which depends on frequency and intesity of incident
æ 4 3ö -38 light.
(a) Volume of proton is approx. ç pr ÷1.5 ´ 10 cm3.
è3 ø (d) electrons come out of metal with different velocities
not greater than a certain value which depends upon
(b) Radius of e– is 42.8 × 10–13 cm3
frequency of incident light and not on intensity.
(c) Density of nucleus is 1014 g/cm3. 5. If E1, E2 and E3 represent respectively the kinetic energies of
(d) All are correct an electron and an alpha particle and a proton each having
2. The potential energy of electron present in ground state of same de-broglie wavelength then
Li2+ ion is represented by : (a) E1 > E3 > E2 (b) E2 > E3 > E1
+ 3e 2 -3e (c) E1 > E2 > E3 (d) E1 = E2 = E3
(a)
4p 0 r
(b) 4p 0 r 6. The angular speed of the electron in n th orbit of Bohr
hydrogen atom is
- 3e 2 - 3e 2 (a) directly proportional to n
(c) (d)
4p 0 r 2 4p 0 r (b) inversely proportional of n
3. Which principle/rule limits the maximum no. of electrons in (c) inversely proportional to n 2
an orbital to two ? (d) inversely proportional to n 3
(a) Aufbau principle 7. The Bohr's energy equation for H atom reveals that the energy
(b) Pauli's exclusion principle level of a shell is given by E = –13.58/n2eV. The smallest
(c) Hund's rule of max. multiplicity amount that an H atom will absorb if in ground state is
(d) Heisenberg's uncertainty principle (a) 1.0 eV (b) 3.39 eV
4. Photoelectric effect is the phenomenon in which (c) 6.79 eV (d) 10.19 eV
(a) photons come out of metal when hit by a beam of 8. If the Planck's constant h = 6.6 × 10–34 Js, the de-Broglie's
wavelength of a particle having momentum of 3.3 × 10–24
electrons
m/s will be
(b) photons come out of the nucleus of an atom under the (a) 0.02Å (b) 0.5Å
action of an electric field (c) 2Å (d) 500Å
JEEMAIN.GURU
downloaded from jeemain.guru
48 Chemistry
9. Ionization potential of hydrogen atom is 13.6eV. Hydrogen 19. The angular distribution functions of all orbitals have
atom in ground state are excited by monochromatic light of (a) l nodal surfaces (b) l – 1 nodal surfaces
energy 12.1 eV. The spectral lines emitted by hydrogen (c) n + 1 nodal surfaces (d) n – l –1 nodal surfaces
according to Bohr's theory will be 20. Which of the following radial distribution graphs correspond
(a) one (b) two to l = 2 for the H atom ?
(c) three (d) four
10. The wavelength of radiations emitted when electrons
falls from 4 th Bohr's orbit to 2 nd in H atom is : (RH =
(a)
1.09678 × 10–7 m –1).
(a) 972 nm (b) 486 nm
(c) 243 nm (d) 182 nm
11. The energy of e– in first orbit of He+ is –871.6 × 10–20 J. The
energy of e– in first orbit of H is:
(a) – 871.6 × 10–20 (b) –435.8 × 10–20 J
–20 (b)
(c) – 217.9 × 10 J (d) –108.9 × 10–20
12. The wave no. of radiation of wavelength 500 nm is :
(a) 5 × 10–7 /m (b) 2 × 107/m
6
(c) 2 × 10 /m (d) 500 × 10–9/m
+
13. In ground state of Cu . The no. of shells occupied, subshells,
filled orbitals, and unpaired electrons respectively are :
(a) 4, 8, 15, 0 (b) 3, 6, 15, 1 (c)
(c) 3, 6, 14, 0 (d) 4, 7, 14, 2
14. The quantum numbers +1/2 and –1/2 for the electron spin
represent
(a) rotation of the electron in clockwise and anticlockwise
direction respectively
(b) rotation of the electron in anticlockwise and clockwise
direction respectively (d)
(c) magnetic moment of the electron pointing up and down
respectively
(d) two quantum mechanical spin states which have no
classical analogue
15. Let mp be the mass of a proton, mn that of a neutron, M1 that
of a 20 nucleus and M2 that of a 40 nucleus. Then 21. Which of the following graphs correspond to
10 Ne 20 Ca one node?
(a) M2 = 2M1 (b) M1<10(mp + mn)
(c) M2 > 2M1 (d) M1 = M2
16. Which of the following pairs have identical values of e/m?
(a) A proton and a neutron (a) (b)
(b) A proton and deuterium
(c) Deuterium and an a- particle
(d) An electron and g-rays
ao
17. The wavelength of the third line of the Balmer series for a
hydrogen atom is
21 100
(a) (b) (c) (d)
100R ¥ 21R ¥
21R ¥ 100R ¥ ao
(c) (d) ao
100 21
22. A body of mass 10 mg is moving with a velocity of
18. Which of the following electronic configurations have zero
-1
spin multiplicity ? 100 ms . The wavelength of de-Broglie's wave associated
with it would be
(a) (b)
(a) 6.63 × 10 -35 m (b) 6.63 × 10 -31 m
(c) (d) (c) 6.63 × 10 -37 m (d) 6.63 × 10 -34 m
JEEMAIN.GURU
downloaded from jeemain.guru
Structure of Atom 49
23. If N 0 represents the Avogadro number, then which of the 31. The ratio of magnetic moments of Fe(III) and Co(II) is
(a) 7 : 3 (b) 3 : 7
following represent correct value of one atomic mass unit.
(c) 7 : 3 (d) 3 : 7
(a) N 0 ´ 10 - 3 kg (b) N0 g
32. The average life of an excited state of hydrogen atom is of
-1 1
(c) N 0 g (d)
16
Mass of 0-16 atom the order 10 -8 s. The number of revolutions made by an
electron when it is in state n = 2 and before it suffers a
24. If the shortest wavelength of the spectral line of H-atom in
transition to state n = 9 are
the Lyman series is X, then the longest wavelength of the
(a) 8.23 × 10 6 (b) 2.82 × 10 6
line in Balmer series of Li 2+ is
x (c) 22.8 × 10 6 (d) 2.28 × 10 6
(a) 9x (b) 33. The number of concentric spherical surfaces for 3s orbital at
9
which the probability of finding electrons is zero, are
5x 4x (a) 3 (b) 2
(c) (d)
4 5 (c) 1 (d) 0
25. If the subsidiary quantum number of a sub-energy level is 4, 34. If the second ionization potential of helium is 54.4 eV, then
the maximum and minimum values of the spin multiplicities
possible energy states of He + ion is/are
are
(a) 10, 2 (b) 4, – 4 (a) 13.6 eV (b) – 13.6 eV
(c) 10, 1 (d) 9, 1 (c) + 3.4 eV (d) None of these
35. If the uncertainties in position and momentum are equal, the
26. Li 3+ and a proton are accelerated by the same potential, uncertainty in the velocity is
then de-Broglie wavelengths l Li and l p have the ratio
1 h h
(a) (b)
(assume m Li = 9 mp ) 2m p 2p
(a) 1: 3 3 (b) 1 : 1 h
(c) 1 : 2 (d) 1 : 4 (c) (d) None of these
p
27. One Bohr magnet on is equal to
36. The de-Broglie wavelength of an electron accelerated by an
c h electric field of V volts is given by
(a) (b)
4phm e 4pem e
1.23 1.23
(a) l= nm (b) l= nm
eh hc V h
(c) (d)
4 me 4 me
1.23 1.23
(c) l= nm (d) l= nm
-1 m
28. The dissociation energy of H 2 is 430.53 KJmol . If V
hydrogen is dissociated by illumination with radiation of 37. The photoelectric current decreases if
wavelength 253.7 nm the fraction of the radiant energy which (a) the intensity of the source of light is decreased
will be converted into kinetic energy is given by (b) the frequency of incident radiation decreases below
(a) 100% (b) 8.76% threshold frequency
(c) 2.22% (d) 1.22%
(c) the exposure time decreases
29. The magnetic moment of M x + (atomic number M = 25) is (d) None of these
38. If a proton and a -particle are accelerated through the same
15 BM. The number of unpaired elections and the value
of x respectively are potential difference, the ratio of de-Broglie wavelengths l p
(a) 5, 2 (b) 3, 2 and l a is
(c) 3, 4 (d) 4, 3
30. The threshold frequency of a metal is 1 × 1015 s -1 . The ratio (a) 3 (b) 2 2
of the maximum kinetic energies of the photoelectrons when (c) 1 (d) 2
the metal is irradiated with radiations of frequencies 1.5 × 39. Which of the following pairs of nucleides are isodiaphers ?
1015 s -1 and 2.0 × 1015 s -1 respectively would be (a) 13
6 C and 16
8 O
(b) 1
1H and 12 H
(a) 4 : 3 (b) 1 : 2
(c) 3 and 42 He (d) 55 and 65
(c) 2 : 1 (d) 3 : 4 1H 25 Mn 30 Zn
JEEMAIN.GURU
downloaded from jeemain.guru
50 Chemistry
40. A system irradiated for 10 min. is found to absorb 39
42. The species 19 K and 19
9 F are called
18
3 × 10 quanta per sec. If the amount of substance (a) isosters (b) isobars
decomposed is 3 × 10 -3 mol ( N A = 6 × 10 23 ). The quantum (c) isotones (d) isodiaphers
43. A particle of mass 1 micro gram is moving with a speed of
efficiency of the reaction is
1 Kms–1. The de-Broglie wavelength of the particle is
(a) 2.5 (b) 2
(c) 1.5 (d) 1 (a) 7.04 × 10 -25 m (b) 6.626 × 10 -28 m
41. If the radius of first orbit of H-atom is a 0 , then de-Broglie (c) 6.626 × 10 -15 m (d) 6.626 × 10 -31 m
wavelength of electron in 4th orbit is
a0
(a) 8pa 0 (b)
4
(c) 16a 0 (d) 2pa 0
JEEMAIN.GURU
downloaded from jeemain.guru
Structure of Atom 51
–
EXERCISE 1 14. (c) Hydride ion H contains two electrons and He contains
238 234
two electrons.
1. Isotopes = U, U
92 92
15. (c)
Isobars = 234
90 Th, 234
91 Pa, 234
92 U 16. (c) The species CO, NO+, CN– and C22–. Contain 14 electrons
each.
2. First energy level.
3. s-orbital 17. (d) Na+, Mg++, O2– contain 10 electrons each Cl– has 18
electrons.
4. Interference and diffraction
18. (b) Nuclear charge of K+ (19) is more than nuclear charge of
5. There is no probability of finding a d electron right at the
Cl– (17).
nucleus.
6. Electron, because of its least mass. hc E1 2 6000
19. (b) E = ; = = = 2 :1
8. K.E. = 7.29 × 10–19J E2 1 3000
9. l = 1.24 × 10–14 m
hc
10. l = 6572 Å 20. (b) DE = hn = ;
l
13. v0= 9.81×1014 Hz.
19. (b) 20. (a) 21. (c) 22. (c) hc 6.63 ´ 10 -34 (3 ´ 108 )
\l = = = 656 nm
23. (a) 24. (b) 25. (b) 26. (d) DE 3.03 ´ 10 -19
27. (c) 28. (c)
h 6.63 ´10-34
EXERCISE 2 21. (a) p = = = 3 ´10-23 kg / s
l 2.2 ´10 -11
1. (c) A neutral atom with Z > 1 can have neutron, proton and
electron. 22. (a) It is in the lowest energy level, it can absorb and not emit
2. (d) Atomic orbitals are 4s, 3s, 3p and 3d. (n + l) values being energy.
4, 3, 4 and 5. Hence 3d has highest energy. 23. (c) See text for Brackett n 1 = 4, n2 = 5, 6, 7 etc.
3. (a) 19 + 1e– = 20 electrons.
æ 1 1 ö 5R
4. (d) Threshold frequency is not the same for all metals. 24. (d) For Balmer n1 = 2 and n2 = 3; n = R çç - ÷÷ = cm -1
2 2 36
è2 3 ø
5. (c) incorrect. (see text).
6. (a) All positive ions are deposited at small part. (nucleus of 25. (a) 350-700 nm lies in visible region hence Balmer Series.
atom). 26. (a) For Balmer n 1 = 2 and n2 = 3, 4, 5. For third line
7. (b) Ratio of mass of proton and electron is approx. n1 = 2 & n2 = 5.
1837 = 1.8 × 103. 27. (d) Li+ and He both have two electrons each.
8. (a) Neutron being chargless particle could not effect certain 13.6 ´ 1
13.6 Z 2 = +3.4 eV .
properties. 28. (a) KE = eV when n = 2. KE =
22
2
40
n
9. (c) 18Ar contains 22 neutrons and 21Sc40 contains 19
neutrons. The number of neutrons = (A – Z)
10. (d) Rutherford used doubly charged helium particle. 13.6Z2 13.6Z 2
29. (a) KE = eV and Total energy = - eV .
(a - particle) n2 n2
11. (b) Number of p = number of e – = 89 and neutrons Hence ratio = –1.
231 – 89 = 142. 30. (c)
12. (a) Z = 11, A = 24. Hence protons = 11 the neutrons
(24 – 11) = 13. nh
31. (c) Angular momentum mvr =
13. (d) For neutral atom . No. of p = No. of e– = 18 and 2p
A = Z + No. of neutrons = 18 + 20 = 38.
JEEMAIN.GURU
downloaded from jeemain.guru
52 Chemistry
JEEMAIN.GURU
downloaded from jeemain.guru
Structure of Atom 53
68. (b) Total number iof orbitals for principal quantum number n 96. (b)
is n2 5p 4f 6s 5d
69. (c) For l = 0, m cannot be –1. (n + l) 5+1 4+3 6+0 5+2
70. (a) m = +2 signifies only one orbital. 6 7 6 7
71. (d) For 4d electron we have n = 4, l = 2, m = –2, –1, 0, Hence the order is 5p < 6s < 4f < 5d
+1, +2 & s = ½ or –½.
97. (d) Fe2+ 1s2, 2s2p6, 3s2p6d6 hence 6 electrons.
72. (b) For f orbital, the values of m are –3, –2, –1, 0, +1,
98. (a) Pauli's exclusion principle.
+2, +3.
99. (c) Write electronic configuration and find unpaired electrons.
ch c Cr (6), Fe (4), Mn (5), Cu (3), Zn (0), Hg (0).
73. (b) E = hu = ;and u =
l l
The more the number of unpaired electrons the more is
the paramagnetic character.
3.0 ´108
8 ´1015 = 100.(c) Not more than two electrons can be present in same atomic
l orbital. This is Paulis exclusion principle.
101.(a) 11Na = 1s2, 2s2p6, 3s1 for 3s1, l = 0. Hence m = 0.
3.0 ´108
\ l= = 0.37 ´ 10-7 = 37.5 ´ 10 -9 m = 4 ´ 101 nm
8 ´ 1015
EXERCISE 3
74. (b)
Number of nodal planes in d orbitals is 2. h
1. (a) We know Dp.Dx ³
4p
75. (a)
Degenerate orbitals have equal energy.
since Dp = Dx (given)
76. (a)
One nodal plane in the YZ plane.
h
77. (a)
Angular nodes = l, spherical nodes (n – l – 1); \ Dp.Dp =
4p
Total (n – 1). Hence spherical nodes for 5f orbits.
= ( 5 –3 –1) = 1 h
or mDv m v. = [\ Dp= mDv]
78. (d) (follow text.) 4
2 h
or ( Dv ) =
79. (d) Mg 2 + = 1s 2 , 2s 2 p 6 , Ti 3+ = 1s 2 2s 2 p 6 3s 2 p 6 d 1 , 4 pm 2
V 3+ = 1s 2 , 2s 2 p 6 , 3s 2 p 6d 2 , Fe2+ = 1s2, 2s 2p6, 3s 2p6d 6 h 1 h
or Dv = =
(4 unpaired electrons in d). 4pm 2m p
2
80. (c) Atomic number 9 is for F and ion is F–. Thus option (a) is the correct option.
81. (c) 1s2, 2s22p5, 3s1. Total electrons (10) excited state of Ne. 2. (a) Dp = mDv
Substituting the given values of Dx and m, we get
82. (d) Heisenberg's uncertainty Principle is applicable to any 1×10–18 g cm s–1 = 9×10–28 g × Dv
moving object.
1´ 10 -18
83. (d) Configuration contains 2 unpaired electrons hence most or Dv =
paramagnetic. 9 ´ 10-28
= 1.1 × 109 cm s–1 ; 1×109 cm s–1
84. (d) For Cu2+ electronic configuration is [Ar]3d9.
i.e. option (a) is correct.
85. (c) Aufbau Principle. 3. (d) K.E per atom
JEEMAIN.GURU
downloaded from jeemain.guru
54 Chemistry
7. (b) Total no. of atomic orbitals in a shell = n2. 23. (b) Electronic configuration of Cr atom (z = 24)
Given n = 4; Hence number of atomic orbitals in 4th shell
will be 16. = 1s 2 ,2s 2 p 6 , 3s 2 p 6 d 5 ,4s1
8. (b) Given E1 = 25eV E2 = 50 eV
when l = 1, p - subshell,
hc hc E1 2
E1 = E2 = = Numbers of electrons = 12
E2
1 2 1 when l = 2, d - subshell,
2 = 25 = 1 Numbers of electrons = 5
1 2 2
1 50 2
9. (a) ns ® (n - 2) f ® (n - 1)d ® np [n = 6] 1 æ 1 1 ö÷
ç
10. (c) Energy of photon obtained from the transition n = 6 to 24. (c) l = R ç 2 - 2 ÷
è n1 n 2 ø
n = 5 will have least energy.
æ 1 1 ö 1 æ1 1 ö
DE = 13.6Z 2 - = 1.097 ´ 10 7 ç - ÷ = 1.097 ´ 10 7
çè n 2 n 2 ÷ø l è1 ¥ ø
1 2
11. (c) c = nl
l = 91.15 ´ 10 -9 m » 91nm
17
c 3 ´10
+
l= = = 50 nm 25. (c) 19 K, 20 Ca 2 + , 21 Sc 3+ ,17 Cl - each contains 18
6 ´ 1015
electrons
12. (c) n = 3 for 3rd shell
26. (d) (n–1)d5ns2 attains the maximum O.S. of + 7
l = 1 for p sub shell.
27. (a) The energy of an orbital is given by (n + l) in (d) and (c).
m = – 1 is possible for two electrons present in an (n + l) value is (3 + 2) = 5 hence they will have same
orbital. energy.
13. (c) Energy of an electron at infinite distance from the
nucleus is zero. As an electron approaches the nucleus, 28. (b) 1. BO33 5 8 3 + 3 = 32
the electron attraction increases and hence the energy 2
CO3 6 8 3 + 2 = 32 iso electronic
of electron decreases and thus becomes negative. Thus
as the value of n decreases, i.e. lower the orbit is, more NO3 7 8 3 + 1 = 32
negative is the energy of the electron in it.
14. (a) 2nd excited state will be the 3rd energy level. 2. SO32 16 8 3 + 2 = 42
13.6 13.6 2
En = eV or E= eV = 1.51 eV. CO3 32 not iso electronic
2 9
n
NO3 32
h
15. (c) Dx. Dp = ;
4p
3. CN 6 + 7 + 1 = 14
-34
6.62 ´ 10
\ Δv = = 2.1´ 10 -28 ms -1 N2 7 2 = 14 iso electronic
-5
4 ´ 3.14 ´ 0.025 ´ 10
2
16. (c) Fe+2 = 3d6, 4s0 C2 6 2 + 2 = 14
17. (a) For s-electron, l = 0 \ angular momentum = zero
18. (b) f-block elements show a regular decrease in atomic size
4. PO34 15 8 4 + 3 = 50
due to lanthanide/actinide contraction.
19. (a) N3–, F– and Na+ contain 10 electrons each. 2
SO 4 16 8 4 + 2 = 50 iso electronic
20. (a) The lines falling in the visible region comprise Balmer
series. Hence the third line would be n1 =2, n 2 = 5 i.e. ClO 4 17 8 4 + 1 = 50
5 ® 2.
29. (b) Accroding to Bohr's theory angular momentum of an
-34
h 6.6 ´ 10
21. (d) l = = = 10 -33 m electron i in nth orbital is given by mvr =
nh
mv 60 ´ 10 -3 ´10 2p
22. (a) The quantum numbers for 4f electron when n = 5
1 5h 2.5h
n = 4, l = 3, m = – 3, –2 –1, 0, 1 , 2 , 3 and S = ± Angular momentum of electron = =
2 2p p
JEEMAIN.GURU
downloaded from jeemain.guru
Structure of Atom 55
30. (a) Given m = 9.1 × 10–31kg 36. (b) According to Heisenberg uncertainty principle.
h = 6.6 × 10–34Js h h
Dx.mDv = Dx =
4p 4pmDv
300 ´ .001
DV = = 0.003ms–1 600 ´ 0.005
100 Here Dv = = 0.03
100
From Heisenberg's uncertainity priciple 6.6 ´ 10 -34
So, Dx =
6.62 ´ 10 -34 4 ´ 3.14 ´ 9.1´ 10-31 ´ 0.03
Dx = = 1.92 ´ 10 - 2 m = 1.92 × 10–3 meter
4 ´ 3.14 ´ 0.003 ´ 9.1 ´ 10 -31
37. (d) Energy required to break one mole of Cl – Cl bonds in
31. (a) N3– = 7 + 3 = 10e–, O–– ––® + 2 = 10e Cl2
P– = 9 + 1 = 10e–, S – – ––® 1 + 2 = 1 e–
242 ´ 103 hc
(not iso electronic) = 23
=
6.023 ´ 10 l
(b) Li+ = 3+1= 4e–, Na+ = 11–1 = 10e–,
Mg++ = 12–2=10e– 6.626 10 34 3 108
=
Ca++ = 20 – 2 = 18e– (not iso electronic)
(c) K+ = 19 – 1= 18e–, Cl– =17 + 1 = 18e–, 6.626 ´ 10 -34 ´ 3 ´108 ´ 6.023 ´10 23
Ca++ = 20 – 2 =18e–, Sc3+ = 21–3 = 18e– (iso electronic) \l=
242 ´ 108
(d) Ba++ 56 – 2 = 54e–, Sr++ 38–2 = 36e– = 0.4947 × 10–6 m = 494.7 nm
K+= 19–1 = 18e–, Ca++= 20–2 = 18e– (not iso electronic)
Z2
32. (c) (a) n = 3, l = 0 means 3s-orbital and n + l = 3 38. (b) I. E = 13.6eV ...(i)
n2
(b) n = 3, l = 1 means 3p-orbital n + l = 4
I1 Z12 n22
(c) n = 3, l = 2 means 3d-orbital n + l = 5 or I ...(ii)
2 n12 Z 22
(d) n = 4, l = 0 means 4s-orbital n + l = 4 Given I1 = – 19.6 × 10–18 , Z1 = 2,
Increasing order of energy among these orbitals is n1 = 1 , Z2 = 3 and n2 = 1
3s < 3p < 4s < 3d Substituting these values in equation (ii).
\ 3d has highest energy.. 19.6 ´10 -18 4 1
33. (a) (DE), The energy required to excite an electron in an – = ´
I2 1 9
atom of hydrogen from n = 1 to n = 2 is given by the
18 9
following relation (difference in energy E2 and E1) or I 2 19.6 10
4
-1.312 ´106 ´ (1)2 = – 4.41 × 10–17 J/atom
E2 = = –3.28 × 105 J mol–1 39. (a) For He+
(2)2
1 æ 1 1 ö
E1 = – 1.312 × 106 J mol–1 v = = RH Z 2 ç 2 - 2 ÷
l è2 4 ø
\ DE = E2 – E1
2 1 1 1 1
= [–3.28 × 105] – [–1.312 × 106 ] J mol–1 RH (2) 2 2÷
RH ÷
= (–3.28 × 105 + 1.312 × 106) J mol–1 2 4 (1)2 (2)2
For H
= 9.84 × 105 J mol–1
Thus the correct answer is (a) 1 1 1÷
34. (c) Species having same number of electrons are v= = RH
n12 n22 ÷
isoelectronic calculating the number of electrons in
each species given here, we get. For same frequency,
CN– (6 + 7 + 1 = 14); N2 (7 + 7 = 14);
O22–(8 + 8 +2 = 18) ; C22– (6 + 6 + 2 = 14); 1 1 1 1
RH 2 ÷ = RH ÷
O2– (8 + 8 + 1 = 17) ; NO+ (7 + 8 – 1 = 14) (1) (2 )2 n12 n22 ÷
CO (6 + 8 = 14) ; NO (7 + 8 = 15)
From the above calculation we find that all the species 1 1 1 1
\
listed in choice (c) have 14 electrons each so it is the n12 1 n22
22 2
JEEMAIN.GURU
downloaded from jeemain.guru
56 Chemistry
41. (c) Among isoelectronic species ionic radii increases as 4. (d) In photoelectric effect K.E., hence velocity is directly
the charge increases. proportional to frequency of the incident light and
Order of ionic radii Ca2+ < K+ < Cl– < S2– independent of the intensity of light.
The number of electrons remains the same but nuclear
charge increases with increase in the atomic number 1 2 h
5. (a) Since K.E. = m and = .
causing decrease in size. 2 m
18 1 1 hc
42. (a) E 2.178 10 2 2÷
= 1 h2 h2
1 2 K.E. = m. = . As is the same.
2 m2 2 2m 2
18 3 hc
2.178 10 = 1
4 K.E. µ
m
34
6.62 10 3 108
= V 1
6. (d) Angular speed is . Vn µ and rn µ n 2 .
r n
34
6.62 10 3 108 4 Angular speed is inversely proportional to n
=
2.178 10 18 3 7. (d) The smallest value of energy of an electron in H atom in
= 1.214 × 10–7m ground state can absorb is = E2 – E1.
43. (c) As per Bohr’s postulate,
13.58 13.58
nh = ÷ = 10.19
mvr = 4 1
2
nh h 6 .6 1 0 3 4
So, v = 8. (c) de-Broglie wavelength = = = 2Å
2 mr m 3 .3 1 0 2 4
1 2 9. (c) After absorbing 12.1 eV the electron in H atom is excited
KE = mv
2 to 3 shell.
2
1 nh 13.6
So, KE = m ÷ En E1 = ( 13.6) = 12.1
2 2 mr n2
a n2 13.6
Since, r = + 13.6 = 12.1
z n2
So, for 2nd Bohr orbit n=3
a 22 The possible transitions are (3 1) = 3
r= = 4a
1
1 1 1
1 22 h 2 10. (b) = RH = 4.86 10 7 m = 486 nm
KE = m 2 2
÷
2 2
4 2
2 4 m (4a )2 ÷
JEEMAIN.GURU
downloaded from jeemain.guru
Structure of Atom 57
20 25. (a) When l = 4, the number of degenrate orbitals
15. (a) 10 Ne contains10 protons and 10 neutrons
= 2l + 1 = 9,
\ M1 = 10 mp + 10mn
1
40 contains 20 protons and 20 neutrons the maximum total spins = 9 × and
20 Ca 2
\ M2 = 20 mp + 20 mn
\ M2 =2M1 1
minimum total spin =
16. (c) Deuterium and an a-particle have identical values of e/m. 2
æ 1 9
1 ç 1 ö÷ Maximum multiplicity = 2s + 1 = 2 × + 1 = 10
17. (b) l = R ¥ ç 2 - 2 ÷ for hydrogen atom. 2
è n1 n 2 ø
1
For the Balmer series n 1 = 2 and n2 = 5 for third line Minimum multiplicity = 2 × +1=2
2
1 æ 1 1 ö 21 100 26. (a) From de-Broglie equation,
\ = R ¥ çç - ÷÷ = R ¥ thus l =
l è2 2 2
5 ø 100 21 R ¥ h
18. (c) Spin multiplicity is given by A = (2 S + 1). represent ½ l= ;
2Vem
and ¯ repr esent – ½ spin values. For
h
l= (for proton)
2Vemp
S=–½
\ A = (2 ´ -½ + 1) = 0 h
l= (for Li 3+ )
19. (a) 2V3emLi
r2 2
lLi 3+ 2Vemp 1
20. (c) l = 2 represent d orbital for which \ = =
lp 6Vemp ´ 9 3 3
r
21. (b) The point at which the radial function acquirs zero value he
is called a node. Examine the graph the answer is (b). (c) 27. (c) One Bohr magneton =
4 mc
graph contains in nodes (a) and (d) none. 28. (b) Energy of 1 mole of photons,
h 6.63 ´ 10 -34 E = N0 × h u
22. (b) l = = = 6.63 × 10 -31 m
mv 10 ´ 10 -6 ´ 100
N0 ´ h ´ c
1 1 =
23. (c) 1 amu = g = N 0 -1 or × mass of C-12 atom l
N0 12
6.023 ´ 10 23 ´ 6.63 ´ 10 -34 ´ 3 ´ 10 8
1 æ ö =
24. (d) = R H Z2 ç 1 - 1 ÷ 253.7 ´ 10 -9
l çn 2 n 2 ÷ = 472.2 kJ
è 1 2 ø
Energy converted into KE = (472.2 – 430.53) kJ
To calculate shortest wavelength take n 2 = ¥ and
(472.2 - 430.53)
longest wavelength take nearest value of n 2 . % of energy converted into KE =
472.2
For H-atom,
= 8.76 %
1 29. (c) Magnetic moment
n 2 = ¥ , Z = 1, n1 = 1
l shortest
n ( n + 2) = 15
1 \ n = 3 number of unpaired electrons
\ = RH (Lyman series)
x 5 2
25 M = 3d , 4s
1
For l longest for Li 2+ , Z = 3, n1 = 2, n 2 = 3 (Balmer M x = 3d3
\ x = 4 for three unpaired electrons
series)
(KE )1 1- 0
1 1 æ 1 1 ö 5 30. (c) =
= × 3 2 çç 2 - 2 ÷÷ = (KE ) 2 2- 0
l longest x è2 3 ø 4x
(1.5 ´1015 - 1 ´1015 ) 1
4x = =
\ l longest = (2.0 ´ 10 15
- 1 ´10 ) 15 2
5
JEEMAIN.GURU
downloaded from jeemain.guru
58 Chemistry
1 h
\ Dv =
2m p
JEEMAIN.GURU
downloaded from jeemain.guru
3
Classification of Elements
and Periodicity in Properties
THE PERIODIC TABLE OF THE ELEMENTS
JEEMAIN.GURU
downloaded from jeemain.guru
60 Chemistry
MENDELEEV’S PERIODIC TABLE : (b) Periods - (i) The 7 horizontal columns (or rows) are called
This is based upon Mendeleev’s periodic law which states that periods. The seven periods of periodic table are
the physical and chemical properties of the elements are a periodic Shortest period - 1st period (1H ® 2He) contains 2 elements.
function of their atomic weights. It is the shortest period.
Mendeleev named Gallium and Germanium elements as eka- Short periods - 2nd period (3Li ® 10Ne) and 3rd period
aluminium and eka-silion respectively. (11Na ® 18Ar) contains 8 elements each. These are short
STRUCTURAL FEATURES OF THE MENDELEEV’S periods.
PERIODIC TABLE: Long periods - 4th period (19K ® 36Kr) and 5th period
(37Rb ® 54Xe) contain 18 elements each and are called long
(i) Mendeleev’s original periodic table consists eight vertical
periods.
columns are called groups I-VIII & seven horizontal rows are
Longest period - 6th period (55Cs – 86Rn) contains 32
called periods 1-7. But modified Mendeleev’s periodic table
elements and is the longest period.
contains nine groups, i.e., I-VIII and zero (of noble gases).
Incomplete period - 7th period (87Fr –) is, however, incomplete
(ii) All groups except VII and zero have been further divided
and contains at present only 26 elements.
into two sub-groups called A and B. A groups of left hand
(c) Blocks - The periodic table is divided into four main blocks
side consist of normal elements while groups B of right
(s, p, d and f) depending upon the subshell to which the
hand side consist of transition elements.
valence electron enters into.
(iii) Elements of group IA are called alkali metals while those of
(i) s-Block - Elements of group 1 and 2 constitute s-block.
group IB (i.e, Cu, Ag, Au) are called coinage metals.
(ii) p-Block - Elements of group 13 to 18 constitute
MODERN PERIODIC LAW : p-block.
Moseley formed the basis of the modern periodic law. He (iii) d-Block - Elements of group 3 to 12 constitute
discovered that the square root of the frequency of the more d-block.
prominent X-rays emitted by a metal was proportional to the atomic (iv) There are three complete series and one incomplete series
number and not the atomic weight of the atom of the metal. Hence of d-block elements. These are:
atomic number should be the basis of classification of the
1st or 3d-transition series which contains ten elements
elements.
with atomic number 21-30 (21Sc–30Zn).
Modern periodic law states, “that the physical and chemical
2nd or 4d-transition series which contains
properties of the elements are a periodic function of their atomic ten elements with atomic number 39–48
number.” (39Y–48Cd).
It was observed that the elements with similar properties reoccurred 3rd or 5d-transition series which also contains ten
at regular intervals of 2, 8, 8, 18 or 32. These numbers (2, 8, 8, 18 elements with atomic number 57 and 72-80 (57La, 72Hf–
and 32) are called magic numbers, and cause of periodicity in
80Hg).
properties.
4th or 6d-transition series which contains only ten
Structural features of the long form of the periodic table elements.
(a) Groups - (v) The f-block elements comprise two horizontal rows
(i) The 18 vertical columns, of the periodic table, are called placed at the bottom of the periodic table to avoid
groups its un-necessary expansion and make the symmetrial
(ii) Elements of groups 1, 2, 13-17 are called normal or nature of periodic table. The two series of f-block
representative elements. elements containing 14 elements each. Lanthanides -
(iii) Elements of groups 3-12 are called transition elements The 14 elements from 58Ce–71Lu in which 4f-subshell is
(iv) The elements belonging to a particular group is known being progressively filled up are called lanthanides or
as a family and is usually named after the first element. rare earth elements. Actinides - Similarly, the 14 elements
For example, Boron family (group 13). In addition to from 90Th – 103Lr in which 5f-subshell is being
this, some groups have typical names. For example, progressively filled up are called actinides.
Elements of group 1 are called alkali metals (vi) Elements of s and p-blocks are called normal or
representative elements, those of d-block are called
Elements of group 2 are called alkaline earth metals
transition elements while the f-block elements are called
Elements of group 3 are called pnicogens inner transition elements.
Elements of group 16 are called chalcogens
(vii)The 11 elements with Z = 93–103 (93Np – 103Lr) which
Elements of group 17 are called halogens occur in the periodic table after uranium and have been
Elements of group 18 are called noble gases prepared by artificial means are called transuranics.
These are all radioactive elements.
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
62 Chemistry
(B) Ionisation energy (I.E.) : The amount of energy (work) (i) EA values are expressed in eV/atom or kcal/mol
required to remove an electron from the last orbit of an isolated or kJ/mol.
(free) atom in gaseous state is known as ionisation potential (ii) The energy change accompanying the addition of first,
or energy or better first ionisation potential of the element, second, third etc. electrons to neutral isolated gaseous
i.e., ¾® M + (g ) + e -
M ( g ) + I.E ¾ atoms are called successive electron affinities and are
designated as EA1, EA2, EA3 etc.
(i) The amount of energies required to remove the
subsequent electrons (2nd, 3rd, ...) from the monovalent (iii) The first EA is always taken as positive. However, the
gaseous cation of the element one after the other are addition of second electron to the negatively charged
collectively called successive ionisation energies. These ion is opposed by coulombic repulsion and hence
are designated as I.E1, I.E2, I.E3, I.E4 and so on. It may be required (absorbed) energy for the addition of second
noted that. I.E4 > I.E3 > I.E2> I.E1 (for a particular element) electron. Thus, second electron affinity (EA2) of an
IE is expressed in eV/atom or kcal mol–1 or kJ mol–1 element is taken as negative. For example,
Note that eV atom–1 = 23.06 kcal mol–1 = 96.3 kJ mol–1
O (g ) + e - ¾
¾® O - (g ); EA1 = +141 KJ mol -1
(ii) In general, the first I.E. increases along the period from
left to right. However there are some exceptions to the (Exothermic)
general trend -
(a) I.E. decreases from elements of group 2 ® 3. O - (g ) + e - ¾
¾® O 2- (g ); EA 2 = -780 KJ mol -1
(b) I.E. decreases from elements of group 15 ® 16. (Endothermic)
(iii) In a group of the periodic table, the ionisation energy (iv) Electron affinity increases in moving along the period
decreases from top to bottom. from left to right due to increase in charge. But the values
(iv) The factors which affect the ionisation energy are are unexpectedly low in elements of group 2, 15 and 18
(a) Atomic size or radius : I.E. decreases as the atomic due to stable electronic configurations of exactly half-
size increases so the attractive force decreases. filled and completely filled orbitals.
(b) Number of electrons in the inner shell (screening (v) Within a group of the periodic table the electron affinities
effect) : On moving down a group, the number of decreases from top to bottom.
inner shells increases which increase the screening
(vi) In general, electron affinity follows the following trend:
effect and hence the ionisation potential tends to
decrease. Halogens > Oxygen family > Nitrogen family > Metals
(c) Nuclear charge : On moving along the period, of groups 1 and 13 and Non-metals of group 14 > Metals
effective nuclear charge increases due to addition of group 2.
of electrons in same valence shell and hence (vii)The electron affinities are indirectly measured with the
ionisation energy increases. help of Born-Haber Cycle, i.e.,
(d) Stable cofiguration : Half filled or completely filled
1
subshells possess extra stable nature and thus it is DH f = S + D + IE + EA + U
more difficult to remove electron and hence more is 2
I.E. Where, S, D, IE, EA and U are the heat of sublimation,
(e) Penetration effect : More penetrating bond dissociation energy, ionization energy, electron
(i.e. more closes) are subshells of a shell to the affinity and lattice energy respectively.
nucleus, more tightly the electrons are held towards (viii)Electron affinity depends upon-
the nucleus and more is I.E. (a) Effective nuclear charge - Greater the effective
I.E. : s > p > d > f for a given shell
nuclear charge, more is the attraction of nucleus
Penetration power µ Surface area of a subshell
towards the electron and hence higher will be the
(v) In second period elements, the correct increasing order
value of E.A.
of ionisation energies is
IE1 : Li < B < Be < C < O < N < F < Ne (b) Atomic size - Greater the atomic radius of the atom,
IE2 : Be < C < B < N < F < O < Ne < Li less will be the attraction of the nucleus to the
(vi) In third period elements, the correct increasing order of electron to be added and hence lower will be the
ionisation is value of E.A.
IE1 : Na < Al < Mg < Si < S < P < Cl < Ar (c) Penetrating power - Due to penetrating power, E.A.
IE2 : Mg < Si < Al < P < S < Cl < Ar < Na for addition of electron show the order
(C) Electron affinity (EA): It is the amount of energy released s>p>d>f
when a gaseous atom accepts the electron to form gaseous (d) Electronic configuration : Half filled and fully filled
anion . subshell are extra stable and thus oppose the
X (g ) + e - ¾
¾® X - (g ) + EA addition of electron which leads to lower, E.A. value
e.g. EA, of C > EA, of N.
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
64 Chemistry
Very Short/Short Answer Questions (ii) Arrange the above five elements is order of increasing
electron gain enthalpy.
1. Name a species which is iso electronic with Al3+.
13. Predict the formula of a stable binary compound that would
2. Helium has a electronic configuration of 1s2 but it is placed
be formed by the following pairs of elements
in p-block in group 18. Explain.
(a) aluminum and phosphorous
3. Name the elements with the lowest and the highest ionisation (b) lithium and nitrogen
energy. (c) calcium and sulphur
4. Predict the position of the element in the Periodic Table
satisfying the electronic configuration (n – 1) d1 ns2 Long Answer Questions
for n = 4.
14. Name the four blocks of elements in the periodic table and
5. Write equations to demonstrate the difference between list the difference in their electronic configurations. Give
electron affinity and the reverse of ionization potential. examples of each type of elements. Write at least four
6. All the lanthanoid elements form stable characteristics of each block.
compounds containing the +3 cation. Of the few other ionic 15. Find the best choice in the following list and give brief reason
forms known, Ce forms the stable + 4 series of ionic com- for your answer
pounds and Eu the stable + 2 series. Account for these (i) highest IE1; Se, S,Te
unusual ionic forms in terms of their electronic configura- (ii) smallest radius; Cl–, Br–, I–
tions. (iii) most parmagnetic; Fe, Co, Ni
7. Nitrogen has positive electron gain enthalpy whereas oxygen (iv) smallest atom; Sn, I, Bi
has negative. However, oxygen has lower ionisation
(v) lowest IE2 ; Ar, K, Ca
enthalpy than nitrogen. Explain.
16. (i) Explain the terms (a) screening effect,
8. Explain the following : (b) penetration effect, (c) metallic character.
(a) Electronegativity of elements increase on moving from (ii) Why are electron affinities of noble gases zero ?
left to right in the periodic table. Arrange halogens in increasing order of electron
(b) Ionisation enthalpy decrease in a group from top to affinity.
bottom. 17. The second ionization enthalpy (IE2) of the elements of the
9. Give the order in which the melting points of halides of second period are given below :
sodium decrease and why ? Element : IE2 (kJ/mol) :
10. The first (IE1) and second (IE2) ionisation enthalpies (kJ Li 7294
mol–1) of three elements I, II and III are given below : Be 1756
I II III B 2430
C 2354
1E1 403 549 1142
N 2856
1E2 2640 1060 2080 O 3396
Identify the element which is likely to be (a) non-metal (b) F 3377
an alkali metal (c) an alkaline earth metal. Ne 3966
11. Show by a chemical reaction with water that Na2O is a basic (i) Explain
oxide and Cl2O7 is an acidic oxide. (a) Why is IE2 of Li so much higher than for all other
12. Consider the ground state electronic configuration of the elements of this period ?
five elements I to V given below : (b) What is the general trend from Be to Ne of
Elements Electronic Configuration increasing IE2?
I 1s2 2s2 2p5 (c) Why IE 2 of F is just about the same
or very slightly less than that of oxygen ?
II 1s2 2s2 2p4
(ii) Would you predict the IE2 of Na in kJ/mol is
III 1s2 2s2 2p6 3s2 (a) greater than 7294
IV 1s2 2s2 2p6 3s1 (b) between 3966 and 7294 or
V 1s2 2s2 2p6 (c) less than 3966 ? Explain.
(i) Which of the above configuration is associated with
the highest and which is associated with the lowest
ionisation enthalpy ?
JEEMAIN.GURU
downloaded from jeemain.guru
Multiple Choice Questions 23. The period number in the long form of the periodic table is
equal to
18. Element A belongs to Group VII in p-block and element B
(a) magnetic quantum number of any element of the period.
belongs to Group I in s-block of the periodic table. Out of
(b) atomic number of any element of the period.
the following assumptions, the correct one is :
(c) maximum Principal quantum number of any element of
(a) A and B are metals
the period.
(b) A and B are non-metals
(d) maximum Azimuthal quantum number of any element
(c) A is a metal and B is a non-metal
of the period.
(d) A is a non-metal and B is a metal 24. The lightest liquid metal is
19. Examine the following elements : (a) Hg (b) Ga
N, O, F, Ne (c) Cs (d) Fr
P, S, Cl, Ar 25. Which of the following elements A, B, C, D and E with atomic
Br, Kr number 3, 11, 15, 18 and 19 respectively belong to the same
I, Xe group?
In modern periodic table, on which side these elements are (a) A, B, C (c) B, C, D
placed (c) A, D, E (d) A, B, E
(a) Top left side (b) Bottom left side 26. Which of the following statement(s) about the Modern
(c) Top right side (d) Middle side Periodic Table is/are incorrect ?
(i) The elements in the Modern Periodic Table are arranged
20. The screening effect of ‘d’ electrons is
on the basis of their decreasing atomic number
(a) Much less than s-electrons (ii) The elements in the Modern Periodic Table are arranged
(b) Much more than s-electrons on the basis of their increasing atomic masses
(c) Equal to s-electrons (iii) Isotopes are placed in adjoining group(s) in the Periodic
(d) Equal to p-electrons Table
21. Which of the following is not an actinoid ? (iv) The elements in the Modern Periodic Table are arranged
(a) Curium (Z = 96) on the basis of their increasing atomic number
(a) (i) only (b) (i), (ii) and (iii)
(b) Californium (Z = 98) (c) (i), (ii) and (iv) (d) (iv) only
(c) Uranium (Z = 92) 27. An element having electronic configuration
(d) Terbium (Z = 65)
22. Electronic configurations of four elements A, B, C and D are 1s 2 2s 2 2p 6 3s 2 3p 6 4s1 forms
given below : (a) Acidic oxide (b) Basic oxide
(i) 1s2 2s2 2p6 (ii) 1s2 2s2 2p4 (c) Amphoteric oxide (d) Neutral oxide
2 2 6
(iii) 1s 2s 2p 3s 1 (iv) 1s2 2s2 2p5 28. An element which is an essential constituent of all organic
compounds belongs to
Which of the following is the correct order of increasing
(a) group 1 (b) group 14
tendency to gain electron ?
(c) group 15 (d) group 16
(a) A < C < B < D (b) A < B < C < D
(c) D < B < C < A (d) D < A < B < C
1. As per the modern periodic law, the physical and chemical 3. The most significant contribution towards the development
properties of elements are periodic functions of their of periodic table was made by
(a) atomic volume (a) Mendeleev (b) Avogadro
(b) electronic configuration (c) Dalton (d) Cavendish
(c) atomic weight 4. Mendeleev’s periodic law is based on
(d) atomic size (a) atomic number (b) atomic weight
2. Eka-aluminium and Eka-silicon are known as (c) equivalent weight (d) valency
(a) Gallium and Germanium 5. Which of these does not reflect the periodicity of the
(b) Aluminium and Silicon elements?
(c) Iron and Sulphur (a) Bonding behaviour (b) Electronegativity
(d) Manganese and Magnesium (c) Ionization potential (d) Neutron/proton ratio
JEEMAIN.GURU
downloaded from jeemain.guru
66 Chemistry
6. The statement that is not true for the long form of the periodic 18. Electronic configuration of most electronegative element is
table is (a) 1s2 2s2 2p4 3s1 (b) 1s2 2s2 2p6 3s2 3p5
(a) It reflects the sequence of filling electrons in the order of (c) 1s2 2s2 2p5 (d) 1s2 2s2 2p6 3s2 3p6
sub-energy levels s, p, d and f. 19. Going from fluorine to chlorine, bromine and iodine, the
(b) It helps to predict the stable valence states of the electronegativity
elements (a) increases
(c) It reflects trends in physical and chemical properties of (b) decreases
the elements (c) first decrease then increases
(d) It helps to predict the relative ionicity of the bond (d) changes randomly
between any two elements. 20. Which of the following is most electronegative?
7. Which of the following pairs of atomic numbers represents (a) Lead (b) Silicon
elements belonging to the same group? (c) Carbon (d) Tin
(a) 11 and 20 (b) 12 and 30 21. On going from right to left in a period in the periodic table,
(c) 13 and 31 (d) 14 and 33 the electronegativity of the elements
8. Which of the following sets of atomic number belong to that (a) increases
of alkali metals? (b) decreases
(a) 1, 12, 30, 4, 62 (b) 37, 19, 3, 55 (c) remains unchanged
(c) 9, 17, 35, 53 (d) 12, 20, 56, 88 (d) decreases first then increases
9. What is the atomic number of the next halogen if discovered? 22. The electronegativity follows the order
(a) 85 (b) 117 (a) F > O > Cl > Br (b) F > Cl > Br > O
(c) 167 (d) 104 (c) O > F > Cl > Br (d) Cl > F > O > Br
10. All the elements of a group in the periodic table have the 23. Electronegativity values for the elements help in predicting
same (a) polarity of bonds
(a) atomic weight (b) dipole moments
(b) number of protons (c) valency of elements
(c) mass number (d) position in the electrochemical series
(d) number of electrons for bonding 24. Which of the following is correctly matched?
11. The elements in which 4f orbitals are progressively filled up (a) C—C bond length — 0.077 nm
are called as (b) Ionic radius of Na+ — 0.136 nm
(a) actinides (b) transition elements (c) C—Cl bond length — 0.176 nm
(c) lanthanides (d) halogens (d) Ionic radius of F– — 0.095 nm
12. Which of the following is not a transition metal? 25. The atomic radius increases as we move down in a group
(a) Zr (b) Tc because
(c) Re (d) Np (a) effective nuclear charge increases
13. Which of the following have same number of electrons in (b) atomic mass increases
the outermost orbit? (c) additive electrons are accommodated in new electron
(a) Pb, Sb (b) N, O level
(c) As, Bi (d) P, Ca (d) atomic number increases
14. Representative elements belong to 26. The correct order of radii is
(a) s- and p-blocks (b) p- and d-blocks (a) N < Be < B (b) F - < O 2 - < N 3-
(c) f-block only (d) d- and f-blocks
15. Element with atomic number 56 belongs to which block? (c) N < Li < K (d) Fe 3+ < Fe 2 + < Fe 4+
(a) s (b) p 27. Which of the following is the smallest cation?
(c) d (d) f (a) Na+ (b) Mg2+
(c) Ca 2+ (d) Al3+
16. Which of the following remains unchanged on descending
in a group in the periodic table? 28. The ionic radii of N , O , F and Na+ are in the order
3– 2– –
(a) Valence electrons (b) Atomic size (a) N 3- > O 2 - > F - > Na +
(c) Density (d) Metallic character
17. Which is true about the electronegativity order of the (b) N 3- > Na + > O 2- > F -
following elements? (c) Na + > O 2 - > N 3- > F -
(a) P > Si (b) C > N
(c) Br > Cl (d) Sr > Ca (d) O 2- > F - > Na + > N 3-
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
68 Chemistry
52. The correct order of ionization energies is 62. Consider the following statements
(a) Zn < Cd < Hg (b) Hg < Cd < Zn I. The radius of an anion is larger than that of the parent
(c) Ar > Ne > He (d) Cs < Rb < Na atom.
53. Which of the order for ionization energy is correct? II. The ionization energy generally increases with increasing
(a) Be < B < C < N < O (b) B < Be < C < O < N atomic number in a period.
(c) Be > B > C > N > O (d) B < Be < N < C < O III. The electronegativity of an element is the tendency of
an isolated atom to attract an electron.
54. First ionization potential will be maximum for
Which of the above statements is/are correct?
(a) Uranium (b) Hydrogen
(c) Lithium (d) Iron (a) I alone (b) II alone
55. The incorrect statement among the following is (c) I and II (d) II and III
(a) the first ionization potential of Al is less than the first 63. Which of the following order is wrong?
ionization potential of Mg (a) NH 3 < PH 3 < AsH 3 — Acidic
(b) the second ionization potential of Mg is greater than the
second ionization potential of Na (b) Li < Be < B < C — IE1
(c) the first ionization potential of Na is less than the first (c) Al 2 O3 < MgO < Na 2 O < K 2 O — Basic
ionization potential of Mg
(d) the third ionization potential of Mg is greater than the (d) Li + < Na + < K + < Cs + — Ionic radius
third ionization potential of Al. 64. Gradual addition of electronic shells in the noble gases causes
56. The second ionization potential of an element M is the energy a decrease in their
required to (a) ionization energy (b) atomic radius
(a) remove one mole of electrons from one mole of gaseous (c) boiling point (d) density
cations of the element
65. Which of the following elements represents highly
(b) remove one mole of electrons from one mole of gaseous electropositive as well as highly electronegative character in
anions its period?
(c) remove one mole of electrons from one mole of (a) Hydrogen (b) Nitrogen
monovalent gaseous cations of the element
(c) Fluorine (d) None of these
(d) remove 2 moles of electrons from one mole of gaseous
atoms 66. The cause of diagonal relationship is
57. Highest ionization potential is shown by (a) similar electronegativities
(a) Alkali metals (b) Transition elements (b) similar ionic or atomic radii
(c) Halogens (d) Inert gases (c) similar polarizing power of ions
58. With reference to ionization potential which one of the (d) All the three
following sets is correct? 67. Variable valency is generally exhibited by
(a) Li > K < Cs (b) B > Li > K
(a) representative elements
(c) Cs > Li > B (d) Cs < Li < K
(b) transition elements
59. Which of the following species has lowest ionization
potential? (c) non-metallic elements
(a) O (b) O2 (d) metallic elements
(c) O2 + (d) O2– 68. Which of the following elements does not belong to first
60. The factor not affecting the ionization energy is transition series?
(a) size of atom (a) Fe (b) V
(b) charge in the nucleus (c) Ag (d) Cu
(c) type of bonding in the crystalline lattice 69. In the periodic table, with the increase in atomic number, the
(d) type of electron involved metallic character of an element
61. The screening effect of inner electrons of the nucleus causes (a) decreases in a period and increases in a group
(a) decrease in the ionization energy (b) increases in a period and decreases in a group
(b) increase in the ionization energy
(c) increases both in a period and the group
(c) no effect on the ionization energy
(d) decreases both in a period and the group
(d) increases the attraction of the nucleus for the electrons
JEEMAIN.GURU
downloaded from jeemain.guru
1. Identify the correct order of the size of the following: 11. Which one of the following ions has the highest value of
(a) Ca2+ < K+ < Ar < Cl– < S2– [CBSE-PMT 2007] ionic radius ? [AIEEE 2004]
2+ + – 2– (a) O2– (b) B3+
(b) Ar < Ca < K < Cl < S
(c) Li+ (d) F–
(c) Ca2+ < Ar < K+ < Cl– < S2– 12. Among Al2O3, SiO2, P2O3 and SO2 the correct order of acid
(d) Ca2+ < K+ < Ar < S2– < Cl– strength is [AIEEE 2004]
2. In which of the following electronic configuration an atom (a) Al2O3 < SiO2< SO2 < P2O3
has the lowest ionisation enthalpy? [CBSE-PMT 2007] (b) SiO2< SO2 < Al2O3 < P2O3
2 2
(a) 1s 2s 2p 3 (b) 1s 2s 2p5 3s1
2 2 (c) SO2< P2O3 < SiO2 < Al2O3
2 2 6 (d) Al2O3 < SiO2< P2O3 < SO2
(c) 1s 2s 2p (d) 1s2 2s2 2p5 13. Beyllium and aluminium exhibit many properties which are
3. Which one of the following ionic species has the greatest similar. But, the two elements differ in [AIEEE 2004]
proton affinity to form stable compound? [CBSE-PMT 2007] (a) forming covalent halides
(a) NH -2 (b) F – (b) forming polymeric hydrides
(c) exhibiting maximum covalency in compounds
(c) I– (d) HS–
(d) exhibiting amphoteric nature in their oxides
4. The stability of + 1 oxidation state increases in the sequence: 14. Which of the following oxides is amphoteric in character?
[CBSE-PMT 2009] (a) SnO 2 (b) SiO 2 [AIEEE 2005]
(a) Tl < In < Ga < Al (b) In < Tl < Ga < Al
(c) CO 2 (d) CaO
(c) Ga < In < Al < Tl (d) Al < Ga < In < Tl
15. In which of the following arrangements, the order is NOT
5. Amongst the elements with following electronic
according to the property indicated against it?
configurations, which one of them may have the highest (a) Li < Na < K < Rb : [AIEEE 2005]
ionization energy? [CBSE-PMT 2009] Increasing metallic radius
2
(a) Ne [3s 3p ] 2 (b) Ar [3d 4s24p3 ]
10
(b) I < Br < F < Cl :
2
(c) Ne [3s 3p ] 1 (d) Ne [3s23p3] Increasing electron gain enthalpy
6. Which of the following represents the correct order of (with negative sign)
increasing electron gain enthalpy with negative sign for the (c) B < C < N < O
Increasing first ionization enthalpy
elements O, S, F and Cl ? [CBSE-PMT 2010]
(a) Cl < F < O < S (b) O < S < F < Cl (d) Al3+ < Mg 2+ < Na + < F -
(c) F < S < O < Cl (d) S < O < Cl < F Increasing ionic size
7. Among the elements Ca, Mg, P and Cl, the order of increasing 16. The increasing order of the first ionization
enthalpies of the elements B, P, S and F (Lowest first)
atomic radii is : [CBSE-PMT 2010]
is [AIEEE 2006]
(a) Ca < Mg < P < Cl (b) Mg < Ca < Cl < P (a) B < P < S < F (b) B < S < P < F
(c) Cl < P < Mg < Ca (d) P < Cl < Ca < Mg (c) F < S < P < B (d) P < S < B < F
8. What is the value of electron gain enthalpy of Na+ if IE1 of 17. Following statements regarding the periodic trends of
Na = 5.1 eV ? [CBSE-PMT 2011 M] chemical reactivity of the alkali metals and the halogens are
(a) –5.1 eV (b) –10.2 eV given. Which of these statements gives the correct picture?
[AIEEE 2006]
(c) +2.55 eV (d) +10.2 eV
(a) Chemical reactivity increases with increase in atomic
9. According to the Periodic Law of elements, the variation in number down the group in both the alkali metals and
properties of elements is related to their [AIEEE 2003] halogens
(a) nuclear masses (b) In alkali metals the reactivity increases but in the halogens
(b) atomic numbers it decreases with increase in atomic number down the
(c) nuclear neutron-proton number ratios group
(d) atomic masses (c) The reactivity decreases in the alkali metals but increases
10. Which is the correct order of ionic sizes (At. No. : Ce = 58, in the halogens with increase in atomic number down the
group
Sn = 50, Yb = 70 and Lu = 71) ? [AIEEE 2003]
(d) In both the alkali metals and the halogens the chemical
(a) Ce > Sn > Yb > Lu (b) Sn > Ce > Yb > Lu reactivity decreases with increase in atomic number down
(c) Lu > Yb > Sn > Ce (d) Sn > Yb > Ce > Lu the group
JEEMAIN.GURU
downloaded from jeemain.guru
70 Chemistry
18. The charge/size ratio of a cation determines its (a) Al3+ > Mg 2+ > Na + > F- > O 2 -
polarizing power. Which one of the following sequences (b) Na + > Mg 2+ > Al3+ > O2- > F-
represents the increasing order of the polarizing power of (c) Na + > F - > Mg 2 + > O 2 - > Al3+
the cationic species, K+, Ca2+, Mg2+, Be2+? [AIEEE 2007]
(d) O2- > F- > Na + > Mg 2+ > Al3+
(a) Ca2+ < Mg2+ < Be+ < K+ 21. The correct order of electron gain enthalpy with negative
(b) Mg2+ < Be2+ < K+ < Ca2+ sign of F, Cl, Br and I, having atomic number 9, 17, 35 and 53
(c) Be2+ < K+ < Ca2+ < Mg2+ respectively, is : [AIEEE 2011 RS]
(d) K+ < Ca2+ < Mg2+ < Be2+. (a) F > Cl > Br > I (b) Cl > F > Br > I
19. In which of the following arrangements, the sequence is not (c) Br > Cl > I > F (d) I > Br > Cl > F
strictly according to the property written against it? 22. The increasing order of the ionic radii of the given
[AIEEE 2008] isoelectronic species is : [AIEEE 2012]
(a) HF < HCl < HBr , HI : increasing acid strength (a) Cl–, Ca2+ , K+, S2– (b) S2–, Cl–, Ca2+ , K+
(b) NH3 < PH3 < AsH3 <SbH3 : increasing basic strength (c) Ca2+ , K+, Cl–, S2– (d) K+, S2–, Ca2+, Cl–
(c) B < C < O < N : increasing first ionization enthalpy 23. Which of the following represents the correct order of
(d) CO2 < SiO2 < SnO2 < PbO2 : increasing oxidising power increasing first ionization enthalpy for Ca, Ba, S, Se and Ar ?
20. The correct sequence which shows decreasing order of the [JEE M 2013]
ionic radii of the elements is [AIEEE 2010] (a) Ca < S < Ba < Se < Ar (b) S < Se < Ca < Ba < Ar
(c) Ba < Ca < Se < S < Ar (d) Ca < Ba < S < Se < Ar
1. An element X occurs in short period having configuration 8. The valence shell of element A contains 3 electrons while the
ns2 np1. The formula and nature of its oxide is valence shell of element B contains 6 electrons . If
(a) XO3, basic (b) XO3 acidic A combines with B, the probable formula of the compound
(c) X2O3, amphoteric (d) X2O3 basic formed will be
2. The law of triads is applicable to a group of (a) AB2 (b) A2B
(a) Cl, Br, I (b) C, N, O
(c) A2B3 (d) A3B2
(c) Na, K, Rb (d) H, O, N
9. Pauling scale of electronegativity of elements helps to
3. Elements of IA group give flame colour due to
determine
(a) low IP
(a) covalent nature of an element
(b) low m.pt.
(c) softness (b) position of an element in EMF series
(d) one electron in outermost shell. (c) dipole moment of molecules
4. The ionic radii of N3–, O2– and F– are respectively given by (d) polarity of bond.
(a) 1.36, 1.40, 1.71 (b) 1.36, 1.71, 1.40 10. The statement that is not correct for the periodic classification
(c) 1.71, 1.40, 1.36 (d) 1.71, 1.36, 1.40 of elements is
5. The first ionisation potential of aluminium is smaller than (a) The properties of elements are the periodic functions of
that of magnesium because their atomic number
(a) Atomic size of Al > Atomic size of Mg. (b) Non-metallic elements are lesser in number than metallic
(b) Atomic size of Al < Atomic size of Mg. elements
(c) Al has one electron in p - orbital (c) The first ionization energies of elements along a period
(d) None of these do not vary in a regular manner with increase in atomic
6. Which of the following halides is not oxidized by MnO2 number.
(a) F– (b) Cl– (d) For transition elements the d-sub shells are filled with
electrons monotonically with increase in atomic number
(c) Br– (d) I–
11. Which is coloured ion
7. Which species has the maximum ionic radius
(a) Na+ (b) O2– (a) [Cu ( NH 3 ) 4 ]+ (b) [Cu( NH 3 ) 4 ]2 +
(c) F– (d) Mg2+
(c) [ Zn(H 2 O) 6 ]2 + (d) [Ca (H 2 O) 6 ]2 +
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
72 Chemistry
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
74 Chemistry
20. (d) All the given species contains 10 e – each i.e. 6. (a) F2 is strongest oxidising agent. F- is not oxidised by
isoelectronic.
MnO2
For isoelectronic species anion having high negative
charge is largest in size and the cation having high 7. (b) O 2 - has minimum effective nuclear charge, hence has
positive charge is smallest. maximum ionic radius
21. (b) As we move down in a group electron gain enthalpy
8. (c) The element A is ns 2 p1 and B is ns2 p 4 . They can form
becomes less negative because the size of the atom
increases and the distance of added electron from the compound of the type A 2 B3
nucleus increases. Negative electron gain enthalpy of F 9. (d) Pauling scale of electronegativity helps to determine
is less than Cl. This is due to the fact that when an polarity of bond
electron is added to F, the added electron goes to the 10. (d)
smaller n = 2 energy level and experiences significant 11. (b) Due to presence of one unpaired electron
repulsion from the other electrons present in this level.
In Cl, the electron goes to the larger n = 3 energy level (Cu 2+ = 3p 6 d 9 ) the complex [Cu ( NH 3 ) 4 ]2 + is
and consequently occupies a larger region of space coloured
leading to much less electron–electron repulsion. So the 12. (a)
correct order is Cl > F > Br > I. 13. (a) In inert gases we have van der waal’s radii which is always
22. (c) higher than atomic radii
23. (c) On moving along a period from left to right I.E. increases 14. (a) The screening effect follows the order s > p > d > f
and on moving down a group I.E. decreases.
15. (b) It is electronic configuration of alkali metal. Hence it will
hence correct order is : Ba < Ca < Se < S < Ar
form basic oxide
EXERCISE 4 16. (c) Atomic no. 17 (Cl) and 53 (I) are present in the same
group
1. (c) ns2 np1 is the electronic configuration of III A period.
17. (d) The energy involved is ionisation energy (I.E.). Further
Al2O3 is amphoteric oxide
the 3rd ionisation energy will be greater than the 2nd and
2. (a) According to the law of triads the atomic wt of the middle 1st.
element is arithmatic mean of I and III. At wt of Br 18. (d) There is a sudden jump in the value of IP when there is
At.wt of Cl + At wt of I
= change of principal energy level
2
3. (a) Due to low value of IP, valence electrons are. migrated to 19. (c) In 3d 6 4s 2 the differentiating electron enters d sub shell,
higher energy levels Hence it represents transition metal, Fe.
20. (b) The process represents the first electron affinity which
4. (c) The ionic radii must follow the order N 3- > O 2 - > F -
is always exothermic. Hence DH is negative
5. (c) Al ( 3s2 p1) and Mg (3s2). Lower energy is required to 21. (b) Ion = Mn 2+ Cu2+ Fe2+ Ni2+
EC = 3d 5 3d 9 3d6 3d8
remove 3p1 electron than 3s1 electron (penetrating
Number of unpaired
effect is s > p > d > f ) . Secondly Mg has stable electrons = 5 1 4 2
electronic configuration than Al Hence lowest paramagnetism is shown by CuSO4.5H2O
JEEMAIN.GURU
downloaded from jeemain.guru
4
Chemical Bonding
and Molecular Structure
CHEMICAL BOND : Only valence electrons are involved in the combilation of
A chemical bond is a sort of attraction which keeps the two atoms two atoms. The representation of valence electrons on an
together. Thus depending upon the variety of force, there may be atom called Lewis Symbol eg.
variety of chemical bonds. (Second Period
Li Be B C N O F Ne
REASONS FOR THE FORMATION OF A CHEMICAL elements)
BOND : TYPES OF CHEMICAL BOND : (By Kossel and Lewis)
(i) Energy concept : When two atoms approach each other, the Depending upon the mode of acquiring the stable electronic
attractive and repulsive forces operate between them. The configuration, the chemical bonds may be
distance at which the attractive forces overweigh the i) Ionic or electrovalent bond
repulsive forces is known as the bond distance, the potential
energy of the system is minimum and the bond is said to be ii) Covalent bond
formed. iii) Coordinate or dative bond
iv) Metallic bond
v) Hydrogen bond
vi) Weak van der Waal's forces of attraction
IONIC BOND (By Kossel and Lewis)
Energy kJ/mol
JEEMAIN.GURU
downloaded from jeemain.guru
76 Chemistry
FACTORS AFFECTING THE FORMATION OF IONIC Where q1 and q2 are the charges of ions in coulombs, 4 0 is the
BOND : permitivity factor and r is the distance between ions. Hence lattice
There are three main factors energy depends upon
(i) Ionisation energy (I) : The lower the value of the ionisation
i) Charge on ions : The higher the charge on ions, the greater
energy of an atom greater will be the ease of formation of
will be the force of attraction between them and greater will
cation from it.
be the lattice energy. The order of lattice energy for different
Note: the size of the cation is always smaller than the atom
solids is as follows
from which it is derived
(ii) Electron affinity (E) : The higher the electron affinity of an bi - bivalent uni - bivalent uni - univalent
> >
atom the greater will be the ease of formation of anion from it. solids solids solids
The size of the anion is always larger than the atom from MgO > CaCl2 > NaCl
which it is derived.
ii) Size of ions : The smaller the size of the ions, the lesser will
(iii) Lattice structure : The electrostatic field of cations and
be distance between them, the greater will be the force of
anions extends in all directions, their union is not limited to
form a single molecule, rather a cluster of ions, having three attraction and so greater will be the lattice energy.
dimensional orderly arrangement, known as the lattice FAJAN’S RULE :
structure is formed. This rule is for covalent character of an ionic bond. Covalent
(iv) Lattice energy (U) : The amount of heat evolved when one character of an ionic bond is favoured by
mole of ionic compound is formed from positive and negative
i) Small positive ion ii) Large negative ion
ions in the crystalline form is known as the lattice energy.
iii) Large charge on ions
BORN HABER CYCLE :
Thus for a fixed cation, the larger the size of anion, the more the
The formation of ionic compounds in terms of energy can be seen
magnitude of the charge, the more is covalent character eg.
by Born Haber cycle eg. formation of NaCl is as follows
covalent character of sodium halides follows the order
sublimation ionisation
Na(s) Na(g) Na (g) + e
+
NaI > NaBr > NaCl > NaF
+ S + I
For fixed anion, the smaller the size of cation, the more the
1 Dissociation Addition of e magnitude of the charge, the more is the covalent character eg.
Cl2 (g) Cl(g) Cl (g)
2 1 E BeCl2 > MgCl2 > CaCl2 > SrCl2 > BaCl2
+ D
2 It has been observed that a cation having 18 (s2p6d10) electrons
crystal formation in outermost shell (pseudo noble gas configuration) can polarise
Na ( g ) + Cl (g )
+
NaCl (s) the anion more than cation having 8 (s2p6) noble gas electronic
U
where S = Heat of sublimation of Na metal configuration. Hence CuCl is more covalent than NaCl. Similarly
I = Ionisation energy of Na AgCl is more covalent than KCl.
D = Heat of dissociation of molecular chlorine POLARISING POWER OF CATION :
E = Electron affinity of chlorine atom It is generally represented by and also known as ionic potential
U = Lattice energy of NaCl
charge density. It can be represented as
The amount of heat liberated (Q) in the overall reaction is the heat
of formation of NaCl. charge on cation
Thus Q = S + I + 1/2 D – E – U =
radius of cation
(The negative sign indicates heat is evolved or liberated)
The important energy terms are I, E and U. The more the negative value POLARISATION :
of Q, the greater will be the stability of ionic compound. Hence formation When cation and anion come closer to each other, the electron
of ionic compound is favoured by cloud of anion is attracted towards the cation, some partial sharing
(i) Low ionisation energy (I) of the metal of electrons take place, the anion is distorted and the effect is
(ii) High electron affinity (E) of the non-metal. known as polarisation.
(iii) Higher lattice energy (U) of the compound
In general the alkali metals have low values of ionisation
energy and halogens have high values of electron affinity. +
Hence they form the stable ionic compounds.
More the effect of polarisation, more is the sharing of electrons and
FACTORS AFFECTING LATTICE ENERGY (U) : the more is covalent character of ionic bond.
The force of attraction between two oppositely charged ions is PROPERTIES OF IONIC COMPOUNDS :
q 1q 2 The important properties are as follows
given by well known Coulombs law as, F = 2
(4 0 )r i) Crystal structure : The crystalline ionic compounds have
well defined crystal structure or crystal lattice eg in NaCl
JEEMAIN.GURU
downloaded from jeemain.guru
Na +
F Mg + +
O Similarly, other than fluorine, the halogens have high covalencies
2,8 2,8 2,8 2,8 equal to 3, 5 and 7. Phosphorous shows covalencies equal to 3
and 5.
Similarly K2S and CaCl2 are isomorphous
K+ S2- K+ Cl- Ca++ Cl- The elements having no d-orbitals do not exhibit variable
2,8,8 2,8,8 2,8,8 2,8,8 2,8,8 2,8,8 covalency
VARIABLE ELECTROVALENCY : EXAMPLES OF COVALENT COMPOUNDS :
It is due to unstable atomic core and inert pair effect. When valence (i) Chlorine (Cl2)
electrons from a metal atom are removed it leaves behind the
atomic core or atomic kernel. The latter with 2 or 8 electrons are
Cl + Cl Cl Cl
stable. In case of transition elements the atomic cores are not very
stable. They may lose one or more electrons thus exhibiting 8e
–
8e
–
variable electrovalency eg. iron and copper etc. (ii) Carbon dioxide (CO2)
Fe (2, 8, 14, 2) 1s2, 2s2p6, 3s2p6 d6, 4s2
++
Fe (2, 8, 14) 1s2, 2s2p6, 3s2p6 d6
+++
Fe (2, 8, 13) 1s2, 2s2p6, 3s2p6 d5 O C O O = C =O
The energy difference between 4s and 3d subshell is not very – –
large. 8e 8e 8e
(iii) Nitrogen (N2)
INERT PAIR EFFECT :
The reluctance of s electron pair of some heavy elements
(p - block elements present at the bottom of group) to take part in N N N N
bonding is known as inert pair effect. Thus Tl (6s2, 6p1) show +1
– –
electrovalence. Similarly Sn(5s2p2) and Pb (6s2p2) show + 2 8e 8e
oxidation state commonly. In such elements the lower oxidation
state is more stable than higher oxidation state.
JEEMAIN.GURU
downloaded from jeemain.guru
78 Chemistry
NATURE OF COVALENT BOND :
+ + Addition
The nature of covalent bond is explained by (a) + 1s bonding
+
(i) Heitler - london theory Valence bond theory 1s + 1s
(ii) Pauling - slater theory
(iii) Hund - mulliken theory } Molecular orbital theory + • Subtraction
(antibonding)
–
+ + – 1s
VALENCE BOND THEORY :
1s – 1s
A covalent bond is formed by the overlapping between two half
filled atomic orbitals having electrons with opposite spin. (b) p x p x or p x p x and p y p y or p y p y overlap to form
JEEMAIN.GURU
downloaded from jeemain.guru
(Nb - Na ) 10 - 4 6
Bond order = = = = 3 \N º N
2 2 2
p (2Px) p (2Py)
(d) Oxygen molecule (O2) - Total number of electrons = 16
2s and electronic configuration is
2s
*(2s) 1s2 < 1s 2 < 2s 2 < 2s 2 < 2p2z
(2s) 2 * 1 * 1
< 2p 2x = 2py < 2px = 2py
N b - N a 10 - 6 4
Bond order = = = =2
1s 1s 2 2 2
*(1s) As shown by electronic configuration the O2 molecule
contains two unpaired electrons, hence it is paramagnetic
in nature
s1s < s*1s < s2s < s* 2s < s2p z < [p2p x = p2p y ] N b - Na 10 - 5 5 1
Bond order = = =2
2 2 2 2
< [p* 2p x = p* 2p y ] < s* 2p z It is paramagnetic
JEEMAIN.GURU
downloaded from jeemain.guru
80 Chemistry
(h) Carbon monoxide (CO) - Total number of electrons = (6 + 8)
(f) O2– (Super oxide ion) Total number of electrons (16 + 1) = 17 .
= 14
Electronic configuration
The electronic configuration is
1s2 < 1s 2 < 2s 2 < 2s 2 < 2p2z
1s2 < 1s2 < 2s2 < 2s2 < 2p2z < 2p2x = 2p2y
< 2p2x = 2p2y < 2p2x 2p1y
Bond order Nb Na 10 4 6
Bond order = = = = 3
2 2 2
(Nb Na ) 10 7 3 1
= 1 It is paramagnetic
=
2
=
2
=
2 2 It is diamagnetic
(i) Nitric Oxide (NO) - Total number of electrons = (7 + 8) = 15
(g) Peroxide ion O 22 - Total number of electrons
1s2 < 1s2 < 2s2 < 2s2 < 2p2z <
(16 + 2) = 18 . The electronic configuration is
1s2 < 1s 2 < 2s 2 < 2s 2 < 2p2z < 2p 2x 2p2x = 2p2y < 2p1x
= 2p 2y < 2p 2x = 2p2y Nb Na 10 5 5 1
Bond order = = = = 2
2 2 2 2
Nb Na 10 8 2
Bond order = = = 1
2 2 2 It is paramagnetic.
It is diamagnetic
( * 2p x )1 ( * 2p y )1
( * 2 p x ) 2 ( * 2 p y )1
CO 14 Same as in N2 3 Diamagnetic
NO 15 Same as in O2+ 2.5 Paramagnetic
NO+ 14 Same as in N2 3 Diamagnetic
JEEMAIN.GURU
downloaded from jeemain.guru
4
, ClO 4 , NH , BF , PO
+
4 4
3
JEEMAIN.GURU
downloaded from jeemain.guru
82 Chemistry
Geometry of molecules/ions having bond pair as well as lone pair(s) of electrons
Type of Bond No. of Hybridi- Bond Expected Actual Examples
molecule pairs lone pairs sation angle geometry geometry
of electrons
AX 3 2 1 sp 2 120º Trigonal V-shape, SO2, SnCl2, NO 2
ClO 2
METHOD FOR FINDING THE TYPE OF VSEPR THEORY VALENCE SHELL ELECTRON PAIR
HYBRIDISATION : REPULSION THEORY :
Apply the following formula to find the hybridisation of central The following types of repulsions between different pair of
atom. electrons change the regular geometry of the molecule.
Lone pair - lone pair repulsion > Lone pair - bond pair repulsion >
Number of valence electrons of central atom Bond pair - bond pair repulsion or lp - lp > lp - bp > bp - bp eg:
1 ÷
(i) Shape of H2O molecule - The hybridisation of oxygen is sp3
+ number of monovalent atoms attached to it ÷ = z
2 ÷ and angle should be 109º 28’. But actually the HOH angle is
+ negative charge if any – positive charge if any
104.5º. The VSEPR theory explains this fact
Value of z 2 3 4 5 6 7
O V-shape
Hybridisation sp sp 2 sp 3 sp3 d sp3d 2 sp3d 3
H H
Examples : All types of repulsions (lp–lp, lp–bp, bp–bp) are present in
1 H2O.
i) Hybridisation of NH3 = [5 + 3 + 0 - 0] = 4; sp3 (ii) Shape of NH3 molecule - The hybridisation of nitrogen is
2
1 sp3. The H–N–H angle is 107.5º instead of 109º28’. Due to
ii) Hybridisation of H2O = [6 + 2 + 0 - 0] = 4; sp3 lp–bp and bp–bp repulsions the value of angle change
2
1 N
iii) Hybridisation of SO3 = [6 + 0 + 0 - 0] = 3; sp2 H H Pyramidal
2 H
1 (iii) Structure of PCl5 : The phosphorous is in sp3d hybridised
iv) Hybridisation of SO42– = [6 + 0 + 2 - 0] = 4; sp3
2 form. The five hybrid orbitals are not equivalent. The bonds
1 pointing towards the three corners of equilateral triangle are
v) Hybridisation of CO32– = [4 + 0 + 2 - 0] = 3; sp2 known as equatorial bonds making an angle of 120° between
2
them. The remaining two bonds are at right angle to the
1
vi) Hybridisation of PCl 5 = [5 +5 + 0 - 0] = 5; sp3d plane of three make an angle of 90° and are called axial bonds.
2 The axial bonds are slightly longer and weaker then equatorial
1 bonds. Since they suffer more repulsive interaction from the
vii) Hybridisation of SF6 = [6 + 6 + 0 - 0] = 6; sp3d2
2 later. Consequently PCl5 is very reactive molecule.
Note : Species having same hybridisation are isostructral in nature.
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
84 Chemistry
(c) Alcohols - The marked difference between the melting (c) Ethyl aceto acetate - It exists in two forms
and boiling points of alcohols and corresponding O
mercaptans is also due to association. ||
CH 3OH C2H 5OH C3H 7OHC4H 9OH CH 3 C CH 2 . COOC 2 H 5
Keto form
Boiling point 64.4ºC 78ºC 97ºC 117ºC
CH3SH C2H5SH C3H7SH C4H9SH OH
|
Boiling point 5.8ºC 37ºC 67ºC 97ºC
CH3 C = CH.COOC2 H 5
R R R R Enol form
– + – + – + – + Enolic form is more volatile due to chelation
O –H O–H O–H O–H
(d) Amides - Amides associate and have higher melting and O H
+
O
boiling points | ||
CH 3 C = CH C OC 2 H 5
R H R H R
| + | | + | | (d) Maleic acid is stronger acid than fumaric acid
H2N C = O H N C= O H N C= O
O
(e) Amines - Primary and secondary amines are associated || – +
and have higher boiling points than isomeric tertiary H C C O H
H C COOH || |
amines. ||
H C COOH H C C O
(f) Fatty acids - In organic solvents, fatty acids form ||
a dimer O
Maleic acid Chelation in maleate ion
– + – (e) Acid character of nitrophenols. It follows the following
O H O
order
R C – C R p - nitrophenol > o - nitrophenol > m - nitrophenol
+ –
O H O Acid character of o - nitrophenol is suppressed by
chelation
It is confirmed by electron diffraction method.
(ii) Applications of Intramolecular H - bonding. O +
H
When the H - bonding takes place within a single molecule –
this is known as intramolecular H - bonding. It also effects O
N
the physical and chemical properties of compound.
(a) Volatile character of nitrophenols - o-nitrophenol is O
more volatile (b.pt 214ºC) as compared to meta (b.pt
(f) Other compounds showing intramolecular
290ºC) and para (b.pt 279ºC). It is due to chelation H - bonding
– O O +
O + + H
H H
O –
O – Cl
– C
N
H
O
o-Chlorophenol o-hydroxy benzaldehyde
In meta and para isomer chelation is not possible due to O +
the formation of desired size of ring. They therefore H
O –
associate to some extent and have higher B.P C
(b) Salicylic acid is stronger acid than o - methoxy benzoic
acid OH
o-hydroxy benzoic acid
O O
METALLIC BOND :
C C
O – O It has been found that metals have generally low ionisation
H
+ CH3 energies indicating that valence electrons are weakly bound to
O O the atomic kernel (or core).
H-bonding in salicylate ion No-H-bonding in
Metals contain few valence electrons and valence orbitals which
are empty. Thus valence electrons are completely delocalised and
o-methoxy benzoate ion
are frequently exchanged between atoms. The atoms thus acquire
JEEMAIN.GURU
downloaded from jeemain.guru
H Cl H Cl Cl H Cl H
2. Thermal conductivity - On heating one part of metal, the
K.E. of electrons is increased and they conduct heat to the This type of interaction is called dipole - dipole interaction. The
other parts of the metal. force of dipole - dipole attraction is inversely proportional to fourth
3. Metallic lustre- The mobile elctrons are promoted to excited 1
states by absorption of light and on coming back from the power of their separation of distance r. F = . The dipole dipole
excited state light of all wavelengths in the visible region is r4
emitted. The surface, therefore emits metallic lustre. attractions in gaseous molecules are particularly small since the
4 Malleability - Metals can be made thin sheets gas molecules are in continuous motion. This attraction increases
5. Ductility - Metals can be drawn into wires since metal kernels the m.pt. and b.pt. of substances and makes their liquification
can easily be shifted. easy.
6. Electrical conductivity decreases with temperature - It is Dipole-induced dipole attraction
due to random motion of mobile electrons which increases The attractive forces operate between polar molecules having
with increase of temperature. permanent dipole and non-polar molecules. The polarity in the
van der Waal's Forces : non-polar molecules is induced by the polar molecule
Attractive forces between uncharged molecules are known as
van der Waals forces. These forces may be divided into three + – + –
groups A B A–A
(i) Dispersion or London forces. These are due to transient
polarisation. Polar molecules Non-polar molecules
–
+
+
–
JEEMAIN.GURU
downloaded from jeemain.guru
86 Chemistry
For e.g. in the figure shown, the resultant dipole moment, H Cl H Cl
= +
C C
1 2
C C
H Cl Cl H
O
Cis ( 0 ) trans ( = 0 )
O
1
(5) Dipole moment is greatest for ortho isomer, zero for para
O 2
isomer and less than that of ortho for meta isomer.
While expressing dipole moments, generally charge is given in o > m > p. e.g.
electrostatic units (esu) and distance in angstrom units (1Aº = Cl
10–10 m). Thus dipole moment of an electron separated from unit Cl Cl
positive charge by a distance 1Aº would be (4.80 × 10–10 esu) × Cl
(10-8 cm) = 4.8 × 10–18 esu cm = 4.8 Debye.
Some compounds and their dipole moments are
Substance Moment Substance Moment Cl
Cl
(Debye) (Debye) ortho meta para
CO2 0.00 = 2.53 Debye = 1.48 Debye = 0
HBr 0.78 (6) Ionic character can be determined by using dipole moment
For e.g. experimental dipole moment for HCl is 1.03 and
CH3Cl 1.85 CH2F2 1.96
= r e
NH3 1.48 O3 0.52 as r = 1.26 and, e = 4.8 × 10-10 esu,
H2O 1.85 CO 1.11 = 6.05 Debye.
CH3I 1.35 CH3OH 1.68
1.03 1
Thus the ionic character 100%
C6H5NO2 4.08 C2H5OH 1.65 6.05 6
CH4 0.00 N2O 0.17 Thus we can say % ionic character
HF 1.91 H2S 0.92 experimental dipole moment
= 100
SO2 1.61 H2O2 1.84 theoretical dipole moment
NF3 0.24 PH3 0.59 (7) Hybridisation can be determined by dipole moment for eg.
C6H5OH 1.70 HCN 2.93 (i) If a molecule AB2 has =0, the orbitals used by
A (z < 21) must be sp hybridised e.g. BeF2
HCl 1.03 CCl4 0.0
(ii) If a molecule AB3 has =0, the orbitals used by
HI 0.38 CS2 0.0
A (z < 21) must be sp2 hybridised e.g. BF3
H2 0.95 PCl5 0.0
(iii) If a molecule AB4 has =0, the orbitals used by
Applications of dipole moment A (z < 21) must be sp3 hybridised e.g. CCl4
(1) Dipole moment is helpful in predicting the geometry of the
molecule. BOND LENGTH :
(2) Dipole moment helps in determining the polarity. It is the distance between the nuclei of two atoms between which
the bond is formed. Other names for bond length are interatomic
(3) Dipole moment can distinguish between symmetrical and
non symmetrical molecules. eg. CO2 has 0 dipole moment as distance or bond distance. It is usually expressed in angstrom
it is symmetrical whereas H2O has a dipole moment of 1.85D. unit (1Å=10-10m). Pauling’s rule states that for covalently bonded
atoms, bond length is sum of covalent radii. Thus for a covalent
O compound AB, the bond length is rA + rB. where rA and rB are
O C O 105º covalent radii of A and B
= 0 Bond length depends on:-
H
H
µ = 1 .8 5
(4) Cis and trans isomers can be distinguished by dipole i) Bond order - Bond length decreases with bond order. For
moments, usually cis isomers have higher dipole moment e.g. C - C length in CH3 - CH3 is 1.54 Å, C = C length in
and hence higher polarity e.g. CH2 = CH2 is 1.34 Å and C C length in CH CH is 1.20 Å.
Larger the s character, smaller is bond length.
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
88 Chemistry
2) Hybridisation - sp3 hybridisation at central atom implies a (2) Expansion of octet : Consider the following molecules
bond angle of 109º 28 each e.g. CH4, CH3CH3 etc. sp2 .. ..
hybridisation leads to 120º bond angle as in BF3 . sp .. Cl .. F ..
..
..
..
..
hybridisation makes angle 180º e.g. BeCl2. Cl
.. F F
..
.. ..
..
..
..
.. P Cl .. .... .. .. S ..
..
3) Lone pair repulsions - Presence of lone pair at central atom Cl
..
.. ..F– Cl – F.. F
.. F
..
..
..
..
..
..
results in repulsion of shared pair of electrons. Thus bonds
Cl
.. F
..
..
..
..
..F
..
at central atom are displaced inside making the value of bond
..
..
angle smaller e.g. bond angle in ammonia is 107º even though (10 electrons around P) (10 electrons around Cl) (12 electrons around S)
hybridisation at nitrogen is sp3. It is due to presence of lone
Explanation for the failure of Octet rule : The concepts given
pair of electrons at nitrogen atom which causes more
repulsion between N and H and hence decreasing the bond below explain the failure of the octet rule :
angle. Bond angle can be measured by X-ray techniques or (a) Sidwick's rule of maximum covalency : The maximum
by I.R. spectroscopy. covalency of an element depends on the period to which
Baeyer’s strain theory states that any shift in normal bond it belongs and octet can be exceeded for n = 1 it is 2, for n
angle causes strain over the molecule making it less stable = 2 it is 4, for n = 3 it is 6 and for n > 4 it is 8.
and more reactive. Thus CH4, C2H6 are quite stable while (b) Sugden's view of singlet linkage : According to Sugden
ethylene is less stable (bond angle 120º). the octet rule is never violated. There can be one electron
OCTET RULE : bond known as Singlet linkage, Singlet or half bond is
formed by sharing of one electron between two atoms. It is
During formation of a covalent bond, the atoms attain an intert represented by half arrow ( ). Thus SF6 and PCl5 have
gas electronic configuration (ns2p6 configuration). This is known the structures :
as Octet rule. There are exceptions of octet rule.
.. ..
(1) Incomplete octet : Consider the following molecules .. F .. .. Cl
..
..
..
..
.. .. F F Cl
..
..
.. ..
..
..
..
.. .. ..F– B – F.. .. .. Cl
..
S P
..
..
..
Cl
.. – Be – Cl
.. F F Cl
..
..
..
..
..
F ..
..
..
..
..
..
..
..
..
..
..
.N ..
O
..
(7 electrons around N)
JEEMAIN.GURU
downloaded from jeemain.guru
..
..
.. _
N = N = O :N N—O:
..
:N—N
..
O+ :
..Cl O.. ..Cl O..
I II III
.. ..
..
.. ..
.. ..
P P
5. Which of the following has higher dipole moment
H3C – CH2 – CH = CH2( 1–butene) or .. Cl.. ..Cl..
..
..
H3C – CH2 – C º CH( 1–butyne)? I II
6. Predict the dipole moment of 16. Draw all possible resonance structures for the sulfate ion,
(i) A molecule AX4 with tetrahedral geometry SO42– on the basis of formal charge
(ii) A molecule AX2 with linear geometry 17. State the hybridization and draw the molecular structure of
(iii) A molecule AX3 with distorted tetrahedral geometry. the following
7. Three elements have the following Lewis symbols: (a) PF5 (b) I3– (c) NH3 (d) XeO3 (e) CH4
A B C 18. Give reasons for following :
(a) Assign groups of the periodic table to these elements. (i) What is the decreasing order of lattice energy of
various ions?
(b) Which elements are expected to form ions and what is
the expected charge over these ions? (ii) PbSO4, BaSO4, AgCl, AgBr, AgI are insoluble in water,
(c) Write the formulae and Lewis structures of the covalent why?
compounds formed between (iii) Which is more ionic and why? FeCl 2 or FeCl3?
(i) A and B (iv) What is the decreasing order of strengths of bonds
(ii) A and C between sp3, sp2 and sp hybrid orbitals?
8. Why are lone pair-lone pair repulsions stronger than lone (v) What is the order of dipole moment of ortho, meta and
pair-bond pair? para disubstituted derivatives?
9. Account for the following : Multiple Choice Questions
(i) N2 has a higher bond dissociation energy than NO. 19. Sodium chloride is an ionic compound whereas hydrogen
(ii) N2 and CO both have the same bond order but CO is chloride is mainly covalent because
more reactive than N2. (a) sodium is less reactive
10. Account for the following : (b) hydrogen is non-metal
(i) He2 is not found to exist in nature (c) hydrogen chloride is a gas
(ii) N2+ is not a diamagnetic substance (d) electronegativity difference in the case of hydrogen
and chlorine is less than 2.1.
(iii) The dissociation energy of H+2 is almost the same as
20. Which one of the following molecules will have unequal
that of He2+.
M – F bond lengths ?
11. Which is more covalent and why : BeCl2 or MgCl2 ?
(a) NF3 (b) BF3
12. Why does Pauli’s exclusion principle permit bonding only if
the electrons are of different spins? (c) PF5 (d) SF4
JEEMAIN.GURU
downloaded from jeemain.guru
90 Chemistry
21. Match List I (Molecules) with List II (Bond order) and select 25. Number of bonds and bonds in the following structure
the correct answer using the codes is H H
List I List II H H
I. Li2 A. 3
II N2 B. 1.5 H H
III Be2 C. 1.0 H H
IV O2 D. 0 (a) 6, 19 (b) 4, 20
E. 2 (c) 5, 19 (d) 5, 20
Codes 26. The states of hybridisation of boron and oxygen atoms in
(a) I - B, II - C, III - A, IV - E boric acid (H3BO3) are respectively
(b) I - C, II - A, III - D, IV - E (a) sp3 and sp2 (b) sp2 and sp 3
(c) I - D, II - A, III - E, IV - C 2
(c) sp and sp 2 (d) sp3 and sp3
(d) I - C, II - B, III - E, IV - A 27. Which of the following statement is not correct from the
22. Polarity in a molecule and hence the dipole moment depends view point of molecular orbital theory?
primarily on electronegativity of the constituent atoms and (a) Be2 is not a stable molecule.
shape of a molecule. Which of the following has the highest
dipole moment? (b) He2 is not stable but He 2 is expected to exist.
+
JEEMAIN.GURU
downloaded from jeemain.guru
1. Chemical bond implies 11. Ground state electronic configuration of valence shell
(a) repulsion electrons in nitrogen molecule (N 2) is written as
(b) attraction
( 2s ) 2 ( *2s ) 2 ( 2p ) 4 ( 2p ) 2 . Hence the bond order of
(c) attraction and repulsion balanced at a particular distance
(d) attraction and repulsion nitrogen molecule is
2. The bonding is electrovalent in (a) 2 (b) 3
(a) NaCl (b) Br2 (c) 0 (d) 1
(c) PF5 (d) XeF4 12. The bond order of NO molecule is
3. Bonding in ferric chloride is (a) 1.5 (b) 2.0
(a) covalent (b) ionic (c) 2.5 (d) 3.0
(c) co-ordinate (d) None of the above 13. Which of the following cannot be formed ?
4. Which of the following species has lowest ionization (a) He2+ (b) He+
potential? (c) He (d) He2
(a) O (b) O2
14. N 2 and O 2 are converted into monoanions, N 2– and O 2
(c) O +
(d) O–
2 2
respectively. Which of the following statements is wrong ?
5. Polarization power of a cation increases when
(a) charge on the cation increases (a) In N – , N – N bond weakens
2
(d) has no relation to its size or charge (c) In O – , O - O bond order decreases
2
6. The correct order of decreasing polarisability of following
ions is (d) N – becomes paramagnetic
2
–
(a) Cl , Br , I , F – – – (b) – – – –
F , I , Br , Cl
15. N2 and O2 are converted into monocations, N +
2
and
– –
(c) F , CI , Br , l – – – –
(d) I , Br , Cl , F – –
O respectively. Which of the following statements is
+
overlapping
(d) The bond formed may or may not be polar (c) In O , paramagnetism decreases
+
(c) BeCl2 (d) BCl3 16. Which of the following molecule is paramagnetic?
9. Consider the following statements: (a) CO2 (b) SO2
(i) A sigma ( ) bond is formed when two s - orbitals overlap (c) NO (d) H2O
(ii) A pi ( ) bond is formed when two 17. In PO 34– , the formal charge on each oxygen atom and the
p- orbitals axially overlap
P - O bond order respectively are
(iii) A -bond is weaker than -bond.
Which of the above statements is/are correct ? (a) –0.75, 0.6 (b) –0.75, 1.0
(a) i and ii (b) ii and iii (c) –0.75, 1.25 (d) –3, 1.25
(c) i alone (d) ii alone 18. Which of the following ion has not bond order of 2.5 ?
10. Number of bonds in naphthalene are (a) O – (b) O +
2 2
(a) 6 (b) 3
(c) 4 (d) 5 (c) N +
2
(d) N– 2
JEEMAIN.GURU
downloaded from jeemain.guru
92 Chemistry
19. Oxygen molecule is 32. The values of electronegativity of atoms A and B are 1.20
(a) diamagnetic with no unpaired electrons and 4.0 respectively. The percentage of ionic character of
(b) diamagnetic with two unpaired electrons A - B bond is
(c) paramagnetic with two unpaired electrons (a) 50% (b) 72.24%
(d) paramagnetic with no unpaired electrons (c) 55.3% (d) 43%
20. The number of electrons that are paired in oxygen molecule 33. The electronegativities of F, Cl, Br and I are 4.0, 3.0, 2.8, 2.5
is
respectively. The hydrogen halide with a high percentage of
(a) 16 (b) 12 ionic character is
(c) 7 (d) 8
(a) HF (b) HCl
21. Which of the following pairs have identical bond
order ? (c) HBr (d) HI
34. Covalent compounds have low melting point because
(a) N , O 2 +
(b) N ,O– 1
2 2 2 2
(a) covalent molecules have definite shape
(c) N – , O2 2
(d) O , N 2 +
2
(b) covalent bond is weaker than ionic bond
22. Which one of the following should be most stable? (c) covalent bond is less exothermic
(a) H +
(b) H+ (d) covalent molecules are held by weak van der Waal’s
2
forces of attraction
(c) H (d) H– 35. The number of sigma ( ) bonds in 1-butene is
23. The number of antibonding electron pairs in O – molecular
2
2
(a) 8 (b) 10
ion on the basis of molecular orbital theory are (at. no. O (c) 11 (d) 12
= 8) 36. The structure of PF5 molecule is
(a) 2 (b) 3 (a) tetrahedral
(c) 4 (d) 5 (b) square planar
24. Which of the following is not paramagnetic ?
(c) trigonal bipyramidal
(a) N +
2
(b) CO (d) pentagonal bipyramidal
(c) O – (d) NO 37. Which of the following has sp 2-hybridization?
2
(a) C2H6 (b) C2H4
25. Which of the following molecular species has unpaired
electron (s) ? (c) BeCl2 (d) C2H2
(a) N2 (b) F2 38. The structure and hybridization of Si(CH3)4 is
(a) bent, sp (b) trigonal, sp2
(c) O – (d) O –2
2 2
3
(c) octahedral, sp d (d) tetrahedral, sp3
26. Which of the following has least covalent P–H bond?
(a) PH3 (b) P2H6 39. Which of the following molecule is not linear in shape
(c) P2H5 (d) PH6+ (a) HgCl2 (b) Hg2Cl2
27. Which contains both polar and non - polar bonds? (c) CO2 (d) SnCl2
(a) NH4Cl (b) HCN 40. Among the following compounds the one that is polar and
(c) H2O2 (d) CH4 has the central atom with sp2 hybridisation is
28. Which of the following has least polarity in bond? (a) H2CO3 (b) SiF4
(a) H – F (b) H – Cl (c) BF3 (d) HClO2
(c) H – O (d) H – S 41. Which one of the following compounds has sp2 hybridisation?
29. Which of the following substances has the least ionic (a) CO2 (b) SO2
character ?
(c) N2O (d) CO
(a) FeCl2 (b) ZnCl2
(c) CdCl2 (d) MgCl2 42. The AsF5 molecule is trigonal bipyramidal. The hybrid
orbitals used by the As atoms for bonding are :
30. The correct order of increasing ionic character is
(a) BeCl2 < MgCl2 < CaCl2 < BaCl2 2
(a) d x 2 y2 , d z , s, p x , p y (b) d xy , s, p x , p y , p z
(b) BeCl2 < MgCl2 < BaCl2 < CaCl2
(c) BeCl2 < BaCl2 < MgCl2 < CaCl2
(c) s, p x , p y , p z, d 2z (d) d , s, p x , p y
(d) BaCl2 < CaCl2 < MgCl2 < BeCl2 x 2 y2
31. Which of the following contains both covalent and ionic bond? 43. The hybridization of S atom in SO42– is
(a) NH4Cl (b) H2O (a) sp (b) sp 2
(c) CCl4 (d) CaCl2 (c) sp 3 (d) sp 3 d
JEEMAIN.GURU
downloaded from jeemain.guru
44. In piperidine , the hybrid state assumed by N is Electron Pair Repulsion (VSEPR) theory will be
N (a) planar triangular (b) pyramidal
H (c) tetrahedral (d) square planar
(a) sp (b) sp 2 56. Among the following ions, the p – d overlap could be
(c) sp 3 (d) dsp 2 present in
45. Which of the following will be octahedral ? (a) NO – (b) PO 3 –
3 4
3
3 2
–
46. The hybridization of atomic orbitals of nitrogen in 57. In NO ion, number of bond pairs and lone pairs of electrons
3
(a) 2, 2 (b) 3, 1
(a) sp2, sp3 and sp2 respectively (c) 1, 3 (d) 4, 0
(b) sp, sp2 and sp3 respectively 58. In OF2, number of bond pairs and lone pairs of electrons are
(c) sp2, sp and sp3 respectively respectively
(d) sp2, sp3 and sp respectivley (a) 2, 6 (b) 2, 8
47. The compound MX4 is tetrahedral. The number of XMX (c) 2, 10 (d) 2, 9
formed in the compound are 59. The compound containing co-ordinate bond is
(a) three (b) four (a) H2SO4 (b) O3
(c) five (d) six (c) SO3 (d) All of these
48. The shape of gaseous SnCl2 is 60. Sulphuric acid provides a simple example of
(a) tetrahedral (b) linear (a) co-ordinate bonds
(c) angular (d) t-shape (b) non-covalent compound
49. Which of the following molecule is linear ? (c) covalent ion
(d) non - covalent ion
(a) SO2 (b) NO +
JEEMAIN.GURU
downloaded from jeemain.guru
94 Chemistry
67. Which of the following molecules will form a linear polymeric 81. The sulphate of a metal has the formula M2(SO4)3. The
structure due to hydrogen bonding ? formula of its phosphate will be
(a) HCl (b) HF (a) M(HPO4)2 (b) M3(PO4)2
(c) H2O (d) NH3 (c) M2(PO4)3 (d) MPO4
68. Among H2O, H2S, H2Se and H2Te, the one with the highest 82. KF combines with HF to form KHF2. The compound contains
boiling point is the species
(a) H2O because of hydrogen bonding (a) K+, F– and H+ (b) K+, F– and HF
(b) H2Te because of higher molecular weight +
(c) K , and [HF2] – (b) [KHF]+and F2
(c) H2S because of hydrogen bonding
83. Which of the following molecular orbitals has two nodal
(d) H2Se because of lower molecular weight
planes ?
69. Which of the following is soluble in water ?
(a) 2s (b) 2p y
(a) CS2 (b) C2H5OH
(c) *2py (d) *2px
(c) CCl4 (d) CHCl3
70. A metallic bond is 84. The electronic configuration of metal M is 1s2 2s2 2p6 3s1.
(a) ionic (b) polar covalent The formula of its oxide will be
(c) non-polar covalent (d) electrostatic in nature (a) MO (b) M2O
71. Type of forces between molecules of C6H6 are (c) SO3 (d) All of these
(a) dipole-dipole interaction (b) dispersive forces 85. The number of possible resonance structure for CO 2 –
is
(c) H-bonding (d) van der Waals’ forces
3
72. Which of the following has the highest dipole moment? (a) 2 (b) 3
(a) AsH3 (b) SbH3 (c) 6 (d) 9
(c) PH3 (d) NH3 86. Match List I (Molecules) with List II (Bond order) and select
73. The molecule having non-zero dipole moment is the correct answer using the codes
(a) H2O2 (b) CH4 List I List II
I. Li2 A. 3
(c) C2H6 BF –
(d) 4
II N2 B. 1.5
74. Which of the following hydrocarbons has the lowest dipole III Be2 C. 1.0
moment ? IV O2 D. 0
H3C CH 3 E. 2
(a) C (b) CH C CCH Codes
3 3
H H (a) I - B, II - C, III - A, IV - E
(b) I - C, II - A, III - D, IV - E
(c) CH CH C CH (d) CH 2 = CH – C CH
3 2
(c) I - D, II - A, III - E, IV - C
75. Which of the following has zero dipole moment?
(d) I - C, II - B, III - E, IV - A
(a) ClF (b) PCl3
87. An ether is more volatile than an alcohol having the same
(c) SiF4 (d) CFCl3
molecular formula. This is due to
76. Dipole moment is shown by
(a) 1, 4-dichlorobenzene (a) dipolar character of ethers
(b) cis 1,2-dichlorobenzene (b) alcohols having resonance structures
(c) trans 1, 3-dichlorobenzene (c) inter-molecular hydrogen bonding in ethers
(d) trans 2, 3-dichloro -2- butene (d) inter-molecular hydrogen bonding in alcohols
77. Which one of the following molecules will have unequal 88. The reason for double helical structure of DNA is operation
M – F bond lengths ? of
(a) NF3 (b) BF3 (a) van der Waal’s forces (b) dipole-dipole interaction
(c) PF5 (d) SF4 (c) hydrogen bonding (d) electrostatic attraction
78. The bond length in LiF will be 89. Among the following, the molecule with the highest dipole
(a) less than that of NaF (b) equal to that of KF moment is
(c) more than that of KF (d) equal to that of NaF (a) CH3Cl (b) CH2Cl2
79. Which has the least bond angle ? (c) CHCl3 (d) CCl4
(a) NH3 (b) BeF2 90. Which of the following represents the given mode of
(c) H2O (d) CH4 hybridisation sp2 –sp2 – sp - sp from left to right ?
80. The correct sequence of decrease in the bond angles of the
following hydrides is (a) H C = CH C
2
N (b) HC C–C CH
(a) NH3 > PH3 > AsH3 > SbH3 CH2
(b) NH3 > AsH3 > PH3 > SbH3 (c) H C = C = C = CH (d) H C
2 2
2
(c) SbH3 > AsH3 > PH3 > NH3
(d) PH3 > NH3 > AsH3 > SbH3
JEEMAIN.GURU
downloaded from jeemain.guru
1. In which of the following pairs, the two species are iso- 9. In which of the following molecules the central atom does
structure? [CBSE-PMT 2007] not have sp3 hybridization? [CBSE-PMT 2010]
(a) SO32– and NO3– (b) BF3 an NF3 (a) NH +4 (b) CH4 (c) SF4 (d) BF4–
(c) BrO3– and XeO3 (d) SF4 and XeF4
2. The correct order of increasing bond angles in the following 10. Which one of the following species does not exist under
triatomic species is : [CBSE-PMT 2008] normal conditions? [CBSE-PMT 2010]
(a) NO 2 < NO +2 < NO 2 (b) NO2 < NO2 < NO2 +
(a) Be 2 +
(b) Be2 (c) B2 (d) Li 2
(c) NO2 < NO 2 < NO2 (d) NO2 < NO2 < NO2 11. Considering the state of hybridization of carbon atoms, find
3. Four diatomic species are listed below in different sequences. out the molecule among the following which is linear ?
Which of these presents the correct order of their increasing (a) CH3– CH = CH–CH3 [CBSE-PMT 2011]
bond order ? [CBSE-PMT 2008] (b) CH3 – C C – CH3
(a) O2 < NO < C22 < He2 (b) NO < C22
+
< O2 < He 2+
(c) CH2 = CH – CH2 – C CH
(c) C 22 < He 2 < NO < O 2 (d) He2 < O2 < NO < C 22 (d) CH3 – CH2 – CH2 – CH3
4. What is the dominant intermolecular force or bond that must 12. Which of the two ions from the list given below have the
be overcome in converting liquid CH3OH to a gas? geometry that is explained by the same hybridization of
(a) Dipole-dipole interactions [CBSE-PMT 2009] orbitals, NO2–, NO3–, NH2–, NH4+, SCN– ?
(b) Covalent bonds [CBSE-PMT 2011]
(c) London dispersion forces (a) NO2– and NO3– (b) NH2– and NO3–
(d) Hydrogen bonding (c) SCN– and NH2– (d) NO2– and NH2–
5. In which of the following molecules / ions BF3, NO 2 , NH 2 13. Which of the following has the minimum bond length ?
and H2O , the central atom is sp2 hybridized ? [CBSE-PMT 2011]
[CBSE-PMT 2009] (a) O2 + (b) O2 –
(a) NH 2 and H2O (b) NO 2 and H2O (c) O2 2– (d) O2
(c) BF3 and NO2 (d) NO2 and NH 2 14. The pairs of species of oxygen and their magnetic
6. According to MO theory which of the following lists ranks behaviours are noted below. Which of the following presents
the nitrogen species in terms of increasing bond order? the correct description ? [CBSE-PMT 2011 M]
[CBSE-PMT 2009] (a) O -2 , O 22 - – Both diamagnetic
(a) N 2–
2 < N 2– < N2 (b) N 2 < N 22– < N 2– (b) O +2 ,O22 - – Both paramagnetic
(c) N 2– < N 2–
2 < N2 (d) N 2– < N2 < N 2–
2 (c) O+2 ,O2 – Both paramagnetic
7. In which one of the following species the central atom has (d) None of these
the type of hybridization which is not the same as that
15. Which one of the following pairs is isostructural (i.e., having
present in the other three? [CBSE-PMT 2010]
the same shape and hybridization) ? [CBSE-PMT 2012]
(a) SF4 (b) I3– (c) SbCl52– (d) PCl5
8. Some of the properties of the two species, NO3 and H3O+ (a) BCl3 and BrCl3 (b) NH3 and NO3
are described below. Which one of them is correct?
[CBSE-PMT 2010] (c) [ NF3 and BF3 ] (d) BF4 and NH 4+
(a) Similar in hybridization for the central atom with different 16. Bond order of 1.5 is shown by : [CBSE-PMT 2012]
structures.
(a) O +2 (b) O 2 (c) O 22 (d) O2
(b) Dissimilar in hybridization for the central atom with
different structures. 17. Which of the following species contains three bond pairs
(c) Isostructural with same hybridization for the central and one lone pair around the central atom ?
atom. [CBSE-PMT 2012]
(d) Isostructural with different hybridization for the central
atom. (a) H2O (b) BF3 (c) NH -2 (d) PCl3
JEEMAIN.GURU
downloaded from jeemain.guru
96 Chemistry
18. The pair of species with the same bond order is : 29. The states of hybridization of boron and oxygen atoms in
[CBSE-PMT 2012] boric acid (H3BO3) are respectively [AIEEE 2004]
(a) O 2– (b) O +2 , NO+ (a) sp3 and sp2 (b) sp2 and sp 3
2 , B2
(c) sp2 and sp2 (d) sp3 and sp3
(c) NO, CO (d) N2, O2
30. Which one of the following has the regular tetrahedral
19. Which of the following is electron - deficient ?
structure ? [AIEEE 2004]
(a) (SiH3)2 (b) (BH3)2 [NEET 2013]
(c) PH3 (d) (CH3)2 (a) BF4 (b) SF4
20. Which one of the following molecules contains no bond?
(a) H2O (b) SO2 [NEET 2013] (c) XeF4 (d) [ Ni(CN) 4 ]2
(c) NO2 (d) CO2 (Atomic nos. : B = 5, S = 16, Ni =28, Xe = 54)
21. Which of the following is paramagnetic ? [NEET 2013] 31. The maximum number of 90º angles between bond pair-bond
pair of electrons is observed in [AIEEE 2004]
(a) O2 (b) CN–
(a) dsp2 hybridization (b) sp3d hybridization
(c) NO+ (d) CO (c) dsp3 hybridization (d) sp3d2 hybridization
22. Dipole-induced dipole interactions are present in which of 32. Which of the following species is diamagnetic in
the following pairs : [NEET 2013] nature? [AIEEE 2005]
(a) Cl2 and CCl4
(a) H 2 (b) H 2+
(d) H2O and alcohol 33. Lattice energy of an ionic compound depends upon
23. In which of the following species the interatomic bond angle (a) Charge on the ion and size of the ion [AIEEE 2005]
is 109° 28’? [AIEEE 2002] (b) Packing of ions only
(a) NH3, (BF4)1– (b) (NH4)+, BF3 (c) Size of the ion only
(c) NH3, BF4 (d) (NH2)1–, BF3. (d) Charge on the ion only
24. Which one of the following pairs of molecules will have 34. The molecular shapes of SF4 , CF4 and XeF4 are
permanent dipole moments for both members ? [AIEEE 2005]
[AIEEE 2003] (a) different with 1, 0 and 2 lone pairs of electrons on the
(a) NO2 and CO2 (b) NO2 and O3 central atom, respectively
(c) SiF4 and CO2 (d) SiF4 and NO2 (b) different with 0, 1 and 2 lone pairs of electrons on the
25. Which one of the following compounds has the smallest central atom, respectively
bond angle in its molecule ? [AIEEE 2003] (c) the same with 1, 1 and 1 lone pair of electrons on the
(a) OH2 (b) SH2 central atoms, respectively
(c) NH3 (d) SO2 (d) the same with 2, 0 and 1 lone pairs of electrons on the
central atom, respectively
26. The pair of species having identical shapes for molecules of
35. Which of the following molecules/ions does not contain
both species is [AIEEE 2003]
unpaired electrons? [AIEEE 2006]
(a) XeF2, CO2 (b) BF3, PCl3
(c) O 22
+
(c) PF5, IF5 (d) CF4, SF4 (a) N2 (b) O2 (d) B2
27. The correct order of bond angles (smallest first) in H2S, NH3, 36. Among the following mixtures, dipole-dipole as the major
BF3 and SiH4 is [AIEEE 2004] interaction, is present in [AIEEE 2006]
(a) H2S < NH3 < SiH4 < BF3 (a) KCl and water
(b) NH3 < H2S < SiH4 < BF3 (b) benzene and carbon tetrachloride
(c) H2S < SiH4 < NH3 < BF3 (c) benzene and ethanol
(d) H2S < NH3 < BF3 < SiH4 (d) acetonitrile and acetone
28. The bond order in NO is 2.5 while that in NO+ is 3. Which of 37. In which of the following molecules/ions are all the bonds
the following statements is true for these two species ? not equal? [AIEEE 2006]
[AIEEE 2004] (a) XeF4 (b) BF4 –
(a) Bond length in NO+ is equal to that in NO
(c) SF4 (d) SiF4
(b) Bond length in NO is greater than in NO+
38. Which of the following species exhibits the diamagnetic
(c) Bond length in NO+ is greater than in NO behaviour ? [AIEEE 2007]
(d) Bond length is unpredictable (a) NO (b) O2 2– (c) O2+ (d) O2
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
98 Chemistry
1. Sodium chloride is an ionic compound whereas hydrogen 10. Which one of the following arrangements of molecules is
chloride is mainly covalent because correct on the basis of their dipole moments?
(a) Sodium is less reactive (a) BF3 > NF3 > NH3 (b) NF3 > BF3 > NH3
(b) Hydrogen is non-metal
(c) NH3 > BF3 > NF3 (d) NH3 > NF3 > BF3
(c) Hydrogen chloride is a gas
11. Which of the following is the correct electron dot structure
(d) Electronegativity difference in the case of Hydrogen and
of N2O molecule?
chlorine is less than 2.1. .. + ..
2. For two ionic solids, CaO and Kl. Identify the wrong (a) : N = N = O : (b) : N = N = O
.. :
statement among the following .. .. .. ..
(a) Lattice energy of CaO is much larger than that of Kl (c) N = N = O : (d) : N = N = O ..
:
..
(b) KI is soluble in benzene 12. Consider the following statements. The common features of
(c) CaO has higher melting point the molecules BF3, CO & NO are that
(d) KI has lower melting point I. all are Lewis acids
3. The correct order of increasing C - O bond length of CO, II. all are gaseous in nature
CO 2 –
, CO2 is III. all contain unpaired electrons
IV. all do not conform to the octet rule
3
–
(a) CO 2
3
< CO 2
< CO (b) CO 2
< CO 2
3
< CO Which of the above statements are correct ?
(a) I and II (b) III and IV
(c) CO < CO – < CO (d) CO < CO < CO –
2
3 2 2
2
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
100 Chemistry
33. In which of the following set of molecules the order of (a) 2.86 D (b) 2.25 D
boiling point is incorrect. (c) 1.5 D (d) 0 D
42. The experimental value of the dipole moment of HCl is 1.03
(a) C3H 8 > C 2H6 > CH 4 (b) Xe > Ar > He
D. The length of H – Cl bond is 1.275 Å. The percentage of
(c) HCl > HF > HBr (d) H 2 O > H 2Se > H 2S ionic character on HCl
34. The stability of ionic crystals depends mainly on (a) 7 (b) 17
(a) low heat of sublimation of cation formed (c) 43 (d) 21
(b) high electron affinity of anion formed 43. CaO and NaCl have the same crystal structure and
(c) low I.E. of cation forming species. approximately the same ionic radii. If U is the lattice energy
(d) lattice energy of crystal of NaCl, the approximate lattice energy of CaO is
35. Silicon carbide is a (a) U/2 (b) U
(a) covalent solid (b) ionic solid (c) 4 C (d) 2 U
(c) molecular solid (d) None of the above 44. Which of the following compounds has the highest lattice
36. If x-axis is the molecular axis of a diatomic molecule, then energy?
molecular orbital are formed by overlap of (a) MgO (b) LiCl
(a) s-atomic orbitals (c) NaCl (d) LiF
(b) s and px atomic orbitals 45. A diatomic molecule has a dipole moment of 1.2 D, if the
(c) py and py-orbitals bond distance is 1 Å, what percentage of electronic charge
(d) px and pz-orbitals exists on each atom.
(a) 25 % of e (b) 29 % of e
37. The molecular size of ICl and Br2 is approximately same, (c) 19 % of e (d) 12 % of e
but boiling point of ICl is about 40°C higher than b.pt. of 46. Which of the following statements is/are true
Br2 , because of 1. PH 5 and BiCl5 donot exist
(a) I has larger size than Br 2. p –d bond is present in SO 2
(b) I-Cl bond is stronger than Br-Br bond
(c) I E of lodine < I E of Br 3. I3 has bent geometry
+
(d) ICl is polar while Br2 is non polar 4. SeF4 and CH 4 have same shape
38. An element forms compounds of the formula ACl3 , A 2O 5 (a) 1, 2, 3 (b) 1, 3
and Mg 3A 2 but does not form ACl5 , the A could be (c) 1, 3, 4 (d) 1, 2, 4
47. Trimethylamine is a pyramidal molecule
(a) Al (b) P
(c) B (d) N N
CH 3 and formamide is a planar molecule
39. The magnitude of the lattice energy of a solid increases if H 3C CH 3
(a) charges on both the ions are small
(b) the ions are large O
(c) the ions are small ||
(d) the ions are of equal size C H
, The hybridisation of Nitrogen in both is
40. The correct representation of H-bond in solid HF H N
(a) H – F H–F H–F |
F F F
H
(b) H H H H H 3 2
F F (a) sp 2 , sp 2 (b) sp , sp
H H H H
(c) F F (c) sp 3 , sp 3 (d) sp 2 , sp
F
H H 48. If climbing of water droplets is made to occur on a coated
(d) F F F F microscope slide, the slide would have to be coated in
H which of the following way
Cl
JEEMAIN.GURU
downloaded from jeemain.guru
EXERCISE 1 3 3
O O
1. Bonding molecular orbital. | |
2. Because b.p. –b.p. repulsion is less in H2S than in H2O. 17. (c) O P O O P= O
3. MgO || |
O O
4. III, because like charges reside on adjacent atoms.
5. 1 – butyne has more dipole moment. 3 3
O O
6. (i) Non-polar due to symmetric structure. || |
(ii) Non-polar due to linear molecular structure. O P O O= P O
(iii) Polar due to non-symmetric molecular structure. | |
O O
7. (a) A – group 1, B – group 14, C – group 17
(b) A, C are expected to form ions A+ and C– Bond order
A Number of bonds 5
.. = = = 1.25
(c) (i) A : B : A (ii) A : C : or A+Cl +
Number of Resonating structures 4
..
A Three unit negative charge is being shared by four O atoms.
11. BeCl2 Since Be2+ ion is small in size. Formal charge = –3/4
19. (b) 20. (c) 21. (b)
18. (a) O – has Bond order 1.5 (see text)
22. (c) 23. (c) 24. (a) 2
2
is 3 (calculate by energy level
3. (b) Covalent ( Fajan's rule see text)
diagram)
4. (d) *2px2 *2py1 antibonding molecular orbitals contain
22. (b) H+
three electrons in O – . Their energy being more and
2
23. (c)
2
* 2 2
* 2 2
*
5. (a) Polarizing power = charge/ radius. Thus µ charge.
2
* 2
6. (d) The larger the size of anion the more is its polarizability 4 pairs
7. (b) Covalent bonds are directional in nature 24. (b) CO is diamagnetic while others are paramagnetic
8. (d) BCl3 is lewis acid and electron deficient. The octet around
25. (c) O – (see text)
B is not complete 2
9. (c) Statement 1 is correct (see text) 26. (d) In PH6 , P – H bond will have ionic character due to
+
10. (d) number of bonds is 5 electron attracting tendency of P carrying +ve charge
and least covalent.
Nb8 2 Na 27. (c)
11. (b) Bond order = = 3 =
2 2 28. (d) The electronegativity of S is least among others hence H
12. (c) Bond order in NO is 2.5 (see text) -S bond is least polar in nature.
13. (d) Bond order in He2 is zero (see text) 29. (b) Polarizing power of Zn2+ is more than others, hence ZnCl2
is least ionic in nature.
14. (c) Species N2 O2 N–2
O–2 30. (a) Electropositive character and size increases down the
Bond order 3 2 2.5 1.5 group, the ionic character increases.
The O-O bond is O – decreases 31. (a) NH 4Cl contains both covalent and ionic bonds
2
+
2 + H
15. (d) b *a2 2
b( *2
2
a
1 2
b ) b (N 2 = 13electrons)
b |
it contains one unpaired electron hence paramagnetic H – N– H Cl –
|
16. (c) NO is paramagnetic H
JEEMAIN.GURU
downloaded from jeemain.guru
102 Chemistry
32. (b) Electronegativity difference is 4.0 - 1.20 = 2.8 percentage (–)
ionic character is 72.24% when the electronegativity O
difference is 1.7, the % ionic character is approx 51%. O–N
57. (d) it has 4 bond pairs and none lone pair..
33. (a) Ionic character follows the order HF > HCl > HBr > HI O
34. (d)
35. (c) H3C – CH2 – CH = CH2. It has 11 bonds 58. (b) F – O – F 2 bond pairs and 8 lone pairs
36. (c) Hybridisation in PF5 is = ½ [5 + 5 + 0 –0] = 5 sp3d, hence
..
structure is trigonal bipyramidal. :O:
H .. ..
H
59. (d) All contain coordinate bond H – O
..
– S –O
..
–H ,
37. (b) C = C Hybridisation of C is sp2 ¯
:O
. .:
H H
38. (d) Hybridisation in Si(CH3)4 ( ½ [4 + 4 + 0 – 0] = 4) is sp3 ..
which is tetrahedral. :O:
..
39. (d) Hybridisation in SnCl2 (½ [4 + 2 + 0 - 0] =3) sp3. It has V- O
shape. S
,
. O :O:
..
.O
..
O
..
..
..
40. (a) H2CO3 and BF3 both have triangular planar structure
..
F H–O 60. (a) Coordinate bond
B–F C = O.
F H–O 61. (c) CO 2 – Its structure is
BF3 is symmetrical
\ m = 0 hence non polar, H2CO3 is not symmetrical
hence polar in nature. 62. (b) It is 4 See H - bonding.
41. (b) SO2 has sp2 hybridisation. 63. (d) NH3 forms intermolecular H - bonding.
64. (b) In H - bonding atoms involved are F, O and N.
42. (c) AsF5 is trigonal bipyramidal and sp3d hybridised.
65. (a) H -bonding interactions.
43. (c)
66. (c) It is due to H - bonding.
44. (c) Hybridisation of N = ½ [5 + 3 + 0 – 0] = 4 hence sp 3 67. (d) In HCl No–H–bonding, H – F form zig zag; (cage like by
45. (a) SF6 is octahedral (see text) H2O, only NH3 forms linear polymeric structures)
46. (b) NO +2 = ½ [5 + O + O –1] = 2 sp; NO 2– = ½ [5 + 0 + 1 –0] = 3 68. (a) H2O (see H - bonding)
69. (b) C2H5OH soluble in water due to H-Bonding
sp2; NH + = ½ [5 + 4 + 0 - 1] = 4 sp3 70. (d) Metallic bond is electrostatic in nature.
71. (b) Non polar molecules have dispersive forces.
X 72. (d) The electronegativity difference is maximum between N &
47. (d) M three angle below M and three above M H hence NH3 will have highest magnetic moment.
X X X
H
hence = 6 O
48. (c)
73. (d) H2O2 it is nonplanar O
49. (b) NO2+ has sp hybridisation hence linear. H
50. (c) O = C = C = C = O is sp hybridised
51. (d) In XeF2 Total number of valence electrons of Xe = 8, two The bonds are not in the plane of paper.
electrons shared with 2F atoms, 6 electrons left hence 3
74. (b) H C . C º C . CH symmetrical and linear. Hence D.M.
lone pairs, in XeF4 4 shared with 4 F atoms 4 left hence 2
lone pairs; in XeF6 6 shared with 6 F atoms 2 left hence 1 ( m ) = 0.
lone pair. 75. (c) In SiF4 DM = zero due to symmetrical structure.
52. (b) In CH3 CH2OH underlined C is forming 4 bonds, hence
Cl
sp3 hybridisation. In others it is sp2 hybridised (due to 3 Cl
bonds). 76. (b) Cis1, 2 - dichloro benzene will have some D.M.
53. (b) dsp2 hybridisation involves d x 2 - y2 . F
F
54. (b) Tetrahedral 77. (c) In PF5 the hybridisation is sp3d P–F axial. P – F bonds
55. (b) Hybridisation is sp3 and shape pyramidal
F F
56. (b) Hybridisation in PO – = ½ [5 + 0 + 3 –0] = 4 sp3. In are longer than equatorial bonds.
bonding only d orbital of P, p orbital of O can be 78. (a) It is due to small size of Li compared to size of Na and K.
involved. Since hybrid atomic orbitals do not 79. (c) Bond angles NH3 (107.5º); BeF2 (180º) H2O (104.5º) and
form bond. CH4 (109º28’)
JEEMAIN.GURU
downloaded from jeemain.guru
80. (a) Bond angles NH PH AsH SbH 3. (d) Calculating the bond order of various species.
10 . º 2 1 0 O-2 : KK s 2s 2 , s* 2 s 2 , s2 pz2 ,
81. (d) M +2 (SO ) – Here metal atom is trivalent. Hence formula
p2 px2 = p2 p 2y , p* 2 px2 = p* 2 p1y
for phosphate will be MPO4
82. (c) Since F form H-bond [HF2]– exists. Therefore KHF2 gives 1
K+ + HF2– B.O. = (Nb - N a )
2
8-5
83. (c) It has two nodal planes. It is p*2py = or 1.5
2
NO =
84. (b) Electronic configuration reveals it is monovalent (in fact K K 2s 2 , 2s 2 ,62 p 2z , 2 p x2 = p2 p 2y , p* 2 p1x
Na) hence its oxide will be M2O.
– – Nb - N a 8 - 3
– – B.O. = = or 2.5
O O O 2 2
85. (b) C–O C=O C–O
2- 2 * 2 2
O O O = C2 : KK s2s , s 2s , p2 px = p2 p 2y , s 2 p z2
– –
Nb - N a 8 - 2
4–2 B.O. = = or 3
86. (b) B.O. = ½ [Nb – Na] Li 2 = = 1; N2 = 3; Be = 0, O2=2. 2 2
2
87. (d) In alcohol intermolecular H-bonding is possible whereas He 22+ = s1s 2 s*1s1
in ether it is not possible.
88. (c) Double helical structure of DNA is stabilised by Nb - N a 2 - 1
B. O. = = or 0.5
H - bonding. 2 2
89. (a) Dipole moment follows the order CH3Cl > CH2Cl2 > CHCl3 From these values we conclude that the correct order
> CCl4 of increasing bond order is
90. (a) CH 2 = C H - C º N He22+ < O 2- < NO < C22-
1 2 3 4
4. (d) Due to intermolecular hydrogen bonding in methanol,
3 bonds (sp 2 hybridisation);2 bonds (sp-
it exist as assosiated molecule.
hybridisation)
5. (c) On determining hybridisation from H = 1/2 (V + M – C + A).
C1 = 3 bonds, C2 = 3 bonds,
The hybridisation of BF3, NO2–, NH2– and H2O are
C3 = 2 bonds
sp2, sp2, sp3 and sp3 respectively.
EXERCISE 3 6. (a) Molecular orbital configuration of
1. (c) Both BrO3 and XeO3 have sp3 hybridization but N 2– 2 2 2 2
2 = s1s s *1s s2 s s * 2 s -
due to presence of one lp of electrons they have 2 1
ïp 2 px ï p * 2 px
trigonal pyramidal geometry. s2 p2z
2 1
2. (b) From the structure of three species we can determine ïp 2 p y ïp * 2 p y
the number of lone pair electron(s) on central atom (i.e. 10 – 6
Bond order = =2
N atom) and thus the bond angle. 2
p2 px2 1
. .N. +
N 2– = s1s 2 s *1s 2 s2 s 2s * 2 s 2 ï s2 pz2
ï p * 2 px
.. ....O.. ..O ......
N N 2 0
..O.. .... O ..O ïp2 p y ï p *2 p y
|
||
|
|
||
||
..
O
..
- + 10 5
(NO )2 NO 2 NO 2 Bond order = = 2.5
2
We know that higher the number of lone pair electron(s) 2 px2
on central atom, greater is the lp – lp repulsion. Thus N 2 = s1s 2 s *1s 2 s 2 s 2 s * 2 s 2 , 2 pz2
2 p 2y
smaller is bond angle.
The correct order of bond angle is 10 – 4
Bond order = =3
+
2
NO -2 < NO 2 < NO 2 i.e., option (b) is correct. \ The correct order is = N 2– –
2 < N2 < N2
JEEMAIN.GURU
downloaded from jeemain.guru
104 Chemistry
1 2 px2 = 2 p y2 , 2 px2 = 2 p 2y
NH2– H = [5 + 2 + 1 + 0] = 4 = sp3
2
Nb - Na 10 - 8 2
1 Bond order = = =1
NH4+, H = [5 + 4 + 0 - 1] = 4 = sp 3 2 2 2
2
SCN– = sp 17. (d) PCl3
i.e., NO2– and NO3– have same hybridisation.
P
13. (a) O2 (16) 1s 2 , *1s 2 , 2s 2 , * 2s 2 , 2 p 2z , Cl
Cl
Cl
2 px2 2 p 2y , * 2 p1x * 2 p1y
18. (a) Both O2–
2 and B2 has bond order equal to 1.
B.O. = ½ (Nb – Na) = ½ (10 – 6) = 2
O2 + (15) 1s 2 , *1s 2 , 2s 2 , * 2s 2 , 2 p z2 , B2 (10) = 1s 2 *
1s 2 2s 2 * 2s 2
2 p1x = 2 p y1
2 px2 2 p 2y , * 2 p1x * 2 p0y
Nb - N a
B.O. = ½ (Nb – Na) = ½ (10 – 5) = 2.5 Bond order =
2
O2 (17) 1s 2 , *1s 2 , 2s 2 , * 2s 2 , 2 p z2 , 6-4 2
= =1
=
2 px2 2 p 2y , * 2 px2 * 2 p1y 2 2
B2 is known in the gas phase
B.O. = ½ (Nb – Na) = ½ (10 – 7) = 1.5
O22 - = (s1s )2 (s *1s)2 ( s2 s ) 2 (s * 2 s ) 2 ( s2 p z )
2
O2 2 (18) 1s 2 , *1s 2 , 2 s 2 , * 2 s 2 , 2 p z2 ,
( )( ) =( )
2 2 2
2 px2 2 p 2y , * 2 px2 * 2 p 2y ( 2 px ) =
2
2 py *
2 px *
2 py
JEEMAIN.GURU
downloaded from jeemain.guru
24. (b) Both NO2 and O3 have angular shape and hence will shape-square pyramidal, one lone pair
have net dipole moment.
CF4 – Configuration of excited C-atom :
25. (b) In H2S, due to low electronegativity of sulphur the l.p. -
3
l. p. repulsion is more than bp. - bp. repulsion and hence 2s1 2p
3
the bond angle is 92º. sp
26. (a) Both XeF2 and CO2 have a linear structure. shape-tetrahedral; no lone pair
27. (a) The order of bond angles XeF6 – configuration of excited Xe atom :
BF3 > SiH 4 > NH 3 > H 2S
120º 109º 28¢ 107 º 92.5º 4 2
5s2 5p 5d
3 2
28. (b) The lower the bond order the greater the bond length sp d hybridization
and vice-versa. shape-square planar, 2 lone pairs
29. (b) In H 3BO 3 hybridisation of B is sp2 and O is sp3. 35. (c) The distribution of electrons in MOs is as follows:
JEEMAIN.GURU
downloaded from jeemain.guru
106 Chemistry
42. (a) For any species to have same bond order we can expect
d+ d-
36. (d) Acetonitrile ( CH 3 - C º N ) and acetone them to have same number of electrons. Calculating
the number of electrons in various species.
d+ O2– (8 + 8 + 1 = 17) ; CN - (6 + 7 + 1 = 14)
( CH3) d– NO+(7 + 8 – 1= 14); CN+ (6 + 7 –1 = 12)
d– C = O) both are polar molecules, hence We find CN– and NO+ both have 14 electrons and bond
( CH3) order 3.
dipole-dipole interaction exist between them. Between 43. (b) The delocalised p p bonding between filled p-
KCl and water ion-dipole interaction is found and in orbital of F and vacant p-orbital of B leads to shortening
benzene-ethanol and benzene-carbon tetra chloride of B–F bond length which results in higher bond
disperion force is present dissociation energy of the B–F bond.
37. (d) In SF4 the hybridisation is sp3d and the shape of
molecule is
F
F
F B F
S F
F
F Vacant Filled
2p-orbital 2p -orbital
38. (b) Diamagnetic species have no unpaired electrons
O 2 2- Þ s1s2, s*1s2, s2s2, s*2s2, 2 p z ,
2
F F
+
p2px2 = p2py2, p*2px2 = p*2py2 B=F B–F
+
Whereas paramagnetic species has one or more F F
unpaired electrons as in +1/3
+
F F
O2 2
1s , 2
1s , 2 s , 2
2s ,2
2 p 2z ,{ 2 p 2x 2 p 2y , +1/3
B–F B F
+1/3
{ 2 p1x = 2 p 1y = 2 unpaired electrons F F
44. (d) Calcium carbide exists as Ca2+ and C22–. According to
O2 1s 2 , 1s 2 , 2 s 2 , 2 s 2 , 2 pz2 , the molecular orbital model, C 2 2– should have
2 molecular orbital configuration :
2 px2 = 2 p y 2 p1x * 2 p0y = 1 unpaired
unpaired electron
electron
s1 s 2 , s *1 s 2 , s 2 s 2 , s *2 s 2 ,
NO 1s 2 , 1s 2 , 2 s 2 , 2s 2 , 2 p 2z ,
{p 2 px2 = p 2 p 2y }, s 2 pz2
* *
p2 px2 = p2 p2y , p 2 p1y =p 2 pz0 = 1 unpaired electron Thus M.O. configuration suggests that it contains one
39. (d) Smaller the size and higher the charge more will be the & 2p bonds.
polarising power of cation. Since the order of the size 45. (c) All the members form volatile halides of the type
AX3. All halides are pyramidal in shape. The bond
of cation is K + > Ca ++ > Mg ++ > Be++ . So the
angle decreases on moving down the group due to
correct order of polarising power is decrease in bond pair-bond pair repulsion.
K+ < Ca2+ < Mg2+ < Be2+ 46. (c) PF5 trigonal bipyramidal
40. (c) (i) N2 : bond order = 3, diamagnetic
N2– : bond order = 2.5, paramagnetic F
F
(ii) C2 : bond order = 2, diamagnetic
F P
C2+ : bond order = 1.5, paramagnetic F
(iii) NO : bond order = 2.5, paramagnetic
F
NO+ : bond order = 3, diamagnetic
(iv) O2 : bond order = 2, paramagnetic BrF5 square pyramidal (distorted due to presence of
one lp of electrons on central atom)
O2+ : bond order = 2.5, paramagnetic
41. (c) Greater the difference between electro-negativity of F
bonded atoms, stronger will be the bond. Since F is F F
most electronegative hence F – H ...... F is the strongest Br
bond. F F
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
108 Chemistry
JEEMAIN.GURU
downloaded from jeemain.guru
:
15. (c) H – C or Resonance Nd
H–C
d- F F d - and m ¹ 0 hence it is polar..
O F d-
O
– 24. (c) In metallic crystals the Kernels constitute the lattice and
electrons are mobile and form sea of electrons.
25. (d) Bond angles are affected by repulsions which are
O
lp – lp > lp – bp > bp – bp.
hybrid H – C due to resonance C – O bond length 26. (d) The hydrated Aluminium chloride trivalent complex ion
O
[Al.(H 2 O)6 ]3+ , formation of which is exothermic process.
is the same.
The energy released is sufficient to cause the ionisation
F :O: of Al.
| ||
16. (c) XeF2 and CO2 have linear structure Xe ; C 27. (b) Since XY2 forms 2 s , 2 p bonds and has 1 lone pair of
| ||
F :O:
electrons. It must have the structure Y = X = Y. Hence Y
1 is divalent. The hybridisation of X is
17. (b) Solubility µ . Lattice energy opposes
lattice energy æ1 ö
sp 2 ç (6 + 0 + 0 - 0)= 3 ÷ . So XY2 is trigonal planar
solubility and Solubility µ heat of hydration . Heat of è 2 ø
hydration favours solubility. For second groups ions heat .
..
of hydration is Be++ > Mg++ > Ca++ > Sr++ > Ba++ hence || X || (like SO 2 ).
solubility decreases down the group. Y Y
Cl 28. (b) For T-shape geometry the molecule must have 3 bonded
18. (b) BiCl3: Cl Bi ; sp2 - Hybridisation (Trigonal pair and 2 lone pair of electrons.
Cl 29. (a) See text
geometry); Bond angle = 120º 30. (c) Ortho-nitrophenol has intramolecular H-bonding
.
. . OH
sp3
P . O and para-nitr ophenol has
In PCl3 (Pyramidal
||
Cl Cl Cl geometry)
. N
Bond angle = O
sp3 below 109o 28’ intermolecular H-bonding.
As and decreases from
In AsCl3– (Pyramidal PCl3 to BiCl3 NO 2 NO 2 NO 2
Cl Cl Cl geometry)
sp3
In BiCl3– Bi (Pyramidal ,
Cl Cl Cl geometry) | | |
O– H O– H O– H
In these, order of bond angle : BCl3 > PCl3 > AsCl3 > BiCl3 Hence former is more volatile than latter.
19. (a) H 3 N ® BF3 where both N, B are attaining tetrahedral
31. (b) SF4 (sp 3 d) has see saw shape, XeF4 (sp 3d 2 ) square
geomerty.
planar and SiF4 (sp 3 ) is tetrahedral.
JEEMAIN.GURU
downloaded from jeemain.guru
110 Chemistry
32. (d) LiCl is covalent in nature due to small size of Li + ion, -10 -8
42. (b) m cal = e × l = (4.802 ´10 esu ) (1.275 ´10 cm)
hence LiCl will ionise less than NaCl.
33. (c) Due H -bonding in H – F its boiling point is more than m obs 1.03
Percentage ionic character = ´100 = =100=17%
HCl. m cal 6.12
34. (d) Although all the factors are correct but out of these lattice
energy is the most important one. (See Born-Haber cycle). Product of charges
43. (c) Lattice energy =
35. (a) Silicon carbide is covalent solid. interionic distance
36. (c) A p bond is formed by orbitals having same symmetry
In NaCl the product of charges = 1 × 1; In CaO product of
about the internuclear axis.
charges = 2 × 2 = 4 while the inter ionic distance is almost
37. (d) The more the polar nature of molecule the more is the
same in both. Thus lattice energy of CaO is almost four
boiling point.
times the lattice energy of NaCl.
38. (d) Nitrogen can form NCl3, N 2 O5 and Mg 3 N 2 but not
44. (a) MgO has highest lattice energy, since 2 × 2 = 4 is maximum
NCl5 due to non availability of d atomic orbitals. in MgO.
39. (c) The smaller the size, the more the charge, the more is the 45. (a) m = e × d
lattice energy.
40. (b) m 1.2 D 1.2 ´ 10-18 esu cm
\ e= = =
d 1. 0 A 1.0 ´ 10-8 cm
Cl 120
1
6 Cl = 1.2 × 10 -10 esu
41. (c) 2 Dipole moments of 2Cl and 5Cl
3 Percentage of electronic charge
Cl 5 4 Cl
1.2 ´ 10 -10 esu
are vectorically cancelled. = ´ 100 = 25 %
4.8 ´ 10 -10 esu
2 2
It is due 1 Cl and 3 Cl m 2 = m1 + m 2 + 2m1 m 21 cos q 46. (a) All the statements are correct (see text).
= (1.5) 2 + (1.5) 2 + 2 ´1.5 ´1.5 cos 120 47. (b) In amine the nitrogen is sp 3 hybridised and in amide the
\ m = 1.5 D
nitrogen is sp 2 hybridised.
48. (c) Since water is polar in nature and like dissolves like, the
coating must be nonpolar to polar manner.
JEEMAIN.GURU
downloaded from jeemain.guru
5
States of Matter
STATES OF MATTER : MEASURABLE PROPERTIES OF GASES :
The three important states of the matter are (i) Solid state (ii) Four measurable properties are.
(i) Mass : It is expressed in grams or kg. 1 kg=103 g moles of
Liquid state (iii) Gaseous state, which can exist together at a
particular temperature and pressure e.g. water has three states Mass in grams m
gas = =
in equilibrium at 4.58 mm and 0.0098ºC. Molar mass M
PLASMA STATE : (ii) Volume : It is equal to the volume of the container and is
expressed in terms of litres (L), millilitres (ml), cubic
It is the gaseous mixture of electrons and positive ions existing at
extremely high temperatures (in the interior of stars) or internal centimeters ( cm 3 ) , cubic meters (m3) or cubic decimeters
electrical fields in discharge tubes. (dm3).
SINGLE SUPER ATOM STATE : 1 l = 1000 ml = 1000 cm 3 = 1 dm 3
At extermely low temperature, all atoms lose their identity and get
1 m 3 = 10 3 dm 3 = 10 6 cm 3 = 10 6 ml = 10 3 l
condensed into a single entity behaving like a single super atom.
(iii) Pressure : It is equal to force per unit area and expressed in
SOME CHARACTERISTICS OF THE THREE COMMON the units such as atmosphere, millimetres (mm), centimetres
FORMS OF MATTER ARE : (cm), torr, bar etc. SI unit of pressure is pascal (Pa) or
Property Gaseous state Liquid State Solid state
kilopascal (kPa)
1 General It has definite mass It has definite It has definite
but no definite shape mass and volume mass, volume 1atm = 76cm of Hg = 760 mmof Hg = 760 torr
and volume but no definite shape and shape.
2. Forces Almost negligible Weaker than those Strongest
1atm = 101.325 kPa = 101325Pa = 101.325 Nm -2
in solids
= 1.01325 bar = 14.7lb m -2 (psi)
3. Density Low Lower than solids High
4. Motion Molecules have large Low values of No translatory 1bar = 105Pa. Pressure is measured with manometer
rotatory, vibratory motions or rotatory
and translatory motion. Possess (iv) Temperature : It is measured in celcius scale (°C)or in Kelvin
motions vibratory motion scale (K). SI unit of temperature is Kelvin (K) or absolute
5. Packing No proper packing Less closely Molecules
packed closely packed degree T (K) = t °C + 273
6. Energy Least Higher than solids Molecules possess GAS LAWS :
maximum energy
7. Thermal High Higher than solid Least
Boyle’s Law - The volume of a given mass of a gas is inversely
Expansion proportional to its pressure at constant temperature.
8. Compression High Slightly higher than Least compressibility
1
solid V or VP = k , a constant
9. Intermixing Spontaneous Spontaneous but slow Least-intermixing P
10. Pressure Exert pressure on Negligible Negligible Value of k depends on mass, temperature and nature of gas.
the walls of container
When mass and temperature are the same we have P1V1 = P2 V2
JEEMAIN.GURU
downloaded from jeemain.guru
112 Chemistry
ISOCHORES :
ISOTHERMS :
A graph of P vs T at constant volume is known as Isochore
Graphs of V vs P or PV vs P at constant temperature are known as
Isotherms. GRAPHICAL REPRESENTATION OF GAY LUSSAC’S
GRAPHICAL REPERSENTATION OF BOYLES LAW : LAW :
T2 V1 V2 > V1
P P PV T1 P V2
V 1/V P T
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
114 Chemistry
DALTON’S LAW OF PARTIAL PRESSURE :
At constant temperature the total pressure, exerted by a mixture r1 V /t d2 M2
= 1 1 = =
of non reacting gases, is the sum of partial pressure of each gas r 2 V2 / t 2 d1 M1
P = p1 + p 2 + p 3 + .....
Partial pressure p of a gas = mole fraction of the gas × total r1 T2 d2 M2
If volume diffused is same = = =
pressure. r2 T1 d1 M1
For a gas A, pA = xA × P
If n 1 , n 2 and n 3 are moles of non reacting gases filled in a r1 V1 d2 M2
vessel of volume V at temperature T. If time of diffusion is same = = =
r 2 V2 d1 M1
The total pressure P is given by PV = (n 1 + n 2 + n 3 )RT
This is the equation of state of a gaseous mixture. Effect of pressure on the rate of diffusion.
RELATIONSHIP BETWEEN TOTAL PRESSURE AND
r1 p1 M2
INDIVIDUAL PRESSURE : Rate of diffusion pressure, therefore, r = p × M
On mixing of gases at constant temperature. If a gas A at pressure 2 2 1
P1 and volume V1 is mixed with gas B at pressure p2 and volume
APPLICATIONS OF GRAHAM’S LAW OF
V2 at same temperature, then
DIFFUSION:
p1V1 +p 2V 2
Total pressure, P = (i) Determination of densities and molecular masses of unknown
V1 +V 2 gases.
AQUEOUS TENSION : (ii) Separating the gases having different densities.
It is the pressure exerted by water vapour at a particular (iii) Separation of Isotopes
temperature. It depends upon temperature.
PRESSURE OF A DRY GAS : ATMOLYSIS :
When a gas is collected over water, its observed pressure is The phenomenon of separation of a mixture of gases due to
equal to the sum of the pressure of dry gas and the pressure of difference in their rates of diffusion is called atmolysis.
water vapour (aqueous tension), then KINETIC THEORY OF GASES :
Pressure of dry gas = pressure of moist gas
Postulates of kinetic theory of gases.
– aqueous tension.
DIFFUSION : (i) A gas consists of large number of tiny particles called
The tendency of every gaseous substance to distribute itself molecules.
uniformly throughout the available space is known as diffusion. (ii) Volume occupied by gas molecules, is negligible as compared
It also takes place through a porous vessel. to the total volume of gas.
EFFUSION : (iii) There is continuous rapid random motion of gas molecules.
The movement of a gas through a small hole when it is subjected The molecules collide with each other and against walls of
to pressure is known as effusion. container.
GRAHAM’S LAW OF DIFFUSION (OR EFFUSION) : (iv) The molecules are perfect elastic bodies and there is no loss
At constant temperature and pressure, the rate of diffusion or of kinetic energy during collisions.
effusion of a gas is inversly proportional to the square root of its
(v) There are no attractive forces between the molecules of gas.
density.
(vi) The pressure exerted by a gas is due to bombardment of gas
1 molecules against the walls of the container.
Rate of diffusion
d
(vii) The different molecules possess different velocities and hence
If r1 and r2 are rates of diffusion of two gases and d1 and d 2 their different energies. The average K.E. is directly proportional
respective densities then, to absolute temperature.
KINETIC GAS EQUATION :
r1 d2 V.D 2 M2
= = = Based upon the postulates of Kinetic theory of gases, the kinetic
r2 d1 V.D1 M1
gas equation is
JEEMAIN.GURU
downloaded from jeemain.guru
KE of one molecule = 1 mv 2 U=
3PV ; In such case molecular volume (22400ml) is
2 M
converted into the volume under given conditions of T and
1 2 1 2
PV = mNU 2 = . mNU 2 = KE = RT
3 3 2 3 P using relation, P1V1 = P 2 V 2
T1 T2
( N = n and m ´ n = M)
MAXWELL’S DISTRIBUTION OF VELOCITIES :
3 The molecules present in a given sample of gas move with different
\ KE = RT for 1 mole of a gas
2 velocites in all possible directions. Velocities and directions of
(i) KE of n moles of gas = 3/2 nRT molecules keep on changing due to intermolecular collisions.
(ii) At absolute zero, KE is zero Hence it is impossible to find out the individual velocity of each
molecule. It is however possible to predict fraction ( DN / N ) of
MAXWELL’S GENERALISATION :
the total number of molecules having specific velocities at a
Kinetic Energy of translation of ideal gas is directly proportional
particular temperature. As shown by the curve,
to absolute temperature of gas or its pressure and is independent
of the nature of gas. The gases show ideal behavior at low presence/large volume.
Since the volume of molecules can be neglected and at high
THERMAL MOTION : temperature since intermolecular forces decrease.
KE U 2 or U 2 T U T
Most probable velocity
The molecular velocity of a gas is proportional to square root of
Fraction (percentage) of
the absolute temperature. The molecular motion is called thermal Average velocity
motion of molecules. RMS velocity
molecules
3 ´ 76 ´ 13.6 ´ 981´ 22400 (ii) Average velocity ( v ) : This is the average of the different
U=
M velocities of all the molecules.
JEEMAIN.GURU
downloaded from jeemain.guru
116 Chemistry
(iii) Root mean square velocity (U) : It is the square root of the (ii) Pressure : The deviation is more at high pressure. CO2 and
mean of the square of the different velocites of the molecules N2 show negative deviation at low pressure and positive
2 2 2
deviation at high pressure.
n 1 c1 + n 2 c 2 + n 3 c 3 + ... (iii) Temperature : The deviation is more at low temperature. H2
U= ;
n 1 + n 2 + n 3 + ....... and He always show positive deviations at 0°C
BOYLE’S TEMPERATURE:
3RT
Mathematically, U = Temperature at which a real gas exhibits ideal behaviour for
M
considerable range of pressure is called Boyle’s temperature.
RELATIONSHIP BETWEEN DIFFERENT TYPES OF Mathematically,
VELOCITIES :
a
Tb = , where a and b are Vander Waal’s constants
2 RT 8RT 3RT 8 bR
a:v:U º : : = 2: : 3
M pM M (i) Boyle temperature is different for different gases
= 1.414 : 1.595 : 1.732 = 1 : 1.128 : 1.224 (ii) Below Boyle’s temperature a gas shows negative deviation.
Calculation of root mean square velocity (Urms) : As already (iii) Above Boyle’s temperature a gas shows positive deviation
discussed, the Urms can be calculated by any of the following
CAUS E OF D EVIATION FRO M THE ID EAL
relations:
BEHAVIOUR :
3RT 3PV 3P It is due to two faulty assumptions of Kinetic theory of gases
Urms = = =
M M D particularly not valid at high pressure and low temperature.
RATIO OF URMS FOR TWO DIFFERENT GASES AT (i) Volume occupied by the gas molecules is negligible as
THE SAME TEMPERATURE compared to the total volume of gas.
(ii) There are no attractive forces between the gas molecules.
U1 M2
= VAN DER WAAL'S EQUATION :
U2 M1
After volume & pressure correction, van derWaals obtained the
RATIO OF URMS FOR THE SAME GAS AT DIFFERENT following equation for n moles of a gas
TEMPERATURE
æ 2 ö
ç P + n a ÷(V - nb) = nRT æ
çç P +
a ö
÷÷ (V - b) = RT
ç , For one mole
U1 T1 è V 2 ÷ø è V2 ø
=
U2 T2
Excluded volume or co-volume, (b) :
EFFECT OF TEMPERATURE ON DISTRIBUTION OF The constant b in van der Waal's equation is known as excluded
MOLECULAR VELOCITIES: volume or co-volume. It is nearly four times the actual volume
Most proabable velocity increases with the rise in temperature occupied by the gas molecules.
but fraction of molecules possessing such velocity decreases. Excluded or co-volume (b) = 4 × actual volume of gas molecules.
Deviation from ideal behaviour of gas :
MAGNITUDE OF ATTRACTIVE FORCES BETWEEN
At high pressure and low temperature the gases deviate
GAS MOLECULES (a) :
considerably from the ideal behaviour. Deviation can be expressed
in terms of compressibility factor (Z), expressed as It is given by van der Waals constant ‘a’. Different gases have
different value for ‘a’.
PV
Z= (i) The greater the value of ‘a’, the greater the strength of van
nRT der Waals forces.
In case of ideal gas, PV = nRT, Z = 1 (ii) The greater the value of ‘a’, the greater is the ease with
In case of real gas, PV ¹ nRT, Z ¹ 1 which a gas can be liquefied.
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
118 Chemistry
CRITICAL PRESSURE (Pc) : JOULE-THOMSON COEFFICIENT ( m J.T. ) :
At critical temperature the pressure needed to liquefy a gas is The temperature change produced per atmosphere drop in
known as critical pressure. pressure under constant enthalpy conditions on passing a gas
CRITICAL VOLUME (Vc) : through the porous plug is called Joule-Thomson coefficient
The volume occupied by one mole of a gas at critical temperature
The quantity æç
Tö
and critical pressure is known as critical volume. ÷ is called Joule -Thomson coefficient.
è P øH
RELATIONSHIP BETWEEN CRITICAL CONSTANTS
AND VAN DER WAAL’S CONSTANT: æ Tö 1 æ 2a ö
ç ÷ = ç - b÷
è P øH C p è RT ø
8a a
V c = 3b, T c = , Pc=
27Rb 27b 2 æ Tö
(i) Joule Thomson Coefficient ç ÷ is positive for real gases,
Relationship between boiling point and critical temperature: è P øH
2 (cooling)
Boiling point = critical temperature.
3 2a
Or Joule Thomson Coefficient will be positive when >b
Compressibility for 1 mole of gas at critical state: RT
Pc Vc 3 æ Tö
z= = = 0.375 , almost constant. (ii) When Joule Thomson Coefficient ç ÷ is negative,
RTc 8 è P øH
(heating)
JOULE THOMSON EFFECT :
2a
When a gas under high pressure is allowed to expand adiabatically Or Joule Thomson Coefficient will be negative when <b
into a region of extremly low pressure, it suffers change of temperature. RT
The phenomenon is kown as Joule -Thomson effect. æ Tö
(iii) When Joule Thomson Coefficient ç ÷ is zero, (no heating
CONDITION FOR JOULE-THOMSON EFFECT è P øH
(INVERSION TEMPERATURE): or cooling)
In Joule -Thomson effect, cooling is observed only if the gas is
2a
present below certain temperature known as inversion temperature, Or Joule Thomson Coefficient will be zero when =b
Ti. It is characteristic of each gas and related to van der Waal’s RT
Since a, b and R are constants, the sign of Joule-Thomson
2a Coefficient will depend only upon the temperature at which
constant a and b as, Ti =
Rb the gas is being allowed to expand. The temperature at which
At exact inversion temperature there is no Joule-Thomson effect. the Joule-Thomson Cofficient changes sign is known as the
Above inversion temperature, there is heating during Joule- inversion temperature.
Thomson effect. Below inversion temperature there is cooling 2a 2a
during Joule-Thomson effect. = b \ Ti =
RTi Rb
Inversion temperature for hydrogen = –80°C and for He = –240°C.
Joule-Thomson effect is zero in an ideal gas and enthalpy remains LAW OF CORRESPONDING STATES :
constant. When an ideal gas expands in vacuum, it does no work When the values of pressure, volume and temperature are
i.e. W=0 ; DE = 0 (Adiabatic condition). Hence internal energy expressed as fractions of the corresponding critical values we
of a given quantity of an ideal gas at constant temperature is P V T
have. = p, = f, =q
independent of its volume. Pc Vc Tc
æ Eö If the two substances have the same reduced temperature and the
(ii) ç ÷ =0 same reduced pressure, they will have the same reduced volume.
è V øT The statement is known as the law of corresponding states.
JEEMAIN.GURU
downloaded from jeemain.guru
æ Hö 5 At constant temperature, Z p2
Cp = ç ÷ = R
è T øP 2 (iii) Collision number (Z1) : Number of collisions undergone by
For one mole of gas, the heat capacities at constant volume a molecule with other molecules per second present in 1cm3.
and constant pressure are denoted by Cv and Cp and are Z1 = Collision number = 2 ps 2 vN
termed as molar heat capacities.
s = diameter of molecules, v = Average velocity,,
RELATION BETWEEN Cp AND Cv : N = Number of molecules per unit volume of the gas
Cp– Cv = R (iv) Mean free path (l) : The average distance travelled by the
R = 1.987 cal or 8.314 Joule molecule between two successive collisions
R= PDV = Work done by one mole of an ideal gas in expansion at 1
constant pressure when heated through 1°C. l=
2
2 N
MOLAR HEAT CAPACITIES FOR POLYATOMIC
GASES: At constant pressure, l T
3 5 1
The values C V = At constant temperature, l
R and C p = R are for monoatomic gases P
2 2
VOLUME COEFFICIENT :
like He, Ar etc. where the energy supplied increases translational
It is defined as the ratio of the increase in volume of the gas at
kinetic energy only. In polyatomic gases heat supplied is utilised
constant pressure per degree rise of temperature to its volume at
to increase vibrational and rotational energy also. Thus we have
0°C
3 5 v t -v 0
CV = R+x and C p = R+x
2 2 aV =
v0 ´ t
5 V0 =Volume of a given mass of a gas at 0°C
Cp R
5
For monoatomic gas, x = 0, g = = 2 = = 1.66 Vt= Volume of a given mass of a gas at t°C
CV 3 3
R V t = V0 (1 +a V t )
2
The value of a v is found be 1/273 for all gases (charle's law)
5
Cp R+R t
7
for diatomic gases, x = R, g = = 2 = = 1.46 Therefore, V t = V0 (1 +
273
)
CV 3 5
R+R
2 PRESSURE COEFFICIENT ( P) :
5 3 It is defined as the ratio of the increase in pressure of the gas at
C R+ R constant volume per degree rise of temperature to its pressure at
3 p
= 2 2 = 8 = 1.33
for triatomic gases, x = R , g = 0°C
2 CV 3 3 6
R+ R
2 2 P t -P 0
ap =
P 0 ´t
COLLISION PROPERTIES : P0=Pressure of given mass of gas at 0°C
(i) Molecular diameter or collision diameter : The distance Pt=Pressure of given mass of gas at t°C
between the centers of the molecules at the point of their
closest approach. P t =P 0 (1 +a p t )
The value found by Ragnault & Gay Lussac was in the vicinity of
1 æ ö t
273 for all gases and hence P t = P0 çè1 + 273 ÷ø
JEEMAIN.GURU
downloaded from jeemain.guru
120 Chemistry
AMAGAT LAW OF PARTIAL VOLUME : Liquefaction is further based on the following principles
The total volume of a mixture of non reacting gases at constant (a) Cooling by freezing mixture : eg NaCl & ice (-22°C), CaCl2
temperature and pressure is equal to the sum of the individual & ice(-55°C), KOH & ice (-65°C)
partial volumes of the constituents (b) Cooling by adiabatic expansion (Claude’s Method) : The gas
in this process suffers a loss in temperature.
V(total)= V1+V2+V3+.....+Vn = Vi
DE = q + w if q = 0 then DE = w or - DE = - w
LOSCHMIDT NUMBER :
Work is done by the gas at the cost of internal energy and
It is the number of molecules present in 1cc of a gas or vapour at temeprature is lowered.
STP. Its value is 2.617×1019 per cc.
(c) Cooling by Joule-Thomson effect ( Linde’s method) :
AVERAGE MOLECULAR WEIGHT OF A GASEOUS Expansion of a gas through a small jet under adiabatic
MIXTURE : conditions results in cooling and liquefaction of gas
JEEMAIN.GURU
downloaded from jeemain.guru
1. The density of a gas at 30°C and 1.3 atmosphere pressure is 2. Density of ammonia is 0.77 g/l. Calculate its vapour density.
0.027 g/cc. Calculate the molecular weight of the gas.
Densityof gas 0.77
Sol. V.D. = = =8.55
RTd Densityof H 2 0.09g / l 0.09
Sol. M = ; R = 0.0821 atm lit K -1 mol-1;
P
3. A gas cylinder containing cooking gas can withstand a
d = .027 g / cc = 27 g / l; pressure of 14.9 atmosphere. The pressure gauge of cylinder
indicates 12 atmosphere at 27°C. Due to sudden fire in the
T = 273 + 30 = 303K; P =1.3 atm
building the temperature starts rising. At what temeprature,
27 ´ .0821 ´ 303 cylinder will explode.
M= = 516 .66 g / mol
1. 3
Sol. P1 = P2 Þ 14.9 12
= Þ T1 = 372.5 K
T1 T2 T1 300
JEEMAIN.GURU
downloaded from jeemain.guru
122 Chemistry
4. The total pressure exerted by a mixture of gases containing 12
0.4g H2, 2.2g of CO2, 1.4 g N2 and 3.2g SO2 is 2.5 atmosphere Second equation 1.1 ´ V = ´ .0821(t + 273 + 10)
120
. What are the partial pressures of each gas under the same
conditions? 1 t + 273
Dividing = or t = - 173°C
Sol. Partial pressure of a gas = mole fraction × total pressure 1.1 t + 283
= 273 - 173° C = 100 K
Total moles = 0.4 + 2.2 + 1.4 + 3.2 = 0.35
2 44 28 64 12
V= ´ 0.0821(100) = 0.821 litre
120
0.2
pH 2 = ´ 2.5 = 1.428 atm; 8. Calculate the molecular mass of a gas if its specific heat at
0.35
constant pressure is 0.125 and at constant volume is 0.075
0.05 Cp
pCO2 = ´ 2.5 = 0.357 atm 0.125 5
0.35 Sol. = = = 3 = 1.66 hence gas is monoatomic
Cv 0.075
0.05
pN 2 = ´ 2.5 = 0.357 atm;
0.35 Molar heat at constant volume C v = 3 2 R = 3 2 2 = 3 cal.
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
124 Chemistry
18. Calculate the average and total kinetic energy of 0.5 mole of
PV 7.57 ´ 103 ´ 10-3
an ideal gas at 0°C \ T= = ´ 6.023 ´ 10 23
nR 2 ´ 10 21 ´ 8.314
3 R T = 274.2 K
Sol. Average KE per molecule of the gas = . T
2 N0
3RT 3 ´ 8.314 ´ 274.2
8.314 ´ 107 U rms = = (M.W.in Kg)
=3 ´ ´ 273 =5.65 ´ 10-14 ergs M 28 ´ 10-3
2 6.023 ´ 1023
Total Kinetic energy of 0.5moles of a gas = 494.22 ms -1
-21
= 5.65 ´ 10 Joules = 3 nRT = 3 ´ 0.5 ´ 8.314 ´ 10 ´ 373
7
2 2 U mp
= 0.82 ; U mp = 494.22 ´ 0.82 = 405.26 ms -1
=1.702 ´ 1010 ergs =1.702kJ U rms
19. The composition of the equilbrium mixture, Cl2 2Cl, 22. A gaseous mixture of helium and oxygen is found to a density
which is attained at 200º C, is determined by measuring the of 0.518 g dm-3 at 25°C and 720 torr. What is the percent by
rate of effusion through a pin hole. It is observed that at 1.80 mass of helium in the mixture?
mm Hg pressure, the mixture effuses 1.16 times as fast as
krypton effuses under the same condition. Calculate the Sol. M av = dRT = 0.518 ´ 0.0821´ 298 = 13.36 g mol -1
fraction of the chlorine molecules dissociated into P 720 / 760
atmosphere. (Atomic wt. of krypton 84) Let x be the mole fraction of helium in the mixture,
Sol. r mix = M kr 84 then M av = xM He + (1 - x ) M O 2
or 1.16 = Þ M mix = 62.425
r Kr M mix M
13.36 = x ´ 4 + (1 - x )32 \ x = 0.666
Dissociation: Cl2 2Cl
1-a 2a 0.666 ´ 4
Total number of moles = 1+a Mass percent of helium = ´ 100
(0.666 ´ 4 + 0.334 ´ 32)
Normal M.wt
= 1+ a ;
71
=1+ a
= 19.95
Experimental M. wt 62.425
23. Using Van der Waal's equation calculate the constant ‘a’
a = 0.137 = 13.7%
when the moles of a gas confined in a 4 l flask exerts a pressure
20. The average speed at T1 K and the most probable speed at of 11.0 atm at a temperature of 30 K. The value of ‘b’ is 0.05 lit
T2 K of CO2 gas is 9×104 cm sec-1. Calculate the value of
mol-1.
T1and T2.
æ n 2a ö
8RT1 Sol. çç P + 2 ÷÷ (V - nb) = nRT
Sol. Average speed at T1K = è V ø
pM
æ 2 ö
Most probable speed at T2 K =
2RT 2 ç11 + 2 a ÷ ( 4 - 2 ´ 0.05) = 2 ´ 0.0821´ 300
ç 4 2 ÷ø
M è
According to Question ,
8RT1
=
2RT2
= 9 ´10 4 a = 6.46 atm lit 2 mol - 2
pM M
24. (a) Calculate the pressure exerted by 5 mol of CO2 in one
8 ´ 8.314 ´10 7 ´ T1 2 ´ 8.314 ´10 7 ´ T2 litre vessel at 47°C using van der Waal's equation. Also
\ = = 9 ´ 10 4
3.14 ´ 44 44 report the pressure of gas if it behaves ideally in nature.
On calculating, we get T2 = 2143.37K and T1 = 1684.0 K Given that a = 3.592 atm ltr2 mol-2 . b = 0.042 litre mol-1
(b) If volume occupied by CO2 molecules is negligible, then
21. A glass bulb of 1 litre capacity contains 2 ´ 1021 molecules calculate the pressure exerted by one mol of CO2 gas at
of N2 exerting pressure 7.57×103 Nm–2. Calculate the RMS 273K .
speed and temperature of gas molecules. If the ratio of Ump
to Urms is 0.82 calculate the Vmp for these molecules at this æ 2 ö
Sol. (a) ç P + n a ÷ ( V - nb) = nRT
temperature. ç
è V 2 ÷ø
Sol. Given P = 7.57 ´103 Nm-2 æ 2 ö
ç P + 5 ´ 3.592 ÷ (1 - 5 ´ 0.0427) = 5 ´ .0821´ 320
V = 1litre = 10 -3 m 3 , R =8.3145 J K -1 mol-1 ç 1 ÷
è ø
P = 77.218 atm
2 ´ 10 21
n= when the gas behaves ideally then PV = nRT
6.023 ´ 10 23 mol
P ´1 = 5 ´ .0821´ 320 . Þ P = 131.36 atm
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
126 Chemistry
Very Short/Short Answer Questions 12. A bacterial culture isolated from sewage produced 41.3 ml of
1. When do real gases behave as ideal gas? methane, CH4 at 31ºC and 753 mm Hg. What is the volume of
2. The size of weather balloon becomes larger and larger as it this methane at STP?
ascends up into higher altitudes. Why? Long Answer Questions
3. What do you mean by Boyle temperature ? Give its expression 13. (i) A quantity of hydrogen is confined in a chamber of
and its relation with inversion temperature.
constant volume. When the chamber is immersed in a
4. Liquid is transferred from a large beaker to a small beaker,
bath of melting ice, the pressure of the gas is 1000atm.
what will be the effect on its vapour pressure ?
5. Explain, why the bubbles of a gas in a boiling liquid generally (a) What is the Celsius temperature when the pressure
increase in volume as they approach the upper surface ? manometer indicates an absolute pressure of 400
6. What is the effect of temperature on the vapour pressure of atm?
a liquid ? (b) What pressure will be indicated when the chamber
7. Two different gases ‘A’ and ‘B’ are filled in separate is brought to 100 ºC?
containers of equal capacity under the same conditions of (ii) A steel tank containing air at 15 atm pressure at 15° C is
temperature and pressure. On increasing the pressure
provided with a safety valve that will yield at a pres-
slightly the gas ‘A’ liquefies but gas B does not liquify even
on applying high pressure until it is cooled. Explain this sure of 30 atm. To what minimum temperature must the
phenomenon. air be heated to blow the safety valve?
8. A gas occupying a volume of 100 litres is at 20°C under a 14. (i) One mole of the CO2 occupies 1.5 L at 25ºC. Calculate
pressure of 2 bar. What temperature will it have when it is the pressure exerted by the gas using:
placed in an evacuated chamber of volume 175 litres ? The
(a) an ideal gas equation
pressure of the gas in the chamber is one-third of its initial
pressure. (b) van der Waal’s equation if:
9. The values of the van der Waal’s constants for a gas are a = a = 3.012 atm mol–2 and b = 0.04 L mol–1.
4.10 dm6 bar mol–2 and b = 0.035 dm3 mol–1. Calculate the (ii) The critical temperature and pressure for NO gas are
values of the critical temperature and critical pressure for
177 K and 64.5 atm. respectively. Calculate the van der
the gas.
Waal’s constants ‘a’ and ‘b’.
pV 15. (i) A spherical balloon of 21 cm diameter is to be filled with
10. Compressibility factor, Z, of a gas is given as Z =
nRT hydrogen at STP from a cylinder containing the gas at
(i) What is the value of Z for an ideal gas ? 20 atm at 27ºC. If the cylinder can hold 2.82 L of water,
(ii) For real gas what will be the effect on value of Z above calculate the number of balloons that can be filled up.
Boyle’s temperature ?
(ii) Two van der Waals gases A and B have volumes 0.112
11. For real gases the relation between p, V and T is given by
and 0.111 L mol –1 r espectively. Calculate the
van der Waals equation :
compressibility factors for one mole of each at 273 K
an2 and 200 atm and hence state which gas is more
p ÷ (V nb) = nRT compressible.
V2
Multiple Choice Questions
where ‘a’ and ‘b’ are van der Waals constants, ‘nb’ is
approximately equal to the total volume of the molecules of 16. Dipole-dipole forces act between the molecules possessing
a gas. permanent dipole. Ends of dipoles possess ‘partial charges’.
‘a’ is the measure of magnitude of intermolecular attraction. The partial charge is
(i) Arrange the following gases in the increasing order of (a) more than unit electronic charge
‘b’. Give reason. O2, CO2, H2, He
(b) equal to unit electronic charge
(ii) Arrange the following gases in the decreasing order of
magnitude of ‘a’. Give reason. (c) less than unit electronic charge
CH4, O2, H2 (d) double the unit electronic charge
JEEMAIN.GURU
downloaded from jeemain.guru
pV
(a) (b) (c) (d) B
27 8 2 1
20. Gases possess characteristic critical temperature which
depends upon the magnitude of intermolecular forces
between the particles. Following are the critical temperature 0 p
of some gases. 23. Increase in kinetic energy can overcome intermolecular
Gases H2 He O2 N2 forces of attraction. How will the viscosity of liquid be
Critical temperature 33.2 5.3 154.3 126 affected by the increase in temperature ?
in Kelvin (a) Increase (b) No effect (c) Decrease
(d) No regular pattern will be followed
1. Which one of the following statements is wrong for gases? 4. Densities of two gases are in the ratio 1:2 and their
(a) Gases do not have a definite shape and volume temperatures are in the ratio 2:1 then the ratio of their
(b) Volume of the gas is equal to the volume of the container respective pressures is
confining the gas (a) 1:1 (b) 1:2
(c) Confined gas exerts uniform pressure on the walls of its (c) 2:1 (d) 4:1
container in all directions 5. Gas equation PV = nRT is obeyed by
(d) Mass of the gas cannot be determined by weighting a (a) only isothermal process
container in which it is enclosed. (b) only adiabatic process
2. Non reacting gases have a tendency to mix with each other. (c) both (a) and (b)
This property is known as
(d) None of these
(a) diffusion (b) fusion
6. The following graph illustrates
(c) mixing (d) None of these V
(a) Dalton’s law
3. Which of the following mixtures of gases does not obey
Dalton’s law of partial pressure ? (b) Charle’s law
(a) O2 and CO2 (b) N2 and O2 (c) Boyle’s law
(c) Cl2 and O2 (d) NH3 and HCl (d) Gay-Lussac’s law
Temp. (ºC)
JEEMAIN.GURU
downloaded from jeemain.guru
128 Chemistry
7. 4.4 g of a gas at STP occupies a volume of 2.24 L, the gas can 15. For an ideal gas, correct relation is-
be
(a) O2 (b) CO é dE ù é dE ù
(a) ê dV ú = 0 (b) ê dT ú = 0
(b) NO2 (d) CO2 ë ûT ë ûP
8. Which of the following volume (V) - temperature (T) plots
represents the behaviour of one mole of an ideal gas at one é dE ù
(c) ê dT ú = 0 (d) All of these
atmospheric pressure ? ë ûV
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
130 Chemistry
45. Same mass of CH4 and H2 is taken in container, The partial 54. The value of van der waals constant ‘a’ for gases
pressure caused by H2 is O2, N2 , NH3 and CH4 are 1.360, 1.390, 4.170 and 2.253 liter 2
atm mol–2 respectively. The gas which can most easily be
8 1 liquefied is :
(a) (b)
9 9 (a) O2 (b) N2
1 (c) NH3 (d) CH4
(c) (d) 1
2
æ dT ö
22 55. Joule- Thomson coefficient ç ÷ for an ideal gas is
46. There are 6.02 ´ 10 molecules each of N2, O2 and H2 è dP ø H
which are mixed together at 760 mm and 273 K. The mass of (a) zero (b) positive
the mixture in grams is
(c) negative (d) None of these
(a) 6.02 (b) 4.12
56. The inversion temperature (T i) for a gas is given by
(c) 3.09 (d) 6.2
(a) a / Rb (b) 2a / Rb
47. The density of air is 0.00130 g/ml. The vapour density of air
will be Rb 2Rb
(a) 0.00065 (b) 0.65 (c) (d)
a a
(c) 14.4816 (c) 14.56 57. The Joule-Thomson coefficient for a gas is zero at
48. An ideal gas is one which obeys the gas laws under (a) Inversion temperature
(a) a few selected experimental conditions
(b) Critical temperature
(b) all experimental conditions
(c) Absolute temperature
(c) low pressure alone
(d) Below 0ºC
(d) high temperature alone
58. Longest mean free path under similar conditions of P and T
49. The temperature at which real gases obey the ideal gas laws
stands for.
over a wide range of pressure is called
(a) N2 (b) O2
(a) Critical temperature
(b) Boyle’s Temperature (c) H2 (d) Cl2
(c) Inversion temperature 59. The mean free path ( l ) of a gas sample is given by
(d) Reduced temperature
1
50. Which of the following exhibits the weakest inter- molecular (a) l = 2ps 2 N (b) l=
forces 2.ps2 N
(a) NH3 (b) HCl
(c) He (d) H2O (c) l = 2pus 2 N (d) None of these
51. The van der Waal’s equation reduces itself to the ideal gas 60. Which of the following statements is false
equation at (a) Avogadro Number = 6.02 × 1021
(a) high pressure and low temperature
(b) The relationship between average velocity (n ) and root
(b) low pressure and low temperature
(c) low pressure and high temperature mean square velocity (u) is (n ) =.9213u
(d) high pressure alone (c) The mean kinetic energy of an ideal gas is independent
52. An ideal gas obeying kinetic theory of gases can be liquefied of the pressure of the gas
if : (d) The root mean square velocity of the gas can be
(a) its temperature is more than critical temperature TC
calculated by the formula (3RT / M)½
(b) its pressure is more than critical pressure PC
(c) its pressure is more than PC at a temperature less than TC 61. At higher altitude the boiling point of water lowers because
(d) it cannot be liquefied at any value of P and T (a) atmospheric pressure is low
53. The ratio of Boyle’s temperature and critical temperature for (b) temperature is low
a gas is : (c) atmospheric pressure is high
8 27 (d) None of these
(a) (b) 62. Which of the following liquid will exhibit highest vapour
27 8
pressure?
1 2 (a) C2H5OH(l) (b) NH3 (l)
(c) (d)
2 1 (c) HF (l) (d) H2O(l)
JEEMAIN.GURU
downloaded from jeemain.guru
1. A weather ballon filled with hydrogen at 1 atm and 27°C has 7. A bubble of air is underwater at temperature 15°C and the
volume equal to 12000 litres. On ascending it reaches a place pressure 1.5 bar. If the bubble rises to the surface where the
where the temperature is –23°C and pressure is 0.5 atm. The temperature is 25°C and the pressure is 1.0 bar, what will
volume of the balloon is [CBSE-PMT 1991] happen to the volume of the bubble ?
(a) 24000 litres (b) 20000 litres [CBSE-PMT 2011M]
(c) 10000 litres (d) 12000 litres (a) Volume will become greater by a factor of 1.6.
2. If a gas expands at constant temperature, it indicates that : (b) Volume will become greater by a factor of 1.1.
[CBSE-PMT 2008] (c ) Volume will become smaller by a factor of 0.70.
(a) kinetic energy of molecules decreases (d) Volume will become greater by a factor of 2.5.
(b) pressure of the gas increases 8. 50 mL of each gas A and of gas B takes 150 and 200 seconds
(c) kinetic energy of molecules remains the same respectively for effusing through a pin hole under the similar
(d) number of the molecules of gas increases condition. If molecular mass of gas B is 36, the molecular
3. The pressure exerted by 6.0g of methane gas in a 0.03 m3 mass of gas A will be : [CBSE-PMT 2012]
vessel at 129°C is (Atomic masses : C = 12.01, H = 1.01 and (a) 96 (b) 128 (c) 20.25 (d) 64
R = 8.314 kpa dm3K–1 mol –1) [CBSE-PMT 2010] 9. A certain gas takes three times as long to effuse out as
(a) 31684 Pa (b) 215216 Pa helium. Its molecular mass will be : [CBSE-PMT 2012]
(c) 13409 Pa (d) 41777 Pa (a) 27 u (b) 36 u (c) 64 u (d) 9 u
4. By what factor does the average velocity of a gaseous 10. Maximum deviation from ideal gas is expected from :
molecule increase when the temperature (in Kelvin) is (a) N2(g) (b) CH4(g) [NEET 2013]
doubled ? [CBSE-PMT 2011] (c) NH3 (g) (d) H2(g)
(a) 2.0 (b) 2.8 (c) 4.0 (d) 1.4 11. For an ideal gas, number of moles per litre in terms of its
5. Two gases A and B having the same volume diffuse through presure P, gas constant R and temperature T is
a porous partition in 20 and 10 seconds respectively. The [AIEEE 2002]
molecular mass of A is 49 u. Molecular mass of B will be : (a) PT/R (b) PRT
[CBSE-PMT 2011] (c) P/RT (d) RT/P
(a) 50.00 u (b) 12.25 u (c) 6.50 u (d) 25.00 u 12. Value of gas constant R is [AIEEE 2002]
(a) 0.082 litre atm (b) 0.987 cal mol–1 K–1
6. A gaseous mixture was prepared by taking equal mole of CO
and N2. If the total pressure of the mixture was found 1 (c) 8.3 J mol–1 K–1 (d) 83 erg mol–1 K–1.
atmosphere, the partial pressure of the nitrogen (N2) in the 13. Kinetic theory of gases proves [AIEEE 2002]
mixture is : [CBSE-PMT 2011] (a) only Boyle’s law
(b) only Charles’ law
(a) 0.5 atm (b) 0.8 atm (c) 0.9 atm (d) 1 atm
(c) only Avogadro’s law
(d) All of these.
JEEMAIN.GURU
downloaded from jeemain.guru
132 Chemistry
14. The heat required to raise the temperature of body by 1 K is 22. If 10–4 dm3 of water is introduced into a 1.0 dm3 flask at
called [AIEEE 2002] 300 K, how many moles of water are in the vapour phase
(a) specific heat (b) thermal capacity when equilibrium is established ? [AIEEE 2010]
(c) water equivalent (d) none of these. (Given : Vapour pressure of H2O at 300 K is 3170 Pa;
15. What volume of hydrogen gas, at 273 K and 1 atm pressure R = 8.314 J K–1 mol–1)
will be consumed in obtaining 21.6 g of elemental boron (atomic
(a) 5.56× 10–3 mol (b) 1.53 × 10–2 mol
mass = 10.8) from the reduction of boron trichloride by –2
hydrogen ? [AIEEE 2003] (c) 4.46 × 10 mol (d) 1.27 × 10–3 mol
(a) 67.2 L (b) 44.8 L 23. When r, P and M represent rate of diffusion, pressure and
(c) 22.4 L (d) 89.6 L molecular mass, respectively, then the ratio of the rates of
16. According to the kinetic theory of gases, in an ideal gas, diffusion (rA / rB ) of two gases A and B, is given as :
between two successive collisions a gas molecule travels [AIEEE 2011 RS]
(a) in a wavy path [AIEEE 2003]
(b) in a straight line path (a) ( PA / PB ) ( M B / M A )1/ 2 (b) ( PA / PB )1/ 2 ( M B / M A )
(c) with an accelerated velocity
(c) ( PA / PB ) ( M A / M B )1/ 2 (d) ( PA / PB )1/ 2 ( M A / M B )
(d) in a circular path
17. As the temperature is raised from 20ºC to 40ºC, the average 24. The molecular velocity of any gas is [AIEEE 2011 RS]
kinetic energy of neon atoms changes by a factor of which (a) inversely proportional to absolute temperature.
of the following ? [AIEEE 2004] (b) directly proportional to square of temperature.
(a) 313 293 (b) (313 / 293) (c) directly proportional to square root of temperature.
(d) inver sely proportion al to the squar e root of
(c) 1 2 (d) 2 temperature.
25. The compressibility factor for a real gas at high pressure is :
18. In van der Waals equation of state of the gas law, the constant
[AIEEE 2012]
‘b’ is a measure of [AIEEE 2004]
(a) volume occupied by the molecules RT pb pb
(b) intermolecular attraction (a) 1 + (b) 1 (c) 1 + (d) 1 –
pb RT RT
(c) intermolecular repulsions
(d) intermolecular collisions per unit volume 26. For gaseous state, if most probable speed is denoted by C*,
average speed by C and mean square speed by C, then for
19. Which one of the following statements is NOT true about
a large number of molecules the ratios of these speeds are :
the effect of an increase in temperature on the distribution
of molecular speeds in a gas? [AIEEE 2005] (a) C* : C : C = 1.225 : 1.128 : 1 [JEE Main 2013]
(a) The area under the distribution curve remains the same (b) C* : C : C = 1.128 : 1.225 : 1
as under the lower temperature (c) C* : C : C = 1 : 1.128 : 1.225
(b) The distribution becomes broader (d) C* : C : C = 1 : 1.225 : 1.128
(c) The fraction of the molecules with the most probable 27. At constant volume and temperature conditions, the rate of
speed increases diffusion DA and DB of gases A and B having densities rA
(d) The most probable speed increases and rB are related by the expression. [IIT-JEE 1993]
20. The volume of a colloidal particle, VC as compared to the
12 12
volume of a solute particle in a true solution VS , could be (a) DA = DB A (b) DA = DB B
[AIEEE 2005] B A
VC ~ 3 VC ~ - 3 12 12
(a) - 10 (b) - 10 B
VS VS (c) A (d) DA = D B
DA =DB ÷ ÷
B A
VC ~ 23 VC ~
(c) - 10 (d) -1 28. The compression factor (compressibility factor) for 1 mole
VS VS of a van der Waal’s gas at 0°C and 100 atm pressure if found
21. Equal masses of methane and oxygen are mixed in an empty to be 0.5. Assuming that the volume of gas molecules is
container at 25°C. The fraction of the total pressure exerted negligible, calculate the van der Waal’s constant 'a'.
by oxygen is [AIEEE 2007]
(a) 1/2 (b) 2/3 [IIT-JEE 2001]
(a) 0.253 L2 mol–2 atm (b) 0.53 L2 mol–2 atm
1 273
(c) ´ (d) 1/3. (c) 1.853 L2 mol–2 atm (d) 1.253 L2 mol–2 atm
3 298
JEEMAIN.GURU
downloaded from jeemain.guru
1
24.6
23.1
Z
1. N2O4 is 20 % dissociated at 27°C and 760 torr. The density of 5. The partial pressure of hydrogen in a flask containing 2.016
the equilibrium mixture is g of H2 and 96.0 g of O2 is
(a) 3.1 g/l (b) 6.2 g/l (a) 1/8 of the total pressure (b) 1/6 of the total pressure
(c) 12.4g/l (d) 18.6 g/l (c) 1/4 of the total pressure (d) 2/3 of the total pressure
2. Helium atom is two times heavier than a hydrogen molecule 6. At 27°C a gas was compressed to half of its volume. To what
at. 298K. The average KE of helium is temperature it must be now heated so that it occupies just
(a) 2 times of H2 molecule its original volume. The pressure remains constant
(b) same as that of H2 molecule (a) 54°C (b) 327°C
(c) 4 times that of hydrogen molecule (c) 600°C (d) 327 °C.
1 7. Equal volumes of the gases which do not react together are
(d) that of H2 molecule
2 confined in separate vessels. The pressure is
3. The units of ‘a’ in van der Waals equation of state is 200 mm and 400 mm of Hg respectively. If the two gases are
mixed together what will be the pressure of the resulting
(a) atm. litre mol–1 (b) atm. litre2 mol–2
2 2 mixture (temperature remaining constant)
(c) atm litre mol (d) atm. litre mol–2
4. A container contains certain gas of mass ‘m’ of high pressure. (a) 400 mm (b) 400 mm
Some of the gas has been allowed to escape from the container
(c) 300 mm (d) 200 mm
and after some time the pressure of the gas becomes half and
its absolute temperature 2/3 rd. The amount of the gas 8. A flask containing air (open to the atmosphere) is heated
from 300 K to 500 K. The percentage of the air escaped into
escaped is
the atmosphere is
(a) 2/3 m (b) 1/2 m
(a) 16.6 (b) 40
(c) 1/4 m (d) 1/6 m
(c) 60 (d) 20
JEEMAIN.GURU
downloaded from jeemain.guru
134 Chemistry
9. A sample of O2 gas is collected over water at 23°C at a 18. A bubble of the gas released at the bottom of a lake increases
barometer pressure of water at 751 mm Hg (Vapour pressure to eight times the original volume when it reaches at the
of water at 23°C is 21 mm Hg). The partial pressure of O2 gas surface. Assuming that the atmospheric pressure is equivalent
in the sample collected is to pressure exerted by a column of water 10 m high, what is
(a) 21 mm Hg (b) 751 mm Hg the depth of the lake
(c) 0.96 atm. (d) 1.02 atm. (a) 80 m (b) 90 m
10. Which of the following is a false statement ? (c) 10 m (d) 70 m
(a) Gases having same molecular masses diffuse at the
19. SO 2 and He are kept in a container at partial pressure P1
same rate
(b) 0.5 litre of nitrogen and 1 litre of helium will have the and P2 . A thin perforation is made in the wall of the container
same number of the atoms at the same temperature and and it is observed that gases effuse at the same rate. The
pressure
ratio of P1 and P2 will be
(c) The value of molar gas constant does not vary with the
nature of the gas (a) 4 : 1 (b) 1 : 4
(d) None is false (c) 1 : 16 (d) 16 : 1
11. The density of SO2 at STP is 2.06 kg m-3. Its density at 819°C 20. Helium has the van der Waals constant b = 24 ml mol -1 . The
and 2 atmosphere is
molecular diameter of helium will be
(a) 2.86 kg m-3 (b) 1.43 kg m-3
-3
(a) 267 pm
(c) 0.715 kg m (d) 4.2686 kg m-3
(b) 133.5 pm
12. When helium is allowed to expand into vacuum, heating effect
(c) 26.7 pm
is observed. Its reason is that
(d) Data not sufficient for calculation the diameter.
(a) helium is an ideal gas
21. At 100°C and 1 atm, if the density of liquid water is
(b) helium is an inert gas
1.0 g cm–3 and that of water vapour is 0.0006 g cm–3, then the
(c) inversion temperature of helium is low volume occupied by water molecules in 1 litre of steam at
(d) the boiling point of helium is the lowest amongst the that temperature is
element. (a) 6 cm3 (b) 60 cm3
13. What would be the vapour density of a gas 260 cm3 of which (c) 0.6 cm 3 (d) 0.06 cm3
at 290 K and 100.40 KPa pressure weights 0.160g 22. Which of the following graphs is not a straight line for an
(a) 17.9 gL-1 (b) 14.2 gL-1 ideal gas?
(a) n ® T (b) T ® p
(c) 7.4 g cm -3 (d) None of these
1 1
14. Reducing the pressure from 1.0 atm to 0.5 atm would change (c) n ® (d) n®
T p
the number of molecules in one mole of ammonia to
23. A volume V of a gas at temperature T1 and a pressure p is
(a) 25% of its initial value
enclosed in a sphere. It is connected to another sphere of
(b) 50% of its initial value
volume V/2 by a tube and stopcock. The second sphere is
(c) 75% of its initial value initially evacuated and the stopock is closed. If the stopcock
(d) None of the above is opened the temperature of the gas in the second sphere
15. The ratio of diffusion of nitrogen at 25°C would be ......... becomes T2. The first sphere is maintained at a temperature
times that of carbon dioxide at 75°C T1. What is the final pressure p1 within the apparatus ?
(a) 0.90 (b) 1.16 2pT2 2pT2
(c) 1.41 (d) 1.76 (a) (b)
2T2 + T1 T2 + 2T1
16. The average kinetic energy of 28 g CO at, 300 K is E kcal.
The average kinetic energy of 2 g H2 at the same temperature pT2 2pT2
would be..... kcal. (c) (d)
2T2 + T1 T1 + T2
(a) E (b) 14 E 24. The molecular velocities of two gases at the same temperature
(c) 1/14 E (c) 28 E are u1 and u2 and their masses are m1 and m2 respectively.
17. The critical temperature of water is higher than that of O2 Which of the following expressions are correct ?
because the H2O molecule has m1 m2
(a) fewer electrons than O2 (a) = (b) m1u1 = m 2 u 2
u12 u 22
(b) two covalent bonds
(c) V-shape m1 m 2
(c) = (d) m1u12 = m 2 u 22
(d) dipole moment. u1 u2
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
136 Chemistry
39. A mixture of 1 mol of H 2 and 1 mole of Cl 2 with little 41. A closed vessel contains He and Ozone at pressure of P
charcoal in a 10 L evacuated flask was irriadiated with light atm. The ratio of He and oxygen atoms is 1 : 1. If He is
until the reaction was completed. Subsequently 5L of water removed from the vessel, the pressure of the system will
was introduced into the flask and the flask was cooled to reduce to
27°C. The pressure exerted by the system is approximately (a) 0.25 P (b) 0.5 P
equal to (c) 0.75 P (d) 0.33 P
42. The factor that has the largest effect on vapour pressure of
2 ´ 0.0821´ 300
(a) atm a liquid is
5 (a) liquid surface area
(b) » 26 mm Hg (b) molecular dipole moment
2 ´ 0.0821 (c) presence of H-bonding
(c) atm (d) molecular mass of liquid
10
43. The molecular mass of a compound does not effected by
4 ´ 0.0821´ 300 (a) vapour pressure of a liquid
(d) atm
5 (b) vapour density
40. The relative humidity of air is 80% at 27°C. If the aqueous (c) vapour pressure of solid
tension at the same temperature is 27 mm Hg. The partial (d) molar volume of vapour
pressure of water vapour in the air will be 44. Which of the following liquids has the highest viscosity?
(a) 21.60 mm Hg (b) 27 mm Hg (a) Benzene (b) Carbon disulphide
(c) 25 mm Hg (d) 23 mm Hg (c) Acetone (d) Ethanol
JEEMAIN.GURU
downloaded from jeemain.guru
P1 d T 1 2 r1 d2 16
4. (a) P d and T, = 1 1 = ´ Þ P1 : P2 = 1 : 1 18. (b) = = = 4 :1
P2 d 2 T2 2 1 r2 d1 1
JEEMAIN.GURU
downloaded from jeemain.guru
138 Chemistry
3RT U CO 2 TCO 2 ´ M N 2 O
19. (c) r U and U = =
M 31. (a)
U N 2O M CO 2 ´ TN 2 O
r1 TM rN T1 ´ 64
= 1 2 or 2
= = 1.625 or
r2 T2 M1 rSO 2 323 ´ 28 x TCO2 44
= ´ TN 2O = 16TCO 2
4x 44 TN 2O
T2 = 373K
2 Mx 1
20. (a) = M x = 64 32. (d) U hence hydrogen (molecular weight being the
1 16 M
lowest) has the maximum root mean square velocity.
21. (b) For effusion of same volume,
t1 M1 t1 t2 U1 d2 1
= = 33. (c) = = =1: 4
t2 M2 U2 d1 16
M1 M2
This is clearly seen from the options that the ratio of U1 T1M 2
34. (b) Apply =
t æ U2 T2 M1
5 20 5 ö
is same for H2 and O2. ç = = ÷÷
M ç
è 2 32 2ø
3RT U1 T1 1200 1
35. (b) U = = = = 2; U2 = U1
M N2 M U2 T2 300 2
rx 28 56 1
22. (a) = = = or rN 2 = 79.19 mls -1
rN 2 Mx 56 rN 2 2 36. (d)
23. (d) NO and C2H6 both have same molecular weight. Hence 37. (b) Due to intermolecular interactions appreciable at high P
their rate of diffusion will be same. and low T, the ideal gas deviates from ideal behaviour.
1 PV
38. (b) Ideal gas strictly follows PV= nRT, Z= =1
24. (d) Rate . The smaller the value of M the more is the nRT
M
rate of diffusion 39. (c) Ideal behaviour at low P and high temperature. The larger
25. (a) At the same temperature KE is the same, as KE T.. the volume the lesser are the interactions, higher the
temperature the more is KE the lesser are interactions
26. (a) The gas molecules are tiny particles and not rigid in nature
between the molecules.
rather they are perfect elastic bodies
PV
3 3 8.313 40. (b) Z = <1 nRT > PV
27. (b) KE = kT = ´ ´ 298 = 6.17 ´10-21 J . nRT
2 2 6.023 ´1023
or 1´ 0.0821´ 273 > 1´ V or V < 22.4
(Average Kinetic energy KE = 3 kT = 3 R T )
2 2 N æ MP ö
41. (b) Higher P lower T greater the density. ç d = ÷
è RT ø
1 2 1 2 2 2
28. (d) PV = mnU = ´ mU = KE = KT .
3 3 3 3
42. (b) PV = RT , PV = w RT , 20P = 120 ´ .0821 ´ 400
M 40
The product PV will have constant value at constant
temperature. This is Boyle’s law or P = 4.92 atm
TN 2 > TH 2
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
140 Chemistry
7. (a) Given 16. (b) According to kinetic theory the gas molecules travel in a
P1 = 1.5 bar T1 = 273 + 15 = 288 K V1 = V straight line path but show zig-zag motion due to
P2 = 1.0 bar T1 = 273 + 25 = 298K V2 = ? collisions.
PV
1 1 = P2V2 3
K ´ 313
T1 T2 K.E of neon at 40 °C 313
17. (a) = 2 =
K.E of neon at 20°C 3 293
1.5 ´V 1´V2 K ´ 293
= 2
288 298
V2 = 1.55 V i.e., volume of bubble will be almost 1.6 time 18. (a) In van der waal's equation ‘b’ is for volume correction
to initial volume of bubble. 19. (c) As temperature rises the most probable speed increases
and the fraction of molecules possessing most probable
VA VB MB speed decreases.
8. (c) =
tA tB MA
20. (a) Particle size of colloidal particle = 1m m to 100 m m
(suppose 10 ml)
200 36 4 36
Þ = Þ =
150 MA 3 MA 4 3
Vc = pr
3
16 36 81
Þ = Þ MA = = 20.25
9 MA 4 4 3
= Vc = p(10)
9. (b) t1 - Time taken by unknown gas 3
t2 - Time taken by helium
Particle size of true solution particle = 1m m
M1 - Molar mass of unknown gas
M2 - Molar mass of helium 4 3
Vs = p (1)
t1 = 3t2 3
t1 M1 3t M1 Vc
= Þ 2 = 3
t2 M2 t2 4 hence now = 10
Vs
JEEMAIN.GURU
downloaded from jeemain.guru
æ 2.06 96.0
an2 ö 5. (c) Moles of H 2 = ; Moles of O 2 = = 6 Total
ç P + 2 ÷ (V - nb) = nRT 2 16
ç V ÷ø
è moles = 8
æ a ö 2 1
PH = P = (partial pressure = Mole fraction × Total
çç 100 + 2 ÷÷
(0.112 - 0) = 0.0821´ 273 2 8 4
è (0.112) ø
pressure )
a = 1.253 L2 mol–2 atm
JEEMAIN.GURU
downloaded from jeemain.guru
142 Chemistry
17. (d) Critical temperature of water is higher than O2 because
V1 V2
6. (b) Let the original volume be V then = at constant H2O molecule has dipole moment which is due to its
T1 T2
V-shape.
V V 18. (d) Let V be the original volume of bubble. The final volume
P, = \ T2 = 600K = 327°C
300 ´ 2 T2 will be 8 V. Let p be the atmospheric pressure and p1 the
7. (c) When vessels are joined the volume is doubled and pressure at the bottom
pressure is reduced to half \ Pressure of mixture
\ p × 8 V = p1 × V;;
200 400
= + = 300mm 8p = p1
2 2
8. (b) P,V and R are constant p1 = atmospheric pressure + pressure due to water lake
\ n l T1 = n 2T2 ,100 ´ 300 = n 2 ´ 500, : n 2 = 60 = p + 7p
Air escaped is 40%. The p = 10 m high, the 7p will be = 70 m high
9. (c) Pressure of gas = (Total pressure of gas - aqueous So the depth = 70 m
tension ) = 751-21 = 730 mm = 0.96 atm.
1 rSO2 P1 M He
10. (d) Moles of 0.5 litre of N 2 = ´ 0.5 = 0.02, 19. (a) =
22.4 rHe P2 M SO 2
JEEMAIN.GURU
downloaded from jeemain.guru
1 1 V1
24 (d) U1 and U 2 But V2 = (given)
m1 m2 2
1
U 12
m
\ = 2 \ m1 U12 = m 2 U 22
2
2
U2 m1 æ ö
ç ÷
V
\ T2 = T1 ç 1 ÷ = T1 2
æ a ö ç V1 ÷
25. (a) van der Waals eqation is ç p + ÷(Vm - b ) = RT ç ÷
ç Vm2 ÷ è 2 ø
è ø
29. (b) Let the difference in two columns be h. Since the
V
Where Vm = = molar volume. At low pressure Vm is atmospheric pressure is more.
n
\ 60 = 74 – h
high and b can be ignored
or, h = 74 – 60 = 14 cm
æ a ö
\ç p + ÷Vm = RT or pVm + a = RT Thus Hg will stand in column B = 84.5 – 14 = 70.5 cm
ç Vm2 ÷ Vm
è ø 30. (a) The final volume will be V1 + V2 + V3 (Amagat’s law).
a pVm a 4 3
\ pVm = RT - or =1- 31. (b) The volume of the balloon = pr
Vm RT RTVm 3
a aP æ 1ö 3
or Z = 1 - = 1- çè since V µ ÷ø 4 22 æ 21 ö
RTVm RT P = ´ ´ ç ÷ = 4851 ml
3 7 è2ø
26. (d) The given equation is cubic equation in the variable V
and, therefore, for a single value of P and T, there should Volume of the cylinder = 2820 ml
be three values of V, all of which may be real or one real
and two imaginary. 20 ´ 2820 ´ 273
Volume of H 2 at NTP = ml
At Tc there values of V become identical. 300 ´ 1
1 = 51324 ml
27.(d) PV = NmU 2rms
3 After filling the cylinder will have H 2 equal to its volume
1 = 2820 ml
æ 3KT ö 2
\ U rms =ç ÷ \ Volume of H 2 for filling balloons = 51324 – 2820
è m ø
= 48504 ml
1 2 3
KE = mv = KT 51324
2 2 Hence no. of balloon to be filled = = 10
3
2820
28. (c) PV 2 = constant.
15 ´ 273 ´ 740
32. (a) 15 L (20°C, 740 mm) = = 13.61 L (NTP)
nRT 293 ´ 760
Again P =
V
13.61
3 70% N 2 = ´ 70 = 9.527 L (NTP)
nRT 100
\ ´V2 = constant (K)
V
28´ 9.527
1 9.527 L (NTP) of N 2 = = 11.91 g
K 22.4
or, TV 2 = = K' (constant)
nR
33. (b) p N 2 = r - rO2 = 90 - 63 = 27 cm
1 1
2 2
For two states, T1V1 = T2 V2 p N2 = mole fraction of N 2 ´ P
1 \ 27 = X N 2 × 90
2
æV ö
T2 = T1çç 1 ÷÷ \ X N 2 = 0.3
è V2 ø
JEEMAIN.GURU
downloaded from jeemain.guru
144 Chemistry
34. (a) Let the distance be x metre.
48
Moles of dimer = = 0.5
R NH3 x M HBr 81 96
\ = = =
R HBr 1- x M NH3 17
1.5 ´ 0.0821 ´ (273 + 273)
\ P= = 2.00 atm
\ x = 0.6856 = 68.56 cm 33.6
JEEMAIN.GURU
downloaded from jeemain.guru
6
Thermodynamics
It is the branch of chemistry which deals with the energy changes EXTENSIVE PROPERTIES :
taking place during physical and chemical changes. The properties which depend upon the quantity of the substance
Terminology used in thermodynamics :- or substances present in the system e.g. volume, enthalpy, free
energy, entropy, heat capacity.
SYSTEM :
A system is that part of universe which is under investigation . INTENSIVE PROPERTIES :
The properties which are independent of the quantity of the
SURROUNDINGS :
substance present in the system e.g. density, molar volume,
The part of the universe other than the system is known as temperature, melting point, boiling point, freezing point etc.
surroundings. Note – Any extensive property if expressed as per mole or per gm
Thus universe = system + surroundings becomes intensive property e.g. mass and volume are extensive
In simple case surroundings implies air or water both. properties but density is an intensive property.
TYPES OF SYSTEM : STATE VARIABLES AND STATE FUNCTIONS :
(i) Open system - A system which can exchange matter as well These are the macroscopic properties of the system which change
as energy with surroundings. with the change in the state of system. They depend upon the
(ii) Closed system – A system which can exchange energy and initial and final state of system. They are temperature, pressure,
not matter with surroundings. volume, chemical composition, energy, entropy, free energy.
(iii) Isolated system - A system which can exchange neither INTERNAL ENERGY, INHERENT ENERGY OR
matter nor energy with surroundings. HIDDEN ENERGY (IE) :
(iv) Homogeneous system – A system consisting of one phase It is the sum of all types of energies (as given below) associated
only e.g. pure solid, a liquid or a mixture of gases. with a system or substance.
(v) Heterogeneous system – It may consists of two or more (i) Translational energy of the molecules, Et
phases e.g. a solid in contact with liquid etc. (ii) Rotational energy, Er
STATE OF SYSTEM : (iii) Vibrational energy, Ev
(iv) Electronic energy, Ee
The condition of existence of a system when its macroscopic
(v) Nuclear energy, En
properties have definite values is known as state of system e.g.
(vi) Interaction energy of molecules, Ei
at 1 atm pressure H2O is (a) Solid below 0°C, (b) liquid between
E = Et + Er + Ev + Ee + En + Ei
0°C - 100°C and (c) gas above 100°C.
It is a state function, depends upon chemical nature of the
MACROSCOPIC PROPERTIES : substance, amount, temperature, pressure etc. Its absolute
The properties which arise out of collective behaviour of large value cannot be determined but change during a chemical
number of chemical entities e.g. pressure, volume, temperature, process can be determined.
composition, colour, refractive index etc. DE = Eproducts - E reactants = EP - ER
JEEMAIN.GURU
downloaded from jeemain.guru
146 Chemistry
If E P > E R DE = +ve change is endothermic (iv) Isochoric process ( DV = 0) : Volume remains constant but
If E P < E R DE = - ve change is exothermic pressure changes.
JEEMAIN.GURU
downloaded from jeemain.guru
Thermodynamics 147
SIGNIFICANCE OF DE : DE AND DH FOR MONOATOMIC GAS :
It represents the heat change taking place during the process For such a gas
occuring at constant volume and constant temperature.
3
q v = DE Internal Energy = KE = RT per mole and
2
ENTHALPY (H) AND ENTHALPY CHANGE (DH) :
Enthalpy is the heat content of the system and related to internal 3
Enthalpy = RT + PV
energy as follows. 2
H = E + PV
3 5
We can measure change in enthalpy and not absolute value of = RT + RT = RT per mole (Q PV = RT )
enthalpy. It is a state function. 2 2
JEEMAIN.GURU
downloaded from jeemain.guru
148 Chemistry
Work done in adiabatic irreversible expansion MOLAR HEAT CAPACITY FOR POLYATOMIC GAS AT
w irr = -Pext DV = -Pext (V2 - V1 ) CONSTANT VOLUME :
3
é RT2 RT1 ù R [ P1T2 - P2 T1 ] Cv = R+X
= - Pext ê - ú = - Pext 2
ë P2 P1 û P1 P2
MOLAR HEAT CAPACITY FOR POLYATOMIC GAS AT
During expansion in vacuum
CONSTANT PRESSURE :
Pext = 0, work done = 0, DE = w = 0 also DT = 0 and DH = 0
5
If V2 > V1 then Wirr = - ve i.e. expansion work or work done by Cp = R+X
2
system. For monoatomic gas X=0, for diatomic gas X=R and for triatomic
If V2 < V1 then Wirr is +ve i.e. compression work or work done
3
on the system. gas X = R
2
HEAT CAPACITY OF A SYSTEM :
LIMITATION OF FIRST LAW OF
It is the amount of heat required to raise the temperature of the
THERMODYNAMICS:
system by 1 degree (K or °C)
It fails to predict the feasibility and the direction of the change
q
C= . SPONTANEOUS PROCESS :
m(T2 - T1 )
A process which has an urge or a natural tendency to occur
In case of single substance, when m=1 g, C is the specific heat of either of its own or after proper initiation under a given set of
system; when m = Mg or 1 mole, it is molar heat capacity. Since conditions. It is irreversible process and may only be reversed
heat capacity varies with temperature its true value is given by by some external agents.
dq (i) Spontaneous processes that need no initiation
C= (differenti al equation ) ; (a) Evaporation of water H2O (l) ® H2O (g)
dt
(b) Dissolution of sugar
dE æ E ö C12H 22O11 (s) ® C12 H 22O11 (aq.)
Heat capacity at constant volume C v = =ç ÷
dt è T ø v
(c) Intermixing of gases
Heat capacity at constant pressure (ii) Spontaneous processes that need initiation
dq dH æ H ö Electric, discharge
(a) 2 H 2( g ) + O 2(g ) ¾¾ ¾ ¾ ¾ ¾¾® 2H 2 O (l )
Cp = = =ç ÷
dt dt è T ø p
(b) Electrolysis of water 2H 2O(l ) ® 2H 2 (g) + O2 (g)
Also C p = c p ´ M and C v = c v ´ M It requires continuous supply of energy.
where c P &c v are specific heats at constant pressure and SECOND LAW OF THERMODYNAMICS :
constant volume respectively. The entropy of the universe increases in every spontaneous
(natural) change. The entropy of the universe is continuously
C P & C v are molar heat capacities at constant pressure and
increasing.
constant volume respectively. Other statements of second law of thermodynamics
Dulong and Petit’s rule : Atomic mass × specific heat = 6.4
(i) Clausius : Heat cannot itself pass from a colder body to
The rule is valid for solid elements except Be, B, Si and C. a hotter body.
Units : In SI units the specific heat or molar heat is expressed in (ii) Kelvin : It is impossible to get a continuous supply of work
terms of Joules ( 1 Cal = 4.184 J)
from a body or engine which can transfer heat from a single
MOLAR HEAT CAPACITY OF A MONOATOMIC GAS heat reservoir.
AT CONSTANT : (iii) Planck : It is impossible to construct a device which will
3 work in a single complete cycle and convert heat into
volume C v = R work without producing any change in the surroundings.
2
(iv) All natural and spontaneous processes take place in one
MOLAR HEAT CAPACITY OF A MONOATOMIC GAS direction and thus are irreversible in nature.
AT CONSTANT PRESSURE : (v) In a reversible process the entropy of the universe is
5 constant. In an irreversible process the entropy of the
Cp = R universe increases.
2
JEEMAIN.GURU
downloaded from jeemain.guru
Thermodynamics 149
ENTROPY (S) : CRITERIA FOR FEASIBILITY OR SPONTANEITY OF
It is a measure of degree of disorder or randomness in a system. A PROCESS :
More the disorder or randomness, the more is entropy.Heat added Enthalpy or entropy alone cannot predict the spontaneity of a
to a system increases randomness and hence the entropy. Heat change. Gibb’s free energy is very useful factor for this
added to a system at lower temperature causes greater randomness G = H – TS
than the system at higher temperature. At higher temperature the DG = DH – TDS (at constant T)
system already has higher randomness. Thus entropy change is DSTotal = DSsys + DSsurr > 0
inversly proportional to temperature. DH surr DH sys
DS surr = =- since
qrev T T
DS = Heat lost by system = Heat gained by surroundings and
T
vice versa.
For a spontaneous process
DSTotal = DSsystem + DSsurr > 0 æ DH sys ö
DSTotal = DSsys + çç - ÷
or DSuniverse >0
è T ÷ø
TDSTotal = TDSsys – DHsys
UNITS OF ENTROPY : = –(DHsys – TDSsys)
Jmol -1K -1 ; It is a state function. The change in entropy is = –(DG)
Hence,
represented by (i) If DG is negative, the process is spontaneous
DS = (Sfinal – Sinitial) = qrev / T (ii) If DG is zero, the process is in equilibrium
qrev is the heat absorbed by the system in a reversible manner (iii) If DG is Positive the process does not occur
and isothermally.
STANDARD FREE ENERGY CHANGE (DG°) AND
ENTROPY CHANGE FOR AN IDEAL GAS UNDER EQUILIBRIUM CONSTANT (K) :
DIFFERENT CONDITIONS: WITH CHANGE IN P, V They are related as follows DGº = –2.303 RT log K
AND T :
FREE ENERGY CHANGE AND CELL POTENTIAL :
T2 V DGº = - nFEº
DS = C V ln + R ln 2 (when T and V are two variables)
T1 V1 VARIATION OF FREE ENERGY WITH
TEMPERATURE AND PRESSURE IN A REVERSIBLE
T2 P
DS = C P ln + R ln 1 (when T and P are two variables) PROCESS :
T1 P2
dG = VdP - SdT
V2 P The equation is called the total differential equation.
For isothermal process (DT = 0), DS = R ln = R ln 1 (a) If temperature is kept constant dT=0 we have
V1 P2
æ Gö
T
(dG )T = (VdP )T or ç ÷ =V
For isobaric process (DP = 0), DS = C P ln 2 è P øT
T1 (b) If pressure is kept constant dP = 0 we have
æ Gö
For isochoric process (DV = 0), DS = CV ln
T2 (dG )P = - (SdT )P or ç ÷ = -S
T1 è T øP
HELMHOLTZ FREE ENERGY (WORK FUNCTION) DS total = 0 , the process is reversible and system is in
(A): The maximum work obtainable from a system is given equilibrium when internal energy and volume are kept
by this energy. constant
( DS ) E, V > 0 the process is irreversible and if ( DS) E ,V = 0 ,
A = E - TS ; E= Internal energy, S = Entropy, T= Temperature
the process is reversible.
JEEMAIN.GURU
downloaded from jeemain.guru
150 Chemistry
(ii) Internal energy : When entropy and volume kept constant (i) For water (liquid ) = water (vapour) we have
If (DE) S, V < 0 , the process is irreversible and if dP DH V
=
( DE) S, V = 0 , the process is reversible. dT T(Vg - Vl ) ;
(iii) Enthalpy (H) : When entropy and pressure are kept constant DH V = molar heat of vaporisation ,
( DH) S,P < 0 , the process is irreversible and if (ii) For water (Solid, Ice) = water (liquid)
( DH) S,P = 0 , the process is reversible. dP DH f
= ;
(iv) Work function : (A) when temperature and volume are kept dT T (Vl - Vs )
constant
DH f = molar heat of fusion of ice
( D ) T ,V < 0 , the process is irreversible and if (iii) For solid = vapour equilibrium
( DA) T ,V = 0 , the process is reversible. dP DH s
=
(v) Free energy (G) : When pressure and temperature are kept dT T(Vg - Vs ) ; DH s = molar heat of sublimation
constant
INTEGRATED FORM OF CLAPEYRON - CLAUSIUS
( DG ) P ,T < 0 , the process is irreversible and if
EQUATION :
( DG ) P,T = 0 , the process is reversible. For Liquid = gas system in Equilibrium
NOTE : Criteria of feasibility or spontaneity in terms of free P2 DH v é T2 - T1 ù
energy is most important since most of the processes are carried log = ê ú
P1 2.303R ë T1T2 û
out at constant temperature and pressure.
ZEROTH LAW OF THERMODYNAMICS : APP LICATIONS OF CLAPE YRON C LAUSIUS
If two bodies have separately equality of temperature with a
EQUATION :
third body, they also have equality of temperature with each (i) Calculation of molar heat of vaporisation
other. (ii) Effect of temperature on vapour pressure of a liquid
(iii) Effect of pressure on boiling point
THIRD LAW OF THERMODYNAMICS :
(iv) Calculation of molal elevation constant (kb) and molal
At absolute zero temperature, the entropy of a perfectly crystalline depression constant (kf ) of a solvent.
substance is taken as zero. This law was formulated by Nernst in
1906. 0.002T 2
kb =
Calculation of absolute value of entropy: lv
Let S0 be the entropy of substance at 0 K and S be its entropy at lv= latent heat of vaporisation per gram of solvent
T K. T= boiling point of pure solvent
T
Cp 0.002T2
DS = S0 - S = dT kf =
T lf
0
T= freezing point of solvent
Where Cp is the heat capacity of the substance at constant
lf = latent heat of fusion per gram of solvent
pressure. According to the third law
HEAT ENGINE :
T
Cp Machine which converts heat into work is called heat engine.
S0 = 0, thus S = dT .
T EFFICIENCY OF HEAT ENGINE :
0
The fraction of the heat absorbed, converted into work is called
The value of the integral can be obtained from a plot of the efficiency of machine.
CP / T Vs T. The area under the curve between 0 and T K gives the
W Work done
value of the integral and hence of S at temperature T. h= =
Q Heat absorbed
CLAPEYRON - CLAUSIUS EQUATION :
CARNOT CYCLE :
It gives the change in pressure dP accompanying change in
temperature dT or vice versa for a system containing two phases It is a process where a system after undergoing a number of
of a pure substance in equilibrium, q is heat exchanged reversibly successive changes returns to its original state. It consists of
per mole of the substance during the phase transformation at four different operations.
temperature T. (i) Isothermal expansion
(ii) Adiabatic expansion
dP q (iii) Isothermal compression
=
dT T (VB - VA ) (iv) Adiabatic compression
JEEMAIN.GURU
downloaded from jeemain.guru
Thermodynamics 151
EFFICIENCY OF CARNOT CYCLE OR ENGINE : TYPES OF REACTIONS AND CORRESPONDING
ENTHALPY CHANGES :
W T -T Q - Q1
h= = 2 1= 2 (i) Heat of reaction at constant volume and certain temperature
Q T2 Q2
It is defined as the change in internal energy ( DE ) of the
system when requisite number of molecules of reactants
T2 - T1
Since is always less than unity, hence efficiency
T2 react to form the products. ( DE ) = E p - E r = q v = heat of
reaction at constant volume
is always less than unity
(ii) Heat of reaction at constant pressure and certain
CARNOT THEOREM : temperature
Efficiency of reversible heat engine is independent of the nature
It is defined as the difference in enthalpies ( DH ) of products
of working substance and depends upon the temperature of
source and sink. and reactants DH = H p - H r = q p = heat of reaction at
Or constant pressure
All machines working reversibly between the same temperature (iii) Relation between heat of reaction at constant volume ( q v )
of source and sink have same efficiency.
RESONANCE ENERGY : and at constant pressure ( q p )
JEEMAIN.GURU
downloaded from jeemain.guru
152 Chemistry
(xi) Heat of neutralization : It is defined as the enthalpy change In polyatomic molecules the bond dissociation energy is
( DH ) accompanying the neutralization of one gram not the same for successive bonds though the bonds are of
equivalent of the acid by a base in dilute solution at that the same type.
temperature.
H3C - H = +425 kJ mol-1 ;
HCl (aq) + NaOH(aq) ® NaCl(s) + H 2O(aq);
H 2 C - H = +470 kJ mol-1
DH = -57.32kJ
Heat of neutralization of every strong acid by a strong base HC - H = +416 kJ mol-1 ;
is identical. When acid or alkali is weak the heat of
neutralization is different because the reaction involves the C - H = +335 kJ mol-1
dissociation of the weak acid or the weak alkali.
Heat of neutralization of weak acids with NaOH at 25°C 425 + 470 + 416 + 335
Hence C - H Bond energy =
Acid Heat of Heat of 4
neutralisation dissociation = 411.5kJ mol-1
(kJ per g eq.) (kJ per g eq.)
Acetic acid –55.23 +2.09 (xvii) Use of bond enthalpy :
Formic acid –56.06 +1.26 (1) Calculating standard enthalpy of reactions
Hydrocyanic acid –12.13 +45.19
DH =[sum of bond energies of reactants]
Hydrogen sulphide –15.90 +41.42
– [sum of bond energies of products]
(xii) Heat of solution : The enthalpy change per mole of solute
= [ Total energy required for breaking the bonds]
when it is dissolved in large excess of solvent (generally
– [Energy given out in forming the bonds]
H2O) so that further dilution of the solution produces no
(2) Calculation of bond energy of some specific bond in the
heat exchange.
molecule
KCl + aq ® KCl(aq) ; DH = 4400 cal (18.58kJ)
THE LAWS OF THERMOCHEMISTRY :
MgSO 4 + aq ® MgSO 4 (aq) ; DH = -20280 cal (1) Lavosier and Laplace law : The heat evolved or absorbed
(xiii) Heat of dilution : The enthalpy change when a solution in the course of a chemical reaction is equal to the heat
containing one mole of a solute is diluted from one absorbed or evolved when the reaction is reversed.
concentration to another.
1 1
(xiv) Heat of hydration : The enthalpy change when one mole of H 2 (g) + Cl 2 (g) ® HCl(g) ; DH = - 92.0 kJ
2 2
a substance combines with the required number of moles of
1 1
water to form a specified hydrate. HCl(g) ® H 2 (g) + Cl 2 (g) ; DH = + 92.0 kJ
Heat of hydration = Heat of solution of the hydrated 2 2
compound – Heat of solution of the unhydrated compound (2) Hess’s law of constant heat summation
(xv) Heat of precipitation : The enthalpy change when one mole TROUTON’S RULE :
of a sparingly soluble substance precipitates on mixing dilute
Fredrick Trouton (1884) found that for many liquids molar heat of
solutions of stable electrolytes is called heat of precipitation.
vaporization in calories per mole divided by the normal boiling
BaCl 2 (aq.) + Na 2SO 4 (aq.) ¾
¾® BaSO4 (s ) + 2 NaCl(aq.) ; point in degree kelvin is a constant.
DH = -19.50 kJ DH v
= 21 cal / kmol = 88 J / K mol
(xvi) Bond enthalpy : It is defined as the average amount of energy Tb
required to break all the bonds of a particular type in one
DH v
mole of the substance. It is also known as bond energy and The quantity is also called entropy of vaporization DSv.
expressed in kJ mol–1. Tb
In a diatomic molecule the bond energy and bond ENDOTHERMIC COMPOUNDS :
dissociation energy are the same. The compounds having positive values of formation are called
endothermic compounds. Ozone is an example.
JEEMAIN.GURU
downloaded from jeemain.guru
Thermodynamics 153
1. Six moles of an ideal gas expand isothermally and reversibly Sol. Work done is irreversible as at constant pressure,
from a volume of 1litre to a volume of 10 litres at 27º C. What
DV = 5 – 3 = 2 dm3 = 2 lit.
is the maximum work done? Express the results in various
units. W = – PDV = – 3 × 2 = – 6 atm. lit. = – 6 × 101.3J
Sol. Work done = 607.8J
This work is used for heating water W = m × s × DT
V2 V
W = nRT ln = 2.303nRT log 2 607.8 = 10 × 18 × 4.184 × DT
V1 V1
Therefore DT = 0.807
10 Hence final temperature = 290 + 0.807 = 290.807 K
= 2.303 ´ 6 ´ 0.0821 ´ 300log = 340.3 lit. atm. 5. 10 g of argon gas is compressed isothermally and reversibly
1
at a temperature of 27º C from 10 litres to
If we put the value of
5 litres. Calculate q, w, DE and DH for this process. R=2.0
R= 8.314 J K–1 mol–1 W = 34464.8J cal K–1 mol–1 log 2 = 0.3010
Atomic weight of Argon = 40
R = 8.314 ´10 7 ergs K -1mol -1 W = 3.44 ´1011 ergs
R = 1.987 cal K -1 mol -1 W = 8236.91 cal V2 10 5
Sol. W =- 2.303nRT log =- 2.303 ´ ´ 2 ´ 300 log
V1 40 10
2. A system performs 101.3J of work on its surroundings and
absorbs 15 kJ of heat from surroundings. What is the change W = 103.635 cal
in internal energy of the system. For isothermal proccess DE = 0, q = –W = – 103.635 cal
Sol. Work done by the system is taken as negative DH = 0
W = –101.3J 6. Show that in an isothermal expansion of an ideal gas
Heat absorbed by the system is taken as positive (a) DE = 0 and (b) DH = 0
q = 15kJ = 15000 J Sol. (a) For one mole of a gas Cv= [ E / T]v
DE = q+w ( First law of thermodynamics) For finite change DE = Cv DT
=15000J-101.3J= 14898.7J For isothermal process DT = 0 therefore DE = 0
3. One mole of liquid water at its boiling point vapourises (b) We know that DH = DE + D( PV) = DE + D( RT)
against a constant external pressure of 1 atm. at the same
(PV = RT)
temperature. Assuming ideal behaviour and initial volume
of water vapours as zero, calculate the work done by the Therefore DH = DE + RDT. Since DT = 0, DE = 0, therefore
system. DH = 0.
7. Calculate the change in free energy at 25º C for the reaction
Sol. For ideal behaviour of water vapour PV = nRT can be applied
to find the volume. 1
CO(g) + O2 (g) ® CO2 (g) DH = -67.37 kcal
1 × V = 1 × 0.0821 × 373 2
V = 30.62 lit. and the change in entropy accompanying the process is –
DV = V2 - V1 = 30.62 lit. – 0 lit. = 30.62 lit. 20.7 cal deg–1 mol–1
Sol. DG = DH – TDS
work done = – PDV = –1 × 30.62 = – 30.62 lit atm.
= – 67.37 – 298 (–20.7 × 10–3)
= – 30.62 × 101.3J = -3101.8 J
= -61.2014 kcal mol -1
4. A gas expands from 3 dm3 to 5 dm3 against a constant
pressure of 3 atm. The work done during expansion is used 8. Calculate DH, DS, DG and DE when 1 mole of water is
to heat 10 mole of water of temperature 290 K. Calculate the vapourised at 100º C and 1 atm pressure. The latent heat of
final temperature of water. Specific heat of water is vapourisation of water is 540 cal g–1
4.184 Jg–1 K–1
JEEMAIN.GURU
downloaded from jeemain.guru
154 Chemistry
Sol. (i) 1 mole of water is 18 g therefore enthalpy change (i) Latent heat of fusion for 900 g ice
DH = 18 × 540 cal = 9720 cal
900 ´ 5.99
(ii) Entropy change DS = DH/ T = 9720/373 DH fus = kJ = 299.5kJ
18
= 26.06 cal K–1
(iii) Free energy change DG = DH – TDS DH fus 299.5 ´1000
DS = = = 1097 JK -1
DG = 9720 – 373 × 26.06 = 0 T 273
(iv) DH = DE + PDV DH fus
(ii) DS for freezing of liquid water = -
therefore DE = DH – PDV = DH – P(V2 – V1) T
V1 = Volume of 1 mole of liquid water = 18 cm3 when liquid water freezes heat is evolved
V2 = Volume of 1 mole of steam at 373 K 5.99 ´ 1000
DS = - = - 21.94 Jmol -1K -1
Applying ideal gas equation, 273
11. Calculate the entropy change in isothermal reversible
P1V1T2 1´ 22400 ´ 373 expansion of 5 moles of an ideal gas from a volume of 10
V2 = =
P2 T1 1´ 273 litres to a volume of 100 litres at 300 K.
Sol. For isothermal process T1 = T2 hence the equation
V2 = 30600 cm3 T2 V
DS = C v ln + nR ln 2 is reduced to
DV= V2 – V1 = (30600 – 18) cm3 = 30600 cm3 T1 V1
(18 negligible) V2 V
3 DS = nR ln = 2.303nR log 2
PDV =1atm ´ 30600 cm = 1 ´ 30.6lit. = 30.6 lit atm. V1 V1
Given n = 5,
30.6 × 24.2 cal = 740.5 cal (1atm lit = 24.2 cal)
V1 =10 litres, V2 = 100 litres, R = 8.314JK -1mol -1
Hence DE = DH – PDV = 9720 – 740.5 = 8979.5 cal
100
9. A certain volume of dry air at NTP is expanded reversibly to DS = 2.303´ 5 ´ 8.314 log = 95.75JK -1
three times its volume (a) isothermally (b) adiabatically. 10
Calculate the final pressure and temperature in each case, 12. Calculate the temperature at which the reaction
assuming ideal behaviour. (Cp/Cv for air is 1.4) 1
Ag 2 O(s) ® 2Ag(s) + O 2 (g) at 1 atmospheric pressure
Sol. Let V1 be the initial volume of dry air at NTP 2
(a) Isothermal expansion. Since will be in equilibrium. The value of DH and DS for the
reaction are 30.58 kJ and 66.11JK–1 respectively and these
DT = 0 hence P1V1 = P2 V2 value do not change much with temperature.
Sol. DG = DH - T DS for equilibrium DG = 0
P1V1 1´ V1
P2 = = = 0.333 atm
V2 3V1 DH DH 30580
DS = T= = = 462.6 K
T DS 66.1
(b) Adiabatic expansion we have 13. Calculate the standard entropy change for the reaction
-1 1.4 -1 A B if the value of DHº = 28.40kJ mol -1 and
T1 é V2 ù 273 é 3V1 ù
=ê ú or =ê ú equilibrium constant is 1.8 × 10-7 at 298K
T2 ë V1 û T2 ë V1 û
Sol. DGº = - 2.303RT log K
c
JEEMAIN.GURU
downloaded from jeemain.guru
Thermodynamics 155
DGº = - 2.303RT log K c 18. The heats of combustion of C2 H 4 ( g ) , C2 H 6 ( g )
3
DGº -28.4 ´10
log k c = - = = -3.708 and H 2 ( g ) are –1409.5, –1558.3 and –285.6 kJ respectively..
2.303 ´ RT 2.303 ´ 8.314 ´ 400
taking antilog, we get Calculate the heat of hydrogenation of ethylene.
-4 Sol. The desired equation is
K c = 1.995 ´10
1 C 2 H 4 (g) + H 2 (g) ® C 2 H 6 (g)
15. Show that the reaction CO(g) + O 2 (g) ® CO 2 (g) at 300
2 DH = Heat of combustion of reactants
K is spontaneous and exothermic, when the standard entropy – Heat of combustion of products
change is – 0.094 kJ mol–1 K–1. The standard Gibb’s free
= – 1409.5 + (–285.6)–(–1558.3) = –136.8 KJ
energies of formation of CO2 and CO are – 394.4 and –137.2
KJ mol–1 respectively. 19. At 300 K the standard enthalpies of formation of
Sol. The given reaction is C6 H5COOH (s), CO2 (g), and H 2 O (l ) are r e s p e c t i v e l y
1 -1
CO (g) + O 2 (g) ® CO 2 (g) - 408, - 393 and - 286 kJ mol . Calculate the heat of
2
DG ° (for reaction) = G° products – DG ° reactants combustion of benzoic acid at (i) Constant pressure (ii)
Constant volume
= G°CO2 - (G°CO + G°O2 )
(R = 8.314 J mol-1K -1 )
= - 394.4 - (-137.2 + 0) = - 257.2
DGº = DHº - TDSº Sol. DH = Enthalpies of formation of products
- Enthalpies of formation of reactants.
-257.2 = DHº + 298 (0.094) or DHº = -285.2KJ
Since DGº is negative the process is spontaneous and DHº Desired equation is
is also negative the process is exothermic. 15
16. The heat of combustion of gaseous methane CH4 at constant C6H5 COOH(s) + O2 (g) ® 7CO2 ( g) + 3H2O (l )
2
volume measured in bomb calorimeter at 298.2 K is found to
be – 885389 J/mol. Find the value of enthalpy change. DH = 7 ( -393) + 3(-286) - ( -408 - 0) = - 3201kJ
Sol. CH 4 (g) + 2O 2 (g) ® CO 2 (g) + 2H 2 O (l)
Also DH = DE + DnRT
Given DE = - 885389 J mol -1
or –3201 kJ = DE + (-0.5) ´ 8.314 ´10 -3 ´ 300
Dn =1 - (1 + 2) =- 2 T = 298.2 K; R =8.314 JK -1mol-1
D E = - 3199.75 kJ
DH = DE + DnRT
20. Given that the bond enthalpies for C– H, Cl –Cl, C – Cl and
= -885389 + (-2) 8.314 ´ 298.2 H – Cl are respectively 99, 58, 78 and 103 k cal / mol, determine
DH for the reaction
= -890.34 kJ
For solving the heat of reaction follow the following rules CH 4 (g) + Cl2 (g) ® CH3 Cl ( g ) + HCl(g)
(i) When standard enthalpy of formation of compounds
are given, apply the equation Sol. DH (reaction) = Bond energy of (bond broken in reactants
– bond formed in products).
DH = DHº f (products) – DH º f (reaction).
(ii) When heat of combustion of compounds are given apply = Bondenergyof [ (C - H + Cl - Cl) - (C - Cl + H - Cl) ]
the equation =[ (99 + 58) - (78 + 103)] =- 24kcal
DH = DH comb of reactants – DH comb of products.
21. Estimate the S – F bond energy in SF6. The standard heat of
17. The molar heats of combustion of C2 H 2 (g) , C(graphite) formaton values of SF6(g), S(g) and F(g) are –1100, 275 and
and H2 (g) are – 310.62, – 94.05 and – 68.32 kcal respectively. 80 kJ mol–1 respectively.
Calculate the heat of formation of C2H2.
Sol. The desired equation is Sol. SF (g) ® S (g) + 6F (g)
6
DH = (DH S + 6DH F ) - DH SF
2 C (graphite) + H 2 (g) ® C 2 H 2 (g) 6
= 275 + 6 ´ 80 - ( -1100) =1855
DH = Heats of combustion of reactants
- Heats of combustion of products 1855
Average bond energy = = 309.17 kJ
6
= 2 (-94.05) + (-68.32) - (-310.62) = 54.2 kcal
JEEMAIN.GURU
downloaded from jeemain.guru
156 Chemistry
22. The heat of reaction (DH) for the formation of water at 25°C
Sol. W = q(T2 - T1 ) = 1897.86 ´ 373 - 283 = 457.92 kJ
is – 68.4 kcal. Find the value at 90°C. The moler heat capacities T2 373
of H2(g), H2O (l ) are 6.62, 6.76 and 18 cal respectively..
28. Calculate DH at 358 K for the reaction
Sol. DH2 - DH1 = DCp (T2 - T1 )
Fe 2O 3 (s) + 3 H 2 (g) ¾
¾® 2Fe(s) + 3H 2 O(l)
DCp = molar heat capacities of products
Given that DH 298 = – 33.29 kJ mol-1 and Cp for Fe 2O 3 (s),
- molar heat capacities of reactants
Fe(s), H 2 O (l) and H 2 (g) are 103.8, 25.1, 75.3 and 28.85 J/K
1
The formation of water is H 2 + O 2 ® H 2 O mol.
2
Sol. DCp = (2 × 25.1 + 3 × 75.3) – (103.8 + 3 × 28.8)
1
DC p =18 - (6.62 + (6.67) = 8 cal = 8 ´10 -3 k cal = 85.9 J/Kmol
2
DH 2 =- 68.4 + 8 ´10-3 (363 - 298) = - 67.88k cal DH 2 - DH1
= DCp ( Kirchoff ’s equation)
23. The heat of solution of MgSO4 and MgSO4.7H2O are T2 - T1
– 20.3 and 3.8 kcal respectively. Find heat of hydration of
DH 358 - (-33290)
MgSO4. = 85.9
358 - 298
Sol. Heat of hydration = Heat of solution of anhydrous salt
DH 358 = – 28136 J/mol
- Heat of solution of hydrated salt.
= – 28.136 kJ/mol
= -20.3 - (3.8) = - 24.1k cal.
29. Ka for CH 3COOH at 25°C is 1.754 × 10 - 5 at 50°C. Kais
24. Integral heat of solution (DH) for 1 mole of KCl dissolved
in 20 moles of water is + 15.90 kJ. When 1 mole is dissolved 1.633 × 10 - 5 . What are DH° and DS° for the ionisation of
in 200 moles of water, DH is 18.58 kJ. Calculate heat of CH 3COOH ?
dilution.
Sol. (DG°) 298 = – 2.303 RTlog Ka
Sol. KCl (s) + 20H 2 O ® KCl (20 H 2 O) DH1 = 15.90 kJ
= – 2.303 × 8.314 × 298 × log 1.754 × 10 - 5
KCl (s) + 200H 2 O ® KCl (200H 2 O) DH 2 = 18.58 kJ
= – 27194 J
Heat of dilution = DH 2 - DH1 = 18.58 - 15.90 = 2.68 kJ -5
25. At what temperature will water boil when the atmospheric (DG°)323 = – 2.303 × 8.314 × 323×log 1.623 × 10
pressure is 528 mm Hg. Latent heat of vaporisation of water = –29605 J
is 545.5 cal g–1 DG° = DH° – T DS°
Sol. The integrated form of Clapeyron equation is 27194 = DH° – 298 DS°
P2 DH v é 1 1ù 29605 = DH° – 323 DS°
log = ê - ú
P1 2.303R ë T1 T2 û DH° = – 1.55 KJ/mol
DS° = – 96.44 J/mol
Here P1 = 528 mm Hg; P2 =1atm = 760mm Hg; T1 = ?; 30. Calculate the heat of neutralisation from the following data
T2 = 100°C = 373K 200 ml of 1 M HCl is mixed with 400 ml of 0.5 M NaOH. The
temperature rise in the calorimeter was found to be 4.4°C.
DH v = 545.5 cal g -1 = 545.5 × 18 = 9819 cal mol–1 Water equivalent of calorimeter is 12 g and specific heat is 1
cal/ml/degree for solution
760 9819 é1 1 ù
log = ê - ú Sol. When HCl and NaOH are mixed (neutralised) the heat
528 2.303 ´ 1.987 ë T1 373 û or T1 = 363 K
produced is taken up by calorimeter and solution in it
26. Calculate the maximum efficiency of a steam engine working \ DH1 = m1s1DT + m 2s 2 DT
between 110°C and 25°C. = 12 × 1×4.4 + 600 × 1 × 4.4
Sol. Efficiency of a heat engine is given by (Total sol. = (200 + 400) ml
T - T1 383 - 298 = 2692.8 cal
h= 2 or h = = 0.222 or 22.2%
= – 2692.8 cal
T2 383
This is neutralisation of 200 Meq
27. Calculate the useful work done by the heat engine which Neutralisation of 1000 Meq. or one equivalent
works between 10°C and 100°C. Heat supplied to engine is = – 2692.8 × 5 = – 13464 cal
1897.86 kJ = – 13.464 kcal
JEEMAIN.GURU
downloaded from jeemain.guru
Thermodynamics 157
Very Short/ Short Answer Questions (b) The entropy of a substance increases in going from
the liquid to the vapour state at any temperature.
1. Predict DH > DU or DH < DU or DH = DU.
(c) Reaction with DG° < 0 always have an equilibrium
(a) C (graphite) + O2 (g) ® CO2(g) constant greater than 1.
(b) PCl5 (g) ® PCl3(g) + Cl2 (g). 11. Give reasons for the following :
2.
In the equation N2(g) + 3H2(g)
2NH3(g), what whould (a) Why the heat produced be different if same mass of
be the sign of work done? diamond and graphite are burnt in oxygen?
3. Give an example of following energy conversions: (b) The dissolution of ammonium chloride in water is en-
(i) Radiation energy into chemical energy. dothermic still it dissolves in water
(ii) Radiation energy into electrical energy. (c) A real crystal has more entropy than an ideal crystal.
4. A system is changed from an initial state to a final state by 12. Calculate the value of log Kp for the reaction N2(g) + 3H2(g)
a manner such that DH = q. If the change from the initial 2NH3 (g) at 25°C. The standard enthalpy of
state to a final state were made by a different path, would formation of NH3(g) is – 46 kJ mol–1 and standard entropies
DH be the same as that for the first path? would q too be of N2(g) , H2(g) and NH3(g) are 191, 130, 192 JK–1 mol–1
the same? respectively.
5. What property of enthalpy provides the basis of Hess’s
Long Answer Questions
law?
6. A chemist while studying the properties of gaseous 13. Define the following terms :
C2Cl 2F2, a chlorofluorocarbon refrigerant, cooled 1.25 g (a) System
sample at constant atmospheric pressure of 1.0 atm from (b) Isothermal processes
320 K to 293 K. During cooling, the sample volume
(c) Adiabatic processes
decreased from 274 to 248 ml. Calculate DH and DU for the
chlorofluorocarbon for this process. (d) State variables/state functions
The value of molar heat capacity is 80.7 J mol –1 K–1 . (e) Work
7. Gobar gas obtained by bacterial fermentation of animal 14. (i) Calculate the standard molar entropy change for the
refuse contains mainly methane. The heat of combustion following reactions at 298 K.
of methane to CO2 and water as gas is given by (a) 4 Fe (s) + 3 O2 (g) ¾¾ ® 2 Fe2O3(s).
CH4(g) + 2O2(g) ® CO2(g) + 2H2O(g) + 809 kJ (b) Ca (s) + 2 H2O (l) ¾¾ ® Ca(OH)2 (aq) + H2 (g)
How much gobar gas would have to be produced per day Given:
for a small village community of 100 families, if we assume S° Fe(s) = 27.28, S°O2(g) = 205.14, S° Fe2O3 (s) = 87.4
that each family has to be supplied 20000 kJ of energy per
S°Ca(s) = 41.42, S°H2O(l) = 69.9, S°Ca(OH)2(aq) = 74.5,
day to meet all its needs and that the methane content in
the gobar gas is 80 percent by weight. S°H2(g) = 130.68,
8. Why is it more convenient to predict the direction of (ii) Calculate the standard molar Gibbs energy of formation
reaction in terms of DGsys instead of DStotal? Under what of CS2, given that its standard enthalpy of formation is
conditions can DGsys be used to predict the spontaneity of 89.7 kJ mol–1 and the standard molar entropies of
a reaction? graphite, S and CS2 are 5.7, 31.8 and 151.3JK–1mol–1
respectively.
9. Which of the following processes are accompanied by
increase of entropy ? 15. For the reaction
(a) Stretching of rubber band, 2H 2 (g) + O2 (g)
2H 2O(l )
(b) Boiling of an egg at 25°C, the equilibrium constant is 7.0 × 10–84.
(c) A deodrant is sprayed. (i) Calculate the standard Gibbs energy formations of
10. Comment on the following statements : water at 25°C.
(a) An exothermic reaction is always thermodynamically (ii) Dr H°H O = – 280 kJ mol–1. Calculate the entropy
2
spontaneous. change for the reaction.
JEEMAIN.GURU
downloaded from jeemain.guru
158 Chemistry
Multiple Choice Questions The work can also be calculated from the pV–plot by using
the area under the curve within the specified limits. When
16. Thermodynamics is not concerned about____. an ideal gas is compressed (a) reversibly or (b) irreversibly
(a) energy changes involved in a chemical reaction. from volume Vi to Vf. Choose the correct option.
(b) the extent to which a chemical reaction proceeds. (a) w (reversible) = w (irreversible)
(c) the rate at which a reaction proceeds (b) w (reversible) < w (irreversible)
(d) the feasibility of a chemical reaction. (c) w (reversible) > w (irreversible)
17. Which of the following statements is correct? (d) w (reversible) = w (irreversible) + pex. DV
(a) The presence of reacting species in a covered beaker 21. During complete combustion of one mole of butane, 2658
is an example of open system. kJ of heat is released. The thermochemical reaction for above
(b) There is an exchange of energy as well as matter change is
between the system and the surroundings in a closed (a) 2C4H10(g) + 13O2(g) ® 8CO2(g) + 10H2O(l)
system. DcH = –2658.0 kJ mol–1
(c) The presence of reactants in a closed vessel made up
of copper is an example of a closed system. 13
(b) C4H10(g) + O (g) ® 4CO2(g) + 5H2O (g)
(d) The presence of reactants in a thermos flask or any 2 2
other closed insulated vessel is an example of a closed DcH = –1329.0 kJ mol–1
system.
13
18. Which one of the following statements is false? (c) C4H10(g) + O (g) ® 4CO2(g) + 5H2O (l)
2 2
(a) Work is a state function
DcH = –2658.0 kJ mol–1
(b) Temperature is a state function
(c) Change in the state is completely defined when the 13
(d) C4H10(g) + O (g) ® 4CO2(g) +5H2O (l)
initial and final states are specified 2 2
(d) None of the above DcH = + 2658.0 kJ mol–1
19. A heat engine absorbs heat Q1 at temperature T1 and heat 22. On the basis of thermochemical equations (1), (2) and (3),
Q2 at temperature T2. Work done by the engine is J (Q1 + find out which of the algebric relationships given in options
Q2). This data (a) to (d) is correct.
(a) violates 1st law of thermodynamics (1) C (graphite) + O2(g) ® CO2(g); DrH = x kJ mol–1
(b) violates 1st law of thermodynamics if Q1 is –ve
1
(c) violates 1st law of thermodynamics of Q2 is –ve (2) C(graphite) + O2(g) ® CO (g); DrH = y kJ mol–1
2
(d) does not violate 1st law of thermodynamics.
20. The pressure-volume work for an ideal gas can be calculated 1
(3) CO (g) + O (g) ® CO2 (g); DrH = z kJ mol–1
Vf
2 2
by using the expression w = - pex dV . (a) z = x + y (b) x = y–z
Vi (c) x = y + z (d) y = 2z – x
JEEMAIN.GURU
downloaded from jeemain.guru
Thermodynamics 159
JEEMAIN.GURU
downloaded from jeemain.guru
160 Chemistry
JEEMAIN.GURU
downloaded from jeemain.guru
Thermodynamics 161
35. According to second law of thermodynamics a process 44. According to third law of thermodynamics, which one of
(reaction )is spontaneous if during the process the following quantities for a perfectly crystalline solid is
(a) DSuniverse > 0 (b) DSuniverse = 0 zero at absolute zero.
(a) Entropy (b) Free energy
(c) DH system > 0 (d) DS universe = DSsystem (c) Internal energy (d) Enthalpy.
36. The law formulated by Nernst is 45. The calorific value of fat is
(a ) first law of thermodynamics (a) less than that of carbohydrate and protein
(b) second law of thermodynamics (b) less than that of protein but more than carbohydrate
(c) third law of thermodynamics (c) less than that of carbohydrate but more than that of
(d) Both (a) and (b) protein
37. If 900 J/g of heat is exchanged at boiling point of water, then (d) more than that of carbohydrate and protein.
what is increase in entropy? 46. Heat of neutralisation of strong acid against strong base is
(a) 43.4 J/mole (b) 87.2 J/mole constant and is equal to
(c) 900 J/mole (d) Zero (a) 13.7 kcal (b) 57 kJ
(c) 5.7 × 10 J4 (d) All of the above
38. Given the following entropy values (in JK-1 mol -1 ) at
298 K and 1 atm : 47. The heat of formation of the compound in the following
H2(g) : 130.6, Cl2(g) : 223.0 and HCl (g) : 186.7. The entropy reaction is
change (in JK-1 mol -1) for the reaction H 2 ( g ) + Cl2 ( g ) ® 2HCl ( g ) + 44kcal
H 2(g) + Cl2 (g) ® 2HCl(g)is
(a) -44 kcal mol-1 (b) - 22 kcal mol -1
(a) +540.3 (b) 727.0
(c) –166.9 (d) 19.8 (c) 11 kcal mol -1 (d) - 88 kcal mol -1
39. Entropy change involved in the conversion of 1 mole of
liquid water at 373 K to vapour at the same temperature will
48. Given that C + O2 ® CO 2 DH o = - xkJ
be (DH vap. = 2.257kJ / g)
2CO + O2 ® 2CO 2 DH o = - ykJ
(a) 0.119 kJ (b) 0.109 kJ
the enthalpy of formation of carbon monoxide will be
(c) 0.129 kJ (d) 0.12 kJ
40. Which relation is correct ? 2x - y y - 2x
(a) (b)
(a) DG = DH - TDS (b) DG = DH + T DS 2 2
(c) DG = TDS - DH (d) D G = D H - SdT (d) 2x - y (d) y = 2x.
41. The value of free energy change at equilibrium is 49. The enthalpy of neutralization of acetic acid and sodium
(a) positive (b) negative hydroxide is –55.4 kJ. What is the enthalpy of ionization of
(c) zero (d) not definite. acetic acid ?
42. The standard Gibb’s free energy change, DG 0 is related to (a) –1.9 kJ (b) +1.9 kJ (c) +5.54 kJ (d) –5.54 kJ
50. The neutralisation of a strong acid by a strong base
equilibrium constant, K P as
liberates an amount of energy per mole of H +
DG o (a) depends upon which acid and base are involved
é e ù
(a) K P =- RT ln DG o
(b) KP =ê ú (b) depends upon the temperature at which the reaction
ë RT û
takes place
DG (c) depends upon which catalyst is used
K P =-
o
(c) (d) K P = e -DG / RT
(d) is always the same
RT
51. Equal volumes of methanoic acid and sodium hydroxide are
43. What is the free energy change. ' DG' when 1.0 mole of water
mixed. If x is the heat of formation of water, then heat
at 100º C and 1 atm pressure is converted into steam at 100°C evolved on neutralization is
and 1 atm. pressure
(a) more than x (b) equal to x
(a) 540 cal (b) –9800 cal
(c) less than x (d) twice x.
(c) 9800 cal (d) 0 cal
JEEMAIN.GURU
downloaded from jeemain.guru
162 Chemistry
60. The heat of combustion of CH4(g), C (graphite), H2(g) are –
3
52. S + O 2 ® SO 3 + 2x kcal 20 kcal, –40 kcal –10 kcal respectively. The heat of formation
2 of methane is
1 (a) –40 kcal (b) + 40 kcal
S O 2 + O 2 ® SO 3 + y kcal (c) –80.0 kcal (c) + 80 kcal
2
Find out the heat of formation of SO2 61. H 2 + Cl2 ® 2HCl, DH = - 194 kJ. In this reaction, heat
(a) (y -2x) (b) (2x + y) of formation of HCl in kJ is
(c) (x + y) (d) 2x/y (a) + 194 kJ (b) + 97 kJ
53. The enthalpy of neutralisation of a weak acid by a strong (c) –97 kJ (d) – 194 kJ
base is 62. Enthalpy of neutralisation of HCl with NaOH is x. The heat
(a) – 57.32 kJ evolved when 500 ml of 2 N HCl are mixed with 250 ml of 4N
(b) +57.32 kJ NaOH will be.
(c) equal to -57.32kJ + enthalpy of ionization of week acid (a) 500 x (b) 100x
(d) more than –57.32 kJ (c) x (d) 10 x
54. The enthalpy of formation for C2H4 (g), CO2 (g) and H2O (l) 63. When 1 M H2SO4 is completely neutralised by sodium
at 25º C and 1 atm pressure are 52, –394 and – 286 kJ mol–1 hydroxide, the heat liberated is 114.64 kJ.
respectively. The enthalpy of combustion of C 2H4 (g) will What is the enthalpy of neutralisation ?
be
(a) +114.64 kJ (b) –114.64 kJ
(a) +1412 kJ mol-1 (b) –1412 kJ mol-1
(c) –57.32 kJ (d) + 57.32 kJ
(c) 141.2 kJ mol -1 (d) –141.2 kJ mol -1 64. The amount of energy released when 20 ml of 0.5 M NaOH
55. When water is added to quicklime, the reaction is are mixed with 100 ml of 0.1 M HCl is x kJ. The heat of
(a) explosive (b) endothermic neutralisation (in kJ mol-1) is
(c) exothermic (d) photochemical. (a) –100x (b) –50x
56. Mark the correct statement (c) + 100 x (d) +50x
(a) For a chemical reaction to be feasible, DG should be 0 65. The DH f 0 for CO 2 (g), CO(g) and H 2 O (g)
(b) Entropy is a measure of order in a system are–393.5, –110.5 and –241.8 kJ mol-1 respectively. The
standard enthalpy change (in kJ) for the reaction
(c) For a chemical reaction to be feasible, DG should be
positive CO2 (g) + H 2 (g) ® CO (g) + H 2O (g) is
(d) The total energy of an isolated system is constant. (a) 524.1 (b) 41.2
57. One mole of an ideal gas is allowed to expand freely and (c) –262.5 (d) -41.2
adiabatically into vaccum until its volume has doubled. The 66. H 2 (g) + Cl 2 (g) ® 2 HCl(g) DH = - 44 kcal
expression which is not true concerning statement is
(a) DH = 0 (b) DS = 0 2 Na (s) + 2 HCl(g) ® 2 NaCl (s) + H 2 (g)
JEEMAIN.GURU
downloaded from jeemain.guru
Thermodynamics 163
1. Consider the following reactions: [CBSE-PMT 2007] 7 From the following bond energies: [CBSE-PMT 2009]
+ –
(i) H (aq) + OH (aq) ¾¾ ® H2O(l), H – H bond energy: 431.37 kJ mol–1
DH = – X1 kJ mol–1 C = C bond energy: 606.10 kJ mol–1
C – C bond energy: 336.49 kJ mol–1
1 C – H bond energy: 410.50 kJ mol–1
(ii) H2(g) + O (g) ¾¾
® H2O(l),
2 2 Enthalpy for the reaction,
DH = – X2 kJ mol–1
H H H H
(iii) CO2(g) + H2(g) ¾¾ ® CO(g) + H2O, | | | |
DH = – X3 kJ mol–1 C = C + H - H ¾¾
® H - C- C - H
| | | |
5 H H H H
(iv) C2H 2 ( g ) + O2 ( g ) ¾¾
® 2CO2(g) + H2O(l),
2
will be:
DH = + 4X4 kJ mol–1 (a) – 243.6 kJ mol–1 (b) –120.0 kJ mol–1
Enthalpy of formation of H2O (l) is (c) 553.0 kJ mol–1 (d) 1523.6 kJ mol–1
(a) + X3 kJ mol– 1 (b) – X4 kJ mol– 1 8. Standard entropies of X2 , Y2 and XY3 are 60, 40 and
(c) + X1 kJ mol– 1 (d) – X2 kJ mol– 1 50 JK–1mol–1 respectively. For the reaction
2. Given that bond energies of H – H and Cl – Cl are [CBSE-PMT 2010]
430 kJ mol– 1 and 240 kJ mol–1 respectively and DfH for HCl
1 3
is – 90 kJ mol– 1, bond enthalpy of HCl is [CBSE-PMT 2007] X 2 + Y2 XY3 , DH = – 30 kJ
2 2
(a) 380 kJ mol–1 (b) 425 kJ mol–1 to be at equilibrium, the temperature should be:
(c) 245 kJ mol–1 (d) 290 kJ mol–1 (a) 750 K (b) 1000 K
3. Which of the following are not state functions ? (c) 1250 K (d) 500 K
[CBSE-PMT 2008] 9. For vaporization of water at 1 atmospheric pressure, the values
(I) q + w (II) q of DH and DS are 40.63 kJmol–1 and 108.8 JK–1 mol–1,
(III) w (IV) H - TS respectively. The temperature when Gibbs energy change
(a) (I) and (IV) (b) (II), (III) and (IV)
(c) (I), (II) and (III) (d) (II) and (III)
( DG ) for this transformation will be zero, is:
4. For the gas phase reaction, [CBSE-PMT 2008] [CBSE-PMT 2010]
PCl3(g) + Cl2(g) (a) 293.4 K (b) 273.4 K
PCl5(g)
(c) 393.4 K (d) 373.4 K.
which of the following conditions are correct ? 10. Match List -I (Equations) with List-II (Type of processes)
(a) DH = 0 and DS < 0 and select the correct option. [CBSE-PMT 2010]
(b) DH > 0 and DS > 0 List I List II
(c) DH < 0 and DS < 0 Equations Type of processes
(d) DH > 0 and DS < 0 (1) Kp > Q (i) Non spontaneous
5. Bond dissociation enthalpy of H2, Cl2 and HCl are 434 , 242 and (2) DG ° < RT lnQ (ii) Equilibrium
431 kJ mol–1 respectively. Enthalpy of formation of HCl is : (3) Kp = Q (iii) Spontaneous and
[CBSE-PMT 2008] endothermic
(a) 93 kJ mol –1 (b) – 245 kJmol–1 DH
(c) – 93 kJmol –1 (d) 245 kJmol–1 (4) T > (iv) Spontaneous
DS
6. The values of DH and DS for the reaction, Options:
C(graphite) + CO2 (g) ® 2CO(g) are 170 kJ and 170 JK–1, (1) (2) (3) (4)
respectively. This reaction will be spontaneous at (a) (ii) (i) (iv) (iii)
[CBSE-PMT 2009] (b) (i) (ii) (iii) (iv)
(a) 910 K (b) 1110 K (c) (iii) (iv) (ii) (i)
(c) 510 K (d) 710 K (d) (iv) (i) (ii) (iii)
JEEMAIN.GURU
downloaded from jeemain.guru
164 Chemistry
11. The following two reactions are known : 18. Standard enthalpy of vapourisation Dvap H° for water at
[CBSE-PMT 2010] 100°C is 40.66 kJ mol–1. The internal energy of vaporisation
of water at 100°C (in kJ mol–1) is : [CBSE-PMT 2012 S]
Fe2O3(s) + 3CO (g) ¾¾
® 2Fe(s) + 3CO2(g); DH = –26.8 kJ (a) + 37.56 (b) – 43.76
(c) + 43.76 (d) + 40.66
FeO(s) + CO(g) ¾¾
® Fe(s) + CO2(g); DH = –16.5 kJ
(Assume water vapour to behave like an ideal gas).
The value of D H for the following reaction 19. Equal volumes of two monoatomic gases, A and B, at same
Fe2O3(s) + CO(g) ¾¾ ® 2FeO(s) + CO2(g) is; temperature and pressure are mixed. The ratio of specific
(a) + 6.2 kJ (b) + 10.3 kJ heats (Cp/Cv) of the mixture will be : [CBSE-PMT 2012]
(c) – 43.3 kJ (d) – 10.3 kJ (a) 0.83 (b) 1.50
12. Three moles of an ideal gas expanded spontaneously into (c) 3.3 (d) 1.67
vacuum. The work done will be : [CBSE-PMT 2010] 20. A reaction having equal energies of activation for forward
(a) Zero (b) Infinite (c) 3 Joules (d) 9 Joules and reverse reaction has : [NEET 2013]
13. If the enthalpy change for the transition of liquid water to (a) DG = 0 (b) DH = 0
steam is 30 kJ mol–1 at 27ºC, the entropy change for the (c) DH = DG = DS = 0 (d) DS = 0
process would be : [CBSE-PMT 2011]
21. If an endothermic reaction is non-spontaneous at freezing
(a) 10 J mol –1 K–1 (b) 1.0 J mol–1 K–1
point of water and becomes feasible at its boiling point,
(c) 0.1 J mol–1 K–1 (d) 100 J mol–1 K–1
then [AIEEE 2002]
14. Enthalpy change for the reaction, [CBSE-PMT 2011]
(a) DH is –ve, DS is +ve
4H( g ) ¾¾
® 2H 2 ( g ) is – 869.6 kJ.
(b) DH and DS both are +ve
The dissociation energy of H–H bond is :
(c) DH and DS both are –ve
(a) – 434.8 kJ (b) – 869.6 kJ
(d) DH is +ve, DS is -ve
(c) + 434.8 kJ (d) + 217.4 kJ
22. A heat engine abosrbs heat Q1 at temperature T1 and heat
15. Consider the following processes :
Q2 at temperature T2. Work done by the engine is J (Q1 +
DH (kJ/mol)
Q2). This data [AIEEE 2002]
1/2 A® B +150 st
(a) violates 1 law of thermodynamics
3B ® 2C + D –125 (b) violates 1st law of themodynamics if Q1 is –ve
E + A ® 2D +350 (c) violates 1st law of thermodynamics of Q2 is –ve
For B + D ® E + 2C, DH will be : [CBSE-PMT 2011 M] (d) does not violate 1st law of themodynamics.
(a) 525 kJ/mol (b) – 175 kJ/mol 23. For the reactions, [AIEEE 2002]
(c) – 325 kJ/mol (d) 325 kJ/mol C + O2 ® CO2 ; DH = -393 J
16. In which of the following reactions, standard entropy
2Zn + O2 ® 2 ZnO ; DH = -412 J
change (DS°) is positive and standard Gibb’s energy change
(a) carbon can oxidise Zn
(DG°) decreases sharply with increase in temperature ?
(b) oxidation of carbon is not feasible
[CBSE-PMT 2012 S]
(c) oxidation of Zn is not feasible
1 (d) Zn can oxidise carbon.
(a) C (graphite) + O (g) ® CO(g)
2 2 24. The internal energy change when a system goes from state
1 A to B is 40 kJ/mole. If the system goes from A to B by a
(b) CO(g) + O (g) ® CO2(g) reversible path and returns to state A by an irreversible path
2 2
what would be the net change in internal energy ?
1 [AIEEE 2003]
(c) Mg(s) + O (g) ® MgO(s)
2 2 (a) > 40 kJ (b) < 40 kJ
1 1 1 (c) Zero (d) 40 kJ
(d) C (graphite) + O2(g) ® CO2(g) 25. If at 298 K the bond energies of C — H, C — C, C = C and H
2 2 2
— H bonds are respectively 414, 347, 615 and 435 kJ mol–1,
17. The enthalpy of fusion of water is 1.435 kcal/mol. the value of enthalpy change for the reaction
The molar entropy change for the melting of ice at 0°C is :
H 2 C = CH 2 (g) + H 2 (g) ® H 3C — CH 3 (g)
[CBSE-PMT 2012 S]
(a) 10.52 cal / (mol K) (b) 21.04 cal / (mol K) at 298 K will be [AIEEE 2003]
(c) 5.260 cal / (mol K) (d) 0.526 cal / (mol K) (a) – 250 kJ (b) + 125 kJ
(c) – 125 kJ (d) + 250 kJ
JEEMAIN.GURU
downloaded from jeemain.guru
Thermodynamics 165
26. In an irreversible process taking place at constant T and P and 34. An ideal gas is allowed to expand both reversibly and
in which only pressure-volume work is being done, the change irreversibly in an isolated system. If T i is the initial
in Gibbs free energy (dG) and change in entropy (dS), satisfy temperature and Tf is the final temperature, which of the
the criteria [AIEEE 2003] following statements is correct? [AIEEE 2006]
(a) ( D S)V, E > 0, ( D G)T, P < 0 (b) ( D S)V, E = 0, ( D G)T, P = 0 (a) (Tf)rev = (Tf)irrev
(b) Tf = Ti for both reversible and irreversible processes
(c) ( D S)V, E = 0, ( D G)T, P > 0 (d) ( D S)V, E < 0, ( D G)T, P < 0
(c) (Tf)irrev > (Tf)rev
27. The correct relationship between free energy change in a
(d) Tf > Ti for reversible process but Tf = Ti for irreversible
reaction and the corresponding equilibrium constant Kc is
process
[AIEEE 2003]
35. The standard enthalpy of formation (DfHº) at 298 K for
(a) – DG = RT ln Kc (b) DGº = RT ln Kc
methane, CH4 (g) is –74.8 kJ mol –1 . The additional
(c) – DGº = RT ln Kc (d) DG = RT ln Kc information required to determine the average energy for C
28. The enthalpy change for a reaction does not depend upon – H bond formation would be [AIEEE 2006]
[AIEEE 2003] (a) the first four ionization energies of carbon and electron
(a) use of different reactants for the same product gain enthalpy of hydrogen
(b) the nature of intermediate reaction steps (b) the dissociation energy of hydrogen molecule, H2
(c) the differences in initial or final temperatures of involved (c) the dissociation energy of H2 and enthalpy of
substances sublimation of carbon
(d) the physical states of reactants and products (d) latent heat of vapourization of methane
29. An ideal gas expands in volume from 1×10 –3 to 36. The enthalpy changes for the following processes are listed
1 × 10 –2 m 3 at 300 K against a constant pressure of below : [AIEEE 2006]
1×10 5 Nm –2 . The work done is [AIEEE 2004] Cl2(g) = 2Cl(g), 242.3 kJ mol –1
JEEMAIN.GURU
downloaded from jeemain.guru
166 Chemistry
40. Identify the correct statement regarding a spontaneous 46. Consider the reaction : [AIEEE 2011 RS]
process: [AIEEE 2007] 4NO2 ( g ) + O 2 ( g ) ® 2N 2O5 ( g ),
(a) Lowering of energy in the process is the only criterion DrH = – 111 kJ.
for spontaneity.
If N2O5(s) is formed instead of N2O5(g) in the above reaction,
(b) For a spontaneous process in an isolated system, the
the DrH value will be :
change in entropy is positive.
(given, DH of sublimation for N2O5 is –54 kJ mol–1)
(c) Endothermic processes are never spontaneous.
(a) + 54 kJ (b) + 219 kJ
(d) Exothermic processes are always spontaneous.
41. Oxidising power of chlorine in aqueous solution can be (c) – 219 J (d) – 165 kJ
determined by the parameters indicated below: 47. A piston filled with 0.04 mol of an ideal gas expands
[AIEEE 2008] reversibly from 50.0 mL to 375 mL at a constant temperature
of 37.0ºC. As it does so, it absorbs 208 J of heat. The values
1
1 D H D eg H of q and w for the process will be: [JEE M 2013]
2 diss
Cl2 ( g ) ¾¾¾¾¾ ® Cl( g ) ¾¾¾¾ ® Cl– ( g )
2 (R = 8.314 J/mol K) (ln 7.5 = 2.01)
(a) q = + 208 J, w = – 208 J
D H
Hyd
¾¾¾¾ ® Cl – (aq) (b) q = – 208 J, w = – 208 J
(using the data, (c) q = – 208 J, w = + 208 J
–1 –1 (d) q = + 208 J, w = + 208 J
D diss H Cl = 240 kJ mol D eg H Cl = –349 kJ mol
2
48. B is
The value of log10 K for a reaction A
–1
D hyd H Cl – = –381 kJ mol ), will be (Given : D r H °298K = -54.07 kJ mol- 1 ,
(a) + 152 kJ mol–1 (b) – 610 kJ mol–1
(c) – 850 kJ mol–1 (d) + 120 kJ mol–1 D r S°298K = 10 JK–1 mol–1 and R = 8.314 JK–1 mol–1;
42. On the basis of the following thermochemical data : 2.303 × 8.314 × 298 = 5705) [IIT-JEE 2007]
+
[Δ f H°(H (aq) = 0)] [AIEEE 2009] (a) 5 (b) 10
(c) 95 (d) 100
H 2O(l ) ® H + ( aq ) + OH – ( aq ); DH = 57.32kJ
49. For the process H2O(l) (1 bar, 373 K) ® H2O(g) (1 bar, 373
1 K), the correct set of thermodynamic parameters is
H2 (g )+ O2 (g ) ¾¾ ® H2O(l); ΔH= –286.20kJ
2 [IIT-JEE 2007]
The value of enthalpy of formation of OH– ion at 25° C is: (a) DG = 0, DS = +ve (b) DG = 0, DS = –ve
(a) –228.88 kJ (b) +228.88 kJ
(c) DG = +ve, DS = 0 (d) DG = –ve, DS = +ve
(c) –343.52 kJ (d) –22.88 kJ
50. The species which by definition has ZERO standard molar
43. The standard enthalpy of formation of NH 3
enthalpy of formation at 298 K is [IIT-JEE 2010]
is – 46.0 kJ mol–1. If the enthalpy of formation of H2 from its
atoms is – 436 kJ mol–1 and that of N2 is – 712 kJ mol–1, the (a) Br2 (g) (b) Cl2 (g)
average bond enthalpy of N – H bond in NH3 is (c) H2O (g) (d) CH4 (g)
[AIEEE 2010] 51. Using the data provided, calculate the multiple bond energy
(a) – 964 kJ mol–1 (b) + 352 kJ mol–1 (kJ mol–1) of a C º C bond in C2H2. That energy is (take the
(c) + 1056 kJ mol–1 (d) – 1102 kJ mol–1 bond energy of a C – H bond as 350 kJ mol–1)
44. For a particular reversible reaction at temperature T, DH 2C(s) + H2(g) ¾¾ ® HC º CH(g); DH = 225 kJ mol–1
and DS were found to be both +ve. If Te is the temperature 2C(s) ¾¾ ® 2C(g) ; DH = 1410 kJ mol–1
at equilibrium, the reaction would be spontaneous when H2(g) ¾¾ ® 2H(g) ; DH = 330 kJ mol–1 [IIT-JEE 2012]
(a) Te > T (b) T > Te [AIEEE 2010] (a) 1165 (b) 837
(c) Te is 5 times T (d) T = Te
(c) 865 (d) 815
45. The value of enthalpy change (DH) for the reaction
52. The standard enthalpies of formation of CO2(g), H2O(l)
C2 H5 OH(l) + 3O2 ( g ) ® 2CO2 ( g ) + 3H 2O(l) and glucose(s) at 25°C are –400 kJ/mol, –300 kJ/mol and –
at 27° C is – 1366.5 kJ mol–1. The value of internal energy 1300 kJ/mol, respectively. The standard enthalpy of
change for the above reaction at this temperature will be : combustion per gram of glucose at 25°C is
[AIEEE 2011 RS] [JEE Advanced 2013]
(a) – 1369.0 kJ (b) – 1364.0 kJ (a) +2900 kJ (b) –2900 kJ
(c) – 1361.5 kJ (d) – 1371.5 kJ (c) –16.11 kJ (d) +16.11 kJ
JEEMAIN.GURU
downloaded from jeemain.guru
Thermodynamics 167
1. For determining the spontaneity of a process which of the 9. What is the free energy change for the conversion of
following is considered ? 1 mole of water into steam at 373.2 K . The heat
(a) DS system of vaporization (DHv) of water of 373.2 K is 9.1 kcal. mol –1.
(b) DS surroundings The entropy change is 25.5 cal/mol deg.
(c) DS system + DS surroundings (a) –401.6 cal/mol (b) –416.6 cal/mol
(d) DS system – DS surroundings (c) 516.5 cal/mol (d) –516.5 cal/mol
2. Which of the following is always true for a spontaneous 10. The ‘thermite reaction’ involving the reaction between ferric
change at all temperatures ? oxide and metallic aluminium produces molten iron. Given
(a) DH > 0 ; DS < 0 (b) DH < 0 ; DS < 0 that
(c) DH < 0 ; DS > 0 (d) DH > 0 ; DS > 0 2Al + 3 / 2 O 2 ® Al 2 O 3 ; DH1 = -400 kcal/ mol
3. What is the change in entropy when ice melts at 0°C, enthalpy
of fusion of one mole of ice is 6.02 kJ ? 2Fe + 3 / 2 O 2 ® Fe 2O 3 ; DH 2 = -200 kcal/mol.
(a) 6.02 kJ K–1 mol–1 (b) 22.1 J K–1 mol–1 What is DH for the formation of 1 mole of iron ?
(c) 1 J K–1 mol–1 (d) 22.0J K–1 mol–1 (a) –100 kcal (b) –200 kcal
4. In which of the following processes, the entropy decreases (c) +100 kcal (d) +200 kcal
? 11. Given the reaction at 927°C and 1 atm.
(a) CaCO3 (s) ® CaO(s) + CO2 (g) CaO(s) + CO2 (g) DH= 176 kJ/mol; then
CaCO3 (s)
(b) 2NH 3 (g) ® N 2 (g) + 3H 2 (g) DE equals
(c) 2H 2 (g) + O 2 (g) ® 2H 2 O(l) (a) 100 kJ (b) 166.03 kJ
(c) 180.0 kJ (d) 186.4 kJ
(d) O 3 (g ) ® O 2 (g ) + O(g) 12. What is the enthalpy change for the reaction
5. For which one of the processes represented by the following H 2 (g ) + C 2 H 4 (g ) ® C 2 H 6 (g )
equations the enthalpy (heat) change is likely to be negative
The bond energies are given below:
(a) Cl - (g) + aq ® Cl - (aq) (b) Cl(g) ® Cl + (g) + e -
( H - H ) ® 103; ( C - H ) ® 99, ( C - C ) ® 80 and
(c) 1 / 2Cl 2 (g ) ® Cl(g ) (d) Cl 2 (l) ® Cl 2 (g)
( C = C ) ® 145 kcal/mol respectively
6. The enthalpy change of formation of CO 2 (g)
is – 393 kJmol–1 and that of H2O (l) is – 286 kJmol–1. The (a) –10 kcal mol–1 (b) +10 kcal mol–1
enthalpy of combustion of one mole of ethanol (C2H5OH) is (c) –30 kcal mol–1 (d) +30 kcal mol–1
–1360. The enthalpy change for the formation of one mole of 13. For the process H2O(l) H2O(g) DH = 45.0 kJ mol–1 and
ethanol form its constituent elements is DS = 1.20 × 102 J K–1 mol–1. At what temperature the above
(a) –681 kJ (b) –284 kJ process is at equilibrium?
(c) +965 kJ (d) 1360 kJ (a) 273 K (b) 373 K
7. What is Dngas for the combustion of 1 mole of benzene, when (c) 370 K (d) 375 K
both the reactants and the products are at 298 K ?
14. Third law of thermodynamics is used to determine the
(a) 0 (b) 1/2
(a) spontaneity of a process
(c) 3/2 (d) –3/2
(b) enthalpy of substance
8. Which of the following statements is false ?
(c) absolute values of entropy of a substance
(a) For 1 mole of an ideal gas, Cp – Cv = R
(d) free energy of a substance
æ Eö 15. In thermodynamics, a process is called reversible when
(b) ç ÷ = 0 for an ideal gas
è T øT (a) surroundings and system change into each other
(b) there is no boundary between system and surroundings
(c) Dq = Dw + pDV (c) the surroundings are always in equilibrium with the
(d) For reversible isothermal expansion of 1 mole of an ideal system
gas from volume V1 to V2, work done is equal to RT ln (d) the system changes in to the surroundings
(V2/V1) spontaneously
JEEMAIN.GURU
downloaded from jeemain.guru
168 Chemistry
16. Which one of the following statements is false? 23. For the reaction
(a) Work is a state function
(b) Temperature is a state function 2C6 H5CO2 H(s) + 15O2 (g) ¾¾
®14CO 2 (g) + 6H 2O(g)
(c) Change in the state is completely defined when the initial DUº = –772.7 kJ mol–1 at 298 K. Calculate DHº
and final states are specified (a) +760.3 kJ mol–1 (b) –760.3 kJ mol–1
(d) Work appears at the boundary of the system (c) +670.3 kJ mol –1 (d) –790.3 kJ mol–1
17. The standard enthalpies of formation of H + and 24. 1 gram equivalent of H2SO4 is treated with 112 g of KOH for
OH– ions in water are zero and –229.6 kJ mol–1 respectively. complete neutralization. Which of the following statements
The standard enthalpy of formation of liquid water is –285.6kJ is correct?
mol–1. Then the enthalpy of neutralization of HCl(aq) by (a) 13.7 kcal of heat is evolved with the formation of
KOH(aq) is 87 g of K2SO4, leaving no KOH.
(a) 229.6 kJ mol–1 (b) –173.4 kJ mol–1
(b) 27.4 kcal of heat is evolved with the formation of
(c) 56.0 kJ mol –1 (d) –56.0 kJ mol–1 87 g of K2SO4, leaving 4 gram equivalent of KOH.
18. Which of the following salts should cause maximum cooling (c) 15.7 kcal of heat is evolved with the formation of 1 gram
when 1 mole of it is dissolved in the same volume of water ? equivalent of K2SO4, leaving 56 g of KOH.
(a) NaCl; DHº = 5.35 kJ mol–1 (d) 13.7 kcal of heat is evolved with the formation of 87g of
(b) KNO3; DHº = 53.5 kJ mol–1 K2SO4, leaving 1 gram equivalent of KOH.
(c) KOH; DHº = –56.0 kJ mol–1 25. From the following data DH of the following reactions
(d) HBr; DHº = –83.3 kJ mol–1
19. The molar enthalpies of combustion of isobutane and n-butane 1
C(s) + O 2 (g ) ¾¾® CO(g); DH = – 110 kJ and
are –2870 kJ mol–1 & –2875 kJ mol–1 respectively at 298 K and 2
1 atm. Calculate DHº for the conversion of 1 mole of n-butane
to 1 mole of isobutane C(s) + H 2 O(g) ¾¾® CO(g) + H 2 (g); DH = 132 kJ
(a) –8 kJ mol–1 (b) +8 kJ mol–1 Calculate the mole composition of the mixture of steam and
(c) –5748 kJ mol –1 (d) +5748 kJ mol–1 oxygen on being passes over coke at 1273 K, keeping the
temperature constant.
20. For the reaction
(a) 1 : 0.6 (b) 0.6 : 1
1 (c) 2 : 3 (d) 3 : 2
CO(g) + O 2 (g) ¾ ¾® CO 2 (g ); DHº = –67650 cal at
2
o -1
25 ºC. Calculate DHº at 100°C, given that the required molar 26. DHf of water is – 285.8 kJmol . If enthalpy of
heat capacities are as follows. neutralisation of monoacidic strong base is
CP(CO,g) = 6.97 cal ºC–1
–57.3 kJmol - 1 . DHf of OH - ion will be
o
CP(CO2,g) = 8.97 cal ºC–1
CP(O2,g) = 7.00 cal ºC–1 (a) – 114.25 kJmol -1 (b) 114.25 kJmol
-1
JEEMAIN.GURU
downloaded from jeemain.guru
Thermodynamics 169
29. At 25°C and 1 bar which of the following has a non-zero 35. The DH at 358 K for the reaction
DHof Fe 2O 3 (s) + 3 H 2 (g) ¾
¾® 2Fe(s) + 3 H 2 O (l)
(a) Br2 (l) (b) C (graphite) -1
given that DH 298 = – 33.29 kJ mol and Cp for Fe 2O 3 (s),
(c) O 3 (g) (d) I 2 (s) Fe(s), H 2 O (l) and H 2 (g) and 103.8, 25.1, 75.3 and 28.8 J/K
mol
30. Bond enthalpies of H 2 , X 2 and HX are in the ratio 2 : 1 : 2.
-1 -1
(a) – 28.136 k J mol (b) – 38.3 k J mol
-1
If enthalpy of formation of HX is – 50 kJmol , the bond
-1 -1
(c) 42.5 k J mol (d) 56.2 k J mol
enthalpy of X 2 is
-1
-1 -1
36. DH°f of NF3 is – 113 k J mol and N–F bond energy is
(a) 100 kJmol (b) 300 kJmol
-1
-1 273.0 k J mol . If N º N and F–F bond energies are in the
(c) 200 kJmol - 1 (d) 400 kJmol
rates 6 : 1, their magnitudes will be
31. When 1 mole of oxalic acid is treated with excess of NaOH in
-1 -1
dilute aqueous solution, 106 kJ of heat is liberated. Predict (a) 780.0 k J mol , 130.0 k J mol
the enthalpy of ionisation of the acid -1 -1
(b) 840 k J mol , 140 k J mol
-1
(a) 4.3 kJmol -1 (b) – 4.3 kJmol -1 -1
(c) 950.0 k J mol , 158.3 k J mol
(c) 8.6 kJmol -1 (d) – 8.6 kJmol -1 -1 -1
(d) 941.3 k J mol , 156.9 k J mol
32. An athlete is given 100 g of glucose (C 6 H12O 6 ) of energy
37. The enthalpy of neutralisation of NH 4 OH and
equivalent to 1560 kJ. He utilises 50% of this gained energy
in the event. In order to avoid storage of energy in the body. CH 3COOH is – 10.5 kcalmol -1 and enthalpy of
Calculate the weight of water he would need to perspire. neutralisation of CH 3COOH with strong base is – 12.5
-1
The enthalpy of evaporation of water is 44 kJmol . kcalmol-1 . The enthalpy of ionisation of NH 4 OH will be
(a) 319.1 g (b) 119.7 g
(a) 3.2 kcalmol -1 (b) 2.0 kcalmol -1
(c) 227.5 g (d) 250.2 g
33. The enthalpy change for hydration (c) 3.0 kcalmol -1 (d) 4.0 kcalmol -1
(c) 71.6 kcalmol -1 (d) – 71.6 kcalmol -1 (c) H 2S > HCOOH > CH 3COOH > HCN
(d) HCOOH > H 2S > CH 3COOH > HCN
JEEMAIN.GURU
downloaded from jeemain.guru
170 Chemistry
41. When 1.8 g of steam at the normal boiling point of water is 43. The enthalpy of atomisation of CH 4 and C 2 H 6 are 360
converted into water at the same temperature, enthalpy and
entropy changes respectively will be ( DHVaporisation for and 620 kcal mol -1 respectively. The C – C bond energy is
expected to be
H 2 O = 40.8 kJ mol-1 )
-1 -1
(a) 210 k cal mol (b) 80 k cal mol
-1 -1
(a) 4.08 kJ, 10.93 J K (b) – 4.08 kJ, – 10.93 J K
-1
(c) 130 k cal mol -1 (d) 180 k cal mol
-1 -1
(c) – 4.08 kJ, – 40.8 J K (d) 4.08 kJ, 40.8 J K
44. A certain reaction is non spontaneous at 298K. The entropy
42. The enthalpy of neutralisation of a weak acid in 1 M solution
change during the reaction is 121 J K -1 . Is the reaction is
with a strong base is – 56.1 kJ mol-1 . If the enthalpy of
endothermic or exothermic ? The minimum value of DH for
ionisation of acid is 1.5 kJ mol-1 an d enthalpy of the reaction is
neutralisation of the strong acid with a strong base is –57.3
(a) endothermic, DH = 36.06 kJ
kJ eq-1 . What is the % ionisation of the weak acid in molar (b) exothermic, DH = – 36.06 kJ
solution (assume the acid is monobasic)
(c) endothermic, DH = 60.12 kJ
(a) 25 (b) 20
(c) 15 (d) 10 (d) exothermic, DH = – 60.12 kJ
JEEMAIN.GURU
downloaded from jeemain.guru
Thermodynamics 171
JEEMAIN.GURU
downloaded from jeemain.guru
172 Chemistry
31. (c) Endothermic process, increase in entr opy, 60. (a) CH 4 + 2O2 ® CO2 + 2H 2 O; DH = 20 kcal........(1)
DH = + ve, DS = + ve
C + O 2 ® CO 2 ; DH = -40 kcal.....(2)
32. (a) DG = DH - T DS, DH + ve, DS is + ve; TDS > DH for
spontaneous process. It will make DG, –ve 2H 2 + O 2 ® 2H 2 O ; DH = -20 kcal........(3)
33. (a) Third law of Thermodynamics. (2) + (3) - (1) we have, C + 2H 2 ® CH 4
34. (b) High pressure reduces volume, decreases entropy, hence
or DH = -20 + (-40) - (-20) = - 40 kcal
DS negative.
35. (a) For spontaneous process, DS total is +ve. -194
61. (c) DH for two moles = -194kJ.For one mole = = -97 kJ
36. (c) Third law of thermodynamics is due to Nernst. 2
DH 900 ´18 62. (c) Enthalpy of neutralisation of HCl with NaOH is x. In
37. (a) DS = = = 43.4 J K -1 mol-1 question gev of HCl
T 373
æ 500 ´ 2 ö æ 250 ´ 4 ö
38. (d) DSº = 2Sº HCl - (Sº H 2 +Sº Cl2 ) ç = 1gev ÷ and NaOH ç = 1 gev ÷ hence the
è 1000 ø è 1000 ø
= 2 ´ 186.7 - (130.6 + 223.0) value x.
-1 -1 63. (c) Enthalpy of neutralisation is enthalpy change when 1
= 19.8JK mol
gev of acid is neutralised by 1 gev of base. In question,
2.257 ´18 2 gev of H 2SO 4 is being neutralised. Hence enthalpy of
39. (b) DS = = 0.109 kJ K -1mol -1
373
-114.64
40. (a) DG = DH - TDS neutralisation is = -57.32 kJ
2
41. (c) At equilibrium, DG = 0 64. (a) In question 0.01 gev of NaOH is being neutralised by
42. (d) DG = -RT ln Kp or Kp = e–DG/RTT 0.01 gev of HCl and value is x kJ, for 1 gev the value is -
100x (exothermic process).
43. (d) Condition of equilibrium, hence DG = 0
65. (b) DH = Hº f (products) - H º f (reactants)
44. (a) Statement of third law.
45. (d) Calorific value of fat > carbohydrate and protein; Butter = –110.5 + (–241.8) – (–393.5+0) = 41.2 kJ
34, Sugar 16, Egg 14. 66. (c) Add equation (I) and (II) divide by 2 the equation
46. (d) All values are same . - 196
47. (b) For one mole the value is - 22 kcal mol-1 obtained – 44 + (–152) = = - 98kcal
2
48. (b) C + O 2 ® CO 2 ; DHº = -x kJ.......(1) 67. (a) Lavoisier and Laplace law.
2CO + O 2 ® 2CO2 ; DHº = - y kJ......(2) EXERCISE 3
multiply equation (1) by 2 and substract equation (2) 1. (d) This reaction shows the formation of H2O, and the – X2
and divide final equation by 2 represents the enthalpy of formation of H2O because
49. (b) 57.3 – 55.4 = 1.9 kJ (57.3 kJ is heat of neutralisation of as the definition suggests that the enthalpy of formation
strong acid and strong base) is the heat evolved or absorbed when one mole of
50. (d) It is infact the formation of one molecule of H2O always substance is formed from its constituent elements.
(H + + OH - ¾¾ ® H 2 O) 2. (b)
1 1
H 2 + Cl2 ¾¾ ® HCl
51. (c) Neutralisation of weak acid with strong base hence < x. 2 2
Extra heat is utilised to effect the ionisation of weak acid. D f H HCl = B.E. of reactants
52. (a) Equation (1) – Equation (2) gives
S + O2 ® SO2 , DH = (y - 2x) - B.E. of products
53. (c) It is always = – 57.32 + ionisation of weak acid
1 1
54. (b) Desired eqn; C2 H 4 + 3O 2 ® 2CO 2 + 2H 2 O -90 = ´ 430 + ´ 240 - B.E. of HCl
2 2
DH = 2(-394) + 2(-286) - (52) = -1412kJ B.E. of HCl = 215 + 120 + 90
55. (c) CaO + H 2O ® Ca (OH) 2 ; Exothermic process. = 425 kJ mol–1
3. (d) We know that heat (q) and work (w) are not state
56. (d) Energy of isolated system is constant.
functions but (q + w) is a state function. H – TS (i.e. G)
57. (d)
is also a state function. Thus II and III are not state
58. (a) Depending upon the value of TDS , DG can be lesser,, functions so the correct answer is option (d).
equal or greater to DH 4. (b) For the reaction
59. (b) The more the energy, the lesser is the stability. PCl5 ( g ) PCl3 ( g) + Cl2 ( g)
JEEMAIN.GURU
downloaded from jeemain.guru
Thermodynamics 173
The reaction given is an example of decomposition 11. (a) Fe2O3(s) + 3CO(g) ¾¾ ® 2Fe(s) + 3CO2(g) ;
reaction and we know that decomposition reactions DH = –26.8 KJ ...(i)
are endothermic in nature, i.e., DH > 0. FeO(s) + CO(g) ¾¾ ® Fe(s) + CO2(g) ;
Further DH = –16.5 KJ ...(ii)
Dn = (1+1) – 1= +1 eq. (i) – 2 × eq. (ii), we get
Hence more number of gaseous molecules are present
Fe2O3(s) + CO(g) ¾¾ ® 2FeO(s)+ CO2(g)
in products which shows more randomness i.e., DS >
0 (DS is positive) D H = –26.8 + 33.0 = + 6.2 kJ
5. (c) The reaction for formation of HCl can be written as 12. (a) Ideal gas during spontaneous expansion into
H2 + Cl2 ® 2HCI vacuum does not do any external work.
H – H + Cl – Cl ® 2 (H – Cl) 13. (d) Given DH = 30 kJ mol–1 T = 273 + 27 = 300 K
Substituting the given values, we get enthalpy of DH T 3 ´ 10 4
formation of DST = = J mol–1
T 300
2HCl = ( 676 – 862) = –186 kJ.
= 100 J mol–1 K–1
-186 14. (c) Given
Enthalpy of formation of HCl = kJ = –93 kJ.
2 4H( g ) ¾¾® 2H 2 ( g ); DH = -869.6 kJ
6. (b) DG = DH – T D S
or 2H 2 ( g ) ¾¾
® 4H( g ); DH = 869.6 kJ
At equilibrium, DG = 0
0 = (170 × 103 J) – T (170 JK– 1) H 2 ( g ) ¾¾
® 2H( g ); DH =
869.6
= 434.8 kJ
T = 1000 K 2
For spontaneity, DG is – ve, which is possible only if 15. (b) Given DH
T > 1000 K. 1
7. (b) Enthalpy of reaction A ¾¾®B + 150 ...(1)
2
= B.E(Reactant)– B.E(Product)
3B ¾¾
® 2C + D –125 ...(2)
= éë B.E (C= C) + 4 B.E.(C–H) + B.E.(H - H) ùû E + A ¾¾ ® 2D +350 ...(3)
To calculate DH operate
- éë B.E.(C - C) + 6 B.E.(C - H) ùû
2 × eq. (1) + eq. (2) – eq. (3)
= [606.1 + (4 × 410.5) + 431.37)] – [336.49 + (6 × 410.5)] DH = 300 – 125 – 350 = – 175
= –120.0 kJ mol–1 16. (a) Since, in the first reaction value of Dn is positive.
1 3 1 1
8. (a) ΔS for the reaction X 2 + Y2 XY3 Dn = 1 - = hence entropy will increase i.e.,
2 2 2 2
Ds = +ve.
ΔS = 50 – (30 + 60) = – 40 J
For equilibrium DG = 0 = DH – T DS C (gr.) + 1 O2(g) ® CO(g); DS° = + ve
DH -30000 2
T= = = 750 K Since, DG° = DH° – TDS hence the value of DG
DS -40 decreases on increasing temperature.
1atm
9. (d) H 2O ( l)
H2O(g) DH 1.435 ´ 103
17. (c) DS = =
DH = 40630 J mol –1 T 273
DS = 108.8 JK–1 mol –1 = 5.260 cal / molK
DG = DH - T DS When DG = 0,
18. (d) H 2O (l) H 2O (g) DH = 40.66 KJmol–1
DH - T DS = 0 T = 373 K
DE = DH – DnRT
DH 40630 J mol-1
T = DS = 108.8 Jk -1 mol-1 = 373.4 K. = 40.66×103 Jmol–1–1× 8.314JK–1mol–1× 373 K
D E = 37558 J / mol
Correct choice : (d) D E = 37.56 kJ mol–1
10. (d)
(1) Kp > 0 (iv) Spontaneous 5
CP 2 R 5
(2) D G < R T ln Q (i) Non 19. (d) = = = 1.67
spontaneous CV 3 3
R
(3) Kp = 0 (ii) Equilibrium 2
DH 20. (b) DH = Ea - Ea = 0
(4) T> (iii) Spontaneous f b
DS
and endothermic
JEEMAIN.GURU
downloaded from jeemain.guru
174 Chemistry
21. (b) At low temperature the DS is – ve which makes DG 34. (c) In a reversible process the work done is greater than in
positive (DG = DH – TDS). But at higher temperature DS irreversible process. Hence the heat absorbed in
is +ve which makes the DG negative (condition for reversible process would be greater than in the latter
spontaneity) case. So
22. (d) It violate 2nd law of thermodynamics, not 1st. Tf (rev.) < Tf (irr.)
23. (d) DH negative shows that the reaction is spontaneous. 35. (c) The standard enthalpy of formation of CH4 is given by
Higher value for Zn shows that the reaction is more the equation :
feasible. C (s ) + 2 H 2 (g ) ¾
¾® CH 4 (g )
24. (c) For a cyclic process the net change in the internal energy Hence, dissociation energy of hydrogen and enthalpy
is zero because the change in internal energy does not of sublimation of carbon is required.
depend on the path. 36. (a) I 2 (s) + Cl 2 (g) ¾¾
® 2ICl(g)
25. (c) CH2 = CH2 (g) + H2 (g) ® CH3 - CH3 (g) DH = [DHI (s) –––®I (g) + DHI–I + DHCl–Cl ]
D H = 1(C = C) + 4 (C - H) + 1 (H - H) - 1 (C - C) - 6 (C - H) – [DHlI – Cl]
2 2
= 1 (C = C) + 1 ( H - H) - 1 (C - C) - 2 (C - H) = 151.0 + 242.3 + 62.76 –2 × 211.3 = 33.46
= 615 + 435 - 347 - 2 × 414 = 1050 - 1175 = – 125 kJ.
26. (a) For spontaneous reaction, dS > 0 and DG and DG should 33.46
DH of (ICl) = = 16.73 kJ / mol
be negative i.e. < 0. 2
27. (c) DGº = – RT lnKc or – DGº = RT lnKc 1
28. (b) Enthalpy change for a reaction does not depend upon 37. (d) C (s ) + O 2 (g ) ¾
¾® CO (g)
the nature of intermediate reaction steps. 2
DH – DU = DnRT
29. (c) W = -PDV = -10 -5 (1 ´ 10 -2 - 1 ´ 10-3 ) = -900J
1
30. (b) = ´ 8.314 ´ 298 = 1238.78 J mol -1
2
(i) C + O2 CO2 ; DH = -393.5 kJmol-1 38. (a) DG° = DH° – TDS°
For a spontaneous reaction DG° < 0
1
(ii) CO + O 2 CO 2 ; DH - -283.0 kJmol -1 DH °
2 or DH° – TDS° < 0 T>
After, DS°
(i) - (ii),
179.1 ´ 103
We have T> > 1117.9K 1118K
160.2
1 39. (d) Given DH = 41 kJ mol–1 = 41000 J mol–1
C+ O 2 ® CO DH = -110.5 kJmol -1
2 T = 100°C = 273 + 100 = 373 K
31. (d) For spontaneous reaction DG should be negative. n=1
Equilibrium constant should be more than one DU = DH – DnRT = 41000 – (1 × 8.314 × 373)
(DG = – 2.303 RT log Kc, If Kc = 1 then DG = 0; = 37898.88 J mol–1 37.9 kJmol–1
If Kc < 1 then DG = +ve). Again DG = -nFE ocell . Eocell 40. (b) Spontaneity of reaction depends on tendency to
acquire minimum energy state and maximum
must be +ve to have DG –ve. randomness. For a spontaneous process in an isolated
32. (b) DH = DU + DnRT for N 2 + 3H 2 ¾ system the change in entropy is positive.
¾® 2 NH 3
41. (b) The energy involved in the conversion of
Dng = 2 – 4 = – 2
1
D H = D U - 2 RT or DU = D H+ 2R T D U > D H Cl2 ( g ) to Cl–1 (aq) is given by
2
33. (N) X 2 + Y2 ¾¾® 2 XY , DH = 2(–200). 1
Let x be the bond dissociation energy of X2. DH = D diss H Cl2 + D eg H Cl + D hyd H Cl
2
Then Substituting various values from given data, we get
DH = -400 = + -2 = x + 0.5x – 2 x = -0.5x
DH = çæ ´ 240 ÷ö + (–349) + (–381) kJmol –1
x-x y- y x-y 1
400 è2 ø
or x = = 800 kJ mol -1 = (120 – 349 – 381) kJ mol–1 = – 610 kJ mol–1
0.5
(In the question paper, this option was not mentioned. So the
i.e., the correct answer is (b)
answer has been marked ‘N’) 42. (a) Given, for reaction
® H + (aq.) + OH – ( aq.);
(i)H2O (l) ¾¾
CH3 CH3 CH3
DH r = 57.32 kJ
H Cl Cl H H Cl
1
Cl H H Cl H Cl ® H 2 O(l);
(ii) H 2 ( g ) + O 2 ( g ) ¾¾
2
CH3 CH3 CH3 DH r = –286.20 kJ
JEEMAIN.GURU
downloaded from jeemain.guru
Thermodynamics 175
For reaction (i)
46. (d) 4NO 2 (g) + O 2 (g) ® 2N 2 O5 (g), D r H = – 111 kJ
+ –
DH r = DH°f (H .aq)+DH°f (OH .aq)–
– 54 kJ
DH°f (H2 O, l) DH'
2N 2 O5 (s)
57.32 = 0 + DH°f (OH – , aq) – DH°f (H 2 O, l) …(iii)
For reaction (ii) – 111 – 54 = D H'
DH r = DH°f (H 2 O, l) – D H' = – 165 kJ
47. (a) Process is isothermal reversible expansion, hence
1 DU = 0, therefore q = – W.
DH°f (H 2 , g) – DH°f (O 2 , g )
2 Since q = + 208 J, W = – 208 J
B
48. (b) A
–286.20 = DH°f (H 2 O, l)
DG° = D H° – TDS°
On replacing this value in eq. (iii) we have DG° = – 2.303 RTlog10 K
57.32 = DH°f (OH – , aq) – (–286.20) – 2.303 RT log10 K = DH° – TDS°
2.303 RT log10 K = TDS° – DH°
DH°f (OH - , aq) = –286.20 + 57.32 T DS ° - DH ° 298×10 +54.07×1000
log10 K = =
= –228.88 kJ 2.303RT 2.303×8.314×298
43. (b) ® 2NH 3 DH = 2 ´ -46.0 kJ mol–1
N 2 + 3H 2 ¾¾ = 9.998 » 10
49. (a) Since, liquid is passing into gaseous phase so
Let x be the bond enthalpy of N – H bond then
entropy will increase and at 373 K during the phase
[Note : Enthalpy of formation or bond formation
transformation it remains at equilibrium. So, DG = 0.
enthalpy is given which is negative but the given
50. (b) The species in its elemental form has zero standard
reaction involves bond breaking hence values should molar enthalpy of formation at 298 K. At 298K, Cl2 is
be taken as positive.] gas while Br2 is liquid.
DH = Bond energies of reactants – Bond energies
of products 51. (d) (i) 2C(s) + H2(g) ¾¾
® H – C º C – H(g)
2 × – 46 = 712 + 3 × (436) – 6x
– 92 = 2020 – 6x DH = 225 kJ mol–1
6x = 2020 + 92
(ii) 2C(s) ¾¾® 2C(g)
6x = 2112
DH = 1410 kJ mol–1
x = + 352 kJ/mol
1410
44. (b) At equilibrium DG = 0 C( s) ¾¾
® C( g ) DH = = 705kJmol -1
Hence, DG = DH – TeDS = 0 2
DH (iii) H2(g) ¾¾
\ DH = TeDS or Te = ® 2H(g)
DS DH = 330 kJ mol–1
For a spontaneous reaction From equation (i) :
DG must be negative which is possible only if DH – TDS < 0
\ DH < TDS 225 = éë 2 ´ DHC(s) ¾¾
® C( g )
+ 1 ´ BE H – H ù
û
DH - [2 ´ BE C – H + 1 ´ BECº C ]
or T > ; Te < T
DS 225 = [1410 + 1 × 330] – [2 × 350 + 1 × BEC º C]
225 = [1410 + 330] – [700 + BEC º C]
45. (b) C2H5 OH(l) + 3O 2 ( g ) ® 2CO 2 ( g ) + 3H 2O(l) 225 = 1740 – 700 – BEC º C
BEC º C = 815 kJ mol–1
Dng = 2 - 3 = -1 52. (c) The standard enthalpy of the combustion of glucose
can be calculated by the eqn.
DU = DH - Dng RT C6H12O6(s) + 6O2(g) ® 6CO2(g) + 6H2O(l)
DHC = 6 × DHf(CO2) + 6 × DHf (H2O) – DHf [C6H12O6]
8.314 DH° = 6 (–400) + 6(–300) – (–1300)
= -1366.5 - ( -1) ´ ´ 300
103 DH° = –2900 kJ/mol
For one gram of glucose, enthalpy of combustion
8.314
= -1366.5 + (1) ´ ´ 300 2900
103 DH° = – = - 16.11kJ / gm
= – 1366.5 + 0.8314 × 3 = – 1364 .006 kJ 180
JEEMAIN.GURU
downloaded from jeemain.guru
176 Chemistry
EXERCISE 4 14. (c) The third law of thermodynamics is about entropy.
15. (c) 16. (a)
1. (c) The criteria for the spontaneity, DS system + DS 17. (d) It is neutralisation of strong acid with strong base.
surroundings, must be + ve 18. (b) Dissolution of KNO3 is endothermic, hence heat is
2. (c) DG = DH – TDS. For spontaneous process DG < 0. To absorbed and cooling is observed.
get DG < 0. we must have DH < 0 ; DS > 0
19. (a) Isobutane + oxygen ® CO 2 + H 2 O
DH fusion 6.02 ´103
3. (d) DS = ; DS = = 22.0 JK -1 mol -1 DH = -2870 kJ mol -1 ......(i)
T 273
4. (c) Examine the chemical equations . If there is decrease in n-butane + oxygen ® CO2 + H 2O
number of moles of gaseous products, the entropy will
decrease and vice versa. DH = -2878 kJ mol -1 ....(ii)
5. (a) Gaseous ions, when dissolved in water, get hydrated (ii) - (i); n-butane – Isobutane,
and heat is evolved (heat of hydration). DH = (–2878 + 2870)
= – 8 kJ mol–1.
Cl - (g) + aq ® Cl- (aq) is such reaction .
DH 2 - DH1
6. (b) Write the proper chemical equations. 20. (d) Apply Kirchoff’s equation = C p - C R = DC p
T2 - T1
C(graphite) + O 2 (g) ® CO2 (g)
21. (b) Bond dissociation energy of PH3(g) = 228 kcal mol–1
DH = -393kJ ........(i)
228
P – H bond energy = = 76 kcal mol-1
1 3
H 2 (g) + O 2 (g) ® H 2 O(l)
2 H H
DH = -286kJ .........(ii)
P P
C2 H 5OH (l) + 3O2 (g) ® 2CO 2 (g) + 3H 2 O(l) H H
....(iii) Bond energy of 4 (P – H) + (P –P) = 355 kcal mol–1
DH = -1360kJ
or 4 × 76 + (P – P) = 355 kcal mol–1
From ( 2 ´ I + 3 ´ II ) – (III) we get P–P bond energy = 51 kcal mol–1
22. (a) DHº solution =U (lattice energy) + DHº hydration
1
2C + 3H 2 + O ® C 2 H 5 OH 23. (b) DH º = DU º + DnRT
2 2
5 ´ 8.314 ´ 298
2(-393kJ) + 3(-286kJ) - (-1360kJ) = -284kJ DHº = -772.7 + = -760.3 kJ mol -1
1000
15
7. (d) C6 H 6 (l) + O2 (g) ® 6CO 2 (g) + 3H 2O (l) 24. (d) H 2SO 4 + 2KOH ® K 2 SO 4 + 2H 2 O
2 98 112 174 2 mole
56
Dn = 6 - 15/2 = –3/2 49 87 1 mole
8. (c) C is incorrect ; The correct is DE = Dq + Dw 13.7 kcal is the heat evolved when 1 gev of strong acid is
9. (b) DG =DH – TDS neutralised by 1 gev of strong base.
DG = 9100 - 373.2 ´ 25.5 = -416.6 cal mol–1 25. (a) The first reaction is exothermic and the second reaction
10. (a) I – II, gives, 2Al + Fe2O3 ® 2Fe + Al2O3 is endothermic. If on passing the mixture of O 2 and
we have -400 - (-200) = -200; For one mole of iron H 2 O (steam) over coke while keeping the temperature
the value is –100 cal constant DH of both the reactions must be same.
11. (c) Moles of O 2 needed to evolve 132 kJ
12. (b) Enthalpy change = ( Energy required for breaking of
bonds – Energy evolved by formation of bonds) 0.5 ´ 132
= = 0.6
H H H H 110
H–H+ C=C H C–C H Hence steam : O 2 ratio must be 1 : 0.6
H H H H 1
( )- ( )
26. (d) H 2 (g) + O 2 (g ) ¾
¾® H 2 O (l);
H -H 103 80 C -C 2
C = C 145 2´99 C -H = -30 kcal mol–1
DH = – 285.8 kJ .... (i)
13. (d) DG = DH – TDS ; At equilibrium DG = 0 ; D =TDS ;
H + (aq) + OH (aq) ¾
¾® H 2 O (l);
–
DH
T= DH = – 57.3 kJ ... (ii)
DS
1
45000 ¾® H + (aq) + e - ; DH = 0
H 2 (g) + aq ¾
T= = 375K 2
1.2 ´ 10 2 (by convention) .... (iii)
JEEMAIN.GURU
downloaded from jeemain.guru
Thermodynamics 177
(i) – (ii) – (iii) gives,
33. (a) CuSO 4 (s) + 5 H 2 O (g) ¾
¾® CuSO 4 .5 H 2 O (s);
1 1
H 2 (g ) + O 2 (g ) + e - + aq ¾
¾® OH - (aq) DH = – 71.5 kcal ........ (i)
2 2
5 H 2 O (l) ® 5 H 2 O (g) ;
DH = – 285.8 + 57.3 = – 228.5 kJ
27. (b) For 5 moles of gas at temperature T, DH = 5 × 10.5 k cal = 52.5 kcal ........ (ii)
(i) + (ii),
PV1 = 5RTT
For 5 moles of gas at temperature T – 2, CuSO 4 (s) + 5 H 2 O (l) ¾
¾® CuSO 4 .5 H 2 O (s)
1 1 DH = – 28136 J mol -1
30. (a) H2 + X2 ¾ ¾® HX
2 2 = – 28.136 kJ mol -1
Let the bond enthalpy of X – X bond be x.
1 3
1 1 36. (d) N 2 (g) + F2 (g) ¾
¾® NF3 ; DH = – 113 kJ
DH f (HX ) = – 50 = DH H– H + DH X - X – DH H - X 2 2
2 2
3
1 1 -x or DH N º N + DH F- F – 3 DH N - F = – 113 kJ
= 2x + x – 2x = 2
2 2 2
Let x kJ mol-1 be the bond energy of F – F bond then
-1
x = 50 × 2 = 100 kJ mol bond energy of N º N bond = 6x
The difference (114.6 – 106) = 8.6 kJ mol-1 is used to 37. (b) DH N for strong base and strong acid
-1
effect of the ionisation of oxalic acid. = – 13.7 kcal eq
32. (a) After the event the energy remained in the body of the
DH ion (CH 3COOH )
1560
athlete =
2
= 780 kJ = – 12.5 – (– 13.7) = 1.2 kcal mol-1
Weight of water to be evaporated by 780 kJ of energy DH ion ( NH 4 OH)
18 = – 10.5 – (– 13.7) – D H ion (CH 3COOH )
= × 780 = 319.1 g
44 = 13.7 – 10.5 – 1.2
= 2 kcalmol -1
JEEMAIN.GURU
downloaded from jeemain.guru
178 Chemistry
JEEMAIN.GURU
downloaded from jeemain.guru
7A
Chemical Equilibrium
CHEMICAL EQUILIBRIUM : K f [ A ]a [ B ]b = K b [C ]c [ D ]d
When a reversible reaction is carried out in a closed vessel a
Kf [C ]c [ D ]d
stage reached when the speed of the forward reaction equals the = Kc =
speed of the backward reaction and chemical equilibrium is said Kb [A]a [B]b
to be established. Kc is called the equilibrium constant.
CHARACTERISTICS OF CHEMICAL EQUILIBRIUM : FACTORS INFLUENCING EQUILIBRIUM
(i) Equilibrium can be attained from either side. CONSTANT:
(ii) Equilibrium is dynamic in nature i.e. at equilibrium, reaction (i) The equilibrium constant is not influenced by :
does not stop. (1) Concentration of reactants and products.
(iii) At equilibrium there is no change in the concentration of (2) Presence of a catalyst.
various species. (3) Pressure.
(iv) The equilibrium state remains uneffected by the presence of (4) Presence of inert materials.
catalyst. Catalyst helps to attain the equilibrium state rapidly. (5) The direction from which the equilibrium state is reached.
JEEMAIN.GURU
downloaded from jeemain.guru
180 Chemistry
(ii) The equilibrium constant is influenced by : RELATION BETWEEN Kc AND Kp FOR DIFFERENT
(A) Temperature : The variation of equilibrium constant is given TYPES OF REACTIONS :
by Van't Hoff equation.
(i) When Dn = 0, Kp = Kc e.g. for reaction A B.
(K p ) 2 DH æ T 2 - T1 ö [H2(g) + I2(g) 2HI(g)]
log = ç ÷
(K p ) 1 2.303R çè T1T 2 ÷ø
(ii) When Dn = +ve, Kp > Kc e.g. for reaction A 2B.
where DH = Enthalpy change , (K p ) 1 and (K p ) 2 = [PCl5(g) PCl3(g) +Cl2(g)]
Equilibrium Constant at temperature T1 & T2 (iii) When Dn = –ve, Kp < Kc e.g. for reaction 2A B.
R = Universal gas Constant
[N2(g) +3H2(g) 2NH3(g)]
For exothermic reaction : Kp decreases with increase of temperature
æ Kf ö THE UNITS OF Kp AND Kc :
since Kf decreases. çç K p = K ÷÷ (i) Unit of Kp = (atm)Dn
è bø
For endothermic reaction. Kp increases with increase of (ii) Unit of Kc = (mol lit–1)Dn
temperature since Kf increases. CHARACTERISTICS OF EQUILIBRIUM CONSTANT :
(B) The mode of representing the reaction :
1. It has definite value for every chemical reaction at a particular
The reaction A + B C + D may be written as temperature
C+D A+ B 2. The more is the value of Kc or Kp, the more is the completion
of reaction or the more is the concentration of products.
K f [C][D] 3. When the reaction can be expressed as sum of two other
Kc = =
K b [A][B] reactions, the Kc of overall reaction is equal to the product
of equilibrium constants of individual reactions.
K ' f [A][B] 1 Illustration :
K 'c = = \ Kc =
K 'b [C][D] K 'c If K1, K2 and K3 are the quilibrium constants for the reaction
(1), (2) and (3) respectively, then prove that K1×K2=K3.
(C) Stoichiometric representation of equation :
H2S HS– + H+ ...(1)
(I) N2 + 3H2 2NH3
HS– S– – + H+ ...(2)
[ NH 3 ]2
Kc = H2S S– – + 2H+ ...(3)
[ N 2 ][H 2 ]3
[HS- ][H + ] [S-- ][H + ]
1 3 Sol. K1 = K2 =
N2 + H2 NH3 [H 2S] [HS- ]
2 2
[ NH 3 ] [S - - ][H + ]2
K' c = On multiplying K1 ´ K 2 = = K3
1 3 [H 2S]
[N 2 ] 2 [H 2
2]
4. The equilibrium constant is independent of initial
\ K c = K 'c concentrations of reacting species.
5. Independent of presence of catalyst.
USE OF PARTIAL PRES SURE INS TEAD OF 6. Kc for backward reaction is inverse of Kc for forward
CONCENTRATIONS : reaction.
For gaseous reactin g substances partial pressures are 7. Kc changes with stoichiometric representation of
conveniently used since at any fixed temperature partial pressure reaction.
is directly proportional to concentration. For a general reaction Illustration :
aA + bB cC + dD For the reaction 2SO2 + O2 2SO3 the equilibrium
constant is 49. Find the equilibrium constant for
éPC ù ´ [ PD ]
c d
K p = ë ûa 1
O2
[ PA ] ´ [ PB ]b SO2 +
2
SO3.
where [SO 3 ]
Dn = [moles of products – moles of reactants] gaseous only. Kc = (II)
1
[SO 2 ][O 2 ] 2
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
182 Chemistry
Since partial pressure of carbon (solid) is taken as unity, the
Concentrat ion terms of products
equilibrium constant is given by viz.
Concentrat ion terms of reactants
p CO ´ p H 2 Jeq means the partial pressure of the products and the reactants at
Kp =
p H 2O the equilibrium. Hence Jeq can be replaced by Kp.
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
184 Chemistry
Consider dissociation of PCl5. Let x be degree of dissociation
1
PCl5 PCl3 + Cl2 D= Molecular mass
2
1– x x x Total moles (1 + x) d is observed vapour density at temperature tºC.
D 1+ x D-d æ 1 ö If nx moles of products are formed, then total number of moles
\ = \x = çQ D µ ÷ after dissociation
d 1 d è moles ø
1 – x + nx = 1 + x (n – 1)
where D is the theoretical vapour density and
D 1 + x ( n - 1) D-d
\ = \x =
d 1 d ( n - 1)
JEEMAIN.GURU
downloaded from jeemain.guru
ê 10 ú ê 10 ú
On solving we get K''p = 0.144 × 10–4 atm. ë û ë û
6. The vapour density of PCl5 when in equilibrium with its \ [O2] = 0.1 mole
dissociation products was found to be 90. Calculate its degree 2
of dissociation. Also calculate the dissociation constant of é2ù
ê10 ú
PCl5 at this temperature if the pressure is in atmosphere. ë û = 100 ;
(ii) 2
é 1 ù é O2 ù
31 + 177.5 ê 10 ú ê 10 ú
Sol. Theoretical density D = = 104.25 ë û ë û
2
Observed density d = 90 [O2] = 0.4 mole
10. 1 mole of N2 is mixed with 3 moles of H2 in a 4 litre container.
D-d 104.25 - 90 If 0.25% N2 is converted into NH3 according to the equilibrium
Degree of dissociation x = = = 0.158
d(n - 1) 90 N2 + 3 H2 2 NH3. Calculate Kc. What will be the value of
Kp can be calculated as PCl5 PCl3 + Cl2 K 'c for the given reaction.
1 – 0.158 0.158 0.158
Total moles = 1 – 0.158 + 0.158 + 0.158 = 1.158 1 3
N2 + H2 NH3
2 2
JEEMAIN.GURU
downloaded from jeemain.guru
186 Chemistry
[SO 3 ][ NO] (1 + x )(1 + x ) when the volume of the container is doubled, the pressure of
Kc = = 16 ; = 16 N2O4 and NO2 shall be reduced to half
[SO 2 ][ NO 2 ] (1 - x )(1 - x)
N2O4 2NO2
3 0.14 0.55
x = = 0.6
5 (0.14 –x ) atm (0.55 + 2x) atm At new equilibrium
\ Concentration of NO = 1 + x = 1 + 0.6 = 1.6 mole
(0.55 + 2x ) 2
Concentration of NO2 = 1– x = 1– 0.6 = 0.4 mole. Kp = = 4.32
0.14 - x
12. Kc for PCl5 PCl3 + Cl2 is 0.04 at 25°C. How many moles
of PCl5 must be added to a 3 litre flask to obtain a Cl 2 of \ x = 0.045
concentration 0.15 M. Since temperature remains the same Kp will not change
Sol. At equil. No. of mole of Cl2 in 3L = 0.15×3 = 0.45 \. p = 0.14 - 0.045 = 0.095 atm
N 2O 4
PCl5 PCl3 + Cl2
x 0 0 Initial moles
and p NO2 = 0.55 + 2 ´ 0.045 = 0.64 atm
x – 0.45 0.45 0.45 Moles at eqb.
( x - 0.45) (0.45) (0.45) 16. The value of Kp at 298 K for the reaction
Molar conc. at eqb.
3 3 3 1/ 2 N 2 + 3/ 2 H 2 NH3
[ PCl 3 ][Cl 2 ] (0.15)(0.15) is found to be 826.0, partial pressures being measured in
Kc = =
[ PCl 5 ] ( x - 0.45) atmospheric units. Calculate DG ° at 298K
3
Sol. D G ° = -2.303 RTlogK p
\ x = 2.1 mole
13. The value of Kc is 0.50 for the reaction = -2.303 ´ 1.98 ´ 298 log 826 = -3980 calories
N2 + 3H2 2NH3 17. If 50% of CO2 converts to CO at the following equilibrium
at 400°C. Calculate the value of Kp for the given reaction at C (s) + CO2 (g) 2CO (g)
the same temperature (R = 0.0821 atm litre/ deg. mol) and the equilibrium pressure is 12 atm calculate Kp .
JEEMAIN.GURU
downloaded from jeemain.guru
18. The density of an equilibrium mixture of N2O4 and NO2 at 1 Sol. DG° = 2 ´ DG °f (N 2 ) + DG °f (O 2 ) - 2 ´ DG °f (N 2O)
atm and 348K is 1.84 g/c. Calculate Kc for the equilibrium
N2O4 (g) 2 NO2 (g) = (2 ´ 0 + 0) - 2 ´104.2 = -2.084 ´105 J / mol
Sol. N2O4 2 NO2 For gas phase reaction DG° is related to Kp as follows
1–x 2x
DG° = -2.303 RT log K p
92(1 - x) + 46 ´ 2x 92
Molecular wt of mixture = =
1+ x 1+ x
- 2.084 ´105 = -2.303 ´ 8.314 ´ 298 log K p
dRT
Further P =
M \ K p = 3.3 ´1036
JEEMAIN.GURU
downloaded from jeemain.guru
188 Chemistry
Very Short/Short Answer Questions If a mixture of 0.482 mol N2 and 0.933 mol of O2 is
placed in a reaction vessel of volume 10L and allowed
1. In a reaction a + b c + d the change in enthalpy is –10 to form N2O at a temperature for which Kc = 2.0 × 10–37.
kcal. If heat is added to the system in which direction the Determine the composition of the reaction mixture.
reaction would proceed? (ii) Bromine monochloride, BrCl, decomposes into bromine
2. What is meant by the statement ‘Equilibrium is dynamic in and chlorine and reaches the equilibrium
nature’? Br2(g) + Cl2(g)
2BrCl(g)
3. A + B AB; K = 1 ´ 102 for which Kc = 32 at 500 K. If initially pure BrCl is present
at a concentration of 3.30 × 10–3 mol L–1; what is its
E + F EF; K = 1 ´ 10 -3 molar concentration in the mixture at equilibrium?
Out of AB and EF, which one is more stable AB or EF ? 13. (i) How much of 0.3 M ammonium hydroxide should be
4. Which will have CO2 to more extent, hot cold drink bottle or mixed with 30 mL of 0.2 M solution of ammonium
chilled cold drink bottle, why ? chloride to give buffer solution of pH 8.65 and 10?
5. Write the expression for equilibrium constant Kp, for the [pKb = 4.75]
reaction. (ii) How much volume of 0.1 M HAc should be added to
Fe3O4(s) + 4H2(g)
3Fe(s) + 4H2O(g) 50 mL of 0.2 M NaAc solution if we want to prepare a
buffer solution of pH 4.91. (pKa = 4.76)
6. In a reaction a + b c + d will addition of c to the system
change the value of K? Multiple Choice Questions
7. The equilibrium constant for a gas phase reaction is 14. Which of the following is not a general characteristic of
4 equilibria involving physical processes ?
[CS2 ][H 2 ]
Kc = (a) Equilibrium is possible only in a closed system at a
[CH 4 ][H 2S]2 given temperature.
Write the balanced chemical equation corres- ponding to (b) All measurable properties of the system remain
this expression. constant.
8. In a gaseous reaction a + b c + 2d, 3 mol of inert gas (c) All the physical processes stop at equilibrium.
is introduced into the vessel at constant pressure. What (d) The opposing processes occur at the same rate and
will be its effect on equilibrium? there is dynamic but stable condition.
9. For the reaction 2a c + d , the equilibrium constant is 15. A reaction is A + B C + D. Initially we start with
1.0 × 10–3 . At equilibrium, the concentrations observed were equal concentrations of A and B. At equilibrium we find that
[c] = 1.2 × 10–3 M, [d] = 3.8 × 10–6 M. the moles of C is two times of A. What is the equilibrium
What was [a] at equilibrium? constant of the reaction?
10. On the reaction 2NH3 (g) N (g) + 3H (g) 1 1
2 2
DH = + 93.6 kJ. Tell us what would be effect of (a) (b)
4 2
(a) temperature (c) 4 (d) 2
(b) pressure 16. In the two gaseous reactions (I) and (II), at 25°C
11. The equilibrium constant for the following reaction is 1.6 ×
105 at 1024 K (I) NO (g) + 1 2 O 2 (g ) NO2 (g), K1
2HBr(g)
H2(g) + Br2(g)
(II) 2NO2 (g) 2NO (g) + O2 (g), K2
Find the equilibrium pressure of all gases if 10.0 bar of HBr
is introduced into a sealed container at 1024 K. the equilibrium constants K1 and K2 are related as
1 K1
Long Answer Questions (a) K 2 = (b) K2 =
K1 2
12. (i) Reaction between nitrogen and oxygen takes place as
following: 1
(c) K 2 = (d) K 2 = K12
2N2O(g)
2N2(g) + O2(g) K12
JEEMAIN.GURU
downloaded from jeemain.guru
1. Which is a reversible reaction? 3. A reaction attains equilibrium when the free energy change
(a) H 2 + I 2 ¾
¾® 2HI accompanying the reaction is
(a) positive and large
(b) H 2SO 4 + Ba (OH ) 2 ¾¾® BaSO 4 ¯ +2H 2 O
(b) zero
(c) NaCl + AgNO 3 ¾
¾® NaNO 3 + AgCl ¯ (c) negative and large
(d) negative and small
(d) 2KClO 3 ¾ ¾® 2 KCl + 3O 2 4. The equilibrium constant for the reversible reaction
2. The standard state Gibb's free energy change for the
N2 + 3H2 2NH3 is K and for the reaction
isomerisation reaction
cis-2-pentene trans-2-pentene is 1 N2 + 3 H 2 NH3, the equilibrium constant is K'.
–1
–3.67 kJ mol at 400 K. If more trans-2-pentene is added to 2 2
the reaction vessel K and K' will be related as
(a) more cis-2-pentene is formed
(a) K = K' (b) K' = K
(b) equilibrium shifts in the forward direction
(c) equilibrium remains unaltered (c) K = (d) K × K' = 1
K'
(d) more trans-2-pentene is produced
JEEMAIN.GURU
downloaded from jeemain.guru
190 Chemistry
5. If K1 and K2 are respective equilibrium constants for the two 12. For a chemical reaction 2A + B C, the thermodynamic
reactions equilibrium constant Kp is
XeF6 (g) + H2O (g) XeOF4 (g) + 2HF (g) (a) in atm–2 (b) in atm–3
XeO4 (g) + XeF6 (g) (c) in atm –1 (d) dimensionless
XeOF4 (g) + XeO3F2 (g) 13. When two reactants, A and B are mixed to give products C
the equilibrium constant for the reaction and D, the reaction quotient Q, at the initial stage of the
reaction
XeO4 (g) + 2HF (g) XeO3F2 (g) + H2O (g)
(a) is zero (b) decreases with time
will be
(c) is independent of time (d) increases with time
K1
(a) (b) K1.K 2 14. In the equilibrium reaction involving the dissociation of
K 22 CaCO3
K1 K2 CaCO3 (s) CaO (s) + CO2 (g)
(c) (d)
K2 K1
the equilibrium constant is given by
6. A cylinder fitted with a movable piston contains liquid water
in equilibrium with water vapour at 25°C. Which operation p CaO ´ p CO 2 p CO 2
(a) (b) C CaO ´
result in a decrease in the equilibrium vapour pressure p CaCO3 C CaCO3
(a) Moving the piston downward a short distance
(b) Removing a small amount of vapour p CaO
(c) (d) p CO2
(c) Removing a small amount of the liquid water pCaCO3
(d) Dissolving salt in the water 15. Steam reacts with iron at high temperature to give hydrogen
7. The volume of the reaction vessel containing an equilibrium gas and Fe3O4 (s). The correct expression for the equilibrium
mixture in the reaction constant is
SO2Cl2 (g) SO2 (g) + Cl2 (g)
is increased when the equilibrium is re-established PH2 (PH 2 ) 4
2
(a) (b)
(a) The amount of SO2 (g) will decrease PH2 O
2
(PH 2O ) 4
(b) The amount of SO2Cl2 (g) will increase
(c) The amount of Cl2 (g) will increase
(d) The amount of Cl2 (g) will remain unchanged (PH 2 ) 4 [Fe 3O 4 ] [Fe3O 4 ]
(c) (d)
8. In gaseous equilibrium the correct relation between Kc and 4
(PH 2O ) [Fe] [Fe]
Kp is
16. In lime kiln, the reversible reaction
(a) K c = K p ( RT) Dn (b) K p = K c ( RT) Dn
CaCO3 (s) CaO (s) + CO2 (g)
Kc Kp proceeds to completion because
(c) = ( K p ) Dn (d) = ( K c ) Dn
RT RT (a) of high temperature (b) CO2 escaped out
9. In which of the following reaction Kp > Kc (c) CaO is removed (d) of low temperature
(a) N2 + 3H2 2NH3 (b) H2 + I2 2HI 17. If 1.0 mole of I2 is introduced into 1.0 litre flask at
(c) PCl3 + Cl2 PCl5 (d) 2SO3 O2 + 2SO2 1000 K, at quilibrium (Kc = 10–6), which one is correct
(a) [I2 (g)] > [I– (g)] (b) [I2 (g)] < [I– (g)]
10. For reaction PCl3 (g) + Cl2 (g) PCl5 (g), the value of
Kc at 250°C is 26 mol–1 litre1. The value of Kp at this 1 -
(c) [I2 (g)] = [I– (g)] (d) [I2 (g)] = [I (g )]
temperature will be 2
(a) 0.61 atm–1 (b) 0.57 atm–1 18. At equilibrium, if Kp = 1, then
(c) 0.83 atm –1 (d) 0.46 atm–1 (a) DG° = 0 (b) DG ° > 1
11. The equilibrium constant for the reaction,
(c) DG ° < 1 (d) None of these
N2 (g) + O2 (g) 2NO (g)
–4
19. Van't Hoff's equation giving the effect of temperature on
is 4 × 10 at 2000 K.
chemical equilibrium is represented as
In presence of a catalyst, equilibrium is attained ten times
faster. Therefore, the equilibrium constant, in presence of the d ln F DH d ln K p DHT 2
(a) = (b) =
catalyst, at 2000 K is dT RT 2 dT R
(a) 40 × 10–4
(b) 4 × 10–4 d ln K p DH d ln K p RT 2
(c) 4 × 10–3 (c) =
2 (d) =
dT RT dT DH
(d) difficult to compute without more data
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
192 Chemistry
35. Kc for the reaction 42. 8 mole of a gas AB3 are introduced into a 1.0 dm3 vessel. It
N2 (g) + O2 (g) 2NO (g) dissociates as, 2AB3 (g) A2 (g) + 3B2 (g). At
–6
at 300 K is 4.0 × 10 . Kp for the above reaction will be equilibrium, 2 mole of A2 are found to be present. The
(R = 2 cal mol–1 K–1) equilibrium constant of reaction is .... in mol2L–2
(a) 2.4 × 10–3 (b) 4 × 10–6 (a) 2 (b) 3
–6
(c) 4 × 10 (RT) 2 (d) 16 × 10–12
(c) 27 (d) 36
36. Which of the following equilibria will shift to right side on
increasing the temperature? 43. DG° for the reaction X + Y Z is –ve 4.606 kcal. The
(a) CO (g) + H2O (g) CO2 (g) + H2 (g) equilibrium constant for the reaction at 227°C is
(b) 2SO2(g) + O2 (g) 2SO3 (g) (a) 100 (b) 10
(c) 2 (d) 0.01
(c) H2O (g) H2 (g) + 1 2 O 2 (g ) 44. The partial pressure of CH3OH (g), CO (g) and H2 (g) in
(d) 4HCl (g) + O2 (g) 2H2O (g) + 2Cl2 (g) equilibrium mixture for the reaction,
37. 1 mole of N2 and 2 moles of H2 are allowed to react in a 1 dm3 CO (g) + 2H2 (g) CH3OH (g) are 2.0, 1.0 and 0.1 atm
vessel. At equilibrium 0.8 mole of NH3 is formed. The respectively at 427°C. The value of Kp for the decomposition
concentration of H2 in the vessel is of CH3OH to CO and H2 is
(a) 0.6 mole (b) 0.8 mole
(a) 102 atm (b) 2 × 102 atm–1
(c) 0.2 mole (d) 0.4 mole 2
(c) 50 atm (d) 5 × 10–3 atm2
38. The equilibrium
45. Which of the following is not affected by pressure change?
SO2Cl2 (g) SO2 (g) + Cl2 (g)
is attained at 25°C in a closed container and an inert gas, (a) 2NO2 (g) N2O4 (g)
helium is introduced. Which of the following statement is (b) CO2 (g) + H2O (l) CO2 solution
correct?
(c) H2 (g) + I2 (g) 2HI (g)
(a) More chlorine is formed
(b) Concentration of SO2 is reduced (d) 2O3 (g) 3O2 (g)
(c) More SO2Cl2 is formed 46. The degree of dissociation of dinitrogen tetroxide
(d) Concentration of SO2Cl2, SO2 and Cl2 do not change
39. For which reaction high pressure and high temperature is ¾® 2 NO 2 (g ) at temperature T and total
N 2 O 4 (g ) ¾
helpful in obtaining a high equilibrium yield pressure P is a. Which one of the following is the correct
(a) 2NF3(g) N2(g) + 3F2(g) – 54.40 kcal expression for the equilibrium constant (Kp) at this temperature?
(b) N2(g) + 3H2(g) 2NH3(g) + 22.08 kcal 2a a 2P
(a) (b)
(c) Cl2(g) + 2O2(g) 2ClO2(g) – 49.40 kcal (1 - a 2 ) 1- a
(d) 2Cl2O7 (g) 2Cl2 (g) + 7O2(g) + 126.8 kcal
40. For the reversible reaction 4a 2 4a 2 P
(c) (d)
N2 (g) + 3H2 (g) 2NH3 (g) (1 - a 2 ) (1 - a 2 )
at 500°C, the value of Kp is 1.44 × 10–5 when partial pressure
47. Calculate the degree of dissociation of PCl5, the density at
is measured in atmospheres. The corresponding value of Kc
230°C is 70
with concentration in mole litre–1, is
(a) 97.8% (b) 48.9%
(a) 1.44 × 10–5 / (0.082 × 500)–2
(b) 1.44 × 10–5 / (8.314 × 773)–2 (c) 4.89% (d) 24.45%
(c) 1.44 × 10–5 / (0.082 × 773)2 48. When heated to 100°C the V.D. of N 2 O 4 becomes
(d) 1.44 × 10–5 / (0.082 × 773)–2 24.5. The degree of dissociation of N2O4 at this temp. will be
41. A 1 M solution of glucose reaches dissociation equilibrium (a) 80% (b) 87.74%
according to the equation given below (c) 40.34% (d) 60%
6HCHO C6H12O6 49. The correct relationship between free energy change in a
What is the concentration of HCHO at equilibrium if reaction and the corresponding equilibrium constant Kc is
equilibrium constant is 6 × 1022 (a) DG = RT ln K c (b) - DG = RT ln K c
(a) 1.6 × 10–8 M (b) 3.2 × 10 –6 M
–4
(c) DG° = RT ln K c (d) - DG° = RT ln K c
(c) 3.2 × 10 M (d) 1.6 × 10–4 M
JEEMAIN.GURU
downloaded from jeemain.guru
1. The following equilibrium constants are given: 4. The value of equilibrium constant of the reaction
1 1
2NH3 ; K1
N 2 + 3H 2 [CBSE-PMT 2003, 2007] HI ( g ) H 2 ( g ) + I 2 is 8.0 [CBSE-PMT 2008]
2 2
The equilibrium constant of the reaction
2NO; K 2
N 2 + O2
H 2 ( g ) + I2 ( g ) 2HI( g ) will be:
1
H 2 O; K 2
H 2 + O 2 1 1 1
2 (a) (b) (c) 16 (d)
16 64 8
The equilibrium constant for the oxidation of NH3 by oxygen 5. In which of the following equilibrium Kc and Kp are not equal?
to give NO is
(a) 2 NO(g ) N 2 (g ) + O 2 (g ) [CBSE-PMT 2010]
K 2 K32 K 22 K3 (b) SO 2 (g )+NO 2 (g ) SO3 (g ) + NO(g )
(a) (b)
K1 K1
(c) H 2 (g )+I2 (g ) 2 HI(g )
JEEMAIN.GURU
downloaded from jeemain.guru
194 Chemistry
8. Given the reaction between 2 gases represented by A2 and 16. In a cell that utilises the reaction
B2 to give the compound AB(g). [CBSE-PMT 2012M]
Zn (s) + 2H + (aq) ® Zn 2+ (aq) + H 2(g ) addition of H2SO4 to
A2(g) + B2(g) 2 AB(g).
cathode compartment, will [AIEEE 2004]
At equilibrium, the concentration
(a) increase the E and shift equilibrium to the right
of A2 = 3.0 × 10–3 M
(b) lower the E and shift equilibrium to the right
of B2= 4.2 × 10–3 M
(c) lower the E and shift equlibrium to the left
of AB = 2.8 × 10–3 M
(d) increase the E and shift equilibrium to the left
lf the reaction takes place in a sealed vessel at 527°C, then
the value of Kc will be : 17. The exothermic formation of CIF3 is represented by the
(a) 2.0 (b) 1.9 (c) 0.62 (d) 4.5 equation :
9. Change in volume of the system does not alter CI 2(g ) + 3F2(g ) 2ClF3 (g ) ; Δ H = – 329 kJ
the number of moles in which of the following
equilibria? [AIEEE 2002] Which of the following will increase the quantity of CIF3 in
(a) N2 (g) + O2 (g) 2NO (g) an equilibrium mixture of CI 2 , F2 and CIF3 ? [AIEEE 2005]
(b) PCl5 (g) PCl3 (g) + Cl2 (g)
(c) N2 (g) + 3H2 (g) 2NH3 (g) (a) Adding F2
(d) SO2Cl2 (g) SO2 (g) + Cl2 (g). (b) Increasing the volume of the container
10. In which of the following reactions, increase in the volume at (c) Removing Cl2
constant temperature does not affect the number of moles at
(d) Increasing the temperature
equilibrium. [AIEEE 2002]
(a) 2NH3(g) ® N2(g) + 3H2(g) 18. For the reaction [AIEEE 2005]
(b) C (s)+ (1/2)O2 (g) ® CO(g) 2 NO 2(g) 2NO (g ) + O 2(g ) ,
(c) H2 (g) + O2 (g) ® H2O2 (g)
(d) None of these. (K c = 1.8 ´ 10- 6 at 184°C) (R = 0.0831 kJ/ (mol. K))
11. For the reaction [AIEEE 2002]
CO (g) + (1/2) O2 (g) CO2 (g), Kp / Kc is When K p and K c are compared at 184°C, it is found that
(a) RT (b) (RT)–1
(c) (RT) –1/2 (d) (RT)1/2 (a) Whether K p is greater than, less than or equal to K c
12. For the reaction equilibrium depends upon the total gas pressure
N2O4 (g) 2 NO2 (g)
the concentrations of N2O4 and NO2 at equilibrium are 4.8 × (b) K p = K c
10–2 and 1.2 × 10–2 mol L–1 respectively. The value of Kc for
the reaction is [AIEEE 2003] (c) K p is less than K c
(a) 3 × 10–1 mol L–1 (b) 3 × 10–3 mol L–1
(d) K p is greater than K c
(c) 3 × 103 mol L–1 (d) 3.3 × 102 mol L–1
13. Consider the reaction equilibrium
19. An amount of solid NH 4 HS is placed in a flask already
2 SO2 (g) + O2(g) 2 SO3 (g) ; DHº = –198 kJ
containing ammonia gas at a certain temperature and 0.50
On the basis of Le Chatelier’s principle, the condition
atm pressure. Ammonium hydrogen sulphide decomposes
favourable for the forward reaction is [AIEEE 2003]
(a) increasing temperature as well as pressure to yield NH 3 and H 2S gases in the flask. When the
(b) lowering the temperature and increasing the pressure decomposition reaction reaches equilibrium, the total
(c) any value of temperature and pressure pressure in the flask rises to 0.84 atm? The equilibrium
(d) lowering of temperature as well as pressure
constant for NH 4 HS decomposition at this temperature is
14. What is the equilibrium expression for the reaction
P4(s) + 5O 2(g ) (a) 0.11 (b) 0.17 [AIEEE 2005]
P4O10(s) ? [AIEEE 2004]
(c) 0.18 (d) 0.30
(a) K c = [O 2 ]5 (b) K c = [ P4 O10 ] / 5[ P4 ][O 2 ] 20. The equilibrium constant for the reaction
JEEMAIN.GURU
downloaded from jeemain.guru
21. The equilibrium constants K p and K p2 for the reactions (a) K1 K 2 = K3 (b) K 2 K3 = K1
1
1. The decomposition of N2O4 to NO2 is carried out at 280 K in 6. For the reaction H2(g)+I2(g) 2HI(g) at 721 K, the value
chloroform. When equilibrium has been established, 0.2 mol of equilibrium constant is 50, when equilibrium concentration
of N2O4 and 2 ´ 10 -3 mol of NO2 are present in a 2l solution. of both is 5M. Value of Kp under the same conditions will be
(a) 0.02 (b) 0.2
The equilibrium constant for the reaction, N2O4 2NO2 is
(c) 50 (d) 50 RT
(a) 1 × 10–2 (b) 2 × 10–3 7. For which one of the following systems at equilibrium, at
(c) 1 × 10–5 (d) 2 × 10–5 constant temperature will the doubling of the volume cause
2. In an equilibrium reaction for which DG° = 0 , the equilibrium a shift to the right?
constant, K , should be equal to (a) H2(g)+Cl2(g) 2HCl(g)
(b) 2CO(g)+O2 (g) 2CO2(g)
(a) 0 (b) 1
(c) N2(g)+3H2(g) 2NH3(g)
(c) 2 (d) 10
3. The pressure change due to which equilibrium is not (d) PCl5 ( g ) PCl3 ( g ) + Cl 2 ( g )
affected is 8. For the reaction C(s)+CO2(g) 2CO(g) , the partial
(a) N 2 ( g ) + O2 ( g ) 2NO ( g ) pressures of CO2 and CO are 2.0 and 4.0 atm respectively at
equilibrium. The Kp for the reaction is.
(b) 2SO2(g)+O 2(g) 2SO3(g) (a) 0.5 (b) 4.0
(c) 8.0 (d) 32.0
(c) 2O3(g) 3O2(g) 9. In a chemical reaction calculate rate constant of backward
reaction when the rate constant of forward reaction is 20 and
(d) 2NO2(g) N2O4(g)
the equilibrium constant is 50
4. A reversible chemical reaction having two reactants in (a) (0.2) (b) (0.1)
equilibrium. If the concentration of the reactants are doubled (c) (0.4) (d) None of these
then the equilibrium constant will 10. The rate constant is given by the equation K=PZe–E/RT.
(a) be doubled (b) be halved Which factor should register a decrease for the reaction to
proceed more rapidly?
(c) become one-fourth (d) remain same (a) T (b) Z
5. 3.2 moles of hydrogen iodide were heated in a sealed bulb at (c) E (d) P
444°C till the equilibrium state was reached. Its degree of 11. For the reaction CO(g) + H2O(g) CO2(g) + H2(g) at a
dissociation at this temperature was found to be 22% The given temperature the equilibrium amount of CO2(g) can be
number of moles of hydrogen iodide present at equilibrium increased by
are (a) adding a suitable catalyst
(a) 2.496 (b) 1.87 (b) adding an inert gas
(c) decreasing the volume of the container
(c) 2 (d) 4 (d) increasing the amount of CO(g).
JEEMAIN.GURU
downloaded from jeemain.guru
196 Chemistry
12. At constant temperature, the equilibrium constant (Kp) for 18. By which of the following reactions, the equilibrium constant
the decomposition reaction N2O4 2NO2 is expressed is related to tempearture?
2 2
by Kp = (4x P)/(1-x ), where P = pressure, x = extent of DH º T2 æ1ö
decomposition. Which one of the following statements is (a) ln K 2 - ln K1 = dç ÷
R T1 èTø
true?
(a) Kp increases with increase of P DHº 1/ T 2 æ 1 ö
(b) ln K 2 - ln K 1 = - d
(b) Kp increases with increase of x R 1/ T1 çè T 2 ÷ø
(c) Kp increases with decrease of x
DH º T2 æ 1 ö
(d) Kp remains constant with change in P and x (c) ln K 2 - ln K1 = - dç ÷
13. Consider the following equilibrium in a closed container R T1 è T ø
N2O4(g) 2NO2(g) At a fixed temperature, the volume DHº 1/ T1 æ 1 ö
(d) ln K 2 - ln K 1 = - d
of the reaction container is halved. For this change, which of R 1/ T 2 çè T ÷ø
the following statements holds true regarding the equilibrium 19. Which of the following expressions is incorrect?
constant (Kp) and degree of dissociation ( a )?
(a) Kp does not changes, but a changes æ ln K p ö æ ln K c ö
(b) Kp changes, but a does not change (a) çç p ÷ø
÷ =0 (b) çç p
÷÷ = 0
è T è øT
(c) both Kp and a change
(d) neither Kp nor a changes æ ln K x ö - Dn
14. Which of the following is true at chemical equilibrium? (c) çç p
÷÷ =
( p / pº ) (d) All of these
è øT
(a) (DG)T, P is minimum and (DS)U,V is also minimum
20. K c for PCl5 (g) PCl3 (g) + Cl 2 (g) is 0.04 at 250°C.
(b) (DG)T,V is minimum and (DS)U,V is maximum
(c) (DG)T,V is maximum and (DS)U,V is zero How many moles of PCl 5 must be added to a 3 L flask to
(d) (DG)T,P is zero and (DS)U,V is also zero obtain a Cl 2 concentration of 0.15 M
15. For the reaction A(g) B(g)+C(g), (a) 4.2 moles (b) 2.1 moles
(a) Kp = a p3 (b) Kp = a2(Kp+p+1) (c) 5.5 moles (d) 6.3 moles
æ Kp + p ö 21. If CuSO 4 .5H 2O (s) CuSO 4 .3H2O(s) + 2H 2O(g)
(c) Kp = a2(Kp+p) (d) K p = a 2 çç ÷
÷
è p ø K p = 1 .086 ´ 10 - 4 atm 2 at 25° C. The eflorecent nature of
16. In the van’t Hoff equation CuSO 4 . 5H 2O can be noticed when the vapour pressure of
d1nK DHº H 2 O in atmosphere is
=
dT RT 2 (a) > 9.72 mm (b) < 7.92 mm
(c) < 7.92 mm (d) < 11.92 mm
(a) when dln K < 0 , the reaction is exothermic 22. In a closed system, A(s) 2B(g) + 3C(g), if partial pressure
dT of C is doubled, then partial pressure of B will be
(a) 2 2 times the original value
(b) when dln K < 0 , the reaction is endothermic
dT 1
(b) times the original value
(c) the slope of the graph is positive throughout 2
(d) the slope of graph increases and then decreases (c) 2 times the original value
17. Consider the expression DG = –RTlnKp+RTlnQp and indicate 1
the correct statement at equilibrium (d) times the original value
2 2
(a) DG = 0, Qp> Kp the equilibrium reaction will shift
from left to right 23. For the reactions
(b) DG = 0, Qp=Kp the equilibrium reaction will shift A B Kc =2
from left to right B C Kc =4
(c) DG = ¥,Qp<Kp the equilibrium reaction will shift
C D Kc =6
from right to left
(d) DG<0, Qp>Kp the equilibrium reaction will shift K c for the reaction A D is
from right to left
2´ 4
where Qp and Kp term refer to reaction quotient and (a) 2 × 4 × 6 (b)
6
equilibrium constant at constant pressure respectively.
4´ 6
(c) 2 + 4 + 6 (d)
2
JEEMAIN.GURU
downloaded from jeemain.guru
3´3 1 1
(a) atm - 2 (b) 0.5 ´ (1.5) 3 atm 2 (a) (b)
0.5 ´ (1.5) 3 3 81
1 1
(c) (d)
0.5 ´ (1.5) 3 (1.5) 3 9 27
(c) atm 2 (d) atm - 2
3´3 0.5 30. Equilibrium constant for the reaction
25. The reactions NH 4 OH (aq) + H + (aq) NH +4 (aq) + H 2 O ( l )
PCl5 (g) PCl3 (g) + Cl 2 (g) and is 1.8 × 10 9 . Hence equilibrium constant for ionisation
COCl 2 (g ) CO(g) + Cl 2 (g) NH 3 + H 2 O NH+4 (aq) + OH- (aq) is
are simultaneously in equilibrium in a vessel at constant (a) 1.80 ´ 10 - 9 (b) 1.80 ´ 10 5
volume. If some CO is introduced into the vessel then at the
new equilibrium (c) 1.80 ´ 10 - 5 (d) 5.55 ´ 10 -10
31. The degree of dissociation of PCl5 (a) obeying the
(a) Cl 2 is greater
equilibrium PCl 5 PCl 3 + Cl 2 is related to the
(b) PCl 5 is less equilibrium pressure by
(c) PCl 3 remain unchanged 1 1
(a) a µ (b) a µ
(d) PCl 5 is greater P4 P
The instability constant of the complex is 33. I - ions react with iodine in aqueous solution to form I3- ion
as
(a) 2.0 ´ 10 - 8 (b) 5.0 ´ 10 9
I - (aq) + I 2 (aq) I3- (aq).
(c) 2.0 ´ 10 - 4 (d) 2.0 ´ 10 4 When L of solution containing 1 mol of KI and 0.25 mol of
I 2 was reacted with excess of AgNO 3 , 0.80 mol of yellow
27. The equilibrium constant for a reaction is 1´ 10 20 at 300 K.
The standard free energy change for the reaction is ppt. was obtained. The stability constant of I3- ion is
(a) + 115 KJ (b) + 166 KJ (a) 0.20 (b) 5.0
(c) – 115 KJ (d) – 166 KJ (c) 20.0 (d) 0.05
34. A reaction A + 2B 2 C + D was studied using the initial
28. At temperature T K, PCl 5 is 50% dissociated at an concentrations of B which was 1.5 times that of A. At the
equilibrium pressure of 4 atm. At what pressure it would quilibrium, concentration of A and C were found to be equal.
dissociate to 80% at the same temperature Then K c for the equilibrium is
(a) 0.75 atm (b) 0.50 atm (a) 8 (b) 4
(c) 0.60 atm (d) 2.50 atm (c) 6 (d) 0.32
JEEMAIN.GURU
downloaded from jeemain.guru
198 Chemistry
35. 1.0 mol of AB5 (g) is placed in a closed container under one 41. When the reactants A and B are mixed to give products C
and D, the reaction quotient Q at the initial stage of reaction
atmosphere and at 300K. It is heated to 600K, when 20% by
is
mass of it dissociates as
(a) zero (b) independent of time
AB5 (g) ¾ ¾® AB(g) + 2 B2 (g). (c) increases with time (d) decreases with time
The resultant pressure is 42. The eqilibrium constant for the reaction
(a) 1.2 atm (b) 2.4 atm CO(g) + 2H 2 (g) CH 3OH(g)
(c) 1.4 atm (d) 2.8 atm is 4.3 at 250° C and 1.8 at 275° C. The reaction is
36. The pressure necessary to obtain 50% dissociation of PCl 5 (a) exothermic (b) endothermic
(c) Both (a) and (b) (d) Neither (a) nor (b)
at 250°C is numerically equal to
43. The element Bi melts at 271°C and has density of 9.73 g/ml
(a) three times of K p (b) 6 times of K p as a solid and 10.05 g/ml as a liquid at this temperature. For
(c) 2.5 times of K p (d) 8 times of K p the equilibrium Bi(s) Bi( l ), the melting point is
favoured in this endothermic reaction either by
37. The activation energies for the forward and reverse reactions (a) increasing temperature, decreasing pressure
in the system A B are 10.303 and 8.000 kcal respectively (b) decreasing temperature, decreasing pressure
at 500 K. Assuming that pre exponential factor to be same for (c) increasing temperature, increasing pressure
both the forward and the reverse steps and R = 2 cal K–1 mol– (d) there is no effect of pressure on melting point
1. Calculate the K of the reaction 44. Consider the gaseous equilibrium of
c
(a) 1.00 (b) 10.0 H 2 (g) + I 2 (g) 2HI (g)
(c) 0.1 (d) 100 In the following graphs the three gases are at equilibrium in
38. 28g N 2 and 6.0 g of H 2 are heated over catalyst in a closed a container. At some time t, extra I 2 is added. Which of the
one litre flask of 450°C. The entire equilibrium mixture following sets will respond to this situation ?
required 500 ml of 1.0 M H 2SO 4 for neutralisation. The value
HI HI
of K c for the reaction
N 2 (g) + 3H 2 (g ) 2 NH 3 (g) is P I2 P I2
H2 H2
(a) 0.06 mol -2 L2 (b) 0.59 mol -2 L2
t t
(c) 1.69 mol 2 L-2 (d) 0.03 mol 2 L-2
A B
39. 2 mol of SO 2 and 1 mol of O 2 are heated in a closed vessel
to reach the equilibrium
HI HI
2 SO 2 (g) + O 2 (g) 2 SO 3
The equilibrium mixture exerted a presure of 5 atm and required P I2 P I2
1/3 mol of K 2Cr2 O 7 in acidic medium. K p for the reaction H2 H2
is t
(a) 1.0 (b) 2.0 t
(c) 0.5 (d) 4.0 C D
40. A gaseous compound of molecular mass 82.1 dissociates on (a) A (b) B
heating to 400 K as (c) C (d) D
X 2 Y4 (g) X 2 (g) + 2 Y2 (g)
The density of the equilibrium mixture at a pressure of 1 atm
and temperature of 400K is 2.0gL-1 . The percentage
dissociation of the compound is
(a) 12.5% (b) 48.5%
(c) 90.1% (d) 25.0%
JEEMAIN.GURU
downloaded from jeemain.guru
( pH ) [Fe and Fe O are solids] 14. (d) Kp = pCO2 others are solids. The concentration terms for
4
2
5. Kp = solids and liquids are taken as unity.
( pH O )
4 3 4
2 15. (b) 3Fe(s) + 4H2O (steam) Fe3O4 (s) + 4 H2 (g)
6. No, K remains constant. (p H 2 ) 4
7. CH4(g) + 2H2S(g) ® 4H2(g) + CS2(g) Kp = (p 4 only gaseous products and reactants.
H 2O )
9. 4.56 × 10–6 mol2/l2
10. (a) Increase in temperature would favour the forward 16. (b) Forward reaction is favoured by removal of products.
reaction while decrease in temperature would favour 17. (a) I2 2I–
the backward reaction. 1–x 2x
(b) Increase in pressure favours the reaction towards less
number of moles of gaseous species. (2x ) 2
Kc = = 10 -6
11. pH = pBr = 2.5 × 10–2 bar (1 - x)
2 2
pHBr = 10.0 – 5.0 × 10–2
Soln. shows that (1 – x) > 2x \ éë I2 ( g ) ùû > éë I ( g ) ùû
-
» 10.0 bar
14. (c) 15. (c) 16. (c) 17. (d) 18. (c)
18. (a) DG° = –2.303 RT log Kpwhen Kp = 1, DG° = 0 since log 1 = 0
19. (b) 20. (a) 21. (a) 22. (d) 23. (b)
d ln K p DH
EXERCISE 2 19. (c) Van't Hoff's Isochore = . Relation between
dt RT 2
1. (a) The product is separated as solid or escapes as gas in an
T and Kc.
irreversible reaction.
20. (a) See Le Chatelier's principle.
2. (a) Le Chatelier's principle, equilibrium shifted in the
21. (b) Reverse reaction, Le Chatelier's principle Dn=2 – 1 = 1.
backward direction.
3. (b) DG = 0 at equilibrium. 22. (c) A + 2B 2C
Initial moles in 2 litres 2 3 2
4. (b) K ' = K
At Equilibrium moles in 2 litres 2.5 4 1
5. (d) Reaction (II) and reverse of reaction (I) gives the desired Molar conc. moles in 2 litres 1.25 2 0.5
1 K (0.5) 2
reaction hence K = K 2 ´ = 2 . Kc = = 0.05
K1 K1
(1.25)(2) 2
6. (d) Dissolution of salt lowers the V.P. It is also effected by
temperature. 23. (a) H2 + I2 2HI
7. (c) It will decrease the concentration. The equilibrium will Initial moles 4.5 4.5 0
shift in the direction where more moles are formed to Moles at eqm. 3 3 3
keep Kc constant.
(3) 2
8. (b) Relation is Kp = Kc (RT)Dn K= = 1 . Note : when there is no change in the
3´ 3
9. (d) Dn = 3 – 2 = 1; Kp = Kc (RT) hence Kp > Kc
number of moles, Dn = 0 the volume or capacity of vessel
10. (a) Q Dn = –1 \ Kp = 26 × (0.0821 × 523)–1 = 0.61 atm–1
can be ignored.
JEEMAIN.GURU
downloaded from jeemain.guru
200 Chemistry
24. (c) A+ B C +D 41. (d) C6H12O6 6HCHO
At eqb. x x 2x 2x Initial 1M
At eqb. 1–x 6x
2x.2x
Kc = =4
x.x [6x]6 1- x
Kc = for reverse reaction = 6 ´ 10 22 ;
1- x 6
(6 x )
25. (d) See Le Chatelier's principle.
On solving 6x = 1.6 × 10–4 M.
26. (b) A+ B C + D
42. (c) 2AB3 A2 (g) + 3B2 (g)
Initial 0.9 0.9 0 0
Initial moles 8 0 0
At eqm. 0.3 0.3 0.6 0.6
Moles at eqb. 8–x x 3x
2 2
0.6 ´ 0.6
Kc = =4
0.3 ´ 0.3 [B2 ]3[A 2 ] (6)3 ´ 2
given x 2 = 2 \ x = 4 Kc= = = 27
27. (c) Le Chatelier's principle since reaction is exothermic hence [AB3 ]2 (4)2
low temperature will favour forward reaction also volume
is decreased by applying high pressure. 43. (a) DGo = – 2.303 RT log K
– 4.606 × 103 = – 2.303 × 2 × 500 log Kc
28. (c) Reaction (II) is 1 2 of (I). \ K = K = 49 = 7 . \ Kc = 100.
29. (c) By addition of SO2 equilibrium will shift to RHS which is p CH 3OH 2
44. (d) K p = = = 200 ;
exothermic. Hence temperature will increase. p CO ´ p H 2 1 ´ (0.1) 2
Kf 2
30. (d) Keqb = = =2 1 1
Kb 1 For reverse reaction = = 5 ´10 -3 atm 2
K p 200
31. (a) H2 + I2 2HI
45. (c) No effect of pressure when Dn = 0.
Initial 1 2 0
46. (d) N2O4 2NO2
At eqb. 0.2 2 – 0.8 = 1.2 2 × 0.8 = 1.6
1–a 2a
32. (c) Le Chatelier's principle.
Total moles at eqb=1 – a + 2a = 1 + a
33. (a) Temperature and pressure (Le Chatelier's principle)
2
Dn ¹ 0 . æ 2a ö
p 2NO ç .P ÷
1+ a ø 4a 2 P
34. (d) A + B 2C Kc = 2
=è =
p N 2O 4 1- a 1- a2
.P
Initial moles 3 1 0 1+ a
At eqb. 3 – 0.75 1 – 0.75 1.5 47. (b) Degree of dissociation
(1.5) 2 D-d 104.25 - 70 M
Kc = =4 a= = = 48.9% (D = )
(2.25)(0.25) d(n - 1) 70(2 – 1) 2
JEEMAIN.GURU
downloaded from jeemain.guru
Kc =
[ AB]2 [ B2 ] or K = (2 x)2 ´ x æ ö
PZ = ç .P
è 1 + ÷ø 1
c
[AB2 ]2 {2(1 - x )}2
JEEMAIN.GURU
downloaded from jeemain.guru
202 Chemistry
9. (a) In this reaction the ratio of number of moles of reactants
1 P é KP ù
ê 1 = 9ú to products is same i.e. 2 : 2, hence change in volume will
or 9 = . 1 not alter the number of moles.
4 P2 ê KP 1ú
ë 2 û 10. (d) In (a), (b) and (c) no. of mole of products is not equal to
P1 36 no. of mole of reactants.
or = or P1 : P2 = 36 : 1
P2 1 æ 1ö 3 1
11. (d) K p = K c ( RT ) Dn ; Dn = 1 - ç1 + ÷ = 1 - =- .
i.e. option (c) is correct answer. è 2ø 2 2
4. (b) Given : Equilibrium constant (K1) for the reaction Kp -1 / 2
1 1 \ K = (RT )
HI( g )
K1
H 2 ( g ) + I2 ( g ); K1 = 8; .........(i) c
2 2
To find equilibrium constant for the following reaction [ NO 2 ]2 [1.2 ´10-2 ]2
12. (b) K C = = = 3 ´10 -3 mol/L
H 2 ( g ) + I2 ( g ) 2HI( g ); K2 = ? .....(ii) [ N2O4 ] -2
[4.8 ´10 ]
For this multiply (i) by 2, we get 13. (b) Due to exothermicity of reaction low or optimum
2HI( g ) H 2 ( g ) + I 2 ( g ); temperature will be required. Since 3 moles are changing
to 2 moles.
K1 = 82 = 64. .....(iii)
\ High pressure will be required.
[Note: When the equation for an equilibrium is multiplied
by a factor, the equilibrium constant must be raised to 14. (d) For P4 (s) + 5O 2 (g) P4O10 (s)
the power equal to the factor] 1
Now reverse equation (iii), we get Kc = . The solids have concentration unity
(O 2 ) 5
1
H 2 ( g ) + I2 ( g ) 2HI( g ); K = .....(iv)
64 Dn
Kp 1
[Note: For a reversible reaction, the equilibrium constant 15. (c) K p = K c (RT ) ; Dn = 1 - 2 = 1 \ =
Kc RT
of the backward reaction is inverse of the equilibrium
constant for the forward reaction.] 16. (a) Zn(s) + 2H + (aq) Zn 2 + (aq) + H 2 (g )
Equation (iv) is the same as the required equation (ii),
0.059 [Zn 2 + ][H 2 ]
1 E cell = E °cell - log
thus K2 for equation (ii) is i.e. option (b) is correct. 2 [H + ]2
64
Addition of H2SO4 will increase [H+]and Ecell will also
5. (d) 2C(s )+O2 (g ) 2 CO 2 (g ) increase and the equilibrium will shift towards RHS
Dn = 2 – 1 = + 1 17. (a) The reaction given is an exothermic reaction thus
\ Kc and Kp are not equal. according to Le chatalier ’s principle lowering of
temperature, addition of F2 and Cl2 favour the forward
6. (c) 2A(g) + B(g) 3C(g) + D(g)
direction and hence the production of ClF3.
Mole ratio 2 1 3 1
Molar concentration 1 1 0 0 at t = 0 18.
(d) For the reaction:- 2NO2 ( g ) 2NO(g) + O2 (g)
Equilibrium molar 1– 0.5 1– 0.25 0.75 0.25
Given Kc = 1.8 × 10–6 at 184 ºC
concentration = 0.50 = 0.75
R = 0.00831 kJ/mol. K
7. (c) 2SO3 K = 278 (given)
2SO2 + O2 Dn g
K p = K c ( RT )
æ 1ö
SO 2 + 1 O2
SO3 K' = ç ÷
Dn g = 3 - 2 = 1
2 è Kø
Kp= 1.8 × 10–6 × 0.00831 × 457
= 6.836 × 10–6
1 –2
= = 35.97 ´ 10-4 = 6 × 10 Hence it is clear that Kp > Kc
278
19. (a) NH 4 HS(s ) NH 3 (g ) + H2S (g )
[AB]2 start 0.5 atm 0 atm
8. 2AB
(c) A2 + B2 Kc = At equib . 0.5 + x atm x atm.
[A 2 ][B2 ]
Then 0.5 + x + x = 2x + 0.5 = 0.84 (given)
(2.8 ´ 10-3 )2 Þ x = 0.17 atm.
Kc =
3 ´ 10 -3 ´ 4.2 ´ 10 -3 p NH3 = 0.5 + 0.17 = 0.67 atm ; p H 2S = 0.17 atm
(2.8)2
= = 0.62 K= p NH3 ´ p H 2S = 0.67 ´ 0.17 atm 2 = 0.1139 = 0.11
3 ´ 4.2
JEEMAIN.GURU
downloaded from jeemain.guru
PT1 1 é K P1 1 ù
20. (c) SO3(g) SO 2 (g ) +
1
O 2 (g) or = êQ = given ú
2 PT2 9 ëê K P2 9 úû
[SO 2 ] [O 2 ]½
KC = = 4.9 ´10 -2 ; PT1 1
[SO 3 ] or = or 1 : 36
PT2 36
On taking the square of the above reaction
[SO 2 ]2 [O 2 ] i.e., (b) is the correct answer.
= 24.01´10 - 4 22. (c) Reaction (c) can be obtained by adding reactions (a)
2
[SO 3 ] and (b) therefore K3 = K1. K2
Now K'C for 2SO2(g) + O2(g) 2SO3 Hence (c) is the correct answer.
[SO 3 ]2 1 23. (a) 2CO
CO2 + C(graphite)
= = = 416
[SO 2 ]2 [O 2 ] 24.01´10 - 4 Pinitial 0.5atm 0
21. (b) Let the initial moles of X be ‘a’ and that of Z be ‘b’ then Pfinal (0.5 – x)atm 2 x atm
for the given reactions, we have Total P at equilibrium = 0.5 – x + 2x = 0.5 + x atm
0.8 = 0.5 + x
X
2Y \ x = 0.8 – 0.5 = 0.3 atm
Initial a moles 0 Now Kp = (PCO ) /PCO
2
2
At equi a(1 – a) 2aa
2
(moles) (2 ´ 0.3) (0.6) 2
= = = 1.8 atm
Total no. of moles = a (1 – a) + 2aa (0.5 – 0.3) (0.2)
= a – aa + 2aa 24. (d) For the reaction
= a (1 + a) N2 + O2 ¾¾ ® 2NO K = 4 × 10–4
Hence for the reaction
Dn
(n y ) 2 æ PT ö 1 1 1 1
KP = ´ç 1 ÷ NO ¾¾
® N2 + O2 K'= = = 50
Now, ç n÷ 2 2 K 4×10 – 4
1 nx
è ø
EXERCISE 4
(2aa )2 .PT1
or, K P1 = 1. (c) N2O4 2NO2
[a(1 - a)][a(1 + a)]
0.2/2 2×10–3 /2 Concentration at equilibrium
Z P + Q
[ NO 2 ]2 = 10 -3 ´ 10 -3
Kc = = 1 ´ 10 - 5
Initial b moles 0 0 [ N 2O 4 ] 0.1
At equi b(1 – a) ba ba 2. (b) D G ° = - R T ln K c for DG° = 0 , Kc = 1; since ln 1 = 0
(moles) 3. (a) When moles of gaseous reactants and the products are the
Total no . of moles = b(1 – a) + ba + ba same on both sides, their is no effect of pressure
= b – ba + ba + ba 4. (d) The equilibrium constant does not vary with any factor
other than temperature
= b(1 + a)
3.20 ´ 22
Dn
5. (a) 2HI H2+I2 .It is 22% decomposed , \ = 0.704
nQ ´ nP é PT ù 100
Now K P2 = ´ê 2 ú (3.2–0.704) is equal to HI present at equilibrium which is
n2 ëê n ûú = 2.496
6. (c) H2(g)+I2(g) 2HI(g)
(ba)(ba).PT2
or K P2 = Kp = Kc (RT) Dn ; Dn = 2 - 2 = 0; \ K p = K c
[b(1 - a)][b(1 + a)] 7. (d) When volume is increased the conc. decreases & the
equilibrium shifts in the direction where more moles are
formed.
K P1 4a 2 .PT1 (1 - a )2 4PT1
or = ´ = 2
PCO 4´4
K P2 (1 - a 2 ) PT2 .a 2 PT2 8. (c) Kp = ; Kp = = 8; C(s) = 1; The concentration
PCO2 2
of solids and liquids are taken as unity
JEEMAIN.GURU
downloaded from jeemain.guru
204 Chemistry
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
206 Chemistry
28 6 PM 1 ´ 82.1
38. (b) Moles of N 2 = = 1, Moles of H 2 = =3 40. (a) D = = = 2.5 g L-1
28 2 RT 0.0821´ 400
500 ´ 1
= 0.5 d = 2.0 g L-1 (given)
Moles of H 2SO 4 required =
1000 D-d 2.5 - 2
Moles of NH 3 neutralised by H 2SO 4 = 1.0 a= = = 0.125 = 12.5%
d(n - 1) 2(3 –1)
( 2NH 3 + H 2SO 4 ¾¾
® (NH 4 ) 2 SO 4 ) 41. (a) The reaction quotient Q is
pC ´ pD
. In the initial stage
pA ´ pB
Hence 1 mol of NH 3 by the reaction between N 2 and
C and D are not present. So p C and p D are zero. Then
H2 .
With the passage of the time p C and p D increase and
N 2 + 3H 2 2 NH 3
1 3 0 initial p A and p B decrease.
1 – 0.5 3 – 0.5 × 3 1 at equilibrium 1
42. (a) For exothermic reaction, K c µ
1´ 1 Temperature
Kc = = 0.592
0.5 ´ (1.5) 3 43. (c) Since the melting is endothermic increasing temperature
will favour melting. Since density of solid is less
39. (a) Eq. wt. of SO 2 = Mol. wt./2 (SO 2 ¾
¾® SO 3 )
æ Mö
2- 3+ çD = ÷ , the high pressure will reduce V and increase
Eq. wt. of K 2Cr2 O 7 = Mol. wt./6 (Cr2 O 7 ® 2Cr ) è Vø
1 6 D, hence more melting.
mol of K 2 Cr2 O 7 =
3 3 p 2HI
44. (b) K p =
or, 2 geq of K 2Cr2 O 7 = 2 geq of SO 2 = 1 mol of SO 2 p H 2 ´ p I2
It means only 1 mole of SO 2 reacted with O 2 . Addition of I 2 will increase p I 2 , hence to keep K p
2 SO 2 + O 2 2SO 3
1 mol 1 mol 0 mol initial constant, either p H 2 should decrease or p HI should
1 mol (1 – 0.5) mol 1 mol at equilibrium increase. Hence the graph (B).
\ Total moles at equilibrium = 1 + 0.5 + 1 = 2.5
2
æ 1 ö
2 ç ´ 5÷
p SO 3 è 2. 5 ø
Kp = = = 1.0
2
p 2SO 2 ´ p O 2 æ 1 ö æ 0.5 ö
ç ´ 5÷ ´ ç ´ 5÷
è 2 .5 ø è 2.5 ø
JEEMAIN.GURU
downloaded from jeemain.guru
7B
Ionic Equilibrium
ARRHENIUS THEORY OF IONISATION : 5. Solvation : The more the solvation, the more is the
On the basis of colligative properties of solutions of salts, acids ionisation.
and bases, Arrhenius proposed the theory of ionisation i.e. 6. Presence of the ions in the solution : Ionisation decreases
spliting of these substances into ions in solution. It is reversible in presence of common ions.
process, effects electrical conductivity, colligative properties like ELECTROLYTE :
depression in freezing point, elevation in boiling point, lowering A substance which splits into ions in solution is called electrolyte.
of vapour pressure, osmotic pressure. It can be an acid, base or salt.
EVIDENCES IN FAVOUR OF IONISATION : (i) Strong electrolyte : Which dissociates almost completely
into ions even in concentrated solution eg. NaOH, KOH,
1. X-ray diffraction studies
HCl, H2SO4, NaCl, CaCl2.
2. Ionic reactions
(ii) Weak electrolyte : Which dissociates to a small extent into
3. Heat of neutralisation ions in solution eg CH3COOH, NH4OH etc.
4. Colour of compounds and their solutions Note : Salts are always strong electrolytes.
5. Colligative properties
OSTWALD'S DILUTION LAW :
6. Conductance of electrolytes in solution
The degree of ionisation or dissociation (a) of weak electrolytes
DEGREE OF IONISATION OR DISSOCIATION (a) : increases with dilution and law of mass action can be applied to
The fraction of the total number of molecules which is ionised at them.
the equilibrium state is known as degree of ionisation or AB A+ + B–
dissociation.
C 0 0 initial conc.
Number of moles ionised C(1-a) Ca Ca equilibrium conc.
a= Ionisation constant K = Ca2
Total number of moles
K 1
FACTORS AFFECTING IONISATION OR \a = aµ
DISSOCIATION : C C
1. Nature of electrolytes : The stronger the electrolyte, the Concentration of A+ or B– = Ca
more is the ionisation and vice versa. a approaches unity with dilution.
2. Nature of solvent : The more the dielectric constant of ACIDS AND BASES :
solvent, the more is the ionisation. 1. Arrhenius concept : An acid is a substance that dissociates
3. Concentration : The lesser the concentration, the more is to give hydrogen ions when dissolved in water eg. HCl,
the ionisation. CH3COOH, H3PO4.
4. Temperature : The higher the temperature, the more is the A base is a substance that dissociates to give hydroxyl ions
ionisation. when dissolved in water eg. NaOH, Ca(OH)2.
JEEMAIN.GURU
downloaded from jeemain.guru
208 Chemistry
2. Lowry and bronsted concept : An acid is a substance which Soft bases : Species having donor atom of lower
has a tendency to donate a proton (H+) to any other electronegativity and higher polarisability e.g. P, As, S, Se
substance. etc. Examples R3P, R2S, I–.
A base is a substance which has a tendency to accept a 7. Lux-flood concept of acids and bases : An oxide ion donor is
proton (H+) from any other substance. a base and an oxide ion acceptor is an acid.
Acid H+ + Base BaO + SiO 2 ¾
¾® BaSiO 3
Acid and base differing by a proton are known as conjugate base acid
pair. The weaker the acid, the stronger the base in conjugate MgO + SO 3 ¾
¾® MgSO 4
pair and vice versa. base acid
Acid1 + Base2 Acid2 + Base1 8. Ingold concept : All electrophiles are acids and nucleophiles
+ – are bases.
HCl + H2O H3O + Cl
+ –
H2SO4 + H2O H3O + HSO4 STRENGTH OF ACIDS AND BASES :
+ –
HCl + NH3 NH4 + Cl The greater the value of Ka or Kb the stronger is the acid or base.
+
Conjugate acid Conjugate base + H the smaller the value of pKa the sronger is the acid.
3. Lewis concept : An acid is a substance which can accept a pKa values of some acids (Acid strength)
pair of electrons from any other substance e.g. BF3, AlCl3 Acid Base Approximate pKa
(incomplete octet), SnCl4, SF4 (central atom has vacant d- 1. HClO4 ClO4– –10
orbital) or cations Fe3+, Cu2+ etc. 2. HI I– –10
A base is a substance capable to donating a pair of electrons –
3. H2SO4 HSO4 –9.5
to any other substance eg. anions X – , OH – ,
4. HBr Br – –9
CN– or neutral molecules having lone pair(s) of electrons on
.. .. 5. HCl Cl – –7
..
one or more atom R O
..H,
NH 3 , H 2 O
. . etc. 6. Ar. SO3H ArSO3– –6.5
Lewis acid may be any of the following types of substances 7. CH(CN)3 C–(CN)3 –5
1. Molecules having an atom with incomplete octet
2. Simple cations 8. H- C-H H- C - H –4
|| ||
3. Molecules with central atom having empty Å OH O
d-orbitals
4. Molecules with a multiple bond between atoms of Å
9. R - O- R R–O–R –3.5
different electronegativities |
Strength of some Lewis acids H
BX3 > AlCl3 > FeX3 > GaX3 > SbX5 > InX3 > SnX4 > 10. H3O+ H2O –1.74
AsX5 > ZnX2 > HgX2 11. HNO3 NO3– –1.4
4. Extended Lewis concept : When the central atom is bonded
12. HSO4– SO4 –– 1.99
to atoms of different electronegativities by multiple bonds,
the substance is known as extended Lewis acid e.g. CO2, 13. HF F– 3.17
CS2 etc. 14. HNO2 NO2– 3.29
Extended Lewis base e.g. CO and unsaturated hydrocarbons +
like alkenes, alkynes etc. are also known as border line Lewis 15. Ar NH 3 ArNH2 3.5
bases. 16. RCOOH RCOO– 4.5
5. Hard acids : Cations of lighter elements, smaller size, higher
17. H2CO3 HCO3– 6.35
charge not easily polarisable e.g. light alkali and alkaline
metal ions of B, Al, Si, Ti4+, Cr3+, Co2+, Fe3+ (lighter transition 18. H2S HS– 7.00
elements). 19. NH4+ NH3 9.24
Soft acids : Cations of heavier elements, larger size, lower 20. ArOH ArO– 8-11
charge and easily polarisable e.g. heavy transition metal 21. HCO3– CO3 –– 10.33
ions (second and third row) e.g. Hg2+, Pd2+, Cd2+, Cu+, 22. H2O OH– 15.74
Ag+, Hg+ etc.
6. Hard bases : Species having donor atoms of higher 23. RCONH2 RCONH 17
electronegativity and low polarisability e.g. N, O, F, Cl etc. 24. RCH2OH RCH2O– 18
Examples H2O, NH3, ROH.
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
210 Chemistry
Ex. :What will be the H+ ion concentration of a solution obtained --
by mixing 500 ml of 0.20 M CH3COOH and 500 ml of 0.30 M Ag2 S Ksp = [Ag+]2 [S ]
CH3COONa (Ka of CH3COOH= 1.8 × 10–5) --
Sb2S3 Ksp = [Sb3+]2 [S ] 3
Sol. :Concentration of CH3COOH in the mixture
Ex.: Ksp of AgCl is 2.8 × 10–10 at 25°C. Calculate the solubility of
0.20 ´ 500 AgCl in (I) Pure Water (II) 0.1 M AgNO3 solution (III) 0.1 M
= = 0.10 mol / l
1000 NaCl.
Concentration of CH3COONa in the mixture Sol. (I) Let S mole/l be the solubility of AgCl
Ksp = [Ag+][Cl–] = S × S = S2;
0.30 ´ 500
= = 0.15 mol / l
1000 \ S = K sp = 2.8 ´ 10 -10 = 1.67 ´10 -5 mol / l
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
212 Chemistry
Ex. :Calculate the pH of an aqueous soln. of 1.0 M ammonium
Kw
(v) Degree of hydrolysis µ = formate assuming complete dissociation (pKa of formic
Kb ´ C acid = 3.8 and ammonia = 4.8) (IIT 1995)
K w .C 1 1
[H + ] = Sol. pH = (pK w + pK a - pK b ) = (14 + 3.8 - 4.8) = 6.5
(vi) Kb 2 2
BUFFERS :
1 1
(vii) pH = 7 - pK b - log C Solutions which resist the change in the value of pH when small
2 2 amount of acid or base is added to them are known as buffers.
4. Hydrolysis of salts of weak bases and weak acids : e.g. Types
CH3COONH4 (I) Simple buffers : Solution of salt of weak acid and weak base
CH3COONH4 + H2O CH3COOH + NH4OH CH3COONH4, NH4CN.
or CH3COO– + NH4+ + H2O CH3COOH + NH4OH (II) Mixed buffers :
(a) Acidic buffers : Solution of equimolar mixture of a weak
(i) The solution may be neutral, acidic or basic depending
upon the relative strength of weak acid CH3COOH acid and its salt with a strong base e.g. (CH3COOH +
and weak base NH4OH formed. The salt is said to be CH3COONa); (H2CO3 + NaHCO3); (Boric acid + borax);
hydrolysed. (H3PO4 + NaH2PO4)
(ii) Hydrolysis is known as cationic as well as anionic (b) Basic buffers : Solution of equimolar mixture of a weak
hydrolysis. base and its salt with a strong acid e.g. (NH4OH + NH4Cl)
Buffer action of simple buffer : CH3COONH4 exist as ions
Kw
(iii) Salt hydrolysis Const., Kh = CH3COO– and N + H 4 in solution. Added acid (H+) combine with
Ka ´ Kb
(iv) pH of the solution may be 7, > 7 or <7 CH3COO– to give feebly ionised CH3COOH and added base
(OH–) combine with NH4+ to give feebly ionised NH4OH. Thus
Kw pH remains unchanged
(v) Degree of hydrolysis, a =
Ka ´ K b Buffer action of mixed buffers :
(a) Acidic buffer :
K w ´ Ka
(vi) H+ = +
Kb
CH3COONa CH 3 COO - + Na CH3COOH
H+
1 1 1
(vii) pH = pK w + pK a - pK b
2 2 2 When small amount of an acid is added to the buffer the
Ex. :Calculate the degree of hydrolysis and hydrolysis constant added H+ ions combine with CH3COO– to form feebly
of decinormal solution of NaCN. The dissociation constant ionised CH3COOH and when small amount of a base is added
of HCN is 7.2 × 10–10 at 25°C. to the buffer the added OH– ions combine with H+ to form
feebly ionised H2O. In the latter case more CH3COOH ionises
Kw 1´ 10-14 to keep K a of acid constant and hence constant
Sol. a = = = 1.178 ´10 - 2
C´ Ka 0.1´ 7.2 ´10 -10 concentration of H+ ions. Thus whether we add acid or a
base, the H+ concentration remain constant and pH of
Kw 1´10 -14 solution does not change
Kh = = = 1.388 ´10 -5
K a 7.2 ´10 -10 (b) Basic buffer :
Ex. :How many grams of sodium acetate must be added NH4Cl NH 4+ + Cl - NH4OH
to 500 ml of water to give a solution of pH = 8.52 OH -
(Ka = 1.8 × 10–5)
When small amount of an acid is added to the buffer the
Sol. Sodium acetate is salt of weak acid and strong base
added H+ ions combine with OH– to form feebly ionised
1 H2O, equilibrium is disturbed. More NH4OH ionises to keep
pH = 7 + pK a + log C
2 [OH–] fixed.
1 When small amount of a base is added to the buffer the
8.52 = (14 + 4.74 + log C) added OH– ions combine with NH4+ to form feebly ionised
2
NH4OH to keep [OH–] fixed. Hence there is no change of pH
(- log K a = pK a \ - log 1.8 ´ 10-5 = 4.74) in both cases.
C = 0.02 mol/litre
Hence wt. of CH3COONa in 500 ml = 0.01 × 82 = 0.82 g
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
214 Chemistry
Consider the ionisation of phenolphthalein which is weakly Methyl Orange :
acidic in nature
–
HPh H+ + Ph– SO3 N=N N(CH3)2
Colourless Pink
Addition of a strong base will disturb the equilibrium (OH– Benzenoid form (Yellow)
+ H+ H2O) and more phenolphthalein will ionise
giving pink solution. Addition of a strong acid will suppress +
–
N=N N(CH ) SO3 NH – N N(CH3)2
the ionisation of phenolphthalein by common ion effect,
solution will be colourless. The indicator is not suitable for
titrating weak base like NH4OH against strong acid.
Benzenoid The
form (Yellow) Quinonoid form (Red)
OH– ions furnished by weak base are insufficient to shift
the equilibrium and pink colour does not appear just at the Types of indicators
end point. Excess of weak base is required. 1. Internal : Which can be added to reacting substances further
Action of methyl orange : Methyl orange is a weak base they can be acid base indicator (phenolphthalein, methyl
and is ionised as follows : orange etc.) redox indicators, used for redox titrations (N-
phenyl anthranilic acid) adsorption indicators (starch).
MeOH Me+ + OH–
2. External : Which can not be added to reacting substances
Yellow Red e.g. potassium ferricyanide for titration of K2Cr2O7 vs.
Addition of a strong acid will disturb the equilibrium (H+ + FeSO4(NH4)2SO4.6H2O.
OH– H2O) and more methyl orange will ionise giving 3. Radioactive : 8O18 and D2 for studying reaction mechanism.
red solution. Addition of a strong base will suppress the Choice of indicator
ionisation of methyl orange by common ion effect hence 1. For strong acid and strong base - methyl orange,
solution will be yellow in colour. The indicator is not suitable phenolphthalein and Litmus.
for titrating weak acid like CH3COOH against strong base.
2. For weak acid and strong base - phenolphthalein.
The H+ ions furnished by weak acid are not sufficient to
shift the equilibrium and red colour does not appear just at 3. For strong acid and weak base - methyl orange.
the end point. Excess of weak acid is required. 4. For weak acid and weak base - Phenol red.
(2) Quinonoid theory : Some important Acid Base Indicators
In the unionised form the indicator is generally in the Indicator pH range Colour in Colour in
benzenoid form which is less intense in colour and in the
acidic sol. alkaline sol.
ionised form it is in the Quinonoid form which is more intense
in colour. Cresol red (acid) 1.2 - 1.8 Red Yellow
Phenolphthalein : Thymol blue (acid) 1.2 - 2.8 Red Yellow
Methyl Orange 3.1 - 4.5 Red Yellow
H–O OH Methyl red 4.2 - 6.3 Red Yellow
Phenol red 6.4 - 8.2 Yellow Red
C
Cresol red (base) 7.0 - 8.1 Yellow Red
Thymol blue (base) 8.1 - 9.6 Yellow Red
O Phenolphthalein 8.1 - 9.8 Colourless Pink
C Alizarin yellow 10.1 - 12.1 Yellow Lilac (violet)
:O: SALTS :
Benzenoid form (colourless) The compounds containing positive and negative ions are known
as salts. Their solutions may be acidic, basic or neutral. They are
– classified as
:O O
(i) Simple salts : Formed by neutralisation of an acid and a
base. They may be further classified as follows.
(a) Normal salts : Salts not containing replaceable
C +H+ hydrogen or a hydroxyl group e.g. Na2SO4, KNO3,
Al2 (PO4)3, CaCl2.
O
(b) Acidic salts : Salts containing replaceable hydrogen
–
C– O: atoms NaHSO4, Na2HPO4, NaHCO3.
(c) Basic salts : Salts containing replaceable hydroxyl
:O: O
groups Zn(OH)Cl, Mg(OH)Cl, Fe(OH)2Cl.
oid form (colourless) Quinonoid form (Pink)
JEEMAIN.GURU
downloaded from jeemain.guru
1. Nicotinic acid (Ka = 1.4 × 10–5) has formula HNiC. Calculate 4. A solution contains 0.1 M H2S and 0.3 M HCl. Calculate the
its percent dissociation in a solution which contains 0.10 concentration of S– – and SH– ions in solution. Given K a1 and
mole of nicotinic acid per 2.0 litre of solution.
Ka 2 for H2S are 10–7 and 1.3 × 10–13 respectively..
Sol. HNiC + H2O H3O+ + NiC–
Ka
Molar concentration of nicotinic acid = 0.05 mole/lit. 1
Sol. (I) H2S H++ HS–
% Degree of dissociation
Ka
2
-5 (II) HS– H+ + S– –
Ka 1.4 ´ 10
a= = ´100 = 1.67.
C 0.05 [H + ][HS - ] [H + ][S -- ]
K a1 = Ka2 =
2. Enthalpy of neutralisation of CH3 COOH by NaOH [H 2S] [SH - ]
is –55.9 kJ/mol. DH for the ionisation of CH3COOH is
Sol. 57.1 – 55.9 = 1.2 KJ/mol [H + ]2 [S- - ]
K a1 ´ K a 2 =
3. Calculate the amount of heat released when [H 2S]
(I) 100 ml of 0.2 M HCl soution is mixed with 200 ml of H2S is weak electrolyte in presence of HCl its ionisation is
0.2 M KOH suppressed due to common ion effect.
(II) 200 ml of 0.2 M H2SO4 is mixed with equal volume of 0.2 K a1 ´ K a 2 [H 2S]
M KOH [S - - ] =
[H + ]2
100 ´ 0.2
Sol. (I) Moles of H+ ions = = 0.02 1 .0 ´ 10 - 7 ´ 1 .3 ´ 10 -13 ´ 0 .1
1000 = = 1 .44 ´ 10 - 20 M
( 0 . 3) 2
200 ´ 0.2 Putting [S– –] in equation (II)
Moles of OH– ion = = 0.04
1000
[H + ][S - - ] 0.3 ´ 1.44 ´ 10 -20
H2O formed is = 0.02 Moles [SH–] = = = 3.3 ´ 10 -8 M
Ka2 1.3 ´ 10 -13
Hence heat released = 57.1 × 0.02 = 1.142 kJ
5. The pH of 0.1 M hydrocyanic acid solution is 5.2. What is
200 ´ 0.2 the value of Ka for hydrocyanic acid.
(II) Moles of H+ ions = = 0.04
1000 1
Sol. log = pH = 5.2
200 ´ 0.2 [H + ]
and Moles of OH– = = 0.04
1000 [H+] = 6.2 × 10–6 M, [H+] = ca = C ´ Ka
Moles of H2O formed is = 0.04
(6.3 ´10 -6 ) 2
Heat released = 57.1 × 0.04 = 2.18 kJ =K a ; \ K a = 3.96 ´10 -10 M
0.1
JEEMAIN.GURU
downloaded from jeemain.guru
216 Chemistry
6. Calculate the pH of Sol. The minimum concentration of S– – ion required to precipitate
(I) 1.0 × 10–8 M HCl (II) 1.0 × 10–8 M NaOH MS is
Sol. K sp 6.0 ´10 -21
(I) [H+] conc. due to water and HCl = [1 × 10–7 + 1 × 10–8] (S- - ) = = = 1.2 ´ 10-19 M
[M + + ] 0.05
[H+] = 10–8 (10 + 1) = 10–8 × 11
–log [H+] = 8 log 10 – log 11 ionisation of H2S; H2S H+ + HS–
pH = 8 – 1.04 = 6.96. [H + ][SH - ]
(II) Total [OH–] = [1 × 10–7 + 1 × 10–8] K1 = 10–7, K1 =
[H 2S]
Solving as in case (I) pOH = 6.96. \ pH = 7.04.
7. What is the hydrogen ion concentration of 0.1 N CH3COOH HS– H+ + S– –; K2 = 1.3 × 10–13
solution. The ionisation constant of CH3COOH is 1.8 × 10–5.
What is the pH of solution. [H + ][S -- ]
K2 =
[SH - ]
+
Sol. [ H ] = C ´K a = 0.1´ 1.8 ´ 10 -5 -3
= 1.34 ´ 10 M On multiplying,
pH = – log [H+] = – log 1.34 × 10–3 = 2.8729. [H + ]2 [S- - ]
8. What volume of 0.10 M sodium formate solution should be K1 × K2 =
[H 2S]
added to 50 ml of 0.05 M formic acid to produce a buffer
solution of pH 4.0, pKa of formic acid is 3.80. [H+ ]2 ´1.2 ´10-19
10-7 ´1.3 ´10-13 =
Salt 0.1
Sol. pH = pKa + log +
Solving for [H ] = 1.04 × 10 –1
Acid
pH = – log [H+] = – log (1.04 × 10–1) = 0.98.
Let the volume added be V ml. then 11. The pH of 0.05 M aqueous solution of diethylamine is 12.
V ´ 0.10 Calculate its Kb.
4 = 3.8 + log Sol. pH + pOH = 14
0.05 ´ 50
pOH = 14 – 12 = 2; [OH–] = 10–2
Solving for V we get V = 39.5 ml. (C2H5)2 NH + H2O (C2H5)2 NH2+ + OH–
9. Freshly precipitated aluminium and magnesium hydroxides 0.05 – 0.01 0.01 0.01
are stirred vigrously in a buffer solution containing 0.05 mol
0.01´ 0.01
L–1 of NH4OH and 0.25 mol L–1 of NH4Cl. Calculate the Kb = = 2.5 ´ 10 -3
conc. of aluminium and magnesium ions in solution. Ksp of 0.04
Al(OH)3 = 6 × 10–32, Ksp of Mg(OH)2 = 6 × 10–10, Kb of NH4OH 12. Ka for butyric acid is 2 × 10–5. Calculate the pH and hydroxyl
= 1.8 × 10–5. ion concentration of 0.2 M aqs. solution of sodium butyrate.
Sol. Sodium butyrate is a salt of weak acid and
K b ´ [BASE] strong base
Sol. The [OH - ] =
[SALT]
Kw ´Ka 1´10 -14 ´ 2 ´10 -5
[H + ] = = = 10 -9
1 .8 ´ 10 -5 ´ 0.05 C 0.2
= = 0. 36 ´ 10 - 5 mol L-1
0. 25 Hence pH = 9
10–14 = [H+] [OH–]
K sp of Al(OH) 3 10–14 = 10–9[OH–]
[Al 3+ ] = [OH–] = 10–5
[OH - ]3
13. Calculate the pH of an aqueous solution of 1.0 M ammonium
formate assuming complete dissociation pK a for formic acid
6 ´ 10-32
= = 1.29 ´10 -10 mol L-1
(0.36 ´10 -5 )3 = 3.8 and pK b of ammonia = 4.8.
Sol. Ammonium formate is a salt of weak acid and weak base.
2+ K sp of Mg (OH) 2 6 ´10 -10 -1
[Mg ]= = = 46.3 mol L 1 1
[OH - ]2 (0.36 ´ 10 -5 ) 2 Hence pH = 7 + pKa – pKb
2 2
10. An aqueous solution of metal bromide MBr2 (0.05 M) is
1 1
saturated with H2S what is the minimum pH at which MS =7+ × 3.8 – × 4.8 = 6.5
will precipitate? Ksp for MS = 6.0 × 10–21. Conc. of saturated 2 2
H2S = 0.1 M. K1 = 10–7 and K2 = 1.3 × 10–13 for H2S.
JEEMAIN.GURU
downloaded from jeemain.guru
HA + OH– A– + H2O -4
18. The Ka for formic acid and acetic acid are 2.1 × 10 and 1.1
JEEMAIN.GURU
downloaded from jeemain.guru
218 Chemistry
[Salt] \ V = 78.36 ml
pOH = – log Kb + log 24. Zn salt is mixed with (NH4)2S of molarity = 0.021 M, what
[Base]
amount of Zn 2+ will remain unprecipitated in 12ml of the
solution . Ksp of ZnS = 4.51 × 10–24
0 .1
= – log 1.8 × 10 - 5 + log Sol. (NH4)2S = 0.021 M ; [S– –] = 0.021 M
0 .1
--
pOH = 4.7447 At equilibrium [ Zn + + ] [S ] = Ksp of ZnS
pH = 14 – 4.7447 = 9.2553
4.51´10 - 24
(a) Addition of 0.02 mole of HCl [ Zn + + ] = = 2.15 × 10 - 22 M
0.021
HCl + NH 4 OH ¾
¾® NH 4 Cl+ H 2 O
JEEMAIN.GURU
downloaded from jeemain.guru
[ Zn 2+ ] left in solution = 2.15 × 10 - 22 × 65 g/litre 26. Calculate pH of a saturated solution of Mg (OH ) 2 . Ksp for
25. Will a precipitate of Mg (OH ) 2 be formed in a 0.001 M Let the solubility of Mg (OH ) 2 be S mole lit -1 ;
Sol. pH = 9; \ [H + ] = 10 - 9 M S = 1.305 × 10 - 4 M
-4
or [OH - ] = 10 - 5 M [OH - ] = 2S = 2 × 1.305 × 10
pOH = 3.5832
Product of ionic conc. = [ Mg 2 + ] [OH - ]2 pH = 10.4168
= [0.001] [10- 5 ]2 = 10 - 13
JEEMAIN.GURU
downloaded from jeemain.guru
220 Chemistry
Very Short/Short Answer Questions 15. (i) How much of 0.3 M ammonium hydroxide should be
1. The equilibrium constants for HCN and HAc are 4.0 ×10–10 mixed with 30 mL of 0.2 M solution of ammonium
and 1.9 ×10–5 mole/L respectively. Which acid is stronger? chloride to give buffer solution of pH 8.65 and 10?
[pKb = 4.75]
2. A certain metal sulphide MS, has a solubility product (ii) How much volume of 0.1 M HAc should be added to
1.3 ×10–18 mole2/l2 . What must be [S – 2] be in a 0.10M 50 mL of 0.2 M NaAc solution if we want to prepare a
buffer solution of pH 4.91. (pKa = 4.76)
solution of M2+ when MS just starts to precipitate.
3. pKa values of acids A, B, C, D are 1.5, 3.5, 2.0 and 5.0. Which
Multiple Choice Questions
of them is strongest acid ? 16. Which of the following can act both as Bronsted acid and
4. Which of the following is strongest Lewis acid ? CCl4, AlCl3, Bronsted base?
NCl3, OCl2. (a) Na2CO3 (b) OH–
5. Which of the following is strongest conjugate base? CH3– (c) HCO3– (d) NH3
, NH2–, OH–, F–. 17. Which equilibrium can be described as an
6. What happens to ionic product of water if temperature is acid-base reaction using the Lewis acid-base definition but
increased? not using the Bronsted-Lowry definition?
7. All Bronsted acids are not Lewis acids. Explain. (a) 2NH3 + H2SO4 2NH4+ + SO42–
8. Calculate the molar concentration of an acetic acid solution (b) NH3 + CH3COOH
which is 2% ionized? ( Ka = 1.8 × 10–5)
NH4+ + CH3COO–
9. Which has the greater molarity in water, AgCl or Mg(OH)2
(c) H2O + CH3COOH
(Ksp (AgCl) = 1.8 ´ 10 -10 ,
(KspMg(OH)2 = 1.2 × 10–11) H3O+ + CH3COO–
10. Calculate the pH of the solution produced when an aqueous (d) [Cu(H2O)4]2– + 4 NH3
solution of pH = 5 is mixed with equal volume of an aqueous [Cu(NH3)4]2+ + 4H2O
solution of pH = 3.
18. The ionisation constant of an acid, Ka, is the measure of
11. A sparingly soluble salt gets precipitated only when the strength of an acid. The K a values of acetic acid,
product of concentration of its ions in the solution (Qsp)
hypochlorous acid and formic acid are 1.74 × 10–5, 3.0 × 10–8
becomes greater than its solubility product. If the solubility
and 1.8 × 10–4 respectively. Which of the following orders
of BaSO4 in water is 8 × 10–4 mol dm–3. Calculate its
of pH of 0.1 mol dm–3 solutions of these acids is correct?
solubility in 0.01 mol dm–3 of H2SO4.
(a) acetic acid > hypochlorous acid > formic acid
Long Answer Questions (b) hypochlorous acid > acetic acid > formic acid
12. (i) A sample of orange juice was found to have a pH of 10– (c) formic acid > hypochlorous acid > acetic acid
3. 80. What were the H+ and OH– concentrations in the (d) formic acid > acetic acid > hypochlorous acid
juice?
19. K a1 , Ka2 and K a3 are the respective ionisation constants
(ii) What is the pH of a 5.0×10–4 M solution of NaOH at
25°C? for the following reactions.
13. (i) What is the pH of a solution that contains 0. 10 M HCl
H 2S H + + HS-
and 0.10 M CH3COOH? For acetic acid, Ka = 1.8×10–5.
(ii) What are the concentrations of all the species present HS- H + + S2 -
in a 0. 50 M solution of acetic acid. For CH3COOH Ka =
1.8 × 10–5. H 2S 2H + + S2 -
14. Carbonic acid, H2CO3, is a weak diprotic acid formed by the
The correct relationship between K a1 , Ka2 and Ka3 is
reaction of carbon dioxide with water, For this acid,
Ka1 = 4.3 × 10–7and K a = 5.6 × 10–11. What are the (a) K a3 = K a1 ´ K a2 (b) K a3 = K a1 + K a2
2
equilibrium concentrations of each species in a 0. 10 M K a3 = K a1 - K a2 (d) K a3 = K a1 / K a2
(c)
solution of carbonic acid?
JEEMAIN.GURU
downloaded from jeemain.guru
1. Which will not affect the degree of ionization? 9. Which of the following is not a Lewis base?
(a) Temperature (b) Concentration (a) CH4 (b) C2H5OH
(c) Type of solvent (d) Current (c) Acetone (d) Sec amine
2. At infinite dilution, the percentage ionisation for both strong 10. Which of the following is not a Lewis acid?
and weak electrolytes is (a) BF3 (b) AlCl3
(a) 1% (b) 20% (c) FeCl3 (d) PH3
(c) 50% (d) 100% 11. In the given anions, the strongest Bronsted base is
3. A 0.2 molar solution of formic acid is 3.2% ionized. Its (a) ClO– (b) ClO2–
ionisation constant is (c) ClO3– (d) ClO4–
(a) 9.6 × 10–3 (b) 2.1 × 10–4 12. Which of the following can act as both Bronsted acid and
(c) 1.25 × 10–6 (d) 4.8 × 10–5 Bronsted base?
4. The hydrogen ion concentration of 0.2 N CH3COOH which (a) Na2CO3 (b) OH–
(c) HCO3 – (d) NH3
is 40% dissociated is
(a) 0.08 N (b) 0.12 N 13. Which of the following is the strongest Lewis acid?
(c) 0.80 N (d) 1.2 N (a) BI3 (b) BBr3
5. Degree of dissociation of 0.1 N CH3COOH is (Dissociation (c) BCl3 (d) BF3
constant = 1 × 10–5) 14. The strongest conjugate base is
(a) 10–5 (b) 10–4 (a) NO3– (b) Cl–
(c) SO4 2– (d) CH3COO–
(c) 10–3 (d) 10–2
15. A base, as defined by Bronsted theory, is a substance which
6. A monoprotic acid in a 0.1 M solution ionizes to 0.001%. Its
can
ionisation constant is
(a) lose a pair of electrons
(a) 1.0 × 10–3 (b) 1.0 × 10–6
(b) donate protons
(c) 1.0 × 10–8 (d) 1.0 × 10–11
(c) gain a pair of electrons
7. The concentration of water molecules in one litre of water at
(d) accept protons
298 K is
16. Which of the following is strongest Lewis base?
(a) 10–7 M (b) 55.5 M
(a) CH3– (b) NH2–
(c) 5.55 M (d) 7.26 M –
(c) OH (d) F–
8. Which of the following will occur if 0.1 M solution of a weak 17. Aluminium chloride is
acid is diluted to 0.01 M at constant temperature
(a) Bronsted Lowry acid (b) Arrhenius acid
(a) [H+] will decrease to 0.01 M (c) Lewis acid (d) Lewis base
(b) pH will decrese 18. BF3 is an acid according to
(c) Percentage ionization will increase (a) Arrhenius concept (b) Bronsted-Lowry concept
(d) Ka will increase (c) Lewis Concept (d) Both (b) and (c)
JEEMAIN.GURU
downloaded from jeemain.guru
222 Chemistry
19. Which of the following is not a Lewis acid? 29. A compound having the formula NH2CH2COOH may behave
(a) CO (b) SiCl4 (a) only as an acid
(c) SO3 (d) Zn 2+ (b) only as a base
20. Ammonium ion is (c) both as an acid and base
(a) a conjugate acid (d) Neither acid nor base
(b) a conjugate base 30. Water is a
(c) both an acid and a base (a) protophobic solvent (b) protophilic solvent
(d) neither an acid nor a base (c) amphiprotic solvent (d) aprotic solvent
21. Among the following, the weakest base is 31. To Ag2CrO4 solution over its own precipitate, CrO42– ions
(a) H– (b) CH3– are added. This results in
(c) CH3O – (d) Cl– (a) increase in Ag+ concentration
In the equation I 2 + I - ¾ (b) decrease in Ag+ concentration
22. ¾® I 3- , which is the Lewis base?
(c) increase in solubility product
(a) I2 (b) I–
–
(d) shifting of Ag+ ions from the precipitate into the solution
(c) I3 (d) None of these
32. To suppress the dissociation of acetic acid, the compound
23. Which one of the following compounds is not a protonic
to be added to it is
acid
(a) sodium oxalate (b) sodium acetate
(a) PO(OH)3 (b) SO(OH)2
(c) sodium carbonate (d) sodium nitrate
(c) SO2(OH)2 (d) B(OH)3
24. Which equilibrium can be described as an acid-base reaction 33. Addition of which chemical will decrease the hydrogen ion
using the Lewis acid-base definition but not using the concentration of an acetic acid solution
Bronsted-Lowry definition? (a) NH4Cl (b) Al2(SO4)3
(c) AgNO3 (d) NaCN
(a) 2NH3 + H2SO4 2NH4+ + SO42–
34. Why only As+3 gets precipitated as As2S3 and not Zn+2 as
(b) NH3 + CH3COOH ZnS when H2S is passed throgh an acidic solution containing
NH4+ + CH3COO– As+3 and Zn+2?
(c) H2O + CH3COOH (a) Solubility product of As2S3 is less than that of ZnS
H3O+ + CH3COO– (b) Enough As+3 are present in acidic medium
(c) Zinc salt does not ionise in acidic medium
(d) [Cu(H2O)4]2– + 4 NH3
(d) Solubility product changes in presence of an acid
[Cu(NH3)4]2+ + 4H2O 35. The precipitation occurs if ionic concentration is
25. Which one of the following is the strongest acid? (a) less than solubility product
(a) ClO3OH (b) ClO2 (OH) (b) more than solubility product
(c) SO(OH)2 (d) SO2(OH)2 (c) equal to solubility product
26. Why are strong acids generally used as standard solutions
(d) None of these
in acid-base titrations?
36. The solubility of AgCl will be minimum in
(a) The pH at the equivalent point will always be 7
(a) 0.001 M AgNO3 (b) pure water
(b) They can be used to titrate both strong and weak bases
(c) Strong acids form more stable solutions than weak acids (c) 0.01 M CaCl2 (d) 0.01 M NaCl
(d) The salts of strong acid do not hydrolyse 37. The solubility of PbCl2 is
27. At a certain temperature the dissociation constants (a) K sp (b) (K sp )1 / 3
of formic acid and acetic acid are 1.8 × 10 –4 and (c) (K sp / 4)1 / 3 (d) (8K sp )1/ 2
1.8 × 10–6 respectively. The concentration of acetic acid
solution in which the hydrogen ion has the same 38. The solubility of calcium phosphate in water is
concentration as in 0.001 M formic acid solution is equal to x mol L–1 at 25°C. Its solubility product is equal to
(a) 0.001 M (b) 0.01 M (a) 108 x2 (b) 36 x3
(c) 36 x5 (d) 108 x5
(c) 0.1 M (d) 0.0001 M
28. What is the decreasing order of basic strengths of 39. Which of the following sulphides has the lowest solubility
OH–, NH2–, H–C º C– and CH3 – CH2– product?
(a) FeS (b) MnS
(a) CH 3 - CH -2 > NH -2 > H - C º C - > OH -
(c) PbS (d) ZnS
(b) H - C º C - > CH 3 CH -2 > NH -2 > OH - 40. The K sp of CuS, Ag 2 S and HgS are 10 –31 ,
10–44 and 10 –54 respectively. The solubility of these
(c) OH - > NH -2 > H - C º C - > CH 3 - CH -2 sulphides are in the order
(a) Ag2S > CuS > HgS (b) AgS > HgS > CuS
(d) NH -2 > H - C º C - > OH - > CH 3 - CH -2
(c) HgS > Ag2S > CuS (d) CuS > Ag2S > HgS
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
224 Chemistry
67. The pH of 0.0001 M NaOH is 80. Which of the following solution cannot act as a buffer?
(a) 4 (b) 10 (a) NaH2PO4 + H3PO4
(c) 12 (d) 11 (b) CH3COOH + CH3COONa
68. The pOH value of a solution whose hydroxide ion (c) HCl + NH4Cl
concentration is 6.2 × 10–9 mol/litre is (d) H3PO4 + NaH2PO4
(a) 8.21 (b) 6.21 81. A buffer solution of pH 9 can be prepared by mixing
(c) 7.75 (d) 7.21 (a) CH3COONa and CH3COOH
69. The pH of a solution obtained by mixing 50 ml of 0.4 N HCl (b) NaCl and NaOH
and 50 ml of 0.2 N NaOH is
(c) NH4Cl and NH4OH
(a) – log 2 (b) – log 0.2
(d) KH2PO4 and K2HPO4
(c) 1.0 (d) 2.0
70. The pH of 1.0 M aqueous solution of a weak acid HA is 6.0. 82. Which of the following is the buffer solution of strong acidic
Its dissociation constant is nature?
(a) 1.0 × 10–12 (b) 1.0 × 10–6 (a) HCOOH + HCOO–
(c) 1.0 (d) 6.0 (b) CH 3COOH + CH 3COO -
71. The pH of a solution is increased from 3 to 6; its H+ ion (c) H2C2O4 + C2O42–
concentration will be (d) H3BO3 + BO33–
(a) reduced to half (b) doubled 83. One litre of a buffer solution containing 0.01 M NH4Cl and
(c) reduced by 1000 times (d) increased by 1000 times 0.1 M NH4OH having pKb of 5 has pH of
72. When CO2 dissolves in water, the following equilibrium is (a) 9 (b) 10
established CO2 + 2H2O H3O+ + HCO3– (c) 4 (d) 6
for which the equilibrium constant is 3.8 × 10–7 and pH = 6.0. 84. A certain buffer solution contains equal concentration of
The ratio of [HCO3–] to [CO2] would be X– and HX. The Ka for HX is 10–8. The pH of the buffer is
(a) 3.8 × 10–13 (b) 3.8 × 10–1 (a) 3 (b) 8
(c) 6.0 (d) 13.4 (c) 11 (d) 14
73. An example of a salt that will not hydrolyse is 85. In a mixture of a weak acid and its salt, the ratio of the
(a) NH4Cl (b) KCl concentration of acid to salt is increased tenfold. The pH of
(c) CH3COONH4 (d) CH3COOK the solution
74. pH of 2 M NaCl will be (a) decreases by one (b) decreases by one tenth
(a) 3 (b) 6.5
(c) increases by one (d) increases by ten-fold
(c) 7 (d) 10
86. How much sodium acetate should be added to 0.1 M solution
75. Dissociation constant of NH4OH is 1.8 × 10–5. The
of CH3COOH to give a solution of pH 5.5
hydrolysis constant of NH4Cl would be
(pKa of CH3COOH = 4.5)
(a) 1.80 × 10–19 (b) 5.55 × 10–10
(c) 5.55 × 10 –5 (d) 1.80 × 10–5 (a) 0.1 M (b) 0.2 M
76. What is the percentage hydrolysis of NaCN in N/80 solution (c) 1.0 M (d) 10.0 M
when the dissociation constant for HCN is 1.3 × 10–9 and 87. For preparing a buffer solution of pH 6 by mixing sodium
Kw = 1.0 × 10–14 acetate and acetic acid, the ratio of the concentration of salt
(a) 2.48 (b) 5.26 and acid should be (Ka = 10–5)
(c) 8.2 (d) 9.6 (a) 1 : 10 (b) 10 : 1
77. The pH of a 1 M CH3COONa solution in water will be nearly (c) 100 : 1 (d) 1 : 100
(a) 2.4 (b) 5.4 88. What is [H+] of a solution that is 0.1 M HCN and 0.2 M
(c) 7.4 (d) 9.4 NaCN? (Ka for HCN = 6.2 × 10–10)
78. A physician wishes to prepare a buffer solution at (a) 3.1 × 1010 (b) 6.2 × 105
pH = 3.58 that efficiently resists a change in pH yet contains (c) 6.2 × 10 –10 (d) 3.1 × 10–10
only small conc. of the buffering agents. Which one of the 89. The pH of a buffer containing equal molar concentrations
following weak acid together with its sodium salt would be of a weak base and its chloride
best to use?
(Kb for weak base = 2 × 10–5, log 2 = 0.3) is
(a) m-chloro benzoic acid (pKa = 3.98)
(a) 5 (b) 9
(b) p-chloro cinnamic acid (pKa = 4.41)
(c) 4.7 (d) 9.3
(c) 2,5-dihydroxy benzoic acid (pKa = 2.97)
(d) Acetoacetic acid (pKa = 3.58) 90. How many ml of 1 M H2SO4 is required to neutralise 10 ml of
79. Which one is Buffer solution? 1 M NaOH solution?
(a) [PO4–3] [HPO42–] (b) [PO43–] [H2PO4–] (a) 2.5 (b) 5.0
(c) [HPO42–] [H2PO4–] (d) All of these (c) 10.0 (d) 20.0
JEEMAIN.GURU
downloaded from jeemain.guru
1. A weak acid, HA, has a Ka of 1.0 × 10–5. If 0.1 mole of this 6. The dissociation constants for acetic acid and HCN at 25°C
acid dissolved in one litre of water, the percentage of acid are 1.5 × 10–5 and 4.5 × 10–10 respectively. The equilibrium
dissociated at equilbrium is closest to [CBSE-PMT 2007] constant for the equilibrium [CBSE-PMT 2009]
(a) 1.0% (b) 99.9% (c) 0.1% (d) 99.0%
CN– + CH3COOH HCN + CH3COO– would be:
2. Calculate the pOH of a solution at 25°C that contains
1× 10– 10 M of hydronium ions, i.e. H3O+. [CBSE-PMT 2007] (a) 3.0 × 10– 5 (b) 3.0 × 10– 4
(a) 4.0 (b) 9.0 (c) 1.0 (d) 7.0 (c) 3.0 × 104 (d) 3.0 × 105
3. Equal volumes of three acid solutions of pH 3, 4 and 5 are 7. Which of the following molecules acts as a Lewis acid ?
mixed in a vessel. What will be the H+ ion concentration in [CBSE-PMT 2009]
the mixture ? [CBSE-PMT 2008]
–4 (a) (CH3)2 O (b) (CH3)3 P (c) (CH3)3 N (d) (CH3)3 B
(a) 1.11 × 10 M (b) 3.7 × 10–4 M
–
(c) 3.7 × 10 M 3 (d) 1.11× 10–3 M 8. The ionization constant of ammonium hydroxide is 1.77 × 10–5
4. If the concentration of OH– ions in the reaction at 298 K. Hydrolysis constant of ammonium chloride is:
JEEMAIN.GURU
downloaded from jeemain.guru
226 Chemistry
10. What is [H + ] in mol/L of a solution that is 0.20 M in 20. 1 M NaCl and 1 M HCl are present in an aqueous solution.
CH3COONa and 0.10 M in CH3COOH ? Ka for CH3COOH The solution is [AIEEE 2002]
(a) not a buffer solution with pH < 7
= 1.8 × 10-5 . [CBSE-PMT 2010]
(b) not a buffer solution with pH > 7
(a) 3.5 × 10 -4 (b) 1.1 × 10 -5 (c) a buffer solution with pH < 7
(d) a buffer solution with pH > 7.
(c) 1.8 × 10 -5 (d) 9.0 × 10 -6
21. Species acting as both Bronsted acid and base is
11. In a buffer solution containing equal concentration of B–
(a) (HSO4)–1 (b) Na2CO3
and HB, the Kb for B– is 10–10. The pH of buffer solution is :
(c) NH3 (d) OH–1.
[CBSE-PMT 2010]
22. Let the solubility of an aqueous solution of Mg(OH)2
(a) 10 (b) 7 (c) 6 (d) 4 be x then its Ksp is [AIEEE 2002]
12. Which one of the following molecular hydrides acts as a Lewis (a) 4x3 (b) 108x5
acid? [CBSE-PMT 2010] (c) 27x4 (d) 9x.
(a) NH3 (b) H2O (c) B2H6 (d) CH4 23. The solubility of Mg(OH) 2 is S moles/litre.
13. A buffer solution is prepared in which the concentration of The solubility product under the same condition
NH3 is 0.30M and the concentration of NH4+ is 0.20 M. If the is [AIEEE 2002]
equilibrium constant, Kb for NH3 equals 1.8 × 10–5, what is (a) 4S 3 (b) 3S 4
the pH of this solution ? (log 2.7 = 0.433). [CBSE-PMT 2011] (c) 4S2 (d) S 3
(a) 9.08 (b) 9.43 (c) 11.72 (d) 8.73 24. Which one of the following statements is not
14. Which of the following is least likely to behave as Lewis true? [AIEEE 2003]
base ? [CBSE-PMT 2011] (a) pH + pOH = 14 for all aqueous solutions
(a) H2O (b) NH3 (c) BF3 (d) OH– (b) The pH of 1 × 10–8 M HCl is 8
15. In qualitative analysis, the metals of Group I can be separated (c) 96,500 coulombs of electricity when passed through a
from other ions by precipitating them as chloride salts. A CuSO4 solution deposits 1 gram equivalent of copper at
solution initially contains Ag+ and Pb2+ at a concentration of the cathode
0.10 M. Aqueous HCl is added to this solution until the Cl–
concentration is 0.10 M. What will the concentrations of Ag+ (d) The conjugate base of H 2 PO -4 is HPO 24-
and Pb2+ be at equilibrium? [CBSE-PMT 2011M] 25. The solubility in water of a sparingly soluble salt AB2 is 1.0
(Ksp for AgCl = 1.8 × 10 , Ksp for PbCl2 = 1.7 × 10–5)
–10 × 10 –5 mol L –1 . Its solubility product number
(a) [Ag+] = 1.8 × 10–7 M ; [Pb2+] = 1.7 × 10–6 M will be [AIEEE 2003]
(a) 4 × 10 –10 (b) 1 × 10 –15
(b) [Ag+] = 1.8 × 10–11 M ; [Pb2+] = 8.5 × 10–5 M
(c) [Ag+] = 1.8 × 10–9 M ; [Pb2+] = 1.7 × 10–3 M (c) 1 × 10–10 (d) 4 × 10–15
(d) [Ag+] = 1.8 × 10–11 M ; [Pb2+] = 8.5 × 10–4 M 26. The conjugate base of H 2 PO -4 is [AIEEE 2004]
16. pH of a saturated solution of Ba(OH)2 is 12. The value of (a) H3PO4 (b) P2O5
solubility product (Ksp)of Ba(OH)2 is : [CBSE-PMT 2012 S]
(a) 3.3 × 10– 7 (b) 5.0 × 10–7 (c) 4.0 × 10–6 (d) 5.0 × 10–6 (c) PO 34- (d) HPO 24-
17. Buffer solutions have constant acidity and alkalinity because 27. The molar solubility (in mol L –1 ) of a sparingly
[CBSE-PMT 2012S] soluble salt MX4 is ‘S’. The corresponding solubility product
(a) these give unionised acid or base on reaction with added is Ksp. ‘S’ is given in term of Ksp by the relation :
acid or alkali. [AIEEE 2004]
(b) acids and alkalies in these solutions are shielded from (a) S = (256Ksp )
1/ 5
(b) S = (128Ksp )
1/ 4
attack by other ions.
(c) they have large excess of H+ or OH– ions (c) S = (Ksp /128)
1/ 4
(d) S = (Ksp / 256)
1/ 5
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
228 Chemistry
45. The Ksp for Cr(OH)3 is 1.6 × 10–30. The solubility of this (a) 3 × 10–1 (b) 1 × 10–3 (c) 1 × 10–5 (d) 1 × 10–7
compound in water is : [AIEEE 2011RS] 49. How many litres of water must be added to 1 litre an aque-
(a) 4 -30 (b) 4
1.6 ´ 10 -30 ous solution of HCl with a pH of 1 to create an aqueous
1.6 ´ 10 / 27
solution with pH of 2 ? [JEE Main 2013]
(c) 1.6 ´ 10-30 / 27 (d) 1.6 ´ 10 -30 (a) 0.1 L (b) 0.9 L
46. A vessel at 1000 K contains CO2 with a pressure of 0.5 atm. (c) 2.0 L (d) 9.0 L
Some of the CO2 is converted into CO on the addition of
50. 2.5 ml of (2/5) M weak monoacidic base (Kb = 1 × 10–12 at 25°)
graphite. If the total pressure at equilibrium is 0.8 atm, the
is titrated with (2/15) M HCl in water at 25°C. The
value of K is : [AIEEE 2011]
concentration of H+ at equivalence point is (Kw = 1 × 10–14 at
(a) 1.8 atm (b) 3 atm (c) 0.3 atm (d) 0.18 atm
25°C) (IIT-JEE 2008S)
47. The equilibrium constant (K c ) for the reaction
N2(g) + O2(g) ® 2NO(g) at temperature T is 4 × 10–4. The (a) 3.7 × 10–14 M (b) 3.2 × 10–7 M
value of Kc for the reaction [AIEEE 2012] (c) 3.2 × 10–2 M (d) 2.7 × 10–2 M
1. How many gms of CaC 2O 4 will dissolve in litre of saturated 6. The solubility of CaF2 in 0.01 M solution of NaF. The Ksp of
solution. Ksp of CaF2 is 3.4 × 10–11
CaC2 O 4 is 2.5 ´10 -9 mol 2 lit -2 (a) 3.4 ´ 10-7 mol / l
(a) 0.0064 g (b) 0.0128 g
(b) 3.4 ´ 10-5 mol / l
(c) 0.0032 g (d) None of these
(c) 3.4 Mol / l
2. For NH3, Kb = 1.8 × 10–5 and Ka for NH +4 would be
(d) None of these
(a) 1.8 ´ 10 -5 (b) 5.56 ´ 10 5 7. If the reaction between CO2 and H2O is
+
(c) 1.8 ´ 1010 (d) 5.56 ´ 10 -10 CO 2+H 2O H 2CO 3 H+HCO 3.
3. The pH of a solution which is 0.1 M in HA and 0.5 M in NaA. If CO2 escapes from the system
-6 (a) pH will decrease
Ka for HA is 1.8 ´ 10
(b) H+ concentration will decrease
(a) 5.44 (b) 6.44
(c) H2CO3 concentration will be altered
(c) 6.0 (d) 4.73
4. The pH of a solution obtained by mixing of 100.0 ml of 0.1 M (d) The forward reaction is promoted
8. A solution contains 0.1 M H2 S and 0.3 M HCl, the
HCl and 100 ml of 0.2 M NH3, Kb for NH3 is 1.8 ´ 10 -5
- -7
(a) 4.74 (b) 9.26 concentration of SH ions is ( K a = 1. ´10 )
(c) Less than 7 (d) None of these
(a) 3.3 ´ 10 -8 M (b) 33 ´ 10 -8 M
5. The percentage hydrolysis of 0.15 M solution of ammonium
acetate, K a for CH 3COOH is 1.8 ´ 10 -5 and K b for (c) 3.3 ´ 10 -7 M (d) 10 -7 M
9. 20 ml of 0.2 M. NaOH are added to 50 ml of 0.2
NH 3 is 1.8 ´10 -5
M CH3COOH (K a = 1.8 ´10 -5 ) the pH of the solution is
(a) 0.556 (b) 4.72
(c) 9.38 (d) 5.56 (a) 4.56 (b) 4.73
(c) 9.45 (d) 6.78
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
230 Chemistry
27. Calculate the pH of a solution containing 0.1 M HCO 3- and (a) 3.52 × 10 -3 (b) 6.75 × 10 -4
0.2 M CO 32- [K1(H2CO3) = 4.2×10–7×10 and K2( HCO 3- ) = (c) 5.38 × 10 -2 (d) 1.74 × 10 - 5
4.8×10–11]. 36. The degree of dissociation of 0.1M weak acid HA is 0.5%. If
2 ml of 1.0 M HA solution is diluted to 32 ml the degree of
(a) 3.18 (b) 10.62
+
(c) 6.62 (d) 9.31 dissociation of acid and H 3O ion concentration in the
28. At what pH will a 1×10–4 M solution of an indicator will (Kb resulting solution will be respectively
indicator) = 1×10–11 change colour? -4
(a) 7.0 (b) 3.0 (a) 0.02 and 3.125 × 10 (b) 1.25 × 10 - 3 and 0.02
(c) 5.5 (d) 11.0 (c) 6.02 and 1.25 × 10 - 3 (d) 0.02 and 8.0 × 10
- 12
29. Calculate the pH of a 0.01 M NaHCO3 solution [K1(H2CO3) = 37. The dissociation constants of a weak acid HA and weak
4×10–7, K2( HCO 3- ) = 4.8×10–11]. base BOH are 2 × 10 - 5 and 5 × 10 - 6 respectively. The
(a) 9.38 (b) 6.38 equilibrium constant for the neutralisation reaction of the
(c) 8.38 (d) 7.38 two is
30. Blood plasma is maintained at a pH of 7.4 largely by the
(a) 1.0 × 10 4
(b) 1.0 × 10 - 4
(a) HCO 3- / H 2 CO 3 buffer - 10
(c) 1.0 × 10 (d) 2.5 × 10 - 1
(b) HPO 24 - / PO 34- buffer 38. The ionisation constant of an acid-base indicator
(a weak acid) is 1.0 × 10 - 6 . The ionised form of the indicator
(c) HCO 3- / H 2 CO 3 is red whereas the unionised form is blue the pH change
required to alter the colour of the indicator from 80% blue to
and HPO 24 - / H 2 PO -4 buffer 80% red is
(d) HPO 24- / H 3 PO 4 and haemoglobin buffers (a) 1.40 (b) 1.20
(c) 0.80 (d) 2.00
31. In the titration of a weak diprotic acid (H2A) with a strong 39. The pH at the equivalence point in the titration of 25 ml of
base (NaOH), [H+] is given by 0.10 M formic acid with a 0.1 M NaOH solution (given that
(a) K a1 C a (b) Ka Ca1 pKa of formic acid = 3.74)
(a) 8.74 (b) 8.37
(c) K a Ca1 (d) K a1 (c) 4.74 (d) 6.06
32. The pH of a solution prepared by mixing 2.0 ml of a strong 40. In H S , I , RNH 2 , NH 3 the order of proton accepting
acid (HCl) solution of pH 3.0 and 3.0 ml of a strong base tendency will be
(NaOH) of pH 10.0
(a) 4.5 (b) 3.4 (a) H S > RNH 2 > NH 3 > I
(c) 2.5 (d) 6.5
(b) I > NH 3 > RNH 2 > H S
33. For a sparingly soluble salt ApBq, the relationship of its
solubility product Ls ® Ksp with its solubility (S) is (c) NH 3 > RNH 2 > H S > I
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
232 Chemistry
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
234 Chemistry
73. (b) Salt of strong acid and strong base give neutral solution
[SALT]
(pH = 7). Hence such salts are not hydrolysed. pH = 7 89. (d) pOH = –log Kb + log
[BASE]
74. (c) NaCl solution (salt of strong base and strong acid) hence
pH = 7.
æ SALT ö
= - log K b ç since = 1÷
Kw 10-14 è BASE ø
75. (b) Kh = = = 5.5 ´10-10 .
K b 1.8 ´10-5 = –log 2 × 10 = 4.7. \ pH = 9.3
–5
JEEMAIN.GURU
downloaded from jeemain.guru
+ é Acid ù
If [OH– ] is decreased by
1
times then for reaction log éë H ùû = log Ka + log ê
4 ë Salt úû
equilibrium constant to remain constant, we have to
increase the concentration of [Fe3+] by a factor of 43 i.e é H + ù = K é Acid ù
ë û aê
4× 4 × 4 = 64. Thus option (c) is correct answer. ë Salt úû
5. (b) The highest pH will be recorded by the most basic 0.1
solution. The basic nature of hydroxides of alkaline earth = 1.8 × 10 -5 ´ = 9 × 10-6 M
0.2
metals increase as we move from Mg to Ba and thus the
solution of BaCl2 in water will be most basic and so it 11. (d) Kb = 10-10 ; Ka = 10-4 or pKa = 4
will have highest pH.
For the buffer solution containing equal concentration
6. (c) Given, CH3COOH CH3COO– + H+ ; of B– and HB
Ka1 , = 1.5 × 10– 5 ....(i) pH = pKa + log 1
JEEMAIN.GURU
downloaded from jeemain.guru
236 Chemistry
16. (b) Given pH = 12 ++
or [H+] = 10–12 28. (c) MX 2 M + 2X -
1S 2S
Since, [H+] [OH–] = 10–14 Where S is the solubility of MX2
10 -14 then Ksp = 4S3; S× (2S)2 = 4×10–12 = 4S3; S = 1 × 10–4
\ [OH–] = = 10–2 \ S = 1[M++] = 1 × 10– 4
10-12
1
Ba(OH)2 Ba 2+ + 2OH 29. (a) pH = –log [H+] = log
s 2s [H + ]
[OH–] = 10–2
1
10-2 5.4 = log
2s = 10–2 or s = [H + ]
2
On solving [H+] = 3.98 × 10–6
æ 10 -2 ö 3 30. (a) Conjugate acid-base pair differ by only one proton.
Ksp = 4s3 = 4 ´ ç ÷ = 5 × 10–7 OH - ¾
¾® H + + O 2 - Conjugate base of OH– is O2–
è 2 ø
17. (a) Lets take an example of an acidic buffer CH3COOH and +5 +3
31. (b) The HNO3 is stronger than HNO 2 . The more the
CH3COONa.
CH3COOH CH3COO – + H + ; oxidation state of N, the more is the acid character.
CH3COONa CH3COO– + Na+
when few drops of HCl are added to this buffer, the H+ 32. (b) Given
of HCl immediatly combine with CH3COO– ions to (i) ¾® Ag + + e -
Ag ¾ E º = - 0.800 V
form undissociated acetic acid molecules. Thus there + -
® AgI + e - Eº = 0.152 V
(ii) Ag + I ¾¾
will be no appreciable change in its pH value. Like wise
if few drops of NaOH are added, the OH – ions will From the eqn (i) and (ii) we have,
combine with H+ ions to form unionised water molecule. ¾® Ag + + I - E º = -0.952 V
AgI ¾
Thus pH of solution will remain constant.
18. (c) Solubility of alkali metal is maximum among the 0.059
Eocell = log K
following. Among ZnS (1.7 × 10–5) & CuS (8 × 10–37) n
ZnS has higher value of Ksp.
19. (b) BF3 is Lewis acid(e– pair acceptor) 0.059
–0.952 = log [Ag+] [I–]
20. (a) A buffer is a solution of weak acid and its salt with 1
strong base and vice versa. HCl is strong acid and
0.952
NaCl is its salt with strong base. pH is less than 7 due - = log K sp
to HCl 0.059
21. (a) (HSO4)– can accept and donate a proton –16.13 = log Ksp
(HSO4)– + H+ ® H2SO4 (conjugate acid) 33. (d) H + HA
H 2A
(HSO4)– – H+ ® SO42–. (conjugate base)
22. (a) Mg(OH)2 ® [Mg2+] + 2[OH–] \ K = 1.0 × 10 –5 = [H + ][HA - ]
1 (Given)
x 2x [H 2 A]
ksp = [Mg] [OH] = [x][2x] = x.4x2 = 4x3.
2 2
HA- ¾¾
® H+ + A--
23. (a) Mg(OH)2 Mg ++ + 2OH- ;
S 2S
[H + ][A -- ] (Given)
Ksp = (s) (2s)2 = 4s3 \ K 2 = 5.0 ´ 10 -10 =
24. (b) An acidic solution cannot have a pH > 7. [HA - ]
25. (d) [A] = 1.0 × 10–5, [B] = [1.0 × 10–5] ,
ksp = [2.B]2 [A] = [2 × 10–5]2 [1.0 × 10–5] [H + ]2 [A 2 - ]
= 4 × 10–15 K= = K1 ´ K2
[H 2 A]
+
–H = (1.0 × 10–5) × (5 × 10–10) = 5 × 10–15
26. (d) H 2 PO–4 HPO2–
4
Acid con ugate base
conjugate é salt ù
34. (d) For acidic buffer pH = pKa + log ê ú
4+ - ë acid û
27. (d) MX4 M + 4X
S 4S
1/ 5
éA- ù
æ K sp ö ë û
or pH = pK a + log
ksp = [S] [4S]4 = 256 S5 \ S = çç ÷
÷ [ HA ]
è 256 ø
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
238 Chemistry
44. (d) pH = 5 M1V1 = M2V2
\ [H+] = 10–5 0.1 × 1 = 0.01 × V2
H + + A -
HA V2 = 10 litres
\ Volume of water added = 10 – 1 = 9 litres
t=0 c 0 0
50. (d) Let the weak monoacidic base be BOH, then the
teq c (1 – a) ca ca reaction that occurs during titration is
[H + ][A - ] (c ) 2 [H + ]2 BOH + HCl ® BCl + H2O
Ka = = =
[HA] c (1 – ) c - [H + ] BOH + H +
Equilibrium : B+ + H 2 O
c (1- h) c.h c.h
(As [H+]) = [A–] = ca)
But, [H+] << c Using the normality equation, N1V1 = N 2 V2
(acid) (base)
\ Ka = (10–5)2 = 10–10
45. (b) Cr 3+ (aq.) + 3OH - (aq.)
Cr(OH)3 (s) Substituting various given values, we get
s 3s 2 2
´ V1 = 2.5´
(s) (3s)3 = Ksp 15 5
27 S 4 = K sp 2 15
or V1 = 2.5´ ´ = 2.5 × 3 = 7.5 ml
1/ 4 -30 ö 1/ 4
5 2
æ K sp ö æ 1.6 ´ 10
s=ç =ç ÷ Then the concentration of BCl in resulting solution is
è 27 ÷ø è 27 ø given by
46. (a) 2CO
CO2 + C(graphite)
2
Pinitial 0.5atm 0 2.5 1
[BCl] = 5 = or 0.1 M
10 10
Pfinal (0.5 – x)atm 2 x atm
Total P at equilibrium = 0.5 – x + 2x = 0.5 + x atm [Total volume = 2.5 + 7.5 = 10 ml]
0.8 = 0.5 + x Kw
\ x = 0.8 – 0.5 = 0.3 atm Since K h =
Kb
Now Kp = (PCO ) /PCO
2
1´10-14
2
(2 ´ 0.3) 2
(0.6) 2 \ Kh = = 10–2
= = = 1.8 atm 1´10-12
(0.5 – 0.3) (0.2)
47. (d) For the reaction 0.1h 2 0.1h 2
Thus K h = or 10-2 =
N2 + O2 ¾¾ ® 2NO K = 4 × 10–4 (1- h) (1- h)
Hence for the reaction
or 10–2 – 10–2 h = 0.1 h2
1 1 1 1
NO ¾¾
® N2 + O2 K'= = = 50 or 0.1 h2 + 10–2 h – 10–2 = 0
2 2 K 4×10 – 4
(Solving this quadratic equation for h, we get)
48. H + Q
(c) HQ
é -b ± b 2 - 4ac ù
c(1–a) ca ca êx = ú
Using ê 2a ú
[H + ] ë û
[H + ] = c a ; a =
c
-10-2 ± (10-2 )2 + 4 ´10-1 ´ 10 -2
10 –3 h=
or a = = 10-2 2 ´ 0.1
0.1
JEEMAIN.GURU
downloaded from jeemain.guru
s 2s
1 Kw 1 ´ 10-14
5. (a) a = = = 0.55
é K sp ù 3 Ka ´ K b 1.8 ´ 10-5 ´ 1.8 ´ 10-5
K sp = s ´ (2 s ) 2 = 4 s3 or s=ê ú
ë 4 û
Ksp 3.4 ´10 -11
3M + X
and for M 3 X + -3 6. (a) [Ca ++ ] = ; Solubility = = 3.4 ´ 10 -7
3s s [F- ]2 [0.01] 2
1
+ –
7. (b) CO2+H2O H2CO3 H +HCO3 .
é Ksp ù 4
Ksp = (3s )3 ´ s = 27 s 4 or s = ê ú If CO2 escapes, the equilibrium will shift to LHS and [H+]
ë 27 û concentration will decrease
From the given values of Ksp for MX, MX2 and – +
8. (a) H S SH + H ;
2
M3 X, we can find the solubilities of those salts at
temperature, T. [SH][H + ] 10-7 ´ 0.1
Ka = ;[SH] = = 3.3 ´ 10 -8
Solubility of MX = 4´10-8 = 2´10-4 [H 2S] 0.3
1
9. (a) NaOH + CH 3COOH CH 3COONa + H 2O
1
é 3.2 ´10-14 ù 3 é 32 -15 ù 3
20×0.2 50×0.2 0 0
Solubility of MX 2 = êê ú
ú or ê ´10 ú
êë 4 úû êë 4 úû 4 10 0 0
0 6 4 4
1 Millimoles 6 4
Conc. = ;[CH3COOH] = ;[CH3COONa] =
= éê8´10-15 ùú 3 or 2 10 5 Total Volume 70 70
ë û
1 pH = – log 1.8 ´10 -5 + log 4 / 70 , pH = 4.56
é 2.7 ´10-15 ù 4 6 / 70
Solubility of M3 X = êê ú
ú
êë 27 úû K sp 1´ 10-11
1 10. (a) [OH - ]2 = ++
= = 10-10 ;
é10-16 ù 4 –4 [Mg ] 0.1
= ê úû or 10
ë
Thus the solubilities are in the order MX > M3 X> MX2 [OH- ] = 10-5 ;[H+ ] = 10-9 ; pH = 9
i.e the correct answer is (d).
11. (b) pH = 9 ; [H+ ] = 10-9 ;[OH- ] = 10-5 ;
EXERCISE 4
2+ 2- [Mg ++ ] = 1´10 -3 ;[Mg++ ][OH - ]2 = 1´10-13
1. (a) CaC O Ca + C O ; Ksp = S2
2 4 2 4
given Ksp of Mg(OH ) 2 = 8.9 ´10 -12 which is more than
-9 -5 mol/litre
\ S = K sp = 2.5 ´ 10 = 5 ´ 10
1 ´ 10 -13 . Hence Mg(OH)2 will not precipitate
solubility = 5 ´10 -5 ´128 = 0.0064 g
JEEMAIN.GURU
downloaded from jeemain.guru
240 Chemistry
12. (b) NaCN is a salt of strong base and weak acid ; pH
NH +4 + H 2 O NH 4 OH + H +
1 1
= 7 + pK a + log C
2 2 NaCN Slightly alkaline due to the reaction
pKa for HCN = 14–4.70 = 9.30 CN - + H 2 O HCN + OH -
1 1 HCl highly acidic
\ pH = 7 + ´ 9.30 + log 0.5; pH = 11.5
2 2 The pH of the solution will follow the order highly acidic
13. (a) HCOONH 4 is a salt of weak acid and weak base ; < slightly acidic < neutral < slightly alkaline
i.e. HCl < NH4Cl < NaCl < NaCN
pH = ½ pKw + ½ pKa – ½ pKb
+ (25 ´ 0.3 - 25 ´ 0.1)
1 1 1 21. (b) [H ] = meq = 0.05M
\ pH = ´ 14 + ´ 3.8 - ´ 4.8 ; pH = 6.5 100
2 2 2
- (20 ´ 0.02) - (30 ´ 0.01)
14. (c) Na2CO3 +2H2O 2NaOH+H2CO3 22. (a) [OH ] = = 0.002M
50
CO3-- + 2H 2 O 2OH - + H 2 CO3 Anionic hydrolysis – log [OH–] = pOH = – log .002 = 2.7
\ pH = 14 – 2.7 = 11.3
15. (c) BaF2 Ba ++ + 2F- , Ba(NO3 )2 23. (a) Isohydric solutions have the same [H+] concentration
24. (a) A B C
-
F- are obtained from BaF2 . Then ½ [F ] = [BaF2] Ka 10–4 10–6 10–10
16. (c) HCN is a weak acid and energy is required to affect its The higher the value of Ka, the stronger the acid and the
ionisation. Hence the enthalpy of neutralisation of HCN lower is pH. Hence order of pH A < B < C.
is less than the enthalpy of neutralisation of strong acid. 25. (b) Fe(OH) 2 Fe + + + 2 OH
The difference of enthalpy gives the enthalpy of
ionisation. 55.9 kJ-12.1 kJ = 43.8 kJ pH = 8, [H+] = 10–8, [OH–] = 10–6
17. (c) Let the volume of KCN to be added is Vml ; Conc.of KCN K sp 1.6 ´ 10-4
= S×V and Fe++ = = = 0.016
[OH - ]2 [10-6 ]2
Conc. of HCN = 10 ×2 ; pH = 9 , \ H+ = 10–9
26. (c) The hydrolysis of C 2 O 24 - is as follows
K [ACID] -9 5 ´ 10 -10 ´ 10 ´ 2
+
H = a ;10 = ;V = 2ml
[SALT] 5´ V C 2 O 24 - + H 2 O HC2 O4- + OH –
18. (c) An acid base indicator is InH. Its ionisation is as follows
K w 1.0 ´10-14 x2
InH In – + H+ Kh = = -5
=
K 2 6.0 ´10 0.01
acid form (Red) basic form (blue)
\ x = 1.3 × 10–6
+
[In][H ] K [InH] 3 ´ 10 -5 ´ 25
Ka = ;[H + ] = a ;[H + ] = = 1 ´ 10 -5 27. (b) HCO 3- ® H + + CO 32-
[InH] [In] 75
19. (b) pH of 1 ´ 10-8 M HCl is below 7. [H + ][CO32- ]
H2PO4– + H2O HPO42– + H3O+ K2 = = 4.8 ´10-11
[HCO3- ]
conjugate base of H2PO–4 is H3PO4
4.8 ´10 -11[HCO 3- ]
H 2 PO4- + H + H3PO4 [H + ] = = 4.8 ´10 -11 (0.1 / 0.2)
[CO 32- ]
K (Autoprotolysis constant of water i.e. ionic product of
water) increases with temperature. For half neutralisation pH = – log [H+] = – log (4.8 × 10–11 × 0.5) =10.62
of a weak acid by a weak base, 28. (b) The basic indicator is InOH
InOH In+ + OH–
[Salt]
pH = pKa + log
[Acid] Kb =
[In + ][OH]
[InOH]
[Salt] = [Acid], \ pH = pKa
20. (b) The characteristics of the given solutions are:
[ In + ]
NaCl neutral solution Indicator will change colour when =1
[ InOH ]
NH4Cl slightly acidic due to the reaction
\ Kb = [OH–] = 1×10–11 and [H+] = 10–3
\ pH = 3
JEEMAIN.GURU
downloaded from jeemain.guru
+ 2 ´ 10 - 3 3 10 -10 20
\ [H ] = + ´ 10 -10 = (2 ´ 10 7 + 3) pH1 = pK In + log = pK In - 2log 2
5 5 5 80
10 -10 2 -3 pH 2 = pK In + log
80
= pK In + 2log 2
or [H + ] = ´ 2 ´ 107 = ´ 10
5 5 20
pH 2 - pH1 = pK In + 2log 2 - (pK In - 2log 2)
– log [H + ] = – log 2 + 3 log 10 + log 5
= 4 log 2 = 1.20
\ pH = – 0.3010 + 3 + 7 = 3.4
39. (b) HCOOH + NaOH HCOONa + H 2 O,
33. (b) ApBq pA + + qB
Sp Sq
HCOONa is salt of weak acid and strong base which is
0.10 M.
Let the solubility be s mol/liter
Thus, 1
pH = (K w + pK a + log C)
2
+ p – q p q p. q p+q
Ksp = [A ] [B ] = [sp] [sq] = p q (s) .
1
34. (a) The solubility decreases by common ion effect. = (14 + 3.74 + log 0.1) = 8.37
2
A[Cl - ] = 0, B[Cl - ] = 0.1 40. (d) The stronger the base, the more is proton accepting
C [Cl - ] = 0.2 D [Cl–] = 0 tendency RNH 2 is stronger than NH 3 and HI is strong
JEEMAIN.GURU
downloaded from jeemain.guru
242 Chemistry
50. (b) To precipitate the AgCl
43. (c) Ksp =4 S3 = 3.2 ´ 16 -11 \ S = 2 × 10 - 4 M
[Ag + ] required
[ OH ] = 2 S = 2 × 2 × 10 -4 M
K sp (AgCl) 1.0 ´10-10
\ pH = 14 – pOH = 14 + log 4 ´ 10 -4 = 10.60 = = = 1.0 ´10-9 M
[Cl - ] 0.1
44. (a) MgCl 2 +2NaOH ® Mg(OH) 2 +2NaCl
100 × 0.1 100 × 0.2 0 0 Initial moles K sp (AgBr) 1.0 ´ 10 –13
[Br - ] left at this stage = =
0 0 10 20 After mixing [Ag + ] 1.0 ´ 10-9
2 = 1.0 × 10–4 M
é 10 ù é 20 ù -4
\ Ksp = ê úê ú = 5 ´10 .
ë 200 û ë 200 û 1.0 ´ 10 -4
% of remaining [ Br - ] = ´100 = 0.1
0.1
But actually Ksp of Mg (OH ) 2 = 1.2 ´ 10 - 11
% of Br - to be precipitated = 100 – 0.1 = 99.9
\ 4S3 = 1.2 ´ 10 -11
- -4 .
51. (c) pH = 8, pOH = 6; [OH - ] = 10 -6 M;
Find S then [OH ] = 2S which is 2.8 ´ 10
-6 2
45. (a) At the half equivalence point we have equal Ionic product of Fe(OH)2 = 0.2 × (1´10 )
concentrations of base left and the salt formed.
= 2 ´ 10 -13 > K sp ( = 8.1 ´ 10 -16 )
[salt]
\ pOH = pKb + log ; pOH = pKb 52. (b) pOH = 14 – pH = 14 – 8.26 = 5.74
[base]
and pH = 14 – pKb [ NH 4 + ]
= pKa + log
46. (b) The pH at which the dipolar ion does not migrate in the [ NH 3 ]
electric field is called isoelectric point. It is given by
pK a1 + pK a 2 [ NH 4 + ]
2.09 + 3.86 = 4.74 + log
= = 2.98. 0.1
2 2
+
47. (a) The solubility S of AgCl, S2 = Ksp; S2 = 1.0 × 10 - 10 ; [ NH 4 ] =1 molL -1
S = 1´10 -5 mol L-1 . 1
\ ( NH 4 ) 2 SO 4 = of [ NH 4 + ] = 0.5 mol L-1 )
The mass dissolved in 10 L 2
= 10 ´ 1.0 ´ 10 -5 ´ 143.5 = 1.435 ´ 10 -2 g 53. (a) CO 2 with H 2 O forms H 2 CO 3
0. 3 0 .1 [H + ][HCO3- ]
at. 1/4 neutralisation K1 = = 4.5 ´10-7
4 4 [CO 2 ]
0 .1 0. 3
4 4
at 3/4 neutralisation Again pH = - log[H + ] = 7.4
1 3 \ [H + ] = 4.0 ´10 -8
pH1 = pKa + log ; pH 2 = pKa + log
3 1
[HCO3- ] 4.5 ´10-7
\ = = 11
1 [CO 2 ] 4 ´ 10-8
pH1 – pH 2 = log – log 3 = 2 log 3
3
JEEMAIN.GURU
downloaded from jeemain.guru
8
Redox Reactions
OXIDATION : REDOX REACTIONS :
Oxidation may be defined in any of the following terms Reactions comprising of simultaneous oxidation and reduction
(a) Addition of oxygen. and called oxidation - reduction or redox reactions.
2 Mg + O2 ® 2MgO SnCl2 + 2HgCl2 ® SnCl4 + Hg2Cl2
(b) Removal of hydrogen
TYPES OF REDOX REACTIONS :
3O2 + 4NH3 ® 2N2 + 6H2O
(c) Addition of electronegative portion (i) Intermolecular redox reactions - In this case one substance
Cu + Cl2 ® CuCl2 is oxidised and another is reduced.
(d) Removal or decrease in the electropositive portion 4 HCl + MnO2 ® MnCl2 + Cl2 + 2H2O
H2S + Cl2 ® 2 HCl + S Here HCl is oxidised and MnO2 is reduced.
(ii) Disproportionation - In this case the same substance is
¾® M n + + ne-
(e) De - electronation M ¾
oxidised and reduced eg.
REDUCTION : +5 +7
Reduction may be defined in any of the following terms 4 KClO3 ® 3KClO 4 + KCl –1
(a) Addition of hydrogen (iii) Intramolecular redox reactions - In this case one element
N2 + 3H2 ® 2NH3
of the compound is reduced while another element of the
(b) Addition of electropositive portion
same compound is oxidised
CuCl2 + Cu ® Cu2Cl2
(c) Removal of oxygen ( NH 4 ) 2 Cr2 O 7 ® N 2 + Cr2 O 3 + 4H 2 O
CuO + H2 ® Cu + H2O Cr is reduced and N is oxidised
(d) Removal or decrease in the electronegative portion
OXIDATION NUMBER :
2HgCl2 + SnCl2 ® Hg2Cl2 + SnCl4
(e) Electronation M + ne– ® Mn– It is the number of electrons lost or gained by an
element during its change from free state in a particular compound.
OXIDANT OR OXIDISING AGENT :
Or
As stated above the oxidising agent may be defined as a substance
It is defined as the formal charge present on an atom in a particular
supplying oxygen or electronegative element, removing hydrogen
compound determined by certain arbitrary rules.
or electropositive element and can accept electrons. They show
decrease in oxidation number Examples. RULES FOR DETERMINING OXIDATION NUMBER:
K2Cr2O7, KMnO4, H2O2, Cl2, Br2, KClO3, FeCl3 etc. (i) O.N. of elements in free state is zero eg Cl 2 , N 2 , Mg, Ca
REDUCTANT OR REDUCING AGENT : (ii) O.N. of hydrogen is always +1 except in ionic metal hydrides
A substance supplying hydrogen or electropositive element, where it is – 1.
removing oxygen or electro negative element and can donate
(iii) O.N. of oxygen is –2 except in OF2 where it is + 2 and in
electrons. They show increase in oxidation number.
peroxides where it is – 1.
Examples SnCl2, H2, H2S, Mg, FeSO4, H2C2O4, H2SO3.
JEEMAIN.GURU
downloaded from jeemain.guru
244 Chemistry
(iv) O.N. of metals is always +ve. For IA group elements it is +1 CALCULATION/ DETERMINATION OF OXIDATION
and for IIA group elements it is +2. NUMBER OF UNDERLINED ELEMENT IN SOME
(v) O.N. of halogens is –1 in metal halides. COMPOUNDS:
(vi) O.N. of ion or radical is the number of electrons it must gain
(a) K 2 Cr 2 O 7 -
or lose to acquire neutrality i.e. it is equal to the electric
Let the O.N. of Cr be x then
charge for SO4– - O.N. is –2. 2 × (+1) + 2 × (x) + 7 × (–2) = 0
(vii) O.N. of an atom within compound can be +ve, –ve integer, 2 + 2x –14 = 0 \ x = +6
zero or fraction. (b) KMnO4 -
(viii) The algebraic sum of all the O.N. of elements is equal to zero. Let the O.N. of Mn be x then
(ix) The algebraic sum of all the O.N. of elements in an ion is 1 × (+1) + 1 × (x) + 4 × (–2) = 0
equal to net charge on the ion. 1 + 1x - 8 = 0 \ x = +7
(c) H2SO4 -
(x) Maximum O.N. of an element is equal to number of valence
Let the O.N. of S be x then
electrons i.e. group number.
2 × (+1) + 1 × (x) + 4 × (–2) = 0
(xi) Minimum O.N. of an element (except metals)
2 + x –8 = 0 \ x = +6
= (8 – group number).
(xii) In metal corbonyl, and amalgams, O.N. of metals is zero. (d) NH4NO3 - Split into two ions NH +4 and NO 3–
COVALENCY AND OXIDATION STATE Let O.N. of N be x in NH +4 ion then
(i) Covalency : It is the number of hydrogen atoms which can 1 × (x) + 4 × (+1) = +1
combine with a given atom x + 4 = +1 \ x = –3
or Let the O.N. of N be x in NO 3– ion then
It is the number of single bonds which an atom can form.
1 × (x) + 3 × (–2) = –1
or
x – 6 = –1 \ x = +5
It is the number of electrons an atom can share. Valency is
always a whole number. (e) PO 3–
4 -
(ii) Oxidation state : It is defined as the O.N. per atom. Let the O. N. of P be x then
STOCK NOTATION : 1 × (x) + 4 × (–2) = –3
Representation of oxidation state of element by Roman numerals x – 8 = –3 \ x = +5
within parenthesis is known as stock notation eg FeCl3 is written (f) HNO3 -
as Iron(III) chloride and FeSO4 as Iron (II) sulphate. Let the O.N. of N be x then
CHEMICAL BONDING METHOD FOR 1 × (+1) + 1 × (x) + 3 × (–2) = 0
DETERMINATION OF OXIDATION NUMBER 1+ x–6=0 \x = 5
Sometimes wrong results are obtained when the O.N. is determined (g) KI3 -
by applying the above mentioned simple rules. In such cases Let the O.N. of I be x then
applying the chemical bonding method is very useful. The rules 1 × (+1) + 3 × (x) = 0
are \ 1 + 3x = 0 \ x = –1/3
(i) For one covalent bond assign one unit negative charge to (h) NaO2 - It is super oxide.
electronegative atom and one unit positive charge to less Let O.N. of O be x then
electronegative atom eg 1 × (+1) + 2 × (x) = 0\ 1 + 2x = 0 \ x = –1/2
(i) Fe3O4 - It is mixed oxide FeO.Fe2O3 and Fe has O.N. +2
A –1 – B +1 (electronegativity A> B).
(ii) No charge when the covalent bond is between like atoms. and +3 respectively.
(iii) In case of coordinate bond assign two unit negative charge (j) Fe0.96 O
to acceptor atom and two unit positive charge to donor atom
Let O.N. of Fe be x then 0.96 x + ( -2 ) = 0
e.g. A 2 – ¬ B 2+ (electronegavity A > B).
(iv) No charge when donor in coordinate bond is more \ 0.96 x - 2 = 0
electronegative than acceptor eg
+2
A ® B (electronegavity A > B). \x =
0.96
(v) When coordinate bond is between similar atoms
assign two unit negative charge to acceptor and (k) N3H (hydrazoic acid)
two unit positive charge to donor e.g., Let O.N. of N be x then
3 × (x) + 1 × (+1) = 0
A 2 – ¬ A 2 + (electronegativity same).
3x + 1 = 0 \ x = –1/3
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
246 Chemistry
EQUIVALENT WEIGHT OF AN OXIDISING AGENT EQUIVALENT WEIGHT OF REDUCING AGENT :
It can be obtained by dividing the molecular weight by the number It can be obtained by dividing the molecular weight by the number
of electrons gained represented in a chemical balanced equation
of electrons lost as represented by a chemical balanced equation
+7 +2
eg. 2K MnO + 3H SO ® K SO + 2MnSO + 3H O + 5O +2 +6 -8 +4 -4
4 2 4 2 4 4 2
H2 C2 O4 + O ¾
¾® 2 C O 2 + H 2 O
Equivalent wt. of KMnO4 in acid medium
Mol.wt of KMnO 4 The change in O.N. of two atoms of carbon is +2. Hence
=
5 Mol.wt of Oxalic acid
Equivalent weight of oxalic acid =
Cr2 O2– + 3+ 2
7 + 14H + 6e ® 2Cr + 7H 2 O
Mol.wt of K 2Cr2 O
Eq. wt. of K2Cr2O7 =
BALANCING OF CHEMICAL EQUATIONS : (b) Balance the total number of atoms undergoing change
For balancing a chemical equation the two important methods are in oxidation state.
(1) Oxidation number method - The certain rules are as follows (c) Balance the number of electrons gained and lost.
(a) Assign oxidation number to the atoms showing a change (d) Balance [O] on both sides by adding H2O.
in oxidation state. (e) Balance H atoms by adding H+ ions
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
248 Chemistry
Very Short/Short Answer Questions (ii) Balance the following reaction by oxidation number
method
1. Why is anode called oxidation electrode whereas cathode is As2S5 + H+ NO3–(conc.) ¾¾ ®
called reduction electrode? H3AsO4 + 5H2SO4 + H2O + NO2
2. 2Cu2S + 3O2 ¾¾ ® 2Cu2O + 2SO2. In this reaction which 14. (i) Balance the following equations using the half-reaction
substance is getting oxidised and which substance is getting
method in the acidic medium.
reduced. Name reducing agent and oxidising agent.
3. Calculate oxidation number of Cr in K2Cr2O7 and S in S2O32– (a) Zn + NO3- ¾¾
® Zn 2+ + NH +4
4. Fe decomposes steam while Cu does not, why?
5. Arrange the following in order of increasing oxidation number (b) MnO 4- + H 2 C 2 O 4 ¾¾
® Mn 2 + + CO 2
of iodine. I2, HI, ICl.
6. In the reaction given below which species is called a spectator (c) Cr2 O 27 - + Cl - ¾¾
® Cr 3+ + Cl 2
ion and why? (ii) Balance the following redox reaction in basic medium
Zn( s) + Cu 2+ (aq) + SO 24- (aq ) ¾¾
® using the half-reaction method:
Zn 2+ (aq) + Cu(s ) + SO24 - (aq ) (a) Mn 2 + + ClO3- ® MnO2 + ClO2
7. Show that oxidation and reduction go side by side by taking
a suitable example. (b) Cl2 ® Cl - + ClO3-
8. MnO 24 - undergoes disproportionation reaction in acidic 15. (i) What are the highest oxidation numbers of N, S and
Cl?
medium but MnO4- does not. Give reason.
(ii) 2CrO24-+ 2H+ a redox reaction?
Is Cr2O27- + H 2O
9. Starting with the correct half-reaction, write the correct overall
net ionic reaction in the following changes. (iii) Calculate oxidation number of :
(i) Chromite ion (CrO3–) is oxidised by H2O2 in strongly (a) Cr in CrO5
basic solution. (b) S in H2SO5
(ii) Iodate ion (IO3– ) oxidises the iodide I– to I2 in acidic (c) Fe in Fe3O4.
solution.
Multiple Choice Questions
(iii) Permanganate ion MnO–4 oxidises the oxalate ion (C2O24–)
to CO2 in acidic solution. 16. Which of the following is not an example of redox reaction?
10. Is it possible to store: (a) CuO + H2 ® Cu + H2O
(i) copper sulphate solution in a zinc vessel? (b) Fe2O3 + 3CO ® 2Fe + 3CO2
(ii) copper sulphate solution in a nickel vessel? (c) 2K + F2 ® 2KF
(iii) copper sulphate solution in a silver vessel? (d) BaCl2 + H2SO4 ® BaSO4 + 2HCl
(iv) copper sulphate solution in a gold vessel? 17. The oxidation number of an element in a compound is
(Take help from electrochemical series) evaluated on the basis of certian rules. Which of the following
11. The standard electrode potential corresponding to the rules is not correct in this respect?
reaction (a) The oxidation number of hydrogen is always + 1.
Au3+(aq) + 3e– ® Au(s) is + 1.42 V. (b) The algebraic sum of all the oxidation numbers in a
Predict if gold can be dissolved in 1 M HCl solution and on compound is zero.
passing H2 gas through gold solution, metallic gold will be (c) An element in the free or the uncombined state bears
precipitated or not? oxidation number zero.
12. Arrange A, B, C, D, E and H in order of increasing electrode (d) In all its compounds, the oxidation number of fluorine is
potential in the electrochemical series: – 1.
A + H2SO4 ® ASO4 + H2 18. Which of the following arrangements represent increasing
ACl2 + C ® CCl2 + A oxidation number of the central atom?
ECl2 + C ® No reaction
2BCl + D ® DCl2 + 2B (a) CrO-2 , ClO3- , CrO24 - , MnO -4
H2SO4 + D ® No reaction
(b) ClO3- , CrO42 - , MnO -4 , CrO -2
Long Answer Questions
(c) CrO-2 , ClO3- , MnO4- , CrO42 -
13. (i) Balance the following reaction by ion–electron method
K+ MnO4 + H+ Cl– ¾¾ ® (d) CrO24 - , MnO4- , CrO2- ,ClO3-
K+Cl– + Mn2+(Cl–)2 + H2O + Cl2
JEEMAIN.GURU
downloaded from jeemain.guru
1. In the following reaction, which is the species being oxidised ? 4. Which substance serves as reducing agent in the following
reaction?
2Fe3+ (aq) + 2I- (aq) ® I 2 (aq) + 2Fe2+ (aq)
(a) Fe + (b) I– 14H + + Cr2 O 2– 3+
7 + 3Ni ® 2Cr + 7H 2O + 3Ni
2+
JEEMAIN.GURU
downloaded from jeemain.guru
250 Chemistry
7. For the redox reaction 17. In which of the following compounds, the oxidation number
– 2– + 2+ of iodine is fractional ?
MnO + C 2O + H ® Mn + CO 2 + H 2 O
the correct coefficients of the reactants for the balanced (a) IF7 (b) I -
reaction are: (c) IF5 (d) IF3
MnO –
C 2O 2–
H+ 18. In which of the following compounds, nitrogen has an
oxidation state of –1 ?
(a) 2 5 16
(b) 16 5 2 (a) N2O (b) NO -2
(c) 5 16 2 (c) NH2OH (d) N2H4
(d) 2 16 5 19. Which of the following involves transfer of five
8. KMnO4 oxidises oxalic acid in acidic medium. The number of electrons ?
CO2 molecules produced as per the balanced equation is
(a) 10 (b) 8 (a) MnO - ® Mn 2+ (b) CrO 2- ® Cr +
(c) 6 (d) 3
(c) MnO2- ®MnO2 (d) Cr2O2- ® 2Cr +
9. Of the following reactions, only one is a redox reaction.
Identify it 20. Oxidation number of nitrogen in (NH4)2SO4 is
(a) Ca (OH) 2 + 2HCl ® CaCl 2 + 2H 2 O (a) –1/3 (b) –1
(c) +1 (d) –3
(b) BaCl 2 + MgSO ® BaSO + MgCl2 21. Oxidation number of carbon in CH2Cl2 is
(a) –4 (b) +4
(c) 2S 2O 2 – + 2H 2 O ® SO 2– + H +
(c) 0 (d) –2
(d) Cu 2S + 2FeO ® 2Cu + 2Fe + SO 2 22. Which of the following elements has least oxidation number ?
10. The reaction of KMnO4 and HCl results in (a) Ni(CN)4 (b) Ni(CO)4
(a) oxidation of Mn in KMnO4 and production of Cl2 (c) Fe2O3 (d) SF6
(b) reduction of Mn in KMnO4 and production of H2 23. The oxidation number of cobalt in K3[Co(NO2)6] is
(c) oxidation of Mn in KMnO4 and production of H2 (a) 0 (b) +4
(d) reduction of Mn in KMnO4 and production of Cl2 (c) +3 (d) +6
11. The reaction, 24. The brown ring complex is formulated as
[Fe(H2O)5 NO]SO4. The oxidation number of iron is
2H 2 O(l) ® 4H + (aq) + O 2 (g) + 4e - is (a) 1 (b) 2
(a) an oxidation reaction (c) 3 (d) 0
(b) a reduction reaction 25. In which of the following complexes, oxidation state of metal
(c) a redox reaction is zero ?
(d) a hydrolysis reaction (a) [Pt(NH3)2Cl2] (b) [Cr(CO)6]
12. The chemical that undergoes self oxidation and self reduction (c) [Cr(NH3)3Cl3] (d) [Cr(en)2Cl2]
in the same reaction is 26. The oxidation state of chromium in potassium dichromate
(a) benzyl alcohol (b) acetone (K2Cr2O7) is
(c) formaldehyde (d) acetic acid (a) –5 (b) +6
13. In which of the following pairs, there is greatest difference in (c) +2 (d) –2
the oxidation number of the underlined elements ?
27. The oxidation state of osmium (Os) in OsO4 is
(a) NO 2 and N 2 O (b) P 2 O and P O10 (a) +7 (b) +6
(c) +4 (d) +8
(c) N 2 O and N O (d) SO2 and SO3
28. In H2O2, the oxidation state of oxygen is
14. Phosphorus has the oxidation state of +3 in (a) –2 (b) –1
(a) phosphorous acid (c) 0 (d) –4
(b) orthophosphoric acid 29. A, B and C are three elements forming a part of compound in
(c) hypophosphorous acid
oxidation states of +2, +5 and –2 respectively. What could
(d) metaphosphoric acid
be the compound ?
15. In which of the compounds does 'manganese' exhibit highest
(a) A2(BC)2 (b) A2(BC4)3
oxidation number ?
(c) A3(BC4)2 (d) ABC
(a) MnO2 (b) Mn 3O4
30. Among the following, identify the species with an atom in
(c) K2MnO4 (d) MnSO4
+6 oxidation state
16. One of the following has both positive and negative oxidation
states (a) MnO – (b) Cr(CN) –
(a) F (b) Cl
(c) He (d) Na (c) NiF2 – (d) CrO 2 Cl 2
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
252 Chemistry
55. In the chemical reaction, 57. The set of numerical coefficients that balances the equation
K 2 Cr2 O + X H 2 SO + YSO 2 ® K 2 CrO + HCl ® K 2 Cr2 O + KCl + H 2 O
K 2SO4 + Cr2 (SO4 )3 + Z H 2O (a) 1, 1, 2, 2, 1 (b) 2, 2, 1, 1, 1
X, Y and Z are (c) 2, 1, 1, 2, 1 (d) 2, 2, 1, 2, 1
(a) 1, 3, 1 (b) 4, 1, 4
58. (X) MnO 4– + (Y)H 2O2 ®
(c) 3, 2, 3 (d) 2, 1, 2
56. Consider the following reaction
2Mn +2 + 5H 2 O + 9O 2 + (Z)e-
– –
5H 2 O2 + X ClO2 + 2OH ® X Cl + Y O2 + 6H 2O
In this reaction, value of (X), (Y) and (Z) are
The reaction is balanced if (a) 2, 5, 6 (b) 5, 2, 9
(a) X = 5, Y = 2 (b) X = 2, Y = 5 (c) 3, 5, 5 (d) 2, 6, 6
(c) X = 4, Y = 10 (d) X = 5, Y = 5
1. The oxidation number of phosphorus in pyrophosphoric 7. Which of the following chemical reactions depict the
acid is [CBSE-PMT 1999] oxidising beahviour of H2SO4? [AIEEE 2006]
(a) +3 (b) +1 (a) NaCl + H 2 SO 4 ¾¾® NaHSO 4 + HCl
(c) +4 (d) +5 (b) 2PCl 5 + H 2SO 4 ¾
¾® 2 POCl 3 + 2HCl + SO 2 Cl 2
2. The oxidation states of sulphur in the anions SO32–, S2O42–
and S2O62– follow the order [CBSE-PMT 2003] (c) 2 HI + H 2 SO 4 ¾
¾® I 2 + SO 2 + 2 H 2 O
(d) Ca (OH ) 2 + H 2SO 4 ¾
¾® CaSO 4 + 2 H 2 O
(a) S 2 O 6 2 - < S 2 O 4 2- < SO 3 2-
(b) S2 O 4 2 - < SO 3 2- < S2 O 6 2- 8. What products are expected from the disproportionation
reaction of hypochlorous acid? [AIEEE 2006]
(c) SO32- < S2 O4 2- < S2O 6 2- (a) HCl and Cl2O (b) HCl and HClO3
(d) S2 O 4 2 - < S 2 O 6 2- < SO 3 2- (c) HClO3 and Cl2O (d) HClO2 and HClO4
9. Consider the following reaction :
3. Oxidation numbers of P in PO3– 2–
4 , of S in SO 4 and that of
z
Cr in Cr2 O 72– are respectively [CBSE-PMT 2009] xMNO4 - + yC2O42- + zH + ® xMn 2+ + 2yCO2 + H 2O
2
(a) + 3, + 6 and + 5 (b) + 5, + 3 and + 6
The value’s of x, y and z in the reaction are, respectively :
(c) – 3, + 6 and + 6 (d) + 5, + 6 and + 6
[JEE M 2013]
4. When Cl2 gas reacts with hot and concentrated sodium
hydroxide solution, the oxidation number of chlorine (a) 5, 2 and 16
changes from : [CBSE-PMT 2012 S] (b) 2, 5 and 8
(a) zero to +1 and zero to –5 (c) 2, 5 and 16
(b) zero to –1 and zero to +5 (d) 5, 2 and 8
(c) zero to –1 and zero to +3 10. The compound YBa 2 Cu 3 O 7 which shows
(d) zero to +1 and zero to –3 superconductivity has copper in oxidation state ..........
5. Which of the following is a redox reaction? [AIEEE 2002] Assume that the rare earth element Yttrium is in its usual +3
(a) NaCl + KNO3 ® NaNO3 + KCl oxidation state
(a) 3/7 (b) 7/3 [IIT 1994]
(b) CaC2O4 + 2HCl ® CaCl2 + H2C2O4
(c) 3 (d) 7
(c) Mg(OH)2 + 2NH4Cl ® MgCl2 + 2NH4OH
11. For H3PO3 and H3PO4 the correct choice is
(d) Zn + 2AgCN ® 2Ag + Zn(CN)2
[IIT SCREENING 2003]
6. The oxidation state of chromium in the final product formed
(a) H3PO3 is dibasic and reducing
by the reaction between KI and acidified potassium
dichromate solution is: [AIEEE 2005] (b) H3PO3 is dibasic and non-reducing
(a) + 3 (b) + 2 (c) H3PO4 is tribasic and reducing
(c) + 6 (d) + 4 (d) H3PO3 is tribasic and non-reducing
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
254 Chemistry
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
256 Chemistry
EXERCISE 3 H
|
1. (d) Pyrophosphoric acid H4P2O7 11. (a) H - O - P - OH , hence it is dibasic. It acts as reducing
Let oxidation state of phosphorus is x
(4 × 1 + (– 2) × 7 + 2 x) = 0 O
\ 2x = 10 or x = +5 agent also.
2. (c) SO 32 - ® S is in + 4 oxidation state EXERCISE 4
S2 O 24- ® S is in + 3 oxidation state 1. (a) ON of S in S8 = 0
ON of S in S2F2 = + 1
S2 O 62- ® S is in + 5 oxidation state ON of S in H2S = -2
2. (c) K2Cr2O7 + 3SO2 + 4H2SO4 ®
3. (d) PO3–
4 = x + 4 (– 2) = – 3; x – 8 = – 3; x = + 5
K 2SO 4 + Cr2 (SO 4 )3 + 3SO 3 + 4H 2 O
SO 2– = x + 4 (– 2) = – 2; x – 8 = – 2; x = + 6 O.N.of chromium changes from +6 to +3
4
loss of 10 e
3. (c) N 2-4 H 4+4 ¾¾¾¾¾ ® N 2+6 (y);
Cr2 O72– = 2x + 7 (– 2) = – 2; 2x – 14 = – 2; N
2x =12; x = + 6 O.N.of N changes from -2 to +3
4. (b) On reaction with hot and concentrated alkali a mixture 4. (a) O.N. of C changes form 0 to + 4 by oxidation. Hence
of chloride and chlorate is formed HNO3 is oxidising agent.
Hot
3Cl2 + 3 NaOH(excess) ¾¾¾ 5. (a) CrO24 - ® Cr2 O72– O.N of Cr does not change . It remains
®
+6 on both sides . Hence there is no oxidation or reduction.
-1 +5
5NaCl + NaClO3 + 3H 2O 6. (d) Xe = 53.5 % \ F = 46.5%
Relative number of atoms Xe
5. (d) The oxidation states show a change only in
reaction (d). 53.5 46.5
= = 0.4 and F = = 2.4
131.2 19
0 +1 0 +2
-2e - Simple ratio Xe = 1 and F = 6 ; Molecular formula is XeF6
Zn + 2A gCN ¾¾¾® 2Ag + Zn(CN) 2
+2e - O.N.of Xe is +6
7. (b) In iodometry, K2Cr2O7 liberates I2 from iodides (NaI or
2- - +
6. (a) Cr2O7 + 6I + 14H ¾¾ ® 2Cr3+ +3I2 +7H 2O KI). Which is titrated with Na2S2O3 solution.
+ 3 oxidation state of Cr. K 2Cr2O7 + I – + H + ¾¾
® Cr3+ + I2
+6 +4 Here, one mole of K2Cr2O7 accepts 6 mole of electrons.
7. (c) 2HI -1 + H 2SO 4 ¾ ¾® I 02 + SO 2 + 2H 2 O molecular weight
In this reaction O.N. of S is decreasing from + 6 to +4 \Equivalent weight =
6
hence undergoing reduction and O.N. of I is increases
from –1 to 0 hence undergoing oxidation therefore H2SO4 8. (c) 4P + 3KOH + 3H 2 O ® KH 2 PO 2 + PH 3
is acting as oxidising agent. O.N of P = 0, In KH2PO2 it is + 1, In PH3 it is –3. Hence P
8. (b) During disproportionation same compound undergo is oxidised and reduced
simultaneously oxidation and reduction. 9. (a) Ozone is reducing as well as oxidising is nature
+1
Oxidation 10. (a) [Co( NH 3 ) 5 Cl.]Cl 2 , H –1 –2 +1
N — O — H,
–3 +1H
- + -1 +5
3HO Cl ¾
¾® 2HCl+ HClO 3 reduction H .. H
H N-N , Mg3N2
Reduction H H
– 1, – 2, –3
9. (c) On balancing the given equations, we get
2MnO 4- + 5C 2 O 4 2- + 16H + ¾¾
® 2Mn ++ 11. (d) In H2SO4 , sulphur is in highest oxidation state (+6),
Hence H2SO4 will be strongest by oxidising agent.
+10CO 2 + 8H 2O -1 +1
So, x = 2, y = 5 & z = 16 12. (d) Cl0 + 2NaOH ® NaCl+ NaClO+ H O
2 2
10. (b) YBa2Cu3O7
+6 +7 +4
3 + 2 × 2 + 3x – (2 × 7) = 0 3M nO-- - –
4 + 2H 2O ® 2 Mn O 4 + M nO 2 + 4OH
3 + 4 + 3x – 14 = 0
3x = 7 +4 +5 +3
2 N O 2 + H 2 O ® HN O 3 + H NO 2
7
x= . All undergo disproportionation
3 13. (c) I2 is less electronegative than Br2
JEEMAIN.GURU
downloaded from jeemain.guru
9
Hydrogen
GENERAL INTRODUCTION : MANUFACTURE OF HYDROGEN :
Symbol of hydrogen is H. Electronic Configuration 1s1. Hydrogen i) From water gas (Bosch process) : By passing water gas
is the lightest and most abundant element in the universe. It was mixed with steam over heated catalyst Fe3O4 and Cr2O3 at
first prepared by Sir Henry Cavendish by the action of sulphuric 450ºC.
acid on Zinc and named by Antoine Lavoisier since it produced
Re d Hot
water on burning. H 2 O(Steam) ¾¾ ¾¾® (CO + H 2 )
Coke
water gas
(Greek : hydra= water, gennas = maker or producing)
PREPARATION OF DIHYDROGEN : Fe O , Cr O
(CO + H 2 ) + H 2 O ¾¾2¾3¾ ¾
2¾3 ® CO + 2 H
450 º C 2 2
i) From cold water : By the action of Na, K, Ca etc.
2 Na + 2H 2 O ® 2 NaOH + H 2 (highly exothermic and H2 The CO2 is removed by dissolving in water under high
pressure.
cathces fire)
ii) By Lane’s process : The superheated steam is passed over
Al-Hg and Zn-Cu couple decompose water to give nascent
heated iron at 600 - 800ºC
hydrogen
Zn + 2H 2 O ® Zn(OH) 2 + 2H 3 Fe + 4H 2 O Fe3O 4 + 4H 2
Hence Couples constitute better reducing agents Iron is regenerated by passing water gas. (H2 + CO)
ii) From hot water : By the action of Mg, Zn, Al etc. Fe 3O 4 + 4CO ® 3Fe + 4CO 2
2Al + 3H 2 O ® Al 2 O 3 + 3H 2 Fe 3O 4 + 4H 2 ® 3Fe + 4H 2 O
iii) From steam : By the action of Fe, Sn etc. In actual practice steam is passed over hot iron for 10 - 15
3Fe + 4H 2 O ® Fe3O 4 + 4H 2 minutes and then water gas is blown over heated oxide for
25 - 30 minutes.
iv) From water : By the action of metallic hydrides of alkali and iii) By electrolysis of water : By the electrolysis of acidified or
alkaline earth metals. alkaline water.
CaH 2 + 2H 2 O ® Ca (OH ) 2 + H 2
H 2O H + + OH -
v) From acids : By the action of dilute acids on Zn, Mg, Fe,
etc. placed above hydrogen in electrochemical series. At cathode 2H + + 2e - ® H 2
Sn + 2HCl ® SnCl 2 + H 2
At anode 4OH - - 4e - ® 4OH ® 2H 2 O + O 2
Zn + H 2SO 4 ® ZnSO 4 + H 2
iv) As by product : When NaOH is manufactured by electrolysis
vi) From alkalies : By the action Zn, Al, Sn etc. of NaCl in Nelson or Castner Kellner cell hydrogen is
Zn + 2NaOH ® Na 2 ZnO 2 + H 2 obtained as by product.
2Al + 2 NaOH + 2 H 2 O ® 2 NaAlO2 + 3 H 2 2 NaCl ® 2 Na + + Cl -
JEEMAIN.GURU
downloaded from jeemain.guru
258 Chemistry
JEEMAIN.GURU
downloaded from jeemain.guru
Hydrogen 259
1 1 ii) Merck process : By passing CO2 through a suspension of
Nuclear spin = + =1 (For ortho-hydrogen) BaO2 in ice cold water.
2 2
1 æ 1ö BaO 2 + H 2 O + CO 2 ® BaCO 3 + H 2 O 2
Nuclear spin = + ç- ÷ = 0 (For para-hydrogen)
2 è 2ø Manufacture :
v) Transportation of hydrogen : It is transported in the form 1) By electrolysis of 50% ice cold H2SO4
of Hydrolith (CaH2) or ammonia (NH3). Ammonia is cracked 2 H 2SO 4 H 2 + H 2 S2 O 8
by passing over heated catalysts yielding a mixture of Persulphuric acid
hydrogen (75%) and N2 (25%). ( Marshall's acid )
2 NH 3 ® 3H 2 + N 2
H 2S2 O 8 + H 2 O ® H 2SO 4 + H 2SO 5
HYDRIDES : Permonosulphuric acid
Binary compounds of hydrogen and other elements are called ( Caro's Acid )
hydrides. Hydrides are classified into the following four classes.
H 2SO 5 + H 2 O ® H 2SO 4 + H 2 O 2
1) Saline or ionic hydrides.
2) Molecular or covalent hydrides. Mechanism : H 2SO 4 H + + HSO -4
3) Metallic or intertitial hydrides.
4) Polymeric hydrides. At anode : 2 HSO -4 ® H 2S 2 O 8 + 2e -
1. Saline or ionic hydrides : These are formed by elements of
group 1, 2 (Except Be and Mg) and lanthanides by heating At cathode : 2 H + + 2e - ® H 2
the metal in hydrogen.
2) Auto oxidation : Most recent method used in America. In
These are white colourless solids (crystalline) having high
this method the anthraquinone is reduced to anthraquinol
mpt. and bpt. easily decomposed by water, alcohol, CO2 or
by dissolving in an organic solvent and passing hydrogen
SO2.
in presence of Pd. On frothing, the anthraquinol derivative
CaH 2 + 2H 2 O ® Ca (OH) 2 + 2H 2 with air, 20% solution of H2O2 is obtained and anthraquinone
CaH 2 + 2C 2 H 5 OH ® Ca (OC 2 H 5 ) 2 + 2H 2 is regenerated.
O OH
CaH 2 + 2CO 2 ® (HCOO) 2 Ca
C2H5 C2H5
They are strong reducing agents. Alkali metal hydrides are H2/Pd O2
used for making LiAlH4, NaBH4 etc and for removing last
traces of water from organic compound. O OH
2) Molecular or covalent hydrides : These are formed by 4th,
5th, 6th, 7th group elements and boron by sharing electrons O
with hydrogen atoms. eg.: NH3, HCl, B2H6, AsH3 . These C2H5
O2
are non electrolytes and are usually gases or liquids. + H2O2
3) Metallic or interstitial hydrides : The transition elements
and rare earth metals combine with hydrogen to give O
interstitial hydrides. They exhibit metallic properties and 3) By electrolysis of ammonium sulphate solution and
are powerful reducing agents. They are non stoichiometric sulphuric acid. When aqueous solution of ammonium
compounds and their composition varies with temperature sulphate and sulphuric acid in equimolar proportion is
and pressure. eg. LaH2.76, TiH1.73 electrolysed at low temperature ammonium persulphate is
4) Polymeric hydrides : These are solids containing molecules, formed. The latter on distillation with sulphuric acid gives
linked together in two or three dimensions by hydrogen 30% solution of hydrogen peroxide.
bridge bonds. e.g.: (BeH2)n, (MgH2)n and (AlH3)n
( NH 4 ) 2 SO 4 + H 2SO 4 ® 2 NH 4 .HSO 4
HYDROGEN PEROXIDE :
Discovery : French chemist Thenard 1818. NH 4 HSO 4 NH 4SO -4 + H +
Occurrence : Traces in air, rain and plants.
At anode :
PREPARATION :
i) Lab method : From true peroxide by the action of ice cold 2 NH 4SO -4 ® ( NH 4 ) 2 S 2 O8 + 2e -
dil. H2SO4.
At cathode :
Na 2 O 2 + H 2SO 4 ® Na 2SO 4 + H 2 O 2
2 H + + 2e - ® H 2 ( g )
BaO 2 + H 2SO 4 ® BaSO 4 + H 2 O 2
( NH 4 ) 2 S2 O8 + 2H 2 O ® 2 NH 4 HSO 4 + H 2 O 2
(HNO3 is not used since it will oxidise H2O2).
JEEMAIN.GURU
downloaded from jeemain.guru
260 Chemistry
CONCENTRATION OF HYDROGEN PEROXIDE : ii) Oxidising agent : It is strong oxidising agent in acidic as
It is very carefully concentrated since it decomposes on heating well as in basic medium.
or on standing.
H 2 O 2 + 2 H + + 2e - ® 2 H 2 O Eº = 1.77 V
2H 2 O 2 ® 2H 2 O + O 2 (auto-oxidation)
Decomposition is catalysed by Cu, Ag, Pt, Co, Fe, MnO2 etc. H 2 O 2 + OH – + 2e - ® 3OH - Eº = 0.88 V
The methods employed for concentration are
i) Evaporation : By careful evaporation of solution on a water or H 2O 2 ® H 2O + O
bath (50% H2O2 is obtained).
PbS + 4O ® PbSO 4
ii) Dehydration in vacuum desicator : The 50% H2O2 is
dehydrated in a vacuum desicator in presence of conc. H2SO4 2KI + H 2 O + O ® 2KOH + I 2
when 90% H2O2 is obtained. 2FeSO 4 + H 2SO 4 + O ® Fe 2 (SO 4 ) 3 + H 2 O
iii) Vacuum distillation : The 90% H2O2 obtained in step (ii) is
distilled under reduced pressure to get 100% H2O2 2K 4 [Fe(CN) 6 ] + H 2 O + O ® 2K 3 [ Fe(CN ) 6 ] + 2KOH
iv) Cooling : The traces of water left are removed by freezing in
a freezing mixture when crystals of hydrogen peroxide H 2 Cr2 O7 + 4O ® 2CrO5 + H2O
Chromic Blue peroxide
separate out. acid of chromium
STRENGTH OF HYDROGEN PEROXIDE :
C 6 H 6 + O ® C 6 H 5 OH
The strength of hydrogen peroxide is indicated in terms of the
volume of oxygen at NTP that 1 volume of H2O2 gives on heating. In basic medium
For example “20 volume H2O2 means 1 volume of H2O2 at NTP
will give 20 volume of oxygen. The normality and percentage 2Cr 3+ + 3H 2 O 2 + 10OH – ® 2CrO42 - + 8H 2 O
strength of H2O2 can be calculated as follows
Mn 2+ + H 2 O 2 + 2OH – ® MnO2 + 2H 2 O
2 H 2 O 2 ® 2H 2 O + O 2
iii) Reducing agent :
2 × 34 = 68 g 1 mole O2 = 22.4 litres of O2 at NTP
22.4 litres of O2 at NTP are evolved from 68g of H2O2 a) In acidic medium
JEEMAIN.GURU
downloaded from jeemain.guru
Hydrogen 261
TEST : TYPES OF HARDNESS OF WATER :
i) It liberates I2 from acidified KI It is of two kinds
2KI + H 2 O 2 ® 2KOH + I 2 i) Temporary hardness : It is due to the presence of
bicarbonates of calcium or magnesium or both.
ii) Perchromic acid :
ii) Permanent hardness : It is due to the presence of chlorides
H 2 Cr2 O 7 + 4H 2 O 2 ® 2CrO 5 + 5H 2 O and sulphates of calcium and magnesium.
Blue colour
(chromium peroxide) REMOVAL OF TEMPORARY HARDNESS :
(acidified H 2 O 2 + amyl alcohol + K 2 Cr2 O 7 ) ® blue colour It can be achieved by following methods
iii) With titanic sulphate it gives orange red pertitanic acid i) By boiling : The soluble bicarbonates are converted into
insoluble carbonates.
Ti(SO 4 ) 2 + H 2 O 2 + 2H 2 O ® 2H 2SO 4 + H 2 TiO 4
Ca(HCO3 ) 2 ® CaCO3 ¯ +H 2O + CO2
iv) Black lead sulphide turned white
PbS + 4H 2 O 2 ® PbSO 4 + 4H 2 O Mg(HCO3 ) 2 ® MgCO3 ¯ +H 2O + CO2
ii) By Clark’s process : By adding lime water or milk of lime
USES :
It is used as a bleaching agent, disinfectant, source of power Ca (HCO 3 ) 2 + Ca (OH ) 2 ® 2CaCO 3 ¯ +2H 2 O
(90% H2O2 as fuel in submarines, rockets and helicopters), in Mg ( HCO 3 ) 2 + 2Ca (OH ) 2 ® 2CaCO 3 ¯ + Mg (OH ) 2 ¯ +2H 2 O
restoration of old paintings in which lead oxide is used as white
paint. REMOVAL OF PERMANENT HARDNESS :
WATER : i) By adding washing soda : The calcium or magnesium salts
are precipitated as carbonates
Water is one of the most abundant substances in nature. The 4/
5th of the earth surface is covered with water. Mg ( HCO 3 ) 2 + Na 2 CO 3 ® MgCO 3 ¯ +2 NaHCO 3
Sources of water : The sources of water are MgCl 2 + Na 2 CO 3 ® MgCO 3 ¯ +2 NaCl
i) Surface water :
a) Flowing water eg.: streams and rivers Ca ( HCO 3 ) 2 + Na 2 CO 3 ® CaCO 3 ¯ +2 NaHCO 3
b) Still water eg.: ponds, lakes and reservoirs CaCl 2 + Na 2 CO 3 ® CaCO 3 ¯ +2 NaCl
ii) Underground water : water from wells ii) By adding Caustic Soda : The temporary and permanent
iii) Rain water hardness can be removed by adding caustic soda
iv) Sea water Ca ( HCO 3 ) 2 + 2 NaOH ® Ca (OH ) 2 ¯ +2 NaHCO 3
TYPES OF IMPURITIES PRESENT IN WATER :
Ca ( HCO 3 ) 2 + Ca (OH ) 2 ® 2CaCO 3 ¯ +2H 2 O
They are
i) Dissolved impurities Mg ( HCO 3 ) 2 + 2 NaOH ® Mg (OH) 2 ¯ +2 NaHCO 3
a) Inorganic salts eg. : Ca2+, Mg2+, Fe2+, Al 3+, Na+, K+
CaCl 2 + 2 NaOH ® Ca (OH ) 2 ¯ +2 NaCl
traces
_
of Zn2+ and _
Cu2+ (cations) and Cl–, SO 24 - ,
–
NO 3 , F or HCO 3 etc. (anions) CaSO 4 + 2 NaOH ® Ca (OH ) 2 ¯ + Na 2SO 4
b) Gases eg.: CO2, N2, O2, oxides of nitrogen, H2S etc.
MgCl 2 + 2 NaOH ® Mg (OH ) 2 ¯ +2 NaCl
c) Organic salts
ii) Suspended impurities : MgSO 4 + 2 NaOH ® Mg (OH ) 2 ¯ + Na 2SO 4
a) Inorganic : eg.: sand and clay iii) By adding Sodium phosphate (Na3PO4) : The phosphates
b) organic : eg.: animal matter, vegetable etc. of calcium and magnesium are precipited
iii) Colloidal impurities : Finely divided clay, Al(OH)3, Fe(OH)3 3Ca ( HCO 3 ) 2 + 2 Na 3 PO 4 ® Ca 3 (PO 4 ) 2 ¯ +6 NaHCO 3
colouring matter etc.
3CaCl 2 + 2 Na 3 PO 4 ® Ca 3 ( PO 4 ) 2 ¯ +6 NaCl
iv) Bacterial impurities : Micro-organisms and bacteria
Effect of impurities : The impurities effect the followings 3CaSO 4 + 2 Na 3 PO 4 ¾
¾® Ca 3 ( PO 4 ) 2 ¯ +3Na 2SO 4
a) Colour b) Taste c) Hardness
d) alkalinity e) Turbidity f) odour etc 3Mg (HCO 3 ) + 2 Na 3 PO 4 ¾
¾®
JEEMAIN.GURU
downloaded from jeemain.guru
262 Chemistry
iv) Calgon process : Calgon is sodium hexa metaphosphate. Ex. A water sample contains 204 mg of CaSO4 per litre. Calculate
The water is passed through the bed of calgon the Ca 2+ and the hardness in terms of CaCO3 equivalent.
Mg2+ form soluble complex.
Sol. CaSO 4 º CaCO 3
2CaSO 4 + Na 2 [ Na 4 (PO 3 ) 6 ] ® 136 g mol -1 100 g mol -1
2 Na 2SO 4 + Na 2 [Ca 2 (PO 3 ) 6 ]
136 mg / L of CaSO 4 º 100 mg / L of CaCO 3 eq.
2MgSO 4 + Na 2 [ Na 4 (PO 3 ) 6 ] ®
2MgSO 4 + Na 2 [Na 4 (PO3 )6 ] ® 2Na 2SO 4 + Na 2 [Mg 2 (PO3 )6 ] 204 mg/L of CaSO4 º 100 mg / L of CaCO 3 ´ 204
136
Water becomes free from Ca++ and Mg++ ions. = 150 mg/L of CaCO3
v) Permutit process : Permutit is hydrated Sodium aluminium Hence hardness = 150 mg/L or ppm.
silicate Na2 Al2 Si2 O8.xH2O. It exchanges its sodium ions
Ex. A sample of water on analysis was found to contain the
for divalent ions such as Ca2+ and Mg2+.
following impurities expressed in mg/litre.
Na 2 Al 2Si 2 O8 + CaCl 2 ® CaAl 2Si 2 O 8 + 2 NaCl
Impurity Ca(HCO3)2 Mg(HCO3)2 CaSO4 MgSO4
Na 2 Al 2Si 2 O8 + MgSO 4 ® MgAl 2Si 2 O8 + Na 2SO 4
Permutit when fully exhausted can be regenerated by Quantity 10.0 8.5 12.0 14.0
treating with 10% solution of sodium chloride Mol. wt. 162 146 136 120
Ca - permutit + 2 NaCl ® 2 Na - permutit + CaCl 2 Calculate the temporary, permanent and total hardness of
water in mg/litre.
Mg - permutit + 2 NaCl ® 2 Na - permutit + MgCl 2
Sol. Conversion into CaCO3 equivalents
It is most efficient method to get water with zero degree
Impurity Amount Multiplication CaCO3
hardness.
factor equivalt.
vi) By synthetic resins : They are of two types :
a) Cation exchange resins : These are giant molecules Ca(HCO3)2 10.0 mg/L 100/162 10.0 × 100/162
containing sulphonic acid group (–SO 3H). It is first = 6.17 mg/L
changed into sodium salt and has the general fomula Mg(HCO3)2 8.5 mg/L 100/146 8.5 × 100/146
R – Na + The hard water is passed through it when Ca2+ = 5.82 mg/L
and Mg2+ are exchanged and removed. CaSO4 12.0 mg/L 100/136 12.0 × 100/136
= 8.82 mg/L
2R - Na + + Ca 2+ ® R 2 Ca + 2 Na +
MgSO4 14.0 mg/L 100/120 14.0 × 100/120
2R - Na + + Mg 2+ ® R 2 Mg + 2 Na + = 11.67 mg/L
The resins like permutit can be regenerated with a Temporary hardness due to Ca(HCO3)2 + Mg(HCO3)2
solution of common salt. = (6.17 + 5.82) = 11.99 mg/L
R 2 Ca + 2 NaCl ® 2RNa + CaCl 2 Permanent hardnesss due to CaSO4 + MgSO4
b) Anion exchange resins : These are also giant molecules = (8.82 + 11.67) = 20.49 mg/L
and can exchange anions. They contain an amino group. Total hardness (11.99 + 20.49) = 32.48 mg/L
+ HYDRATES :
RNH 2 + H 2 O ® RNH 3OH - The substances (salts) containing water molecules are called
hydrates. These are of three types:
2RNH 3+ OH + CO 32 - (RNH 3+ ) 2 CO 3 + 2OH
– –– –
JEEMAIN.GURU
downloaded from jeemain.guru
Hydrogen 263
HEAVY WATER/DEUTERIUM OXIDE (D2O) : ii) Reaction with Na :
It was discovered by Urey, who showed that ordinary water 2 Na + D 2 O ® 2 NaOD + D 2
contains one part of heavy water in 6,000 parts of it. iii) with acid oxides :
PREPARATION :
P2 O 5 + 3D 2 O ® 2D 3 PO 4
It is prepared by exhaustive electrolysis of water containing alkali Heavy phosphoric acid
with nickel electrodes. About 20 litres of ordinary water gives 0.5
ml of heavy water. SO 3 + D 2 O ® D 2SO 4
Heavy sulphuric acid
PROPERTIES :
iv) with metallic carbides :
Heavy water is a colourless, odourless, tasteless mobile liquid.
Its physical properties in comparision to ordinary water are as Al 4 C3 + 12D 2 O ® 4Al(OD)3 + 3CD 4
follows : CaC 2 + 2D 2 O ® Ca (OD) 2 + C 2 D 2
Physical constants : D2O H2O
v) Deuterolysis : AlCl3 + 3D 2 O ® Al(OD) 3 + 3DCl
Melting point 276.8K 273K
vi) As water of crystallisation : It gives deuterohydrates
Boiling point 374.4K 373K
CuSO4.5D2O, MgSO4.7D2O, etc.
Sp. gravity at 20º C 1.106 0.998
Theoretically six different types of heavy water are possible
Temperature of max. density 284.6K 277K
Specific heat at 20º C 1.018 1.000 16 17 18
eg. : H – O – D, H – O – D, H – O – D,
Viscosity at 293 K 14.2 10.87
Surface tension 67.8 72.8 16 17 18
D – O – D, D – O – D, & D – O – D
Latent heat of vaporisation 2330kJkg–1 2255 kJkg–1
BIOLOGICAL AND PHYSIOLOGICAL EFFECTS :
Dielectric Constant 82 80.5 It does not support life, and is injurious to living organism. It
Solubility of NaCl at 20ºC 30.5% 35.9% checks the growth of plants and animals.
Refractive index 1.328 1.33 USES :
CHEMICAL PROPERTIES : (i) As a tracer compound
i) Electrolysis : (ii) For production of heavy hydrogen.
(iii) As moderator in nuclear reactors.
2D 2 O ®
¬ 2D 2 + O 2
JEEMAIN.GURU
downloaded from jeemain.guru
264 Chemistry
Very Short/ Short Answer Questions 18. Complete the following reactions :
1. Why is 2-ethylanthraquinol preferred in the commercial (i) P4O10 + H2O ® (ii) AlCl3 + H2O ®
production of H2O2? (iii) SiCl4 + H2O ® (iv) Ca3P2 + H2O ®
2. Give an example to show that ionic hydrides forms (v) NaH + H2O ®
complexes. Multiple Choice Questions
3. Which gas is evolved when Mg3N2 (Magnesium nitride)
19. Hydrogen resembles halogens in many respects for which
is treated with H2O? Give chemical reaction.
several factors are responsible. Of the following factors
4. How would you prepare a sample of ND3? which one is most important in this respect?
5. How does heavy water react with Al4C3? (a) Its tendency to lose an electron to form a cation.
6. Arrange H2, D2 and T2 in the decreasing order of their boiling (b) Its tendency to gain a single electron in its valence
points. shell to attain stable electronic configuration.
7. Conc. H2SO4 cannot be used for drying H2, why? (c) Its low negative electron gain enthalpy value.
8. Why ice is less dense than water ? (d) Its small size.
9. Statues coated with white lead on long exposure to 20. Which of the following reactions increases production of
atmosphere turn black and original colour can be restored dihydrogen from synthesis gas?
on treatment with H2O2. Why?
1270 K
10. How will you show that H2O2 will act like oxidizing agent in (a) CH 4 ( g ) + H 2 O( g ) ¾¾¾¾ ® CO( g ) + 3H 2 ( g )
Ni
acidic as well as basic medium?
11. Why hard water is not used in industrial boilers for producing 1270K
(b) C( s ) + H 2 O( g ) ¾¾¾¾
® CO( g ) + H 2 ( g )
steam?
673K
12. Hydrogen forms compounds with elements having atomic (c) CO( g ) + H 2O( g ) ¾¾¾¾ ® CO2 (g) + H 2 (g)
Catalyst
number 9, 11, 12 and 17. What are their chemical formulae?
Compare their chemical behaviour. 1270K
(d) C 2 H 6 + 2H 2 O ¾¾¾¾
® 2CO + 5H 2
13. What happens when– Ni
(i) Water reacts with cyanamide of calcium 21. Which of the following reactions is an example of use of
(ii) Peroxosulphuric acid is hydrolysed. water gas in the synthesis of other compounds?
(iii) Moist silver oxide reacts with H2O2 1270K
(a) CH4(g) + H2O(g) ¾¾¾¾
Ni
® CO(g) + H2(g)
14. Describe the industrial application of H2 dependent on
673K
(i) the heat liberated when its atoms are made to combine (b) CO(g) + H2O(g) ¾¾¾¾
Catalyst
® CO (g) + H (g)
2 2
on the surface of a metal
(ii) its effect on unsaturated organic system is presence of 1270K
(c) CnH2n+2 + nH2O (g) ¾¾¾¾
Ni
® nCO + (2n + 1)H2
catalyst
(iii) its ability to combine with N2 under specific conditions Cobalt
(d) CO(g) + 2H2(g) ¾¾¾¾
Catalyst
® CH OH(l)
3
15. A mixture of hydrazine and H2O2 with Cu (II) catalyst is
used as a rocket propellant. Why? 22. Consider the following statements :
1. Atomic hydrogen is obtained by passing hydrogen
Long Answer Questions through an electric arc.
16. (i) What are the ways in which water molecules are bound 2. Hydrogen gas will not reduce heated aluminium oxide.
to an anhydrous salt to form hydrate? 3. Finely divided palladium absorbs large volume of
hydrogen gas.
(ii) Why water is an excellent solvent?
4. Pure nascent hydrogen is best obtained by reacting
17. How does dihydrogen react with Na with C2H5OH.
(i) O2 (ii) C Which of the above statements is/are correct ?
(iii) N2 (iv) F2 (a) 1 alone (b) 2 alone
(v) Cl2? (c) 1, 2 and 3 (d) 2, 3 and 4
JEEMAIN.GURU
downloaded from jeemain.guru
Hydrogen 265
23. Elements of which of the following group(s) of periodic table Codes
do not form hydrides. (a) 1–C, 2–D, 3–B, 4–A
(a) Groups 7, 8, 9 (b) Group 13
(b) 1–B, 2–A, 3–C, 4–D
(c) Groups 15, 16, 17 (d) Group 14
24. Water contracts on heating (c) 1–B, 2–D, 3–C, 4–A
(a) to 100 °C (b) from 0°C to 4°C (d) 1–C, 2–A, 3–B, 4–D
(c) to 273 K (d) from 10°C to 20°C 26. Consider the reactions
25. Match list I with list II and select the correct answer using
(A) H2O2 + 2HI ® I2 + 2H2O
the codes given below the lists :
List I List II (B) HOCl + H2O2 ® H3O+ + Cl– + O2
1. Heavy water A. Bicarbonates of Which of the following statements is correct about H2O2
Mg and Ca in with reference to these reactions? Hydrogen peroxide is
water ______ .
2. Temporary B. No foreign ions
hard water in water (a) an oxidising agent in both (A) and (B)
3. Soft water C. D2O (b) an oxidising agent in (A) and reducing agent in (B)
4. Permanent hard D. Sulphates & (c) a reducing agent in (A) and oxidising agent in (B)
water chlorides of (d) a reducing agent in both (A) and (B)
Mg & Ca in water
1. Which of the following metal evolves hydrogen on reaction 8. Which one of the following pairs of substances on reaction
with cold dilute HNO3 ? will not evolve H2 gas ?
(a) Mg (b) Al (a) Iron and H2SO4 (aq)
(c) Fe (d) Cu (b) Iron and steam
2. The metal which gives hydrogen on treatment with acid as (c) Copper and HCl (aq)
well as sodium hydroxide is (d) Sodium and ethanol
(a) Fe (b) Zn 9. Which of the following will not displace hydrogen
(c) Cu (d) None of these (a) Ba (b) Pb
3. The metal that cannot displace hydrogen from dil HCl is (c) Hg (d) Sn
(a) Al (b) Fe 10. The adsorption of hydrogen by palladium is called
(c) Cu (d) Zn (a) hydration
4. Action of water or dilute mineral acids on active metals can (b) reduction
give (c) occlusion
(a) monohydrogen (b) tritium (d) hydrogenation
(c) dihydrogen (d) trihydrogen 11. Reaction of potassium with water is
5. The property of hydrogen which distinguishes it from other (a) exothermic (b) endothermic
alkali metals is (c) hydrolysis (d) absorption
(a) its electropositive character 12. Consider the following statements :
(b) its affinity for non-metals 1. Atomic hydrogen is obtained by passing hydrogen
(c) its reducing character through an electric arc.
(d) its non-metallic character 2. Hydrogen gas will not reduce heated aluminium oxide.
6. 2 g of aluminium is treated separately with excess of dilute 3. Finely divided palladium adsorbs large volume of
H2SO4 and excess of NaOH. The ratio of the volumes of hydrogen gas
hydrogen evolved is 4. Pure nascent hydrogen is best obtained by reacting Na
(a) 2 : 3 (b) 1 : 1 with C2H5OH
(c) 2 : 1 (d) 1 : 2 Which of the above statements is/are correct ?
7. Which of the following statements is correct ? (a) 1 alone (b) 2 alone
(a) Hydrogen has same IP as alkali metals (c) 1, 2 and 3 (d) 2, 3 and 4
(b) Hydrogen has same electronegativity as halogens 13. Metal hydride on treatment with water gives
(c) It has oxidation number of –1 and +1 (a) H2O2 (b) H2O
(d) It will not be liberated at anode. (c) acid (d) hydrogen
JEEMAIN.GURU
downloaded from jeemain.guru
266 Chemistry
14. H2O2 is commonly prepared in lab. by the reaction of 27. When two ice cubes are pressed over each other, they unite to
(a) PbO2 + H2SO4 (b) MnO2 + H2SO4 form one cube. Which of the following forces is responsible to
(c) BaO2 + H2O + CO2 (d) Na2O2 + H2O hold them together ?
15. Calculate the normality of 10 volume H2O2 ? (a) Hydrogen bond formation
(a) 1.7 N (b) 12 N (b) van der Waals forces
(c) 30.3 N (d) 0.0303 N (c) Covalent attraction
16. Commercial 10 volume H2O2 is a solution with a strength of (d) Ionic interaction
approximately 28. The process used for the removal of hardness of water is
(a) 30% (b) 3% (a) Calgon (b) Baeyer
(c) 1% (d) 10% (c) Serpeck (d) Hoope
17. A, 6 volume sample of H2O2 29. Pure water can be obtained from sea water by
(a) will contain 6% V/V of H2O2 (a) centrifugation (b) plasmolysis
(b) will contain 6% W/V of H2O2 (c) reverse osmosis (d) sedimentation
(c) would give 6 volumes of oxygen per unit volume of H2O2 30. Polyphosphates are used as water softening agents because
sample at STP they
(d) would give 6 volumes of oxygen per unit weight of H2O2 (a) form soluble complexes with anionic species
sample at STP (b) precipitate anionic species
18. The structure of H2O2 is (c) form soluble complexes with cationic species
(a) planar (b) non planar (d) precipitate cationic species
(c) spherical (d) linear 31. What is heavy water ?
19. In which of the following reactions, H2O2 is acting as a (a) H2O18 (b) H2O16
reducing agent (c) H2O3 (d) D2O
(a) H 2 O 2 + SO 2 ® H 2SO 4 32. D2O is used in
(b) 2KI + H 2 O 2 ® 2KOH + I 2 (a) industry (b) nuclear reactor
(c) medicine (d) insecticide
(c) PbS + 4H 2 O 2 ® PbSO 4 + 4H 2 O 33. Match list I with list II and select the correct answer using
(d) Ag 2 O + H 2 O 2 ® 2Ag + H 2 O + O 2 the codes given below the lists :
List I List II
20. Which of the following is formed by the action of water on
1. Heavy water A. Bicarbonates of Mg
sodium peroxide
and Ca in water
(a) H2 (b) N2
2. Temporary B. No foreign ions
(c) O2 (d) CO2
hard water in water
21. The percentage by weight of hydrogen in H2O2 is
3. Soft water C. D2O
(a) 5.88 (b) 6.25
(c) 25 (d) 50 4. Permanent hard D. Sulphates & chlorides of
22. In which of the following reactions, H2O2 acts as a reducing water Mg & Ca in water
agent? Codes
(a) 1–C, 2–D, 3–B, 4–A (b) 1–B, 2–A, 3–C, 4–D
(a) PbO 2 (s ) + H 2 O 2 (aq ) ® PbO(s) + H 2 O(l) + O 2 (g)
(c) 1–B, 2–D, 3–C, 4–A (d) 1–C, 2–A, 3–B, 4–D
(b) Na 2 SO 3 (aq ) + H 2 O 2 (aq ) ® Na 2SO 4 (aq ) + H 2 O (l) 34. What is formed when calcium carbide reacts with heavy
(c) 2KI(aq ) + H 2 O 2 (aq) ® 2KOH (aq ) + I 2 (s) water?
(d) KNO 2 (aq ) + H 2 O 2 (aq ) ® KNO 3 (aq ) + H 2 O (l) (a) C2D2 (b) CaD2
(c) Ca2D2O (d) CD2
23. The low density of ice compared to water is due to
35. The correct order of the O–O bond length in O2, H2O2 and
(a) hydrogen bonding interactions
O3 is
(b) dipole – dipole interactions
(c) dipole – induced dipole interactions (a) O2 > O3 > H2O2 (b) O3 > H2O2 > O2
(d) induced dipole – induced dipole interactions (c) H2O2 > O3 > O2 (d) O2 > H2O2 >O3
24. The alum used for purifying water is 36. The hydride ion H– is stronger base than its hydroxide ion
(a) Ferric alum (b) Chrome alum OH–. Which of the following reactions will occur if sodium
(c) Potash alum (d) Ammonium alum hydride (NaH) is dissolved in water ?
25. The boiling point of water is exceptionally high because (a) H - (aq ) + H 2 O ® H 3O -
(a) there is covalent bond between H and O (b) H - (aq ) + H 2 O(l) ® OH - + H 2
(b) water molecule is linear (c) H - + H 2 O ® No reaction
(c) water molecules associate due to hydrogen bonding
(d) None of these
(d) water molecule is not linear
26. The H–O–H angle in water molecule is about 37. The component present in greater proportion in Coal gas is
(a) 90º (b) 180º (a) CH4 (b) CO2
(c) 102º (d) 105º (c) CO (d) H2
JEEMAIN.GURU
downloaded from jeemain.guru
Hydrogen 267
1. The O – O – H bond angle in H2O2 is [CBSE-PMT 1994] 6. Which of the following statements in relation to the
(a) 106° (b) 109°28' hydrogen atom is correct ? [AIEEE 2005]
(c) 120° (d) 94.8° (a) 3s, 3p and 3d orbitals all have the same energy
2. When H2O2 is oxidised the product is [CBSE-PMT 1999] (b) 3s and 3p orbitals are of lower energy than 3d orbital
(a) OH– (b) O2
(c) 3p orbital is lower in energy than 3d orbital
(c) O2– (d) HO2–
3. Some statements about heavy water are given below: (d) 3s orbital is lower in energy than 3p orbital
(A) Heavy water is used as a moderator in nuclear reactors. 7. In context with the industrial preparation of hydrogen from
(B) Heavy water is more associated than ordinary water. water gas (CO + H2), which of the following is the correct
(C) Heavy water is more effective solvent than ordinary statement? [AIEEE 2008]
water. (a) CO and H2, are fractionally separated using differences
Which of the above statements are correct?
in their densities
[CBSE-PMT 2010]
(a) (A) and (C) (b) (A) and (B) (b) CO is removed by absorption in aqueous Cu2Cl 2
(c) (A), (B) and (C) (d) (B) and (C) solution
4. Which one of the following processes will produce hard (c) H2 is removed through occlusion with Pd
water ? [AIEEE 2003] (d) CO is oxidised to CO2 with steam in the presence of a
(a) Saturation of water with MgCO3 catalyst followed by absorption of of CO2 in alkali
(b) Saturation of water with CaSO4 8. The critical temperature of water is higher than that of O2
(c) Addition of Na2SO4 to water
because H2O molecule has [IIT 1997]
(d) Saturation of water with CaCO3
5. Which of the following species is diamagnetic in nature? (a) fewer electrons than oxygen
(b) two covalent bonds
(a) H -2 (b) H +2 [AIEEE 2005]
(c) v-shape
(c) H2 (d) He +2
(d) dipole moment
1. Hydrogen is not obtained when Zn reacts with 5. The m.pt. of most of the solid substances increase with an
(a) cold water (b) dil H2SO4 increase of pressure. However ice melts at a temperature
lower than its usual melting point when pressure is increased.
(c) dil. HCl (d) 20% NaOH
This is because
2. True peroxide is (a) ice is less denser than H2O
(a) BaO 2 (b) MnO 2 (b) pressure generates heat
(c) the chemical bonds break under pressure
(c) PbO 2 (d) NO2
(d) ice is not a true solid
3. An inorganic compound gives off O2 when heated, turns an
6. Acidified K 2 C r2 O 7 on oxidation by H 2 O 2 gives
acidic solution of KI violet and reduces acidified KMnO4.
The compound is (a) Blue solution (b) CrO5
(a) SO3 (b) KNO3 (c) Chromium peroxide (d) All of these
(c) H2O2 (d) All of these 7. Which reaction shows oxidising nature of H 2 O 2
4. Acidified solution of chromic acid on treatment with H2O2 (a) H 2 O 2 + 2 KI ¾
¾® 2 KOH + I 2
yields (b) Cl 2 + H 2 O 2 ¾
¾® 2 HCl + O 2
(a) CrO3 + H 2 O + O 2 (b) Cr2 O 2 + H 2 O + O 2 (c) H 2 O 2 + Ag 2 O ¾
¾® 2Ag + H 2 O + O 2
(c) CrO 5 + H 2 O + K 2SO 4 (d) H 2 Cr2 O 7 + H 2 O + O 2 (d) NaClO + H 2 O 2 ¾
¾® NaCl + H 2 O + O 2
JEEMAIN.GURU
downloaded from jeemain.guru
268 Chemistry
JEEMAIN.GURU
downloaded from jeemain.guru
Hydrogen 269
JEEMAIN.GURU
downloaded from jeemain.guru
270 Chemistry
JEEMAIN.GURU
downloaded from jeemain.guru
10 A
The s-block Elements –
Alkali Metals
THE ELEMENTS OF GROUP I ARE: (b) The ionic radii like atomic radii of all these alkali metal
Li - Lithium Na - Sodium K - Potassium ions goes on increasing on moving down the group
Rb - Rubidium Cs - Caesium Fr - Francium because of the same reason.
These elements are known as alkali metals. (iv) Density -
Lithium is known as a bridge element and was discovered by (a) These are light metals having low densities. Lithium is
Arfwedson. the lightest known metal.
Sodium and potassium were discovered by Davy, rubidium and (b) On moving down the group, both the atomic size and
caesium by Bunsen and Kirchoff while francium by Perey. atomic mass increases and since the increase in latter is
These do not occur in the native state (i.e.,do not occur free in not compensated by increase in former,consequently
nature ). density increases from Li to Cs.
(c) The density of potassium is lesser than that of sodium
GENERAL CHARACTERISTICS
because of the abnormal increase in size on moving
Physical properties of alkali metals are from Na to K.
(i) Electronic configuration :- These are s-block elements and
(v) Melting and Boiling points :-
have one electron in the valence shell in
(a) The melting and boiling points of alkali metals are quite
s-orbital. In general their electronic configuration may be
low and decreases down the group due to weakening of
represented as [noble gas ] ns1 where ‘n’ represents the
metallic bond.
valence shell.
(b) Fr is a liquid at room temperature.
Element Atomic no. Electronic Valence shell
(vi) Softness - These are soft,malleable and ductile solids which
configuration configuration
can be cut with knife. They possess metallic lustre when
Li 3 [He] 2 s1 2 s1
1
freshly cut due to oscillation of electrons.
Na 11 [Ne] 3 s 3 s1
1 (vii) Atomic volume- Atomic volume of alkali metals is the highest
K 19 [Ar] 4 s 4 s1
1 in each period and goes on increasing down the group
Rb 37 [Kr] 5 s 5 s1
Cs 55 [Xe] 6 s 1 6 s1 Eleme nt Li Na K Rb Cs
Fr 87 [Rn] 7 s 1 7 s1 Gram atomic 13 24 46 56 71
volume in cm 3
(ii) Size of the atoms - Atomic radii.
(a) The alkali metals atoms have the largest atomic radii in (viii)Ionisation energy:-
their respective periods. (a) The first ionisation energy of alkali metals is the lowest
(b) Atomic radii increases as we move down the group from amongst the elements in their respective periods and
Li to Cs due to the additon of a new shell at each step. decreases on moving down the group.
(iii) Size of the ion - Ionic radii -
Element Li Na K Rb Cs Fr
(a) The ions of the alkali metals are much smaller than their
corresponding atomic radii due to lesser number of shells IE, (kJ mol–1) 520 496 419 403 376 ----
and contractive effect of the increased nuclear charge.
JEEMAIN.GURU
downloaded from jeemain.guru
272 Chemistry
(b) The second ionisation energies of all the alkali metals (xiv)Photoelectric effect :- Due to low I.E., alkali metals especially
are very large because on releasing an electron from the K and Cs show photoelectric effect (i.e. eject electrons when
elements, the resulting ions acquire noble gas (stable) exposed to light) and hence are used in photelectric cells.
configurations. (xv) Electrical conductivity :- Due to the presence of loosely
(ix) Electropositive character :- Because of their low ionisation held valence electrons which are free to move throughout
energies, alkali metals are strongly electropositive or metallic the metal structure, the alkali metals are good conductors of
in nature and this character increases from Li to Cs. heat and electricity. Electrical conductivity increases from
(x) Crystal structure :- All alkali metals possess body centred top to bottom in the order
cubic structures with co-oridination number 8
(xi) Oxidation state :- Li + < Na + < K + < Rb + < Cs +
(a) The alkali metal atoms show only +1 oxidation state, (xvi) Reducing character :-
because their unipositive ions have the stable gas (a) All the alkali metals are good reducing agents
and it is due to their low ionisation energies.
electronic configuration (ns 2 or ns 2 p 6 ) in the valence
Their reducing character, follows the order
shell.
Na < K < Rb < Cs < Li
(b) Since the alkali metal ions have noble gas configuration
with no unpaired electrons, they are diamagnetic and (b) Among the alkali metals Li has the highest negative
colourless but their permanganates and dichromates electrode potential, which depends upon its (i) heat of
compounds are coloured. vaporisation (ii) ionisation energy and (iii)heat of
(xii) Hydration of ions :- hydration and hence Li is the strongest reducing agent.
(a) All alkali metal salts are ionic (except Lithium) and soluble Elements Li Na K Rb Cs Fr
in water due to the fact that cations get hydrated by
E o (V)at –3.05 –2.71 –2.93 –2.99 –2.99 —
water molecules. The degree of hydration depends upon at 298 K
the size of the cation. Smaller the size of a cation, greater
is its hydration energy. CHEMICAL PROPERTIES :
Relative ionic radii : (i) Alkali metals form ionic compounds (Lithium can form
covalent compounds because of its high ionisation energy)
Cs + > Rb + > K + > Na + > Li + and others form ionic compounds because of their large
Relative ionic radii in water or relative degree of atomic size and low I.E.
(ii) Due to low I.E. and high electropositive character the alkali
hydration : Li + > Na + > K + > Rb + > Cs +
metals are chemically very reactive.
(b) The alkali metal ions exist as hydrated ions M + (H 2 O )x (iii) Action of Air :- On exposure to moist air, their surface is
tarnished due to the formation of their oxides, hydroxides
in the aqueous solution.
and carbonates at the surface.
(c) Since the degree of hydration of M + ions decreases as
4 Na (s)+ O 2 (g) ¾
¾® 2 Na 2 O(s)
we go down the group, the hydration energy of alkali
Sodium Sodium oxide
+ +
metal ions decreases from Li to Cs .
Na 2 O(s) + H 2 O (l ) ¾
¾® 2 NaOH(s)
(xiii) Flame colouration :- sodium hydroxide
(a) All alkali metals and their salts impart characteristic
colours to the flame because of the bonding of the ¾® Na 2 CO 3 (s) + H 2 O(l)
2 NaOH (s) + CO 2 (g ) ¾
outermost electron.The outer eletrons of these atoms sodium carbonate
are excited to higher energy levels. On returning to the Hence they are kept under inert liquid kerosene oil but lithium
original state they give out visible light of characteristic is kept wrapped in paraffin wax because it floats on
wavelength. This gives a characteristic colour to the the surface of kerosene oil due to its very low density.
flame. (iv) Action of oxygen :-
(b) On moving down the group, the ionisation energy goes (a) All the alkali metals when heated with oxygen form
on decreasing and hence the energy or the frequency of different types of oxides for example, lithium forms lithium
emitted light goes on increasing in the order Li < Na < K
oxide (Li 2 O) , sodium forms sodium peroxide ( Na 2 O 2 ) ,
< Rb < Cs. As a result, the colour shows following trend
while K, Rb and Cs form their respective superoxides
Li Na K Rb Cs
( MO 2 where M=K, Rb or Cs). The increasing stability
crimson golden pale purple sky blue
of peroxides and superoxides of alkali metals from Li to
red yellow violet (violet)
Cs is due to stabilisation of larger anions by larger cations
through lattice energy.
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
274 Chemistry
+ The thermal stability of carbonates increases with the
M + + xNH 3 ® [M(NH 3 )x ] increasing basic strength of metal hydroxides on moving
- down the group.Thus the order is
e - + yNH3 ® [e(NH 3 )y ] Li 2 CO 3 < Na 2 CO 3 < K 2 CO 3 < Rb 2 CO 3 < Cs 2 CO 3
+ - (b) The bicarbonates of all the alkali metals are known. All
M + (x + y )NH 3 ® [ M ( NH 3 ) x ] + [e( NH 3 ) y ]
Ammoniated cation
the bicarbonates (except LiHCO3 which exits in
Ammoniated electron
(a) Colour -The blue colour is due to the excitation of solution) exist as solids and on heating form carbonates.
ammoniated electron to higher energy levels and the D
2 NaHCO 3 ¾¾® Na 2 CO 3 + CO 2 + H 2 O
absorption of photons occurs in the red region of the
spectrum.Thus the solution appears blue.But at very (c) The solubility of the carbonates and bicarbonates
increases on moving down the group due to lower lattice
high concentration the solution attains the colour like
energies. Thus order is
that of metallic copper.
(b) Conductivity :- It is highly conducting because of the LiHCO3 < NaHCO3 < KHCO3 < RbHCO3 < CsHCO3 .
presence of ammoniated electrons and ammoniated ( xv)Nature of Nitrates:- LiNO3 on heating decomposes to give
cations.However, on cooling,the conductivity increases
further. NO 2 and O 2 while the nitrates of the other alkali metals
(c) Paramagnetism :- It is paramagnetic due to the presence decompose on heating to form nitrites and O2 .
of an unpaired electrons and ammoniated
cations.However the paramagnetism decreases with D
4LiNO3 ¾¾® 2Li 2 O + 4 NO 2 + O 2
increasing concentration due to the association of D
2 NaNO3 ¾¾® 2 NaNO 2 + O 2
ammoniated electrons to yield diamagnetic species
containing electron pairs. All nitrates are soluble in water.
(xvi)Nature of sulphates :-
2[e - (NH 3 )y ] ® [e - (NH 3 )y ]2
(a) Li 2SO 4 is insoluble in water whereas the other
(d) Reducing property :- Due to the presence of ammoniated
electrons, solution is a very powerful reducing agent sulphates i.e, Na 2SO 4 , K 2SO 4 are soluble in water..
and used in organic chemistry under the name Birch (b) Lithium sulphate does not form alums and is also not
reduction. amorphous with other sulphates.
(xii)Complex formation :- Alkali metals have a weak tendency to ANOMALOUS BEHAVIOUR OF LITHIUM :
form complexes but polydentate ligands such as crown ethers Lithium, the first member of the alkali metal family shows an
and cryptands form highly stable complexes collectively anomalous behaviour because of the following main reasons:-
called as Wrap Around Complexes. Cryptands are (a) It has the smallest size in the group
macrocyclic molecules with N and O atoms and their
(b) It has very high ionization energy and highest
complexes are called cryptates. The name cryptate came from
electronegativity in the group.
the fact that metal ion is hidden in the structure.
(c) It has no vacant d-orbital in the valence shell.
(xiii)Nature of hydroxides :- Alkali metals hydroxides are very
As a result, it differs from the other member of the alkali metal
strong bases, highly soluble in water and are not decomposed
family in following respects:
on heating.However, LiOH decomposes on heating to give
(i) Lithium is harder than other alkali metals, due to strong
Li 2 O because latter is more stable than former.. metallic bond.
2LiOH ® Li 2 O + H 2 O (ii) Lithium combines with O 2 to form lithium monoxide,
Their basic strength increases from LiOH to CsOH due to a Li 2 O , whereas other alkali metals form Peroxides,
corresponding decresae in the I.E., of the metal in a group,i.e.,
M 2 O 2 and superoxides MO 2 .
the order:-
LiOH < NaOH < KOH < RbOH < CsOH (iii) Lithium, unlike the other alkali metals, reacts with nitrogen
(xiv)Nature of carbonates and bicarbonates :- to form the nitride.
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
276 Chemistry
of Na 2 CO 3 is treated with milk of lime, Ca (OH )2 . (b) Formation of unstable hydroxides, e.g.
2AgNO3 + 2 NaOH ® 2 NaNO3 + 2AgOH
Na 2 CO3 + Ca (OH)2 ® CaCO3 ¯ +2 NaOH
2AgOH ® Ag 2 O ¯ + H 2 O
(ii) Electrolytic process :- In this process a concentrated solution Brown
of sodium chloride is electrolysed where Cl 2 is evolved at (c) Formation of insoluble hydroxides which dissolve in
excess of NaOH e.g. Zn, Al, Sb, Pb, Sn and As.
the anode and H 2 at the cathode. However Cl2 gas reacts
with NaOH forming NaCl and sodium hypochlorite. ZnSO 4 + 2 NaOH ® Zn (OH ) 2 ¯ + Na 2SO 4
Mercury cathode process ( Castner - Kellner cell ):- This Zn (OH) 2 + 2 NaOH ® Na 2 ZnO 2 + 2H 2 O
Sodium zincate
process is used to avoid reaction between NaOH and
Cl2 .NaOH is obtained by the electrolysis of (aqueous) (d) Formation of ammonia from ammonium salts :-
solution of brine. The cell has three compartments and D
NH 4 Cl + NaOH ¾¾® NaCl + NH 3 + H 2 O
involves following reactions :-
(iii) Reaction with halogens:-
In outer compartment -
Anode - Graphite rods X 2 + 2 NaOH(cold ) ® NaX + NaXO + H 2O
Sodium hypohalite
Cathode - Mercury 3X 2 + 6 NaOH(hot ) ® 5 NaX + NaXO 3 + 3H 2 O
Electrolyte -Brine solution Sodium halate
Reaction - At Anode : (where X= Cl,Br or I)
- - (iv) Reaction with metals :- Less electropositive metals
Cl ® Cl + e ;
like Zn, Al and Sn etc. give H 2 gas with NaOH.
Cl + Cl ® Cl2
Zn + 2 NaOH ® Na 2 ZnO 2 + H 2
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
278 Chemistry
JEEMAIN.GURU
downloaded from jeemain.guru
1. Which of the following is a man made element? 17. Which one of the following has highest electropositive
(a) Ra (b) Fr (c) Rn (d) Lr character?
2. Which one of these is most reactive ? (a) Cu (b) Cs (c) Ba (d) Cr
(a) Na (b) K (c) Pb (d) Mg 18. Which of the following has the highest conductivity ?
3. Alkali metals are generally extracted by
(a) reduction methods (a) Li + (b) Cs + (c) Na + (d) K +
(b) double decomposition methods 19. The metal that dissolves in liquid ammonia, giving a dark
(c) displacement methods blue coloured solution is
(d) electrolytic methods (a) tin (b) lead
4. The alkali metal which is a liquid at room temperature is (c) sodium (d) silver
(a) Fr (b) Cs (c) Rb (d) Na 20. Highly pure dil. solution of Na in liquid ammonia
5. The alkali metal which can emit its outermost electron under (a) shows blue colour
the influence of even candle light is (b) exhibits electrical conductivity
(a) Na (b) Rb (c) K (d) Cs (c) produces sodium amides
6. Francium was discoverd by (d) produces hydrogen gas
(a) Arfwedson (b) Davy 21. Which of the following alkali metal form complex hydrides
(c) Perey (d) Bunsen & Kirchoff (a) Li (b) Na (c) K (d) Rb
7. Sodium is usually kept under
22. Which of the following has the highest melting point?
(a) alcohol (b) kerosene oil
(a) NaCl (b) NaF (c) NaBr (d) NaI
(c) ammonia (d) water
23. Which of the following has lowest melting point?
8. Sodium metal cannot be stored under
(a) benzene (b) kerosene oil (a) Li (b) Na (c) K (d) Cs
(c) alcohol (d) toluene 24. With the increase in atomic weights melting points of the
alkali metals
9. Among KO 2 , AlO2- , BaO2 and NO +2 , unpaired (a) increase
electron is present in (b) decrease
(a) NO 2+ and BaO 2 (b) KO 2 and AlO -2 (c) remain constant
(d) do not show definite trend
(c) KO2 only (d) BaO 2 only
25. Lithium shows diagonal relationship with
10. The one with the largest size is (a) magnesium (b) beryllium
(a) Na (b) Na + (c) K (d) K + (c) aluminium (d) boron
11. The increasing order of atomic radius for the elements Na, 26. The electronic configuration of metal M is 1s2, 2s2 2p6, 3s1.
Rb, K and Mg is The formula of its oxide would be
(a) Na < K < Mg < Rb (b) K < Na < Mg < Rb
(a) MO (b) M 2 O (c) M 2 O3 (d) MO2
(c) Na < Mg < K < Rb (d) Rb < K < Mg < Na
12. Smallest among these species is 27. Which of the following electronic configurations corresponds
(a) hydrogen (b) helium to an element with the lowest ionization energy ?
(c) lithium (d) lithium ion (a) 1s 2 2s 2 2 p 3 (b) 1s 2 2s 2 2 p 5
13. Which of the following has largest size ?
(c) 1s 2 2s 2 2 p 6 (d) 1s 2 2s 2 2 p 6 3s1
(a) Na (b) Na + (c) Na - (d) None of these
14. Which of the following alkali metal ions has the lowest 28. Solution of sodium metal in liquid ammonia is strongly
mobility in aqueous solution ? reducing due to the presence of the following in solution
(a) sodium hydride (b) sodium amide
(a) Li + (b) Na + (c) K + (d) Cs +
(c) sodium atoms (d) solvated electrons
15. Which of the following has the least ionization potential? 29. Lithium is strongest reducing agent among alkali metals due
(a) Li (b) He (c) N (d) Zn to which of the following factor?
16. In view of their low ionization energies, the alkali metals are (a) Ionization energy (b) Electron affinity
(a) weak oxidising agents (b) strong reducing agents (c) Hydration energy (d) Lattice energy
(c) strong oxidising agents (d) weak reducing agents
JEEMAIN.GURU
downloaded from jeemain.guru
280 Chemistry
30. Microcosmic salt is : (c) NaCl > KCl > LiCl > CsCl
(a) Na 2 HPO 4 .2H 2 O (b) (NH 4 )2 HPO 4 .2H 2 O (d) KCl > CsCl > NaCl > LiCl
42. The order of solubility of lithium halides in non polar solvents
(c) Na (NH 4 )HPO 4 .4H 2 O (d) None of these
follows the order :
31. Which of the following has lowest thermal stability ? (a) LiI > LiBr > LiCl > LiF
(a) Li2CO3 (b) Na 2CO3 (c) K 2CO3 (d) Rb2CO3 (b) LiF > LiI > LiBr > LiCl
32. Which one of these is basic ? (c) LiCl > LiF > LiI > LiBr
(a) CO 2 (b) SiO 2 (c) Na 2O (d) SO 2 (d) LiBr > LiCl > LiF > LiI
33. Sodium nitrate decomposes above 800°C to give 43. Which among the following is most soluble in water?
(a) N 2 (b) O2 (c) NO2 (d) Na 2O (a) CsClO4 (b) NaClO 4
34. Fires , that result from the combustion of alkali metals can be (c) LiClO4 (d) KClO 4
extinguished by 44. When sodium is treated with sufficient oxygen/air the
(a) CCl4 (b) sand product obtained is
(c) water (d) kerosene (a) Na 2O (b) Na 2 O 2 (c) NaO2 (d) NaO
35. The alkali metal that reacts with nitrogen directly to from 45. Choose the compound which does not possess a peroxide
nitride is group
(a) Li (b) Na (c) K (d) Rb (a) Na 2 O 2 (b) CrO5
36. Which of the following bicarbonates does not exist as solid?
(c) Fe 2 O 3 (d) BaO 2
(a) KHCO 3 (b) NaHCO 3 46. Which of the following alkali metals burns in air to form only
(c) CsHCO3 (d) LiHCO3 monoxide ?
(a) Na (b) Li (c) K (d) Cs
37. Which of the following is most stable?
47. Alkali metals form peroxides and superoxides except
(a) Na 3 N (b) Li 3 N (c) K 3 N (d) Rb3 N (a) Na (b) Rb (c) Li (d) Cs
38. LiNO3 on heating gives 48. Which is the most basic of the following?
(a) O2 (b) NO2 (a) Na 2O (b) BaO
1. Which one of the following properties of alkali metals 2. Which of the following is known as fusion mixture?
increases in magnitude as the atomic number rises ? [CBSE-PMT 1994]
[CBSE-PMT 1989] (a) Mixture of Na2CO3 + NaHCO3
(a) Ionic radius (b) Melting point (b) Na2CO3.10H2O
(c) Electronegativity (d) First ionization energy (c) Mixture of K2CO3 + Na2CO3
(d) NaHCO3
JEEMAIN.GURU
downloaded from jeemain.guru
1. On heating sodium metal in a current of dry ammonia gas the 3. Gun powder is
compound formed is (a) KNO3+ Charcoal + S (b) NaNO3 + KNO3 + S
(a) sodium nitrate (b) sodium hydride (c) NaNO3 + S (d) None of these
(c) sodium amide (d) sodium azide
4. Sodium carbonate is manufactured by Solvay process. The
2. The pair of compounds which cannot exits together in
products which can be recycled are
solution is
(a) CO2 and NH3 (b) CO2 and NH4Cl
(a) NaHCO3 and NaOH (b) Na2CO3 and NaHCO3
(c) Na2CO3+ NaOH (d) NaHCO3 and NaCl (c) NaCl and CaO (d) CaCl2 and CaO.
JEEMAIN.GURU
downloaded from jeemain.guru
282 Chemistry
5. Which of the following statements is false for alkali metals? 14. Sodium thiosulphate, Na2S2O3. 5H2O is used in photography
(a) Lithium is the strongest reducing agent to
(b) Sodium is amphoteric in nature (a) reduce the silver bromide grains to metallic silver
(c) Li+ is exceptionally small (b) convert the metallic silver to silver salt
(d) All alkali metals give blue solution in liquid ammonia (c) remove undecomposed AgBr as soluble silver
6. Fusion of AgCl with Na2CO3 gives thiosulphate complex.
(a) Ag2CO3 (b) silver carbide (d) remove reduced silver
(c) Ag (d) Ag2O 15. The salt on heating does not give brown coloured gas is
7. A mixture of Al(OH)3 and Fe(OH)3 can be separated easily
(a) LiNO3 (b) KNO3
by treating it with :
(a) HCl (b) NH4OH (c) Pb(NO3)2 (d) AgNO3
(c) HNO3 (d) NaOH 16. Sodium carbonate solution in water is alkaline due to
8. When sulphur is heated with NaOH (aq). The compounds (a) hydrolysis of Na+
formed are
(b) hydrolysis of CO 32-
(a) Na 2S + H 2 O
(b) Na 2SO 3 + H 2 O (c) hydrolysis of both Na+ and CO 32- ions
JEEMAIN.GURU
downloaded from jeemain.guru
24. If NaOH is added to an aqueous solution of Zn 2+ ions, a 27. Na 2SO 3 and NaHCO 3 may be distinguished by treating
white precipitate appears and on adding excess NaOH, the their aqueous solution with :
precipitate dissolves. In this solution zinc exists in the : (a) MgO (b) Mg SO 4
(a) both in cationic and anionic parts (c) litmus solution. (d) dil. acid
(b) there is no zinc left in the solution 28. Which hydride is most stable :
(c) cationic part (a) NaH (b) KH
(c) CsH (d) LiH
(d) anionic part.
29. A and B are two salts. A with dil. HCl and A & B with conc.
25. Sodium cannot be extracted by the electrolysis of brine
H 2SO 4 react to give reddish brown vapours, hence A & B
solution because
respectively are :
(a) electrolysis cannot take place with brine solution.
(a) NaNO3 , NaBr (b) NaBr, NaNO3
(b) sodium reacts with water to produce NaOH + H 2
(c) NaBr, NaNO 2 (d) NaNO 2 , NaBr
(c) sodium being more electropositive than hydrogen, H 2
30. When CO 2 is bubbled into an aqueous solution of
is liberated at cathode and not sodium.
Na 2 CO 3 the following is formed :
(d) None of these
26. The raw materials in Solvay Process are : (a) NaHCO 3 (b) H 2 O
JEEMAIN.GURU
downloaded from jeemain.guru
284 Chemistry
EXERCISE 1
9. (c) In NO +2 odd ( unpaired ) electron is removed. In peroxides
1. Because they have low ionisation energy and can lose
electrons when light falls on them. (O 2 2– ) no unpaired electrons are present as the
antibonding pi M.O.’s acquired one more electron each
2. Alkali metals acquire, noble gas configuration after losing 1 for pairing. AlO2– containing Al3+ (2s22p6 configuration)
electron. and 2 oxide (O2–) ions each of which does not contain
3. (i) As washing soda in laundry. unpaired electron. Superoxide O2– has one unpaired
(ii) For softening of hard water. electron in pi antibonding M.O.
4. Li. 10. (c) The size increases down the group.
5. Monohydrate (Na2CO3 . H2O) is formed as a result of 11. (c) 12. (d) 13. (c)
efflorescence. 14. (a) Li+ is most highly hydrated [Li+(H2O)6]+. Therefore its
6. Due to ammoniated electrons and cations. effective size becomes greater than any other hydrated
alkali metal cation and hence has the lowest mobility .
7. It turns white due to formation of NaOH and Na2CO3.
15. (a)
10. NaNO3 is very readily soluble in water because it is ionic in
16. (b) Alkali metals are strong reducing agents and have less
nature while LiNO3 is not readily soluble in water because it value for I.P.
is covalent in nature.
17. (b) Alkali metals are more electropositive and this character
12. Alkali metals contain unpaired electrons and hence are increases down the group.
paramagnetic. But in the salts of alkali metals there are alkali 18. (b) Cs+ due to its very high ionic mobility has the highest
metal cations which don’t have unpaired electrons. Hence conductivity.
these are diamagnetic.
19. (c)
16. (d) 17. (c) 18. (b) 19. (c) 20. (b)
20. (b) Dilute solution of Na in liquid NH3 will not produce sodium
21. (d) 22. (c) 23. (a) 24. (d) 25. (c) amide and hydrogen gas instantaneously. These are
EXERCISE 2 metastable and when catalysed give hydrogen and amide.
21. (a) Li forms LiAlH4 and Na forms NaBH4 as the complex
1. (d) Lr. all transuranics ( 93 Np -103 Lr ) are man-made
hydrides besides simple hydrides of MH type.
elements.
22. (b) NaF due to its largest lattice energy has the highest
2. (b) melting point.
3. (d) Alkali metals are highly electropositive and thus highly 23. (d) Melting point of alkali metals decreases with increase in
reducing .Therefore reduction , double decomposition size.
and displacement methods for their extraction are not 24. (b)
suitable .Only electrolytic methods are useful for their 25. (a)
extraction.
26. (b) Electronic configuration indicates that the metal is
4. (a) univalent (alkali metal). Its oxide will be M2O.
5. (d) Cs, because of its low I.E. emits electron under the 27. (d) Electronic configuration of the alkali metals correspond
influence of even candle light. to lowest I.E.
6. (c) 28. (d)
7. (b) Alcohols , NH3 and H2O all react with sodium 29. (c) Li due to highest hydration energy among the alkali metals
is the strongest reducing agent.
2ROH + 2Na ® 2RONa + H 2 ; 30. (c)
31. (a) The weaker the base, the less stable is its carbonate.
Na(s) + NH3 (x + y) ® Na + (NH3 ) x + e - (NH3 ) y Since LiOH is the weakest base, hence Li2CO3 has the
lowest thermal stability.
2Na + 2H 2 O ® 2NaOH + H 2
32. (c)
Only kerosene does not react . D
33. (b) 2NaNO3 ¾¾¾¾
® 2NaNO2 + O 2
8. (c) above 800ºC
JEEMAIN.GURU
downloaded from jeemain.guru
BaO2 is Ba 2+ ( -
)
O - O - while Fe2 O3 consists of
of hydrides is
LiH > NaH > KH > RbH > CsH
only Fe3+ and O2 - ions. Thus Fe2 O3 does not contain i.e. option (d) is correct answer.
9. (c) 2Al(s) + 2NaOH (aq) + 2H2O (l) ¾¾
® 2NaAlO2 + 3H2
a peroxide - O - O- linkage. sod. meta aluminate
46. (b) 10. (b) All alkali metal salts are ionic (except Lithium) and soluble
47. (c) Li + does not allow its O 2 - ion to combine with other O in water due to the fact that cations get hydrated by
atom(s) to form peroxides and superoxides . water molecules. The degree of hydration depends upon
48. (a) the size of the cation. Smaller the size of a cation, greater
49. (c) Because KO2 not only provides O2 but also removes is its hydration energy.
CO2 as follows Relative ionic radii :
JEEMAIN.GURU
downloaded from jeemain.guru
286 Chemistry
12. (d) Smaller the size of cation higher is its hydration energy 17. (d) It must be sodium thiosulphate
and greater is its ionic mobility hence the correct order Na 2S 2 O 3 + 2HCl ® 2 NaCl + SO 2 + S + H 2 O
is Li+ < Na+ < K+ < Rb+
SO 2 + Br2 + 2H 2 O ® H 2SO 4 + 2HBr
13. (a) 4LiNO 3 ® 2Li 2 O + 4NO 2 + O 2
18. (b) LiCl is covalent in nature . It is, thus soluble in polar
14. (b) solvents.
EXERCISE 4
19. (c) Na 2 S + I 2 + Na 2SO 3 ® Na 2S 2 O 3 + 2 NaI
1. (a) Na + NH3 ® NaNH 2 + 1/ 2 H 2 20. (c) Iodine is soluble in water in presence of KI forming a
Sodium
amide complex I 2 + KI ® KI 3
2. (a) NaHCO3 + NaOH ® Na 2 CO3 + H 2 O 21. (c) CsBr3 may be represented as Cs+Br3–
22. (b) It is hygroscopic and deliquescent. It absorbs moisture
(NaHCO3 is an acidic salt)
and CO 2 to form Na 2 CO 3
3. (a) Mixture of KNO 3 + Charcoal + S is gun powder . It is an
explosive 2NaOH + CO 2 ¾ ¾® Na 2 CO 3 + H 2 O
4. (a) CO2 and NH3 formed are reused (See Solvay process) 23. (d) Electropositive character and reactivity increases down
5. (b) Na is basic in nature the group.
JEEMAIN.GURU
downloaded from jeemain.guru
10B
JEEMAIN.GURU
downloaded from jeemain.guru
288 Chemistry
(viii)Electropositive character: (ii) Reaction with oxygen:
(a) These are strong electropositive elements due to their The affinity for oxygen increases down the group. Thus, Be,
large size and comparatively low ionisation energies. Mg and Ca when heated with O2 form monoxides while Sr, Ba
(b) On moving down the group, the electropositive character and Ra form peroxides.
increases due to increase in atomic radii.
D
(ix) Oxidation state: 2M + O 2 ¾¾® 2MO (M = Be, Mg or Ca )
Metal oxide
(a) Alkaline earth metals uniformly show an oxidation state
of +2 despite the presence of high ionisation energy D
because M + O 2 ¾¾® MO 2 (M = Ba, Sr or Ra )
Metal peroxide
Þ In the solid state, the dipositive ions M2+ form strong
lattices due to their small size and high charge (i.e., high (iii) Reaction with acids:
lattice energy). (a) Alkaline earth metals except Be, displace H2 from acids.
Þ In the aqueous solution, the M2+ cations are strongly
M + H 2SO 4 ¾
¾® MSO 4 + H 2
hydrated due to their small size and high charge. The
hydration energy released by the M2+ cation is very (where M = Mg, Ca, Sr or Ba)
large. (b) Reactivity, however, increases down the group from Mg
(b) The divalent ions are diamagnetic and colourless due to to Ba i.e.,
the absence of upaired electron. Mg < Ca < Sr < Ba
(x) Conductivity: These are good conductors of heat and (c) Only Mg displaces H2 from a very dilute HNO3.
electricity due to the presence of two loosely held valence (iv) Reaction with hydrogen:
electrons. (a) Except Be, all other elements combine with hydrogen on
(xi) Flame colouration: heating to form hydride (MH2).
(a) Like alkali metal salts, alkaline earth metal salts also impart
M + H2 ¾
¾® MH 2 ( where M = Mg , Ca , Sr or Ba )
characteristic flame colouration.
(b) As we move down the group from Ca to Ba, the ionisation (b) The hydride of beryllium can be prepared indirectly by
reducing beryllium chloride with lithium aluminium
energy decreases, hence the energy or the frequency of
hydride.
the emitted light increases. Thus,
Ca Sr Ba Ra 2BeCl 2 + LiAlH 4 ¾
¾® 2BeH 2 + LiCl + AlCl 3
Brick red Crimson red Apple green Crimson (c) BeH2 and MgH2 are covalent and polymeric whereas
(c) Be and Mg because of their high ionization energies, the hydrides of Ca, Sr and Ba are ionic and monomeric in
however, do not impart any characteristic colour to the nature.
bunsen flame. (d) CaH2 is also called hydrolith.
CHEMICAL PROPERTIES: (e) All the hydrides react with water to evolve H2 and thus
(a) Alkaline earth elements are quite reactive due to their low behave as strong reducing agents.
ionisation energies but are found to be less reactive than MH 2 + 2H 2 O ¾
¾® M (OH ) 2 + 2H 2
alkali metals because the alkaline earth metals have
(v) Reaction with halogens:
comparatively higher ionisation energy.
(a) All the elements of group 2 combine with halogens at
(b) Reactivity of the group 2 elements increases on moving down
high temperature and form their halides (MX2).
the group because their ionisation energy decreases.
D
(i) Reaction with water: M + X 2 ¾¾® MX 2
(a) Group 2 elements are less reactive with water as compared (b) Beryllium halides (BeF2, BeCl 2 etc.) are covalent,
to alkali metals. They react with H2O evolving H2 gas. hygroscopic and fume in air due to hydrolysis. The
halides of other alkaline earth metals are fairly ionic and
M + 2H 2 O ¾
¾® M (OH ) 2 + H 2 this character increases as the size of the metal increases.
(c) The halides are soluble in water and their solubility
where M = Mg, Ca , Sr or Ba
decreases in the order:
(b) The chemical reactivity of the metal with H2O, however MgX2 > CaX2 > SrX2 > BaX2
increases as we move from Mg to Ba, i.e., Be does not (d) BeF2 is very soluble in water due to the high solvation
react even with boiling water and Ba react vigorously
even with cold water. Thus, increasing order of reactivity energy of Be 2+ in forming [Be(H 2 O) 4 ]2 + but the
with water is fluorides of other alkaline earth metals have high melting
Mg < Ca < Sr < Ba point and they are insoluble in water.
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
290 Chemistry
increases down the group. The lattice energy remains (iv) With conc. HNO3, both are rendered passive due to the
constant because sulphate ion is so large, so that small formation of a thin film of their respective oxides on the metal
change in cationic sizes do not make any difference. surface.
Thus the order: (v) Both react with conc. NaOH liberating H2.
BeSO 4 > MgSO 4 > CaSO 4 > SrSO 4 > BaSO 4
Be + 2 NaOH ¾
¾® Na 2 BeO 2 + H 2
The negligible solubility of BaSO4 in water is used in Sodium berylate
both qualitative and quantitative analysis.
(c) Solubility of carbonates: The solubility of the 2Al + 2 NaOH + 2H 2 O ¾
¾® 2 NaAlO2 + 3H 2
carbonates in water decreases down the group due to Sodium metaaluminate
the decrease in the magnitude of hydration energy. (vi) Oxides and hydroxides of both are amphoteric in nature.
However these insoluble metal carbonates are dissolved (vii) Carbides of both liberate methane on hydrolysis.
in water having CO2 as shown:
Be 2 C + 4H 2 O ¾
¾® CH 4 + 2 Be(OH ) 2
MgCO3 (s) + CO 2 (g) + H 2 O ¾¾
® Mg(HCO3 ) 2
Insolub le Magnesium bicarbonate Al 4 C 3 + 12H 2 O ¾
¾® 4 Al(OH ) 3 + 3 CH 4
(Soluble)
(viii)Anyhydrous chlorides of both i.e., BeCl2 and AlCl3 act as
Mg (HCO3)2 Mg2+ (aq) + 2HCO3– (aq.)
Lewis acids and dissolve in organic solvents.
The order of solubility of carbonates:
(ix) Both do not impart any colour to the flame.
BeCO3 > MgCO3 > CaCO3 > SrCO3 > BaCO3
Magnesium along with KClO3 or BaO2 is used in photography
ANOMALOUS BEHAVIOUR OF BERYLLIUM : flash blubs, fire works and as a deoxidiser in metallurgical process.
Beryllium, the first member of group 2 differs from the rest of the MgCl2.5MgO xH2O is called Sorel’s cement or Magnesia cement
members of its group due to the following reasons: and used to fill the cavities of teeth.
(i) It has a small atomic size as well as small ionic size. Mg(OH)2 in water is used in medicine as an antacid under the
(ii) It has no vacant d-orbitals in valence shell. name ‘Milk of Magnesia’, while 12 gm of MgCO3 per 100 c.c. of
(iii) It has high electronegativity value. H2O containing CO2 is known as ‘Fluid Magnesia’.
(iv) It has a high charge density. The finely divided BaSO4 is called Blanc fire and used in paints.
(v) Its hydration energy is high. Suspension of slaked lime in water is called white wash (milk of
Some points of difference are: lime).
(i) Be is harder and denser than other members of the group. A solution of MgCl2 + NH4Cl in ammonia is known as Magnesia
(ii) The m.p., b.p., and ionisation energy of Be are the highest of Mixture.
all the alkaline earth metals. Plaster of paris CaSO4.1/2 H2O is used in surgery for setting broken
(iii) Be does not react with water even at higher temperature bones.
where as other metals do. Pure Ca(H2PO4)2 is used as American baking powder.
(iv) BeO and Be(OH)2 are amphoteric in character whereas oxides Gypsum gives different products on heating as
and hydroxides of the group 2 metals are basic.
120ºC Plaster of paris [CaSO41/2 H2O]
(v) Be is least metallic of all the alkaline earth metals and forms
covalent compounds.
(vi) Be forms nitride Be3N2 with nitrogen which is volatile while CaSO4.2H2O 200ºC Dead burnt plaster [CaSO4]
nitrides of others are non-volatile. Gypsum 400ºC CaO, SO2, O2
(vii)Be does not liberate H2 from acids (HCl, H2SO4) where as
other metals do. Most abundant alkaline earth metal in the earth’s crust is Ca.
(viii)Be forms Be2C with carbon while the other members of the Be and Mg crystallize in hcp, Ca and Sr in ccp and Ba in bcc
group form ionic carbide MC2. structures.
Because of comparatively higher electronegativity both Be and
DIAGONAL RELATIONSHIP OR RESEMBLANCE
Mg form a large number of organometallic compounds.
BETWEEN Be AND Al :
CaCl2.6H2O is widely used for melting ice on roads, particularly in
The first member of group-2, Beryllium, shows similarities in the very cold countries, because a 30% eutectic mixture of CaCl2/H2O
properties with its diagonally opposite member aluminium of the freezes at –55ºC as compared with NaCl/H2O at –18ºC.
next group 13 of the next higher period, due to the similar polarizing
Magnesium perchlorate, Mg(ClO4)2 is known as anyhydrone and
power. i.e., ionic charge/(ionic radius)2 of Be and Al.
used as drying agent.
(i) Both the metals are stable in air.
Mostly kidney stones containing calcium oxalate, CaC2O4.H2O
(ii) Both have a strong tendency to form covalent compounds.
which dissolves in dil. strong acids but remains insoluble in bases.
(iii) Both form fluoro complex anions BeF42– and AlF63– in solution.
JEEMAIN.GURU
downloaded from jeemain.guru
¾® Mg 2 + + 2Cl -
MgCl 2 ¾
USES OF CALCIUM :
(i) It is used to remove air from vaccum tubes, sulphur from
At Cathode : Mg2+ + 2e- ¾¾
® Mg petroleum and oxygen from molten steel.
(ii) It is used as a reducing agent in the extraction of such metals
At anode: Cl- ¾¾
® Cl + e - ; Cl + Cl ¾¾
® Cl2 from their oxides where carbon is ineffective.
USES OF MAGNESIUM : COMPOUNDS OF CALCIUM
(i) Mg being a light metal forms alloys with Al and Zn which are
CALCIUM OXIDE, QUICK LIME, BURNT LIME, LIME,
used in aircraft construction. e.g., elektron (95% Mg + 5%
CaO :
Zn) used in construction of aircraft, magnalium (1-15% Mg +
85-99% Al) used in construction of aircraft and light Preparation:
instruments. (i) By the thermal decomposition of calcium carbonate.
(ii) Magnesium powder is used in flash bulbs used in 1070 -1270 K
CaCO 3 ¾¾ ¾ ¾ ¾
¾® CaO + CO 2 ; DH = +1080 kg
photography.
Properties:
COMPOUNDS OF MAGNESIUM (i) It is a basic oxide.
MAGNESIUM OXIDE, MAGNESIA, MgO : (ii) Its aqueous suspension is known as slaked lime Ca(OH)2.
With MgCl2, it forms a mixture of composition MgCl2.5MgO.xH2O hissing sound
CaO + H 2 O ¾¾¾¾¾ ® Ca(OH) 2 + Heat
which is known as Sorel’s cement or magnesia cement. Burnt lime Slaked lime
MAGNESIUM HYDROXIDE, MILK OF MAGNESIA, (iii) On heating with ammonium salts it gives ammonia
Mg(OH)2: D
Its aqueous suspension is used in medicine as an antacid. CaO + 2 NH 4 Cl ¾¾® CaCl 2 + 2 NH 3 + H 2 O
(iv) It reacts with carbon to form calcium carbide.
MAGNESIUM SULPHATE OR EPSOM SALT,
MgSO4.7H2O: CaO + 3C ¾¾
® CaC 2 + CO
It shows isomorphous nature with ZnSO4.7H2O, deliquesence Calcium carbide
and efflorescence. It is used as a purgative in medicine and as a (v) It is used as basic flux, for removing hardness of water for
stimulant to increase the secretion of bile. preparing mortar (CaO + Sand + Water).
JEEMAIN.GURU
downloaded from jeemain.guru
292 Chemistry
CALCIUM HYDROXIDE, SLAKED LIME, LIME WATER, (ii) On heating at about 200ºC, it also forms dead burnt plaster of
Ca(OH)2 : paris (it has no tendency to set).
Preparation: CALCIUM CARBIDE OR CALCIUM ACETYLIDE, CaC2:
(i) By dissolving quick lime in water. Preparation:
CaO + H 2 O ¾¾ ® Ca(OH) 2 ; DH = -63kJ (i) By heating a mixture of quick lime (CaO) and powdered coke
in an electric furnace at 3300K.
Properties:
(i) Its suspension in water is known as milk of lime. 3300K
CaO + 3C ¾¾ ¾ ¾® CaC 2 + CO
(ii) It gives CaCO3 (milky) and then Ca(HCO3)2 with CO2.
Properties:
Ca(OH)2 + CO2 ¾¾
® CaCO3 + H 2O (i) It reacts with water to form acetylene.
Lime water (Milkiness)
CaC 2 + 2 H 2 O ¾
¾® Ca ( OH ) 2 + HC º CH
CaCO3 + H 2 O + CO 2 ¾
¾® Ca (HCO3 ) 2 (ii) When heated with nitrogen, it forms calcium cyanamide
(Excess) (Soluble) which on reaction with steam under pressure gives NH3.
(iii) It reacts with Cl2 to give bleaching powder CaOCl2. 1373K
CaC 2 + N 2 ¾¾ ¾
¾®CaCN 2 + C
14243
Ca (OH ) 2 + Cl 2 ¾
¾® CaOCl 2 + H 2 O Nitrolim
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
294 Chemistry
JEEMAIN.GURU
downloaded from jeemain.guru
1. The one which does not show variable valency is 13. The first ionization potentials (eV) of Be and B respectively
(a) barium (b) titanium are
(c) copper (d) lead (a) 8.29, 9.32 (b) 9.32, 9.32
2. Alkaline earth metals form ions of the general formula (c) 8.29, 8.29 (d) 9.32, 8.29
(a) M2+ (b) M+ (c) M (d) M 2– 14. Which of the following has maximum ionization energy
3. The number of covalent bonds formed by beryllium is
(a) 2 (b) 3 (c) 4 (d) 5 ¾® Ba + + e -
(a) Ba ¾ ¾® Be + + e -
(b) Be ¾
4. Alkaline earth metals show typical characteristics of (c) Ca ¾¾ ® Ca 2+ + 2e- (d) Mg ¾ ¾® Mg 2 + + 2e -
(a) inner transition elements (b) noble gases
(c) representative elements (d) transition elements. 15. The alkaline earth metals Ba, Sr, Ca and Mg may be arranged
5. The elements of group-2 are called alkaline earth metals in the order of their decreasing first ionisation potential as
because (a) Mg, Ca, Sr, Ba (b) Ca, Sr, Ba, Mg
(a) they are alkaline in nature (c) Sr, Ba, Mg, Ca (d) Ba, Mg, Ca, Sr
(b) they occur in earth’s crust and form alkaline salts 16. The first ionization energy of magnesium is lower than the
(c) their oxides are alkaline and occur in earth’s crust first ionization energy of
(d) these are s-block elements. (a) lithium (b) sodium
6. Alkaline earth metals are (c) calcium (d) beryllium
(a) reducing agents (b) oxidising agents 17. The most electropositive amongst the alkaline earth metals
(c) amphoteric (d) acidic is
7. Of the following, most reactive alkaline earth metal is (a) beryllium (b) magnesium
(a) beryllium (b) barium (c) calcium (d) barium
(c) calcium (d) strontium 18. The most electronegative alkaline earth metal is
8. The oxidation state shown by alkaline earth metals is (a) Be (b) Mg
(a) +2 (b) +1, +2 (c) –2 (d) –1, –2 (c) Ca (d) Ra
9. Which of the following ions has the largest ionic radius? 19. Which of the following metals has the highest melting point ?
(a) Be2+ (b) Mg2+ (a) Be (b) Mg
(c) Ca 2+ (d) Sr2+ (c) Ca (d) Ba
10. Density is lowest for 20. Which of the following has exceptionally high melting point
(a) Mg (b) Ca (c) Sr (d) Ba (a) MgO (b) NaOH
11. The first ionization energies of alkaline earth metals are higher (c) NaCl (d) KCl
than those of the alkali metals. This is because 21. The compounds of alkaline earth metals have the following
(a) there is an increase in the nuclear charge of the alkaline magnetic nature
earth metals (a) diamagnetic (b) paramagnetic
(b) there is a decrease in the nuclear charge of the alkaline (c) ferromagnetic (d) antiferromagnetic
earth metals 22. Among the alkaline earth metals, the element forming
(c) there is no change in the nuclear charge predominantly covalent compound is
(d) None of these (a) Ba (b) Sr
12. The first ionization potential of Mg is (c) Ca (d) Be
(a) less than Al 23. As the nuclear charge increases from neon to calcium, the
(b) more than Al orbital energies
(c) equal to Al (a) increase (b) increase very rapidly
(d) can be less or more than Al (c) increase very slowly (d) decreases
JEEMAIN.GURU
downloaded from jeemain.guru
296 Chemistry
24. The following compounds have been arranged in order of 38. A salt on treatment with dil. HCl gives a pungent smelling
their increasing thermal stabilities. Identify the correct order. gas and a yellow precipitate. The salt gives green flame test
K2CO3 (I) MgCO3 (II) and a yellow precipitate with potassium chromate. The salt
CaCO3 (III) BeCO3 (IV) is
(a) I < II < III < IV (b) IV < II < III < I (a) NiSO4 (b) BaS2O3
(c) IV < II < I < III (d) II < IV < III < I (c) PbS2O3 (d) CuSO4
25. One which is not dissolved by dilute hydrochloric acid is 39. A metal is burnt in air and the ash on moistening smells of
(a) ZnS (b) MnS NH3. The metal is
(c) BaCO3 (d) BaSO4 (a) Na (b) Fe
26. The hydroxide which is best soluble in water is (c) Mg (d) Al
(a) Ba(OH)2 (b) Mg(OH)2 40. The carbide of which of the following metals on hydrolysis
(c) Sr(OH)2 (d) Ca(OH)2 gives allylene or propyne?
27. The order solubility in water of alkaline earth metal sulphates (a) Be (b) Ca
down the group is Be > Mg > Ca > Sr > Ba. This is due to (c) Al (d) Mg
increases in 41. Magnesium burns in CO2 to form
(a) ionization energy (b) melting point (a) MgO + C (b) MgO + CO
(c) coordination number (d) All of these (c) MgCO3 (d) MgO
28. Which of the following are arranged in increasing order of 42. Which of the following will liberate hydrogen by its reaction
solubilities? with hydrochloric acid?
(a) CaCO3 < KHCO3 < NaHCO3 (a) Copper (b) Phosphorus
(b) NaHCO3 < KHCO3 < CaCO3 (c) Mercury (d) Magnesium
43. Alkaline earth metals are not found free in nature because of
(c) KHCO3 < NaHCO3 < CaCO3
(a) their thermal instability
(d) CaCO3 < NaHCO3 < KHCO3
(b) their low melting points
29. Which of the following is least soluble in water?
(c) their high boiling points
(a) BeSO4 (b) BaSO4
(d) their greater chemical reactivity
(c) CaSO4 (d) SrSO4
44. Ionic hydride is not formed by
30. Which of the following sulphates has highest solubility in
(a) Be (b) Ca
water?
(c) Ba (d) Sr
(a) BaSO4 (b) CaSO4
45. Which of the following alkaline earth metal hydroxides is
(c) BeSO4 (d) MgSO4 amphoteric in character
31. The ion having highest mobility in aqueous solution is (a) Be(OH)2 (b) Ca(OH)2
(a) Be 2+ (b) Mg2+ (c) Sr(OH)2 (d) Ba(OH)2
(c) Ca 2+ (d) Ba2+ 46. A chloride dissolves appreciably in cold water. When placed
32. Which one of the following is least soluble in water? on a Pt wire in Bunsen flame, no distinctive colour is noted.
(a) BaF2 (b) MgF2 Which cation could be present?
(c) CaF2 (d) SrF2 (a) Be2+ (b) Ba2+
33. The characteristic outer electronic configuration of alkaline (c) Pb 2+ (d) Ca2+
earth metals is 47. Halides of alkaline earth metals form hydrates such as
(a) ns 1 (b) ns 2 MgCl2.6H2O, CaCl2.6H2O, BaCl2.2H2O and SrCl2.2H2O. This
2
(c) ns np 2 (d) ns2 np1 shows that halides of group 2 elements
34. Which of the following is strongest base? (a) are hygroscopic in nature
(a) Al(OH)3 (b) Mg(OH)2 (b) act as dehydrating agents
(c) Ca(OH)2 (d) Ba(OH)2 (c) can absorb moisture from air
35. As the alkaline earth metals (except Be) tend to lose their (d) All of the above
valence electrons readily, they act as 48. Which of the followng has lowest melting point?
(a) weak oxidising agents (b) weak reducing agents (a) SrF2 (b) BeF2
(c) strong oxidising agents (d) strong reducing agents (c) MgF2 (d) CaF2
36. Which of the alkaline earth metals is the strongest reducing 49. Amongst LiCl, RbCl, BeCl2 and MgCl2 the compounds with
agent? greatest and the least ionic character, respectively, are
(a) Ca (b) Sr (a) LiCl and RbCl (b) RbCl and BeCl2
(c) Ba (d) Mg (c) RbCl and MgCl2 (d) MgCl2 and BeCl2
37. The correct order of increasing ionic character is 50. Melting point of calcium halides decreases in the order
(a) BeCl2 < MgCl2 < CaCl2 < BaCl2 (a) CaF2 > CaCl2 > CaBr2 > CaI2
(b) BeCl2 < MgCl2 < BaCl2 < CaCl2 (b) CaI2 > CaBr2 > CaCl2 > CaF2
(c) BeCl2 < BaCl2 < MgCl2 < CaCl2 (c) CaBr2 > CaI2 > CaF2 > CaCl2
(d) BaCl2 < CaCl2 < MgCl2 < BeCl2 (d) CaCl2 > CaBr2 > CaI2 > CaF2
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
298 Chemistry
1. The correct order of increasing thermal stability of K2CO3, 9. Match List – I with List –II for the compositions of
MgCO3, CaCO3 and BeCO3 is [CBSE-PMT 2007] substances and select the correct answer using the code
(a) BeCO3< MgCO3 < CaCO3 < K2CO3 given below the lists : [CBSE-PMT 2011M]
List - I List - II
(b) MgCO3 < BeCO3 < CaCO3 < K2CO3
Substances Composition
(c) K2CO3 < MgCO3 < CaCO3 < BeCO3
(A) Plaster of paris (i) CaSO4.2H2O
(d) BeCO3 < MgCO3 < K2CO3 < CaCO3 (B) Epsomite (ii) CaSO4.½ H2O
2. In which of the following the hydration energy is higher (C) Kieserite (iii) MaSO4.7 H2O
than the lattice energy? [CBSE-PMT 2007] (D) Gypsum (iv) MgSO4. H2O
(a) MgSO4 (b) RaSO4 (v) CaSO4
(c) SrSO4 (d) BaSO4 Code :
3. Which of the following oxides is not expected to react with (A) (B) (C) (D)
sodium hydroxide? [CBSE-PMT 2009] (a) (iii) (iv) (i) (ii)
(a) CaO (b) SiO2 (b) (ii) (iii) (iv) (i)
(c) BeO (d) B2O3 (c) (i) (ii) (iii) (v)
4. Which of the following alkaline earth metal sulphates has (d) (iv) (iii) (ii) (i)
hydration enthalpy higher than the lattice enthalpy? 10. Equimolar solutions of the following substances were
prepared separately. Which one of these will record the
[CBSE-PMT 2010]
highest pH value ? [CBSE-PMT 2012S]
(a) CaSO 4 (b) BeSO 4 (a) BaCl2 (b) AlCl3
(c) LiCl (d) BeCl2
(c) BaSO 4 (d) SrSO4
11. A metal M readily forms its sulphate MSO4 which is water-
5. Property of the alkaline earth metals that increases with their soluble. It forms its oxide MO which becomes inert on heating.
atomic number is [CBSE-PMT 2010] It forms an insoluble hyroxide M(OH)2 which is soluble in
(a) solubility of their hydroxides in water NaOH solution. Then M is [AIEEE 2002]
(a) Mg (b) Ba
(b) solubility of their sulphates in water
(c) Ca (d) Be.
(c) ionization energy
12. The solubilities of carbonates decrease down the magnesium
(d) electronegativity group due to a decrease in [AIEEE 2003]
6. The compound A on heating gives a colourless gas and a (a) hydration energies of cations
residue that is dissolved in water to obtain B. Excess of CO2 (b) inter-ionic attraction
is bubbled through aqueous solution of B, C is formed which (c) entropy of solution formation
is recovered in the solid form. Solid C on gentle heating (d) lattice energies of solids
gives back A. The compound is [CBSE-PMT 2010]
13. In curing cement plasters water is sprinkled from time to
(a) CaSO4.2H2O (b) CaCO3 time. This helps in [AIEEE 2003]
(c) Na2CO3 (d) K2CO3 (a) developing interlocking needle-like crystals of hydrated
7. Which of the following compounds has the lowest melting silicates
point ? [CBSE-PMT 2011] (b) hydrating sand and gravel mixed with cement
(a) CaCl2 (b) CaBr2 (c) converting sand into silicic acid
(c) CaI2 (d) CaF2 (d) keeping it cool
14. Which of the following on thermal decomposition yields a
8. Which one of the following is present as an active ingredient
basic as well as acidic oxide ? [AIEEE 2012]
in bleaching powder for bleaching action ? [CBSE-PMT 2011]
(a) NaNO3 (b) KClO3
(a) CaOCl2 (b) Ca(OCl)2
(c) CaCO3 (d) NH4NO3
(c) CaO2Cl (d) CaCl2
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
300 Chemistry
EXERCISE 1 10. (b) Ca contains vacant 3d orbitals which leads much increase
in atomic volume of the element hence has the lowest
1. Gypsum is added to retard the rate of setting of cement. density.
2. Anhydrous CaSO4 can absorb water to form CaSO4 . 2H2O. 11. (a)
Plaster of paris is not used as a drying agent because it sets 12. (b) Mg has more IE1 than Al since the electron has to be
into a hard mass by absorbing water. removed from completely filled s-valence shell of Mg.
3. Caves in limestone regions get formed due to the dissolution 13. (d) 14. (d) 15. (a) 16. (d)
of calcium carbonate in water containing carbon dioxide. 17. (d) 18. (a)
4. This is because alkaline earth metals have smaller size and 19. (a) Being small and hard, Be atoms pack closely in the lattice
higher nuclear charges as compared to alkali metals. and hence Be has the highest m.pt.
5. By treating quick lime with water, slaked lime is formed. 20. (a) Higher the charge on the ions, greater is the lattice energy
and hence higher the m.pt. of the ionic solid.
7. (i) 3Ca(s) + N2(g) ¾¾
® Ca3N2(s)
21. (a) M2+ ions are present in alkaline earth metal compounds
(ii) Ca(s) + H2SO4(aq) ¾¾
® CaSO4(aq) + H2(g) thus leaving all paired electrons in (n-1) s 2 p 6
configuration and are diamagnetic.
(iii) 2Ca(s) + SO2(g) ¾¾
® 2CaO (s) + S(s)
22. (d)
(iv) Ca(s) + 2H2O (l) ¾¾ ® Ca(OH)2(aq) + H2(g) 23. (d) After neon (At No-18), the next electron enters into 4s
8. (i) Plaster of paris quickly solidifies to gypsum with the orbital which has lower energy than 3d orbitals.
evolution of heat and also expands slightly. 24. (b) 25. (d) 26. (a)
473K
27. (c) In crystalline sulphates, the co-ordination number of the
(ii) CaSO 4 . 2H 2 O ¾¾¾® CaSO 4 + 2H 2 O ions increases from Be to Ba and so also the lattice energy
Dead burnt plaster hence solubility in H2O decreases.
9. (i) BeCl2 < MgCl2 < CaCl2 < SrCl2 28. (d) Lesser the lattice energy, more will be the solubility in
H2O.
(ii) Be(OH)2 < Mg(OH)2 < Sr(OH)2 < Ba(OH)2
29. (b) 30. (c)
(iii) BaSO4 < SrSO4 < CaSO4 < BeSO4. 2+
31. (d) Ba is least hydrated hence its size becomes lesser than
12. Both Na and K can react with water. But Na also reacts with any other hydrated alkaline earth metal cation and
alcohol whereas calcium does not or react slowly. therefore has the highest ionic mobility.
15. (a) 16. (d) 17. (a) 18. (b) 19. (c) 32. (b) As we move down the group, the lattice energies of
fluorides decrease more rapidly than the hydration energy
20. (a) 21. (d) 22. (a) 23. (a) 24. (a) and hence the solubilities of the fluorides increase from
top to bottom within a group.
EXERCISE 2 33. (b) 34. (d)
1. (a) Barium shows fixed valency whereas Ti and Cu (transition 35. (d) Lower the I.E. or higher the negative electrode potential,
stronger is the reducing agent.
metals) and Pb (due to inert pair effect) show variable
valency. 36. (c) 37. (a)
38. (b) Since the salt on treatment with dil. HCl gives a pungent
2. (a)
smelling gas (SO2) and a yellow ppt., it must contain
3. (a) Since Be has two valence electrons, it forms only two S2O32– (thiosulphate ion) and further since it gives green
covalent bonds. flame test, it must contain Ba2+ ion. Hence salt is BaS2O3.
4. (c) 39. (c) Mg burns in air to form Mg3N2 which then reacts with
H2O to form NH3.
5. (c) Their oxides are alkaline and occur in earth’s crust.
40. (d) 41. (a)
6. (a) Because of low I.E. and high hydration energies.
42. (d) Since the electrode potential of Mg is lower than that of
7. (b) Ba is most electropositive amongst the listed and hence hydrogen (Eº = 0.0 volt), it will reduce H+ ions to H2 gas.
most reactive. 43. (d)
8. (a) 9. (d) 44. (d) BeH2 is covalent.
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
302 Chemistry
12. (a) The solubility is governed by DH solution 13. (d) K and Mg are formed at cathode
Due to increase in size the magnitude of hydration energy Chlorine is formed at anode 2C l - 2e - ® Cl 2 .
decreases and hence the solubility.
14. (b) The mixture of MgCl2 and MgO is known as sorel’s
13. (a) Setting of cement is exothermic process which develops cement.
interlocking crystals of hydrated silicates
15. (d) K and Mg, both form oxides
14. (c) Calcium carbonate on thermal decomposition gives CaO
(Basic oxide) and CO2 (Acidic oxide) K + O 2 ® KO 2 ;2Mg + O 2 ® 2MgO
D Mg form nitride also 3Mg + N 2 ® Mg 3 N 2
CaCO 3 CaO + CO 2
Basic oxide Acidic oxide K does not form nitride.
16. (b) Statement (b) is correct.
EXERCISE 4 1
17. (c) CaSO 4 . H 2 O ¾setting
¾¾ ¾® CaSO 4 .2H 2 O
1. (c) Plaster of Paris reacts with water to form gypsum which 2
is hard. Plaster of paris Gypsum (orthorhombic)
CaSO4 .1/ 2 H 2 O + 3/ 2 H 2 O ® CaSO 4 .2H 2 O hardening
¾¾ ¾¾ ¾® CaSO 4 .2H 2O
2. (d) Hasenclever and Batchmann’s plants are used for the
Gypsum (monoclinic)
manufacture of bleaching powder (See theory).
18. (b) CaO (Quick lime) is hygroscopic in nature.
3. (a) 2CaOCl2 + dil.H 2SO4 ® CaCl2 + CaSO 4 + 2HClO
19. (a) Mg + + + Na 2 HPO 4 + NH 4 OH
HClO ® HCl + O
4. (d) Portland cement is a complex mixture of silicates and
¾® Mg(NH 4 )PO 4 + 2 Na + + H 2 O
¾
aluminates of Ca.
White ppt
5. (c) The higher the covalent character, the lower the solubility
of compound in water. 20. (a) Ca + H 2 ¾¾® CaH 2 + 2H 2 O ¾ ¾® Ca (OH ) 2 + H 2
6. (c) Mg is more reducing in nature than carbon
21. (c) Be(OH)2 is insoluble in water and thus has lowest value
CO 2 + 2Mg ® 2MgO + C of K sp .
D
7. (a) MgCl 2 .6H 2 O ¾¾® D
MgCl 2 .2H 2 O ¾¾® 22. (b) The Be(OH)2 and Al(OH)3 are amphoteric in nature.
Mg (OH )Cl ¾
¾® MgO + HCl 23. (b) CaO + CO 2 ¾
¾® CaCO 3 .
8. (a) Dicalcium silicate sets at the lowest rate. But the CO 2 does not react with NaHCO 3 .
9. (b) Ba++ with CrO -4 - give yellow BaCrO4. It is insoluble in
24. (d) CaO + CO 2 ¾
¾® CaCO 3
CH3COOH.
CaO + H 2 O ¾
¾® Ca (OH) 2
(
10. (a) CaC2 calcium carbide is ionic Ca 2+ C22- . ) hissing sound and DH = – ve
11. (b) The bicarbonates of alkaline earth metals exist in solution
only 25. (d) Na 2 Z + Ca 2 + ¾
¾® CaZ + 2 Na +
12. (c) Be2+ being small in size is heavily hydrated and heat of
hydration exceeds the lattice energy. Hence BeF2 is
soluble in water.
JEEMAIN.GURU
downloaded from jeemain.guru
11A
The p-Block Elements :
Boron Family
The elements of group 13 are Element B Al Ga In Tl
B - Boron Al - Aluminium Ga - Gallium M.p. (K) 2453 933 303 430 576
In - Indium Tl - Thallium
B.p. (K) 3923 2740 2676 2353 1730
Amongst the elements of this group, Al is the third most abundant
element found in the earth’s crust after oxygen and silicon. (b) The m. p. decreases from B to Ga and then increases,
due to structural changes in the elements
GENERAL CHARACTERISTICS (i.e., PHYSICAL
PROPERTIES) OF BORON FAMILY : (c) Boron has a very high m. p. because of its three
(i) Electronic configuration : The elements of group 13 belong dimensional (B12- icosahedral) structure in which B
to p-block of the periodic table and these elements contain atoms are held together by strong covalent bonds.
three electrons in the valence shell, therefore, their valence (d) Low m. p. of Ga is due to the fact that it consists of only
shell electronic configuration is ns2np1. Ga2 molecules, and Ga remains liquid upto 2273K
Element At. No. Electronic Valence therefore it is used in high temperature thermometry.
Confg. Shell Confg.
(v) Ionisation energy :
B 5 [He] 2s2, 2p1 2s 22p 1
(a) The first I.E. values of group 13 elements are lower than
Al 13 [Ne] 3s2, 3p1 3s 23p 1
the corresponding values of the alkaline earth metals,
Ga 31 [Ar]3 3d10, 4s24p1 4s 24p 1
due to the fact that removal of electron is easy in former
In 49 [Kr] 4d10, 5s25p 1 5s 25p 1
case (p-electron) than latter (s-electron)
Tl 81 [Xe] 4f14, 5d10, 6s2p 1 6s 26p 1
This results in the increase of nuclear charge.
(ii) Atomic radii and ionic radii : Consequently the valence electrons are more tightly
(a) Atoms and their ions of group 13 elements have smaller held leading to high I.E. Similarly we can explain the
size than those of alkaline earth metals of group-2, due irregularity in case of Tl on the basis of ineffective
to greater nuclear charge of former group than latter shielding of intervening electrons
group.
(b) On moving down the group IE, decreases from B to Al
(b) Atomic radii increase on going down in the group with
but the next element Ga has slightly higher IE, than Al,
an abnormaly at gallium and the unexpected decrease in
it again decreases in In and increases in the last element
the atomic size of Ga is due to the presence of electrons
Tl as follows :
in d- orbitals which do not screen the nucleus effectively.
(c) The ionic radii regularly increases from B 3+ Element B Al Ga In Tl
to Tl3+ IE, (kJ mol–1) 800 577 578 558 590
(iii) Density : It increases regularly on moving down the group
from B to Tl (c) The irregularity observed in case of Gallium is due to
(iv) Melting and boiling points : the ineffective shielding of nuclear charge because of
(a) M.P. and b. p. of group 13 elements are much higher intervening d electrons, which cause the increase in
than those of group 2 elements nuclear charge leading to high I.E.
JEEMAIN.GURU
downloaded from jeemain.guru
304 Chemistry
(vi) Inert pair effect : (ii) Reaction with nitrogen : The elements of group 13 form
(a) It is the reluctance of the s-electrons of the valence their corresponding nitrides with the reaction of nitrogen.
shell to take part in bonding and occurs due to These nitrides undergo hydrolysis with steam and evolve
ineffective shielding of the ns 2 electrons by the NH3
intervening d and f electrons.
(b) It increases down a group and thus the lower elements 2B + N 2 ¾¾®
D
2BN
of group show lower oxidation states. Boron nitride
(vii) Oxidation states :
(a) B and Al show an oxidation state of +3 only while Ga, In D
2Al + N 2 ¾¾® 2AlN
and Tl show oxidation states of both +1 Aluminium nitride
and +3.
(b) As we move down in the group 13, due to inert pair BN + 3H 2 O ® H3 BO3 + NH3
effect, the tendency to achieve +3 oxidation state goes orthoboric acid
on decreasing and the tendency to acquire +1 oxidation
state goes on increasing. (iii) Action of water :
(c) Stability of +1 oxidation state follows the order Ga < In (a) Both B and Al do not react with water but amalgamated
< Tl aluminium does react with H2O evolving H2.
(d) Tl+ compounds are more stable than Tl3+ compounds. 2Al(Hg) + 6H2O ® 2Al(OH)3 + 3H2 +Hg
(viii) Electropositive (metallic) character : Aluminium amalgam
(a) These elements are less electropositive than the (b) Ga and In do not react with pure cold or hot water but Tl
elements of the group 1 and 2 due to their smaller size
forms an oxide on the surface.
and higher ionisation energies.
(b) On moving down the group, the electropositive (iv) Reaction with alkalies :
character first increases from B to Al and then decreases (a) Boron dissolves in alkalies on fusion and gives borates.
from Ga to Tl, due to the presence of d and f orbitals in
latter elements. 2B + 6NaOH ¾fuse¾¾® 2Na3BO3 + 3H2
(ix) Reducing character : It decreases down the group from Al (b) Al and Ga dissolve in concentrated alkalies on heating
to Tl because of the increase in electrode potential values and form meta-aluminate and gallate respectively.
for M3+/M. Therefore it follows the order.
D
Al + 2NaOH + 2H2O ¾¾® 2NaAlO2 + 3H2
Al > Ga > In > Tl
Element B Al Ga In Tl Sod. metaaluminate
Eº (V) at 298 K for M3+/M –1.66 –0.56 –0.34 +1.26
(x) Complex formation : Due to their smaller size and greater Ga + 2NaOH + 2H2O ¾¾® D 2NaGaO +3H
2 2
charge, these elements have greater tendency to form Sod. gallate
complexes than the s-block elements.
(xi) Nature of compounds : (v) Reaction with carbon :
(a) The tendency of formation of ionic compounds (a) B and Al form carbides with carbon on heating.
increases from B to Tl. D
(b) Boron forms only covalent compounds where as Al can 4B + C ¾¾® B4C
;
form both covalent (e.g., anhydrous AlCl3) and ionic Boron carbide
compounds (e.g., hydrated AlCl 3 ) because when
anhydrous AlCl3 is hydrated, the hydration energy 4Al + 3C ¾
¾® Al 4 C3
released is sufficient to overcome the ionisation energy Aluminium carbide
of Al.
(b) Aluminium carbide is ionic and forms methane with
(c) Gallium forms mainly ionic compounds although
anhydrous GaCl3 is covalent . water, while boron carbide is covalent having molecular
CHEMICAL PROPERTIES : formula B12C3 and it is very hard, hence used as an
Crystalline B is unreactive whereas amorphous B is reactive. It abrasive.
reacts with air at 700ºC as follows : (vi) Hyrides :
(a) 4B + 3O2®2B2O3; (a) Elements of group 13 do not combine directly with H2 to
2B + N2 ®2BN form hydrides, therefore, their hydrides have been
(b) Al is stable in air due to the formation of protective oxide prepared by indirect methods for example.
film. Some properties are given below
dry ether
(i) Action of Air : BF3 + 3LiBH4 ¾¾¾¾® 2B2H6 + 3LiF
(a) 4Al + 3O2 ®2 Al2O3 diborane
(b) Thallium is more reactive than Ga and In, due to the (b) Boron forms a number of hydrides which are called
formation of unipositive ion Tl+. boranes with general formula BnHn+4(e.g., B2H6) and
4Tl + O2 ®2 Tl2O BnHn+6 (e.g., B4H10)
JEEMAIN.GURU
downloaded from jeemain.guru
Aluminium amalgam
4p
Hb Ha
m
Hb
Ha Ha (b) On moving down the group, there is a change from
acidic to amphoteric and then to basic character of
In above structure B atoms are in sp3 hybrid state. There oxides and hydroxides of group 13 elelments.
are six B-H bonds out of which four B-Ha bonds are (x) Preparation of halides :
normal convalent bonds (two centre electron - pair (a) All the elements of boron family (except thallium which
bonds i.e, 2c–2e) present in the same plane while rest forms thallous monohalides ) form trihalides of type
two B-Hb bonds behave as bridges containing three MX3 where X= F, Cl, Br and I.
centre two electron pairs bonds i.e., 3c–2e (known as B2O3 + 3C + 3Cl2 ® 2BCl3 + 3CO
banana bonds) and present above and below the plane Al2O3 + 3C + 3Cl2 ® 2AlCl3 + 3CO
of the molecules which do not have sufficient number (b) All the boron trihalides, BX3 and aluminium trihalides
of electrons to form normal covalent bonds are called AlX 3 (except AlF 3 which is ionic) are covalent
electron - deficient molecules. Ex. B2H6. compounds whereas former exist as only monomers and
(g) Aluminium forms a polymeric hydride of general formula latter as dimers, because boron atom is too small to co-
(AlH3)x which decomposes into its elements on heating. ordinate with four large halide ions and in case of much
(h) B, Al and Ga form complex anionic hydrides, like lithium smaller F– ion , the energy released during the formation
borohydride, Li[BH4], lithium aluminium hydride , of the bridge structure is not sufficient for the cleavage
Li[AlH4] etc. due to the presence of a vacant p-orbital in of the typical pp-pp bond in BF3.
their outermost shells which accepts electron pair from
X
H– ion.
XH3 + H– ® [XH4]– where X= B, Al and Ga.
B X
(vii) Oxides :
(a) Except Tl all the elements of group 13 form oxides
(general formula, M2O3) on heating with oxygen X
BX3
4M + 3O2 ¾¾® D 2M2O3 (M = B to In)
X X X
(b) Tl forms thallium (I) oxide, Tl2O which is more stable
than thallium (III) oxide, Tl2O3 because of inert pair
Al Al
effect.
(c) B2O3 and Al2O3 can also be prepared by following
X X X
method :
Al2X6
JEEMAIN.GURU
downloaded from jeemain.guru
306 Chemistry
(c) BF3 is a colourless gas, BCl3 and BBr3 are colourless (viii)It does not react with steam but other elements decompose
fuming liquids whereas BI3 is a white fusible solid at steam.
room temperature. (ix) It can be oxidised by concentrated HNO3 while aluminium is
(d) The covalent character of trihalides decreases on passive due to the formation of oxide layer on the surface.
moving from Ga to Tl. 2B +6HNO3 ® 2H3BO3 + 6NO2
(e) Hybridisation of Boron in BCl3 is sp2
Boric acid
(xi) Nature of Trihalies :
DIAGONAL RELATIONSHIP BETWEEN BORON AND
(a) Trihalides of group 13 elements behave as lewis acids
due to having a strong tendency to accept a pair of
SILICON :
electrons. Boron shows resemblance with its diagonal element silicon of
group 14. Some of the important points are given below :
(b) The relative strength of lewis acids of boron trihalides
(i) Both B and Si are non- metals.
increases in the order :
(ii) Both are semi- conductor.
BF3 < BCl3 < BBr3 < BI3. (iii) Both do not form ions, i.e., B 3+ and Si4+.
(c) The halides of group 13 elements behave as lewis acids (iv) Both B and Si form covalent hydrides : boranes i.e., B2H6,
and the acidity character decreases as follows: B4H6 etc. and silanes, i.e., SiH4, Si2H6 etc. respectively, which
BX3 > AlX3 > GaX3 > InX3 (where X=Cl, Br or I) catch fire when exposed to air.
(d) BF3 and anhydrous AlCl3 are used as a catalyst in Friedel B2H6 + 3O2 ® B2O3 + 3H2O
Crafts reactions. SiH4 + 2O2 ® SiO2 + 2H2O
(e) TlCl3 decomposes to TlCl and Cl2 above 40ºC and hence (v) Both form covalent, and volatile halides which fume in moist
acts as an oxidising agent, whereas TlBr3 converts into air due to release of HCl fumes.
Tl[TlBr4] at room temperture. BCl3 + 3H2O ® H3BO3 + 3HCl
SiCl4 + 4H2O ® H4SiO4 + 4HCl
D (vi) Both form solid oxides which are acidic and dissolve in
TlCl3 ¾¾® TlCl + Cl2 ; 2TlBr3 ® Tl[TlBr4] +Br2 alkalies forming borates and silicates respectively.
> 40 º C
B2O3 + 2NaOH ® 2NaBO2 + H2O
While TlI3 is an ionic compound containing Tl(I) and
SiO2 + 2NaOH ® Na2SiO3 + H2O
I 3- ions. (vii) Both react with electropositive metals and form binary
compounds, which yield mixture of boranes and silanes on
ANOMALOUS BEHAVIOUR OF BORON : hydrolysis. Both B and Si form hydroxides boric acid B(OH)3
Boron shows anomalous behaviour as compared to other member and silicic acid Si(OH)4 respectively which are weak acids.
of the group, due to the following reasons. D
3Mg + 2B ¾¾® Mg3B2
(i) It has smallest size in the group.
(ii) It has high ionisation energy. H O / H+
Mg3B2 ¾¾2 ¾ ¾
¾® Mixture of boranes
(iii) It has highest electronegativity in the group.
D
(iv) It does not have any vacant d-orbital in valance shell 2Mg + Si ¾¾® Mg2Si
A few points of difference are : +
Mg2Si ¾H O/H
¾2 ¾ ¾
¾® mixture of silanes
(i) It is a non-metal while other members of the group are metallic
in character. METALLURGY OF BORON
(ii) It shows allotropy as crystalline and amorphous while other OCCURRENCE AND IMPORTANT MINERALS OF
members do not. BORON :
(iii) It has the highest m. p. and b.p. amongst the elements of It does not occur in the free state in nature. It forms electron
group 13. deficient compounds.
(iv) It forms only covalent compounds while other members form Its important minerals are
both ionic and covalent compounds. (a) Borax (or Tincal), Na2B4O7.10H2O or
(v) It forms a number of hydrides which are quite stable while Na2[B4O5(OH)4]8H2O
those of other members are less stable. (b) Kernite, Na2B4O7.2H2O or Na2[B4O5(OH)4]
(vi) The halides of boron exist as monomers while AlCl3 exists (c) Orthoboric-acid H3BO3
as a dimer. (d) Colemanite, Ca2B6O11.5H2O or Ca2[B3O4(OH)3]2 2H2O
(e) Boracite, 2Mg3B8O15. MgCl2
(vii)The oxides and hydroxides of boron are weak acidic while
those of aluminium are amphoteric and those of other ISOLATION :
elements are basic. Elemental boron in the form of dark brown powder is obtained by
following methods :
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
308 Chemistry
H METALLURGY OF ALUMINIUM
O OCCURRENCE AND IMPORTANT MINERALS :
H B It is the most abundant metal found in the earth’s crust. It does
O O not occur in the free state in nature.
H H Its important minerals are :
O OH H (a) Bauxite, Al2O3. 2H2O
OH B O (b) Diaspore, Al2O3. H2O
(c) Corundum, Al2O3
B HO H B (d) Cryolite, Na3 AlF6
H
O O O O (e) Alunite or alum stone, K2SO4. Al2(SO4)3. 3Al(OH)3
(f) Feldspar, K2O. Al2O3 6SiO2
H H H (g) Mica, KAl3Si3O10(OH)2
BORON HALIDES , BX3, (WHERE, X= F, Cl, Br OR I): (h) Kaolinite, Al2O3. 2SiO2 .2H2O
Preparation : By the reaction of boron and halogens at high EXTRACTION :
temperature.
Aluminium metal is extracted from bauxite. It involves following
2B + 3X2 ¾heat
¾ ¾® 2BX3 steps.
Properties : (i) Purification of bauxite : Bauxite usually contains silica as
(i) BF3 and BCl3 are gases, BBr3 is a volatile liquid and BI3 is a impurity. These impurities must be removed before
solid at room temperature. electrolysis, since aluminium, once prepared, cannot be freed
(ii) These are covalent in nature and act as lewis acids. The of other metals by refining it. The bauxite is first purified by
decreasing order of acid strength is. any of the following processes depending upon the nature
BI3 > BBr3 > BCl3 > BF3 of impurities present in it.
(a) Bayer’s process :
BORAZINE OR BORAZOLE OR TRIBORINE
Roasted
TRIAMINE, B3N3H6 : Finely powdered bauxite ¾¾ ¾¾® Roasted ore
FeO ®Fe 2O 3
It is a colourless liquid having a six membered ring of alternating
B and N atoms. It is also called inorganic benzene. It is prepared Caustic soda solution
¾¾¾¾¾¾¾¾
heat
® Al(OH) 3 ¾¾¾® Al 2O 3
by B2H6 as follows: High pressure(150ºC,80atm) pure
filtered, Fe2O3 as residue
3B2H6 + 6NH3 ¾180 ºC
¾ ¾® 2B3N3H6 + 12H2 The reactions involved are given below.
The p electrons in borazine are only partially delocalised. It is Al2O3.2H2O +2NaOH ® 2NaAlO2 + 3H2O
much more reactive than benzene, because there is a retention of
Bauxite Sod. meta
partial negative charge by nitrogen atoms in latter case. It is
aluminate
isosteric (presence of same number of atoms and electrons) with
benzene. NaAlO2 + 2H2O ® Al(OH)3 ¯ + NaOH
H
2Al(OH)3 ¾1473
¾¾
K
¾® Al2O3 + 3H2O
H B
– Alumina
B (b) Hall’s process :
H N: :N H H N+ +N H
2 3 + Na CO
Bauxite (Fine powder) ¾¾¾¾¾¾¾® solution
H B B H H B– –B H fused,extracted with water
r esidueSiO 2 , Fe 2 O 3
N +
N
CO Heat
¾¾ ¾ ¾2¾¾® ppt. Al(OH)3 ¾¾¾® PureAl2O3
H H 50 - 60 º C and filtraed
Borazine filtrate ( Na 2CO 3 )
H
The reactions involved are given below.
C Al2O3. 2H2O + Na2CO3 ®
2NaAlO2 + CO2 + 2H2O
H C C H
2NaAlO2 + 3H2O+ CO2 ¾323 -333K
¾ ¾¾ ¾®
H C 2Al(OH)3 ¯ + Na2CO3
C H
(c) Serpek’s process : This process is employed when silica
C content of ore is high.
H
Benzene Finely powdered bauxite ¾+¾coke
¾ ¾¾
+ N2
®
Heated to1800º C
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
310 Chemistry
THERMITE :
A mixture of aluminium powder and ferric oxide in the ratio 1: 3.
ALUMINIUM SULPHATE, Al2(SO4)3 :
It is used for obtaining H2S in pure form and for making fire proof clothes.
ALLOYS OF ALUMINIUM :
Alloy Composition Properties Uses
(iv) Magnalium Al + Mg + Ca Light, tough and strong Balance beams and machinery
(83%) (15%) ( 2%)
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
312 Chemistry
22. AlCl3 on hydrolysis gives 24. Ionisation enthalpy (DiH1kJ mol–1) for the elements of Group
(a) Al2O3. H2O (b) Al(OH)3 13 follows the order.
(c) Al2O3 (d) AlCl3.6H2O (a) B > Al > Ga > In > Tl
23. Which is not correct? (b) B < Al < Ga < In < Tl
(a) Al acts as a reducing agent (c) B < Al > Ga < In > Tl
(b) Al does not react with steam even at higher temperature (d) B > Al < Ga > In < Tl
(c) Al forms a number of alloys with other metals
(d) Al is ionic in all its compounds
1. The state of hybridization of B in BCl3 is 11. Which of the following hydroxide is acidic ?
(a) sp 3 (b) sp 2 (a) Al(OH)3 (b) Ca(OH)3
(c) sp (d) sp 3d 2 (c) Tl(OH)3 (d) B(OH)3
2. The type of hybridization of boron in diborane is 12. BF3 acts as an acid according to the concept of
(a) sp (b) sp 2 (a) Lewis (b) Bronsted
(c) sp 3 (d) sp 3d 2 (c) Arrhenius (d) None of these
3. Specify the coordination geometry around and hybridization 13. Which of the following is electron deficient ?
of N and B atoms in a 1: 1 complex of BF 3 and NH3 (a) NH3 (b) BCl3
(a) N : tetrahedral, sp3; B : tetrahedral, sp3 (c) PCl3 (d) None of these
(b) N : pyramidal, sp3; B : pyramidal, sp3 14. NH3 and BF3 form an adduct readily because they form
(c) N : pyramidal, sp3; B : planar, sp3 (a) a coordinate bond
(d) N : pyramidal, sp3; B : tetrahedral, sp3 (b) a hydrogen bond
(c) an ionic bond
4. Which one of the following elements has the highest melting
point ? (d) a covalent bond
15. BF3 is used as a catalyst in several industrial processes due
(a) Boron (b) Aluminium
to its
(c) Gallium (d) Thallium
(a) strong reducing nature
5. The element which shows least metallic character is
(b) weak reducing action
(a) Indium (b) Boron
(c) strong Lewis acid nature
(c) Aluminium (d) Gallium
(d) weak Lewis acid character
6. Which of the following does not form M3+ ion? 16. Among the halides of the elements of group 13 the one
(a) Boron (b) Aluminium which is most acidic is
(c) Indium (d) Gallium (a) BF3 (b) AlCl3
7. Which of the following does not react with aqueous (c) BCl3 (d) BBr3
NaOH ? 17. In diborane
(a) B (b) Al (a) 4–bridged hydrogens and two terminal hydrogens are
(c) Ga (d) Tl present
8. B2O3 is (b) 2– bridged hydrogens and four terminal hydrogens are
(a) acidic (b) basic present
(c) amphoteric (d) None of these (c) 3–bridged and three terminal hydrogens are present
9. Boric acid is polymeric due to (d) None of these
(a) its acidic nature 18. Identify the statement that is not correct as far as structure
(b) the presence of hydrogen bonds of diborane is concerned
(c) its monobasic nature (a) There are two bridging hydrogen atoms and four terminal
(d) its geometry hydrogen atoms in diborane
10. B(OH)3 is (b) Each boron atom forms four bonds in diborane
(c) The hydrogen atoms are not in the same plane in
(a) monobasic acid (b) dibasic acid
diborane
(c) tribasic acid (d) triacidic base
(d) All, B – H bonds in diborane are similar
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
314 Chemistry
46. The aluminium salt commonly used to stop bleeding is (b) washing soda gets easily decomposed
(a) aluminium sulphate (b) potash alum (c) washing soda reacts with aluminium to form soluble
(c) aluminium chloride (d) aluminium fluoride aluminate
47. The nature of the solution of Potash alum is (d) washing soda reacts with aluminium to form insoluble
(a) basic (b) acidic aluminium oxide
(c) neutral (d) amphoteric 49. Which out of the following is potash alum ?
48. Aluminium vessels should not be washed with materials
containing washing soda because (a) K2SO4.Al2(SO4)3.24H2O (b) K2SO4. Cr2(SO4)3.24H2O
(a) washing soda is expensive (c) K2SO4.Fe2(SO4)3.24H2O (d) [NH4]2SO4.FeSO4.6H2O
JEEMAIN.GURU
downloaded from jeemain.guru
1. On adding ammonium hydroxide solution to 10. The two type of bonds present in B2H6 are covalent and
Al2(SO4)3 (aq) : (a) ionic (b) co-ordinate
(a) A precipitate is formed which does not dissolve in excess (c) hydrogen bridge bond (d) None of these
of ammonium hydroxide 11. Orthoboric acid when heated to red hot gives
(b) A precipitate is formed which dissolves in excess of (a) metaboric acid (b) pyroboric acid
ammonia solution (c) boron and water (d) boric anhydride
(c) No precipitate is formed 12. Anodised aluminium is
(d) None of these (a) Al obtained at anode
2. The purification method used for mineral Al 2 O 3 .2H 2 O is (b) Al prepared electrolytically
(a) froth floatation (b) leaching (c) Alloy of Al containing 95% of Al
(c) liquation (d) magnetic separation (d) Al electrolytially coated with aluminium oxide
3. The process used for purification of bauxite ore containing 13. Which statement regarding H3BO3 is not correct ?
high silica content as impurity is (a) It is a strong tribasic acid
(a) Baeyer’s process (b) Hall’s process (b) It is prepared by acidifying an aqueous solution of borax
(c) Hoope’s process (d) Serpeck’s process (c) It has a layer structure in which planar BO3 units are
4. Hydrogen forms a bridge in the chemical structure of : joined by H- bonds
(a) sodium peroxide (b) diborane (d) It does not act as proton donor but acts on lewis acid by
(c) hydrogen peroxide (d) lithium hydride accepting OH– ions
14. The precious Ruby stone is
5. The role of fluorspar ( CaF2) which is added in small quantities
in the electrolytic reduction of alumina dissolved in fused (a) alumina
cryolite (Na3AlF6) is (b) aluminium silicate
(a) as a catalyst (c) sodium aluminium silicate
(b) to make the fused mixture very conducting (d) sodium silicate
(c) to increase the temperature of the melt. 15. The hybridisation of boron atom in orthoboric acid is
(d) to decrease the rate of oxidation of carbon at the anode. (a) sp (b) sp 2
6. In Gold Schmidt reaction, certain metallic oxides are reduced (c) sp 3 (d) sp 3 d
to the metallic state by heating with 16. Which of the following statements is not correct ?
(a) metallic magnesium (b) metallic aluminium (a) Al acts as a reducing agent
(c) metallic iron (d) sodium metal (b) Al does not react with steam even at higher temperature
7. The dissolution of Al(OH)3 by a solution of NaOH results in (c) Al forms a number of alloys with other metals
the formation of (d) Al is ionic in all its compounds
17. Which of the following processes does not involve a catalyst?
(a) [Al(H 2 O) 4 (OH)]2 + (b) [Al(H 2 O) 2 (OH) 4 ]-
(a) Thermite process (b) Ostwald process
(c) [Al(H 2 O) 3 (OH) 3 ] (d) [Al(H 2 O) 6 (OH)3 ] (c) Contact process (d) Haber process
8. Which of the following is pseudo alum ? 18. The factor responsible for weak acidic nature of B–F bonds
in BF3 is
(a) (NH 4 )2 SO 4 .Fe2 (SO4 )3.24H 2O
(a) large electronegativity of fluorine
(b) K 2SO 4 .Al2 (SO4 )3 .24H 2O (b) three centred two electron bonds in BF3
(c) pp - dp back bonding
(c) MnSO 4 .Al2 (SO4 )3 .24H 2O
(d) pp - pp back bonding
(d) None of these 19. An aqueous solution of FeSO4, Al2(SO4)3 and chrome alum
9. Which of the following statements about anhydrous is heated with excess of Na2O2 and filtered. The materials
aluminium chloride is correct ? obtained are :
(a) It exist as AlCl3 molecule (a) a colourless filtrate and a green residue
(b) It is a strong lewis base (b) a yellow filtrate and a green residue
(c) It sublimes at 100°C under vaccum (c) a yellow filtrate and a brown residue
(d) It is not easily hydrolysed. (d) a green filtrate and a brown residue
JEEMAIN.GURU
downloaded from jeemain.guru
316 Chemistry
20. Which of the following has the minimum heat of dissociation: 22. Which reaction cannot give anhydrous AlCl3 :
(a) Passing dry Cl2 over heated aluminium powder.
(a) (CH3 )3 N : ® BF3
(b) Heating a mixture of alumina and coke in a current of dry
Cl2.
(b) (CH3 )3 N : ® B(CH3 )2 F
(c) Passing dry HCl over heated aluminium powder.
(c) (CH3 )3 N : ® B(CH 3 ) 3 (d) Heating of AlCl3 .6H 2 O .
23. The process used for purification of bauxite ore containing
(d) (CH3 )3 N : ® B(CH 3 )F2 iron oxide impurity is known as :
21. Purification of alumina is essential because : (a) Hoope’s process (b) Serpeck’s process
(c) Baeyer’s process (d) Electrolytic process
(a) impure alumina has a very high melting point. 24. Which statement is not true about potash alum ?
(b) impure alumina is a very poor conductor of electricity. (a) On heating it melts and loses its water of crystallization.
(c) impure alumina cannot react with the oxidizing agent. (b) It’s aqueous solution is basic in nature.
(c) It is used in dyeing industries.
(d) it is difficult to purify aluminium metal.
(d) It’s empirical formula is KAl(SO 4 )2 .12H 2 O .
JEEMAIN.GURU
downloaded from jeemain.guru
N+ +N N Al Al
– +
–B B B– –B Cl Cl Cl
JEEMAIN.GURU
downloaded from jeemain.guru
318 Chemistry
CH2–OH
–
HO–CH2
– 9. (c) AlCl3 is Lewis acid, exists as dimer (Al2Cl6) and easily
HO OH CH2–O O–CH2
+ B + B hydrolysed
CH2–OH HO OH HO–CH2 CH2–O O–CH2
10. (c) B2H6 contains hydrogen bridge bonds. These are one
Stable chelated complex ion
electron bonds also known as banana bonds.
EXERCISE 4 °C 160°C
11. (b) H 3 BO 3 ¾100
¾ ¾® HBO 2 ¾¾ ¾® H
1. (a) Al2 (SO 4 )3 + 6NH 4 OH ® 2Al(OH)3 + 3(NH 4 ) 2 SO 4
JEEMAIN.GURU
downloaded from jeemain.guru
11B
The p-Block Elements –
Carbon Family
GENERAL CHARACTERISTICS · The compounds in +2 oxidation state are ionic in nature
1. Electronic configuration : and in +4 oxidation state are covalent in nature (Fajan’s
rule)
Element Atomic No. Electronic configuration Valence shell
configuration 7. Negative oxidation states- Carbon forms C 4- and C 22- in
certain compounds e.g.
Carbon 6 [He] 2s 2 2 p 2 2s2 2 p2
Be 2 C (Be 2+ and C 4- ), Al 4 C3 (Al3+ , C 4 - )
Silicon 14 [Ne] 3s 2 3 p 2 3s 2 3 p 2 and CaC 2 (Ca 2 + and C 22 - )
8. Ionisation energy - It decreases from C to Sn . For Pb it is
Germanium 32 [Ar] 3d 10 4s 2 4 p 2 4s 2 4 p 2 slightly higher than Sn.
9. Electronegativity values - The values decrease from C to Pb
Tin 50 [Kr] 4d 10 5s 2 5 p 2 5s 2 5 p 2
but not in a regular manner probably due to filling of d-
orbitals in Ge and Sn and f-orbitals in Pb.
Lead 82 [Xe] 4 f 14 5d 10 6 s 2 6 p 2 6s 2 6 p 2
10. Catenation - It is the tendency of an element to form long
2. Metallic character - C and Si are non metals, Ge is a metalloid chains of identical atoms. The greater the strength of element-
and Sn and Pb are metals. element bond, the greater is the strength of catenation.
3. Appearance - C is black , Si is light-brown , Ge greyish white, C >> Si > Ge » Sn > Pb (catenation )
Sn and Pb are silvery white.
4. Density - Density increases with the increase in atomic Bond ® C– C Si–Si Ge– Ge Sn–Sn
number due to increase in mass per unit volume. Bond kJ/mole 353.3 225.7 167.2 155.0
5. Melting points and Boiling points - The melting points and
11. Allotropy - All the elements except Pb show allotrpy.
boiling points decrease from carbon to lead but carbon and
silicon have very high melting and boiling points due to Allotropic forms of carbon - Diamond, Graphite and Fullerene
their giant structure. Amorphous forms of carbon - coal, charcoal etc.
6. Oxidation states - They are as follows Silicon (Si) - crystalline and amorphous
C Si Ge Sn Pb Tin (Sn) - grey tin, white tin and rhombic tin
Germanium - two crystalline forms
(+2) <+ 4 (+2 )<+ 4 +2 <+ 4 +2 <+ 4 +2> + 4
12. Valency - All elements exhibit tetravalency. In case of Carbon
· The compounds of Ge and Sn in +2 oxidation state are 406 kJ/ mole of energy is required for promotion of 2s electron
reducing in nature. Since their higher oxidation states +4 to 2p. Formation of two extra bonds provide this energy .
are more stable . 13. Inert- pair effect - On descending the group, the stability of
· The compounds of Pb in +4 oxidation state are powerful +4 oxidation state decreases and that of +2 oxidation state
oxidising in nature. Since +2 oxidation state of Pb is increases.
more stable .
JEEMAIN.GURU
downloaded from jeemain.guru
320 Chemistry
14. Atomic and ionic radii - Both increase from C to Pb (iii) Oxides - They form two types of oxides
15. Atomic volume - Atomic volume shows a regular increase (a) Mono-oxides of the type MO
from C to Pb. CO(neutral) and SiO, GeO, SnO, PbO(all basic)
16. Formation of complexes - C does not give any complex due CO forms a number of coordination compounds with
to non availability of empty d orbitals in valence shell. transition metals e.g. Ni (CO )4 , Fe (CO )5 and Cr (CO) 6
The valence shell of Si and other elements contain d-orbitals (b) Dioxides of the type MO2
CO2 , SiO2 GeO2 , SnO2 and PbO2
and can accomodate more than 8 e - and can therefore form 14243 1444 424444 3
Acidic Amphoteric
complexes e.g.
CO2 is linear, gas at ordinary temperatue. Solid CO2 is
SiF4 + 2F - ® [SiF6 ]2 -
known dryice or drikold. SiO2 is solid with three
SnCl 4 + 2Cl - ® [SnCl 6 ]2 - dimensional network having Si bonded to four oxygen
The hybridisation in these complexes is sp 3 d 2 which is atoms tetrahedrally and covalently.
| |
octahedral. - Si - O - Si - O - Si -
17. Reactivity : Increases from C to Pb. | | |
O O O
18. Multiple bonding : Carbon forms pp - pp multiple bonds | | |
with itself and with S, N and O. Other elements show - Si - O - Si - O - Si -
| |
negligible tendency of this type due to their large size. Others
form dp - pp multiple bonds. The bond energy of Si - O bond is 368kJ/mol, therefore
SiO 2 is chemically inert and has high melting point.
FORMATION OF COMPOUNDS
GeO2 , SnO2 and PbO 2 all are network solids. PbO 2 is
(i) Hydrides : All form covalent hydrides .Their number and a powerful oxidising agent
ease of formation decreases down the group. PbO 2 + 2HNO 3 ® Pb(NO3 )2 + H 2 O + O 2
· Hydrides of carbon are known as Alkanes, Alkene or · Carbon also gives suboxide
Alkynes. C 3O 2 , O = C = C = C = O
· Hydrides of Si and Ge are known Silanes and Germanes · Lead also gives mixed oxide
but their number is limited. Pb 3 O 4 , 2PbO.PbO 2
· The only hydrides of Sn and Pb are SnH4 (Stannane) (iv) Acids - All elements give acids of the type H 2 MO3 e.g.
and PbH4 (Plumbane) . H 2 CO3 (carbonic acid), H 2SiO 3 (silicic acid), H 2SnO 3
· Their thermal stability decreases down the group. (meta stannic acid), H 2 PbO 3 (meta plumbic acid). Carbonic
· Their reducing character increases down the group. acid forms two series of salts, bicarbonates (HCO 3- ) and
(ii) Halides : All the elements give tetrahedral and covalent carbonates (CO 3- - ) .
halides of the type MX4 except PbBr 4 and PbI 4 , since SILICATES
-
Pb 4 + is strong oxidising and Br and I - are strong Silicates are metal derivatives of silicic acid H 2SiO 3 and can be
reducing agent. SnF4 is ionic. obtained by fusing metal oxides or metal carbonates with sand e.g.
(a) Stability - Order of thermal stability with common Fuse
Na 2 CO3 + SiO 2 ¾¾¾¾
®(Na 2SiO3 )n
halogen 1780K
CX 4 > SiX 4 > GeX 4 > SnX 4 > PbX 4 Type of silicates - Silicates contain SiO44- tetrahedra formed by
sp 3 hybridisation, depending upon the number of O-atoms shared
· Order of thermal stability with common metals
between tetrahedra and fashion, Silicates have been classified
MF4 > MCl 4 > MBr4 > MI 4
into following groups
(b) Hydrolysis - Except CX4 other tetrahalides are (i) Orthosilicates -They contain discrete SiO44- tetrahedra,
hydrolysed Examples are phenacite Be2SiO4 , willimite
SiX 4 + 2H 2 O ® SiO 2 + 4HX Zn 2SiO 4 , zircon ZrSiO4 , forsterite Mg2SiO4 .
· Ease of hydrolysis (ii) Pyrosilicates - Here two tetrahedra units are
SiX 4 > GeX 4 > SnX 4 > PbX 4 joined by one oxygen atom forming a large discrete Si 2 O 67- .
· CX4 are not hydrolysed due to absence of vacant Examples are thorteveitite Se2 (Si 2O7 ) , hemimorphite
d-orbitals in valence shell of carbon. Zn3 ( Si 2O7 ) .Zn ( OH )2 .H 2O
Dihalides -Except carbon other elements form dihalides of (iii) Chain silicates - Here two oxygen atoms per SiO4 tetrahedra
the type MX2 which are more ionic and have higher melting are shared giving polymeric anion chains. Discrete unit is
points and boiling points e.g . SnCl 2 is a solid whereas (SiO 32- ) n . Examples: synthetic sodium silicate Na 2SiO3 ,
SnCl 4 is a liquid at room temperature. lithium silicate Li 2SiO3 , natural spodumene LiAl(SiO 3 )2 ,
· C, Si and Ge form trihalides of the type MHCl3 . Pb and jodeite NaAl(SiO 3 )2 , enstalite MgSiO3 and diposide
Sn do not form trihalides of the type MHX3 CaMg (SiO 3 )2 .
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
322 Chemistry
Uses - Reducing agent in Iron and steel industry for making water (iv) Lime water -
gas and graphite.
Ca (OH )2 + CO 2 ® CaCO 3 ¯ + H 2 O ¾¾¾
2 ® Ca (HCO )
CO
Wood charcoal -It is obtained by strongly heating wood without 3 2
ppt clear solution
access to air. When heated with steam it becomes more activited.
Uses -To remove colouring matters and odoriferous gases. (v) Reduction - CO2 + C(red hot coke) ® 2CO
Bone-black or animal charcoal - It is obtained by destructive
(vi) Photosynthesis-
distillation of bones in iron retort. By products are bone oil or
pyridine. Chlorophyll
6CO2 + 6H 2 O ¾¾¾¾¾® C6 H12 O6 + 6O2
Uses - As adsorbant. On burning it gives bone ash which is
calcium phosphate and used in the manufacture of phosphorous 6xCO 2 + 5xH 2 O ® (C6 H10 O5 ) x + 6xO 2
and phosphonic acid. Uses - In household as fire extinguisher. Dry powder fire
Lamp black - It is obtained by burning vegetable oils in limited
extinguisher contains ( NaHCO3 + sand ) which is decomposed
supply of air.
Uses - In the manufacture of printing ink , black paint, varnish and by heat.
carbon paper. 2NaHCO3 ® Na 2CO3 + CO 2 + H 2O
Carbon black - It is obtained by burning natural gas in limited Foamite extinguisher contains baking soda and aluminium
supply of air. sulphate and is used for oil fires.
Uses - Added to rubber mixture for making automobile tyres. Structure O = C = O . Linear, dipole moment is zero.
Gas carbon and petrolium coke - When coal is subjected to Carbon monooxide CO :
destructive distillation carbon deposited on walls is scraped and
Preparation -
called gas carbon. Similarly petroleum coke is deposited while
(i) Lab method -
distilling crude petroleum.
Uses - Both are good conductors of electricity when pressed into Conc.H SO
COOH ¾¾ ¾¾ ¾¾® CO2 + CO + H 2O
2 4
sticks they make good electrodes, known as gas electrodes. | D
COOH
Sugar charcoal - It is obtained by heating sugar in absence of air. oxalic acid
It is purest form of carbon. (ii) Manufacture -
CARBONDIOXIDE CO2 Red hot coke
(a) Air ¾¾¾¾¾¾ ® N 2 + CO (producer gas)
Preparation -
Red hot coke
(i) Lab method (b) Steam ¾¾¾¾¾® CO + H 2
CaCO3 + 2 dil. HCl ® CaCl2 + CO2 + H 2 O (water gas synthesis gas or blue gas )
(ii) Manufacture (iii) Other methods - Heating K 4 [Fe ( CN )6 ] with
(a) CaCO 3 ® CaO + CO 2
Conc.H 2SO4
(b) Fermentation C6 H12 O6 ® 2C 2 H 5OH + CO 2
(c) From fuel gases K 4 [ Fe(CN )6 ] + 6H 2SO 4 + 6H 2 O ®
K 2CO3 + CO 2 + H 2O ® 2KHCO3 2K 2SO 4 + FeSO 4 + 3( NH 4 ) 2 SO 4 + 6CO
Physical Properties -Colourless, 1.5 times heavier than air, can be
poured downwards like H 2 O .Animals die in its presence due to Properties - Neutral, colourless, poisonous, burns with blue
lack of O 2 , it is also known as black damp. flame. Sparingly soluble in water. With haemoglobin it gives
Chemical properties : “carboxy haemoglobin” which destroys its capacity to
(i) Stability - Fairly stable, decomposed at 1775K. supply oxygen to the body.
2CO2 ® 2CO + O 2 (a) Burning -Non supporter of combustion. Burns in air
(ii) Incombustible and non supporter of combustion but active with blue flame.
metals e.g. Mg, Na, K continue burning in a jar of the gas. 2CO + O 2 ® 2CO 2
Reduces ammonical AgNO3
CO 2 + 2Mg ® 2MgO + C
2[Ag(NH 3 ) 2 ]OH + CO ® 2Ag + CO 2 + H 2O + 4NH 3
CO 2 + 4Na ® 2Na 2O + C
Reduces Fehling-solution
Na 2 O + CO 2 ® Na 2 CO 3
2CuO + CO ® Cu 2O + CO 2
(iii) Acidic nature - (b) Reducing nature - Metal oxides are reduced to metals.
CO2 + H 2O H 2CO3 117 K
Fe 2 O3 + 3CO ¾¾¾® 2Fe + 3CO 2
2 NaOH + CO2 ® Na 2CO3 + H 2O
high
Na 2CO3 + H 2O + CO2 ® 2 NaHCO3
CO + H 2 O ¾¾¾ ®H 2 + CO 2
T,P
JEEMAIN.GURU
downloaded from jeemain.guru
3. Producer gas : Burning coke + limited air ® producer gas ( Al 2 O 3 .2SiO 2.2H 2 O ) .
Composition : CO = 31.7%, N2 = 65.7%, CO2 = 2.5% PREPARATION OF AMORPHOUS FORM
Properties and uses : Poisonous, combustible but non supporter It is very common and may be obtained by heating powdered
of combustion, has low calorific value. Mainly employed as fuel. quartz or finely divided silica with Mg powder.
4. Coal gas :
SiO 2 + 2Mg ® Si + 2MgO
Preparation : By destructive distillation of coal
JEEMAIN.GURU
downloaded from jeemain.guru
324 Chemistry
PREPARATION OF CRYSTALLINE FORM (x) Silica garden- Aqueous solution of sodium silicate containing
crystals of various coloured salts e.g. copper sulphate, cobalt
By reduction of SiCl 4 with molten Al
nitrate , manganese chloride, nickel chloride etc.
3SiCl 4 + 4Al ® 3Si + 4AlCl3 (xi) Hydro flurosilicic acid H2SiF6
By reduction of highly purified SiCl4 with hydrogen 3SiF4 + 4H 2 O ® H 4SiO 4 ¯ +2H 2SiF6 soluble
SiCl4 + 2H 2 ® Si + 4HCl (xii)Permutit -Artificially perpared sodium aluminium silicate
containing varying composition of sodium ,aluminium and
ZONE-REFINING
silica Na 2Al2Si 2O8 .xH 2O .Used for softening hard water..
Silicon is purified by Zone-refining process because the impurities
present in it are more soluble in the liquid phase than in the solid (xiii)Zeolites -They have honey comb like structure and have the
Mx
phase.
general formula
n
( AlO2 ) x .(SiO2 ) y .zH2O
PROPERTIES
Crystalline form possesses metallic lustre. It is very hard and M = Na + , K + or Ca ++
scratches glass. Crystalline silicon is isomorphous with diamond. n = Charge on metal
CHEMICAL REACTIONS OF AMORPHOUS SILICON : They act as ion exchanger and molecular sieves. They can
be artificially perpared by heating China clay, Silica and
Burns in air Si + O 2 ® SiO 2 Na2CO3 .
Si + 2F2 ® SiF4 (xiii)Ultramarines - Zeolite type silicates, containing ions like
Si + 2Cl2 ® SiCl4 Cl - , SO 24 - , S 2 - and not water, are known as ultramarines
Si + 2NaOH + H 2 O ® Na 2 SiO 3 + 2H 2 e.g. Na 2 (Al6Si6O24 )S2 Many of them are coloured and
used as pigments and calicoprinting.
Si + 2H 2 O (steam) ® SiO 2 + 2H 2
(xiv)Carborundum - silicon carbide
USES SiO 2 + 2C ® Si + 2CO
Silicon chips used for computing devices are doped with P,As, Al Si + C ® SiC
or Ga to enhance the semiconductor properties. It is nearly as hard as diamond .
COMPOUNDS OF SILICON GLASS
Amorphous, hard, brittle, transparent, transluscent super cooled
(i) SiO 2 (silica) - It exists in three crystalline forms Quartz,
solution of various silicates and borates of K, Ca and Pb . It has
Trydimite and crystobalite. Further each form has a and no definite formula but roughly can be represented as
b form. At low temperature the a form is stable and at high M '2 O.M ''O.xSiO 2 where M ' = Na, K and M " = Ba, Zn, Pb
temperature the b form is stable . Raw material used in the manufacture of glass.
(ii) Sand - It is crushed form of quartz produced in nature by (i) SiO2
weathering of rocks . (ii) Na 2CO3, K 2CO3 or NaNO3 or KNO3
(iii) Flint - It is amorphous silica associated with quartz .
(iv) Kiesulguhr - Siliceous rock composed of the remains of sea (iii) Alkaline earth metals e.g. CaCO3 , BaCO3
organisms. Used as absorbent for nitroglycerine. (iv) oxides of heavy metals
(v) Quartz or rock crystal - It is purest form of silica It is optically (v) Cullets (pieces of glass)
active. (vi) Colouring matter
(vi) Silicic acid Colouring materials -
(a) Ortho silicic acid H 4SiO 4 or Si(OH) 4 Colour Substances Colour Substances
(b) Meta silicic acid H 2SiO 3 or SiO(OH) 2 Yellow Ferric iron, Lemon yellow CdS
uranate of Na
Na 2SiO3 + 2HCl ® 2NaCl + H 2SiO3
Purple MnO2 Black NiO
(vii) Silicic acid sol -Colloidal solution of silicic acid.
(viii)Silica gel -Transparent gel of bluish white colour Ruby AuCl3 Milky white Na 3 AlF6
SiO2 .xH 2 O . Blue CuO, CoO Peacock Blue cupric Salts
JEEMAIN.GURU
downloaded from jeemain.guru
(ii) Hard or potash glass Sand+lime stone + K 2CO3 Hard Hard glass apparatus
(iii) Flint glass Sand +Red lead+ K 2CO3 High refractive index Optical instrument, prisms
(iv) Pyrex glass Na 2 O.B2 O3 Al2 O3 SiO2 Low coefficient Glass ware
(v) Jena glass Zn and Barium Borosilicate Low coefficient of expansion Glass wares
(vi) Crookes glass K 2O.PbO.CeO 2 .SiO 2 Cuts off U.V. rays Eye lenses
(vii) Quartz glass or silica glass Pure SiO 2 Low coefficient of expansion Scientific wares
(viii) Safety glass or Between two glass layers Automobile wind
shatter proof a transparent plastic layer shields, goggles etc.
glass of vinyl acetate resin is placed
Annealing - The process of slow cooling of glass is known as Chemical properties - With acids
annealing .The glass becomes soft.
Sn + 2HCl ® SnCl2 + H 2
TIN ( Sn ) :
Sn + dilH 2SO4 ® SnSO 4 + H 2
[Kr]4d 10 4 s 2 4 p 2 Sn + 4H 2SO 4 (Conc.) ® Sn(SO 4 ) 2 + 2SO2 + 4H 2 O
Principal ores of tin - (i) Cassiterite or Tin stone, Sn O 2 (ii)Tinpyrites, 4Sn + 10HNO3 (dil.) ® 4Sn(NO3 ) 2 + NH 4 NO3 + 3H 2 O
SnS.Cu2S. FeS.
Extraction - Sn + 4HNO3 (conc.) ® H 2SnO3 + 4NO2 + H 2 O
(i) Concentration - By gravity process washing with water
Meta stannic acid
and then magnetic separation.
(ii) Roasting -To remove volatile impurities With alkali : Sn + 2NaOH + H 2O ® Na 2SnO3 + 2H 2
S + O2 ® SO2 o
WithO2 at 1500 C: Sn + O2 ® SnO2
4As + 3O2 ® 2As2O3 With steam : Sn + 2H2 O ® SnO2 + 2H 2
(iii) Smelting - It is carried out in reverberatory furnace with COMPOUNDS OF TIN :
coal (powdered anthracite )and lime stone.
SnO2 + 2C ® Sn + 2CO (i) Stannic Oxide ( SnO2 ) - It occurs naturally as cassiterite.
(slag)
CaCO3 + SiO2 ® CaSiO3 + CO2 Preparation - Sn + O 2 D
¾¾® SnO 2
Sn so obtained contains iron and other metals and called D
black tin . H 2SnO 3 ¾¾® SnO 2 + H 2 O
(iv) Refining by (a) Liquation (b) Poling and (c) Electrolytic Properties - White solid, insoluble in water and amphoteric in
Properties - Soft silvery white metal, ductile and malleable. It has nature.
maximum number of isotopes and three allotropic forms.
SnO 2 + 2H 2SO 4 ® Sn ( SO 4 ) 2 + 2H 2 O
18°C 161° C
Grey
White
Rhombic SnO 2 + 2NaOH ® Na 2SnO3 + H 2 O
Tin cry - It produces a peculiar cracking sound on bending which is
Uses - As polishing powder, in glass and pottery manufacture.
known as tin cry.
(ii) Stannous oxide (SnO) -
Tin plague - It is the conversion of white tin to grey tin at low
temperature which crumbles into powder. D
Preparation - SnC 2 O 4 ¾¾ ® SnO + CO + CO 2
Tinning - Since tin is not attacked by organic acids the utensils are
Sn(II) oxalate
protected by thin layer of tin .A pinch of NH 4 Cl is sprinkled over
Properties : It is black solid and amphoteric in nature.
hot and clean surface, when HCl liberated removes the oxide film.Tin
then rubbed over the clean surface with the help of rag dipped in SnO + 2H + ® Sn 2 + + H 2 O
NH 4 Cl powder. The utensil is immediately dipped in water to avoid
SnO + 2OH - ® SnO 22 - + H 2 O
oxide formation .
Tin plating - It involves the depositing of thin protective layer of tin (iii) Sulphides - SnS precipitated by H 2 S .It is dark brown solid,
over sheets of iron electrolytically. soluble in yellow ammonium sulphide forming (NH 4 ) 2 SnS3
JEEMAIN.GURU
downloaded from jeemain.guru
326 Chemistry
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
328 Chemistry
Very Short/ Short Answer Questions (ii) (a) Why N(CH3)3 is pyramidal but N(SiH3)3 is planar?
1. Explain why silicon shows a higher covalency than carbon? (b) Why (SiH3)3N is a weaker base than (CH3)3N ?
2. Why is diamond a bad conductor of electricity but a good (iii) Account for the following:
conductor of heat? PbO2 is a stronger oxidizing agent than SnO2.
3. Which oxide of carbon is an anhydride of carbonic acid ? Or
4. Why carbon forms covalent compounds whereas lead forms
ionic compounds? PbO2 can act as an oxidizing agent.
5. What name is given to the compounds formed by more 16. Glass made up of SiO2 reacts with HF to form SiF62– anion.
electropositive elements with carbon? The analogous CF62– anion does not form. Why?
6. What are silicates?
7. Silanes gets hydrolysed by water whereas alkanes do not, Multiple Choice Questions
why? 17. Which of the following is most stable?
8 (CH3)3N is basic but (CF3)3N is not basic. Explain.
9. (a) CO2 is a gas while SiO2 is a solid. Explain.
(a) Sn 2+ (b) Ge2+
(b) Give one chemical reaction to show that: (c) Si 2+ (d) Pb 2+
(i) Tin (II) is a reducing agent whereas Pb (II) is not. 18. Cement, the important building material is a mixture of oxides
(ii) Tin (II) reduces mercuric salt to mercurous salt. of several elements. Besides calcium, iron and sulphur, oxides
10. (a) Carbon monoxide is readily absorbed by ammonical of elements of which of the group (s) are present in the
cuprous chloride solution but carbon dioxide is not. mixture?
Explain. (a) Group 2
(b) Silanes are few in number whereas alkanes are large in (b) Groups 2, 13 and 14
number. Explain. (c) Groups 2 and 13
(c) Diamond is covalent, yet it has high melting point. Why? (d) Groups 2 and 14
11. Give reason : 19. The most commonly used reducing agent is
(a) Silicon form compounds with coordination number of (a) AlCl3 (b) PbCl2
5 and 6.
(c) SnCl4 (d) SnCl2
(b) Si—F bond is stronger than C—F bond although Si is
20. Lead pipes are not suitable for drinking water because
larger in size than C.
(a) lead forms basic lead carbonate
12. Arrange the following in increasing order of the property
indicated: (b) lead reacts with water containing air to form Pb(OH)2
(a) CCl2, SiCl2, GeCl2, SnCl2 and PbCl2 (c) a layer of lead dioxide is deposited over lipes
(stability) (d) lead reacts with air to form litharge
(b) CO, SiO, SnO, GeO, PbO (basicity) 21. Catenation i.e., linking of similar atoms depends on size and
(c) SiF4, SiCl4, SiI4, SiBr4 (stability) electronic configuration of atoms. The tendency of
catenation in Group 14 elements follows the order :
13. Out of CCl4 and SiCl4 which one reacts with water?
(a) C > Si > Ge > Sn (b) C >> Si > Ge » Sn
14. [SiF6]2– is known whereas [SiCl6]2– is not. Give possible
reasons. (c) Si > C > Sn > Ge (d) Ge > Sn > Si > C
22. Graphite is a soft solid lubricant extremely difficult to melt.
Long Answer Questions The reason for this anomalous behaviour is that graphite
15. (i) C and Si are almost always tetravalent but Ge, Sn and (a) is an allotropic form of diamond
Pb show bivalency. Why? (b) has molecules of variable molecular masses like
Or polymers
Why the tendency to exhibit + 2 oxidation state (c) has carbon atoms arranged in large plates of rings of
increases with increasing atomic number in group 14. strongly bound carbon atoms with weak inter plate
Or
bonds
+ 2 oxidation of lead is more stable than + 4 oxidation
state. Give reasons. (d) is a non-crystalline substance
JEEMAIN.GURU
downloaded from jeemain.guru
1. Which of the following is most electronegative? 10. The element that does not form a monoxide is
(a) Pb (b) Si (a) lead (b) tin
(c) C (d) Sn (c) germanium (d) silicon
2. The most stable +2 oxidation state is exhibited by 11. Pyrosilicate ion is
(a) Fe (b) Sn
(c) Pb (d) Si (a) SiO 22 - (b) SiO 24 -
3. The electronic configuration of four different elements is
(c) Si 2 O67 - (d) Si 2 O76 -
given below. Identify the group 14 element among these
12. Freon -12 is used as a
(a) [He] 2s1 (b) [Ne] 3s 2
(a) refrigerant (b) insecticide
(c) [Ne] 3s 2 3 p 2 (d) [Ne] 3s 2 3 p 5 (c) fungicide (d) herbicide
4. The catenation tendency of C,Si and Ge is in the order Ge 13. Which one of the following allotropic forms of carbon is
-1
isomorphous with crystalline silicon?
<Si<C.The bond energies (in kJ mol ) of C-C,Si-Si and Ge- (a) Graphite (b) Coal
Ge bonds, respectively are (c) Coke (d) Diamond.
(a) 167,180,348 (b) 180,167,348
(c) 348,167,180 (d) 348,180,167 14. The structure and hybridization of Si ( CH 3 ) 4 is
5. Ge(II)compounds are powerful reducing agents
whereas Pb(IV)compounds are strong oxidants .It is because (a) Bent, sp (b) Trigonal, sp 2
(a) Pb is more electropositive than Ge
(c) Octahedral, d 2 sp 3 (d) Tetrahedral, sp 3
(b) ionization potential of lead is less than that of Ge
(c) ionic radii of Pb2+ and Pb4+ are larger than those of Ge2+ 15. Silicon is an important constituent of
and Ge4+ (a) rocks (b) minerals
(d) of more pronounced inert pair effect in lead than (c) alloys (d) vegetables.
in Ge 16. In laboratory, silicon can be prepared by the reaction of
6. Which among CH4, SiH4, GeH4, SnH4 is most volatile? (a) SiO2 with Mg
(a) CH4 (b) SiH4 (b) by heating C in electric furnace
(c) GeH4 (d) SnH4 (c) by heating potassium fluorosilicate with potassium
7. Which of the following halides is the most stable? (d) None of these
(a) CF4 (b) CI4 17. Silica is soluble in
(c) CBr4 (d) CCl4 (a) HCl (b) HNO3
8. Which of the following conceivable structures for CCl4 will
(c) H2SO4 (d) HF
have a zero dipole moment ?
18. Quartz is a crystalline variety of
(a) Square planar
(a) Si (b) SiO2
(b) Square pyramid (carbon at apex)
(c) Irregular tetrahedron (c) Na2SiO3 (d) SiC
(d) None of these 19. Carborundum is
9. PbF4, PbCl4 exist but PbBr4 and PbI4 do not exist because of (a) Al2(SO4)3 (b) Al2O3. 2H2O
(a) large size of Br– and I– (c) AlCl3 (d) SiC
(b) strong oxidising character of Pb4+ 20. Which one of the following is a correct set for SiO2?
(c) strong reducing character of Pb4+ (a) Linear acidic (b) Linear,basic
(d) low electronegativity of Br– and I–. (c) Tetrahedral, acidic (d) Angular, basic.
JEEMAIN.GURU
downloaded from jeemain.guru
330 Chemistry
21. A pseudo solid is 35. White lead is
(a) diamomd (b) glass (a) Pb3O4
(c) rock salt (d) CaCO3
(b) PbO
22. Pyrex glass is a mixture of
(a) sodium borosilicate and aluminium borosilicate (c) 2PbCO3 .Pb ( OH ) 2
(b) sodium silicate and calcium silicate
(c) sodium silicate and lead silicate (d) Pb ( CH 3COO ) 2 .Pb ( OH ) 2
(d) sodium silicate and aluminium borosilicate 36. The oxide which cannot act as reducing agent is
23. The variety of glass used in making lenses and prisms is
(a) SO2 (b) NO2
(a) soda glass (b) borosilicate glass
(c) flint glass (d) crooke’s glass (c) CO2 (d) ClO2
24. Cassiterite is an ore of
37. A solid element (symbol Y) conducts electricity and forms
(a) Mn (b) Ni
two chlorides YCln (colourless volatile liquid) and YCln - 2
(c) C (d) Sn
25. The shape of gaseous SnCl2 is (a colourless solid). To which one of the following groups of
the periodic table does Y belong?
(a) tetrahedral (b) linear
(c) angular (d) T-shaped (a) 13 (b) 14
26. Butter of tin is (c) 15 (d) 16
(a) SnCl4 .6H 2 O (b) SnCl4 .4H 2 O 38. Which of the following bonds has the most polar
(c) SnCl4 .5H 2 O (d) SnCl4 .2H 2 O character?
27. An alloy of Pb and Sn in equal proportion is called (a) C-O (b) C-Br
(a) pewter (b) type metal (c) C-S (d) C-F
(c) solder (d) constantan 39. The ion that can be precipitated by HCl as well as H2S is
28. Red lead is
(a) Pb 2 + (b) Fe3+
(a) PbO (b) Pb3O4
(c) PbO 2 (d) Pb 4 O3 (c) Zn2+ (d) Cu 2+
29. An oxide of lead which is used in lead storage battery, in 40. Which of the following is most dense?
safety matches and is a powerful oxidising agent is
(a) Fe (b) Cu
(a) PbO (b) PbO 2
(c) B (d) Pb
(c) Pb3O4 (d) 2PbO.PbO 2
41. C and Si have
30. Lead sulphate is soluble in
(a) conc. HNO3 (a) Same physical properties
(b) conc. HCl (b) Different physical properties
(c) solution of ammonium acetate (c) Same physical but different chemical properties
(d) water (d) Different chemical and physical properties
31. The percentage of lead in lead pencil is 42. Mark the oxide which is amphoteric in character
(a) zero (b) 20 (a) CO2 (b) SiO 2
(c) 80 (d) 70
32. The important ore of lead is (c) SnO2 (d) CaO
(a) chalcopyrites (b) haematite 43. Which of the following sulphate is insoluble in water?
(c) galena (d) bauxite (a) CuSO4 (b) CdSO4
33. Which of the following lead oxides is present in ‘Sindhur’?
(a) PbO (b) PbO 2 (c) PbSO4 (d) Al 2 ( SO 4 )3
(c) Pb 2 O3 (d) Pb3O4
44. Which of the following molecule has highest bond energy?
34. Which of the following reactions occurs at the cathode during
the charging of a lead storage battery? (a) F-F (b) C-C
(c) N-N (d) O-O
(a) Pb 2 + + 2e - ® Pb
45. The metal used for making radiation shield is
(b) Pb 2 + + SO 24 - ® PbSO 4 (a) Al (b) Fe
(c) Zn (d) Pb
(c) Pb ® Pb 2 + + 2e -
JEEMAIN.GURU
downloaded from jeemain.guru
1. The straight chain polymer is formed by: [CBSE-PMT 2009] 8. In silicon dioxide [AIEEE 2005]
(a) hydrolysis of CH 3 SiCl3 followed by condensation (a) there are double bonds between silicon and oxygen
polymerisation atoms
(b) hydrolysis of (CH3)4Si by addition polymerisation (b) silicon atom is bonded to two oxygen atoms
(c) hydrolysis of (CH3)2SiCl2 followed by condensation (c) each silicon atom is surrounded by two oxygen atoms
polymerisation and each oxygen atom is bonded to two silicon atoms
(d) hydrolysis of (CH3)3 SiCl followed by condensation (d) each silicon atom is surrounded by four oxygen atoms
polymerisation and each oxygen atom is bonded to two silicon atoms.
4. Name the type of the structure of silicate in which one oxygen 9. A metal, M forms chlorides in its +2 and +4 oxidation states.
2tom of [SiO4]4– is shared ? [CBSE-PMT 2011] Which of the following statements about these chlorides is
correct? [AIEEE 2006]
(a) Linear chain silicate (b) Sheet silicate
(a) MCl2 is more ionic than MCl4
(c) Pyrosilicate (d) Three dimensional (b) MCl2 is more easily hydrolysed than MCl4
3. The basic structural unit of silicates is : [NEET 2013] (c) MCl2 is more volatile than MCl4
(a) SiO 44- (b) SiO32- (d) MCl2 is more soluble in anhydrous ethanol than MCl4
10. The stability of dihalides of Si, Ge, Sn and Pb increases
(c) SiO 24- (d) SiO steadily in the sequence [AIEEE 2007]
4. Graphite is a soft solid lubricant extremely difficult to melt. (a) PbX 2 << SnX 2 << GeX 2 << SiX 2
The reason for this anomalous behaviour is that graphite
(b) GeX2 << SiX2 << SnX2 << PbX2
[AIEEE 2003]
(a) is an allotropic form of diamond (c) SiX2 << GeX2 << PbX2 << SnX2
(b) has molecules of variable molecular masses like polymers (d) SiX2 << GeX2 << SnX2 << PbX2.
(c) has carbon atoms arranged in large plates of rings of 11. In context with the industrial preparation of hydrogen from
strongly bound carbon atoms with weak interplate bonds water gas (CO + H2), which of the following is the correct
(d) is a non-crystalline substance statement? [AIEEE 2008]
5. Glass is a [AIEEE 2003] (a) CO is oxidised to CO2 with steam in the presence of a
(a) super-cooled liquid (b) gel catalyst followed by absorption of of CO2 in alkali
(c) polymeric mixture (d) micro-crystalline solid (b) CO is removed by absorption in aqueous Cu2Cl2
6. For making good quality mirrors, plates of float glass are used. solution
These are obtained by floating molten glass over a liquid metal (c) H2 is removed through occlusion with pd
which does not solidify before glass. The metal used can be (d) CO and H2, are fractionally separated using differences
[AIEEE 2003] in their densities
(a) tin (b) sodium 12. Among the following substituted silanes the one which will
(c) magnesium (d) mercury give rise to cross linked silicone polymer on hydrolysis is
7. The soldiers of Napolean army while at Alps during freezing [AIEEE 2008]
winter suffered a serious problem as regards to the tin buttons (a) R4Si (b) R2SiCl2
of their uniforms. White metallic tin buttons got converted (c) RSiCl3 (d) R3SiCl
to grey powder. This transformation is related to
13. In view of the signs of D r G ° for the following reactions :
[AIEEE 2004]
(a) a change in the partial pressure of oxygen in the air PbO 2 + Pb ® 2PbO, D r G° < 0
(b) a change in the crystalline structure of tin SnO 2 + Sn ® 2SnO , D r G° > 0
(c) an interaction with nitrogen of the air at very low Which oxidation states are more characteristics for lead and
temperature tin ? [AIEEE 2011RS]
(d) an interaction with water vapour contained in the humid
(a) For lead + 2, for tin + 2 (b) For lead + 4, for tin + 4
air
(c) For lead + 2, for tin + 4 (d) For lead + 4, for tin + 2
JEEMAIN.GURU
downloaded from jeemain.guru
332 Chemistry
14. Name of the structure of silicates in which three oxygen atoms 16. The species present in solution when CO2 is dissolved in
of [SiO4]4– are shared. [IIT-JEE 2005 S] water are [IIT-JEE 2006]
(a) Pyrosilicate (a) CO 2 , H 2CO3 ,HCO3- ,CO32-
(b) Sheet silicate
(b) H 2CO3 ,CO32 -
(c) Linear chain silicate
(d) Three dimensional silicate (c) CO32- , HCO3
15. When PbO2 reacts with conc. HNO3 the gas evolved is (d) CO2, H2CO3
[IIT-JEE 2005 S]
(a) NO2 (b) O2 (c) N2 (d) N2O
1. On addition of excess of sodium hydroxide solution to 10. Which gas is essential constituent of almost all fuel gases ?
stannous chloride solution, we obtain : (a) CO2 (b) N2
(a) Sn( OH)2 (b) SnO2 .H2O (c) CO (d) H2O
(c) Na2SnO2 (d) None of these 11. Which does not exist
2. Lead pipes are readily corroded by
(a) [SnCl 6 ]2- (b) [GeCl 6 ]2-
(a) H 2SO 4 (b) HCl
(c) CH 3COOH (d) pure water (c) [SiCl 6 ]2- (d) [CCl 6 ]2-
3. A salt which gives CO2 with hot H2SO4 and also decolourises 12. Newly shaped glass articles when cooled suddenly become
acidified KMnO4 on warming is brittle, therefore these are cooled slowly, this process in
(a) bicarbonate (b) carbonate known as
(c) oxalate (d) acetate (a) tempering (b) annealing
4. Which halide is least stable and has doubtful existence (c) quenching (d) galvanising
(a) CI4 (b) GeI4 13. Mark the correct statement
(c) SnI4 (d) PbI4 (a) Water gas is used in manufacture of methyl alcohol
5. R3SiCl on hydrolysis forms (b) Water gas has highest calorific value
(c) Water gas burns with luminous flame
(a) R3SiOH (b) R 3Si - O - SiR 3
(d) The production of water gas is exothermic process.
(c) R 2Si = O (d) None of these 14. H2SO4 is not used for preparation of CO2 from marble chips
6. Which melts in boiling water ? because
(a) Gun metal (b) Wood’s metal (a) it does not react
(c) Monel metal (d) Bell metal (b) huge amount of heat is evolved
7. Incomplete combustion of petrol or diesel oil in automobile (c) the reaction is vigorous
engines can be best detected by testing the fuel gases for (d) calcium sulphate is sparingly soluble and gets deposited
the presence of on marble chips and stops the reaction.
(a) CO + H 2 O (b) CO 15. CO2 is used for extinguishing fire because
(c) NO 2 (d) SO 2 (a) it has a relatively high critical temperature
8. Which of the following is/ are methanide (s) ? (b) in solid state, it is called dry ice
(a) Be2C (b) Al4C3 (c) it is neither combustible nor a supporter of combustion
(c) Mg2C3 (d) Both (a) and (b) (d) it is a colourless gas
9. Which of the following statements is false? 16. Lead pipes are not suitable for drinking water because
(a) Water gas is a mixture of hydrogen and carbon monoxide (a) lead forms basic lead carbonate
(b) Producer gas is a mixture of CO and nitrogen (b) lead reacts with water containing air to form
(c) Water gas is a mixture of water vapour and hydrogen Pb(OH)2
(d) Natural gas consists of methane, ethane and gaseous (c) a layer of lead dioxide is deposited over pipes
hydrocarbons. (d) lead reacts with air to form litharge
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
334 Chemistry
JEEMAIN.GURU
downloaded from jeemain.guru
EXERCISE 3 9. (a) Metal atom in the lower oxidation state forms the ionic
bond and in the higher oxidation state the covalent bond
1. (c) Hydrolysis of substituted chlorosilanes yield because higher oxidation state means small size and great
corresponding silanols which undergo polymerisation. polarizing power and hence greater the covalent character.
Hence MCl2 is more ionic than MCl4.
CH3 Cl H OH – 2HCl CH3 OH
Si + Si 10. (d) Reluctance of valence shell electrons to participate in
CH3 Cl H OH CH3 OH bonding is called inert pair effect. The stability of lower
Dialkyl silandiol oxidation state (+2 for group 14 element) increases on
going down the group. So the correct order is
Polymerisation of dialkyl silandiol yields linear
SiX2 < GeX2 < SnX2 < PbX2
thermoplastic polymer.
11. (a) On the industrial scale hydrogen is prepared from water
CH3 CH3 gas according to following reaction sequence
catalyst 2NaOH
HO — Si — OH + H O —Si — OH CO + H 2 + H 2 O ¾¾¾¾
® CO 2 + 2H 2 ¾¾¾¾ ® Na 2 CO3 + H 2 O
1424 3 (alkali)
water gas
CH3 CH3
From the above it is clear that CO is first oxidised to CO2
which is then absorbed in NaOH. So the correct answer
CH3 CH3 in option (a)
12. (c) The cross linked polymers will be formed by RSiCl3
HO — Si — O — Si — OH
OH
CH3 CH3 |
3nH O
nRSiCl3 ¾¾¾¾
2 ® nR - Si - OH ¾¾
®
-3nHCl |
O– O– OH
| |
2. (c) O O
Si Si | |
–
O O O– R - Si - O - Si
| |
O
– O– O O
| |
Pyrosilicate [Si2O7]6– R - Si - O - Si - R
| |
3. (a) SiO44– is basic structural unit of silicates. O O
| |
4. (d) Statement (c) is correct (Cross linked polymer)
5. (a) Glass is a transparent or translucent super cooled liquid. The correct choice is (c)
6. (d) It is because mercury exists as liquid at room °
13. (c) Negative D r G value indicates that + 2 oxidation state
temperature.
is more stable for Pb. Also it is supported by inert pair
7. white tin. Grey tin is brittle and crumbles
(b) Grey tin effect that + 2 oxidation state is more stable for Pb and
as DrG° value is positive in second reaction it indicates
down to powder in very cold climate.
that + 4 oxidation state is more stable for Sn.
8. (d) In SiO2 (quartz), each of O-atom is shared between two
i.e., Sn++ < Pb++, Sn4+ > Pb4+
SiO44– tetrahedra.
14. (b) Two dimensional sheet structures of the formula
— —
— —
— —
— —
— Si — O —Si — O — Si — O —Si — (SiO5 ) n2n - are formed when tetrahedral are shared.
O O O O 16. (a)
— —
— —
— —
— —
Structure of SiO2
JEEMAIN.GURU
downloaded from jeemain.guru
336 Chemistry
14. (d) Sparingly soluble CaSO4 deposits on marble and stops 34. (d) The bicarbonates of Ca and Mg are decomposed to Ca
the reaction. and Mg carbonates by boiling.
15. (c) CO2 is incombustible and non supporter of combustion. 35. (c) Cr2 O 3 impart green colour to glass.
16. (b) 2Pb + 2H 2 O + O 2 ® 2Pb(OH ) 2 36. (d) Doping of Ge with In produces p-type semiconductor.
17. (c) CO2 being more dense covers the igniting material more 37. (b) H 2 O (steam) + C (coke) ¾
¾® CO + H 2
effectively than N2.
38. (b) Graphite and boron nitride have similar structure.
JEEMAIN.GURU
downloaded from jeemain.guru
12A
Purification,
Qualitative and Quantitative
Analysis of Organic Compounds
The organic compounds obtained from natural sources or conditions of temperature and pressure without
synthesised in the lab are often contaminated with impurities. decomposition and containing non volatile impurities are
They are purified by specialised methods purified by simple distillation.
METHODS OF PURIFICATION OF SOLIDS (ii) Fractional distillation: It is employed for separating two or
(i) Cystallisation: A saturated solution of impure substance is more volatile liquids having boiling points close to each
prepared in hot solvent and is heated with vegetable or other eg. acetone (bpt 60ºC) and methanol (bpt 65ºC). The
animal charcoal which adsorbs the impurities . The solution vapours of the liquids pass through the fractionating column
is filtered while hot through a hot water funnel. The filtrate which provides greater space for their cooling. The vapours
on cooling deposits crystals of pure compound. Success of of high boiling fractions condense and fall back into
the process depends upon the selection of the solvent. The distillation flask. The process is repeated till fractions of
impurities must be least soluble while hot and most-soluble high volatility go up followed by of lower volatility. They
while cold. The quick cooling gives tiny but pure crystals are collected separately.
while slow cooling gives bigger but impure crystals. When (iii) Distillation under reduced pressure or vacuum distillation:
crystal formation is initiated by adding crystals of substance Some liquids decompose when heated to their boiling points
it is called “Seeding”. eg. glycerol. Such liquids can be purified by distillation under
(ii) Fractional crystallisation : It is based on the differential reduced pressure much below their boiling points. The lower
solubilities of different compounds in a solvent. The the pressure lower is the boiling point and vice versa.
compound having less solubility crystallises out first on (iv) Steam distillation: The liquids insoluble in water, steam
cooling leaving behind others in solution. Sometimes mixture volatile in nature, having high molecular weight and having
of two solvents eg. Alcohol & water; Chloroform & high vapour pressure are purified by steam distillation
Petroleum ether, Alcohol or ether give better results. provided the impurities present are not steam volatile.
(iii) Sublimation: Some solids directly pass into vapour when Theory of steam distillation: The liquid boils when its
heated and vapour directly pass into solid when cooled vapour pressure becomes equal to the atmospheric
without the intermediate formation of liquid. This is known pressure. For a mixture of liquid (pl) and steam (ps) we have
as sublimation. The substances which sublime can be at boiling point
purified by this method provided the impurities present do P = pl + ps \ pl = (P – ps)
not sublime.
Hence liquid will boil at lower temperature than its normal
Camphor, napthalene, anthracene, benzoic acid, phthalic
boiling point. Examples Aniline, o-nitrophenol,
anhydride and anthraquinone are purified by sublimation.
bromobenzene, salicyaldehyde, essential oils etc.
METHODS OF PURIFICATION OF LIQUIDS
CHROMATOGRAPHIC METHODS
(i) Simple distillation: The vapourisation of a liquid by heating
It was discovered by Tswett (1906) and developed by Kuhn,
and subsequent condensation of vapours by cooling is
Winterstein and Karrer.
known as distillation. The liquids boiling under ordinary
JEEMAIN.GURU
downloaded from jeemain.guru
338 Chemistry
(i) Principle: Selective adsorption or distribution of various EXTRACTION
components of mixture beween the two phases - fixed phase The process of removing a substance from its aqueous solution
and mobile phase. by shaking with a suitable solvent is known as extraction. (partition
(ii) Classification: law) The greater the number of operations the greater is the
(a) Adsorption chromatography: Fixed phase - Solid or recovery of substance. Soxhlet extractor is used for continuous
ion exchange resin extraction.
Mobile phase - Liquid or gas DRYING OF ORGANIC SUBSTANCES
Hence it is further known as liquid - solid Stable solids may be dried in a steam or air oven; by heating on a
chromatography, gas-solid chromatography or ion free flame. In a vacuum desicator using anhy. CaCl , conc H SO
2 2 4
exchange chromatography. or P2O5 etc.
(b) Partition Chromatography: Fixed phase - liquid Alcohols are dried over : Quick lime, anhy. K CO , MgSO or
2 3 4
supported on inert solid Na2SO4
Mobile phase - liquid or gas Aldehydes and Ketones : Anhy. MgSO4, Na2SO4 or CaCl2
Hence we have liquid - liquid partition chromatography Organic acids: Anhy. MgSO , Na SO or P O
4 2 4 2 5
and liquid gas partition chromatography
Organic bases: Solid KOH, Quick lime or Soda lime
Paper chromatography is the example of partition
chromatography CRITERIA OF PURITY
(iii) Column chromatography: (i) Mixed melting point: The purified substance is mixed with
Example of Adsorption chromatography pure substance (100%) and melting point is taken. If it is
sharp the substance is pure otherwise not. Impurities lower
Adsorbents used are: alumina, silica gel, cellulose powder,
the melting point.
sucrose, animal charcoal, magnesium oxide or keiselguhr
etc. (ii) Boiling Point : The boiling point of a liquid is defined as the
temperature at which its vapour pressure becomes equal to
Liquid Solvents used are : benzene, petrolium ether,
atomospheric pressure. Sharp and concordant boiling point
chloroform, alcohol etc.
is the criteria of purity of organic substance. Impurities
When the solvent is poured over the mixture present at the increase the boiling point.
top of a column packed with adsorbent the components are
separated into number of layers called Zones, bands or DETECTION OF CARBON AND HYDROGEN
chromatograms due to preferential adsorption. The process Strong
(C) organic compound + CuO ¾¾ ¾ ¾®
being known as development. D
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
340 Chemistry
• Percentage of carbon (iii) Estimation of halogens (Carius method)
(a) Organic compound + Fuming HNO3 + AgNO3
12 Wt. of CO 2 ´ 100
= ´ ® AgX.
44 Wt. of organic substance
It is estimated gravimetrically
• Percentage of hydrogen Percentage of halogen =
2 Wt. of H 2 O ´ 100
= ´ wt . of halogen atom ´ wt. of AgX ´ 100
18 Wt. of organic substance =
Mol. wt. of AgX ´ wt . of organic compound
(ii) Estimation of nitrogen: It is estimated by Dumas or (b) Schiff's and Piria method :
Kjeldahl’s method
organic compound (small amount)
(a) Duma’s Method: This method can be applied to all
nitrogenous compounds. Though tedious better than Pt Crucible
+ (CaO + Na 2 CO 3 ) ¾¾ ¾ ¾¾® cooled +
Kjeldahl's method. D Strong
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
342 Chemistry
EUDIOMETRY
Determination of molecular formula of gaseous hydrocarbon by exploding with excess of oxygen in a eudiometer is known as
Eudiometry.
Hydrocarbon (known volume) + O2 (Exces known volume)
(i ) Exploded (ii ) Coo l Contraction in volume (iii) KOH contraction in (iv) Remaining
¾¾ ¾ ¾ ¾® CO 2 ¾¾ ¾¾® ¾¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾® ¾¾ ¾ ¾ ¾ ¾ ¾ ¾¾® ® ¾¾¾¾¾¾¾¾¾¾®
gives volume of H 2O volume gives volume of CO 2 volume is of uncreated O2
H 2O
O 2 (unreacted)
It is absorbed by alkaline pyrogallol. Hence volume of O2 reacted can be known and molecular formula can be calculated with the
help of following equation
æ yö y
C x H y + ç x + ÷ O 2 ® XCO 2 + H 2 O
è 4 ø 2
(x) Aromatic 1° amines : Give diazo compound with NaNO 2 and HCl.
(xiv) Isocyanide : On reduction with Na + C 2 H 5 OH give 2° amines. On acid hydrolysis give 1° amine and formic acid.
(xv) 1° amine : Give isocyanides with CHCl 3 + NaOH, which have unpleasant odour..
(xvi) Nitro compounds : Give 1° amine with Sn + HCl.
(xvii) Amides : Give NH 3 when heated with NaOH.
(xviii) Anilides : They are hydrolysed to 1° amines.
JEEMAIN.GURU
downloaded from jeemain.guru
1. 0.280 gm. of an organic substance gave on combustion 0.560 4. 0.147 gm. of an organic compound containing chlorine was
gm. of carbon dioxide and 0.14 gm. of water. Calculate the heated with nitric acid and silver nitrate which gave 0.287
percentage of carbon, hydrogen and oxygen present in the gm. of silver chloride. Calculate the percentage of chlorine
compound. in the compound.
Sol. Percentage of carbon Sol. Percentage of chlorine
12 Wt. of CO 2 ´ 100 12 ´ 0.560 ´ 100 35.5 ´ Wt. of AgCl ´ 100 35.5 ´ 0.287 ´ 100
= ´ = = 54.54% = = = 48.29%
44 Wt. of substance 44 ´ 0.280 143.5 ´ Wt. of substance 143.5 ´ 0.147
JEEMAIN.GURU
downloaded from jeemain.guru
344 Chemistry
8. 0.596 gm. of chloroplatinate of a monoacidic base gave on 13. 20 ml. of gaseous hydrocarbon was exploded with excess of
ignition 0.195 gm. of Platinum. Find the molecular weight of oxygen in an eudiometer tube. On cooling volume was
the base. reduced by 50 ml. On further treatment with KOH solution
Sol. Molecular weight of a base there was further contraction of 40 ml. What is the molecular
Acidity æ Wt. of platinum salt ´195 ö formula of hydrocarbon ?
= çç - 410 ÷÷
2 è Wt. of platinum ø æ yö y
Sol. C x H y + ç x + ÷O 2 ¾
¾® xCO 2 + H 2 O
1 æ 0.596 ´ 195 ö è 4 ø 2
= 2 ç 0.195 - 410 ÷ = 93
è ø
9. 0.22 gm. of a substance when vaporised by Victor Meyer's æ yö y
1 vol. çè x + ÷ø vol. x vol. vol.
method displaced 45.0 ml. of air measured over water at 4 2
20°C and 755 mm pressure. Calculate the molecular weight
of the substance (vapour pressure of water at 20°C is 17.4 æ yö
20 vol. 20ç x + ÷ vol. 20 x vol.
mm). è 4 ø
Sol. Calculation of volume at NTP
CO2 produced is 40 ml. Therefore 20x = 40 Þ x = 2
P1V1 P2 V2 (755 - 17.4) ´ 45 760 ´ V2
= ; = Contraction produced on explosion and cooling
T1 T2 (273 + 20) 273
æ yö
\ V2 = 40.70 ml. 20 + 20ç x + ÷ - 20 x
è 4 ø
Wt. of 40.7 ml. of vapour at NTP = 0.22 gm.
\ Wt. of 22400 ml. of vapour at NTP Contraction on explosion as given in question is 50.
0.22 æ yö
= ´ 22400 = 121.1 gm. \ 20 + 20ç x + ÷ - 20 x = 50
40.7 è 4 ø
Hence molecular weight of the substance = 121.1
10. The molal freezing point constant of benzene is 4.90 and its y
20 ´ = 30 \y = 6
melting point is 5.51°C. A solution of 0.816 g of a compound 4
A dissolved in 7.5 g of benzene freezes at 1.59°C. Calculate the Hence formula of hydrocarbon = C2H6.
molecular weight of compound A. 14. A dibasic acid gave the following results on analysis
Sol. DTf = 5.51°C - 1.59°C = 3.92°C (a) 0.177 gm. of acid gave on combustion 0.2642 gm. of CO2
K f ´ w ´ 1000 4.9 ´ 0.816 ´ 1000 and 0.081 gm. of water.
m= = = 136 (b) 0.2988 gm. of its Ag salt left 0.1944 gm. of Ag on ignition.
DTf ´ W 3.92 ´ 7.5
Determine the molecular formula of the acid and write
11. The boiling point of pure acetone is 56.38°C at normal down the structural formula of its possible isomers.
pressure. When 0.707 gm. of a substance is dissolved in 10
gm. acetone, the solution boils at 56.88°C. Calculate the 12 0.2642 ´ 100
Sol. % of C = ´ = 40.70
molecular weight of the substance. Ebullioscopic constant 44 0.177
Kb for acetone is 1.67.
Sol. Molecular weight M 2 0.081´ 100
% of H = ´ = 5.07
K b ´ w ´ 1000 1.67 ´ 0.707 ´1000 18 0.177
= = = 236.13 % of O = 100 – (40.70 + 5.07) = 54.23
DTb ´ W (56.88 - 56.38) ´ 10
Element % At. wt. Relative Simple
12. 0.177 gm. of a monobasic acid requires 30 cc of N/10 NaOH
for complete neutralisation. Calculate the molecular weight no. of atoms ratio
of the acid. 40.70 3.39
C 40.70 12 = 3.39 = 1´ 2 = 2
1 1 12 3.39
Sol. geq. of NaOH used = 30 ´ ´ = 0.003
10 1000 5.07 5.07
H 5.07 1 = 5.07 = 1.5 ´ 2 = 3
geq. of acid neutralised by NaOH = 0.003 1 3.39
0.003 geq. º 0.177 g. of acid 54.23 3.39
O 54.23 16 = 3.39 = 1´ 2 = 2
16 3.39
1 geq. º 0.177 = 59 g of acid,
0.003 Empirical formula of dibasic acid = C2H3O2
Hence equivalent of acid = 59 Empirical formula weight of the acid = 59
Since the acid is monobasic. Therefore molecular weight of
acid = 59 × 1 = 59.
JEEMAIN.GURU
downloaded from jeemain.guru
15. 0.56 g of an organic compound gave 0.589 g of silver iodide. CO 2 and 0.324 g H 2 O . 0.295 g compound gives 56 cc
Calculate the % of I in the compound. N 2 by Dumas method . The compound is monoacidic
127 wt. of AgI base and its platinichloride contains 36.89% platinum. Find
Sol. % I = × × 100
235 wt. of organic compound the mol. formula of the compound.
12 0.528
127 0.589 Sol. %C= × × 100 = 61.02
= × × 100 = 56.84 44 0.236
235 0.56
16. 2.79 g of an organic compound was heated in a Carius tube 2 0.324
%H= × × 100 = 15.25
with conc HNO 3 and H 3PO 4 formed was 18 0.236
converted into Mg NH 4 PO 4 ppt. The precipitate on heating 28 56´ 100
%N= × = 23.74
gave 1.332 g of Mg 2 P2 O 7 . What is the % of P in the 22400 0.295
compound? Element % At. wt. Relative Simple
62 wt. of Mg 2 P2 O 7 no. of atoms ratio
Sol. % P = × × 100
222 wt. of organic compound 61.02 5.08
C 61.02 12 = 5.08 =3
12 1.69
62 1.332
= × × 100 = 13.33%
222 2.79 15.25 15.25
H 15.25 1 = 15.25 =9
17. A dibasic acid contain C = 32%, H = 4%. 0.91 g silver salt of 1 1.69
the acid gives 0.54 g silver on ignition. Determine the
molecular formula of the compound. 23.74 1.69
N 23.74 14 = 1.69 =1
Sol. 14 1.69
Empirical formula of compound C 3 H 9 N .
Element % At. wt. Relative Simple
no. of atoms ratio Mol. wt. of compound
JEEMAIN.GURU
downloaded from jeemain.guru
346 Chemistry
\ Mol. formula of compound = C 3 H 9 N SOME PRACTICE PROBLEMS ON THE
It can have any one of the following structures : ESTIMATION OF ELEMENTS
CH 3 1. 0.4950 g of CO 2 and 0.2025 g of H 2 O were obtained
CH - NH 2 by combustion of 0.275 g of an organic compound. Find
CH 3CH 2 CH 2 NH 2 CH 3 the percentage of C and H
n propylamine Isopropylamine (Ans C = 54.54%, H = 9.09%)
H 3C 2. 0.236 g of an organic compound gave 0.528 g CO 2 and
C2 H5
NH 0.324 g H 2 O on complete combustion. Determine the
CH 3 H 3C N
% of C and H in the organic compound.
H 3C (Ans C = 61.02 %, H = 15.25%)
3. 1 g of an organic compound was analysed by Kjeldahl’s
Ethylmethylamine Trimethylamine method. Ammonia evolved was absorbed in 80 ml
19. Find the molecular formula of the compound from the N N
following data H 2SO 4 . The residual acid required 35 ml NaOH
5 10
C = 16.27%, H = 0.677%, Cl = 72.20% for neutralisation. Calculate the % N in the compound.
In victor Meyer’s method 0.2950 g of compound displaces (Ans 17.64%)
50.44 ml moist air at 24°C and 735.7 mm pressure. The 4. In Duma’s experiment 0.204 g of an organic
aqueous tension at 24°C is 22.2 mm compound gave 18.6 ml moist N 2 at 17°C and 756 mm
Sol. Element % At. wt. Relative Simple pressure. Calculate the % N in the compound. (Aq.
no. of atoms ratio tension at 17°C = 14.5 mm) (Ans 10.468%)
5. 0.2046 g of an organic compound in Dumas
16.27 1.356
C 16.27 12 = 1.356 =2 experiment gave 30.4 ml N 2 at 15°C and 732 mm
12 0.677 pressure. Aq. tension at 15°C is 12.7 mm. Find the % N
in the compound. (Ans 16.68%)
0.677 0.677
H 0.677 1 = 0.677 =1 6. Ammonia obtained in Kjeldahl’s method neutralised 20
1 0.677
N
ml H SO . What is the % N in the compound.
72.20 2.03 10 2 4
Cl 72.20 35.5 = 2.03 =3
35.5 0.677 (Ans 14.0%)
7. In carius method 0.378 g of an organic compound gave
10.853 0.678 0.64 g of AgBr. Calculate the % Br in the
O 10.853 16 =0.678 =1 compound. (Ag = 108, Br = 80) (Ans 73.60%)
16 0.677
8. 0.75 g of an organic compound containing phosphorous
Empirical formula of compound C 2 HCl 3O
was heated with conc HNO 3 in the carius tube. The
Mol. wt. of compound by victor Meyer's method
H 3PO 4 formed was precipitated with Magnesia mixture
2´ W
= as MgNH 4 PO 4 . The latter when ignited after washing
V0 ´ 0.00009
and drying left a residue of 1.2545 g of Mg 2 P2 O 7 .
Where W = wt. of organic compound Calculate the % P in the compound (Mg = 24, P = 31, O
V0 = volume of dry air at NTP = 16). (Ans 46.71%)
9. 0.32 g of an organic compound containing sulphur gave
273 (753.7 - 22.2) after suitable treatment 0.2334 g of BaSO 4 . Calculate
V0 = × × 50.44 = 44.62
760 24 + 273 the % S in the compound. (Ba = 137.4 , S = 32, O = 16)
(Ans 10 %)
2 ´ 0.2950
M. wt. = = 146.9 10. An organic compound containing C, H, N and O gave
44.62 ´ 0.00009 following results on analysis.
Mol. wt. 146.9 (i) 0.50 g of the compound gave 0.726 g CO 2 and
n= = =1
Emperical wt. 147.5 0.450 g H 2 O .
(ii) Same compound gave 62.4 ml N 2 at NTP. Find the
Molecular formula of organic compound = C 2 HCl 3O
percentage of all the elements presents in the
The compound is Cl 3 C.CHO chloral. compound.
(Ans C = 39.6%, H = 10.0%, N = 15.6%, O = 34.8%)
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
348 Chemistry
1. For the separation of two immiscible liquids which method (a) sodium hydroxide (b) sodium sulphate
(or apparatus) is used? (c) calcium chloride (d) sodium bicarbonate
(a) chromatography (b) fractionating column 12. In sodium fusion test of organic compounds, the nitrogen
(c) fractional distillation (d) separating funnel of the organic compound is converted into
2. A mixture of benzene and chloroform is separated by (a) sodamide (b) sodium cyanide
(a) sublimation (b) separating funnel (c) sodium nitrite (d) sodium nitrate
(c) crystallization (d) distillation 13. The Lassaigne’s extract is boiled with dil. HNO3 before
3. Which of the following has molecular weight of 92 ? testing for halogens because
(a) Toluene (b) Benzene (a) silver halides are soluble in HNO3
(c) Methylene (d) Propene (b) Na2S and NaCN are decomposed by HNO3
4. Aniline is usually purified by (c) Ag2S is soluble in HNO3
(a) chromatographic technique (d) AgCN is soluble is HNO3
(b) steam distillation 14. Which of the following compounds does not show
Lassaigne’s test for nitrogen ?
(c) by addition of oxalic acid
(a) Urea (b) Hydrazine
(d) fractional crystallization
(c) Phenylhydrazine (d) Azobenzene
5. An organic compound contains 49.3% carbon, 6.84%
hydrogen and its vapour density is 73. Empirical formula of 15. When pieces of human hair are heated strongly with soda-
the compound is lime, smell of ammonia can be detected. Which one of the
following conclusion can be drawn form this observation?
(a) C3H5O2 (b) C6H10O4
(a) Ammonia is present in the human hair
(c) C3H10O2 (d) C4H10O4
(b) Ammonium salt is present in hair
6. Distillation under reduced pressure is employed for
(c) Hair contains amino acids
(a) C6H6
(d) None of the above
(b) petrol
16. Which of the following is the best scientific method to test
(c) CH2OHCHOHCH2OH
presence of water in a liquid ?
(d) organic compounds used in medicine
(a) Smell
7. Impure glycerine is purified by
(b) Taste
(a) steam distillation (b) simple distillation
(c) Use of litmus paper
(c) vacuum distillation (d) None of these
(d) Use of anhydrous copper sulphate
8. Absolute alcohol is prepared by
17. Liebig’s method is used for the estimation of
(a) fractional distillation (b) Kolbe’s method
(a) nitrogen (b) sulphur
(c) azeotropic distillation (d) vacuum distillation
(c) carbon and hydrogen (d) halogens
9. The latest technique used for purification of organic
18. 0.765 g of an acid gives 0.535 g of CO2 and 0.138 g of H2O.
compounds is
Then the ratio of the percentage of carbon and hydrogen is
(a) chromatography (b) vacuum distillation
(a) 19 : 2 (b) 18 : 11
(c) fractional distillation (d) crystallization
(c) 20 : 17 (d) 1 : 7
10. In paper chromatography
19. Nitrogen in an organic compound can be estimated by
(a) moving phase is liquid and stationary phase in solid
(a) Kjeldahl’s method only (b) Duma’s method only
(b) moving phase is liquid and stationary phase is liquid
(c) Both (a) and (b) (d) Neither (a) nor (b)
(c) moving phase is solid and stationary phase is solid
20. Duma's method involves the determination of nitrogen
(d) moving phase is solid and stationary phase is liquid content in the organic compound in form of
11. A is a lighter phenol and B is an aromatic carboxylic acid. (a) NH3 (b) N2
Separation of mixture of A and B can be carried out easily by
(c) NaCN (d) (NH4)2SO4
using a solution of
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
350 Chemistry
1. Lassaigne’s test is used in qualitative analysis to detect 7. The best method for the separation of naphthalene and
[CBSE-PMT 1989] benzoic acid from their mixture is:
(a) Nitrogen (b) Sulphur [CBSE-PMT 2005]
(c) Chlorine (d) All of these (a) distillation (b) sublimation
2. Kjeldahl’s method is used in the estimation of
(c) chromatography (d) crystallisation
[CBSE-PMT 1990]
8. The compound formed in the positive test for nitrogen with
(a) Nitrogen (b) Halogens the Lassaigne solution of an organic compound is
(c) Sulphur (d) Oxygen
[AIEEE-2004]
3. In sodium fusion test of organic compounds, the nitrogen of
(a) Fe4[Fe(CN)6]3 (b) Na3[Fe(CN)6]
the organic compound is converted into
[CBSE-PMT 1991] (c) Fe(CN)3 (d) Na4[Fe(CN)5NOS]
(a) Sodamide (b) Sodium cyanide 9. In a compound C, H and N atoms are present in 9 : 1 : 35 by
weight. Molecular weight of compound is 108. Molecular
(c) Sodium nitrite (d) Sodium nitrate
formula of compound is [AIEEE 2002]
4. A is a lighter phenol and B is an aromatic carboxylic acid.
Separation of a mixture of A and B can be carried out easily (a) C2H6N2 (b) C3H4N
by using a solution of [CBSE-PMT 1992] (c) C6H8N2 (d) C9H12N3.
(a) Sodium hydroxide 10. The ammonia evolved from the treatment of 0.30 g of an organic
(b) Sodium sulphate compound for the estimation of nitrogen was passed in 100
(c) calcium chloride mL of 0.1 M sulphuric acid. The excess of acid required 20 mL
of 0.5 M sodium hydroxide solution for complete neutralization.
(d) Sodium bicarbonate
The organic compound is [AIEEE 2004]
5. The most suitable method for separtion of a 1 : 1 mixture of ortho
and para nitrophenols is [CBSE-PMT 1994] (a) urea (b) benzamide
(a) Sublimation (b) Chromatography (c) acetamide (d) thiourea
(c) Crystallization (d) Steam distillation 11. Sodium nitroprusside, when added to an alkaline solution
6. The first organic compound, synthesized in the laboratory, of sulphide ions, produces purple colour ion due to the
was [CBSE-PMT 1995] formation of [IIT 1995, Orissa JEE 2008]
(a) alcohol (b) acetic acid (a) Na[Fe(H2O)5 NOS] (b) Na2[Fe(H2O)5 NOS]
(c) urea (d) none of these (c) Na3[Fe(CN)5NOS] (d) Na4[Fe(CN)5NOS]
JEEMAIN.GURU
downloaded from jeemain.guru
1. In Kjeldahl’s method nitrogen present is estimated as 11. Liquid benzene burns in oxygen according to
(a) N2 (b) NH3
2C6H6 (l) +15O2 (g) ®12CO2 (g) + 6H2O(g) . How many litre
(c) NO2 (d) None of these
2. Lassaigne’s test for the detection of nitrogen will fail in of O2 at STP are needed to complete the combustion of 39g
case of of liquid benzene:
(a) 11.2 litre (b) 22.4 litre
(a) NH 2 CONH 2 (b) H 2 NCONHNH 2 .HCl
(c) 84 litre (d) 74 litre
(c) H 2 N.NH 2 .2HCl (d) H 6 C5 NHNH 2 .2HCl 12. 0.75 g platinic chloride of a mono- acidic base on ignition
3. The most suitable method of separation of 1:1 mixture of gives 0.245 g platinum. The molecular weight of the base is
ortho and para nitrophenols is (a) 75.0 (b) 93.5
(a) distillation (b) crystallisation (c) 100 (d) 80.0
(c) sublimation (d) chromatography 13. An organic compound has C and H percentage in the ratio 6
4. In kjeldahl's method of estimation of nitrogen, K2SO4 acts as : 1 and C and O percentage in the ratio 3:4 the compound is
(a) oxidising agent (b) catalytic agent (a) HCHO (b) CH3OH
(c) hydrolysing agent (d) boiling point elevator (c) CH3CH2OH (d) (COOH)2
5. For detection of sulphur in an organic compound sodium 14. Before testing halogens the sodium extract is boiled with
nitroprusside is added to the sodium extract. A violet colour conc. HNO 3 to
is obtained due to formation of (a) bring common ion effect
(a) Fe(CN ) 2 (b) K 3 Fe(CN ) 5 NS (b) make solution clear
(c) destroy CN– and S– – ions
(c) Na 4 [Fe(CN ) 5 NOS] (d) Na 4 Fe(CN ) 6
(d) make the solution acidic
6. Which of the following reagents is useful for separating 15. The sodium extract prepared from sulphanilic acid, contains
aniline and nitrobenzene?
SCN - . It gives blood red colouration with
(a) NaOH (aq) (b) H 2 O
(a) a mixture of Na 2S and CS 2
(c) NaHCO3 (d) HCl (aq)
7. 0.5g of an organic compound containing nitrogen on (b) FeCl 3
Kjeldahlising required 29 mL of N/5 H2SO4 for complete
neutralization of ammonia. The percentage of nitrogen in the (c) FeSO 4
compound is (d) Na 2SO 3
(a) 34.3 (b) 16.2
(c) 21.6 (d) 14.8 16. An organic compound is treated with NaNO 2 and dil. HCl
8. Kjeldahl’s method cannot be used for the estimation of at 0°C. The resulting solution is added to an alkaline solution
nitrogen in of b -naphthol where by a brilliant red dye is produced. It
(a) pyridine (b) nitro compounds shows the presence of
(c) azo compounds (d) All of these
(a) – NO 2 group (b) aromatic – NH 2 group
9. A compound contains 38.8% C, 16% H and 45.2% N. The
formula of compound would be : (c) – CONH 2 group (d) aliphatic – NH 2 group
(a) CH 3 NH 2 (b) CH 3CN 17. Methanol and ethanol can be distinguished by
(a) iodoform reaction (b) Esterification
(c) C 2 H 5 CN (d) C H2(NH2)2
(c) Victor Meyer test (d) Acrolein test
10. 0.22 g of organic compound C x H y O which occupied 112 ml 18. 0.532 g of the chloroplatinate of an organic base (M. wt. 264)
gave 0.190 g of Pt on ignition. Then the number of nitrogen
at NTP and on combustion gave 0.44 g CO2. The ratio of x to
atoms per molecule of the base is
y in the compound is
(a) 4 (b) 3
(a) 1 : 1 (b) 1 : 2
(c) 1 (d) 2
(c) 1 : 3 (d) 1 : 4
JEEMAIN.GURU
downloaded from jeemain.guru
352 Chemistry
19. 0.59 g of an organic substance when treated with caustic 27. To detect iodine in presence of bromine, the sodium extract
soda evolved ammonia which required 20 cc of N/2 sulphuric is treated with NaNO 2 + glacial acetic acid + CCl 4 . Iodine
acid for neutralisation. The percentage of nitrogen is
is detected by the appearance of
(a) 26.32% (b) 40%
(c) 53.6% (d) 63.6% (a) yellow colour of CCl 4 layer
20. Which of the following compounds will give foul odour (b) purple colour of CCl 4
of isocyanide when heated with chloroform and alcoholic
KOH ? (c) brown colour in the organic layer of CCl 4
(a) Sulphanilic acid (b) Para toluidine
(d) deep blue colour in CCl 4
(c) Glycine (d) Anthranilic acid
21. 10.0 ml mixture of methane and ethylene was exploded with 28. Which of the following compounds will give silver mirror
30 ml (excess) of oxygen. After cooling the volume was 21.0 test ?
ml. On treatement with KOH solution the volume was reduced (a) CH 3COOH (b) HCOOH
to 7.0 ml. The amount of methane and ethylene in the mixture
respectively are (c) CH 3 CO. COOH (d) None of these
(a) 5 ml CH 4 + 5 ml C 2 H 4 29. Benzaldehyde and acetone can be distinguished by
(c) CH 3COOC 2 H 5 (d) CH 3COCH 3 31. In Kjeldahl’s method for the estimation of N 2 , potassium
24. Beilstein’s test is given by which of the following? sulphate and copper sulphate are used. On the basis of their
(a) Halogens (b) Thiourea functions which of the following statement(s) is/are correct?
(c) Pyridine (d) All of these I. Potassium sulphate raises the bpt. and ensures complete
25. The molecular mass of an organic compound which contains reaction.
only one nitrogen atom can be II. Copper sulphate acts as catalyst.
(a) 152 (b) 146 III. Potassium sulphate acts as catalyst and copper sulphate
(c) 76 (d) 73 raises the bpt.
26. Which of the following observations is correct and useful in (a) Only III is correct (b) I and II are correct
identifying carboxylic acids ? (c) Only II is correct (d) None is correct
(a) Carboxylic acids liberate CO 2 gas from NaHCO 3 32. 2.79 g of an organic compound when heated in Carius tube
solution with conc. HNO 3 and H 3PO 4 formed converted into
(b) Acids liberate I 2 from a mixture of KIO 3 and KI MgNH 4 .PO 4 ppt. The ppt. on heating gave 1.332 g of
(c) They produce fruity smell of esters when heated with Mg 2 P2 O 7 . The percentage of P in the compound is
alcohol in presence of conc. H 2SO 4
(a) 23.33% (b) 13.33%
(d) All of these (c) 33.33% (d) 26.66%
JEEMAIN.GURU
downloaded from jeemain.guru
EXERCISE 1 Na 2S + 2AgNO 3 ¾
¾® 2 NaNO 3 + Ag 2S ¯
1. By fractional distillation. Black
2. o–nitrophenol is steam volatile while p–nitro phenol is not NaCN + AgNO 3 ¾
¾® NaNO3 + AgCN ¯
and hence these can be separated by steam distillation. White
3. Vacuum distillation and steam distillation. NaCl + AgNO 3 ¾
¾® NaNO3 + AgCl ¯
5. Fractional crystallisation using benzene as a solvent. white
6. Al2O3 (alumina). boil
Na 2S + 2HNO 3 ¾¾¾® 2 NaNO 3 + H 2S
7. V.D. is 42, Mol. wt. = 2 × V.D. = 2 × 42 = 84 therefore, molecular boil
formula is C6H12. NaCN + HNO 3 ¾¾
¾® NaNO 3 + HCN
8. Every pure substance has fixed melting point and refractive 14. (b) Hydrazine (NH2NH2) does not contain carbon and hence
index. Impurities reduce the melting point and change on fusion with Na metal, it cannot form NaCN;
refractive index. consequently hydrazine does not show Lassaigne’s test
9. Tap water usually contains dissolved chlorine which gives for nitrogen.
test for halogens. 15. (c) Hair contains amino acids which upon fusion with soda
13. Percentage of Br = 34.04% lime (NaOH + CaO) evolve NH3.
14. Percentage of nitrogen = 56% 16. (d) Hydrated CuSO4 is blue in colour, while anhydrous is
17. (b) 18. (d) 19. (d) 20. (d) white.
21. (d) 22. (b) 23. (b) 24. (a) CuSO 4 + 5H 2 O ¾
¾® CuSO 4 .5H 2 O
White Blue
EXERCISE 2 17. (c)
1. (d)
2 (d) Benzene (b.p. 80ºC) and chloroform (b.p. 61.5ºC) have 18. (a) % of C = 12 ´ 0.535 ´ 100 = 19.07 %
44 0.765
different boiling points.
2 0.138
3. (a) Mol. wt. of toluene, C6H5CH3 = 72 + 5 + 12 + 3 = 92 % of H = ´ ´ 100 = 2.004 %
4. (b) Aniline is miscible in steam and has b.p. lower than water, 18 0.765
hence it is collected as distillate along with steam. Ratio of C : H = 19 : 2
5. (a) % of O = 100 – (49.3 + 6.84) = 43.86 19. (c) 20. (b) 21. (c)
Relative ratio of C : H : O =
49.3 6.84 43.86
: : 22. (b) % of S = 32 ´ 0.233 ´ 100 = 10 %
12 1 16 233 0.32
= 4 : 6.84 : 2.74 12 0.147
23. (a) % of C = ´ ´ 100 = 20.045 %
= 1.49 : 2.49 : 1 44 0 .2
= 3 : 5 : 2 (multiplying by 2) 2 0.12
\ Empirical formula = C3H5O2 % of H = ´ ´ 100 = 6.666 %
18 0.2
6. (c) Glycerol decomposes at its boiling point, hence it should
be purified by distillation under reduced pressure. % of O = 100 - (20.045 + 6.666) = 73.29 %
7. (c) Vaccum distillation means distillation under reduced 24. (a) Relative ratio of wts.
pressure. C H Cl O
8. (c) Since alcohol and water form a constant boiling mixture 18.5 1.55 55.04 24.81
(azeotrope). 35.5 16
12 1
9. (a) 10. (b) = 1.55 = 1.55 = 1.55 = 1.55
11. (d) Carboxylic acids dissolve in sodium bicarbonate, while
\ Relative No. of atoms
phenol does not.
12. (b) 1 1 1 1
13. (b) Na2S and NaCN, formed during fusion with metallic Hence empirical formula is CHClO
sodium, must be removed before adding AgNO 3 , 25. (c) As in above question,
otherwise black ppt. due to Na2S or white precipitate due
to AgCN will be formed and thus white precipitate of 40 13.33 46.67
C= = 3.33; H = = 13.33; N = = 3.34
AgCl will not be identified easily. 12 1 14
JEEMAIN.GURU
downloaded from jeemain.guru
354 Chemistry
Relative No. of atoms, 85.72 14.28
38. (a) C : H = : = 7.15 : 14.28 = 1 : 2
3.33 13.33 3.34 12 1
C= = 1; H = = 4; N = =1
3.33 3.33 3.33 \ Empirical formula = CH2
\ Empirical formula = CH4N From the give options, simple multiple of CH2 is only C2H4
75 . 8 24 . 2 39. (a) % of O = 100 – (52.2 + 13.04) = 34.76%
26. (d) Relative No. of atoms : X = = 2;Y = = 3 Relative ratio of
75 16
C H O
\ Empirical formula = X2Y3
27. (b) Relative No. of atoms 52.2 13.04 34.76
C H 12 1 16
83.70 16.30 4.35 13.04 2.17
=7 = 16.30
12 1 2 6 1
\ Empirical formula = C2H6O
7 16.30
or =1 = 2.33
7 7 2 ´ 23
Mol. formula = ´ C 2 H 6O = C 2 H 6 O
or 1 × 3 = 3 2.33 × 3 = 8 24 + 6 + 16
\ Empirical formula = C3H8 At. wt. of Se
40. (a) % of Se = ´100
80 20 6.66 20 Min. mol. wt.
28. (c) C : H or = 6.66 ; = 20 or =1; =3
12 1 6.66 6 .66
\ Empirical formula = CH3 \ Min. mol. wt. = At. wt. of Se ´100
29. (b) % of O = 100 – (40 + 6.7) = 53.33 % of Se
78.4 ´ 100
40 6.7 53.33 = = 1.568 ´ 10 4
C:H:O = : : = 3.33 : 6.7 : 3.33 = 1 : 2 : 1 0.5
12 1 16 41. (c) Mol. wt. of the compound
\ Empirical formula = CH2O = Mass of 1 mole of the compound = 42
30. (a) Mass ratio of H : C = 1 : 12 empirical formula wt. of CH2 = 12 + 2 = 14
However, given mass ratio of H : C = 1 : 3
Therefore, for every C atom, there are 4 H atoms, hence 42
\ Molecular formula = CH 2 ´ = C3 H 6
empirical formula = CH4 14
42. (c) Relative ratio of wts. of C : H : N = 9 : 1 : 3.5
31. (d) V.D. = Wt. of 45 ml. of vapours at NTP
Wt. of 45 ml. of H 2 at NTP 9 1 3.5
Relative No. of atoms : : =0.75:1: 0.25=3: 4:1
12 1 14
0.24 g \ Empirical formula = C3H4N
= = 59.93
45 ml. ´ 0.000089 g ml -1 Mol. wt.(given) = 108
32. (c) 25 ml of 0.12 N NaOH = 0.1914 g of acid 108
\ Mol. formula = ´ C3 H 4 N = C 6 H8 N 2
0.1914 ´ 1000 36 + 4 + 14
1000 ml of 1 N NaOH = = 63.8 43. (c) Relative No. of atoms or molecule
25 ´ 0.12
\ Eq. wt. of the acid = 63.8 16.08 4.19 16.78 62.95
Na : C : O : H 2 O = : : :
33. (c) 34. (c) 23 12 16 18
35. (c) Mol. wt. = 2 × V.D. = 2 × 90 = 180 = 0.70 : 0.35 : 1 : 3.50
Empirical formula wt. = 12 + 2 + 16 = 30 = 2 : 1 : 3 : 10
Mol. wt. \ Empirical formula = Na2CO3.10H2O
\ Molecular formula = EF wt. ´ empirical formula
EXERCISE 3
180 1. (d) Nitrogen, sulphur and halogens are tested in an organic
= ´ CH 2 O = C6 H12 O6
30 compound by Lassaigne's test. The organic compound
36. (b) The simplest acid is HCOOH whose mol. formula is CH2O2 is fused with sodium metal as to convert these elements
which coincides with the given empirical formula. into ionisable inorganic substances,
85 15 Na + C + N ¾¾
® NaCN
37. (d) C : H = : = 7 : 15 » 1 : 2
12 1
\ Empirical formula = CH2 2Na + S ¾¾
® Na 2S
Mol. wt. = 2 × 28 = 56
2Na + X 2 ¾¾
® 2NaX
56
Mol. Formula = ´ CH 2 = C 4 H 8 The cyanide, sulphide or halide ions can be confirmed in
12 + 2 aqueous solution by usual test.
JEEMAIN.GURU
downloaded from jeemain.guru
EXERCISE 4 % of C = 6 ´ 100 = 40 40 / 12 = 3 . 33 = 1
15
1. (b) In Kjeldahl’s method nitrogen is converted into
1
(NH4)2 SO4, then to NH3 %H= ´ 100 = 6.6 6.6 / 1 = 6.6= 2
2. (c) For detection of nitrogen by Lassaigne’s method, the 15
8
compound must contain C and N both to form NaCN. % O = ´100 = 53.3 53.3 / 16 = 3 . 3= 1
3. (a) o- nitrophenol is more volatile due to intramolecular H- 15
bonding . p - nitrophenol is less volatile due to simple ratio CH2O
intermolecular H-bonding \ The compound is H.CHO
JEEMAIN.GURU
downloaded from jeemain.guru
356 Chemistry
14. (c) It decomposes NaCN and Na 2S to avoid their Vol. of CO 2 produced + O 2 left = 21 ml
interference Vol. of CO 2 produced = 21 – 7 = 14 ml
NaCN + HNO 3 ¾
¾® NaNO3 + HCN CO 2 produced is
Na 2S + 2 HNO 3 ¾
¾® 2 NaNO3 + H 2S a + 2(10 – a) = 14
\ a=6
NaCN + AgNO 3 ¾
¾® AgCN ¯ + NaNO3 \ Vol. of CH 4 = 6 ml and vol. of C 2 H 4 = 4 ml
22. (d)
Na 2S + 2 AgNO 3 ¾
¾® Ag 2S ¯ + 2 NaNO3
NO 2
- +++
15. (b) SCN + Fe ¾
¾® Fe(SCN ) 3
blood red ppt. 23. (d) C = O + H 2 N.NH NO 2 ¾
¾®
OH
16. (b) N 2 Cl + NO 2
¾
¾®
C = NNH NO 2
OH
N=N orange red ppt.
24. (d) Pyridine and thiourea form volatile cupric cyanide and
Red dye also give bluish green flame like volatile cupric halides.
I 2 / NaOH
25. (d) The compounds with odd number of N-atoms have odd
17 (a) CH 3COCH 3 ¾¾¾¾ ¾® CHI3 (iodoform) masses and with even number of N-atoms have even
18. (a) The equivalent wt. of base masses. This is “nitrogen rule”.
26. (d) All the points are correct.
1 æ 0.532 ö
E= ç ´ 195 - 410 ÷ = 68
2 è 0.190 ø 27. (b) 2NaI + 2 NaNO 2 + 4 CH 3COOH ¾
¾®
I 2 + 2NO + 4 CH 3COONa + 2 H 2 O
264
Acidity = =4 28. (b) HCOOH is reducing in nature
68
Acidity of base = number of N atoms per molecule of Ag 2 O + HCOOH ¾ ¾® 2Ag + H 2 O + CO 2
base = 4 silver mirror
19. (a) Percentage of nitrogen by Kjeldahl’s method 29. (d) Benzaldehyde does not give iodoform test while acetone
1.4 ´ N ´ V 1.4 ´ 20 1 forms CHI3 .
= = ´ = 26.32%
Wt. of organic compound 0.532 2 30. (d) When organic compound contains nitrogen, upon
combustion it will produce oxides of nitrogen soluble in
20. (b) H 3 C – NH 2 + CHCl3 + 3KOH ¾
¾®
KOH solution. The copper will convert them into N 2
CH 4 + 2 O 2 ¾
¾® CO 2 + 2 H 2 O (liquid) 62 wt. of Mg 2 P2 O 7
32. (b) Percentage of P = × × 100
a ml 2a ml a ml negligible volume 222 wt. of compound
C2H 4 + 3 O2 ¾ ¾® 2 CO 2 + 2 H 2O 62 1.332
= × × 100 = 13.33%
(10 – a) ml 3(10 – a) ml 2(10 – a) ml negligible 222 2.79
JEEMAIN.GURU
downloaded from jeemain.guru
12B
Classification and
Nomenclature of Organic
Compounds
CLASSIFICATION OF ORGANIC COMPOUNDS (iii) Homocyclic : The ring system is made up of one type of
The ability of carbon to combine with large number of elements atoms generally carbon
especially O, N, S, X etc, to undergo catenation to form chains of (a) Alicyclic : The cyclic compounds resembling open chain
varying lengths and shapes and existance of isomers has led to aliphatic compounds.
the formation of more than five million organic compounds. These For example: Cycloalkanes
have been classified into the following main groups (b) Aromatic : The benzene, napthalene and their derivatives
etc are homocyclic aromatic compounds
Organic
Compounds
NH2
Homocyclic
Benzene Aniline
Heterocyclic
OH
n-Butane Isobutane n-Butanol
Napthalene Anthracene
2, 4-Dimethyl pent-1-ene
JEEMAIN.GURU
downloaded from jeemain.guru
358 Chemistry
(a) Alicyclic : eg. HOMOLOGOUS SERIES
A group of a particular class of compounds where a preceeding or
succeeding member differ by one–CH2. The members of the series
••
N are known as homologues. The homologues
O
•• H (i) have the same general formula CnH2n+2 or CnH2n+1 X
Tetrahydrofuran Pyrrolidine (ii) molecular weight differing by 14 of two successive members
O (iii) can be prepared by general methods of preparation
O O (iv) have almost similar chemical properties
N (v) show regular gradation in physical properties such as mpt,
H Oxirane
1,4-Dioxane bpt, density etc
Piperidine or Epoxyethane
(b) Aromatic : eg. NOMENCLATURE
The most widely accepted and the latest system of naming organic
compounds is IUPAC (International Union of Pure and Applied
O N S
Furan H Chemists) system, according to which the name essentially
Thiophene
Pyrrole consists of three parts.
(i) Word root : It indicates the nature of the basic carbon
skeleton. From C1 to C4 common names have been retained
N and from C5 upwards Greek number roots have been used
Pyridine N
Chain length Word root Chain length Word root
Quinoline
C1 Meth- C7 Hept-
CLASSIFICATION BASED ON FUNCTIONAL GROUPS
On the basis of functional groups which confer characteristic C2 Eth- C8 Oct-
properties on them, the organic compounds have been classified C3 Prop- C9 Non-
as follows C4 But- C10 Dec-
Class Functional group C5 Pent- C11 Undec-
Halides X (Cl, Br, I) Halo C6 Hex- C12 Dodec
The generic word root for any carbon chain is “alk”.
O
|| (ii) Suffix : These are of two types
Esters — C— O — R
(a) Primary suffix : It is added to the word root to designate
Olefins Alkenes >C = C< saturation or unsaturation in a carbon chain
O Type of Primary Generic name
||
Acid halides — C— X Carbon chain Suffix
Acetylenes / Alkynes —C º C — Saturated - ane Alkane
O O Unsaturated with - ene Alkene
|| || one C=C
Anhydrides — C— O — C— Unsaturated with - yne Alkyne
Alcohols —OH (Hydroxy) one C º C
Amines —NH2 (b) Secondary suffix : It is added to indicate the functional
group present in the compound. The terminal ‘e’ is
O
Aldehydes || dropped, if secondary suffix begins with a vowel (a, e, i,
— C— H o, u, y) but it is retained if the secondary suffix begins
with a consonant.
O
||
Ketones C — C— C Functional Secondary Generic name
Sulphonic acid —SO3H group suffix
O – OH – ol Alkanol
|| –CHO – al Alkanal
Acids — C— O — H
>C = O – one Alkanone
O – COOH – oic acid Alkanoic acid
||
Amides –COX – oyl halide Alkanoyl halide
— C — NH 2
– CONH2 – amide Alkanamide
JEEMAIN.GURU
downloaded from jeemain.guru
ALKYL GROUPS :
Univalent groups formed by the removal of one hydrogen atom from an alkane are known as alkyl groups or alphyl groups. Their
names are obtained by changing the suffix –ane of parent hydrocarbon by –yl.
Alkane Group Short-hand notation IUPAC name
Methane Methyl CH3– Me Methyl
Ethane ethyl C2H5– Et Ethyl
Propane n-propyl CH3CH2CH2– n-Pr, Pra or Pr 1-propyl
|
Iso propyl CH 3 – C H – CH 3 Iso- Pr , Prb , Pri 2-propyl
JEEMAIN.GURU
downloaded from jeemain.guru
360 Chemistry
3. Alkynes C2H2 CnH2n–2 Acetylene Alkyne Ethyne
or Acetylenes C3H4 Methyl acetylene Propyne
4. Alkyl CH3Cl R–X Methyl chloride Haloalkanes Chloromethane
halides C2H5Cl Ethyl chloride Chloroethane
5. Dihalogen CH2Cl CnH2nX2 Ethylene 1,2-dichloroethane
derivatives (Alkylene halide) chloride
CH2Cl
(vicinal)
CHCl 2
Ethylidine Chloride 1,1-dichloroethane
CH 3
Geminal
6. Trihalogen CHCl3 CnH2n–1X3 Chloroform 1,1,1-trichloromethane
derivatives
7. Tetra halogen CCl4 CnH2n–2X4 Carbon tetra 1,1,1,1-tetra-
derivatives chloride chloromethane
8. Alcohols CH3OH CnH2n+1OH Methyl Alkanol Methanol
(Monohydric) alcohol
JEEMAIN.GURU
downloaded from jeemain.guru
11. Acid chlorides CH3COCl R–COCl Acetyl chloride Alkanoyl halide Ethanoyl chloride
O
12. Esters CH3 – C – OC2H5 RCOOR' Ethyl acetate Alkyl alkanoate Ethyl ethanoate
(here alkyl
O O attached to oxygen)
O O
||
17. Ketones CH3–C–CH3 R – C– R Acetone Alkanone Propan-2-one
O
CH3–C–CH2–CH3 Ethylmethyl Butan-2-one
ketone
18. Cyanides HC º N R–CN Hydrogen cyanide Alkanenitrile Methanenitrile
CH3C º N Methyl cyanide Ethanenitrile
CH2 – CN Butan-1, 4 dinitrile
CH2 – CN
Propanl-1, 2,
CH2 – CN
3-tricarbonitrile
CH – CN
CH2 – CN
JEEMAIN.GURU
downloaded from jeemain.guru
362 Chemistry
LINE ANGLE FORMULA (iv) If two or more of the same alkyl groups are present, use the
Bonds are represented by lines, carbon atoms are assumed to be prefixes di, tri etc to avoid repetition
present at the start and finish of a line. Nitrogen, oxygen and 5 1
halogens are labelled, but hydrogens are only shown when 3
bonded to a drawn atom. Each atom is assumed to have sufficient 4 2
hydrogen atoms around it to make it neutral. For example: 3, 3-Dimethylpentane
6 4 2 (v) Alphabetical order : The side chains are cited in alphabetical
n-Hexane CH3(CH2)4CH3 order
7 5 1
5 3 1
4 3
CH2 O 6 2
6 O
CH2 C 5
1 4-Ethyl-3, 3-dimethylheptane
2-Cyclohexenone CH2 CH 4 2
(vi) Longest chain with maximum number of side chains : If two
CH 3
or more chains of the same length are possible, choose the
one with maximum number of side chains.
But-1, 3-diene CH 2 = CH – CH = CH 2
2 4 6
1
3
3
1 5
4 2
CH3 OH
| |
3-methyl but-2-ol CH 3 – C H – CH – CH 3
(vii) Locant sum : Sum of the locants must be minimum. But out
of two sets of the sum of the locants, the set having the
3 1 lowest number when compared by term is preferred. For
4 2 example out of (2+6+7=15) and (3+4+7=14), the first set is
OH correct.
4
NOMENCLATURE OF COMPLEX HYDROCARBONS 6
3 2
The following rules are followed
5 1
(i) Longest chain rule : The longest continuous chain of carbon
atoms is picked up which forms the base name of the 2,3, 5-Trimethylhexane (not 2,4,5-Trimethylhexane)
compound. (viii) The name of a complex radical is considered to begin with
(ii) Numbering : The longest chain is numbered by arabic the first letter of its complete name
numerals beginning with the end nearest a substituent.
i.e. including the numerical affix (di, tri, tetra etc are numerical
(iii) If two or more side chains are in equivalent positions, then affix) for alphabetical order.
the one cited first in the name is assigned the lower number.
12 10 8 6 4 2
11 9 7
8 6 4 2 13 3 1 5 3 1
5
5 2
7 3 1 4
8 6 2 2 4
4
4 3 2 1
5
1 3
7 3 1
12 10 8 6 4 2
4-isopropyl-5-propyl octane 13 11 9 7 5 3 1
(not 5-Isopropyl-4-propyloctane) 6-(1-Methylbutyl)-8-(2-methyl butyl) tridecane
(not 6-(2-Methylbutyl)-8-(1-Methylbutyl) tridecane)
JEEMAIN.GURU
downloaded from jeemain.guru
4 6
5
3-n-propylhexa-1,5-diene methyl cyclo pentane
It contains longest chain of 7C atoms, but both the double
bonds are not included. Hence longest chain of 6C catoms CH3 CH3
is picked up)
(ii) If both, the double and triple bonds, are present the — CH — CH — CH3
compound is regarded as derivative of alkyne. In such cases 1 2 3
the terminal 'e' of -ene is dropped if it is followed by suffix (1, 2-dimethyl propyl) cyclohexane
starting with a,i,o,u,y. For example :
(iii) When there are more acyclic than cyclic carbons the cyclic
6 4 2
part becomes cycloalkyl substituent
7 5 3 1
Hept-4-en-1-yne 2 6 8
(not Hept-4-ene-1-yne) 4
3
(iii) If double and triple bonds are at equidistance from either 1 5 7
side, the preference is given to double bond. 4-Cyclopropyl-3-methyloctane
2 4 6 8 (iv) When acyclic portion contains a multiple bond or a functional
1 3
group, the cyclic portion is treated as substituent.
5 7
oct-1-en-7-yne
(not oct-7-en-1-yne)
O
(iv) If the compound contains two or more double or triple bonds CH = CH – C – CH3
4 3 2 1
a terminal "a" is added to the word root.
2 4 6 2 4 6
4-Cyclohexyl but-3-en-2-one
1 3 5 1 3
5 7
Hexa-2,4-diene Hepta-2,5-diyne
(v) In case when both contain the same functional group, the
(not Hex-2,4-diene) (not Hept-2,5-diyne) base name is decided by the number of c-atoms.
(v) The terminal 'a' is not added to the word root when the OH
complete primary suffix do not start with a numerical affix 1 3
1 2
2 4 6 2 4 6 6
2
5 3 OH
1 3 5 7 1 3
5 7 4
Hepta-1,6-dien-3-yne Hept-3-ene-1,6-diyne 2-(2-Hydroxy propyl) cyclohexan-1-ol
(Note that di, tri, tetra.. are numerical affix) (vi) When both contain the different functional groups, the base
(vi) Side chains containing multiple bonds are named as follows name is decided by principal characteric group
CH2= CH2=CH–CH2– CH3–CH= CH2=CH–
Allyl Ethylidene Vinyl 5 6
3 2 1
HO 4 CH2–CH2–COOH
2 6 2 6 1
8
4 4 2
3
Examples : 1 3 7 5 1 3 5 7 3-(4-Hydroxyclohexyl)propanoic acid
4-Vinylocta-1,7-diene 4-Methylidenhepta-1,6-diene
JEEMAIN.GURU
downloaded from jeemain.guru
364 Chemistry
(vii) When the acylic ring is directly attached to benzene ring, it Numbering of C-atoms in fused rings and bridge rings : The
is named as derivative of benzene numbering starts from bridge head carbon, proceeds along the
longest bridge passing through the second bridge head atom,
proceeds to the next longest bridge and completed along the
shortest path.
Numbering of C-atoms in spiro compounds : The numbering
Cyclohexyl benzene
(viii)Presence of certain groups starts from the carbon atom, next to spiro atom, present in the
Functional gp. Suffix smaller ring giving minimum number to atoms containing functional
–COOH Carboxylic acid groups.
–COOR Alkyl carboxylate (i) Fused Rings : Fused rings share two adjacent carbon atoms
and the bond between them eg. :
–COX Carbonyl halide
–CONH2 Carboxamide
-C º N Carbonitrile
–CHO Carbaldehyde Bicyclo [4.4.0]decane
(ii) Bridged Rings : These share two non adjacent carbon atoms
(the bridgehead carbons) and one or more carbon atoms
between them 7
1
6
2
5 4
3
CONH 2
CHO Bicyclo [2.2.1]heptane
6 1
2
CH 3 More examples of bridge Compounds
2
5 3 1
OH 3
4 6
2-Methylcyclohexane-1-carboxamide 3-hydroxy cyclohexane carbaldehyde
C N COCl 7
4
5
CH 3
2, 6, 6-Trimethyl bicyclo[3.1.1]hept-2-ene
1
7
2-Methyl cyclohexane carbonitrile cyclohexane-1-carbonyl chloride 1
2 4 2
NOMENCLATURE OF POLYCYCLIC ALKANES 6
There are three ways that rings can be joined. 3 4
3 5
Bicyclo [1.1.0] butane Bicyclo[2.2.1]hept-2-ene
(i) Fused rings (iii) Spirocyclic Compounds : The two rings share one carbon
atom 1 5 6
4
(ii) Bridged rings 2 7
3 8
Spiro [4.3] octane
(iii) Spirocyclic compounds
More examples of spiro Compounds
The carbon atoms common to both the rings are called bridge
7 6 1
head atoms. The chain of carbon atoms connecting the bridge 2 Br
5
head atoms is called a bridge.
3
8 9 4
2-Bromo spiro[4.4] nonane
7 6 1
2 CH3
1 5
5 6 8
4 3
2 7 10
9 4
3 9
spiro atom
8 2-methyl spiro[4.5]deca-1, 6-diene
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
366 Chemistry
NOMENCLATURE OF COMPOUNDS Naming of substituted substituents : In this case the subsidiary
containing substituents (not regarded principal functional groups) substituents are named as prefixes. For example
–C º C – – yne Ethyl-3-hydroxybutanoate
–N=N Azo – CH3
6 4 3 2 1
– NO2 Nitro – 9.
5
HO–CH2–C–CH=CBr–CH2–CHO
– NO Nitroso –
– X (Cl, Br, I) Halo (Cl, Br, I)
The terminal e of the primary suffix is replaced by the suffix
name of functional group.
3-Bromo-5-cyclopentyl-6-hydroxy-5-
Alphabetical order for substituents : These should be placed in methylhex-3-en-1-al
alphabetical order.
JEEMAIN.GURU
downloaded from jeemain.guru
Benzene
4-Carbethoxypent-3-en-1-oic acid Methyl benzne Ethyl benzne
O NH2
CH3 CH3
1 CH3
12. Br 4
2
3
5
CH3
O
1, 2-dimethylbenzene 1, 3-dimethylbenzene
2-(Bromomethyl)-3-oxopentanamide (o-xylene) (m-xylene)
13. MeO 2 OEt CH3
3 1
1-ethoxy-3-methoxypropane CH
3
2 4 1, 3-dimethylbenzene CH3
14. 1, 4-dimethylbenzene
1 5
6 (p.xylene)
CH3 H3 C – CH – CH3
2-Ethenyl-3-methylcyclohexa-1, 3-diene
3 OH
4 H3C CH3
2
15. 1, 3, 5-trimethylbenzene 2-propylbenzene
5 1
6 (mesitylene) (cummene)
H – – CH CH = CH2
4-ethylhex-4-en-2-ol
JEEMAIN.GURU
downloaded from jeemain.guru
368 Chemistry
(iii) Aryl groups:
OH OH
CH2– CH OH
OH
1, 2-dihydroxy benzene 1, 3-dihydroxybenzene
(Catechol) (Resorinol)
Phenyl Benzyl Benzal
OH
Phenol 2-methylphenol
(o-cresol) Benzenamine 2-methylbenzenamine
(Aniline) (o-Toluidine)
NH2
CH3 CH3
NH2
OH
JEEMAIN.GURU
downloaded from jeemain.guru
(ix) Aldehydes:
JEEMAIN.GURU
downloaded from jeemain.guru
370 Chemistry
—
—
—
(v) Br OH
CHO CH3
7. Write IUPAC names for 12. Give IUPAC names of
(i) CH3 – CH = C(NO2) CH2CH3 CH3 O
CH3 +
Cl N -
| OH O
(ii) H 2 C = CHCH - CHCH - CHCHMe2 (a) Cl (b)
|
CH(Me)CH2CH3
CH3
HO
CH3
(iii) (c)
C2H5
OH
(iv) (H2C = CH)2 CHCH2CH = CHCH3
8. Write the condensed structural formula of
Multiple Choice Questions
(a) 4-ethyl-3-methyl heptane 13. Correct IUPAC name of
(b) 3, 3-dimethyl octane H3C - CH - CH - CH 3 is _________ .
| |
9. Write the structural formula of C2 H5 C2 H5
(i) o-methoxyethylbenzene
(a) 2 –ethyl-3-methylpentane
(ii) 2,3-dibromo-1-phenylpentane
(b) 3,4-dimethylhexane
(iii) 4-ethyl-1-fluoro-2-nitrobenzene
(c) 2-sec-butylbutane
10. Name the compounds whose line formulae are given below:
(d) 2, 3-dimethylbutane
O NO2 14. Which of the following is the correct IUPAC name?
(a) 3-Ethyl-4, 4-dimethylheptane
(i) (ii) (b) 4,4-Dimethyl-3-ethylheptane
(c) 5-Ethyl-4, 4-dimethylheptane
(d) 4, 4-Bis(methyl)-3-ethylheptane
JEEMAIN.GURU
downloaded from jeemain.guru
CH3 CH 3CH 2 CH 3
C
(a) 1-Chloro-2-nitro-4-methyl benzene CH 3 CH 2 OH
(b) 1-Chloro-4-methyl-2-nitrobenzene (a) 2-ethylbutan-2-ol
(c) 2-Chloro-1-nitro-5-methyl benzene (b) 1-ethyl-1-methylpropan-1-ol
(d) m-Nitro-p-chlorotoluene (c) 3-methyl pentan-3-ol
17. Which of the following compounds has wrong IUPAC name? (d) diethylethanol
(a) CH3–CH2–CH2 –COO–CH2CH3 ® ethyl butanoate 21. The IUPAC name for
JEEMAIN.GURU
downloaded from jeemain.guru
372 Chemistry
1. The kind of valency that exists in CaH2 & C2H2 is 8. The IUPAC name of this compound
(a) electrovalency in CaH2 and covalency in C2H2 CH 3 - C H - CH 2CH 2CH 3 is
(b) electrovalency in both |
CH(CH3 ) 2
(c) covalency in CaH2 and electrovalency in C2H2
(a) 2- isopropylpentane (b) 2, 3 -dimethylhexane
(d) covalency in both
(c) Isononane (d) 2, 4- dimethylhexane
2. The compound which has one isopropyl group is
9. The IUPAC name of the compound
(a) 2, 2, 3, 3 - Tetramethylpentane
CH 3 - CH - CH2- CH 2 - Cl
(b) 2, 2 - Dimethylpentane |
(c) 2, 2, 3- Trimethylpentane CH 3
(d) 2- Methypentane (a) 1-chloro -3- methylbutane
3. Which of the following statements is false for isopentane ? (b) 2- methyl-4- chlorobutane
(a) It has three CH3 groups (c) 2-methyl-4-chlorobutane
(b) It has one CH2 group (d) 1-chloropentane
(c) It has one CH group 10. IUPAC name of the given compound will be
(d) It has a carbon which is not bonded to hydrogen (CH3)2C(CH2CH3)CH2CH(Cl)CH3
4. Which of the following IUPAC names is correct? (a) 5-chloro-3-, 3-dimethylhexane
(a) 2-Methyl-3-ethylpentane (b) 4-chloro-2-ethyl-2-methylpentane
(b) 3-Ethyl-2-methylpentane (c) 2-chloro-4-ethyl-4-methylpentane
(c) 2-Ethyl-3-methylpentane (d) 2-chloro-4, 4- dimethylhexane
(d) 3-Methyl-2-ethylpentane 11. The IUPAC name of (CH3)3 C – CH = CH2 is
5. The correct IUPAC name of the compound with molecular (a) 2 , 2- dimethylbut -3-ene
formula, (CH3)3 C – CH3 is (b) 2, 2- dimethylpent -4-ene
(a) Pentane (c) 3, 3- dimethylbut - 1- ene
(b) 1, 1, 1 -trimethylethane (d) Hex -1-ene
(c) 2, 2- dimethylpropane 12. The IUPAC name of the following
(d) Neopentane CH3C(CH3)2CH2CH=CH2 is
6. The IUPAC name of (a) 2, 2- dimethyl -4- pentene
CH 3 - CH - CH - CH 2 CH 2 - C H - CH 3 (b) 4, 4- dimethyl -1- pentene
| | | (c) 1, 1, 1- trimethyl -3- butene
CH 3 CH 3 CH 3
(d) 4, 4, 4- trimethyl -1- butene
(a) 2, 5, 6- trimethylhexane 13. The IUPAC name of the compound
(b) 2, 3, 6- trimethylheptane
(c) 2, 3, 6- trimethylhexane CH3 – CH – C – CH 2 CH 3
| ||
(d) 2, 5, 6- trimethylheptane CH 3 CH 2
7. The IUPAC name of
(a) 2- ethyl -3- methylbut -1- ene
H C 4H9 (b) 2- isopropylbut -1- ene
| |
CH 3CH 2 - C - C - CH 3 is (c) 2- methyl - 3 ethyl - 3- butene
| | (d) 2- (1- methylethyl) but -1- ene
CH 3 CH3
14. CH3CH2CH2CH(CH=CH2)CH2CH2CH3 is
(a) 3, 4, 4- trimethylheptane (a) 4-ethenylheptane
(b) 3, 4, 4- trimethyloctane (b) 3-n-propyl-1-hexene
(c) 2- butyl -2-methyl-3-ethylbutane (c) 4-ethenylhexane
(d) 2-ethyl-3, 3- dimethylheptane (d) 3-ethenylheptane
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
374 Chemistry
30. The incorrect IUPAC name is 36. The IUPAC name of CH3CH=CHCOOC2H5 is
(a) CH 3 - C - C H - CH 3 (a) Ethyl but-1-enoate (b) Ethyl but-2-enoate
|| | (c) Ethyl prop-2-enoate (d) None of these
O CH3
37. The IUPAC name of the compound
2-methyl-3-butanone
CH 3CH = CHCH 2 C HCH 2 COOH is
(b) CH3 – C H – C H – CH 3 |
| | NH 2
CH3 CH 2 CH 3
(a) 5- amino - 2 - heptenoic acid
2, 3 -dimethylpentane (b) b - amino- d - heptanoic acid
(c) CH3– C º CCH(CH3)2 (c) 5- amino hex - 2- enecarboxylic acid
4-methyl-2-pentyne
(d) 3- amino -5- heptenoic acid
(d) CH3 - CH - CH - CH3 38. Indicate the wrongly named compound
| |
Cl Br (a) CH 3- C H - CH 2 - CH 2 - CHO
3-chloro-2-bromobutane |
CH 3
31. The systematic name of (CH3)2 CH – COOH is
(a) 2- propanoic acid (4-methyl -1- pentanal)
(b) isobutanoic acid (b) CH 3- CH - C º C - COOH
(c) 2- methylpropanoic acid |
CH 3
(d) 2- methylbutanoic acid
32. The IUPAC name of the formula, (4- methyl -2- pentyne -1- oic acid)
JEEMAIN.GURU
downloaded from jeemain.guru
CH3 O CH2OH
| ||
CH 3- C H - C - CH 2 - CH 2 OH is (c) (d) None of these
JEEMAIN.GURU
downloaded from jeemain.guru
376 Chemistry
1. 2-Methyl 2-butene will be represented as [CBSE-PMT 1992] 6. IUPAC name for the compound [CBSE-PMT 1998]
CH 3 Cl CH2CH3
| C=C
(a) CH 3 - CH - CH 2 CH 3 is
H3C I
(b) CH 3 - C = CH - CH 3 (a) trans-3-iodo-4-chloro-3-pentene
|
CH 3 (b) cis-2-chloro-3-iodo-2-pentene
(c) trans-2-chloro-3-iodo-2-pentene
(c) CH 3 - CH 2 - C = CH 2
(d) cis-3-iodo-4-chloro-3-pentene
|
CH 3 7. The correct structure of trans-2 hexenal is
[CBSE-PMT 1999]
(d) CH 3 - CH - CH = CH 2
| CHO
CH 3
(a) (b) CHO
2. The IUPAC name of [CBSE-PMT 1992]
(c) CHO (d)
CHO
CH 3 - CH - CH = C - CHO 8. The incorrect IUPAC name is [CBSE-PMT 2001]
| |
OH CH 3 (a) CH 3 - C - C H - CH 3
|| |
(a) 4-Hydroxy-1-methylpentanal O CH 3
(b) 4-Hydroxy-2-methylpent-2-en-1-al 2-Methyl-3-butanone
(c) 2-Hydroxy-4-methylpent-3-en-5-al
(b) CH 3 - CH - C H - CH 3
(d) 2-Hydroxy-3-methylpent-2-en-5-al | |
3. Which of the following IUPAC names is correct for the CH3 CH 2CH 3
compound? [CBSE-PMT 1994] 2,3-Dimethylpentane
H 3C - C H - CH - CH 2 - CH 3
| | (c) CH 3 C H - C H - CH 3
CH3 CH 2CH3 | |
Cl Br
(a) 2-Methyl-3-ethylpentane 2-Bromo-3-chlorobutane
(b) 3-Ethyl-2-methylpentane
(d) CH 3 - C º CCH (CH 3 ) 2
(c) 2-Ethyl-3-methylpentane
4-Methyl-2-pentyne
(d) 3-Methyl-2-ethylpentane
9. Name of the compound given below is [CBSE-PMT 2003]
4. The first organic compound, synthesized in the laboratory,
was [CBSE-PMT 1995]
CH3
(a) alcohol (b) acetic acid
H3C
(c) urea (d) none of these CH3
5. The IUPAC name of [CBSE-PMT 1996]
H 3C — C H — CH — CH 2 —CH 2— C H — CH 3 is CH3
| | |
CH3 CH3 CH3
(a) 5-ethyl-6-methyloctane
(a) 1, 3-isopropyl-3-methylpropane
(b) 4-ethyl-3-methyloctane
(b) 2, 3, 6-trimethylheptane
(c) 3-methyl-4-ethyloctane
(c) 2, 5, 6-trimethylheptane
(d) 2, 3-diethylheptane
(d) 2, 6, 3-trimethylheptane
JEEMAIN.GURU
downloaded from jeemain.guru
3-Methyl-4-ethyl heptane
(d) COOH
(b) CH3 - CH - CH - CH3
| |
OH CH3
3- Methyl - 2- butanol 14. The structure of isobutyl group in an organic compound is
CH 3
is [CBSE-PMT 2011] (d) CH - CH 2 -
CH 3
(a) 4-Ethyl-3-propyl hex-1-ene 15. Which of the following compounds has wrong IUPAC name?
(b) 3-Ethyl-4-ethenyl heptane [AIEEE 2002]
(c) 3-Ethyl-4-propyl hex-1-ene (a) CH3–CH2–CH2 –COO–CH2CH3 ® ethyl butanoate
(d) 3-(1-ethylpropyl) hex-1-ene
(b) CH3 - CH - CH 2 - CHO ® 3-methyl-butanal
12. The IUPAC name of the following compound is |
CH3
Cl CH2CH3
(c) CH3 - C H - CH - CH3 ® 2-methyl-3-butanol
C C | |
OH CH3
CH3 I
JEEMAIN.GURU
downloaded from jeemain.guru
378 Chemistry
18. The IUPAC name of the compound is 21. The IUPAC name of is
HO
Br
CN
(a) 3-bromo-1-chlorocyclohexene Br
(b) 1-bromo-3-chlorocyclohexene (a) 4-Bromo-3-cyanophenol
(c) 2-bromo-6-chlorocyclohex-1-ene (b) 2-Bromo-5-hydroxybenzonitrile
(d) 6-bromo-2-chlorocyclohexene (c) 2- Cyano-4-hydroxybromobenzene
(d) 6-Bromo-3-hydroxybenzonitrile
JEEMAIN.GURU
downloaded from jeemain.guru
Cl
Cl H
(c) H 2 N H CH 2 CH 3
OEt O
(a) cis – 2 – ethyl – 3 – methyloxirane
(b) trans – 1 – ethyl – 2 – methyl oxycyclopropane
(c) trans – 2 – ethyl – 3 – methyloxirane
(d) Me 2 N (d) trans – 1 – ethyl – 2 – methyl ethane epoxide
OEt
JEEMAIN.GURU
downloaded from jeemain.guru
380 Chemistry
16. The IUPAC name of the following compound (a) 1, 1 – dimethyl – 1 – cyclopentyl methane
(b) 2 – cyclopentyl propane
(c) 1 – (1 – methyl) ethyl cyclopentane
(d) Cumene.
(a) E – 1 – cyclopentyl – 2 – hexene 22. The accepted IUPAC name of the following compound.
(b) E – 2 – cyclohexyl – 2 – hexene
(c) Z – 1 – cyclopentyl – 1 – hexene
(d) Z – 2 – cyclopentyl – 2 – hexene
17. The IUPAC name of the following compounds is
O
N (a) Propanoic anhydride
| (b) Butanoic propanoic anhydride
H O (c) Ethyl butanoate
(a) N – phenyl ethanamide (b) N – phenyl ethanone (d) 4, 6 – dioxo heptane
(c) N – phenyl methanamide (d) None of these 23. The IUPAC name of the compound
18. What is the name of the following compound ?
H COOH
O
||
O O
H CHO
Cl
(a) 4-formyl-3-oxo cyclohexane-1-carboxylic acid
(a) 2 – chlorohexyl ethanoate
(b) 2, 4-dioxo cyclohexanoic acid
(b) ethyl – 2 chloro hexanoate
(c) 2, 4-dioxo heptanoic acid
(c) 1 – chlorohexyl ethanoate
(d) None of these
(d) ethyl – 1 chloro hexanoate
24. The correct IUPAC name of the compound
19. The IUPAC name of the following compound.
HC CH 3 CH 3
||
HO CH 3
O
OH
(a) 2, 6 – dimethyl octa – 2, 6 – dien – 1 – al
(a) 4 – hydroxy – 3 – methyl butanoic acid
(b) 3, 7 – dimethyl hepta – 2, 6 – dien – 1 – al
(b) 1 – hydroxy – 2 – methyl butanoic acid
(c) 3, 7 – dimethyl octa – 2, 6 – dien – 1 – al
(c) 3 – hydroxy – 2 – methyl butanoic acid
(d) 2, 6 – dimethyl – 2, 6 – dien – 8 – al
(d) 3 – (hydroxymethyl) butanoic acid
25. The IUPAC name of the compound
20. What is the IUPAC name of the following compound ?
CONH 2
COOH CHO
Br
JEEMAIN.GURU
downloaded from jeemain.guru
COOH NH 2
(a) o, o’ – diamino – o, o’ – dicarboxy biphenyl (a) Tetraphenyl methane
(b) 6, 6’ – diamino diphenyl – 2, 2’ – dicarboxylic acid (b) 1, 1, 1, 1 – tetra phenyl methane
(c) diamino dicarboxy biphenyl (c) 1, 1, 1, 1 – tetra cyclohexyl methane
(d) None of these (d) Neophenyl
32. The IUPAC name of 38. Which of the following numberings is correct ?
OH FF 1 2 FF 3 2
C A 3 B 1
|| Br Br
5 4 4 5
O
(a) 3 – phenyl prop – 2 – enoic acid F 5 4 FF 5 1
(b) Cinnamic acid C 3 D 2
1 Br Br
(c) 1 – Styrene acid 2 4 3
(d) 3 – Cyclohexyl – 2 – propenoic acid (a) A (b) B (c) C (d) D
JEEMAIN.GURU
downloaded from jeemain.guru
382 Chemistry
CH 3 CH3
CH3 CH3 5 4 3 2 1
| | |
12. (b) CH3 CCH2CH = CH2
CH 3 C - C HCH 2 CH 3 CH 3 C HCH 2 CH 2CH 3
| CH3
CH3 (d )
(c ) 4 3 2
13. (a) CH3 – CH – C – CH2CH3
3. (d) In isopentane, (CH3)2CH CH2 CH3, every carbon is having
hydrogen atom(s). CH3 CH2
1
4. (b) When the sum of locants is same, viz. 2 + 3 = 5, lower
Here numbering should be done in a way that simpler
alkyl group should be given lower numeral number, i.e.,
alkyl group(s) is (are) present on the main chain
here it should be 2-methyl and 3-ethyl and not the reverse.
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
384 Chemistry
EXERCISE 3 1 2 3 4
8. (a) CH3 C CH CH3
CH3
| O CH3
1. (b) 1 CH3 - 2C = 3CH - 4 CH3 3 Methyl-2- butanone
2-Methyl-2-butene 1 2 3
CH3 CH CH CH3
2. (b) 5 CH - 4 CH - 3CH = 2
C - 1CHO 4 5
3 CH3 CH2 CH3
| |
OH CH 3 2,3dimethyl pentane
4-Hydroxy-2-methylpent-2-en-1-al 4 3 2 1
CH3 CH CH CH3
3. (b) 1 CH 3 - 2 CH - 3CH - 4 CH 2 - 5 CH 3 Cl Br
| |
H 3C CH 2 CH 3 2 Bromo 3 chlorobutane
5CH
3-Ethyl-2-methylpentane 3
1 2 3 4
4. (c) The vital force theory suffered first death blow in 1828 CH3 C C CH
when Wohler synthesized the Ist organic compound
urea in the laboratory from inorganic compounds CH3
reported below : 4 - Methyl-2-pentyne
to isomeric charge 9. (b) CH3 CH3 5 7
NH 4 CNO ¾¾ ¾ ¾ ¾ ¾ ¾¾® NH 2 CONH 2 1 3
4
rearrangement leading CH3
Urea 2 6
Later on a further blow to vital force theory was given CH3
by Kolbe (1845) who prepared acetic acid, the first
organic compound, in laboratory from its elements. 4 ethyl - 3 methyl octane
10. (a) Correct IUPAC name of
5. (b) When many substituents are present, the numbering is
done from the end where the sum of locants is the lowest CH 3
|
(lowest sum rule)
CH 3 CH 2 CH 2 - C H - C H - CH 2 CH 3
|
7 6 5 4 3 2 1
CH 2CH 3
C H3 - CH - CH - C H 2 - C H 2 - C H - C H3
| | | is 4-Ethyl-3–methyl heptane
CH3 CH3 CH3
11. (a) The given compound is
2, 5, 6 trimethyl heptane (wrong)
2 1
2 + 5 + 6 = 13 CH = CH2
1 2 3 4 5 6 7
CH3 — CH — CH — CH 2 — CH 2 — CH — CH3 Ch3 — CH2 — CH2 — CH — CH — CH2 — CH3
| | | 3 4
CH3 CH3 CH3 CH2 – CH3
5 6
2 + 3 + 6 = 11
4 ethyl- 3-propyl hex – 1 – ene
2, 3, 6 TriMethyl Heptane (correct)
4 5
Cl CH2 – CH3 12. (a) Cl CH2CH3
6. (c) C C C=C
H3C I 2 3
CH3 I
1
As in this compound the common groups i.e highly
electronegative halogen atoms are on opposite side, Correct IUPAC name of above compound is trans-2-
hence it is a trans isomer. chloro-3-iodo-2-pentene
Thus its name is trans-2-chloro-3-iodo-2-pentene. OH
7. (a) When similar atoms are on opposite side the compound 1
3 2
is in trans-form H3C COOH
13. (a) 4
6
H CHO CH 3
5
C C
IUPAC name of the structure is 3-ethyl-2-hydroxy-4-
C3H7 H methylhex-3-en-5-ynoic acid
JEEMAIN.GURU
downloaded from jeemain.guru
CH 3 EXERCISE 4
14. (d) CH - CH 2 - (iso-butyl group) 1. (b) The compound contains longest chain of 5C - atoms and
CH 3 e of ene is retained as the suffix name starts with constant
2. (d) The compound is an enol containing chain of 5C atoms.
15. (c) The correct name is 3 - methylbutan 2-ol
3. (b) The compound is a derivative of butane
O CH3 4. (b) It contains longest chain of three C atoms having CHO
1 2| | 3| 4
16. (c) CH3 - C - CH - CH3 ; 3- methyl-2-butanone and double bond
5. (d) The compound contains longest chain of 5 C - atoms
having > C = O and - NH2 groups
17. (a) CnH2nO2 is general formula for carboxylic acid
6. (d) The compound contains longest chain of 3 C - atoms and
three -COOH groups and one -OH group attached to it
(latest convention).
18. (a) 1 3
2 7. (b) The compound contains longest chain of 6C atoms and
HO amino group. Hence it is an alkanamine.
IUPAC name – 3, 3-Dimethyl -1 cyclohexanol 8. (c) The compound is derivative of aniline. The positions of
19. (b) The compounds containing two similar assymmetric C- groups are shown by numbering the nuclear C-atoms.
atoms have plane of symmetry and exist in meso from 9. (d) The compound is an ester. Its IUPAC name is derived
from alkyl alkanoate.
10. (a) Select the longest chain of C-atoms which includes both
plane of symmetry the double bonds. Further ethenyl and methyl groups at
C3 and C 4 are on the same side. Hence it is Z-isomer..
11. (a) It contains chain of 4C atoms. Double bond is given
meso 2, 3 dichlorobutane preference over Cl-atom.
12. (b) The compound is a ketone containing longest chain of
Cl 7C-atoms and side chains.
1
6 2 13. (d) The compound is an aldehyde containing longest chain
20. (a)
5 of 6 C-atoms and side chains.
3 Br
4 14. (b) The compound is a derivative of benzaldehyde. Start
3-bromo-1chlorocyclohexene numbering C-atoms of benzene nucleus from C-atom
bearing – CHO group.
CH 3
7 6 5 4| 3 2 1 *
15. (c) The compound is derivative of oxyrane CH * .
2 - CH 2
21. (a) CH3 - CH 2 - CH 2 - C - CH - CH 2 - CH3
| |
CH3 CH 2 O
| *
CH3 The hydrogen atoms attached to C –atom are on the
3- ethyl - 4,4 - dimethylheptane opposite side hence it is trans isomer.
16. (b) When acyclic portion contains a multiple bond or
22. (a) The correct order of priority for the given functional functional group, the cyclic portion is treated as
group is substituent.
O O 17. (a) It is derivative of ethanamide having N-phenyl group.
|| ||
–COOH > –SO3 H > – C - NH 2 > - C - H 18. (b) The compound is an ethyl ester of hexanoic acid.
19. (a) The compound is a derivative of butanoic acid.
23. (a) CH3 20. (b) The compound is a derivative of benzoic acid. The
|
1
positions of substituents attached to benzene nucleus
3 2
H3C- C - CH3 are represented by number of C-atoms and not by ortho,
|
CH3 meta and para.
Neopentane 21. (c) The cyclic portion contains more C-atoms than
or 2, 2- Dimethylpropane acyclic portion. Hence it is derivative of cyclopentane.
22. (b) The compound is anhydride of butanoic and propanoic
24. (b) – CN has highest priority. Further the sum of locants is acid.
7 in (b) and 9 in (d). 23. (a) It is derivative of cyclohexane. The C-atom bearing
– COOH group is to be assigned the number 1.
JEEMAIN.GURU
downloaded from jeemain.guru
386 Chemistry
24. (c) The compound is an aldehyde containing longest chain 32. (a) It is derivative of propanoic acid
of 8 C-atoms. O
25. (a) The compound is an amide containing longest chain of 5 ||
C-atoms – CHO is substituent group. CH = CH - C - OH
3 2 1
26. (d) The compound is derivative of ethane.
3-phenyl prop-2-enoic acid
27. (b) It is spiro compound. The numbering begins with the
33. (b) In such compounds the numbering is done as follows
ring atom next to the spiro atom around the smaller ring
and then to the spiro atom and finally around the large 3'
ring. The total number of C-atoms decides the parent 2 2' '
hydrocarbon. 1 1' 2' 1' '
1 2 CH 3 3' '
7 6 3
1, 1' , 2' , 1' ' tercyclopropane
8
5 2 1 6 7
9 10 4 3
34. (a) 5 8 spiro [4.5] decane
Hence it is 2-methyl spiro[4.5] deca-1-ene. 3 4 10 9
28. (b) When – CHO is treated as side chain, its name is 35. (c) It is an ester of ethanoic acid
carbaldehyde.
O
3 2 1 6 || 2
C H2 - C H - C H2 1 O - C - CH 3
5
| | | 1
Hence CHO CHO CHO is propane – 1, 2, 3 tri 2
4 COOH
carbaldehyde. 3
29. (a) It is derivative of cyclopentanone having 2-carboxy phenyl ethanoate
36. (a) It is an ethyl ester of butanoic acid
O
|| CH 3 O
– C– O – C2 H5 carbethoxy group at 2C. | ||
CH 3 - CH - CH - C - O - C 2H 5
30. (a) It is a bridge compound 4 3 2 1
1 6 1 2
6 O
7 2 3
5 NO 2
5 3 4
4 ethyl-3-methyl-2-(3-nitro) phenyl butanoate
1, 7, 7-trimethyl bicyclo [2. 2. 1] heptan-2-one 37. (c) It is derivative of methane 1, 1, 1, 1-tetracyclohexyl
31. (b) It is biphenyl derivative methane.
38. (d) F *1
NH 2 COOH 5
5' 6' 2 3
Br
2
4' 4 **
1' 1 4 3
3' 2' 6 5 * **
The numbering of C-atom starts from C or C . But
COOH NH 2 *
numbering from C give minimum locant (2) to Br which is
correct.
JEEMAIN.GURU
downloaded from jeemain.guru
12C
Hybridisation & Shapes
of Organic Molecules
HYBRIDISATION
Sigma bonds are the most common bonds in organic chemistry.
All single bonds are sigma (s) bonds and formed by the
C
overlapping between s-s, s-p and p-p (head on) atomic orbitals
present on different atoms. A pi (p) bond results from the overlap
of two p-orbitals that are oriented perpendicular to the axis of the
nuclei. A p bond is not cylindrically symmetrical. A s bond is These hybrid orbitals can overlap with four s atomic orbitals
stronger than p bond due to better overlap. All multiple bonds provided by four hydrogen atoms to form methane molecule.
contain one s bond and others p bond(s).
To have more efficient overlapping and to provide more H
symmetrical structure to the molecule the atomic orbitals on the H
same atom interact to provide hybrid atomic orbitals and the
interaction is known as hybridisation. The hybrid atomic orbitals H 109.5°
have enhanced electron density. C
9Å C
HYBRIDISATION OF CARBON
H 1. 0 H
H
The ground state electronic configuration of carbon is
H
2 2 H
1s , 2s 2p1x 2p1y 2p 0z . The electronic configuration of carbon in
sp3 hybridisation:
H H
If we superimpose one s and three p atomic orbitals we get 4sp3
hybrid orbitals.
3 4 H
s-atomic p-atomic C C
hybrid H
orbital orbital orbital
Each hybrid orbital contains single electron, has 25% s character
and 75% p character. They are directed towards the four corners H H
of a regular tetrahedron with the carbon located in the centre. The
angle between any two sp3 hybrid orbitals is 109º 28' (109.5º). Bonding in Ethane
JEEMAIN.GURU
downloaded from jeemain.guru
388 Chemistry
sp hybridisation:
H H
If we superimpose one s and one p atomic orbitals we get 2sp
hybrid orbitals.
109.5°
1.54Å
9Å C C
1. 0 H 1
H s-atomic orbital p-atomic orbital
H H
sp2 hybridisation: If we superimpose one s and two p atomic 1 2
orbitals we get 3sp2 hybrid orbitals
hybrid orbital
2 Each sp hybrid orbital has 50% s character and 50% p character.
s-atomic orbital p-atomic orbital They are diagonally present with their axis forming an angle of
180º. The unhybridised 2p y and 2p z atomic orbitals are
perpendicular to each other and perpendicular to hybrid orbitals
2 3 also.
hybrid orbital pz
Each sp2 hybrid orbital has 33% s character and 67% p character. • • py
They lie in the same plane with their axis directed towards the • •
sp
corner of an equilateral triangle and are 120º apart from each other.
The unhybridised pz atomic orbital is perpendicular to the plane
of sp2 hybrid orbitals. BONDING IN ACETYLENE
pz
• • • • py
H • • • • H
C
sp
H—C C—H
pz
HYBRIDISATION OF NITROGEN
The ground state electronic configuration of nitrogen is
BONDING IN ETHYLENE
Consider two sp2 hybridised carbon atoms approaching to each 7N = 1s 2 , 2s 2 2p1x 2p1y p1z
other and four hydrogen atoms which provide four s atomic
orbitals One s and three p atomic orbitals superimpose and give 4 sp3 hybrid
orbitals. These are tetrahedrally present.
C C
N
N H
H H H 107°
H
H H H
JEEMAIN.GURU
downloaded from jeemain.guru
H BOND LENGTHS
Some importants bond lengths are as follows
C N
C–C sp3 – sp3 1.54 Å C–O sp3 – O 1.41 Å
sp3 – sp2 1.50 Å sp2 – O 1.34 Å
sp3 – sp 1.46 Å C=O sp2 – O 1.20 Å
H H
sp2 – sp2 1.48 Å sp – O 1.16 Å
Carbon Nitrogen
sp2 – sp 1.43 Å C–N sp3 – N 1.47 Å
H sp – sp 1.38 Å sp2 – N 1.36 Å
p
s C=C sp2 – sp2 1.34 Å C=N sp2 – N 1.28 Å
C N
sp2 – sp 1.31 Å CºN sp – N 1.16 Å
H H sp – sp 1.28 Å
sp hybridisation: when nitrogen is attached to only one atom its CºC sp – sp 1.21 Å
hybridisation is sp. In H - C º N both carbon and nitrogen are in C–H sp3– H 1.11 Å
sp hybridised form
sp2 – H 1.10 Å
• • • •
sp – H 1.08 Å
H • • • •• H—C N BOND ANGLES IN SELECTED MOLECULES
H Cl
Carbon Nitrogen
HYBRIDISATION OF OXYGEN C C
H H Cl Cl
2 2 109.5° 109.5°
The electronic configuration of oxygen is 1s 2s 2p 2x 2p1y 2p1z . H Cl
sp3hybridisation : When oxygen is attached to two atoms the CH3 Cl
hybridisation is sp3.
112° 112°
C C
H CH3 H Cl
106° 112°
H H
.. CH3
O .O.
N
111° H H
O
H H 104.5° H CH3 H 107°
H H H H
sp2 hybridisation: When oxygen is attached to one atom as in 104.5° 118° C C
O
case of aldehydes and ketones e.g. in Formaldehyde carbon and H H 121° H
oxygen, both are in sp2 hybrid form.
Cl Cl 120°
CH3
H
114° C C 120° C O
Cl 123° Cl CH3
C O 127° 121°
CH3 CH3
110° C O 114° C O
Cl 123° CH3HN 125°
H
AROMATICITY AND AROMATIC COMPOUNDS
Carbon Oxygen Aromatic indicates a stable system which undergoes substition
H rather than addition, retaining the closed p-electron system. Many
..
C O such systems contain only six p electrons, but generally they
.. contain (4n+2) p electrons, where n is an integer.
H
JEEMAIN.GURU
downloaded from jeemain.guru
390 Chemistry
In general, higher polyclic aromatic compounds are somewhat
n=1 less stable than benzene.
n = 0 cyclopropenyl cation contains 2p - electrons and is aromatic
H
Benzene Cyclopentadienyl
anion H
+
ANTIAROMATICITY
H The less stability of monocyclic compounds containing (4n)p
electrons than their acyclic analogues is called anti aromaticity.
H For example
Cycloheptatrienyl
cation Cyclobutadiene is less stable than 1,3-Butadiene
(Tropylium cation)
Nonbenzenoid heterocyclic compounds with 6p electrons are Here Resonance is the cause of destabilisation (hence the concept
aromatics of antiaromaticity)
¬¾
®
N O S N
More examples of antiaromatic compounds
Pyridine H
Furan Thiophene Pyrrole
H
The hetero atom contributes to non bonded electrons, to complete –
the sextet.
n=2
Cyclooctatetraene
(8 p electrons) Cycloheptatrienyl anion
Naphthalene Cyclo octatetraenyl (8p electrons)
dianion
H + H –
n=3
JEEMAIN.GURU
downloaded from jeemain.guru
Very Short/ Short Answer Questions 9. Will the following compound be aromatic. Explain.
1. Out of ethylene and acetylene which is more acidic and
why?
2. Write the type of hybridisation involve in CH4, C2H4 and
C2H2.
3. What types of hybridisation are involved with the central
atom of a molecule having following shapes:
(i) planar, (ii) a regular tetrahedral, (iii) an equilateral Multiple Choice Questions
triangle. 10. Butyne-2 contains :
4. State the hybridisation of the carbon labelled (x) and (y) in
(a) sp hybridised carbon atoms only
acetic acid.
(b) sp 3 hybridised carbon atoms only
H O
H— C — C — O —H (c) both sp and sp 2 hybridised carbon atoms
y x
H (d) both sp and sp 3 hybridised carbon atoms
5. How hybridization of ‘C’ atom changes when ethene is 11. The correct order towards bond length is
hydrogenated? (a) C - C < C = C < C º C (b) C º C < C = C < C - C
6. Ethane is stable while ethene is quite reactive, explain why?
(c) C = C < C º C < C - C (d) C = C < C - C < C º C
7. Give hybridisation state of each carbon atom in the following
compounds. 12. The C–H bond length is minimum in the bond formed by
(i) CH2 = C = O (a) sp-s overlapping (as in alkynes)
(ii) CH3CH = CH2 (b) sp2-s overlapping (as in alkenes)
(iii) (CH3)2 CO (c) sp3-s overlapping (as in alkanes)
(iv) CH3CH2– (d) None of these
13. Triple bond of ethyne is made of or Cylindrical shape of an
Long Answer Questions alkyne is due to
8. The ring systems having following characteristics are (a) Three s – bonds
aromatic. (b) Three p – bonds
(i) Planar ring containing conjugated p bonds. (c) Two s and one p – bond
(ii) Complete delocalisation of the p-electrons in ring (d) Two p and one s – bond
system i.e, each atom in the ring has unhybridised p-
14. The hybridization of carbon atom in benzene is:
orbital, and
(iii) Presence of (4n + 2) p-electrons in the ring where n is (a) sp (b) sp2 (c) sp3 (d) dsp2
an integer (n = 0, 1, 2 ...........) [Huckel rule] 15. The conditions for aromaticity is :
Using this information classify the following compounds (a) molecule must have cyclic clouds of delocalised p
as aromatic /non-aromatic. electrons
(b) molecule must contain (4n + 2) p electrons
(c) Both (a) and (b)
N – (d) None of the above
+
(A) (B) (C) 16. Which one of the following has the shortest carbon carbon
bond length ?
(a) Benzene (b) Ethene (c) Ethyne (d) Ethane
17. Shape of methane molecule is
(a) tetrahedral (b) pyramidal
+
(D) (c) octahedral (d) square planar
(E)
JEEMAIN.GURU
downloaded from jeemain.guru
392 Chemistry
18. Which of the following has the shortest C – C bond length? (a) sp3 orbital (b) sp2 orbital
(a) C2H5OH (b) C2H6 (c) sp orbital (d) sp3 and sp respectively
(c) C2H2 (d) C2H4 21. In ethene, the bond angle(s) is/ are
19. The compound 1, 2 - butadiene has (a) 109°28 (b) 120°
(a) only sp hybridized carbon atoms (c) 180° (d) Both (a) and (c)
(b) only sp2 hybridized carbon atoms 22. Electronegativity of carbon atoms depends upon their state
(c) both sp and sp2 hybridized carbon atoms of hybridisation. In which of the following compounds, the
(d) sp, sp2 and sp3 hybridized carbon atoms carbon marked with asterisk is most electronegative?
20. In the following molecule, the two carbon atoms marked by (a) CH3 – CH2 – *CH2 – CH3
asterisk (*) possess the following type of hybridized orbitals (b) CH3 – *CH = CH – CH3
(c) CH3 – CH2 – C º *CH
H3C - C*º C*- CH3
(d) CH3 – CH2 – CH = *CH2
JEEMAIN.GURU
downloaded from jeemain.guru
(a) (b)
(a) (b)
+
+
(c) (d)
+ –
(c) (d) N
30. As the s - character of hybrid orbital increases, the bond
21. The change in the state of hybridization of the asterisked angle
carbon in the following reaction. (a) increases (b) decreases
(c) does not change (d) becomes zero
* H O *
CH3 CN ¾¾¾
2 ® CH CONH
3 2 is 31. Which of the following bonds is strongest ?
(a) sp3 to sp2 (b) sp3 to sp (a) – C – C– (b) > C = C <
(c) sp to sp2 (d) sp2 to sp3
22. Which of the following carbon atoms is most |
(c) - C - C = (d) – C º C –
electronegative? | |
JEEMAIN.GURU
downloaded from jeemain.guru
394 Chemistry
32. sp3-hybridization
leads to which shape of the molecule ? 34. The maximum number of carbon atoms arranged linearly in
(a) Tetrahedral (b) Octahedral the molecule,
(c) Linear (d) Trigonal planar CH3 – C º C – CH = CH2 is
33. The cylindrical shape of alkynes is due to (a) 5 (b) 4
(a) three sigma C – C bonds (c) 3 (d) 2
(b) three p C – C bonds 35. Which of the following is planar in shape ?
(c) two s C – C and p C – C bonds (a) Methane (b) Acetylene
(d) one sigma C – C and two p C – C bonds (c) Benzene (d) Isobutane
1. The Cl – C – Cl angle in 1,1,2,2- tetrachloroethene and (a) CH3C º CCH2 – CH = CHCH = CH2
tetrachloromethane respectively will be about (b) CH3CH2– CH = CHCH = CHC º CH
[CBSE PMT 1988] (c) CH3CH = CHCH2 – C º CCH = CH2
(a) 120° (b) 90° and 109.5° (d) CH3CH = CHCH2 – CH = CH = C º CH.
(c) 109.5° and 90° (d) 120° and 109.5° 8. When the hybridization state of carbon atom changes from
2. Which of the following possesses a sp-carbon in its sp3 to sp2 and finally to sp, the angle between the hybridized
structure? [CBSE PMT 1989] orbitals [CBSE PMT 1993]
(a) CH2 = CCl – CH = CH2 (a) decreases gradually
(b) CCl2 = CCl2 (b) decreases considerably
(c) CH2 = C = CH2 (c) is not affected
(d) CH2 = CH – CH = CH2. (d) increases progressively.
3. Cyclic hydrocarbon ‘A’ has all the carbon and hydrogen
9. The restricted rotation about carbon carbon double bond in
atoms in a single plane. All the carbon carbon bonds have
2-butene is due to [CBSE PMT 1993]
the same length, less than 1.54 Å, but more than 1.34 Å. The
C – C – C bond angle will be [CBSE PMT 1989] (a) Overlap of one s- and sp 2 - hybridized orbitals
(a) 109°28' (b) 100°
(b) Overlap of two sp 2 - hybridized orbitals
(c) 180° (d) 120°
4. An organic compound X (molecular formula C 6 H 7 O 2 N ) (c) Overlap of one p- and one sp 2 - hybridized orbitals
has six carbon atoms in a ring system, two double bonds and (d) Sideways overlap of two p- orbitals.
a nitro group as substituent, X is [CBSE PMT 1990] 10. Huckel's rule states that a monocyclic conjugated compound
(a) Homocyclic but not aromatic will be aromatic if it contains [CBSE PMT 1996]
(b) Aromatic but not homocyclic (a) (4n + 2p) electrons
(c) Homocyclic and aromatic
(b) (4p + 2n) electrons
(d) Heterocyclic and aromatic
(c) 4p electrons
5. The shortest C – C bond distance is found in
(d) (4n + 2)p electrons
(a) Diamond (b) Ethane [CBSE PMT 1991]
11. The structural formula of a compound is CH3 – CH = C = CH2.
(c) Benzene (d) Acetylene
The types of hybridization at the four carbons from left to
6. An sp3 hybrid orbital contains [CBSE PMT 1991]
right are [CBSE PMT 1999]
(a) 1/4 s-character (b) 1/2 s-character
(a) sp , sp , sp , sp (b) sp , sp , sp2, sp2
2 2 2 3 2 3
(c) 1/3 s-character (d) 2/3 s-character.
(c) sp3, sp2, sp, sp2 (b) sp3, sp2, sp2, sp2
7. A straight chain hydrocarbon has the molecular formula
C8H10. The hybridization of the carbon atoms from one end 12. The correct order regarding the electronegativity of hybrid
of the chain to the other are respectively sp3, sp2, sp2, sp3, orbitals of carbon is [CBSE PMT 2006]
sp2, sp2, sp and sp. The structural formula of the hydrocarbon (a) sp > sp2 > sp3 (b) sp < sp2 > sp3
would be : [CBSE PMT 1991] (c) sp < sp2 < sp3 (d) sp > sp2 < sp3
JEEMAIN.GURU
downloaded from jeemain.guru
CH3 CH3 17. Which one of the following does not have sp2 hybridized
| | carbon ? [AIEEE 2004]
CH3 C CH = CH CH C º CH (a) Acetonitrile (b) Acetic acid
7 6| 5 4 3 2 1
CH3 (c) Acetone (d) Acetamide
18. In allene (C3H4), the type(s) of hybridisation of the carbon
is in the following sequence: atoms is (are) : [IIT-JEE 2012]
(a) sp3, sp2, sp2 and sp (b) sp, sp2, sp2 and sp3 (a) sp and sp3 (b) sp and sp2
(c) sp, sp2, sp3 and sp2 (d) sp, sp3, sp2 and sp3 (c) only sp3 (d) sp2 and sp3
1. The bond between carbon atom (1) and carbon atom (2) in 6. Allyl isocyanide has
1 2 (a) 9 s and 4 p - bonds
compound N º C - C H = CH 2 involves the hybridisation (b) 8 s and 5 p - bonds
(a) sp2 and sp2 respectively (a) sp3 and sp respectively (c) 9 s , 3 p and 2 non- bonded electrons
(c) sp and sp2 respectively (d) sp and sp respectively (d) 8 s , 3 p and 4 non - bonded electrons
x 7. During elimination reactions, the hybrid state of carbon
2. The compound in which C uses its sp3 - hybrid orbitals for atoms involved change as shown below:
bond formation is (a) sp3 to sp2 nature
X X
(a) HCOOH (b) (H2 N)2 CO (b) sp3 to sp nature
(c) No change in hybridised state
X X (d) Either (a) or (b)
(c) (CH 3 )3COH (d) CH 3C HO
8. In the dehydration reaction,
3. Of the following compounds which will have a zero dipole
P O
5 ® CH C º N ,
moment CH 3CONH 2 ¾¾
2¾
3
(a) 1, 1 - dichloroethylene the hybridisation state of carbon changes from
(b) Trans -1, 2 - dichloroethylene (a) sp3 to sp2 (b) sp to sp
(c) Cis - 1 , 2 - dichloroethylene (c) sp2 to sp (d) sp to sp3
(d) None of these ·
4. The number of s - and p - bonds in but- 1 - ene - 3 - yne are 9. Unpaired electron in CH3 occupies
(a) 5s - and 5p - (b) 7s - and 3p - (a) sp - hybrid orbital (b) sp3 - hybrid orbital
(c) p - orbital (d) sp2 - hybrid orbital
(c) 8s - and 2p - (d) 8s - and 4p - 10. The hybridisation of carbon atom in C - C single bond of
5. The species which use sp2 - hybrid orbitals in its bonding H - C º C - CH = CH 2 is
(a) PH 3 (b) NH 3 (a) sp3 - sp3 (b) sp2 - sp2
(c) CH 3+ (d) CH 4 (c) sp - sp2 (d) sp3 - sp
JEEMAIN.GURU
downloaded from jeemain.guru
396 Chemistry
11. Which of the following represents the given mode of 15. Which of the following species would be expected to exhibit
hybridisation sp2 – sp2 – sp – sp from left to right? aromatic character ?
(a) H 2 C = CH – C º CH . –. +
(b) HC º C – C º CH
(c) H 2 C = C = C = CH 2 (i) (ii)
CH2
(d) H C . –. +
2
12. The structure of H2C = C = CH2 is
(a) linear (iii) (iv)
(b) planar
(c) non-planar (a) (i) and (iv) (b) (ii) and (iv)
(d) has several resonance structures (c) (i) and (iii) (d) (ii) and (iii)
13. Aromatic character of benzene is proved by 16. Which among the following is aromatic ?
(a) resonance theory (b) aromatic sextet theory 2– –
(c) orbital theory (d) All of these
14. Which of the following will show aromatic behaviour ?
I II III IV V
(a) I (b) II and V
(a) (b) (c) III (d) IV
17. Which of the following is not aromatic ?
+ (a) Benzene
(b) Cyclooctatetraenyl dianion
(c) Tropylium ion
(c) (d) (d) Cyclopentadienyl cation
EXERCISE 1 EXERCISE 2
1. Acetylene, due to greater electronegativity of the
1º
sp–hybridized carbon. CH3
1º 2º 3º 4º 2º 2º 1º
2. CH4 = sp3 1. (c) CH – CH – CH – C – CH – CH – CH ;
3 2 2 2 3
C2H4 = sp2 CH3 CH3
1º 1º
C2H2 = sp
Thus there are five 1º carbon atoms.
3. (i) sp2, (ii) sp3, (iii) sp2.
4. The carbon atom x is sp2 and carbon atom y is sp3 hybridised. 1º 1º
CH3 CH3
5. Ethene (C2 H 4 ) has sp 2 hybridized carbon atoms. On 1º 4º 2º 1º
2. (b) CH3 – CH – C – CH2 – CH3 ;
hydrogenation, it changes to ethane (C2H6) in which carbon 3º
atoms are sp3 hybridized. Cl
10. (d) 11. (b) 12. (a) 13. (d) 14. (b) 15. (c) Thus all the four types of carbon atoms are present in
16. (c) 17. (a) 18. (c) 19. (d) 20. (c) 21. (b) this compound.
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
398 Chemistry
10. (d) Huckel’s rule states that for aromaticity 6. (c) Allyl isocyanide has the structure
there must be (4n + 2) p electron present in compound ®
H 2 C = CH - CH 2 - N = C
where n is an integer it has 9 s and 3p bonds along with 2 non- bonded
sp3 sp 2 sp sp 2 electrons
11. (c) CH - CH = C = CH
3 2 7. (d) CH3 - CHX 2 ® CH 2 = CHX ® CH º CH
12. (a) Among the three given hybrid orbitals, sp hybrid orbital sp3 sp2 sp
is most electronegative. Contribution of s in sp hybrid
orbital is maximum (50%) so this orbital is closer to O
||
nucleus. Naturally it will have greater tendency to pull 8. (c) CH 3 - C - NH 2 ® CH 3 - C º N
electron towards it. Hence it becomes more
electronegative and sp3 becomes least electronegative sp 2 sp
•
as it have only 25% S character. 9. (b) CH3 is sp3 hybridised and unpaired electron is present
13. (b) C – 1 is sp hybridized (C º C) in sp3 hybridised orbital
C – 3 is sp3 hybridized (C– C) 10. (c) Count s and p bonds to get answer
C – 5 is sp2 hybridized (C = C) sp 2 sp 2 sp sp
Thus the correct sequence is sp, sp3, sp2. H 2C = CH - C º CH
11. (a) ¾¾ ¾ ¾ ¾ ¾ ¾ ¾®
CH3 CH3 from left to right
3|
sp sp sp |
2 sp 3
14. (d) CH 3 C CH = CH CH — C º C H
12. (c) The hydrogen atoms on terminal C-atoms lie in
7 6| 5 4 3 2 1 perpendicular planes and hence the molecule as a whole
CH3 is non-planar. H2C = C = CH2
15. (d) Presence of 6p orbitals, each containing one unpaired 13. (d)
electron, in a six membered cyclic structure is in
accordance with Huckel rule of aromaticity.
16. (b) In molecules (a), (c) and (d), the carbon atom has a 14. (b)
multiple bond, only (b) has sp3 hybridization.
O Non-aromatic
sp3 || sp3 (unconjugated 6p electrons)
17. (a) H3C - C - CH3
sp 2
Acetone
O O
sp3 || sp3 sp sp3 ||
; CH3 - C - OH ; CH3 - C º N ; C H 3 - C - NH 2
2
sp 2
sp
Aromatic Alicyclic
Acetic acid Acetonitrile Acetamide (conjugated 6p electrons)
sp 2 sp sp 2 +
18. (b) Allene (C3H4) is H 2 C = C = CH 2
EXERCISE 4
1. (c) The C1 forms 2s bonds and 2p - bonds (sp-hybridisation) Antiaromatic
(conjugated 4p electrons)
and C2 forms 3s bonds and 1p bond (sp2 hybridisation)
x 15. (d) (ii) and (iii) have delocalized six p electrons and hence
2. (c) See the number of s bonds formed by C in each case. In
x x x x these are aromatic; (i) has 8 conjugated p electrons, while
HCOOH , (H 2 N)2CO and CH3C HO, C forms 3s (iv) has 4 conjugated p electrons.
bonds and 1 p bond, hybridisation is sp 2 . In 16. (a) Only structure I has 8 + 2 = 10p electrons, hence it is
x x aromatic; II has 4, III has 8, IV has 9 and V has 4 electrons,
(CH3 )3C OH , C forms 4s bonds, hence hybridisation thus II to V are not aromatic.
is sp3 17. (d) No. of delocalized p electrons in benzene (a),
s- cyclooctatetraenyl dianion (b), and tropylium ion (c) are
Cl H
3. (b) C= C s- has zero dipole moment 6, 10 and 6 respectively. Further all the three species are
H Cl cyclic, hence all of these are aromatic. Cyclopentadienyl
cation (d) has 4 p electrons, hence it is not aromatic but
4. (b) H2C = CH- C º CH has 7s and 3p actually it is antiaromatic.
+
5. (c) CH3 is sp2 hybridised
JEEMAIN.GURU
downloaded from jeemain.guru
12D
General Organic
(Basic Concepts)
ELECTRONEGATIVITY Hence transmission can be ignored after the second C-atom. An
A covalent bond, where the electrons are shared equally is called atom or group which attracts electrons more strongly than
a non-polar bond (eg H–H) and an unequal sharing of the pair of hydrogen is said to have a negative inductive effect (–I). An atom
bonding electrons results in a polar bond. The unequal sharing of or group which attracts electrons less strongly than hydrogen is
electrons is due to the ability of an atom to attract electrons said to have a positive inductive effect (+I).
towards itself which is known as Electronegativity. + +
Elements with higher electronegativity values have greater N R 3 > N H 3 > NO 2 > CN > COOH > F > Cl > Br > I
attraction for bonding electrons.
> OAr > OR > OH > C º CR > Ar > H
H
2.2 ¬
¾¾ Increasing – I effect (Electrons attracting )
Li Be B C N O F
1.0 1.6 1.8 2.5 3.0 3.4 4.0 O - > COO - > CR 3 > CHR 2 > CH 2 R > CH 3 > D > H
Na Mg Al Si P S Cl
0.9 1.3 1.6 1.9 2.2 2.6 3.2 ¬
¾¾ Increasing + I effect (electrons repelling)
Br Inductive effect does not change the covalency. The more the
3.0 inductive effect between a bond, the more is the ionic character of
I the bond.
2.7 Applications :
Electronegativity increases from left to right and decreases from (I) Acid character of Acids : Formic acid is stronger than acetic
top to bottom. acid.
INDUCTIVE EFFECT (I)
O d+ O
The displacement of shared pair of electrons towards the more H–C CH3 C d–
electronegative atom in a molecule is called inductive effect. It is O–H O–H
a permanent effect e.g. Formic acid Acetic acid
d+ d- The oxygen atom in acetic acid holds the hydrogen atom
H ® Cl more tightly after acquiring negative charge due to +I effect
• It develops polarity in a bond or molecule. of methyl group. Hence it is less ionised
• It is transmitted along a chain of atoms but the intensity Acid character of halogens substituted acids. Chloro
goes on decreasing with the increase in the size of chain. For substituted acetic acids follow the following order for acid
example,
character.
d+
C ® C ®® C ®®® X d -
JEEMAIN.GURU
downloaded from jeemain.guru
400 Chemistry
(II) Reactivity of Alkyl halides. It follows the following order
d–
Cl R R
O
d– –
Cl C C O H R C Cl R C Cl
d–
Cl R H
3° 2°
Trichloro acetic acid
H H
d– R C Cl H C Cl
Cl
O
d– – H H
Cl C C O H 1°
H R .N. H R N:
.. H
Monochloro acetic acid Acetic acid
¬
¾¾ Increasing acid character 2ºamine 1ºamine
JEEMAIN.GURU
downloaded from jeemain.guru
·
The attack of Br on terminal carbon atom (see step III) results in
..
the formation of more stable secondary free radical. This is the
reason that addition takes place anti to markownikoff's rule. HCl ..
•
and HI do not show peroxide effect. HCl does not give Cl atoms
and HI gives molecular I2. ..
RESONANCE :O: :O: :O: :O: :O:
Representation of certain molecules by various electronic ..
configurations is known as Resonance. Electronic configurations
differ only in location of electrons, the atoms must stay in the
same conditions. e.g.
JEEMAIN.GURU
downloaded from jeemain.guru
402 Chemistry
(a) NO 3- ion
Due to resonance the unshared pair of electrons present on
nitrogen atom is delocalised within benzene nucleus and not
available for protonation (to accept H+). Hence basic
character is suppressed.
III. Stability of cations : Methoxy methyl cation is more stable
by 76 kcal/mole than methyl Cation.
4
H H B.O. = = 1.33
.. | Å | 3
CH 3 - O
. . - C- H ¬¾® CH 3 - O
. . = C- H
Å
(b) CO3- - ion
More stable (every atom has octet)
JEEMAIN.GURU
downloaded from jeemain.guru
ER = E0 – EC
ER = Resonance energy, E0 = Observed heat of formation (II) Extra stability : Each C-atom in 1, 3-butadiene is sp2
and EC = Calculated heat of formation of the most stable of hybridised and contains one pz atomic orbital parallel to each
the resonating structures. other and perpendicular to the plane of hybrid atomic orbitals.
In case of unsaturated compunds, Resonance energy is the By sidewise overlapping these pz atomic orbitals form a
difference between a measured and calculated heat of delocalised p molecular orbital which provides the extra
hydrogenation e.g., stability to the molecule.
Benzene Cyclohexane
(III) Bond length : Conjugation affects the bond length. The C2 –
C3 bond length in 1,3-butadiene is 1.47 Å and C1 – C2 bond
Calculated value of heat of hydrogenation of benzene length is 1.35Å due to conjugation.
= 28.6 × 3 = 85.8 kcal/mole, RE = 36.0 kcal / mole. (IV) Heat of hydrogenation :
The greater the RE, the more is the stability. Calculated heat of hydrogenation of 1,3 butadiene
MESOMERIC EFFECT (ME) : = 28.6 × 2 = 57.2 kcal.
It is a permanent effect and similar to electromeric effect. Like Observed heat of hydrogenation of 1,3-butadiene
Inductive effect it may be +ME or –ME. = 53.7 kcal.
+ME atoms or groups donate electrons to the double bond or R.E. = 57.2 – 53.7 = 3.5 kcal/mole
conjugated system e.g. –Cl, –Br, –I, NH2, –NHR, –NR2, –OH, – Thus due to conjugation 1,3-butadiene is stabilised by 3.5
OR, –SH, –SR etc. kcal/mol.
.. – + HYPERCONJUGATION :
CH2 = CH – Cl:
.. CH2 – CH = Cl
. .:
Introduced by Baker and Nathan (1935). The electron release by
–ME atoms or groups withdraw electrons eg. –NO2, CN, COOH, C–H bond by the effect similar to electromeric effect is known as
CHO, HSO3. hyperconjugation. It is a permanent effect.
Å ..
CH 2 = CH - C º N ¾
¾® C H 2 - CH = C = N
.. H
| H+ ..
- C - C = C- ¬¾® - C = C - C-
CONJUGATION : | | | | |
The compounds containing alternate single and double bonds (I) (II)
Hyperconjugated forms
are known as conjugated compounds. Such compounds exhibit
certain abnormal properties due to interaction between single and Since there is no apparent bond between C and H + , the
double bonds, known as conjugation hyperconjugation is also known as No bond Resonance. The
(I) Abnormal addition reactions : Addition of HBr to 1,3- magnitude of inductive effect and hyperconjugation follows the
butadiene. order.
–CH , - C H , - CH (CH ) , - C ( CH )
Increasing Hyperconju gation ¬¾ ¾3 ¾ ¾
2¾5 ¾¾ ¾¾
3 2¾ ¾ ¾ ¾
3¾
3®
H + / Br -
CH 2 = CH - CH = CH 2 ¾¾ ¾¾®
Electrophilic Increasing Inductive effect
+
attack of H
JEEMAIN.GURU
downloaded from jeemain.guru
404 Chemistry
Effects of hyperconjugation : Types of reagents :
(I) Heat of hydrogenation of Substituted Olefins : (I) Electrophilic reagents : They have high affinity for electrons
+ + + + + + ..
The greater the number of H.C. forms the more is the stability. H + , H 3O + , N O 2 , H S O 3 , X (Cl, Br, I), R + , R C O, NO, - N º N
Compound Heat of hydrogenation They may be neutral in nature also AlCl3, BF3, ZnCl2, FeCl3,
CH2 = CH2 Ethylene 32.8 kcal/mol SnCl4 etc.
CH3–CH = CH2 Propylene 30.1 kcal/mol (II) Nucleophilic reagents : Electron rich species and have
(Due to H.C. forms) affinity towards nucleus (which is positively charged).
JEEMAIN.GURU
downloaded from jeemain.guru
.. ..
CH 2 = CH - C H 2 ¬¾® C H 2 - CH = CH 2
Benzyl Carbanion
+
CH2 CH2
:CH2 CH2 CH2
:
The order of stability of different carbonium ions
+ + +
(C 6 H 5 ) 3 C > (C 6 H 5 ) 2 C H > (C 6 H 5 ) C H 2 >
+ + + + + CH2 :CH2
CH 2 = CH . CH 2 > R 3 C > R 2 CH > R CH 2 > C H 3
:
JEEMAIN.GURU
downloaded from jeemain.guru
406 Chemistry
CH2 CH2
Multiplicity is A = 2 × 1 + 1 = 3
æ 1 1 ö
ç S = + = 1, Two unpaired electrons have parallel spin ÷
è 2 2 ø
Order of stability of various free radicals
Triplet is more stable than singlet.
g g g g g g g g
(C6 H5 )3 C > (C6 H 5 ) 2 C H > C6 H 5 CH 2 > CH 2 = CH - CH 2 > (CH 3 )3 C > (CH 3 ) 2 CH
. . > CH 3 CH 2 > CH 3
Nitrenes : R - N
. . Nitrenes are nitrogen analogs of carbenes,
g g g g g g
C6 H5 CH 2 > CH 2 = CH - CH 2 > (CH3 )3 C > (CH3 ) 2 CH > CH3 CH 2 > CH 3
nitrogen is sp2 hybridised.
¬
¾¾ Stability
.. .. ..
D or hv
Generation R - N
..- N º N
. . ¾¾ ¾¾® R - N
. . + N2
CARBENES C : These are uncharged reactive intermediates
Azide
that contain a divalent carbon atom which is sp2 hybridised. There
is a perpendicular vacant p-orbital. Structure singlet :
Generation :
2pz
U.V.
(I) CH 2 N 2 ¾¾¾® : CH 2 + N 2
Diazomethane Carbene
R R
N OR N N
U.V.
(II) CH 2 = C = O ¾¾¾® : CH 2 + CO
Ketene
OH - Multiplicity A = 2s + 1 = 2 × 0 + 1 = 1
(III) CHCl3 ¾¾¾® : CCl 2 + HCl
Chloroform Dichloro carbene
Singlet carbenes :
R
2pz Triplet : N OR N
C Or C
Multiplicity A = 2s + 1 = 2 × 1 + 1 = 3
Arynes : The derivatives of benzyne are called arynes :
°
Z
H H
C Or C Benzyne Aryne
H H
Generation :
H
NH2 –
+ NH3 + Cl
æ 1 1 ö
Multiplicity is A = 2s + 1 = 2 × 0 + 1 = 1 çs = + 2 - 2 = 0÷ Cl
è ø
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
408 Chemistry
(b) Mesomeric effect (M) (b) Mesomeric effect (M)
:O – H O–H O–H
C N C N C N
+
O–H O–H :O – H
C N C N
+M
+ +
activation –M
deactivation
Ortho and para positions become the points of high The o,p-positions become the points of low electron
electron density as + M > > – I. The electrophilic reagent density, therefore the electrophilic reagent will attack at
will attack at o- and p- positions. Hence OH gp. is o, p- the m position. Hence CN is meta directing in nature
directing in nature with activation of benzene nucleus.
with deactivation of benzene nucleus.
.. .. .. ..
Other examples are - NH 2 , - NHR, - NR2 , - OR Other examples are : - NO 2 , COOH , HSO 3 , CHO
..
(IV) Directive influence of –Cl atom :
(II) Directive influence of –CH3 group :
(a) Inductive effect (I)
(a) Inductive effect (I) ..
:Cl:
CH3
– I deactivation
+ I activation
..
:
.. .. .. ..
:Cl + :Cl :Cl:
H H +M
H–CH H–C–H activation
..
+ HC
activation By mesomeric effect the o,p positions become the points
of high electron density. Further –I > +M, hence Cl is
The o, p-positions become the points of high electron o, p directing in nature with deactivation of benzene
density. The electrophilic reagent will attack at o- and p- nucleus.
positions. Hence methyl group is o,p-directing in nature Other examples are : –F, Br, I
with activation of benzene nucleus.
EASE OF ELECTROPHILIC SUBSTITUTION OF
Other examples are : -C 2 H 5 , - C3 H 7 , - C 4 H 9 etc. BENZENE AND ITS DERIVATIVES :
(III) Directive influence of –CN group : 1. Strongly activating (o, p directing) :
(a) Inductive effect (I) .. .. ..
CN
- N H 2 , - NHR, - N R 2 , - O
..
H
2. Moderately activating (o, p directing) :
– I deactivation
.. .. ..
-O
..
CH 3 , - O C H , -N
.. 2 5 ..
HCOCH3
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
410 Chemistry
g
HS– , BF3, ROH
g g
(i) C6H5 CHCH3 , C6H5 C HCH = CH2, C6H5CH2CH 2 , Multiple Choice Questions
g
C6H5 C(CH 3) 2 in order of increasing stability.. 16. Select the most stable carbocation from amongst the
following
(ii) CH3CH2+, C6H5CH2+, (CH3)3C+, CH2 = CHCH2+ in
order of decreasing stability. +
(a)
(iii) HC º C–, CH2 = CH–, CH3CH2–, CH3–, (CH3)2CH–,
C6H5CH2– in order of increasing stability. (b)
5. What are carbocations (carbonium ion)? Discuss their types. +
6. What are free radicals ? Discuss their types.
7. How does (i) an electron withdrawing group (EWG) and (ii)
an electron donating group (EDG) influence the acid strength (c) +
of carboxylic acid?
8. Which of the following species behaves as (i) a nucleophile,
(ii) an electrophile, (iii) both, or (iv) neither? (d) +
....I ..– , H N, BeCl , NO+ , CH C º N :,
.. 3 2 2 3 17. What is the correct order of decreasing stability of the
... following cations ?
H , H C = C., CH
2 2 4 Å
9. What are carboanions? Discuss their types. I. CH3 — CH— CH3
10. The structure of triphenylmethyl cation is given below. This
Å
is very stable and some of its salts can be stored for months. II. CH3 — CH— OCH3
Explain the cause of high stability of this cation.
Å
III. CH3 — CH— CH 2 — OCH3
(a) II > I > III (b) II > III > I
C (c) III > I > II (d) I > II > III
18. The order of decreasing stability of the carbanions
(CH3 )3 C - (I) ; (CH3 ) 2 CH - (II) ; CH3CH -2 (III);
11. Identify the most stable species in the following set of ions C 6 H 5 CH -2 ( IV ) is
giving reasons: (a) I > II > III > IV (b) IV > III > II > I
+ + + + (c) IV > I > II > III (d) I > II > IV > III
(i) CH 3 , CH 2 Br , CH Br2 , CBr3 19. The most stable free radical among the following is
– – – – · ·
(ii) CH 3 , CH 2Cl , CHCl2 , CCl3 (a) C6 H 5 CH 2 CH 2 (b) C 6 H 5 CHCH 3
JEEMAIN.GURU
downloaded from jeemain.guru
1. Which of the following is correct regarding the – I effect of 8. Select the most stable carbocation from amongst the following
the substituents?
+
(a) – NR2 < – OR < – F (b) – NR2 > – OR < – F (a)
(c) – NR2 < – OR > – F (d) – NR2 > – OR > – F
2. Polarization of electrons in acrolein may be written as (b)
d- d+ d- d+ +
(a) CH 2 = CH - CH = O (b) CH 2 = CH - CH = O
d- d- d+ d-
(c) CH 2 = CH- CH = O (d) CH 2 = CH - CH = O (c) +
3. Heterolytic fission of a covalent bond in organic molecules
gives
(a) free radicals (b) cations and anions
(c) only cations (d) only anions (d) +
4. In which of the following homolytic bond fission takes place ?
(a) Alkaline hydrolysis of ethyl chloride 9. The most stable carbonium ion among the following is
(b) Addition of HBr to double bond
(c) Photochlorination of methane + +
(d) Nitration of benzene (a) C6 H5 CHC6 H5 (b) C6 H5CH 2
5. Homolytic fission of C–C bond in ethane gives an
+ +
intermediate in which carbon is (c) CH3 CH 2 (d) C6 H5CH2CH 2
(a) sp3-hybridised (b) sp2-hybridised
(c) sp-hybridised (d) sp2d-hybridised 10. Which of the following is most stable?
6. Among the following, the true property about (a) Ph3C+ (b) Ph2CH+
CH3 (c) PhCH2+ (d) Tropylium cation
+
C – CH3 is 11. Consider the following carbocations
CH3 + +
I. C6 H5 CH 2 II. C6 H5 CH 2CH 2
(a) it is non-planar
(b) its C+ is sp2-hybridized
+ +
(c) an electrophile can attack on its C+ III. C6 H5CHCH3 IV. C6 H5C(CH3 )2
(d) it does not undergo hydrolysis
7. Which of the following is the most stable carbocation The correct sequence for the stability of these carbocations
(carbonium ion)? is
+
(a) CH 3CH 2 + (b) (CH ) CH (a) II < I < III < IV (b) II < III < I < IV
3 2
+ +
(c) III < I < II < IV (d) IV < III < I < II
(c) (CH 3 )3 C (d) C6 H5CH 2
JEEMAIN.GURU
downloaded from jeemain.guru
412 Chemistry
12. The most stable carbanion among the following is 22. Which of the following has the highest nucleophilicity?
(a) F - (b) OH -
CH2 – CH2– CH2–
(c) CH 3- (d) NH -2
23. The correct nucleophilicity order is
(a) (b)
(a) CH 3- < NH -2 < HO - < F -
(b) CH 3- ~
- NH -2 > HO - ~- F-
CH2– CH2– (c) CH 3- > NH -2 > HO - > F -
(d) NH -2 > F - > HO - > CH 3-
24. What is the decreasing order of strength of the bases
(c) (d)
OH - , NH -2 , HC º C - and CH 3CH -2 ?
OCH3 NO2 (a) CH 3 CH -2 > NH -2 > HC º C - > OH -
13. The order of decreasing stability of the carbanions (b) HC º C - > CH 3CH -2 > NH -2 > OH -
(CH 3 )3C - (I) ; (CH 3 ) 2 CH - (II); CH 3CH 2- (III); (c) OH - > NH 2- > HC º C - > CH 3CH -2
(a) I > II > III > IV (b) IV > III > II > I 25. Which is the correct symbol relating the two Kekule
structures of benzene ?
(c) IV > I > II > III (d) I > II > IV > III
14. The most stable free radical among the following is (a) ®¬ (b) ®
(c) º (d) «
· ·
(a) C 6 H 5 CH 2CH 2 (b) C6 H 5 CHCH 3 26. Point out the incorrect statement about resonance?
(a) Resonance structures should have equal energy
· ·
(c) CH 3CH 2 (d) CH 3CHCH 3 (b) In resonating structures, the constituent atoms must be
in the same position
15. Intermediate involved in Reimer-Tiemann reaction is (c) In resonating structures, there should not be same
(a) carbocation (b) carbanion number of electron pairs
(c) carbene (d) free radical (d) Resonating structures should differ only in the location
16. For the reaction of phenol with CHCl3 in presence of KOH, of electrons around the constituent atoms
the electrophile is 27.
-
: CH 2 - C - CH3 and CH 2 = C - CH 3 are
(a) +
CHCl 2 (b) : CCl2 || |
O. .: :O -
. .:
·
(c) CHCl (d) CCl4 (a) resonating structures (b) tautomers
2
17. In the mechanism of Hofmann reaction which intermediate (c) geometrical isomers (d) optical isomers
rearranges to alkyl isocyanate? 28. The most unlikely representation of resonance structures of
(a) Bromamide (b) Nitrene p-nitrophenoxide ion is
(c) Nitroso (d) Amide –O
+ O –O O–
18. Which of the following is an electrophile? +
N N
(a) H2O (b) NH3
(c) AlCl3 (d) C2H5NH2
19. Which of the following is not a nucleophile? (a) (b)
(a) CN– (b) OH–
(c) NH3 (d) BF3 O– O
20. Which of the following is not a nucleophile?
(a) H2O (b) CH3OH –O
O + O O
(c) H2 (d) NH3 +
N N
21. Which of the following behaves both as a nucleophile and
as an electrophile ?
(c) (d)
(a) CH 3C º N (b) CH 3OH
–
(c) CH 2 = CHCH 3 (d) CH 3 NH 2 O– O
JEEMAIN.GURU
downloaded from jeemain.guru
1. For (i) I–, (ii) Cl–, (iii) Br–, the increasing order of nucleophilicity 4. Base strength of : [CBSE-PMT 2008]
would be [CBSE-PMT 2007] (A) H 3CCH 2 ,– (B) H 2C = CH and
(a) Cl– < Br– < I– (b) I– < Cl– < Br– (C) H - C º C
(c) Br– < Cl– < I– (d) I– < Br– < Cl– is in the order of :
2. The order of decreasing reactivity towards an electrophilic (a) (B) > (A) > (C) (b) (C) > (B) > (A)
reagent, for the following would be [CBSE-PMT 2007]
(c) (A) > (C) > (B) (d) (A) > (B) > (C)
(i) benzene (ii) toluene 5. The stability of carbanions in the following :
(iii) chlorobenzene (iv) phenol
(a) (ii) > (iv) > (i) > (iii) (b) (iv) > (iii) > (ii) > (i) (I) RC = C (II)
(c) (iv) > (ii) > (i) > (iii) (d) (i) > (ii) > (iii) > (iv)
(III) R 2C = CH (IV) R 3C - CH 2
3. Which one of the following is most reactive towards
electrophilic attack ? [CBSE-PMT 2008] is in the order of : [CBSE-PMT 2008]
CH2OH (a) (I) > (II) > (III) > (IV) (b) (II) > (III) > (IV) > (I)
(a) (b) (c) (IV) > (II) > (III) > (I) (d) (I) > (III) > (II) > (IV)
6. Cyclohexanol (I), acetic acid (II), 2, 4, 6-trinitrophenol (III)
Cl and phenol (IV) are given. In these the order of decreasing
OH acidic character will be : [CBSE-PMT 2010]
(a) III > II > IV > I (b) II > III > I > IV
(c) (d)
(c) II > III > IV > I (d) III > IV > II > I
JEEMAIN.GURU
downloaded from jeemain.guru
414 Chemistry
7. The correct order of increasing reactivity of C – X bond 12. Some meta-directing substituents in aromatic substitution
towards nucleophile in the following compounds is: are given. Which one is most deactivating? [NEET 2013]
[CBSE-PMT 2010] (a) –SO3H (b) –COOH
X (c) –NO2 (d) –C º N
X
NO2 13. Arrangement of (CH3)3 – C –, (CH3)2 – CH –, CH3 – CH2 –
(CH3)3 C – X, (CH3)2CH – X when attached to benzyl or an unsaturated group in
increasing order of inductive effect is [AIEEE 2002]
(a) (CH3)3 –C – < (CH3)2 – CH – < CH3 – CH2–
NO2 (b) CH3 –CH2– < (CH3)2– CH – < (CH3)3 –C –
(I) (II) (III) (IV) (c) (CH3)2 – CH– < (CH3)3 –C – < CH3—CH2–
(a) I < II < IV < III (b) II < III < I < IV (d) (CH3)3 – C– < CH3 –CH2 – < (CH3)2 –CH –
(c) IV < III < I < II (d) III < II < I < IV 14. The reaction:
H O
8. Among the given compounds, the most susceptible to (CH3)3C – Br ¾¾2¾® (CH3)3 – C –OH is a/an
nucleophilic attack at the carbonyl group is: [AIEEE 2002]
[CBSE-PMT 2010] (a) elimination reaction (b) substitution reaction
(a) CH3COOCH3 (b) CH3CONH 2 (c) free radical reaction (d) displacement reaction.
15. In the anion HCOO– the two carbon-oxygen bonds are found
(b) CH3COOCOCH3 (d) CH 3 COCl
to be of equal length. what is the reason for it ?
9. Which one of the following is most reactive towards [AIEEE 2003]
electrophilic reagent ? [CBSE-PMT 2010, 2011] (a) The C = O bond is weaker than the C — O bond
CH3 CH3 (b) The anion HCOO– has two resonating structures
(a) (b) (c) The anion is obtained by removal of a proton from the
OCH3 OH acid molecule
(d) Electronic orbitals of carbon atom are hybridised
CH3 CH3 16. Rate of the reaction [AIEEE 2004]
(c) (d) O O
NHCOCH3 CH2OH R – C + Nu R–C +Z
Z Nu
10. Which one is a nucleophilic substitution reaction among the
is fastest when Z is
following ? [CBSE-PMT 2011]
(a) OC2H5 (b) NH2
(a) CH3 – CH = CH2 + H2O CH3 – CH – CH3 (c) Cl (d) OCOCH3
OH 17. Due to the presence of an unpaired electron, free radicals
(b) RCHO + R¢ MgX R – CH – R¢ are: [AIEEE 2005]
(a) cations (b) anions
OH (c) chemically inactive (d) chemically reactive
CH 3 18. The decreasing order of nucleophilicity among the
(c) CH3 – CH2–CH–CH2Br + NH 3 nucleophiles [AIEEE 2005]
(a) CH 3C - O -
CH3
||
CH 3–CH 2–CH–CH2NH 2 O
(b) CH 3O -
(d) CH3CHO + HCN ¾¾ ® CH3CH (OH) CN
11. Which of the following compounds undergoes nucleophilic (c) CN -
O
substitution reaction most easily ? [CBSE-PMT 2011 M] ||
(d) H 3C S – O – is
Cl ||
Cl O
(a) (b) (a) (c), (b), (a), (d) (b) (b), (c), (a), (d)
NO2 (c) (d), (c), (b), (a) (d) (a), (b), (c), (d)
CH3 19. The reaction [AIEEE2005]
O
O
||
||
Cl R–C + Nu R–C +X
Cl X Nu
is fastest when X is
(c) (d)
(a) OCOR (b) OC 2 H 5
JEEMAIN.GURU
downloaded from jeemain.guru
NO2
O
H Å
(b)
+ E Å N
(a) (b) +
O
H E
NO2 NO2 O
H (c) Å
E Å N
(c) + (d) + H
E O
23. Arrange the carbanions, [AIEEE 2009]
(b) CCl3 > C6 H5 CH2 > (CH3 )2 CH > (CH3 )3 C 28. Hyperconjugation involves overlap of the following orbitals
[IIT-JEE 2008]
(c) (CH3 )3 C > (CH3 )2 CH > C6 H5 CH 2 > C Cl3 (a) s-s (b) s - p (c) p- p (d) p-p
29. The correct stability order for the following species is
(d) C6 H5 CH2 > CCl3 > (CH3 )3 C > (CH3 )2 CH
[IIT-JEE 2008]
24. The correct order of increasing basicity of the given conjugate
+ + +
bases (R = CH3) is [AIEEE 2010]
O O +
(a) RCOO < HC º C < R < NH 2 (I) (II) (III) (IV)
(a) (II) > (IV) > (I) > (III) (b) (I) > (II) > (III) > (IV)
(b) R < HC º C < RCOO < NH 2
(c) (II) > (I) > (IV) > (III) (d) (I) > (III) > (II) > (IV)
(c) RCOO < NH 2 < HC º C < R 30. In the following carbocation, H/CH3 that is most likely to
migrate to the positively charged carbon is [IIT-JEE 2009]
(d) RCOO < HC º C < NH 2 < R H H
1 2 4 5
25. A solution of ( – ) – 1 – chloro –1– phenylethane in toluene H3C — C
+
—3C — C — CH3
racemises slowly in the presence of a small amount of SbCl5,
due to the formation of : [JEE M 2013] HO H CH3
(a) carbanion (b) carbene
(a) CH3 at C-4 (b) H at C-4
(c) carbocation (d) free radical
(c) CH3 at C-2 (d) H at C-2
JEEMAIN.GURU
downloaded from jeemain.guru
416 Chemistry
31. Among the following compounds, the most acidic is O
[IIT-JEE 2011] Cl
H3C – Cl Cl Cl
(a) p-nitrophenol (b) p-hydroxybenzoic acid
(c) o-hydroxybenzoic acid (d) p-toluic acid
32. KI in acetone, undergoes SN2 reaction with each of P, Q, R P Q R S
and S. The rates of the reaction vary as (a) P > Q > R > S (b) S > P > R > Q
(JEE Advanced 2013) (c) P > R > Q > S (d) R > P > S > Q
1. In E2 elimination, some compounds follow Hofmann’s rule (a) Carbanion (b) Carbene
which means (c) Free radical (d) Carbocation
(a) the double bond goes to the most substituted position 8. Which of the following is singlet carbene ?
(b) the compound is resistant to elimination ..
(c) no double bond is formed (a) (CH3)3C+ (b) C 2 H 5 C CH 3
(d) the double bond goes mainly towards the least – +
substituted carbon (c) CH3CHCH 3 (d) CH 2 = CH - CH 2
2. SN1 reaction on optically active substrates mainly gives 9. The reaction,
(a) retention in configuration
C 2 H 5 I + KOH ® C 2 H 5 OH + KI is called
(b) inversion in configuration
(c) racemic product (a) hydroxylation substitution
(d) No product (b) electrophilic substitution
3. Which of the following contains only three pairs of electrons? (c) nucleophilic substitution
(a) Carbocation (b) Carbanion (d) dehydroiodination
(c) Free radical (d) None of these 10. An organic compound C5H11X an dehydrohalogenation
4. The addition of HBr on butene -2 in presence of peroxide gives pentene - 2 only. What is halide
follows the (a) CH 3CH 2 CHXCH 2 CH 3
(a) electrophilic addition (b) free radical addition
(c) nucleophilic addition (d) None of these (b) (CH 3 )2CHCHXCH3
5. The stability of 2, 3 - dimethyl-but - 2- ene is more than 2- (c) CH3CH 2 CH 2 CHXCH3
butene. This can be explained in terms of
(a) resonance (b) hyperconjugation (d) CH3CH 2 CH 2 CH 2 CH 2 X
(c) electromeric effect (d) inductive effect 11. Sulphur trioxide is
6. (CH3)4N+ is neither an electrophile, nor a nucleophile because (a) an electrophile (b) a nucleophile
it (c) a homolytic reagent (d) a base
(a) does not have electron pair for donation as well as cannot 12. Intermediate product formed in the acid catalysed
attract electron pair dehydration of n- propyl alcohol is
(b) neither has electron pair available for donation nor can
(a) CH 3 - CH 2 - CH 3 (b) CH 3 - CH = CH 2
accommodate electron since all shells of N are fully
occupied + +
(c) can act as Lewis acid and base (c) CH 3 - C H - CH 3 (d) CH 3 - CH 2 - C H 2
(d) None of these 13. Which of the following is most stable
7. A solution of (+) - 2 - chloro - 2 - phenylethane in toluene
(a) CCl 3CH (OH ) 2 (b) (CH3)2.C.(OH)2
racemises slowly in the presence of small amounts of SbCl5
due to the formation of (c) CH3C.Cl(OH)2 (d) CH3CH(OH)2
JEEMAIN.GURU
downloaded from jeemain.guru
: :
| O
A
CH3 CH3
H –C
: :
(c) CH3– CH 2 – CH 2 – CH 2 OH (d) CH3 - CH - CH 2 - CH3 O:
| B
OH Which C – O bond is longer ?
16. Among the following compounds which is most reactive (a) A
towards nitration (b) B
(a) Benzene (b) Nitrobenzene (c) Both are equal
(c) Toluene (d) Chlorobenzene
(d) Structure shown is not correct
17. Example of chlorinolysis is
24. Which of the following resonance structure is lowest in
(a) CH 2 = CH 2 ¾¾
® C 2 H 4 Cl 2 energy?
(b) CCl4 + H 2 O ¾¾
® COCl2 + 2HCl
H O
:
H O : : : :
(c) CHCl3 + 4NaOH | || |
(A) H – C – C (B) H – C – C
¾¾
® HCOONa + 3NaCl + 2H 2 O +
| |
: :
Cl2 O– H O– H
(d) C3 H8 ¾¾¾ ® CCl 4 + C 2 Cl6 + 8HCl HB HB
:
18. During debromination of meso - dibromobutane, the major
:
H O : :
compound formed is : | |
(a) n - butane (b) 1 - butene (C) H – C – C
| +
: :
JEEMAIN.GURU
downloaded from jeemain.guru
418 Chemistry
26. How many degrees of unsaturation are there in benzene 31. Which of the followings is most stable ?
CH 3
CH3
? |
(a) 2 (b) 3 (a) H (b) +
(c) 4 (d) More than 4
Y
27. Which is incorrect for the following pairs ? H Y
Column I Column II CH 3 CH3
| H |
(a) resonance +
(c) Y (d)
+
O O
|| H Y
(b) equilibrium
OH OH
Å 32. The stable resonating form of vinyl methyl ketone is
: O: -
:
(c) equilibrium Å |
(a) CH2 – CH = C –CH3
O OH : O:
|| |
(d) equilibrium Å - ||
(b) C H 2 – C H – C – CH 3
28. What is the mechanistic intermediate in the following reaction
:O: -
:
O O O O |
|| (i ) NaOMe || (c) CH 2 = CH - C - C H 3
Å
¾¾¾¾¾® OEt
OEt (ii ) MeI | :O:
:
(d) Å
:
O O CH 2 - CH - C - C H 3
O– O
|| || | || 33. Hyperconjugation involves
(a) OEt (b) OEt
| (a) s - p conjugation (b) s - p delocalisation
OMe (c) no bond resonance (d) All of these
34. The following reaction
O O
Br
|| + HBr ¾
¾®
(c) OEt (d) None of these
| is an example of
(a) elimination reaction (b) nucleophilic subsitution
29. In the reaction shown below the six membered ring is (c) electrophilic addition (d) nucleophilic addition
generated by shifting which bond 35. Which of the following reactions is elimination reaction?
(a) O + Ph 3 P = CH 2 ¾
||
B ¾®
CD HBr
¾¾¾® Br
A
| CH 2 + Ph 3 PO
||
H
OH
(b) C 2 H 5 Cl + KOH ® C 2 H 5 OH + KCl
(a) A (b) B (c)
(c) C (d) D H
30. When HI is added on to propene in presence of peroxide the |
Alc KOH
:
JEEMAIN.GURU
downloaded from jeemain.guru
CH 3
+ (ii)
H3 O (i)
CH - CH 3 ¾¾¾ ® Product.
| D + –
OH NH3 O
CH 3
CH 3
(a) (b) CH = CH 2
CH 3 (iii) ( iv)
(b) +
|| || O
O O
CH 3
Anhy. ZnCl 2 + NaOH
(c) R 3COH ¾¾ ¾ ¾ ¾
¾® Turbidity
Conc. HCl O
(d) All of these
O O–
40. Which of the following reactions cannot proceed by SN1
mechanism ? CH 3 CH 2
:
(a) (b)
CH 2 Cl O
O
| O– O–
(a) (b) Cl CH 3 CH 3
(c) (d)
(c) (d) Cl O O–
Cl
JEEMAIN.GURU
downloaded from jeemain.guru
420 Chemistry
EXERCISE 1 EXERCISE 2
1. No. It is 1°. 1. (a) Greater the electronegativity, higher is the -I effect. Thus
2. (i) –NO2 > –CN > –COOH > –F > –I – F > –OR > – NR2
(ii) –C(CH 3 ) 3 > –CH(CH 3 ) 2 > –CH 2 CH 3 > 2. (d) Due to – I effect of the – CHO group, oxygen acquires-d
–CH3 > –D. - charge and the terminal carbon acquires d + charge.
. . d+ d-
4. (i) C6H5CH2 C H 2 < C6H5CHCH3 < C6H5 C (CH3)2 < CH2 = CH – C = O
. H
C6H5 CH –CH=CH2.
(ii) (CH3)3C+ > C6H5CH2+ > CH2 = CHCH2+ > CH3CH2+ 3. (b) 4. (c)
5. (b) Homolytic fission of the C – C bond gives free radicals
(iii) (CH3)2CH– < CH3CH2– < CH3– < CH2 = CH–
in which carbon is sp2- hybridised.
< C6H5CH2– < HC º C–. 6. (b) In carbocations, carbon bearing positive charge is
.. –
8. (i) Nucleophiles : ....I .. , H3N .. always sp2-hybridised
7. (d) Higher the possibility of delocalisation of the positive
(ii) Electrophiles : BeCl2 and NO +2 charge, greater is stability of the species. Thus
.. + + +
(iii) Both : CH3C º N.. and H2C = C .. C6H5 C H2 > (CH3 )3 C+ > (CH3 ) 2 C H > CH3 C H2
(iv) Neither : CH4 and H2. Benzyl carbocation is more stable than tert-butyl due to
10. Stabilised due to nine possible canonical structures. resonance in the former.
8. (b) Structure (b) is a 3º carbocation, while (a) is 2º and (c)
and (d) are 1º carbocations; thus (b) is the most stable.
9. (a) Higher the possibility of delocalisation, greater is its
C +
stability; in C6 H5CHC6 H5 , +ve charge can delocalise
over two benzene rings.
10. (a) Same as above, in Ph3C+, +ve charge can delocalise over
three benzene rings.
Other + +
C canonical 11. (a) I. C6 H5 CH 2 II. C6 H5 CH 2CH 2
structures 1º Benzylic 1º
+ +
16. (b) 17. (a) 18. (b) 19. (b) 20. (d) 21. (b) III. C6 H 5 CHCH3 IV. C6 H 5 C(CH3 )2
2º benzylic 3º benzylic
22. (a) 23. (b) 24. (b)
3º Benzylic (IV) > 2º Benzylic (III) > 1º Benzylic
(I) > 1º (II)
12. (d) –NO 2 group, being strong electron-withdrawing,
disperses the –ve charge, hence stabilizes the concerned
carbanion.
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
422 Chemistry
increases the reactivity of the – Cl towards nucleophiles. Hence, the correct order of nucleophilic substitution
reactions
(CH3)3 – C – X > (CH3)2 – CH2 – X >
JEEMAIN.GURU
downloaded from jeemain.guru
> NO2 > – CN > – SO3H > – COOH RCOO - < CH º C - < - NH 2 < R -
—NO2 group is most deactivating group due to strong 25. (c) Carbocations are planar hence can be attacked on
– E, – I and – M effects. either side to form racemic mixture.
13. (b) –CH3 group has +I effect, as number of –CH3 group Å
SbCl
5 ® Ph - C H - CH + SbCl- ¾¾
increases, the inductive effect increases. Cl - CH - CH3 ¾¾¾¾ 3 6 ®
Toluene
| (carbocation)
14. (b) The reaction is nucleophilic sustitution reaction
Ph
(-)
O O
15. (b) H–C–O H–C=O
Ph - CH - CH3 + SbCl5
16. (c) Cl– is the best leaving group among the given options. |
Cl
17. (d) Free radicals are electrically neutral, unstable and very (d + l) mixture
reactive on account of the presence of odd electrons.
26. (d) Higher stability of allyl and aryl substituted methyl
18. (b) The stronger the base the more is the nucleophilic
carbocation is due to dispersal of positive charge due
character and vice versa.
to resonance
Basic character
+ +
CH 2 = CH - C H 2 ¬¾® CH 2 - CH = CH 2
CH 3O - > CN - > CH 3 COO - > H 3C - Resonating structures of allyl carbocation
–
SO3
+
Hence the nucleophilic character. CH2 CH2 CH2 CH2
Å Å
O
||
19. (d) R - C - X ; when X is Cl the C–X bond is more polar
Å
and ionic which leaves the compound more reactive for Resonating structures of benzyl carbocation
nucleophilic substitution reaction.
20. (b) The order of stability of free radicals whereas in alkyl carbocations dispersal of positive charge
on different hydrogen atoms is due to hyperconjugation.
• • • •
(C6 H5 )3C > (C6 H5 ) 2CH > (CH3 )3C > (CH3 ) 2CH Hence the correct order of stability will be
Å
The stabilisation of first two is due to resonance and last CH2
two is due to inductive effect. Å Å
21. (a) Nitro group is electron withdrawing group, so it > CH 2 = CH - CH2 > CH3 - CH 2 - CH 2
Allyl, I Propyl, II
deactivates the ring towards electrophilic substitution. Benzyl, III
22. (b) In option (b) the complex formed is with benzene 27. (a) Due to similar charges on adjacent atoms, the
whereas in other cases it is formed with nitrobenzene structure (a) is least stable.
with –NO2 group in different position (o-, m-, p-). The
28. (b) Alkyl groups with at least one hydrogen atom on the
complex formed with nitrobenzene in any position of
a-carbon atom, attached to an unsaturated carbon
–NO2 group is less stable than the complex formed
atom, are able to release electrons in the following
with benzene so the correct answer is (b). The most
way.
stable complex has lowest energy.
JEEMAIN.GURU
downloaded from jeemain.guru
424 Chemistry
32. (b)
O
Cl
Compounds : CH3 – Cl : Cl : Cl
Note that the delocalisation involves s and p bond orbitals S P R Q
(or p orbitals in case of free radicals) ; thus it is also known
Relative reactivities 1,00,000 : 200 : 79 : 0.02
as s – p conjugation. This type of electron release due to towards SN 2 reaction
the presence of the system H—C—C = C is known as
hyperconjugation
29. (d) The correct stability order is EXERCISE 4
I > III > II > IV 1. (d) During E2 elimination the double bond goes mainly
toward the least hindered carbon
+ +
O O 2. (c) The intermediate planar carbonium ion has equal chances
I III to be attacked from either side leading to racemisation
+ M effect, 6 hyper- +
conjugative H’s, + M, 3 hyperconjugative
. H’s, one CH 3 group 3. (a) R 3 C has three pairs of electrons in three bonds
2 CH 3 groups
(+ I effect) 4. (b) It is free radical addition (See mechanism of peroxide
effect)
+
+
IV CH3 CH3
II | |
5 hyperconjugative 5 hyperconjugative H’s 5. (b) H 3C - C = C - CH 3 . The more substituted alkenes
H’s 2 R groups one R group
have greater number of hyperconjugated forms. Hence
30. (d) Migrating tendency of hydride is greater than that of
they are more stable
alkyl group. Further migration of hydride from C–2 gives
more stable carbocation (stabilized by +R effect of OH 6. (b) The octet around N is complete, hence it has no
group and +I and hyperconjugative effects of methyl electrophilic character. N has no unshared pair of electrons
group). to act as nucleophile
JEEMAIN.GURU
downloaded from jeemain.guru
:
–
O O O O
|| || || ||
- MeI
.. .. +
OEt ¾¾
¾® OEt
14. (c) CH 2 = CH - Cl: « CH 2 - CH = Cl: a double bond is
.. ..
Na
formed between C and Cl. Hence it is less reactive due to
resonance 29. (a) Five membered ring is being converted into six membered
ring. Hence the sixth bond must come from within the
15. (b) (CH 3 ) 3 COH gives tert (CH 3 ) 3 C + . The order of ring.
+ 30. (a) HI does not add on to propene by peroxide effect. Even
stability of carbonium ions is 3° > 2° > 1° > CH 3
in presence of peroxide the addition is according to
16. (c) Due to hyperconjugation toluene is most reactive for Markownikoff’s rule forming intermediate carbonium ion.
electrophilic substitution reaction ( see theory)
17. (d) Chlorinolysis is substitution by chlorine CH 3
18. (d) It gives trans - 2 - butene
+
19. (d) In I the unshared pair of electrons on N always available 31. (d) The structure carring +ve charge nearest to
for protonation in III due to presence of electronegative
O atom the electron density on N is decreased . In II and
IV resonance suppresses the basic character H Y
20. (b) The more the electrons withdrawing groups attached to
electrons repelling -CH 3 group is most stable.
- O atom, the more is the ease of leaving
21. (b) The addition of HCl to propene proceeds by ionic 32. (a) In (a) the separation of charges is maximum and
mechanism and not by free radical mechanism. Hence it electronegative atom oxygen carry –ve charge.
forms intermediate carbonium ion 33. (c) correct. (See text.)
22. (c) BrCH2CH2CO2H is the weakest acid as Br has less -I 34. (c) Addition reactions of alkenes are known as electrophilic
effect compared to F and is also far from -CO2H group. addition reactions.
23. (c) Formate ion 35. (c) The reaction (c) is Hoffmann elimination (see Reaction
Mechanisms.)
O O – 36. (d) The second ring has o/p directing O-atom and first ring
H–C H–C
O – O has m-directing -C - group. o/p directing group activate
||
Hence A, B bonds are of same length. O
24. (a) The order of stability of resonating structures carrying the benzene nucleus.
no charge > carrying minimum charge and each atom
having octet complete. – –
37. (a) ¬
¾® ¬
¾® ¬
¾®
25. (d) In A nitrogen is bivalent, in B and C carbon is pentavalent.
–
26. (c) The degree of unsaturation is equal to number of
hydrogen molecules needed to convert the given –
compound into an alkane. – –
¬
¾® ; ¬
¾®
27. (b) In (b) the pair has resonance. –
O O
|| || MeO- –
28. (b) ¾¾¾¾® –
OEt - MeOH RCH 2 (1°); (2°)
JEEMAIN.GURU
downloaded from jeemain.guru
426 Chemistry
-
CH 3 43. (b) CH3C H 2 > HC º C - > CH 3CH 2 O - basic character..
CH 3
-H O CH - CH 3 + The acid character being
¾¾¾
2¾®
+
2° CH 3 CH 3CH 2 OH > HC º CH > CH 3CH 3 . The weaker the
3° H
acid, the stronger the base (conjugate pair)
44. (b) (a),(c) and (d) are resonating structures.
+
CH 3
-H
O
–O
CH 3
CH 3 CH 3
Anhy. ZnCl
39. (c) R 3COH ¾¾ ¾ ¾ ¾
¾2®
R 3C.Cl
Conc. HCl O O
JEEMAIN.GURU
downloaded from jeemain.guru
12E
Isomerism
ISOMERISM
CH3 CH3 CH3
Berzelius introduced the term Isomer (Gr. Isos=Same, Mers=parts)
to different compounds with the same molecular formula and the CH3
phenomenon was called Isomerism.
Types of isomerism : There are two main types of Isomerism
(i) Structural or constitutional isomerism : It is due to CH3
difference in the arrangement of atoms within the molecule. o-xylene m-xylene CH3
(ii) Stereo isomerism or space isomerism : It is due to different p-xylene
spatial arrangement of some atoms and groups.
Types of structural isomerism Position Isomers are also Known as regiomers.
(i) Chain isomerism : This is due to difference in the structure (iv) Metamerism : This is due to different alkyl groups attached
of the carbon chains. Examples. to the same functional group.
CH3 CH3
CH3CH2.CH2.CH2–CH3 CH–CH2–CH3
CH CH3–NH–CH2CH2CH3 CH 3 - NH - CH C 2H 5NH.C 2H 5
n-Pentane 3
Iso-Pentane CH3
Diethyl amine
Methyl n-propyl amine Methyl Isopropyl amine
CH3
|
CH 3 – C – CH 3 CH3
CH 3 - O - CH 2CH 2CH 3 CH 3 - O - CH C 2H 5 - O - C 2H 5
|
CH3 CH3 Diethyl ether
Neo-Pentane Methyl n-propyl ether Methyl Isopropyl ether
(ii) Functional isomerism : This is due to difference in the (v) Ring chain isomerism : Cyclic/acyclic Isomerism
functional groups
C2H5OH CH 3OCH 3 CH 3 - CH = CH 2
ethyl alcohol dimethyl ether Propene
Cyclopropane
CH3COOH HCOOCH3
Acetic acid Methyl formate
CH 3CH 2 CHO CH 3COCH 3 CH 3 - CH 2 - CH = CH 2
Propionaldehyde Acetone. But -1-ene Cyclobutane
(iii) Position or region isomerism : This is due to difference in
the positions of the same functional groups (vi) Tautomerism (Tauto = Same, Mers = Parts) : It is due to the
presence of a mobile atom in the molecule and the same
OH
| substance behaves in such a way as if it is a mixture of two or
CH 3 – CH 2 – CH 2 OH CH 3 – C H – CH 3 more compounds. Further we have
n- Propyl alcohol Iso - Propyl alcohol
JEEMAIN.GURU
downloaded from jeemain.guru
428 Chemistry
(a) Dyad system : When the mobile atom oscillates between
S SH
two adjascent atoms eg || |
H-C º N H–N C H 2 N - C- NH 2 HN = C - NH 2
Thio Urea Enolic form
Hydrocyanic acidIso-hydrocyanic acid
(b) Triad system : When the mobile atom oscillates between
atoms one position ahead eg. NO O= N – OH
HO
O OH
|| | p-Nitrosophenol Keto form
CH 3 - C - CH 2 .COOC 2 H 5 CH3 - C = CH.COOC2 H5
Types of stereo isomerism :
93% Keto form 7% Enol form
(I) Optical Isomerism
Aceto acetic ester Aceto acetic ester
(II) Geometrical Isomerism and
Aceto acetic ester reacts with HCN, NH 2 OH,
(III) Conformational Isomerism
C6H5NHNH2 showing the properties of a ketone and
(I) Optical isomerism : The compounds having the same
also reacts with CH 3COCl, PCl5, Na showing the
molecular formula, the same structural formula but different
properties of OH group.
behaviour towards the plane polarised light are known as
It gives colour change with 1% FeCl3 a characteristic Optical Isomers.
Terminology used in optical isomerism.
æ OH ö
test of ç | ÷ (enol group) • Plane polarised light : Light having vibrations restricted
çè - C| = C| -÷ø to one plane only is called plane polarised light.
• Optically active compounds : The compounds capable
There exists an equilibrium between the two forms which of rotating the plane of polarisation of plane polarised
is dynamic in nature. light are known as optically active compounds.
• Optical activity : It is the ability of a substance to rotate
O OH the plane of polarisation of plane polarised light.
|| |
CH 3 - C - CH 3 CH 3 - C = CH 2 • Dextrorotatory compounds (d or +) : The compounds
which rotate the plane of polarisation of plane polarised
Acetone 99.5% Acetone (enol form) 0.5% light towards the right hand side are called dextro rotatory.
• Laevo rotatory compounds (l or –) : The compounds
O OH
|| | which rotate the plane of polarisation of plane polarised
CH3 - C- CH2 .COCH3 CH 3 - C = CH.CO CH 3 light towards the left hand side are called laevo rotatory.
• Specific rotation : The rotatory power of optically active
Acetyl acetone (keto form) Acetyl acetone (enol form)
compounds is compared in terms of specific rotation.
Specific rotation
OH O
Observed rotation in degrees
H =
Length of tube in decimeter ´ Concentration of solution in g/ml
H
q
[a]Dt =
Phenol l´C
Keto form of Phenol
• D corresponds to D line of Sodium light (l = 5893Å)
Triad system containing nitrogen • t corresponds to temperature
• Rotation is observed and measured with a polarimeter
O O–H
CH 3 - CH 2 - N CH3 – CH = N The specific rotation varies with light l and temperature.
O O • Optical activity due to crystalline strcuture : Some
Nitro ethane Aci Nitro ethane compounds are optically active only in crystalline form.
It dissolves in NaOH on account of aci form. Tautomeric They loss their optical activity when dissolved or fused
form which is less stable is called labile form. e.g. Quartz.
• Optical activity due to molecular structure : Some
O OH compounds are optically active in solid as well as in
|| |
H 2 N - C - NH 2 HN = C - NH 2 solution e.g. tartaric acid. Hence their optical activity is
Urea ( Keto form ) Enolic form due to their molecular structure which remains the same
in solid form and in solution.
JEEMAIN.GURU
downloaded from jeemain.guru
Isomerism 429
• Asymmetric carbon atom : A carbon atom attached to
four different atoms and groups is called asymmetric COOH COOH
*
carbon atom. e.g. CH C . H OH HO H
3 H OH COOH
• Chirality : If the mirror image of the molecule is different
from the molecule it is said to be a chiral molecule. In CH3 CH3
such case if one configuration of the molecule is placed Dextrorotatory (d or +) Laevorotatory (lor –)
above its mirror image configuration, the similar atoms Lactic acid Lactic acid
and groups do not fall over each other and the (Source meat extract) (Obtained during
fermentation of
configurations are said to be nonsuperimposable.
Sucrose)
If object and mirror image configurations are superimposable
Racemic Lactic acid : It is an equimolar mixture of
(similar atoms and groups fall over each other) the molecule
d- and l- forms. It is optically inactive due to external
is said to be "achiral”.
Chirality is the necessary condition for a compound to be compensation of optical rotation. It is present in sour milk. It
optically active. can be resolved.
Enantiomers : Pairs of nonsuperimposable mirror images Examples of optically active compounds containing one
are called enantiomers. asymmetric C-atom.
Fischer Projections : Fischer projections are drawn with a
COOH COOH C2H5
cross, with chiral atom at the centre of the cross.
H OH H OH H CH2OH
A A A
D CH2 COOH C6H5 CH3
B C B C Malic acid Mandelic acid Amyl alcohol
B C D
D Number of optically active forms is given by 2n where n is
The horizontal line represents wedges (bonds) coming out number of asymmetric C-atoms different in nature.
of the plane of the paper. The vertical line represents dashed Resolution : The separation of d- and l- forms present in a
lines (bonds) in the plane of the paper (Bow-tie convention). racemic mixture is known as resolution.
The carbon chain is drawn along the vertical line of the Conditions for Chirality : Absence of (I) Plane of symmetry
projection with most highly oxidised carbon substituent at (II) Centre of symmetry and (III) Alternating axis of
the top. Fischer projections are very useful to determine symmetry.
chirality of a compound. Plane of Symmetry : A plane which divides the molecule in
Lebel and Van't Hoff’s theory about optical isomerism :
two portions in such a way that one portion is the mirror
The tetrahedral structure of a compound containing
asymmetric carbon atom (*Cabed) gives two configurations image of the other eg. Tartaric acid.
related to each other as object and its mirror image but are COOH
non-superimposable. H OH
Plane of symmetry
H OH
d d
COOH
c c
e b b e Meso tartaric acid
a a It is optically inactive due to internal compensation of optical
d or + l or – rotation. It can not be resolved.
Enantiomers or Enantiomorphs
Centre of Symmetry : It is a point from which lines, when
drawn on one side to meet the groups and produced to an
d d
equal distance on the other side of the point will meet the
same original groups.
e b b e
H NH CO CH3
a a
d or + l or –
(I) (II) C C
Enantiomers or Enantiomorphs CO NH
CH3 H
* Trans:1,4-dimethyl diketo piperazino (Inactive)
Optical isomerism of Lactic acid : CH 3 CHOH.COOH
Contains centre of symmetry
JEEMAIN.GURU
downloaded from jeemain.guru
430 Chemistry
erazino (Inactive) cis: 1,4-dimethyldiketo piperazino (Active) • l-tartaric acid is prepared by resolving racemic acid. Its
No centre of symmetry mpt is 170°C.
Alternating axis of symmetry : If a molecule is rotated • Meso-tartaric acid is obtained by oxidation of maleic
acid, heating d-tartaric acid with water at 170°C. Its mpt
360° is 143°C.
through an angle of about the axis and then reflected
n
• Racemic tartaric acid (dl or ±). It is obtained from Argol.
in a plane perpendicular to the axis, gives back the original Its mpt is 206°C. It is an equimolar mixture of d and l
molecule it is said to possess the n fold alternating axis of forms.
symmetry.
• Racemic tartaric acid can be resolved into d and l forms.
90° It is a mixture of two compounds.
CH3 H H CH3
• Meso-tartaric acid cannot be resolved. It is a single
2 1 1 4 compound.
H CH3 CH3 H
Optical Isomerism of the compound containing two dissimilar
H H3C H3C H C-atoms : Example a,b-dibromo cininamic acid and 2,3-
3 4 2 3 dihydroxy butanoic acid.
CH3 H H CH3
1,2,3,4-tetramethyl cyclo butane Mirror
CH3 H
H CH3
H H3C
CH3 H
H OH HO H
H OH HO H
COOH COOH
Meso tartaric acid
(I) (II)
l
COOH COOH COOH
Let optical rotation due to chiral centre C3 and C2 be A and B
and further A > B. In the above case I-II and III-IV are pairs of
H OH HO H enantiomers where as I-III; I-IV, II-III, and II-IV are pairs of
HO H H OH diastereo-isomers.
Diastereo Isomers : Stereo isomers which are not mirror
COOH COOH COOH images of each other are called diastereo isomers. They have
different physical properties (mpt, bpt, solubility) and are
d-tartaric acid l-tartaric acid
often easy to separate by distillation, recrystallisation,
(III) (IV)
chromatography etc.)
JEEMAIN.GURU
downloaded from jeemain.guru
Isomerism 431
The same compound pair are called the meso diastereoisomer (II) Substituted allenes : Unsymmetrically substituted allene
(I-II in case of Tartaric acid see above). Most diastereo- (CH2 = C = CH2) are optically active.
isomers are either geometric isomers or compounds with two a x a a
or more chiral atoms. C=C=C C=C=C
b y b b
Enantiomers : Enantiomers are non superimposable mirror (I) (II)
image isomers. They have identical physical properties (bpt, active Inactive
mpt, density etc.) except for their rotation of plane polarised
a x a a a x a b
light. They are much more difficult to separate. In nature C=C=C C=C=C
very often only one enantiomer
b y
is produced. Living organisms
b b b x b a
(I)
are one of the best sources of optically active compounds (III) (IV)
Inactive Active
(plants, enzymes, animals, cells etc.).
Enantiomeric excess (Optical Purity) : It is given by
Asymmetric synthesis : The synthesis of an optically active Optical purity = O.P.
compound from optically inactive compound under the
Observed rotation d -l
influence of an optically active compound without resolution = ´ 100% Or O.P. = ´ 100%
Pure enantiomer rotation d+l
is known as asymmetric synthesis.
where d and l are ratio of two forms
Geometrical isomerism : Alkenes with double bonds cannot
ROH
CH 3COCOOH ¾¾¾¾¾¾® CH 3COCOOR ¾¾¾
2H undergo free rotation
® CH 3CHOH.COOR ¾¾¾
H Oand can have different geometrical shapes
® CH CHOH.COOH
Pyruvic acid Optically active alcohol Optically active ester with two
Active lac different groups on3 each end of the double bond. e.g.
molecules C2a2b2, C2a2bd or C2abde.
2H H O a a a b a a
OCOOR ¾¾¾
® CH 3CHOH.COOR ¾¾¾
2 ® CH CHOH.COOH
3
y active ester Active lactic ester l -lactic acid
C=C C=C ; C=C
b b b a b d
(I) (II) (III)
Racemisation : The transformation of an optically active
a
isomer under the influence a light
of heat, a or some breagents
a a a d a d a e
into an inactive isomer is called racemisation. C=C ; C=C C=C
b b b a b d b a b e b d
Walden inversion / Optical (I)inversion : The conversion of (III) (IV) (V) (VI)
an enantiomer into another is called Walden inversion. I-II, III-IV and V-VI are pairs of geometrical isomers.
Nomenclature :
CH2 COOH CH2 COOH Cis Isomer : Contains the similar atoms or groups on the same
PCl5 side.
HO H H Cl Trans Isomer : Contains the similar atoms or groups on the
KOH
COOH COOH opposite side.
Examples :
d-Malic acid l-Chlorosuccinic acid CH3 CH3 CH3 H
C=C C=C
H H H CH3
CH2COOH
Cis-But-2-ene Trans But-2-ene
AgOH
H OH
H–C–COOH H–C–COOH
COOH
H–C–COOH HOOC–C–H
-Chlorosuccinic acid l-Malic acid
Cis-But-2-ene Trans But-2-ene Maleic acid Fumaric acid
Geometrical Isomerism of Oximes
Optical isomerism due to restricted rotation : Aldoximes :
(I) Diphenyls :
R H2NOH R
C=O C = NOH
H –H2O H
SO3H SO3H
H H
Aldehyde Aldoxime
R R H R H
C = NOH C C
SO3H SO3H H
H H
N N
OH HO
Enantiomers of diphenyl disulphonic acid
Syn Aldoxime Anti Aldoxime
JEEMAIN.GURU
downloaded from jeemain.guru
432 Chemistry
Ketoximes : (III) By Oxidation :
COOH
R H2NOH R H COOH
C=O C = NOH C H OH
–H2O Dil. aq. KMnO4
R' R'
Unsymmetrical Ketone Ketoxime C or OsO4
H OH
H COOH
Maleic acid COOH
R R R' R R' meso-Tartaric acid
C = NOH H COOH
C C C Dil. aq. KMnO4
N N C or OsO4
OH HO HOOC H
Syn (R', OH) Anti (R', OH) Fumaric acid
COOH
COOH
Geometrical isomerism of azo compounds : Example azobenzene
COOH
H OH HO H
+
C6H5 HO H H OH
N=N HOOCN = N
C6H5 C6H5 C6H5 COOH COOH
d-Tartaric acid l-Tartaric acid
Syn-azo benzene Anti-azo benzene
Hence Maleic must be cis and fumaric must be trans.
E,Z system of Nomenclature for Geometrical Isomers:
Geometrical isomerism in cyclo alkanes : Cyclo alkanes also
If two high-priority groups are on the same side, the configuration
cannot undergo free rotation.
is Z (German, Zus ammen = togehter). If they are on opposite side,
the configuration is E (German; entgegen = opposite)
JEEMAIN.GURU
downloaded from jeemain.guru
Isomerism 433
(IV)The molecule is drawn in three dimensions in such a way that Molecules with two or more chiral atoms.
the bond between the chiral carbon and the lowest priority 1 CH3
group heeds back into the paper. CH3
2
(V) Draw an arrow from the group of highest priority, to the H Br
second, to the third priority group. H Br
3
(VI)If the arrow is clockwise, the chiral carbon is assigned (R). If H Cl
CH.Cl.CH3
the arrow is anticlockwise the chiral carbon is assigned (S). 4
CH3
Example : Alanine
NH2 NH2 (3)
COOH H
Cl CH3 CH3 Cl
C C (1)
H CH3 CH3 COOH HC Br Br CH (2)
CH3 H H CH3
R-enantiomer
2S
NH2 CH3
H
CH.Br.CH3
C C H Br
COOH HOOC CH3 H Cl
H Cl CH3
(S) enantiomer CH3
(Always exchange the groups twice to get the same
compound. If you exchange the groups once you get the CHBrCH3 CHBrCH3
enantiomer).
CH3 Cl Cl CH3
By using Fischer Projections :
H H
NH2 NH2 3R
H COOH CH3 COOH
CH3
CH3 H
H Br
Hence the compound is (2S, 3R).
H Cl
NH2
COOH HOOC CH3 CH3
H (2S, 3R)
(S) enantiomer
b - hydroxybutyric aldehyde
JEEMAIN.GURU
downloaded from jeemain.guru
434 Chemistry
(i) Acids are chain isomers 4 Write all possible isomers of each formula and report what
(ii) Acids,esters and aldol are functional isomers type of isomerism exists in each
(iii) Aldol contains asymmetric C-atom and can exist in (a) C4H11N (b) C4H8
two optically active forms and one racemic form Sol.
NH 2
OH |
|
CH 3 - CH 2 - CH 2 - CH 2 - NH 2 CH3 - CH 2 - C H - CH3
CH 3 - C*- CH 2 .CHO
| 1- amino butane (I) 2 - amino butane (II)
H
CH 3
2. Write the possible isomers of C 4 H 8 O and type of CH 3 |
CH 3 - C - CH3
isomerism | |
CH 3 - C H - CH 2 - NH 2 NH 2
CH 3 CH 3
Sol. C = O n - C3H 7 | 1 - amino 2- methyl propane (III) 2- amino 2- methyl propane (IV)
C2 H5 C=O CH 3 - CH - CHO
H CH3
|
(I) (II) (III)
CH 3 - CH 2 - CH 2 - NH - CH 3 CH3 - CH - NH - CH3
Ethyl methyl Ketone n -butyraldehyde Isobutyraldehyde
Methyl propylamine (V) methyl isopropylamine (VI)
Functional isomers I and II, I and III
Chain isomers II and III CH3
3. Write the possible isomers of C3 H 6 O 3 and type of isom- |
C2H5 - NH - C2 H5 CH3 - N - C 2 H5
erism existing between them
diethyl amine (VII) ethyl dimethylamine (VIII)
Sol. (HCHO) 3 CH 3CHOHCOOH CH 2 OH.CH 2 COOH Position isomers I and II, III and IV
(I) (II) (III) Chain isomers I and III, I and IV
Functional isomers 1°, 2° and 3° amines are functional iso-
Meta formaldehyde a - hydroxy b- hydroxy mers
propionic acid propionic acid Metamers :- VI, V, VII
Functional isomers I and II, I and III
C 4H8 :
Position isomers II and III
Ring chain isomers I and II, 1 and III (i) CH 3CH 2 .CH = CH 2 but -1-ene
(ii) CH 3CH = CH CH 3 but - 2 - ene
CH 2
O O CH 3 H CH 3 CH 3
C=C C= C
CH 2 CH 2 H CH 3 H H
O trans (A) cis (B)
CH 3
Trioxane (meta formaldehyde) (iii) C = CH 2 2 - methyl propene
Stereoisomers :- II will show optical isomerism due to the CH 3
presence of an asymmetric C- atom.
(iv) Cyclobutane
COOH COOH
CH 3
H OH HO H
(v) methyl cyclopropane
CH 3 CH 3 Chain isomers I and III, II and III
Position isomers I and II
Ring chain isomers I and IV, II and IV
It will have the one racemic formed (dl, ± ) Geometrical isomers A and B forms of II
JEEMAIN.GURU
downloaded from jeemain.guru
Isomerism 435
CH 3
CH - O - CH 3
CH 3
N -methyl aniline Benzylamine
methyl iso-propyl ether
6. Write possible isomers of C8 H 8 O 2
9. Write Keto-enol tautomers of phenol C 6 H 5 OH
CH 3 CH 3 CH 3 O
OH
COOH H
Sol. Sol. H
COOH
COOH enol form Keto form
o- Toluic acid m - Toluic acid p - Toluic acid 10. Write possible isomers of C 4 H 4 O 4 and type of isomerism
exhibited by them
COOCH 3 OCOCH 3 CH 2COOH
Sol. H - C - COOH HOOC - C - H
|| ||
H - C - COOH H - C - COOH
Maleic acid Fumaric acid
methylbenzoate phenyl acetate phenylacetic acid
These are Geometrical isomers.
JEEMAIN.GURU
downloaded from jeemain.guru
436 Chemistry
JEEMAIN.GURU
downloaded from jeemain.guru
Isomerism 437
(a) configuration (b) conformation 18. The molecular formula of diphenyl methane,
(c) structure (d) chirality
CH2 , is C13H12.
How many structural isomers are possible when one of the
hydrogens is replaced by a chlorine atom?
(a) 6 (b) 4 (c) 8 (d) 7
JEEMAIN.GURU
downloaded from jeemain.guru
438 Chemistry
16. The compound C4H10O can show 28. Which of the following compounds exhibits geometrical
(a) metamerism (b) functional isomerism isomerism ?
(c) position isomerism (d) All of these (a) C2H5Br (b) (CH)2(COOH)2
17. Isomers of propionic acid are (c) CH3CHO (d) (CH2)2(COOH)2
(a) HCOOC2H5 and CH3COOCH3 29. Which is a pair of geometrical isomers ?
(b) HCOOC2H5 and C3H7COOH
Cl Br Cl Br
(c) CH3COOCH3 and C3H7OH
I. C=C II. C=C
(d) C3H7OH and CH3COCH3 H Br H CH3
r
18. C6H5C º N and C6H5N = C are which type of isomers? Br
Cl CH3 H
(a) Position (b) Functional III. C=C IV. Cl C=C
Br H CH3
(c) Tautomerism (d) Linkage
19. A functional isomer of 1-butyne is (a) I and II (b) I and III
(a) 2-butyne (b) 1-butene (c) II,III and IV (d) III and IV
(c) 2-butene (d) 1, 3-butadiene 30. Which of the following compounds will exhibit geometrical
20. The number of primary amines of formula C4H11N is isomerism ?
(a) 1-phenyl-2-butene (b) 3-phenyl-1-butene
(a) 1 (b) 2
(c) 2-phenyl -1-butene (d) 1,1-diphenyl-1-propene
(c) 3 (d) 4
31. But-2-ene exhibits cis-trans-isomerism due to
21. The number of isomers possible for C7H8O is
(a) rotation around C3 – C4 sigma bond
(a) 2 (b) 3
(b) restricted rotation around C = C bond
(c) 4 (d) 5
(c) rotation around C1 – C2 bond
22. The total number of isomeric alcohols with the molecular
(d) rotation around C2 – C3 double bond
formula C4H9OH is
32. The restricted rotation about carbon-carbon double bond
(a) 2 (b) 3
in 2- butene is due to
(c) 4 (d) 5
(a) overlap of one s- and one sp2-hybridized orbitals
23. The number of possible acyclic structural isomers of C4H10O is (b) overlap of two sp2-hybridized orbitals
(a) 5 (b) 6 (c) overlap of one p-and one sp2-hybridized orbitals
(c) 7 (d) 8 (d) sideways overlap of two p-orbitals
24. Tautomerism will be exhibited by 33. Which of the following has zero dipole moment?
(a) (CH3)3CNO (b) (CH3)2NH (a) cis-2-butene (b) trans-2-butene
(c) R3CNO2 (d) RCH2NO2 (c) 1-butene (d) 2-methyl-1propene
25. IUPAC name for the compound 34. Which of the following has zero dipole moment?
Cl CH 2CH 3 (a) 1, 1-dichloromethane
C=C is (b) cis-1, 2-dichloroethene
H 3C I (c) trans-1, 2-dichloroethene
(a) E-2-chloro-3-iodopentene-2 (d) 1-chloroethane
(b) Z-2-chloro-3-iodo-2-pentene 35. The number of geometrical isomers of
(c) E-3-iodo-4-chloro-3-pentene CH3CH=CH–CH=CH–CH=CHCl is
(d) Z-3-iodo-4-chloro-3-pentene (a) 2 (b) 4
26. The prefixes syn and anti are used to denote (c) 6 (d) 8
(a) structural isomers (b) conformational 36. The number of isomers for the compound with molecular
isomers formula C2BrClFI is
(a) 3 (b) 4 (c) 5 (d) 6
(c) geometrical isomers (d) optical isomers
37. Fischer projection indicates
27. How many structural (including stereoisomers) isomers
could be obtained by replacing one hydrogen of propene (a) horizontal substituents above the plane
with chlorine ? (b) vertical substituents above the plane
(a) 2 (b) 4 (c) both horizontal and vertical substituents below the plane
(c) 3 (d) 5 (d) both horizontal and vertical substituents above the plane
JEEMAIN.GURU
downloaded from jeemain.guru
Isomerism 439
38. An organic compound will show optical isomerism if 49. An organic molecule necessarily shows optical activity if it
(a) four groups attached to C atom are different (a) contains asymmetric carbon atoms
(b) three groups attached to C atom are different (b) is non-polar
(c) two groups attached to C atom are different (c) is non-superimposable on its mirror image
(d) all the groups attached to C atom are same (d) is superimposable on its mirror image
39. Which of the following molecules contain asymmetric carbon 50. Optically active isomers but not mirror images are called
atom ? (a) enantiomers (b) mesomers
(a) CH3CHClCOOH (b) CH3CH2COOH (c) tautomers (d) diastereomers
(c) ClCH2CH2COOH (d) Cl2CHCOOH 51. The two compounds shown in the figure below are
40. Which of the following compound is not chiral?
O O
(a) DCH2CH2CH2Cl (b) CH3CHDCH2Cl
or
(c) CH3CHClCH2D (d) CH3CH2CHDCl
41. Consider the following
1 2 3 4 5 6 7 (a) diastereomers (b) enantiomers
C H 3 - C H 2 - C H 2 - C H 2 - C H 2 - C H 2 - C H3
(c) epimers (d) regiomers
To make it a chiral compound, the attack should be on carbon 52. Which of the following is optically active ?
(a) 1 (b) 3 (c) 4 (d) 7 (a) Oxalic acid (b) Ethylene glycol
42. The (R)- and (S)- enantiomers of an optically active (c) Glycerol (d) Tartaric acid
compound differ in 53. How many stereoisomers are possible for tartaric acid?
(a) their reactivity with achiral reagents (a) 2 (b) 3
(b) their optical rotation of plane polarized light (c) 4 (d) 5
(c) their melting points 54. Meso- tartaric acid is optically inactive due to the presence
(d) None of these of
43. (+)-Mandelic acid has a specific rotation of + 158º. What (a) molecular symmetry (b) molecular asymmetry
would be the observed specific rotation of a mixture of 25% (c) external compensation (d) two asymmetric C atoms
(–)- mandelic acid and 75% (+)-mandelic acid ? 55. The correct statement about the compounds A, B, and C
(a) + 118.5º (b) –118.5º
COOCH3 COOH COOH
(c) – 79º (d) + 79º H OH H OH H OH
44. Optical activity is measured by H OH H OH HO H
is
(a) Polarimeter (b) Refractometer COOH COOCH3 COOCH3
(c) Spectrograph (d) Tracer technique (A) (B) (C)
45. Which one of the following compounds is not optically (a) A and B are identical
active ? (b) A and B are diastereomers
(a) CH3CH2CH(CH3)CH2Cl (b) CH3CH2CH(CH3)2 (c) A and C are enantiomers
(c) CH3–CHOH–COOH (d) CH3–CHCl–CH2Br (d) A and B are enantiomers
46. An optically active compound is 56. How many optically active stereoisomers are possible for
(a) 1-bromobutane butane-2, 3- diol ?
(b) b-bromobutyric acid (a) 1 (b) 2
(c) 2-bromo-2-methylpropane (c) 3 (d) 4
(d) 1-bromo -2-methylpropane 57. The number of possible enantiomeric pairs that can be
produced during monochlorination of 2-methylbutane is
47. Which of the following is optically active ?
(a) 2 (b) 3
(a) butane (b) 4-methylheptane
(c) 4 (d) 1
(c) 3-methylheptane (d) 2-methylpentane
58. The number of enantiomers of the compound
48. Which of the following compounds exhibits stereoisomerism ? CH3CHBrCHBrCOOH is
(a) 2-methylbutene-1 (b) 3-methylbutyne-1 (a) 0 (b) 1
(c) 3-methylbutanoic acid (d) 2-methylbutanoic acid (c) 3 (d) 4
JEEMAIN.GURU
downloaded from jeemain.guru
440 Chemistry
59. Which of the following has a chiral carbon? 67. Which one of the following is the stablest structure of
(a) 2,3-dimethylpentane cyclohexatriene ?
(b) CH3–CH2–CH2–CHO (a) Chair form (b) Boat form
(c) (CH3)3CCH2CH2CH3 (c) Half chair form (d) Planar form
(d) (CH3)2CHCH2CH2CH2CH3 68. The isomers which can be converted into another form by
rotation of the molecule around single bond are
60. Me (a) geometrical isomers (b) conformers
Me H H (c) enantiomers (d) diastereomers
69. The most stable conformation of n-butane is
(a) skew-boat (b) eclipsed
Me H
(c) gauche (d) staggered -anti
Hydrogenation of the above compound in the presence of 70. In the following structures, which two forms are staggered
poisoned palladium catalyst gives conformations of ethane ?
(a) optically active compound
(b) an optically inactive compound H
H
H H H
(c) a racemic mixture H
H
(d) a diastereomeric mixture H
H
H H H
61. HO– H H
– CH = CH – CH – COOH will show.. H H
H H
OH (1) (2) (3)
(a) geometrical isomerism
(b) optical isomerism
H
(c) geometrical and optical isomerism H
(d) neither geometrical nor optical isomerism H
H H H
62. Number of stereoisomers of the compound, 2-chloro-4-
(4)
methylhex-2-ene is/are
(a) 1 (b) 2 (a) 1 and 4 (b) 2 and 3
(c) 4 (d) 6 (c) 1 and 2 (d) 1 and 3
63. The number of stereoisomers for pent-3-en-2-ol is 71. Which of the following is the most stable form of
(a) 2 (b) 4 cyclohexane ?
(c) 3 (d) 5 (a) boat (b) chair
H (c) twist boat (d) half chair
|
64. C6 H 5 CHO + HCN ¾¾
® C6 H 5 - C - CN 72. In the boat conformation of cyclohexane, the most
| destabilizing interaction is
OH
The product would be (a) eclipsing (b) 1, 3-diaxial
(a) a racemate (c) 1, 3-diequatorial (d) flagpole -flagpole
(b) optically active 73. The stability of the compounds
(c) a meso compound
(d) a mixture of diastereomers
65. The process of separation of a racemic modification into d -
and l- enantiomers is called
(i) (ii) (iii) (iv)
(a) resolution (b) dehydration
(c) revolution (d) dehydrohalogenation (a) (iv) > (iii) > (i) > (ii) (b) (i) > (iii) > (ii) > (iv)
66. An important chemical method to resolve a racemic mixture (c) (ii) > (iii) > (i) > (iv) (d) (iv) > (i) > (iii) > (ii)
makes use of the formation of 74. The Baeyer’s angle strain is expected to be maximum in
(a) a meso compound (b) enantiomers
(a) cyclodecane (b) cyclopentane
(c) diastereomers (d) racemate
(c) cyclohexane (d) cyclooctane
JEEMAIN.GURU
downloaded from jeemain.guru
Isomerism 441
1. CH3 – CHCl – CH2 – CH3 has a chiral centre. which one of the 7. Which of the following does not show geometrical
following represents its R-configuration? [CBSE-PMT 2007] isomerism? [AIEEE 2002]
(a) 1,2-dichloro-1-pentene (b) 1,3-dichloro-2-pentene
C 2 H5 C2 H5 (c) 1,1-dichloro-1-pentene (d) 1,4-dichloro-2-pentene
| |
(a) H - C - CH3 (b) Cl - C - CH3 8. Racemic mixture is formed by mixing two [AIEEE 2002]
| | (a) isomeric compounds (b) chiral compounds
Cl H (c) meso compounds (d) optical isomers.
9. Among the following four structures I to IV, [AIEEE 2003]
CH3 C2 H5 O CH3
| | CH3 || |
|
(c) H - C - Cl (d) H 3C - C - Cl C 2 H 5 - CH - C3 H 7 , CH 3 - C - C H - C 2 H 5 ,
| |
C 2 H5 ( I) ( II )
H
<
O O |
|| || (a) CH3 - C -
CH3 - C- CH 2 - C- CH 3 |
C2H5
II
CH3
OH O |
| || (b) CH3 - CH 2 - CH - CH3
CH 3 - C = CH - C - CH 3
III (c) CH 3 - CH 2 - CH 2 - CH 3
(d) CH 3 - CH 2 - C º CH
(a) III > II > I (b) II > I > III
(c) II > III > I (d) I > II > III 11. Which of the following compounds is not chiral?
5. The type of isomerism present in nitropentamine chromium [AIEEE 2004]
(III) chloride is [AIEEE 2002] (a) 1-chloro-2-methyl pentane
(a) linkage (b) ionization (b) 2-chloropentane
(c) polymerisation. (d) optical (c) 1-chloropentane
6. A similarity between optical and geometrical isomerism is (d) 3-chloro-2-methyl pentane
that [AIEEE 2002] 12. Increasing order of stability among the three main
(a) each forms equal number of isomers for a given conformations (i.e. Eclipse, Anti, Gauche) of 2-fluoroethanol
compound is [AIEEE 2006]
(b) if in a compound one is present then so is the other
(c) both are included in stereoisomerism (a) eclipse, anti, gauche (b) anti, gauche, eclipse
(d) they have no similarity. (c) eclipse, gauche, anti (d) gauche, eclipse, anti
JEEMAIN.GURU
downloaded from jeemain.guru
442 Chemistry
13. Which of the following molecules is expected to rotate the (a) S, S (b) R, R (b) R, S (c) S, R
plane of plane-polarised light? [AIEEE 2007] (a) 3-methyl-2-pentene (b) 4-methyl-1-pentene
COOH CHO (c) 3-methyl-1-pentene (d) 2-methyl-2-pentene
16. The alkene that exhibits geometrical isomerism is :
(a) H2N H (b) HO H
[AIEEE 2009]
H (a) 2- methyl propene (b) 2-butene
CH2OH
(c) 2- methyl -2- butene (d) propene
H2N NH2
17. The number of stereoisomers possible for a compound of the
(c) (d) H H molecular formula
Ph Ph CH3 – CH = CH – CH(OH) – Me is: [AIEEE 2009]
SH
14. Which one of the following conformations of cyclohexane is (b) 2 (c) 4 (d) 6 (d) 3
chiral? [AIEEE 2007] 18. Out of the following, the alkene that exhibits optical isomerism
(a) Boat (b) Twist boat is [AIEEE 2010]
(c) Rigid (d) Chair. (a) 3-methyl-2-pentene (b) 4-methyl-1-pentene
15. The absolute configuration of [AIEEE 2008] (c) 3-methyl-1-pentene (d) 2-methyl-2-pentene
HO2C CO2H 19. The number of stereoisomers obtained by bromination of
trans-2-butene is [IIT-JEE 2007]
OH
(a) 1 (b) 2 (c) 3 (d) 4
HO H H
1. The molecular formula of a saturated compound is 5. The maximum number of stereoisomers possible for
C 2 H 4 Br2 . This formula permits the existence of 3 - hydroxy - 2 -methyl butanoic acid is
(a) 1 (b) 2
(a) functional isomers (b) optical isomers
(c) positional isomers (d) cis-trans isomers (c) 3 (d) 4
2. The production of an optically active compound from a 6. The optically active tartaric acid is named as D - (+) - tartaric
symmetric molecule without resolution is termed acid because it has a positive
(a) Walden inversion (b) Partial racemisation (a) optical rotation and is drived from D - glucose
(c) Asymmetric synthesis (d) Partial resolution (b) pH in organic solvent
3. Which of the following is optically active (c) optical rotation and is derived from D - (+) -
(a) n - propanol (b) 2 - chlorobutane glyceraldehyde
(c) n - butanol (d) 3 - hydroxy pentane (d) optical rotation when substituted by deuterium
4. Geometrical isomerism is not shown by 7. The enol form of acetone after treatment with D2O gives:
CH3 O
OD
| | ||
(a) CH 3CH 2 C = C CH 2 CH 3 (a) CH 3 - C = CH 2 (b) CH 3 - C - CD 3
|
CH3
OH OD
| |
(b) C 2 H 5 - C = C - CH 2 I (c) CH 2 = C - CH 2 D (d) CD 2= C - CD 3
| |
H H 8. Two geometrical isomers are given by the following
compound
(c) CH 2 = C(Cl)CH3
(a) ethylidene bromide (b) acetylene tetrachloride
(d) CH 3 - CH = CH - CH = CH 2 (c) acetylene tetrabromide (d) acetylene dibromide
JEEMAIN.GURU
downloaded from jeemain.guru
Isomerism 443
9. Only two isomeric monochloro derivatives are possible for : 16. How many stereoisomers are possible for the molecule?
(a) n - butane
(b) 2, 4 - dimethylpentane H CH 3
(c) benzene C=C OH
H C=C
(d) 2 - methylbutane
10. Keto-enol tautomerism is observed in CH 3
HO–C
O O
|| ||
(a) C 6 H 5 - C - H (b) C 6 H 5 - C - CH 3
O
(a) 2 (b) 4
(c) C 6 H 5 - C - C 6 H 5 (d) (d) None of these
|| (c) 6 (d) 8
O 17. The configuration of the compound
11. Ethoxy ethane and methoxy propane are
Cl
(a) geometrical isomers (b) optical isomers
(c) functional group isomers (d) metamers
12. The number of structural and configurational isomers of a (a) E (b) Z
bromo compound, C5H9Br, formed by the addition of HBr to (c) Both (a) and (b) (d) Neither (a) nor (b)
2 - pentyne respectively are 18. The alcohol product(s) of the reduction of 2-methyl-3-
(a) 1 and 2 (b) 2 and 4 pentanone with LiAlH4 is (are)
(c) 4 and 2 (d) 2 and 1 O
13. The structure, (i ) LiAlH diethyl ether
¾¾ ¾ ¾4¾ ¾ ¾ ¾¾®
CH3 H (ii) H 2O
C=C H
CH3 C (a) a single enantiomer (b) racemic mixture
COOH shows :
CH3 (c) two diastereoisomers (d) two structural isomers
19. How many stereoisomers of phenyl propylene oxide are there ?
(a) geometrical isomerism
H O H
(b) optical isomerism
(c) geometrical and optical isomerism
(d) tautomerism CH 3
14. Which of the alkenes shown below are member of a pair of E
- Z isomers ? (a) 1 (b) 2
H Cl (c) 4 (d) None of these
20. What is the R and S configuration for each stereogenic centre
(A) Cl (B) Cl in this sugar from top to bottom ?
O H
H H
H Cl H OH
HO H
(C) (D) H OH
H H CH 2 OH
H Br (a) R, R, S (b) R, S, S
(a) A and C only (b) B and C only (c) R, S, R (d) S, S, R
(c) A and D only (d) None of these 21. How many isomers have the compound bromomethyl
15. The correct priorities for the substituents shown below, cyclopentane (ignoring chirality) ?
according to the E-Z sequence rule is (a) 4 (b) 5
I. – CN II. – CBr (CH 3 ) 2 (c) 6 (d) 7
O 22. The structure shown below has the configuration
|| CH 2 CH 3
III. – COOH IV. – CH 2 - C - OCH3
|
O
C C(CH 3 ) 3
||
V. – C - H CH(CH 3 ) 2
(a) II, III, V, I, IV (b) V, II, I, IV, III (a) R (b) S
(c) III, IV, I, II, V (d) II, V, I, IV, III (c) Both (a) and (b) (d) Neither (a) nor (b)
JEEMAIN.GURU
downloaded from jeemain.guru
444 Chemistry
23. The structure of allene is 29. Which of the following optically active compounds racemizes
CH 2 = C = CH 2 in dil. KOH/ CH 3OH solution ?
(a) staggered (b) planar O O
(c) eclipsed (d) None of these H CH 3
(a) (b)
24. The compound showing geometrical isomerism
CH 3 C6 H5
Br
(a) C 6 H 5 CH = NOH (b)
Br O
O
H 3C C6 H 5
(c) (d) All of these (c) (d)
H CH 3
25. Which of the following will show tautomerism ?
30. How many stereoisomeric aldohexoses are there ?
O (a) four (b) eight
(c) sixteen (d) eighteen
31. What is the relationship between open chain forms of D-
(a) glucose and D-altrose ?
(a) enantiomers
O (b) constitutional isomers
(c) diastereomers
(d) different conformations of the same compound
(b) O = = =O 32. Which of the following compounds will not have diastereo
isomers ?
O (a) COOH (CHOH ) 2 COOH
(b) CH 3 CHOH.COOH
(c)
(c) CH 2 OH (CHOH ) 4 CHO
O (d) CH 2 OH (CHOH ) 4 CH 2 OH
33. The correct number of chiral centres in
O C 2 H5 C 2 H 5
(d)
(a) 1 (b) 3
O (c) 4 (d) 2
34. Give the correct relationship among the followings :
26. Identify the Keto form of the following enol
CHO CH 2 OH CHO
H OH H OH H OH
OH H OH H OH HO H
(a) 1-penten-3-one (b) (E)-3-penten-2-one CH 2 OH CH 2 OH CH 2 OH
(c) 2-pentanone (d) (E)-3-pentanal
(A) (B) (C)
27. What is the relationship between keto and enol tautomers? (a) A and B are identical
(a) Resonance forms (b) A and B are diastereomers
(b) Constitutional isomers (c) A and C are diastereo isomers
(c) Stereoisomers (d) A and C are enantiomers
(d) Different conformations of the same compound 35. The number of metamers given by the compound
28. Which of the following has the highest percentage of enol in
a Keto-enol equilibrium ? – O – CH 2 .CH 3
(a) Hexanal (b) 2-hexanone (a) 3 (b) 4
(c) 2, 4-hexanedione (d) 2, 5-hexanedione (c) 5 (d) 6
JEEMAIN.GURU
downloaded from jeemain.guru
Isomerism 445
36. The number of asymmetric C-atom created and number of 39. The stereo isomers formed when cis-2-butene is reacted with
possible stereoisomers when benzil (Ph.CO.CO.Ph) is reduced Br2 .
with LiAl H 4 . (a) meso-2, 3-dibromo butane
(a) 2, 3 (b) 2, 2 (b) racemic 2, 3-dibromo butane
(c) pair of diastereomers
(c) 2, 4 (d) 3, 2
(d) cannot be predicted
37. An optically active compound (A) is treated with NaI/acetone 40. Which of the followings is Z-isomer ?
(B) is obtained
Cl CH 3
(a) C=C
CH 3 CH 3 FF C 2 H5
NaI
H I ¾¾ ¾
¾® I H FF Br
acetone (b) C=C
C2 H5 C2 H 5 Cl H
O
(A) (B)
What is true about (B) ? CHO C–H
(c)
(a) optically active C=C
H H
(b) optically inactive and racemic form
CH 3OOC CH 3
(c) optically inactive
(d) C=C
(d) None of these H OH
38. The following compounds A, B, C have R or S configurations 41. The two compounds given below are
JEEMAIN.GURU
downloaded from jeemain.guru
446 Chemistry
5. (c) C5H10 has 1º degree of unsaturation since the isomers 9. (b) 2, 2, 4, 4 - Tetramethylhexane has 10 carbon atoms, only
are acyclic, all of these are alkenes. For writing the 4-isopropylheptane has also 10 carbon atoms so these
isomers, first introduce the double bond at different two are isomers.
possible positions, and then consider the possibility of 10. (c) Convert these Newmann projections into open chain
branching in the alkyl group. structures.
CH3CH2CH2CH =CH2 CH3CH2CH=CHCH3 CH3 CH3
1-pentene (i) 2- pentene, (cis,- trans) (ii), (iii) H Cl H H
H H H H
CH 3 CH3
| | CH3 CH2Cl
CH 3- C H - CH = CH 2 CH 3CH 2 C = CH 2 Both structures have same molecular formula C4H9Cl,
thus these are isomers. However, the two have different
3-methyl-1-butene, (iv) 2-methyl-1-butene, (v)
groups, viz CH 3 and CH 2Cl, so these are neither
CH 3 enantiomers nor diastereomers. Hence these are
| structural isomers.
CH 3 - C = CHCH 3
11. (b) 12. (b) 13. (a) 14. (a) 15. (c)
2-methyl-2-butene, (vi) 16. (d) 17. (a) 18. (b) 19. (d)
JEEMAIN.GURU
downloaded from jeemain.guru
Isomerism 447
20. (d) Introduce - NH2 at various possible positions to get
C6H5
different isomers which is possible only, on C1 and C2. |
Now observe isomerism in the alkyl part C 6 H 5 CH 2 CH = CHCH 3 CH 2 = CH CHCH3
(C4H9–) of the amine which is three
1-phenyl-2-butene 3-phenyl-1-butene
NH 2
| C6 H 5
CH3CH2CH2CH2NH2 CH 3CH 2 C HCH 3 |
CH 2= C CH 2 CH 3 (C6H5)2C=CHCH3
(CH3)2CHCH2NH2 (CH3)3CNH2
2-phenyl-1-butene 1, 1- diphenyl -1-propene
21. (d) Molecular formula C7H8O points out the presence of
one benzene ring (relatively less number of H atoms); so Note that only in first structure both of the doubly
it can be C6H5CH2OH and its other isomers. bonded carbon atoms have different groups.
C6H5CH2OH C6H5OCH3 OH.C6H4.CH3 31. (b) 32. (d) 33. (b) 34. (c)
Benzylalcohol (i) Anisole (ii) o -, m-, p- Cresols, (iii), 35. (d) The given structure has three double bonds whose each
(iv) and (v) carbon atom is differently substituted hence number of
22. (c) Alcohol may be 1º, 2º and 3º; further analyse the geometrical isomers will be 2n = 23’ = 8, where n is the
possibility of isomerism in each type of alcohol number of double bonds whose each carbon atom is
differently substituted.
CH 3 36. (d) Consider one doubly bonded carbon atom first, attach
|
CH3CH2CH2CH2OH CH 3CH 2 C HO H any one halogen atom (say F) on this C on one bond,
and then attach the three remaining halogen atoms, of
1-butanol, 1º 2-methylpropanol, 1 º course one by one, on the other bond.
OH CH3 F F F
| | C=C ; C=C ; C=C
CH 3CH 2 C HCH 3 CH 3- C - OH Cl Br I
|
CH3 Now attach the remaining two halogen atoms in each of
the above structures, for which there are two possibilities
2-butanol, 2º 2-methyl-2-propanol, 3º for every structure; so on the whole there will be 6
23. (c) There are four isomeric alcohols (mentioned in geometrical isomers.
the above question) and three isomeric ethers
F Br F I F Cl
corresponding to the formula C4H10O; CH3OC3H7–n; C=C C=C C=C
CH3OC3H7–iso and C2H5OC2H5 Cl I Cl Br Br I
24. (d) Only RCH2NO2 has a -hydrogen atom (I) (II) (III)
O OH F I F Cl F Br
+ + C=C C=C C=C
RCH2 – N RCH = N Br Cl I Br I Cl
O– O– (IV) (V) (VI)
25. (a) 26. (c) 37. (a) 38. (a) 39. (a)
27. (b) Replace three different types of hydrogen atoms,one by 40. (a) None of the carbon atoms in DCH2CH2CH2Cl is chiral
one. i.e., each carbon atom is achiral (symmetric).
1 2 3 4 5 6 7
CH3 C=CH2 CH3 CH=CH2 CH2CH=CH2 41. (b) C H 3 - C H 2 - C H 2 - C H 2 - C H 2 - C H 2 - C H 3
JEEMAIN.GURU
downloaded from jeemain.guru
448 Chemistry
51. (a) Since the configuration at the chiral centre is same , the
CH3 CH3
two structures (optical isomers) are not mirror images, |
hence these are diastereomers. *|
59. (a) CH 3 - CH - CH - CH 2 CH 3
52. (d) 53. (b) 54. (a) 2, 3 - dimethylpentane
55. (d) Rotation of B through 180º within the plane of the paper (has chiral C)
gives D which is an enantiomer of A, hence A and B are
enantiomers CH3
|
COOH CH 3 - C - CH 2 CH 2CH 3
|
H OH CH3
Rotate through 180º
H OH ¾¾¾¾¾¾¾¾¾ ®
with the plane of the paper 2, 2 - dimethylpentane
COOCH3 (No chiral carbon)
(B)
CH3
COOCH3 COOCH3 |
CH 3 - CH - CH 2 CH 2 CH 2 CH 3
OH H H OH
HO H H OH 2 - Methylhexane
(No chiral carbon)
COOH COOH
(D) (A)
JEEMAIN.GURU
downloaded from jeemain.guru
Isomerism 449
* EXERCISE 3
63. (b) CH 3 - CH - CH = CH CH 3 ;
|
OH 2
Pent - 3 - en - 2 - ol C2H5
3
As in above question, total number of stereoisomers
1. (b) Cl — C — CH3
=2×2=4 1
64. (a) Since during the reaction, a chiral carbon is created and
further since the CN– ion can attack the planar aldehyde H 4
group both from the top and the bottom face of the R-configuration
aldehyde group with equal ease, therefore, a 50:50 mixture
of the two enantiomers, i.e. a racemic mixture is obtained. 2. (a) In the molecule
65. (a)
CH3CH = CH CH 2 CH - CH3,
66. (c) Diastereomers have different solubility, m.p. and b.p., |
hence they can be separated by fractional crystallisation. Br
67. (d) Since all the six carbon atoms of cyclohexatriene the number of stereoisomers is given by sum of
(benzene) are sp2 hybridized, therefore its stablest geometrical isomers (because of presence of C = C) and
structure is planar form. optical isomers (because of presence of chiral carbon
68. (b) 69. (d) atom).
70. (c) Note that in structures 1 and 2, every two adjacent Number of geometrical isomers = 2 (one C = C is present).
hydrogen atoms are at maximum possible distance from Number of optical isomers = 2 (one chiral carbon atom).
each other (staggered conformation). Total number of stereoisomers = 2 + 2 = 4
71. (b) 3. (d) Alkenes with double bonds cannot undergo free rotation
72. (d) Boat conformation of cyclohexane has two types of and can have different geometrical shapes with two
destabilizing interactions, i.e. eclipsing and flagpole- different groups on each end of the double bond.
flagpole. Out of these flagpole-flagpole interaction is
the most destabilizing. CH3 CH3 CH3 H
C=C C=C
73. (a) Cyclohexane (iv) is non-planar and has chair H H H CH3
conformation. In this conformation, the bond angle is cis-But-2-ene trans-But-2-ene
the normal tetrahedral angle (109°, 28’) and thus has no
4. (a) Enolic form predominates in compounds containing
angle strain and hence is most stable. The rest of the
two carbonyl groups separated by a – CH2 group. This
molecules are nearly planar and hence their stability
is due to following two factors.
depends upon the angle strain in accordance with
Baeyer’s strain theory. Since cyclopropane has higher (i) Presence of conjugation which increases stability.
(ii) Formation of intramolecular hydrogen bond
æ 109° 28'– 60° ö
angle strain ç = 24°, 44' ÷ than between enolic hydroxyl group and second
è 2 ø carbonyl group which leads to stablisation of the
molecule. Hence the correct answer is III > II > I.
æ 109° 28'–108° ö
cyclopentane ç = 0°, 44' ÷ . Therefore 5. (b) The nitro group can attach to metal through nitrogen as
è 2 ø (–NO2) or through oxygen as nitrito (–ONO).
cyclopentane (iii) is more stable than cyclopropane (i). 6. (c) Optical and geometrical isomers are stereoisomers
Further, because of the presence of a double bond in a
three membered ring, cyclopropene (ii) is the least stable. Cl
7. (c) C = CH-CH 2 - CH 2 CH3 does not show geometrical
Thus the order of stability is (iv) > (iii) > (i) >(ii). Cl
74. (a) As the size of the ring increases, the internal angle isomerism due to presence of two similar Cl atoms on the
increases accordingly. As a result, the deviation from same C-atom.
the tetrahedral angle and hence the angle strain increases 8. (d) Racemic mixture is formed when enantiomers are mixed in
as the size of the ring increases. Thus, planar equimolar proportion
cyclodecane is expected to have the maximum angle
9. (a) A chiral object or structure has four different groups
strain.
attached to the carbocation.
JEEMAIN.GURU
downloaded from jeemain.guru
450 Chemistry
10. (a) Only 2- cyclopropyl butane has a chiral centre. 18. (c) For a compound to show optical isomerism, presence
11. (c) 1-chloropentane is not chiral while others are chiral in of chiral carbon atom is a necessary condition.
nature
H
Cl Cl |
C–C–C–C–C; C–C–C–C–C; H 2 C = CH — C* — CH 2 - CH3
1–chloropentane *
2–chloropentane |
CH3
3- methyl-1-pentene
Cl C C Cl
C–C–C–C–C C–C–C–C–C
*
1–chloro-2-methyl pentane
*
3–chloro-2-methyl pentane
19. (a) Anti addition of Br2 on trans alkene provides meso
compound.
12. (c) The greater the distance between the atoms or groups
CH3
the more is the stability of conformers. Hence the order
H 3C H H Br
of stability is C= C + Br2 ¾CCl
¾¾ 4®
H CH 3 H Br
F F H F CH3
H H HO H
Therefore, no. of stereoisomers = 1
HO
H H H H H H
OH H H EXERCISE 4
anti or staggered eclipsed Skew or
Gauche 1. (c) C 2 H 4 Br2 represents 1, 1-dibromoethane and 1, 2 -
dibromethane which are position isomers
13. (b) The organic compounds which have chiral carbon atom 2. (c) It is definition of asymmetric synthesis
(a carbon atom attached to four different group or atoms
and do not have plane of symmetry rotate plane Cl
|
polarised light. 3. (b) CH3 - CH - CH 2 CH3 contains asymmetric C - atom
CHO
| 4. (c) The condition for geometrical isomerism is
HO - C*- H (C* is asymmetric carbon) a a a e
| c=c
CH 2 OH
or c=c
b b b d
JEEMAIN.GURU
downloaded from jeemain.guru
Isomerism 451
OH N C CH 3
| |
7. (a) The enol form of acetone is CH3 - C = CH 2 with | |
15. (a) - C - N , - C - CH 3 ,
| | |
OD N C Br
|
D2O it gives CH 3 - C = CH 2
(i) (ii)
a a
8. (d) BrCH = CHBr . It fulfills the condition of c=c OH H O-C
b b | | |
- C - O, - C - C - OCH 3 ,
| | | |
Cl O C H O
|
9. (a) CH3 - CH 2 CH - CH3 , CH3CH 2 CH 2CH 2 - Cl (2 from (iii) (iv)
n-butane)
O-C
Cl | |
-C-O
(1from benzene) (All positions are the same) |
H
C C
(v)
C–C–C–C–C
o Arrange (NNN), (BrCC), (OOO), (CHH), (OOH) in
(3 from 2, 4 - dimethylpentane) ( there are three different increasing atomic number. The order is ii, iii, v, i, iv.
positions, ·, c, and o) 16. (a)
·C
17. (a) The groups of higher priority Cl and – C 2 H 5 are on
|
opposite sides.
· C- C - C- C
* o
18. (b) The resulting compound is C3 H 7 .CHOH.C 2 H 5 which
(4 from 2 - methyl butane) ( there are 4 different is optically inactive and reaction leads the racemisation.
positions, ·, c, o and *)
11. (d) There are metamers Each structure will have two configurations.
Br
| O H C - O
12. (b) C - C = C - C - C structural : 1, geometrical : 2 C 2
| H OH O - C - H
H 20. (c) HO H 4 H - C - OH 1
H OH HO - C - H
H CH 2 OH
| H - C - OH 3
C - C = C - C - C structural : 1, geometrical : 2.
| CH 2 OH
Br
JEEMAIN.GURU
downloaded from jeemain.guru
452 Chemistry
3 OCH 3 OCH 3
CH 3 , ,
2 C 1 R configuration CH 3
4
H 3C – OCH 3
H H
23. (a) Allene has the structure C=C=C staggered
H H OH OH
| |
24. (d) Write cis and trans configuration for each. 36. (a) Ph.CO.CO. Ph ¾LiAlH
¾ ¾¾ 4®
Ph - C x - C x - Ph The
| |
O OH H H
product contains two similar asymmetric carbon atoms
25. (a) are tautomers. and two optically active and one optically inactive meso
form.
O O CH3
|
37. (b) The reaction proceeds through planar CÅ
3 5 H C2 H 5
26. (b) 1
| 2 4 leading to racemisation.
OH O 38. (d)
The keto form has E configuration. Br Br
27. (b) The keto enol tautomers are constitutional isomers. CH 3 CH 3 | |
39. (b) Br2
C=C ¾¾
¾® CH3 - C - C - CH3
28. (c) Enol form of 2, 4-hexane dione
H H | |
O H O H H
CH 3C = CH - C - CH 2 - CH 3 Racemic form
40. (c)
is stabilised by H-bonding.
41. (a) The given compounds are identical.
O 42. (d) None can have the enol form due to absence of H-atom
||
29. (d) The compounds containing - C - group adjacent to O
||
asymmetric carbon atom carrying a hydrogen easily on the carbon adjacent to - C - group.
racemise.
JEEMAIN.GURU
downloaded from jeemain.guru
13
Hydrocarbons
SATURATED HYDROCARBONS, PARAFFINS OR (II) Derived names : In this system the higher hydrocarbons are
ALKANES : considered as derived from methane, eg.
They are open chain compounds of carbon and hydrogen having
all the atoms linked together by single covalent bonds, least H H CH3
reactive in nature | |
CH 3 - C - CH 2 - CH 3 CH 3 - C - CH
(Parum = little; affins = affinity) and having general formula CnH2n+2 | | CH3 ;
;
H H
NOMENCLATURE : ethyl m ethyl m ethane methyl iso propyl methane
(I) Trivial names : The first four members have the trivial names
derived from their preparation from corresponding alcohols (III) IUPAC system
containing same number of carbon atoms eg. methane from Types of carbon atoms :
methyl alcohol, ethane from ethyl alcohol and so on. After
(I) Primary (1°) - It is attached to one carbon atom only.
butane they are named according to Latin or Greek numerals
(II) Secondary (2°) - It is attached to two carbon atoms.
of the number of Carbon atoms present in them with class
suffix-ane. eg. Pentane (penta = 5) : hexane (hexa = 6) and so (III )Tertiary (3°) - It is attached to three carbon atoms.
on. (IV) Quaternary (4°) - It is attached to four carbon atoms.
The straight chain hydrocarbons are called normal (n) and
1° 1°
contain 1° or 1° & 2° carbon atoms. The branched chain C C
1° 2° 1°
hydrocarbons containing the group (CH 3 ) 2 CH - are called C – C 4°
–C–C–C
3°
Iso and contain 1° & 3° or 1°, 2° and 3° carbon atoms. The C1°
hydrocarbons containing a quaternary carbon atom are
called neo (new). Isomerism : They exhibit chain isomerism
CH 3 - CH 2 - CH 2 - CH 3 CH 3 - C H - CH 3
; | ;
n -Bu tan e
CH 3
Iso - butane n-Pentane Isopentane Neopentane
JEEMAIN.GURU
downloaded from jeemain.guru
454 Chemistry
Occurrence : The crude petroleum and natural gas contain (IX) By Wolf. Kishner reduction : From Carbonyl compounds
hydrocarbons from C1 to C40. Ozokerite (a neutral wax) is a mixture
NH .NH
of higher solid hydrocarbons. Waxes of some plants and animals C = O + 4H ¾¾ ¾
2 ¾¾
2® CH 2 + H 2 O
KOH / glycol
also contain some higher paraffins.
GENERAL METHODS OF PREPARATION OF (X) By Berthlot's reaction :
ALKANES Electric arc
C + 2H 2 ¾¾ ¾ ¾¾® CH 4
(I) From unsaturated hydrocarbons : (Sabatier and Senderen's 1200°C
reaction)
(XI) From metal carbides :
H 2 / Ni
C n H 2 n + H 2 ¾¾ ¾
¾® C n H 2 n + 2
200°-300°C Al 4 C 3 + 12 H 2 O ¾
¾® 4Al(OH ) 3 + 3CH 4
Ni / H Be 2 C + 4H 2 O ¾
¾® 2Be(OH ) 2 + CH 4
C n H 2n - 2 + 2H 2 ¾¾ ¾
¾2® C H
n 2n + 2
300°C
(XII) From carbon monooxide
(II) By heating anhydrous sodium salt of fatty acid with soda
lime (Lab method). Ni + C
CO + 3H 2 ¾¾¾® CH 4 + H 2 O
255°C
CaO
RCOONa + NaOH ¾¾¾ ® RH + Na 2 CO 3 (XIII) By reduction of alcohols, aldehydes, ketones and
Δ
carboxylic acids :
(III) By reduction of alkyl halides with nascent hydrogen.
Red P
ROH + 2HI ¾¾ ¾® RH + I 2 + H 2 O
RX + 2H ¾
¾® RH + HX 200°C
JEEMAIN.GURU
downloaded from jeemain.guru
Hydrocarbons 455
Halogenation (Cl2)
CH 3Cl . CH 2 Cl 2 . CHCl 3 . CCl 4 (from methane)
UV light / or D
Direct Sun Light
C + 4HCl (explosive reaction) (from methane)
2Cl2
• Ease of replacement of hydrogen atom 3° > 2° > 1°. The relative rates being 5:3.8:1
• Order of reactivity of halogens F2 > Cl2 > Br 2 > I 2
• Iodination is reversible CH4 + I 2 CH3I + HI
5HI + HIO3 3I2 + 3H2O
It requires the use of oxidising agent such as HNO3, HIO3 etc.
• Fluro compounds are obtained from bromo or chloro compounds
2RBr + HgF2 2RF + HgBr2
• Chlorination and bromination proceed by free radical mechanism.
Sulphuryl Chloride
R – Cl + SO2 + HCl (Chlorination)
SO2Cl2+ light or peroxide
NO2
Nitration HNO3 |
CH 3CH 2 CH 2 NO 2 + CH 3 C H - CH 3 + CH 3 CH 2 NO 2 + CH 3 NO 2 (from propane)
450°C vapour phase
2CH 3 COOH + CO 2 + H 2 O (from neopentane)
Sulphonation
RSO3H + H 2O
H2SO4 400°C Alkyl sulphonic acid
,
Oxidation O2 Cu tube 100 atm.
CH 3OH ü
200°C ï
MoO / O2 ï
ï
RH HCHO + H 2 O ý From methane
Alkane (CH3COO)2 Mn/O2 ï
ï
HCOOH + H 2 Oþï
Alk. KMnO4 [O]
R 3COH (From Isobutane)
Alkanes containing 2° and 1° H atoms are generally not
oxidised by K2Cr2O7 and KMnO4
Combustion
CO 2 + H 2 O
O2 Excess D
CH 3
Isomerisation |
Anhy. AlCl3 + Conc. HCl CH 3 - C H - CH 3 (from n - butane)
Aromatisation Cr2O3
+ 4H2 (from n-Hexane)
450–500°C
Dehydrogenation
CH 3 - CH = CH 2 + H 2 (from propane)
Cr2O3 / Al2O3 D
CH 3 CH3
Alkylation | |
CH 3 - C - CH 2 - C H - CH 3
Isobutane + Isobutylene |
CH 3
2,2,4 - trimethyl pentane (common name isoctane)
Cracking D
CH 3 - CH = CH 2 + CH 4 + CH 2 = CH 2 + CH 3 - CH3
n-butane gives
CH3 CH3
(CH 3 ) 3 CH + CH3 COCH 3 | |
CH 3 - C - C - CH 3
Conc. H2SO4 | |
CH3 OH
2,3,3- trimethyl butanol - 2
JEEMAIN.GURU
downloaded from jeemain.guru
456 Chemistry
CONFORMATIONAL ANALYSIS :
H H
Ethane – H
H H H
C
C
H H H
H H H
Sawhorse projection Newman projection
Different arrangements of atoms in a molecule convertible into one another by rotation about single bond are called conformers
or conformations. Their study is known as conformational analysis. If the energy barrier to the rotation is nil or small, the rotation
is said to be free or almost free. Ethane can exist in an infinite number of conformations. They are
HH H H H
H H
H
H H
H HH H
H H H H
Eclipsed q = 60° Staggered q < 60° > 0 Skew
q = It is dihedral angle between C–H bonds on the front of a Newman projection and those on the back.
Order of stability : Staggered > Skew > Eclipsed
Energy barrier between eclipsed and staggered is 2.8 kcal/mol.
Conformations of Propane C3H8 :
H3C CH
3
H3C CH
3
CH3 CH3 H CH3
H CH3 H H
H H
H H H H
HH CH3
H H H H H
H
CH3
H H
q = 0° q < 60° > 0 q = 60° Gauche q = 180° Anti or Trans q= 120 ° Eclipsed
Fully Eclipsed Skew
Staggered
Order of stability : Anti > Gauche > Skew > Eclipsed > Fully Eclipsed
Energy barrier between fully eclipsed and fully staggered (anti) is 5.3 kcal / mol or 22 kJ/mol.
Conformations of Cyclohexane : It exists in two nonplanar, strainless forms, the boat and the chair form.
a Axial a a
e e
e e e
e
a a equatorial
a a
e
e
e e
e e
a a
Move up Move Down
Move Down a a
JEEMAIN.GURU
downloaded from jeemain.guru
Hydrocarbons 457
Equatorial hydrogens lie in the plane of the ring carbons. Nomenclature :
Axial hydrogens lie (up or down) the plane of the ring. (I) Common System : The suffix -ane of alkane is replaced
There are six equatorial and six axial hydrogens. In the flipping by -ylene, and named as Alkylenes eg. ethylene,
and reflipping between conformations, axial becomes propylene etc.
equatorial and vice versa. Chair form has the lowest energy. (II) IUPAC System : The suffix -ane of alkane is replaced
Cyclohexane can assume other shapes also. by -ene and hence named as Alkenes.
(III) Derived Names : They are named as substituted
derivatives of ethylene. For example
CH 3 - CH = CHCH 3 Common
IUPAC Derived
Name
Name name
Chair form Half Chair a -Butylene
But-2-ene s-Dimethyl
Most Stable or 2-Butylene ethylene
Isomerism : Alkenes show four types of isomerism
(I) Chain Isomerism :
5 3 1 2 3 1
4
6 4 2 5 3 1 4 2
Twist Boat Boat form Hex-1-ene 4-methyl pent-1-ene 3,3-dimethyl but-1-ene
(Least Stable)
Baeyer's Strain Theory : When ring compounds are formed, (II) Position Isomerism :
the bonds deviate from normal positions which produces a But-1-ene But-2-ene
condition of strain in the molecule. The strain is directly (III) Ring Chain Isomerism :
proportional to angle of deviation and can be calculated as
follows. The more the angle of deviation, the less is the
stability. But-1-ene Cyclo butane
Angle of deviation of cyclic compound (IV)Geometrical Isomerism :
JEEMAIN.GURU
downloaded from jeemain.guru
458 Chemistry
(IV)By dehalogenation of gem. halides : Alkenes with odd or even number of carbon atoms and
having any position of double bond can be prepared.
RCHX 2 + 2 Zn + X 2 CHR ¾
¾® R - CH = CHR + 2 ZnX 2
(VI)By partial reduction of alkynes :
(V) By electrolysis of Sodium or potassium salt of succinic Pd - CaCO Lindlar 's Catalyst
acid or its derivatives R - C º CR + 2H ¾¾ ¾ ¾ ¾
3 ¾ ¾ ¾ ¾¾
¾® R - CH = CHR
Quinoline (always cis Isomer )
HX
CH 3 .CH 2 X (Order of reactivity of HX HI > HBr > HCl)
(Anti and Syn addition)
HOX hypohalous acid
CH 2 OH.CH 2 Cl ethylene chlorohydrin
CH2Cl . CH2NO
Ethylene nitroso chloride
O3 O
CH2 CH2 H2O
Ozone 2HCHO + H2O2 2HCOOH
O O H2/Zn
2HCHO + H2O
CH2
O
CH2
Ethylene Oxide
1% alk. KMnO4 Cold CH2OH
(Test for unsaturation)
Baeyer's reagent CH2OH
Hydroxylation
Ethylene glycol (Syn. addition)
JEEMAIN.GURU
downloaded from jeemain.guru
Hydrocarbons 459
[O]acid KMnO4
or acid K2Cr2O7 CH2 OH [O]
2HCOOH
CH2OH
The double bond is completely cleaved; the molecule is split into two
molecules. If carbon has two hydrogens it will become CO 2. If carbon has one
hydrogen it will become carboxylic acid. If carbon has no hydrogens it will
become a ketone. For example,
CH3 + CH3
KMnO4/H
C = CH2 C = O + CO2
CH3 CH3
CH3 H +
KMnO4/H CH3 OH
C=C C=O+O=C
Periodic acid HIO4 CH3 CH3 CH3 CH3
or lead tetra acetate
(H2O + O) CH3 CH3
COH C = O + HCHO
CH3 CH3
CH2 OH
H2O2 / CH3COOH CH2OH
CH2OH
C6H5.CO.OOH H2 O
C–C C–C
Perbenzoic acid 160
O OH OH
Oxide Glycol
Oxy-mercuration - demercuration
R-CH-CH3 (from R-CH= CH)2
OH
or (Addition of H2O according to
H2O + acid or Catalyst BF3,Mn phosphate Markownikoffs rule)
Cl(500–
2 600ºC)
Cl CH2– CH = CH2 (from propene)
Allylic substitution Allyl chloride
CH2
methyl cyclopropane
JEEMAIN.GURU
downloaded from jeemain.guru
460 Chemistry
Isomerisation Al2(SO4)3
at 200 – 300ºC
CH 3 - CH 2 - CH = CH 2 ¾
¾® CH 3 - CH = CH - CH 3
or D above 500º – 700º C
But-1-ene gives But-2-ene
Polymerisation
–(CH2 – CH2)n polythene
O2 D
Combustion
CO2 + H2O + heat
JEEMAIN.GURU
downloaded from jeemain.guru
Hydrocarbons 461
(A) Electrophilic Addition Reactions :
Addition of HX CH 2 HX
CH 3
|| ¾¾¾® |
CHX CHX 2
Ethylidene halide
CH 3 CH 3
H O
R–C CH | ¾¾2¾® |
CH(HSO 4 ) 2 CHO
Ethylidene hydrogen Sulphate ( Acetaldehyde)
HCN / Ba (CN)2
CH2= CHCN
Acrylonitrile
CH3COOH / Hg2+
CH 2 = CHOOC.CH 3 ¾
¾® CH 3 - CH(OOCCH 3 ) 2
Vinyl acetate Ethylidene acetate
JEEMAIN.GURU
downloaded from jeemain.guru
462 Chemistry
Addition of CO + HO
2
CH2= CH.COOH
Ni (CO)4 Acrylic acid
Cl
CuCl (aq.) + NH4Cl HCl
|
CH 2 = CH - C º CH ¾¾
¾® CH 2 = CH - C = CH 2
Vinyl acetylene Chloroprene
( monomer of Neoprene rubber )
Polymerisation
hot copper tube
Benzene
HCHO under pressure Partial
HC º C.CH 2 OH ¾¾¾
¾® CH 2 = CH.CH 2 OH
Propargyl alcohol reduction Allyl alcohol
K2Cr2O7 + H2SO4[O]
CH3COOH
Acetic acid
SeO2 CHO
| glyoxal
CHO
N2 electric spark
2HCN
Na or NaNH2 (alc.)
HC º CNa ¾
¾® NaC º CNa
Sod. acetylide di Sod. acetylide
Cu2Cl 2/ NHO4H
Cu.C º C.Cu
Copper acetylide (Red ppt.)
O O O O Formic acid
Ozonide Glyoxal
Combustion
CO2 + H2O
S
Thiophene
H
Pyrrole
All the products obtained in the above reactions are from acetylene.
JEEMAIN.GURU
downloaded from jeemain.guru
Hydrocarbons 463
AROMATIC HYDROCARBONS : distill
Benzene C6H6 ¾¾¾® Benzene + Some toluene + Thiophene
110°C
A Benzene
Preparation - A Small scale preparation : Again distill
¾¾ ¾ ¾ ¾® Almost pure benzene
(I) From acetylene : at 80-82°C
OH SO3H
Sulphonation Conc. HS2O4
Zn dust + ZnO +
distillation Electrophile SO3 or HSO3
Benzene
Sulphonic acid
(IV) From Chlorobenzene : Cl
Cl Halogenation Cl / Fe2Cl3
+
Mg/dil. HCl Electrophile Cl Chlorobenzene
+ 2H + HCl
CH 3
Friedel Crafts's Alkylation
(V) From benzene sulphonic acid : CH3Cl/Anhy Al3Cl
+
SO3H Electrophile CH
(Carbonium ion) Toluene
200°C + H2SO4
+ 2H2O COCH 3
Friedel Crafts's Acylation
Steam CH3COCl/Anhy AlCl3
(VI) From benzene diazonium chloride : +
Electrophile CH3CO
acylium ion Acetophenone
N2Cl
(B) Addition reaction :
H3PO2
+ N2 + HCl 3H2/Ni
+
Cu
Cyclohexane
(B) Large Scale preparation :
(I) From Petroleum : n-hexane fraction of petroleum
Cl
3Cl2, UV light Cl Cl
Cr2O3 / Al2O3
CH3 (CH 2 )CH3 ¾¾¾¾¾¾
® + 4H2
n - Hexane 550°C Cl Cl
Cl
(II) From light-oil fraction of Coal tar BHC - Benzene Hexa Chloride,
Gammexane,Lindane used as insecticide.
Conc. H SO
2 4 ® ¾¾¾¾ NaOH
Light oil fraction ¾¾¾¾¾¾ ® ¾¾¾® + +
- pyridene - phenol 110°
JEEMAIN.GURU
downloaded from jeemain.guru
464 Chemistry
4 or
benzene a planar compound whereas above structure
is non planar.
delocalised p
. M.O.
JEEMAIN.GURU
downloaded from jeemain.guru
Hydrocarbons 465
PETROLEUM
CaC 2 + 2H 2 O ¾
¾® C 2 H 2 + Ca (OH ) 2
Petroleum (petra = rock, oleum = oil). A thick dark coloured
complex liquid, mixture of organic compounds obtained from below Polymerisa tion
3C 2 H 2 ¾¾ ¾ ¾ ¾¾® C 6 H 6 ;
the surface of the earth is petroleum. The chief components of
petroleum are hydrocarbons, aliphatic, alicyclic (naphthalenes) C2H 2 + H 2 ¾
Polymerisa tion
¾® C 2 H 4 ¾¾ ¾ ¾ ¾¾® C 6 H12
or aromatic in varying proportions and 1 to 6 percent of Sulphur,
Nitrogen and Oxygen compounds. The theory was supported by Moissan, Sabatier and
Senderens. It fails to explain the presence of optically active
Natural Gas : Found along with petroleum and roughly contains
compounds, Compounds of N and S, chlorophyll and haemin
60 to 80 percent methane 5 to 9 percent ethane, 3 to 18 percent
derivatives.
propane, 2 to 14 percent higher hydrocarbons. It is used as fuel.
(II) Engler's Theory : Petroleum is a product of slow
Partial combustion of natural gas yields Carbon blocks (reinforcing
decomposition of dead marine animals under high
agents for rubber).
temperature and pressure. It explains the presence of brine,
Theories of origin :
fossils, compounds of N and S.
(I) Mendeleef 's Carbide Theory :
It explains the presence of all the above mentioned
¾® Al 4 C 3 ;
4Al + 3C ¾ compounds including chlorophyll. Hence petroleum is of
animal as well as vegetable origin.
Ca + 2C ¾
¾® CaC 2 (III)Modern Theory : Petroleum is produced by partial
decomposition of marine animals and sea weeds etc.
¾® 3CH 4 + 4Al(OH ) 3 ;
Al 4 C 3 + 12 H 2 O ¾ Mining and Refining : Recovery from oil wells and separation
of individual components.
Flash Point : The minimum temperature at which an oil gives Anti Knock Compounds : 59% Tetra ethyl lead, 13% Ethylene
off sufficient vapours to form an explosive mixture with air is bromide, 24% Ethylene chloride, 4% Kerosene and dye is
called Flash Point. anti knock mixture.
Knocking : A sharp metallic sound emitted by internal In presence of aromatic compounds tetramethyl lead is more
combustion engine owing to immature ignition of the air effective.
gasoline mixture. Knocking is maximum in presence of straight Octane number : The percentage of iso octane (2, 2, 4-
chain hydrocarbons and minimum in presence of aromatic trimethyl pentane) in a mixture of iso octane and n-heptane
and branched chain hydrocarbons. having the same knocking properties as the fuel under
consideration.
JEEMAIN.GURU
downloaded from jeemain.guru
466 Chemistry
The higher the octane number, the better is the fuel. (V) Aromatisation :
Octane number of compunds : Aromatic Compounds > Cyclo
alkanes > Olefins > Branched chain alkanes > Straight
Chain alkanes. CH 3 - (CH 2 ) 4 - CH 3 ¾
¾® + 4H2
Cetane number : It is the percentage of cetane
(n-hexadecane) in a cetane and a-methylnaphthalene mixture
that has the same ignition qualities as the fuel. (VI) Chain Fission :
Cracking : The conversion of less valuable higher fraction
C16 H 34 ¾
¾® C 8 H18 + C 8 H16 or C 6 H14 + C10 H 20
to the more valuable lower fraction by the application of heat
is known as cracking. Synthetic Petrol :
(I) Liquid Phase Cracking : (I) Bergins Process :
475° -530°C
Heavy Oil (C18 - C 43 ) ¾¾ ¾ ¾ ¾ ¾ ¾ ¾
¾®(C 4 - C10 )
Catalyst 1000-1200 lbs psi
Sn, Pb or Mo Compounds
Catalyst : Silica, titanium dioxide, zinc oxide, ferric oxide, Powdered Coal + Heavy Oil ¾¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾
¾®
H 2 400 -500°C, 200 -700 Atm
alumina etc. High pressure keeps the oil in liquid state.
Octane number of product : 65-70.
(II) Vapour phase Cracking :
600-800°C Petrol
Kerosene oil or gas oil ¾¾¾ ¾¾® Lower fractions
50-150 lbs psi
F.D. Middle Oil
(III) Cracking in presence of hydrogen : Product ¾ ¾¾ ®
Catalyst
R - R + H 2 ¾¾ ¾¾® 2RH ü Heavy Oil
ï
ROH + H 2 ¾ ¾® RH + H 2 O ïï
ý Product free from O, S & N Heavy oil is reused.
¾® 2RH + H 2S ï
R 2S + 2H 2 ¾
ï (II) Fischer-Tropsch Process :
¾® 2RH + NH 3 þï
R 2 NH + 2H 2 ¾
S team + Coke (Red hot) ¾¾® CO + H 2
water gas
Reactions taking place during cracking :
JEEMAIN.GURU
downloaded from jeemain.guru
Hydrocarbons 467
cold dilute
+
cold dilute (D)
(i) (ii) KMnO4
(E)
KMnO4
17. Convert the following :
hot (a) Ethyne to ethanal
(iii) K2Cr2O7/H2SO4 (b) Tert. butyl chloride to 2,2,3,3 tetra methyl butane.
(c) Ethyne to benzene.
13. You are given three jars containing ethane, ethylene and
(d) Benzoic acid to benzene
acetylene, respectively. How will you identify each of them
by chemical test? (e) But 1–ene to butane 1,2– diol.
JEEMAIN.GURU
downloaded from jeemain.guru
468 Chemistry
Multiple Choice Questions 23. Arrange the following alkyl halides in decreasing order of
the rate of b–elimination reaction with alcoholic KOH.
18. Arrange the following in decreasing order of their boiling
points. H
— —
(A) n–butane (B) 2-methylbutane
(C) n-pentane (D) 2, 2–dimethylpropane (A) CH3—C—CH2Br
(a) A > B > C > D (b) B > C > D > A CH3
(c) D > C > B > A (d) C > B > D > A
19. Arrange the halogens F2, Cl2, Br2, I2, in order of their (B) CH3—CH2—Br
increasing reactivity with alkanes. (C) CH3—CH2—CH2—Br
(a) I2 < Br2 < Cl2 < F2 (b) Br2 < Cl2 < F2 < I2 (a) A > B > C (b) C > B > A
(c) F2 < Cl2 < Br2 < I2 (d) F2 < I2 < Cl2 < F2 (c) B > C > A (d) A > C > B
20. An alkene having molecular formula C7H14 was subjected
24. The addition of HBr to 1-butene gives a mixture of products
to ozonolysis in the presence of zinc dust. An equimolar
A, B and C
amount of the following two compounds was obtained
CH3 CH3 Br C2H5
C = O and C=O
CH3 CH3CH2 C C
(A) H5C2 CH3 (B) H CH3
The IUPAC name of the alkene is H Br
(a) 3, 4-dimethyl-3-pentene (b) 3, 4-dimethyl-2-pentene
(C) CH3—CH2—CH2—CH2—Br
(c) 2, 3-dimethyl-3-pentene (d) 2, 3-dimethyl-2-pentene
21. Which of the following reactions of methane is incomplete The mixture consists of
combustion ? (a) A and B as major and C as minor products
Cu / 523K /100atm 2CH OH
(a) 2CH4 + O2 ¾¾¾¾¾¾¾® (b) B as major, A and C as minor products
3
Mo2O3 HCHO + H O (c) B as minor, A and C as major products
(b) CH4 + O2 ¾¾¾¾ ® 2
(d) A and B as minor and C as major products
(c) CH4 + O2 ® C(s) + 2H2O(l)
25. Among the following compounds, the decreasing order of
(d) CH4 + 2O2 ® CO2 (g) + 2H2O(l)
22. The correct IUPAC name of following alkane is reactivity towards electrophilic substitution is
H2C—CH2—CH—CH2—CH2—CH—CH2—CH3
—
— —
CH CH2
CH3 CH3 CH3
CH3 OCH3 CF3
(a) 3,6 – Diethyl – 2 – methyloctane I II III IV
(b) 5 – Isopropyl – 3 – ethyloctane
(c) 3 – Ethyl – 5 – isopropyloctane (a) III > I > II > IV (b) IV > I > II > III
(d) 3 – Isopropyl – 6 – ethyloctane (c) I > II > III > IV (d) II > I > III > IV
1. Successive alkanes differ by 4. When petroleum is heated gradually, the first batch of
(a) CH2 (b) CH vapours evolved will be rich in
(c) CH3 (d) C2H4 (a) kerosene (b) petroleum ether
2. An alkyne has the general formula (c) diesel (d) lubricating oil
(a) CnH2n (b) CnH2n+2 5. The order of appearance of the following with rising
temperature during the refining of crude oil is
(c) CnH2n–2 (d) CnH2n+1
(a) kerosene oil, gasoline, diesel
3. Which of the following is not a mixture of hydrocarbons?
(b) diesel, gasoline, kerosene oil
(a) Candle wax (b) Kerosene (c) gasoline, diesel, kerosene oil
(c) Vegetable oil (d) Paraffin oil (d) gasoline, kerosene oil, diesel
JEEMAIN.GURU
downloaded from jeemain.guru
Hydrocarbons 469
6. LPG contains 20. Formation of alkanes by action of Zn on alkyl halides is
(a) methane (b) ethane called
(c) butane (d) None of these (a) Frankland's reaction (b) Cannizaro's reaction
7. Petrol for aviation purposes must contain (c) Wurtz's reaction (d) Kolbe’s reaction
(a) straight chain hydrocarbons 21. For preparing an alkane, a concentrated solution of sodium or
(b) aromatic hydrocarbons potassium salt of a saturated carboxylic acid is subjected to
(c) olefinic hydrocarbons (a) hydrolysis (b) oxidation
(d) highly branched chain paraffins (c) hydrogenation (d) electrolysis
8. In commercial gasoline, the type of hydrocarbons which are 22. Pure methane can be produced by
desirable is (a) Wurtz reaction
(a) Branched hydrocarbons (b) Kolbe’s electrolytic method
(b) Straight chain hydrocarbons (c) Soda-lime decarboxylation
(c) Linear unsaturated hydrocarbons (d) Reduction with H2
(d) All of these 23. Which of the following liberates methane on treatment with
9. Fischer-Tropsch process is used in the manufacture of water ?
(a) synthetic petroleum (b) ethanol (a) Silicon carbide (b) Calcium carbide
(c) benzene (d) ethanoic acid (c) Beryllium carbide (d) Magnesium carbide
10. Octane number is zero for 24. Which of the following methods is most appropriate for the
(a) isoheptane (b) n-heptane manufacture of methane ?
(c) isooctane (d) n-octane (a) Reduction of CH2Cl2
11. Which of the following has lowest octane number ? (b) Wurtz reaction
(a) Iso-octane (b) n-Heptane (c) Liquefaction of natural gas
(c) n-Hexane (d) n-Hexadecane (d) None of these
12. Which of the following has highest octane number ? 25. The reaction/method that does not give an alkane is
(a) n-Hexane (b) n-Heptane (a) catalytic hydrogenation of alkenes
(c) n-Pentane (d) 2, 2, 4-Trimethylpentane (b) dehydrohalogenation of an alkyl halide
13. The process in which higher hydrocarbons are broken down
(c) hydrolysis of alkylmagnesium bromide
into lower hydrocarbons by controlled pyrolysis is called
(d) Kolbe’s electrolytic method
(a) Hydrolysis (b) Cracking
26. Ethyl bromide on treatment with alcoholic KOH gives
(c) reforming (d) Both (a) and (b)
(a) ethylene (b) ethanol
14. A fuel has the same knocking property as a mixture of 70%
(c) acetic acid (d) ethane
isooctane (2,2,4-trimethylpentane) and 30% n-heptane by
volume. The octane number of the fuel is 27. When n-propyl iodide is heated with alcoholic KOH, one of
the products is
(a) 100 (b) 70
(c) 50 (d) 30 (a) Propene (C3H6) (b) Cyclopropane (C3H6)
15. Cetane number of a diesel fuel will increase with the addition (c) C3H4 (d) C3H8
of 28. 1-Chlorobutane, on reaction with alcoholic potash (KOH),
(a) n-Decane (b) n-Hexadecane gives
(c) n-Pentane (d) a-Methylnaphthalene (a) 1-Butene (b) 1-Butanol
16. Which one is used as an antiknock in petrol fuel ? (c) 2-Butene (d) 2-Butanol
(a) Basic lead carbonate (b) Lead tetraacetate 29. In preparation of alkene from alcohol using Al2O3 which is
(c) Tetraethyl-lead (d) Basic lead sulphate effective factor ?
17. Wurtz reaction involves the interaction of alkyl halides in (a) Porosity of Al2O3 (b) Temperature
dry ether with (c) Concentration (d) Surface area of Al2O3
(a) sodium (b) zinc 30. Which one of the following heptanols can be dehydrated to
(c) copper (d) platinum hept-3-ene only ?
18. Ethane is formed by the reaction of methyl iodide and (a) Heptan-3-ol (b) Heptan-4-ol
sodium metal in dry ether solution. The reaction is known (c) Heptan-2-ol (d) Heptan-1-ol
as 31. Which of the principle is applied in the following reaction ?
(a) Clemmensen reduction (b) Kolbe’s reaction alc. KOH
CH 3CHBrCH 2 CH 3 ¾¾ ¾ ¾®
(c) Wurtz reaction (d) Cannizzaro's reaction
19. Which one of the following cannot be prepared by Wurtz CH 3CH = CHCH 3 + CH 2 = CHCH 2 CH 3
reaction ? ( Major ) ( Minor )
(a) CH4 (b) C2H6 (a) Markovnikov’s rule (b) Saytzeff's rule
(c) C3H8 (d) C4H10 (c) Kharasch's effect (d) Hofmann's rule
JEEMAIN.GURU
downloaded from jeemain.guru
470 Chemistry
32. The conversion of 2, 3-dibromobutane to 2-butene with Zn 44. How many monochlorobutanes will be obtained on
and alcohol is chlorination of n-butane?
(a) redox reaction (b) a-elimination (a) 5 (b) 2
(c) b-elimination (d) Both (a) and (b) (c) 3 (d) 4
33. Coal-tar is a main source of 45. Conversion of CH4 to CH3Cl is an example of ......... reaction
(a) aromatic compounds (b) aliphatic compounds (a) electrophilic substitution
(c) cycloalkanes (d) heterocyclic compounds (b) nucleophilic substitution
34. Which of the following metal powder is used to convert (c) free radical substitution
trichloromethane into acetylene by heating the latter with it ? (d) free radical addition
(a) Na (b) Mg 46. The molecule having dipole moment is
(c) Ca (d) Ag (a) 2,2-dimethylpropane
35. Tetrabromoethane on heating with Zn gives (b) trans-2-pentene
(a) ethyl bromide (b) ethane (c) hexane
(c) ethene (d) ethyne (d) 2,2,3,3-tetramethylbutane
36. What is formed when calcium carbide reacts with heavy 47. Olefins can be hydrogenated by
water ? (a) zinc and hydrochloric acid
(a) C2D2 (b) CaD2 (b) raney nickel and hydrogen
(c) Ca2D2O (d) CD2 (c) nascent hydrogen
37. Monosodium acetylide reacts with an alkyl halide to form (d) lithiumaluminium hydride in ether
(a) an alkane 48. Which one of the following compounds would have the
(b) an alkene highest heat of hydrogenation ?
(c) an unsymmetric higher alkyne (a) CH 2 = CH 2
(d) a symmetric higher alkyne
38. Fractional distillation of coal-tar produces the following (b) CH 3 - CH 2 - CH = CH 2
fractions. Phenol is the main component of which fraction ? (c) CH 3CH = CHCH 3
(a) Light oil (b) Middle oil
(c) Heavy oil (d) Green oil (d) (CH3 ) 2 C = C(CH3 ) 2
39. Benzene is obtained by fractional distillation of 49. The reaction,
(a) light oil (b) middle oil CH 2 = CHCH 3 + HBr ® CH 3CHBrCH 3 is a type of
(c) anthracite oil (d) heavy oil
(a)electrophilic addition reaction
40. Heating a mixture of sodium benzoate or benzoic acid and
(b)nucleophilic addition reaction
soda-lime gives
(c)free radical addition reaction
(a) benzene (b) methane
(d)electrophilic substitution reaction
(c) sodium benzoate (d) calcium benzoate
41. Crude naphtha is a mixture of 50. CH 3 - CH = CH 2 + HI ¾ ¾® X , X is
(a) alkanes (b) conjugated dienes (a) CH3–CH2–CH2–I (b) CH3–CHI–CH3
(c) alkynes (d) alkyl halides (c) CH3CH2CH3 (d) None of these
42. Hydrocarbon which is liquid at room temperature is 51. When propene is treated with HBr in the dark and in absence
(a) pentane (b) butane of peroxide, the main product is
(c) propane (d) ethane (a) 1-Bromopropane (b) 2-Bromopropane
43. Which of the following isomers will have the highest boiling (c) 1,2-Dibromopropane (d) 1,3-Dibromopropane
point ? 52. Pentene-1 with HCl gives
(a) 3-Chloropentane (b) 2-Chloropentane
(a) CH 3 - CH 2 - CH 2 - CH 2 - CH 2 - CH 3 (c) 1,2-Dichloropentane (d) 1-Chloropentane
(b) CH 3 - CH - CH 2 - CH 2 - CH 3 53. Addition of HI to double bond of propene yields isopropyl
| iodide and not n-propyl iodide as the major product, because
CH3 addition proceeds throughs
(a) a more stable carbonium ion
(c) CH 3 - CH - CH - CH 3
| | (b) a more stable carbanion
CH 3 CH 3 (c) a more stable free radical
(d) homolysis
CH 3 54. Propene is reacted with HBr in presence of peroxides, the
|
(d) CH 3 - C - CH 2 - CH 3 product is
| (a) 2-Bromopropane (b) 1-Bromopropane
CH 3 (c) 3-Bromopropane (d) None of these
JEEMAIN.GURU
downloaded from jeemain.guru
Hydrocarbons 471
55. The principal organic product formed in the reaction, 64. Ozonolysis of C7H14 gave 2-methyl-3-pentanone. The alkene
peroxide is
CH 2 = CH(CH 2 )8 COOH + HBr ¾¾¾ ¾® is
(a) 2-ethyl-3-methyl-1-butene
(a) CH3CHBr(CH2)8COOH (b) 3-ethyl-2-methyl-3-butene
(b) CH2 = CH(CH2)8COBr (c) 2,5-dimethyl-3, 4-dimethylhex-3-ene
(c) CH2BrCH2(CH2)8COOH (d) 3-ethyl-2-methyl-1-butene
(d) CH2 = CH(CH2)7CHBrCOOH 65. Which one of the following is a free-radical substitution
56. Markovnikov’s rule is applicable to reaction ?
(a) CH2 = CH2 (b) CH3–CH2–CH3
CH3 CH3 Anh. AlCl3 CH3
(c) CH3–CH = CH–CH3 (d) C=C (a) + CH3Cl
CH3 C2H5
57. Which of the following compound gives similar products
obeying Markovnikov’s rule and peroxide effect ? CH2Cl CH2NO2
(b) + AgNO2
(a) CH3–CH=CH2 (b) CH3CH = CH–CH3
(c) C2H5–CH = CH–CH3 (d) C2H5–CH = CH2
58. The addition of HBr is easiest in (c) CH 3CHO + HCN ® CH 3CH (OH)CN
(a) CH2=CHCl (b) ClCH=CHCl
CH3 Boiling CH2Cl
(c) CH3–CH=CH2 (d) (CH3)2C=CH2
(d) + Cl2
59. 1, 3-Butadiene when treated with Br 2 gives
(a) 1, 4-dibromo-2-butene (b) 1, 3-dibromo-2-butene
(c) 3, 4-dibromo-1-butene (d) 2, 3-dibromo-2-butene 66. Ethylene reacts with 1% cold alkaline KMnO4 to form
60. Ozonolysis of 2, 3-dimethyl-1-butene followed by reduction (a) oxalic acid (b) ethylene glycol
with zinc and water gives (c) ethyl alcohol (d) HCHO
(a) methanoic acid and 3-methyl-2-butanone 67. Baeyer’s reagent is used in the laboratory for
(b) methanal and 2-methyl-2-butanone (a) detection of double bond
(c) methanal and 3-methyl-2-butanone (b) reduction process
(d) methanoic acid and 2-methyl-2-butanone (c) oxidation process
61. Position of double bond in alkenes can be identified by (d) detection of glucose
(a) bromine water 68. Baeyer’s reagent is
(b) ammonical silver nitrate solution (a) saturated KMnO4 soln. (b) neutral KMnO4 soln.
(c) ozonolysis (c) alkaline KMnO4 soln. (d) acidic KMnO4 soln.
(d) None of these 69. Which of the following has the lowest dipole moment ?
62. Which alkene on ozonolysis gives CH3 CH3
CH3CH2CHO and CH3COCH3 (a) C=C (b) CH 3C º CCH 3
H H
CH3
(a) CH3CH2CH = C (c) CH 3CH 2 C º CH (d) CH 2 = CH - C º CH
CH3 70. 3-Hexyne reacts with Na/liq. NH3 to produce
(b) CH3CH2CH = CHCH2CH3 (a) cis-3-Hexene (b) trans-3-Hexene
(c) CH3CH2CH=CHCH3 (c) 3-Hexylamine (d) 2-Hexylamine
(d) CH 3 - C = CHCH 3 71. The most suitable catalyst for the hydrogenation of
| 2-Hexyne ¾ ¾® 2-cis-Hexene is
CH 3 (a) Pd–BaSO4 (b) (Ph3P)3RhCl
63. An alkene having molecular formula C7H14 was subjected (c) 10% Pd—C (d) Raney Ni
to ozonolysis in the presence of zinc dust. An equimolar 72. Lindlar’s catalyst is
amount of the following two compounds was obtained (a) Na in alcohol (b) Raney nickel
CH3 CH3 (c) Pd/BaSO4 (d) Na/liq. NH3
C = O and C=O 73. Acetylene when reacts with two molecules of HBr, then it
CH3 CH3CH2
gives
The IUPAC name of the alkene is (a) Br - C º C - Br (b) Br - CH = CH - Br
(a) 3, 4-dimethyl-3-pentene (b) 3, 4-dimethyl-2-pentene
(c) 2, 3-dimethyl-3-pentene (d) 2, 3-dimethyl-2-pentene (c) Br2 CH - CHBr2 (d) CH 3 - CHBr2
JEEMAIN.GURU
downloaded from jeemain.guru
472 Chemistry
74. In the following reaction, 84. Propyne and propene can be distinguished by
(a) conc. H2SO4 (b) Br2 in CCl4
H 2O
C2H2 X CH3CHO (c) dil. KMnO4 (d) AgNO3 in ammonia
HgSO 4/H 2SO 4, 60ºC 85. Identify the reagent from the following list which can easily
what is X ? distinguish between 1-butyne and 2-butyne
(a) bromine, CCl4
(a) CH3CH2OH (b) CH3–O–CH3 (b) H2, Lindlar catalyst
(c) CH3CH2CHO (d) CH2 = CHOH (c) dilute H2SO4, HgSO4
75. When 2-pentyne is treated with dil. H2SO4 and HgSO4, the (d) ammonical Cu2Cl2 solution
product formed is 86. An organic compound, on treatment with Br2 in CCl4 gives
bromoderivative of an alkene. The compound will be
(a) 1-pentanol (b) 2-pentanol
(a) CH3 - CH = CH 2 (b) CH 3 CH = CHCH 3
(c) 2-pentanone (d) 3-pentanone
(c) HC º CH (d) H 2 C = CH 2
76. In which of the following hydrogen is most acidic?
87. Which of the following will yield a mixture of 2-chlorobutene
(a) Acetylene (b) Methane
and 3-chlorobutene on treatment with HCl ?
(c) Ethane (d) Ethylene
77. Match List I (Reagents used with ethyne) with List II (a) CH 2 = C = CH – CH3 (b) H 2 C = C - CH = CH 2
|
(products) and select the correct answer using the codes CH3
given below in the lists.
(c) CH 2 = CH - CH = CH 2 (d) HC º C - CH = CH 2
List I List II
88. An unknown compound A has a molecular formula C4H6,
I. Hydrogen chloride A Benzene
when A is treated with an excess of Br2, a new substance B
II. Hydrogen in presence B Acetaldehyde with formula C4H6Br4 is formed. A forms a white precipitate
of Ni at 573 K with ammonical silver nitrate solution. A may be
III. Hydrogen in presence C Ethene (a) Butyne-1 (b) Butyne-2
of Pd and BaSO4 at (c) Butene-1 (d) Butene-2
473 K 89. The hydrocarbon which decolourises alkaline KMnO 4
IV. Water in presence of D Ethane solution, but does not give any precipitate with ammonical
silver nitrate is
H2SO4 and HgSO4
(a) benzene (b) acetylene
Codes :
(c) propyne (d) butyne-2
(a) I-B, II-C, III-D, IV-A (b) I-A, II-D, III-C, IV-B 90. Select the true statement about benzene from amongst the
(c) I-A, II-D, III-B, IV-C (d) I-D, II-A, III-C, IV-B following
78. In its reaction with silver nitrate, acetylene shows (a) Because of unsaturation benzene easily undergoes
(a) oxidising property (b) reducing property addition
(c) basic property (d) acidic property (b) There are two types of C—C bonds in benzene molecule
(c) There is cyclic delocalisation of pi-electrons in benzene
79. When an alkyne, RC º CH , is treated with cuprous ion in
(d) Monosubstitution of benzene gives three isomeric
an ammonical medium, one of the products is
products
(a) RC º CCu (b) CuC º CH 91. Aromatic hydrocarbons undergo
(c) CuC º CCu (d) RC º CR (a) nucleophilic addition reactions
80. Which of the following does not give a white precipitate (b) electrophilic addition reactions
with AgNO3 solution ? (c) electrophilic substitution reactions
(d) None of these
(a) Propyne (b) 1-Butyne
92. Benzene on treatment with a mixture of conc. HNO3 and
(c) 2-Butyne (d) 1-Pentyne conc. H2SO4 at 100ºC gives
81. A compound is treated with NaNH2 to give sodium salt. (a) Nitrobenzene (b) m-Dinitrobenzene
Identify the compound (c) p-Dinitrobenzene (d) o-Dinitrobenzene
(a) C2H2 (b) C6H6 93. Which species represents the electrophile in aromatic
(c) C2H6 (d) C2H4 nitration ?
82. KMnO4 will oxidise acetylene to (a) NO -2 (b) NO +2
(a) ethylene glycol (b) ethyl alcohol (c) NO 2 (d) NO 3-
(c) oxalic acid (d) acetic acid 94. In the Friedel-Craft's synthesis of toluene, reactants in
83. Which one of the following gives Tollen’s reagent test ? addition to anhydrous AlCl3 are
(a) 1-Butanol (b) 2-Butanol (a) C6H6 + CH4 (b) C6H6 + CH3Cl
(c) 1-Butyne (d) 2-Butyne (c) C6H5Cl + CH3Cl (d) C6H5Cl + CH4
JEEMAIN.GURU
downloaded from jeemain.guru
Hydrocarbons 473
95. When CH3Cl and AlCl3 are used in Friedel-Craft's reaction, 106. The correct order of reactivity towards the electrophilic
the electrophile is substitution of the compounds aniline (I), benzene (II) and
nitrobenzene (III) is
(a) Cl + (b) AlCl-4
(a) II > III > I (b) I < II > III
(c) CH 3+ (d) AlCl+2 (c) I > II > III (d) III > II > I
96. Benzene reacts with CH3COCl + AlCl3 to give 107. Addition of Br2 to 1-butene would give 1, 2-dibromobutane
(a) chlorobenzene (b) toluene which is
(c) benzyl chloride (d) acetophenone (a) achiral (b) racemic
97. Which of the following is not a meta-directing group ? (c) meso (d) optically active
(a) SO3H (b) NO2
(c) CN (d) NH2 108. Addition of Br2 to trans-2-butene would give a product
98. In the reaction of C 6 H 5 Y, the major product which is
( > 60%) is m-isomer, so the group Y is (a) chiral (b) meso
(a) —COOH (b) —NH2 (c) racemic (d) optically active
(c) —OH (d) —Cl 109. Name of following reaction is
99. A group which deactivates the benzene ring
towards electrophilic substitution but which directs the
incoming group principally to the o- and p-positions is + || ¾
¾®
(a) –NH2 (b) –Cl CN CN
(c) –NO2 (d) –C2H5 (a) Claisen Condensation
100. The most reactive compound for electrophilic nitration is (b) Diel’s Alder reaction
(a) benzene (b) nitrobenzene
(c) Dieckmann cyclisation
(c) benzoic acid (d) toluene
101. Which of the following will be most easily attacked by an (d) Michael addition reaction
electrophile? 110. The cycloalkane having the lowest heat of combustion per
Cl CH 2 group
(a) (b)
(a) (b)
OH CH3
(c) (d) (c) (d)
C º C-H
(b)
I II III
(a) II > III > I (b) III < I < II
(c) I > II > III (d) I = II > III CºC
103. The most reactive among the following towards (c)
sulphonation is
(a) toluene (b) chlorobenzene
(c) nitrobenzene (d) m-Xylene (d) CH 3 - C º C - CH 3
104. Which of the following is the most reactive towards ring 112. Which of the following will give alkene in Kolbe’s electrolytic
nitration ? method ?
(a) Benzene (b) Mesitylene
CH. COOK
(c) Toluene (d) m-Xylene ||
105. Aromatic compounds burn with a sooty flame because (a) CH 3 - C. COOK (b) CH 3CH 2 COOK
(a) they have a ring structure of carbon atoms
(b) they have a relatively high percentage of hydrogen CH 2 COOK
(c) they have a relatively high percentage of carbon |
(c) CH 3 - CH COOK (d) All of these
(d) they resist reaction with oxygen of air
JEEMAIN.GURU
downloaded from jeemain.guru
474 Chemistry
JEEMAIN.GURU
downloaded from jeemain.guru
Hydrocarbons 475
10. In the following reaction : [CBSE-PMT 2012 S] 17. Acid catalyzed hydration of alkenes except ethene leads to
the formation of [AIEEE 2005]
CH3
+
(a) mixture of secondary and tertiary alcohols
H 2O/H (b) mixture of primary and secondary alcohols
C CH —
— CH2
(c) secondary or tertiary alcohol
CH3 (d) primary alcohol
18. Which one of the following conformations of cyclohexane
A B is chiral? [AIEEE 2007]
Minor Product + Major Product
(a) Boat (b) Twist boat
The major product is :
(c) Rigid (d) Chair.
CH3 19. The compound formed as a result of oxidation of ethyl
benzene by KMnO4 is [AIEEE 2007]
(a) C CH CH3 (a) benzyl alcohol (b) benzophenone
(c) acetophenone (d) benzoic acid.
OH CH3 20. Which of the following reactions will yield
CH3 2, 2-dibromopropane? [AIEEE 2007]
(a) CH3 – CH = CH2 + HBr ®
(b) C CH2 CH3 (b) CH3 – C º CH + 2HBr ®
(c) CH3CH = CHBr + HBr ®
OH CH3 (d) CH º CH + 2HBr ®
21. The reaction of toluene with Cl2 in presence of FeCl3 gives
CH3
predominantly [AIEEE 2007]
(c) (a) m-chlorobenzene (b) benzoyl chloride
C CH CH3
(c) benzyl chloride (d) o- and p-chlorotoluene.
CH3 OH 22. Toluene is nitrated and the resulting product is reduced
with tin and hydrochloric acid. The product so obtained is
CH3 diazotised and then heated wth cuprous bromide. The
reaction mixture so formed contains [AIEEE 2008]
(d) C CH2 CH2 (a) mixture of o- and p-bromotoluenes
(b) mixture of o- and p-dibromobenzenes
CH3 OH (c) mixture of o- and p-bromoanilines
11. Which of these will not react with acetylene? [AIEEE 2002] (d) mixture of o- and m-bromotoluenes
(a) NaOH (b) ammonical AgNO3 23. In the following sequence of reactions, the alkene affords
(c) Na (d) HCl. the compound ‘B’
12. What is the product when acetylene reacts with hypochlorous O H O
acid? [AIEEE 2002] CH 3 - CH = CH - CH 3 ¾¾3¾
® A ¾¾¾
2 ® B.
Zn
(a) CH3COCl (b) ClCH2CHO The compound B is [AIEEE 2008]
(c) Cl2CHCHO (d) ClCHCOOH. (a) CH3CH2CHO (b) CH3COCH3
13. On mixing a certain alkane with chlorine and irradiating it (c) CH3CH2COCH3 (d) CH3CHO
with ultraviolet light, it forms only one monochloroalkane. 24. The hydrocarbon which can react with sodium in liquid
This alkane could be [AIEEE 2003] ammonia is [AIEEE 2008]
(a) pentane (b) isopentane
(a) CH 3CH 2 CH 2 C º CCH 2 CH 2CH3
(c) neopentane (d) propane
14. Butene-1 may be converted to butane by reaction (b) CH 3CH 2 C º CH
with [AIEEE 2003]
(c) CH 3CH = CHCH3
(a) Sn – HCl (b) Zn – Hg
(c) Pd/H2 (d) Zn – HCl (d) CH 3CH 2 C º CCH 2CH3
15. Which one of the following has the minimum boiling point ?
25. The treatment of CH3MgX with CH 3C º C - H produces
[AIEEE 2004]
(a) 1 - Butene (b) 1 - Butyne [AIEEE 2008]
(c) n- Butane (d) isobutane (a) CH 3 - CH = CH 2
16. 2-Methylbutane on reacting with bromine in the presence of
(b) CH 3C º C - CH3
sunlight gives mainly [AIEEE 2005]
(a) 1-bromo-3-methylbutane H H
(b) 2-bromo-3-methylbutane | |
(c) 2-bromo-2-methylbutane (c) CH 3 - C = C - CH3
(d) 1-bromo-2-methylbutane (d) CH4
JEEMAIN.GURU
downloaded from jeemain.guru
476 Chemistry
26. One mole of a symmetrical alkene on ozonolysis gives two
moles of an aldehyde having a molecular mass of 44 u. The
alkene is [AIEEE 2010] (a) CHO (b) CHO
(a) propene (b) 1-butene
(c) 2-butene (d) ethene CO 2 H
27. Ozonolysis of an organic compound 'A' produces acetone (c) COOH (d)
CO 2 H
and propionaldhyde in equimolar mixture. Identify 'A' from
the following compounds: [AIEEE 2011] 31. The synthesis of 3-octyne is achieved by adding a
(a) 1 – Pentene bromoalkane into a mixture of sodium amide and an alkyne.
(b) 2 – Pentene The bromoalkane and alkyne respectively are
(c) 2 – Methyl – 2 – pentene [IIT-JEE 2010]
(d) 2 – Methyl – 1 – pentene (a) BrCH2CH2CH2CH2CH3 and CH3CH2C º CH
28. The non aromatic compound among the following is : (b) BrCH2CH2CH3 and CH3CH2CH2C º CH
[AIEEE 2011RS] (c) BrCH2CH2CH2CH2CH3 and CH3C º CH
(d) BrCH2CH2CH2CH3 and CH3CH2C º CH
32. The bond energy (in kcal mol–1) of a C–C single bond is
(a) (b) approximately [IIT-JEE 2010]
S (a) 1 (b) 10
(c) 100 (d) 1000
33. The number of optically active products obtained from the
(c) (d) complete ozonolysis of the given compound is :
[IIT-JEE 2012]
–
CH3 H
29. 2-Hexyne gives trans-2-Hexene on treatment with :
(a) Pt/H2 (b) Li / NH3 [AIEEE 2012]
CH3 CH CH C CH CH C CH CH CH3
(c) Pd/BaSO4 (d) Li AlH4
30. Cyclohexene on ozonolysis followed by reaction with zinc
dust and water gives compound E. Compound E on further H CH3
treatment with aqueous KOH yields compound F. (a) 0 (b) 1
Compound F is [IIT-JEE 2007] (c) 2 (d) 4
1. To prepare a pure sample of n-hexane using sodium metal as 5. An alkane C7H16 is produced by the reaction of lithium di(3-
one reactant, the other reactant will be pentyl) cuprate with ethyl bromide. The structural formula
(a) Ethyl chloride and n-butyl chloride of the product is
(b) Methyl bromide and n-pentyl bromide (a) 3-ethylpentane (b) 2-ethylpentane
(c) n-Propyl bromide (c) 3-methylhexane (d) 2-methylhexane
6. When ethyl alcohol is heated with conc. H2SO4 at 443 K,
(d) Ethyl bromide and n-butyl bromide
ethylene is formed by
2. Indicate the expected structure of the organic product when
(a) intramolecular hydration
ethyl magnesium bromide is treated with heavy water (D2O)
(b) intermolecular hydration
(a) C2H5–C2H5 (b) C2H5OD (c) intermolecular dehydration
(c) Sodium benzoate (d) C2H5D (d) intramolecular dehydration
3. (CH3)3CMgCl on reaction with D2O produces 7. Electrolysis of cold concentrated aqueous solution of
(a) (CH3)3CD (b) (CH3)3COD potassium succinate yields
(c) (CD)3CD (d) (CD)3COD (a) ethane (b) ethyne
4. The reagent used for the conversion, (c) ethene (d) ethane-1, 2-diol
8. When CH3CH2CHCl2 is treated with NaNH2, the product
CH 3CH 2 COOH ® CH 3CH 2 CH 3 is formed is
(a) LiAlH4 (a) CH 3 – CH = CH 2 (b) CH 3 – C º CH
(b) Soda-lime
NH2 Cl
(c) Red P and concentrated HI (c) CH3CH2CH (d) CH3CH2CH
(d) Zn – Hg/conc. HCl NH2 NH2
JEEMAIN.GURU
downloaded from jeemain.guru
Hydrocarbons 477
9. 1,2-Dibromopropane on treatment with X moles of NaNH2 17. Which of the following alkenes will react fastest with H2
followed by treatment with ethyl bromide gave pentyne. under catalytic hydrogenation conditions ?
The value of X is R R R H
(a) 1 (b) 2 (a) (b)
H H R H
(c) 3 (d) 4
R R R R
10. In the reaction, (c) (d)
R H R R
oxidation NaOH Soda - lim e 18. The conversion of ClCH=CHCl to Cl2CH–CHCl2 can be
C6 H 5CH3 ¾¾¾¾® A ¾¾¾® B ¾¾¾¾¾
®C,
D carried out with
the product C is (a) Cl2 (b) Cl2/hn
(a) C6H5OH (b) C6H6 (c) Cl2/AlCl3 (d) Cl2/aq. NaOH
(c) C6H5COONa (d) C6H5ONa 19. The products formed by the action of chlorine on ethene in
11. Reactivity of hydrogen atoms attached to different carbon saturated solution of KBr is/are
atoms in alkanes has the order (a) ClCH2CH2Cl + ClCH2CH2Br
(a) Tertiary > Primary > Secondary (b) ClCH2CH2Cl
(c) ClCH2CH2Cl + BrCH2CH2Br
(b) Primary > Secondary > Tertiary
(d) ClCH2CH2Cl + BrCH2CH2Br + ClCH2CH2Br
(c) Tertiary > Secondary > Primary
20. In methyl alcohol solution, bromine reacts with ethylene to
(d) Both (a) and (b) yield BrCH2CH2OCH3 in addition to 1, 2-dibromoethane
12. In the free radical chlorination of methane, the chain initiating because
step involves the formation of (a) the ion formed initially may react with Br – or CH3OH
(a) chlorine atom (b) hydrogen chloride (b) the methyl alcohol solvates the bromine
(c) methyl radical (d) chloromethyl radical (c) the reaction follows Markovnikov’s rule
13. Consider the following reaction, (d) this is a free-radical mechanism
·
21. The intermediate during the addition of HCl to propene in
H 3C - CH - CH - CH 3 + Br ®' X '+ HBr the presence of peroxide is
| |
D CH3 ·
+
(a) CH3CHCH 2 Cl (b) CH 3CHCH 3
Identify the structure of the major product ‘X’ +
·
(c) CH3CH 2CH 2 (d) CH 3CH 2C H 2
· ·
(a) CH3 - CH - CH - CH 2 (b) CH 3 - CH - C - CH 3 22. In presence of peroxide, hydrogen chloride and hydrogen
| | | |
D CH3 iodide do not give anti-Markovnikov’s addition to alkenes
D CH 3
because
· ·
(a) both are highly ionic
(c) CH 3 - C - C H - CH 3 (d) CH3 - C H - CH - CH3 (b) one is oxidising and the other is reducing
| | |
D CH 3 CH3 (c) one of the steps is endothermic in both cases
(d) all steps are exothermic in both cases
14. A hydrocarbon with molecular formula C8H18 gives only 23. Arrange the following compounds in increasing order of
one monochloro derivative. The hydrocarbon is reactivity towards the addition of HBr.
(a) n-Octane RCH=CHR, CH2=CH2, R2C=CHR, R2C=CR2
(b) 2-Methylheptane (a) CH2=CH2<RCH=CHR<R2C=CHR <R2C=CR2
(c) 2,2,4-Trimethylpentane (b) R2C=CHR<RCH=CHR<CH2=CH2 <R2C=CR2
(d) 2,3,3,3-Tetramethylbutane (c) RCH=CHR<R2C=CR2<R2C=CHR <CH2=CH2
15. Which of the following compounds has the lowest boiling (d) R2C=CR2<R2C=CHR<RCH=CHR <CH2=CH2
point ? 24. Which of the following is the predominant product in the
reaction of HOBr with propene?
(a) CH3CH2CH2CH2CH3
(a) 2-Bromo-1-propanol (b) 3-Bromo-1-propanol
(b) CH3CH = CHCH2CH3
(c) 2-Bromo-2-propanol (d) 1-Bromo-2-propanol
(c) CH3CH = CH–CH = CH2
25. The reaction of propene with HOCl proceeds via the addition
(d) CH3CH2CH2CH3 of
16. Among the following alkenes : 1-butene(I), cis-2-butene(II), (a) H+ in the first step
trans-2-butene(III), the decreasing order of stability is (b) Cl+ in the first step
(a) III > II > I (b) III > I > II (c) OH– in the first step
(c) I > II > III (d) II > I > III (d) Cl+ and OH– in a single step
JEEMAIN.GURU
downloaded from jeemain.guru
478 Chemistry
26. The products obtained via oxymercuration (HgSO4 + H2SO4) 34. Indicate the organic structure for product expected when 2-
of 1-butyne would be methylpropene is heated with acetyl chloride in the presence
of anhydrous ZnCl2 ?
(a) CH 3 - CH 2 - CO - CH 3
CH 3
(b) CH 3 - CH 2 - CH 2 - CHO |
(a) CH 3 - C - C = CH 2 (b) CH 3 - C - C - CH 3
(c) CH 3 - CH 2 - CHO + HCHO || | || |
O CH 3 O CH 3
(d) CH 3CH 2 COOH + HCOOH
27. Which set of products is expected on reductive ozonolysis CH 3 H
| |
of the following diolefin ? (c) CH 3 - C - CH 2 COCH 3 (d) CH 3 - C - CH 2 - COCH 3
| |
CH3 Cl CH 3
|
CH3CH = C - CH = CH 2 Hg2+ / H +
35. Ph - C º CCH3 ¾¾¾¾
¾® A , A is
(a) CH 3CHO ; CH 3COCH = CH 2 O
(a) Ph (b) Ph
(b) CH3CH = C - CHO ;CH 2O O
|
CH3 (c) Ph OH (d) Ph
OH
(c) CH 3CHO ; CH 3COCHO ; CH 2 O
36. Excess of CH3COOH is reacted with CH º CH in presence
(d) CH 3CHO ; CH 3COCH 3 ; CH 2 O of Hg2+, the product is
28. The alkene C6H10 producing (a) CH 3CH (OOCCH 3 ) 2
OHC(CH2)4CHO on ozonolysis is
(a) Hexene-1 (b) Hexene-3 (b) CH 2 = CH (OCOCH 3 )
(c) Cyclohexene (d) 1-Methylcyclohexene (c) (CH 3COO )CH 2 - CH 2 (OOCCH 3 )
29. 2.8 g of pure alkene containing only one double bond per (d) None of these
molecule, react completely with 8 g of bromine (in an inert 37. When acetylene reacts with arsenic trichloride in the
solvent). What is the molecular formula of the alkene ? presence of anhydrous aluminium chloride it produces
(a) C2H4 (b) C4H8 (a) b-Chlorovinyldichloroarsine
(c) C3H4 (d) C6H12 (b) Lewisite
(c) Nitrobenzene
CH 3 (d) Both (a) and (b)
|
30. The compound CH 3 - C = CH - CH 3 on reaction with 38. Which one of the following compounds will react with
methylmagnesium iodide ?
NaIO4 in the presence of KMnO4 gives
(a) CH3CH2CH2CH2CH3 (b) CH3CH=CH–CH=CH2
(a) CH3COCH3 + CH3COOH
(c) CH 3C º CCH 2 CH 3 (d) CH 3 CH 2 CH 2 C º CH
(b) CH3COCH3 + CH3CHO
(c) CH3CHO + CO2 39. Propyne on polymerization gives
(a) mesitylene (b) benzene
(d) CH3COCH3
(c) ethylbenzene (d) propylbenzene
+
CH3 H Br2, CCl4
40. 1-Butyne reacts with cold alkaline KMnO4 to produce
[F] C4H8Br2 (a) CH3CH2COOH
31. H3C OH –H 2O
(b) CH3CH2CH2COOH
5 such products
are possible (c) CH3CH2COOH + CO2
How many structures of F are possible ? (d) CH3CH2COOH + HCOOH
41. Two gases, P and Q decolourise aqueous bromine but only
(a) 2 (b) 5
one of them gives a white precipitate with aqueous ammonical
(c) 6 (d) 3 silver nitrate solution. P and Q are likely to be
32. When CH2 = CH – COOH is reduced with LiAlH4, the (a) ethane and ethyne (b) But-1-yne and but-2-yne
compound obtained will be (c) ethane and but-2-yne (d) ethyne and propyne
(a) CH3–CH2–COOH (b) CH2=CH–CH2OH 42. The compound X (C5H8) reacts with ammonical AgNO3 to
(c) CH3–CH2–CH2OH (d) CH3–CH2–CHO give a white precipitate, and on oxidation with hot alkaline
33. Ethyne can be oxidised to oxalic acid by using KMnO4 gives the acid, (CH3)2CHCOOH. Therefore, X is
(a) chromic acid (b) alkaline KMnO4 (a) CH2 = CHCH = CHCH3 (b) CH 3 (CH 2 ) 2 C º CH
(c) hypochlorous acid (d) Any of these
(c) (CH 3 ) 2 CH - C º CH (d) (CH3)2C = C = CH2
JEEMAIN.GURU
downloaded from jeemain.guru
Hydrocarbons 479
43. Choose the compound which can react with [Ag(NH3)2 ]+ 52. Two organic compounds A and B both containing only
and on treatment with alk. KMnO4 gives (CH3)3CCOOH carbon and hydrogen, on quantitative analysis gave the
(a) CH 3CH 2 CH 2 - C º C - CH 3 same percentage composition by weight :
C = (12/13) × 100%, H = (1/13) × 100%
(b) (CH 3 ) 2 CHCH 2 - C º CH
A decolourises bromine water but B does not. A and B
(c) (CH 3 ) 3 C - C º CH respectively are
(a) C2H2 and C6H6 (b) C6H6 and C2H2
(d) (CH 3 ) 3 C - C º C - CH 3
(c) C2H4 and C2H6 (d) C2H2 and C2H6
44. Which of the following possesses the highest melting point
53. What is the correct product of reaction ?
?
(a) Chlorobenzene (b) o-Dichlorobenzene CH 3
(c) m-Dichlorobenzene (d) p-Dichlorobenzene 1. BH , THF
¾¾ ¾3¾ ¾® ?
45. The function of AlCl3 in the Friedel-Craft's reaction is 2. H 2O 2 , OH -
(a) to absorb water (b) to absorb HCl
(c) to produce electrophile (d) to produce nucleophile CH 3 CH 3
46. Which one of the following will undergo metasubstitution
(a) H (b)
on monochlorination ? H
(a) Ethoxybenzene (b) Chlorobenzene H
(c) Ethyl benzoate (d) Phenol H
47. Which of the following deactivates benzene towards further
substitution reaction ? CH 3 CH 3
(a) —NHR (b) —OH (c) (d) H
H H
(c) —COOR (d) —OR
48. Which of the following will have fastest rate of reaction H
with Br2/FeBr3? 54. Choose the correct alkyne and reagents for the preparation
NO2
(a) (b) of
CH3 OCH3
(a) , HgSO 4 , H 2SO 4 , H 2 O
(c) (d)
JEEMAIN.GURU
downloaded from jeemain.guru
480 Chemistry
56. Which sets of reagents would give the correct product ? 59. The product of the following reaction
CH 2
¾
¾® ||
CH I , Zn (Cu )
¾¾ ¾
2 2¾ ¾ ¾
¾®
Diethyl ether
O
||
(a) Hg (O - C - CF3 ) 2
(c) BH 3 , NaOH / H 2 O 2
CH 3 C º CH C CH 3
CH 2 HO C
NBS, CCl ( heat )
HO
NaOH
¾¾ ¾ ¾ ¾
4 ¾¾®
¾¾¾¾®
benzoyl peroxide
CH 3 (c) (d)
CH 3
61. The major product obtained in the following reaction
Method II : O
|| Br
CH 3 ¾¾
¾2®
?
FeBr3
Br / FeBr Mg / ethane
(i ) H C = O
3 ® ¾¾ ¾¾¾®
¾¾2¾¾¾ ¾¾ ¾2¾ ¾¾® O
(ii ) H 3O + ||
(a) Br
CH 3
O
(a) Method I ||
(b) Method II (b) Br
(c) Both (I) and (II) are equally good
(d) Neither (I) nor (II) O
||
58. The reaction of cis-2-butene with CH 2 I 2 and Zn(Cu) to
(c) Br Br
give cis-1, 2-dimethyl cyclopropane is
(a) stereospecific reaction
O
(b) enantiospecific reaction ||
(c) diastereoselective reaction (d)
(d) regioselective reaction Br
JEEMAIN.GURU
downloaded from jeemain.guru
Hydrocarbons 481
62. The unsaturated hydrocarbon which on ozonolysis gives 69. Bromination of ethyl benzene in presence of light gives
one mole each of formaldehyde, acetaldehyde and methyl
C2 H5 C2 H5
glyoxal ( CH 3 CO.CHO)
Br
(a) CH 3 – CH = C( CH 3 ) – CH 3 (a) (b)
(b) CH 2 = CH – CH 2 – CH = CH 2
(c) CH 2 = CH – C( CH 3 ) = CH – CH 3 Br
(d) (CH 3 ) 2 C = CH - CH 3 Br
63. Which of the following is not the mechanistic step during
CH - CH 3
chlorination of methane by Cl2 / hn ? (c) (d) Both (a) and (b)
·
(a) Cl 2 ® 2Cl
· ·
70. Pair of enantiomers of 1, 2-dimethylcyclopentane having
(b) Cl + CH4 ® CH3 + HCl structures
· ·
(c) Cl + CH 4 ® CH 3Cl + H
· · H CH 3 H H
(d) Cl + CH3 ® CH3Cl CH 3 H
The X may be H H
(a) cyclohexene (b) cyclohexadiene
(c) cyclogexatriene (d) None of these HgSO 4 / H 2SO 4
X
Na liquid NH 3 72. 1- Pentyne
68. R - CH = CH 2 ¾¾ ¾ ¾ ¾¾ ® R. CH 2 . CH 3 Y
Et. OH BF3 , THF, H 2 O 2 , OH -
The reaction is called X and Y can be distinguished by
(a) Birch's reduction (b) Clemensen's reduction (a) silver-mirror test (b) iodoform test
(c) Catalytic reduction (d) None of these
(c) Both (a) and (b) (d) Neither (a) nor (b)
JEEMAIN.GURU
downloaded from jeemain.guru
482 Chemistry
73. Which of the following change is correct 76. PhCH 3 on reaction with Cl2 / hn followed by Na/ether will
I 2 , CH3COOAg give
(a) C=C ¾¾ ¾ ¾¾ ¾
¾® C -C
wet CH3COOH
OH OH
OH (a)
I , CH COOAg
(b) C=C ¾¾
2 ¾¾
3 ¾¾
¾® C -C
dry CH3COOH Me Me
OH
(c) Both (a) and (b) one correct (b)
(d) Neither (a) nor (b)
74. Choose the correct among the following (c) Me Me
H
H (d) - CH 2 - CH 2 -
(a) H
H 77. In the following changes which is correct.
S - trans (transoid), less stable Reagent HCOOOH
A ¾¾ ¾¾® B ¾¾ ¾¾
¾® Erythroracemic
R
(b) H H
H H (a) A is 2-hexyne and R is Na-liquid NH 3
S - cis (cisoid), more stable (b) A is 3-hexyne and R is H 2 – Lindlar
(c) S-refers to geomectrical isomerism with respect to single
(c) B is 2-hexene and R is H 2 – Lindlar
bond.
(d) All are correct (d) A is 3-hexyne and R is H 2 /Ni
75. Choose the correct product of the following reaction
O
O ||
||
Cl 78. The compound reacts with MeMgI to give A and
(1) OOH
CH 3
? Cl
(2) H3 O +
CH 3 with Me 2 CuLi to give B. What are A and B ?
O O Me OMgI O
CH 3 || || ||
OH
(a) CH 3 (b) OH
(a) (b)
CH 3 OH
H CH 3
Me Me Me Cl Me
CH 3 OH Me OMgI Me Me OMgI Me O Li
(c) OH (d) CH 3
CH 3 H (c) (d)
OH CH 3
Cl Me Me Cl
JEEMAIN.GURU
downloaded from jeemain.guru
Hydrocarbons 483
JEEMAIN.GURU
downloaded from jeemain.guru
484 Chemistry
42. (a) Recall that first four alkanes are gaseous in nature at CH3 CH3 CH3 CH3
room temperature. 63. (d) C=O+O=C C=C
CH3 C2H5 CH3 CH2CH3
43. (a) Among isomeric alkanes, boiling point decreases with
2,3-Dimethyl-2-pentene
increase in branching
1 2 2 1 64. (a) Since the ozonolysis product, 2-methyl-3-pentanone,
44. (b) n-Butane, C H 3 C H 2 C H 2 C H 3 has two different contains only six carbon atoms, while the alkene has seven
hydrogen atoms, marked by 1 and 2. carbon atoms, the other ozonolysis product should be
45. (c) 46. (b) 47. (b) CH2O, the only carbonyl compound having one carbon
48. (a) The heat of hydrogenation of an alkene depends upon atom. Hence, the structure of the alkene C7H14 can be
its stability. Higher the stability, lower the heat of established as below
hydrogenation. Since CH2=CH2 has no substituent, it is
CH 3 CH 2CH 3
the least stable alkene and hence has the highest heat of | |
hydrogenation CH 3 - C H - C = O + O = CH 2
49. (a) 50. (b) 51. (b) 52. (b) 2- Methyl -3pentanone
53. (a) All are examples of electrophilic addition reactions and
involve the formation of stable carbocation leading toCH3 CH 2CH3 CH3 CH 2CH3
the formation of addition product according to| |
ozonolysis
| |
Markovnikov’s rule CH 3 - CH - C = O + O = CH 2 ¬¾¾¾¾ ¾ CH 3 - CH - C = CH 2
2- Methyl- 3pentanone 2 - Ethyl - 3- methyl -1- butene
54. (b)
55. (c) (See Anti Markovnikov's rule) 65. (d) 66. (b) 67. (a) 68. (c)
56. (d) Markovnikov’s rule is applicable only to unsymmetrical
69. (b) CH 3C º CCH 3 , being symmetrical, has the lowest dipole
alkenes, which is option (d) here
57. (b) Symmetrical alkenes (option b) give similar products moment
whether the addition is according to Markovnikov’s rule 70. (b) Reduction of alkynes with Na/liq. NH3 gives
or according to peroxide effect. trans-alkenes
58. (d) Addition of HBr on alkenes is an electrophilic reaction, 71. (a) Reduction of alkynes with Lindlar’s catalyst (Pd-BaSO )
4
hence more the number of electron-releasing groups on gives cis-alkenes
the double bond easier will be the addition
72. (c)
59. (a) The intermediate 2º carbocation shows resonance
HBr
é +
Br + ù 73. (d) CH º CH ¾¾¾® CH 2 = CHBr
CH 2 = CH - CH = CH 2 ¾¾¾
® êCH 2 Br - CH - CH = CH 2 ú
ë û HBr
¾¾¾ ¾ ¾¾ ¾ ¾® CH 3CHBr2
Markovnikov addition
+ ù
« CH 2 Br - CH = CH - CH 2 úû 74. (d) 75. (c) 76. (a) 77 (d)
78. (d) 79. (a)
80. (a) 2-Butyne (CH3CºCCH3 ) , being a non-terminal alkyne,
-
Br
¾¾
¾® CH 2 Br - CH = CH - CH 2 Br does not have acidic hydrogen atom
1, 4 - Dibromo - 2 - butene 81. (a) Only terminal alkynes, react with bases like NaNH2,
60. (c) In such questions, break the molecule at double bond by CH3MgI, ammonical AgNO3 and ammonical cuprous
adding oxygen atom at each doubly bonded carbon chloride
82. (c)
CH3
| 83. (c) Tollen’s reagent (ammonical silver nitrate) reacts with
i) O terminal alkynes
CH 2 = C - CHCH3 ¾¾¾
3
® CH 2O + O = C - CHCH3
| ii) Zn/H 2O Methanal | | 84. (d) Ammonical silver nitrate and ammonical cuprous chloride
CH3 CH3 CH3
2,3- Dimethyl -1- butene 3- Methyl - 2 - butanone
give precipitate only with terminal alkynes (propyne,
CH 3C º CH )
61. (c)
62. (a) In such questions follow the following points: (i) write 85. (d) Ammonical cuprous chloride gives precipitate (red) only
down the structure of the given carbonyl compound(s), with terminal alkynes, i.e. alkynes having acidic hydrogen
(ii) remove oxygen atoms of the two carbonyl compounds, atom, such as butyne-1 ( CH º CCH 2 CH 3 )
(iii) join the two carbon atoms of the two carbonyl groups
to each other to get the structure of the parent alkene 86. (c) Only alkynes, which is CH º CH in the present question,
react with Br2 to give bromoderivative of an alkene
CH 3CH 2 C = O + O = C - CH 3 ¬
¾¾ CH 3CH 2 C = C - CH 3
| | | |
H CH3 H CH3 CH º CH + Br2 ¾
¾® BrCH = CHBr
JEEMAIN.GURU
downloaded from jeemain.guru
Hydrocarbons 485
+
101. (c) Phenol as well as toluene have electron-releasing groups,
87. (a) CH 2 = C = CH - CH 3 ¾H
¾
¾® however –OH group, in phenol, is more electron-releasing
(due to +R effect) than the –CH3 group in toluene, so
+ + phenol is more easily attacked by an electrophile.
é ù
= C = CH - CH3 ¾¾¾
® êCH 2 = C- CH 2CH3 + CH 2 = CH - CHCH3 ú
ë û 102. (c) OCH3 NO2
Cl-
¾¾¾
® CH 2 = C - CH 2CH3 + CH 2 = CH - CHCH3
| | > >
Cl Cl
2- Chlorobutene 3- Chlorobutene
Electron-releasing No group Electron withdrawing
88. (a) Conversion of C 4H 6 to C 4H 6Br 2 indicates that the group present is present group is present
compound is either butyne-1 or butyne-2. However, white
precipitate with ammonical silver nitrate solution indicates
that it is a terminal alkyne, i.e. butyne-1 and not butyne-
2 103. (d) Cl NO2 CH3
89. (d) Since the hydrocarbon decolourises KMnO4 solution, it
must be unsaturated, i.e. alkene or alkyne. However, it
does not give any precipitate with ammonical AgNO3, it
must be a non-terminal alkyne, i.e. butyne-2 (b) (c) (a)
90. (c) Electron-withdrawing One electron-
91. (c) groups are present releasing group
92. (b) Mononitration occurs at about 60º C, but at 100ºC
dinitration occurs. Since –NO 2 is m-directing,
m-dinitrobenzene is formed at 100ºC CH3
93. (b)
94. (b)
95. (c) RCl + AlCl3 ® R+ + AlCl -4
Electrophi le CH3
(a) (d)
96. (d)
One electron- Two electron-releasing groups, hence
97. (d) releasing group most reactive towards sulphonation
98. (a) Since the major product (>60%) is a m-isomer, the group
Y must be m-directing which is –COOH
104. (a) Mesitylene (1,3,5-trimethylbenzene) has three electron-
99. (b) –Cl group is o-, p-directing due to +R effect ; however it
releasing (–CH3) groups, while m-xylene, toluene and
is deactivating due to strong –I effect of Cl (difference
from other o-, p-directing groups which are activating). benzene have 2, 1 and 0 electron-releasing (–CH3) groups
The net result is that chlorobenzene undergoes o-, p- 105. (c)
substitution, but with difficulty 106. (c)
100. (d) NO2 COOH 107. (b) CH3 - CH 2 - CH = CH 2 + Br2 ¾
¾®
Br
|
CH3 - CH 2 - CH - CH 2 Br Racemic mixture.
Benzene Nitrobenzene Benzoic acid
108. (b) Always remember cis 2-butene + Br2 ® Racemic 2, 3-
No group is present Deactivating group present
dibromobutane \ Trans 2-butene + Br2 ® Meso 2, 3-
CH3 dibromobutane.
109. (d) The given reaction is Diel’s Alder reaction
110. (a) More is the stability, lower is the heat of combustion
(See Baeyer’s strain theory). Cyclohexane is more stable.
111. (b) Only 1-Alkynes form alkynides
Benzoic acid Toluene 112. (c) K salt of succinic acid or its derivatives give alkenes by
ivating group present Activating group present Kolbe’s electrolytic method.
JEEMAIN.GURU
downloaded from jeemain.guru
486 Chemistry
EXERCISE 3 8. (a) Due to hydrogen bonding between the two OH groups,
1. (c) This reaction occurs according to Markownikoff’s rule gauche conformation of ethylene glycol (a) is the most
which states that when an unsymmetrical alkene undergo stable conformation.
hydrohalogenation, the negative part goes to that
C-atom which contain lesser no. of H-atom. H
O
CH3 - CH 2 - C º CH + HCl H O
H
¾¾
® CH3 - CH 2 - C = CH 2
|
Cl
H H
I H
|
HI
¾¾® CH3 - CH 2 - C - CH3 \ Correct choice : (a)
|
Cl
CH3
2. (d) H3C — C = CH — CH3 9. (b) CH3 — CH — CH — CH3 H+/ Heat
CH3 OH
H3C O H
O3
C C CH3 CH3
H3C CH3 H / Heat
O CHO — CH — CH — CH CH3 — C = CH — CH3 + CH3 — CH — CH = CH2
2 methyl 3 methyl
O O butene-1 (20%)
H 2O
butene-2
CH3 – C – CH3 + CH3 – C – H (80%) (B)
–H2O 2 acetone acetaldehyde (A)
+
H
C 6 H 5 CH 2 Mg Br ¾¾¾ CH3
® C H CH + MgBr(OH)
H OH 6 5 3 HBr, dark
(CH3)2 — CH — CH — CH3 + CH3 — C — CH2 – CH3
6. (c) When both double and triple bonds are present, then Br Br
triple bond is considered as the principal group. (Minor) (Major)
JEEMAIN.GURU
downloaded from jeemain.guru
Hydrocarbons 487
CH3 H / Pd
14. (c) Butene - 1 ¾¾2 ¾ ¾® Butane
15. (d) Bpt. follows the order
10. (a) C CH CH2 Alkynes > Alkenes > Alkanes (Straight chain) > Alkanes
(branched chain) of comparable molecular weights.
CH3
CH3 CH3
| |
+ Br
H 16. (c) CH3 - CH - CH 2 - CH3 ¾¾¾
2 ® CH - C - CH CH
3 2 3
sunlight |
Br
2 - bromo - 2 - methyl butane
CH3
H2O
Ease of replacement of H-atom 3° > 2° > 1°.
C CH CH3 +
Å –H
H SO
CH3 17. (c) CH3 - CH = CH 2 + H 2 O ¾¾¾¾
2 4 ® CH - CH - CH
3 3
|
1,2-methyl shiftting OH
2° alcohol
CH3 CH3
CH3 CH3 | |
H 2SO 4
Å
CH3 - C = CH 2 + H 2 O ¾¾¾¾
® CH3 - C - CH3
CH3 C CH CH3 |
C CH CH3 OH
3° alcohol
CH3 H3C OH Addition follows Markownikoff’s rule.
3° carbocaction
(more stable)
A (Minor) 18. (b) Chiral conformation will not have plane of symmetry. Since
twist boat does not have plane of symmetry it is chiral.
H2O 4 1
OH CH3
3 6
C CH CH3
CH3
B (Major) 5 2
11. (a) Acetylene reacts with the other three as: 19. (d) When alkyl benzene are oxidised with alkaline KMnO4,
(strong oxidising agent) the entire alkyl group is oxidised
CH2
CH º CNa Na
CH º CH +HCl to –COOH group regardless of length of side chain.
liq. NH3
CHCl CH2CH3 COOH
CH2 CH3 ( O ), KMnO4 / OH -
+HCl ¾¾¾¾¾¾¾¾ ®
CHCl CHCl2 Benzoic acid
Ethyl benzene
[AgNO3+NH4OH]
CH º CH AgCºCAg + NH4NO3 20. (b) The reaction follows Markownikov’s rule which states
white ppt. that when unsymmetrical reagent adds across
CHOH unsymmetrical double or triple bond the negative part
12.(c) CH º CH + HOCl adds to carbon atom having lesser number of hydrogen
® ||
¾¾¾¾ atoms.
CHCl
HBr
CH 3 - C º CH + HBr ® CH3 - C = CH2 ¾¾¾ ®
+ HOCl é CH(OH) 2 ù -H O CHO |
¾¾¾¾® ê | 2 ® |
ú ¾¾¾¾ Br
êëCHCl2 úû CHCl2
Br
dichloroacetaldehyde |
13. (c) In neopentane all the H atoms are same (1º). CH3 - C - CH3
|
CH3 Br
|
CH 3 - C - CH 3 2, 2-dibromopropane
|
CH3
JEEMAIN.GURU
downloaded from jeemain.guru
488 Chemistry
21. (d) FeCl 3 is Lewis acid. In presence of FeCl 3 o- and 25. (d) Writing the reaction we get
p-chlorotoluene is formed.
CH 3 MgX + CH 3 – C º C – H ¾¾
®
CH3 CH3 CH3
Cl CH3 – C º CMgX + CH 4 ( g )
FeCl3
+ Cl2 ¾¾¾® + So we find that CH4 is produced in this reaction.
Toluene o-chlorotoluene
Cl 26. (c) The given molecular formula suggests that the aldehyde
p-chloro toluene formed will be acetaldehyde hence the alkene will be
CH3CH = CHCH3
CH3 2-butene
CH3 O
NH2
|
anilines when diazotized and then treated with CuBr forms CH3 - C = O + CH 3 - CH 2 - C
o-, p- bromotoluenes.
23. (d) Completing the sequence of given reactions, H
Acetone Propionaldehyde
CH 3 – CH = CH - CH 3 ¾¾3¾
®
O
H H
28. (d) sp3 Carbon
O
Zn / H O
CH3– CH CH – CH3 ¾¾¾¾®
2
JEEMAIN.GURU
downloaded from jeemain.guru
Hydrocarbons 489
8. (b)
1.O3 CHO
30. (a) 9. (c) CH 2 BrCHBrCH3 ¾¾ ¾ ¾¾
2® i ) xNaNH
Pentyne
2.H2O/Zn CHO
ii ) C 2 H5Br ( No. of C atoms=5)
[E]
The reaction can be summed up as below
KOH(aq), D
CHO 2 NaNH NaNH
– H 2O CH 2 BrCHBrCH3 ¾¾ ¾ ¾
2 ® CH º CCH ¾¾ ¾
3 ¾2 ® NaC
aldol condensation 1, 2 - Dibromopropane
[F]
BrCH CH
31. (d) Only (d) can form 3-Octyne NaC º CCH 3 ¾¾ ¾2¾¾
3 ® CH CH C º CCH
3 2 3
Pentyne- 2
® CH 3CH 2 C º C - Na +
NaNH
CH 3 CH 2 C º CH ¾¾¾¾ 2
- NH 3 10. (b)
CH CH CH CH Br 11. (c) Reactivity of H-atoms depends upon the stability of free
¾¾¾¾¾¾¾
3 2 2
(S 2)
2
® radicals (3º > 2º > 1º) produced by them
N
CH 3 CH 3
H CH3 | |
CH 3 - C - C - CH 3
O3/Zn/H2O | |
CH 3 CH3
15. (d) Option (d) has the lowest number of carbon atoms
CH3
16. (a)
17. (a) See the order of stability of substituted alkenes. Lesser
2 H3C CH O + 2O CH C CH O the stability more is the reactivity.
(achiral) 18. (a)
H 19. (a) Reaction of chlorine on ethene is an electrophilic addition
(achiral) and involves the formation of carbocation which is
JEEMAIN.GURU
downloaded from jeemain.guru
490 Chemistry
26. (a) Oxymercuration leads to hydration in Markovnikov’s 42. (c) Since the compound X(C5H8) reacts with ammonical
manner AgNO3 to give a white precipitate, it must be a terminal
é OH ù
alkyne, i.e. it should have -C º CH grouping. Further,,
ê |
HgSO4 + H 2SO 4 ú since X gives (CH3)2CHCOOH on oxidation, X must have
CH 3CH 2 C º CH ¾¾ ¾ ¾¾ ¾
¾® ê CH 3CH 2 C = CH 2 ú
ê ú (CH 3 ) 2 CHC º C - group. Thus the compound X is
ë û
(CH 3 ) 2 CHC º CH
® CH 3CH 2 COCH 3 43. (c) Similar to that of above question
CH3 CO 2 + (CH 3 ) 3 C - COOH ¬¾
alk.
¾¾ (CH 3 ) 3 C - C º CH
|
i ) O3 KMnO 4
27. (c) CH 3CH = C - CH = CH 2 ¾¾¾® CH 3CHO +
ii ) Zn / H 2O
[ Ag ( NH ) ]+
CH ¾¾ ¾ ¾3 ¾
2¾® (CH ) C - C º CAg
3 3
CH3 ( white ppt.)
|
O = C - CHO+ CH 2 O 44. (d) p-Dichlorobenzene, being symmetrical, fits closely in the
28. (c) Since the alkene on ozonolysis gives a single compound, crystal lattice and hence will have the highest melting
having two aldehydic groups, it must be cyclic point
45. (c)
46. (c) OC2H5 Cl OH
CH = O CH
(CH2)4 (CH2)4 or
CH = O CH
Cyclohexene
29. (a) 8g Br2 react with 2.8g of alkene Ethoxybenzene Chlorobenzene Phenol
\ 80g Br2 react with 28g alkene
Thus the molecular wt. of alkene is 28 which indicates o-p-directing
C2H4 COOC2H5
30. (a) 31. (d) 32. (b) 33. (b)
é + ..
+ - ù
34. (c) CH 3COCl + ZnCl 2 ® êCH 3 - C = O
. . « CH 3 - C º O ú + ZnCl 3
êë úû
Acylium ion
é OH OH ù
Most electron- Electron releasing
ê
cold alk.
| | ú releasing due to due to –OH group
40. (c) CH 3CH 2 C º CH ¾¾ ¾¾®ê CH 3CH 2 C - C - H ú –ve charge on O
KMnO 4 ê | | ú
ë OH OH û O O
–
oxidation OH O – C – CH3 C – CH3
® CH 3CH 2 COCHO ¾¾¾¾® CH 3CH 2COOH + CO 2
41. (b) Since both gases decolourise KMnO4 solution, both must
be unsaturated, i.e. alkene or alkyne ( >option b or d). > >
However, only one of them gives a white precipitate with
ammonical AgNO3 solution, it must be terminal alkyne
Electron releasing Less electron releasing due to presence of Electron-
and thus the other should be either a non-terminal alkyne –CO grouping which shows resonance withdrawing group
or an alkene. The datas coincide with the option b with the electrons on O
JEEMAIN.GURU
downloaded from jeemain.guru
Hydrocarbons 491
NO2
CH3 CH3
> H C = O
¾¾2 ¾ ¾
¾®
MgBr H 3O +
Electron-releasing Strong electrons
CH 2OH
as welll as electron- withdrawing group CH3 CH3
O
NaH
¾¾¾® ||
CH3I - C - CH 2 - - Br
JEEMAIN.GURU
downloaded from jeemain.guru
492 Chemistry
O O
62. (c) CH 2 = CH - C(CH 3 ) = CH - CH 3 ¾¾3¾
® ||
Zn H 2O 72. (c) In the reactions X is CH 3 - CH 2 - CH 2 - C - CH 3
| Me
Cl
JEEMAIN.GURU
downloaded from jeemain.guru
14
Environmental
Chemistry
POLLUTION (iv) Mesosphere : The region of the earth’s atmosphere above
Pollutant :- Any material affecting the life is known as pollutant the stratosphere and below the thermosphere. It is the
and the phenomenon is known as pollution. The pollutants may coldest region (temp. –2 to –92ºC) of atmosphere.
be inorganic, biological or radiological in nature. (v) Exosphere : The uppermost region of atmosphere. It
(i) Primary pollutants : These are emitted directly from the contains atomic and ionic O2, H2 and He.
sources. eg. inorganic gases such as H2S, SO2, CO, NO, HF, (b) Hydrosphere :- The aqueous envelop of the earth eg. oceans,
NH3 radioactive substancs or particulates such as smoke, lakes etc.
ash, dust, fumes. (c) Lithosphere :- The solid rocky portion of the earth.
(ii) Secondary pollutants : These are formed in the atmosphere (d) Biosphere :- The biological envelop which supports the life.
by chemical interactions among primary polluntants eg. SO3, AIR POLLUTION :
NO2, CH4, aldehydes, ketones, nitrates, sulphates, phenols.
(I) Major air pollutants: The major air pollutants are following:-
(iii) Bio-degradable pollutants : These are domestic wastes which
(a) Carbon monoxide (CO) :- It is produced by incomplete
are rapidly decomposed by micro-organisms.
combustion of gasoline in motor vehicles, wood, coal,
(iv) Non-degradable pollutants : These include chemicals,
inceneration and forest fires.
mercuric salts, lead compounds, pesticides etc.
It is treacherous and deadly poisonous gas. It induces
(v) Natural pollution : It is caused by radioactive substances,
headache, visual difficulty coma and death. It blocks
volcanic eruptions, forests and mines fires, floods etc.
the normal transport of oxygen from the lungs to other
(vi) Artificial pollution : It is caused by industries, thermal plants, parts of the body.
automobile exhausts, sewage etc.
(b) Sulphur dioxide ( SO 2 ) :- It is produced by petrol
ENVIRONMENT :
combustion, coal combustion, petrol refining and
The conditions existing around animal or human life. It is further
smelting operations.
classified as
It hinders the movement of air in and out of lungs. It is
(a) Atmosphere :- The gaseous envelop surrounding the earth.
particularly poisonous to trees causing chlorosis and
(i) Stratosphere : The layer of the earth’s atmosphere above
the troposphere and below the mesosphere. dwarfing. In presence of air it is oxidised to SO 3 which
(ii) Troposphere : The lowest region of the atmosphere is also irritant.
extending from earth’s surface to the lower boundary of
2 SO 2 + O 2 (air) ¾
¾® 2 SO 3
the stratosphere. It contains water vapour and is greatly
affected by air pollution. In presence of moisture SO 3 is converted into highly
(iii) Thermosphere : The upper region of the atmosphere corrosive sulphuric acid.
above the mesosphere. It is the hottest region (temp
upto 1200ºC). SO 3 + H 2 O (moisture ) ¾
¾® H 2SO 4
JEEMAIN.GURU
downloaded from jeemain.guru
494 Chemistry
It attacks marble, limestone,vegetation, paper and textiles Hydrocarbons + O2, NO2, NO, O, O3 ® Peroxides,
and injurious to human beings. formaldehyde, peroxyacetylnitrate (PAN), acrolein etc.
(c) Oxides of nitrogen :- NO 2 and NO It is oxidising in nature and causes irritation to eyes,
lungs, nose, asthamatic attack and damage plants.
(Source - combustion of coal, gasoline, natural gas,
(IV) Acid rain :- The oxides of C, N and S present in the atmosphere,
petroleum refining, chemical plants manufacturing
dissolve in water and produce acids and lower the pH of
explosives and fertilizers, tobacco smoke.
water to below 5.5.
Breathing NO 2 causes chlorosis to plants and
2-
H 2 O + CO 2 ¾
¾® H 2 CO 3 2 H + + CO3
chronic lung conditions leading to death. NO 2 reacts
with moisture to form acids. 2 H 2 O + 2 SO 2 + O 2 ® 2 H 2SO 4
2 NO 2 + H 2 O ¾
¾® HNO 2 + HNO 3 2 H + + SO 24 -
3 HNO 2 ¾ ¾® 2 NO + HNO 3 + H 2 O -
2 H 2 O + 4 NO 2 + O 2 ® 4 HNO 3 4H + + 4NO3
(d) Smoke, dust :-
The acids are toxic to vegetation, react with marble and
Sources foundries, cement works, iron and steel works,
damage buildings.
gas works, power generating stations.
(e) Ammonia : Ammonia works CaCO 3 + H 2SO 4 ¾
¾® CaSO 4 + H 2 O + CO 2
(f) Chlorine and hydrogen chloride : Chlorine works Acids corrode water pipes and produce salts with heavy
(g) Chlorinated hydrocarbons : Dry cleaning works metals ions viz Cu, Pb, Hg and Al toxic in nature.
(h) Mercaptans : Oil refineries, coke ovens (V) Green House effect :- The retention of heat by the earth and
(i) Zn and Cd : Zinc industries atmosphere from the sun and its prevention to escape into
(j) Freon : Refrigeration works. the outer space is known as green house effect. Green house
(II) Photochemical pollutants :- The nitrogen dioxide by gases such as CO 2 , ozone, methane, the chlorofluoro carbon
absorbing sunlight in blue and U. V. region decomposes into compounds and water vapour form a thick cover around the
nitric oxide and atomic oxygen followed by a series of other earth which prevents the IR rays emitted by the earth to
reactions producing O 3 formaldehyde, acrolein and escape. It gradually leads to increase in temperature of
peroxyacylnitrates. atmosphere.
Ozone causes bronchial irritation even at 1 ppm level. Ozone Consequences of green house effect
affects tobacco plants, spinach, tomato, potato etc. The (i) Global warming would result in rise in sea level due to
photochemical pollutants are powerful eye irritants. The increased rate of melting of glaciers and floods.
reactions are as follows (ii) Increase in infectious diseases like malaria, dengue etc.
(VI) Ozone layer and its depletion :- The ozone layer, existing
NO 2 + h u ¾
¾® NO + O, O + O2 ¾
¾® O 3
between 20 to 35 km above the earth’s surface, shield the
earth from the harmful U. V. radiations from the sun. The U. V.
¾® RO · ,
RH + O ¾ ¾® RO ·3
RO · + O 2 ¾
radiations cause skin cancer, cataract of eye, and harmful to
RO ·3 + RH ¾
¾® Aldehydes + Ketones vegetation.
Depletion of ozone is caused by oxides of nitrogen
RO ·3 + NO ¾
¾® RO ·2 + NO 2 N 2O + h u ¾ ¾® NO + N
reactive nitric oxide
RO ·2 + NO 2 ¾
¾® Peroxyacylnitrate
NO + O 3 ¾
¾® NO 2 + O 2
(III) Smog : It is a mixture of smoke (composed to tiny particles of
carbon, ash and oil etc. from coal combustion) and fog in O3 + h u ¾
¾® O 2 + O
suspended droplet form. It is of two types :
(a) London smog or classical smog : It is coal smoke plus NO 2 + O ¾
¾® NO + O 2
fog. The fog part is mainly SO2 and SO3. It has sulphuric 2 O3 + h u ¾
¾® 3 O 2 (Net reaction)
acid aerosol. It causes bronchial irritation and acid rain.
The presence of oxides of nitrogen increase the
It is reducing in nature.
decomposition of O 3 . Depletion of ozone by chlorofluoro
(b) Photochemical smog or Los Angeles smog : The
oxidised hydrocarbons and ozone in presence of carbons.
humidity cause photochemical smog.
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
496 Chemistry
AEROBIC AND ANAEROBIC OXIDATION : SEWAGE TREATMENT :
The oxidation of organic compounds present in sewage in The artificial treatment is called sewarage and involves the
presence of good amount of dissolved or free oxygen (approx. 8.5 following steps :
ml/l) by aerobic bacterials is called aerobic oxidation. When (i) Preliminary process : Passing sewage through screens to
dissolved or free oxygen is below a certain value the sewage is remove large suspended matter and then through mesh
called stale anaerobic bacterias bring out purification producing
screens to remove solids, gravels, silt etc.
H2S, NH3, CH4, (NH4)2S etc. This type of oxidation is called
anaerobic oxidation. (ii) Settling process (sedimentation) : The residual water when
The optimum value of D.O. for good quality of water is 4-6 ppm (4- allowed to stand in tanks, the oils and grease float on the
6 mg/l). The lower the concentration of D.O., the more polluted is surface and skimmed off and solids settle down. The colloidal
the water. meterial is removed by adding alum, ferrous sulphate etc.
BIOLOGICAL OXYGEN DEMAND (BOD) : and we get primary sludge.
It is defined as the amount of free oxygen required for biological (iii)Secondary treatment or Biological treatment : It is aerobic
oxidation of the organic matter by aerobic conditions at 20°C for chemical oxidation or aeration which converts carbon of the
a period of five days. Its unit is mg/l or ppm. An average sewage organic matter to CO2, nitrogen into NH3 and finally into
has BOD of 100 to 150 mg/l. nitrites and nitrates, dissolved bases form salts such as
CHEMICAL OXYGEN DEMAND (COD) : NH4NO2, NH4NO3 and Ca(NO3)2 etc. and secondary sludge
It is a measure of all types of oxidisable impurities (biologically is obtained.
oxidisable and biologically inert organic matter such as cellulose) The primary and secondary sludge (combined) is
present in the sewage. COD values are higher than BOD values.
subjected to anaerobic digestion to CO2 and CH4
COD DETERMINATION :
A known volume of sample is refluxed with known volume of 2[CH 2 O] ¾
¾® CO 2 + CH 4
standard K2Cr2O7 + dil. H2SO4 in presence of Ag2SO4 (catalyst)
(iv) Tertiary treatment : It is treatment of waste water with lime
for 1½ hours. The unreacted K2Cr2O7 is then titrated against
FeSO4.(NH4)2SO4.6H2O solution. The oxygen equivalent of for removal of phosphate which is coagulated by adding
K2Cr2O7 consumed is taken as a measure of COD. alum and ferric chloride and removed by filtration. Water is
1 ml. of 1 N K2Cr2O7 º 0.008 g oxygen disinfected by adding chlorine.
SOIL OR LAND POLLUTION : Secondarty sludge forms a good fertilizer for soil as it contains
nitrogen and phosphorous compounds.
The addition of substances in an indefinite proportion changing
the productivity of the soil is known as soil or land pollution. PESTICIDES :
Sources of soil pollution : The chemical substances used to kill or stop the growth of
(i) Agricultural pollutants : Chemicals like pesticides, fertilizers, unwanted organisms are called pesticides. They are further
fumigants, insecticides, herbicides, fungicides. classified as
(ii) Domestic refuge and industrial wastes (a) Insecticides : They are used to kill insects. The most common
(iii) Radioactive wastes from research centres, and hospitals insecticides are
(iv) Soil conditioners containing toxic metals like Hg, Pb, As, Cd
Cl
etc. Cl
Cl
(v) Farm wastes from poultries, dairies and piggery forms Cl
(vi) Improper disposal of human and animal excreta. (i) Cl3C.CH (ii)
Cl Cl
(vii) Pollutants present in air from chemical works Cl Cl
CONTROL OF WATER POLLUTION : BHC, 666, gamexane
D.D.T.
The water pollution can be reduced by following techniques OCONHCH3
(i) Recycling of waste water : by aeration and use of trickling OCONHCH3
filter (iii) CH(CH3)2 (iv)
(ii) Use of chemicals : Effective filtration and chlorination
Sevin, Carbaryl
(iii) Special techniques : Such as adsorption, ion-exchangers, Baygon
reverse osomosis, electrodialysis etc. S
||
(iv) Waste-water reclamation : Sewage water can be directly (v) (C 2 H 5 ) 2 - P - O - NO
used for irrigation and fish farms. Since it contains N, P and K.
Parathion
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
498 Chemistry
Very Short/ Short Answer Questions 19. Which of the following is not a consequence of green-
house effect?
1. In what regions of the atmosphere, the temperature (a) Climatic conditions will be changed resulting in
increases with altitude and in which regions it decreases? (b) Plants in warmer climates with adequate rainfall would
2. What is the most important sink of CO pollutant? grow faster
3. What is marine pollution? (c) The incidence of infectious diseases is likely to
increase
4. Why COD is preferred over BOD ?
(d) Malaria will be controlled as the mos
5. What should be the tolerable limit of fluoride ions in drinking quitoes will not survive.
water? What happens if it is higher than10 ppm ? 20. Which of the following statements is not true about classi-
6. Name any four methods for waste management. cal smog?
7. Write the name of gas produced in Mathura refineries which (a) Its main components are produced by the action of
can damage the great historical monument “Taj Mahal”? sunlight on emissions of automobiles and factories.
8. What are 'asbestosis' and 'silicosis'? (b) Produced in cold and humid climate.
9. (i) Why there is ozone depletion mainly over Antarctica? (c) It contains compounds of reducing nature.
(ii) In which season the depletion of ozone on Antarctica (d) It contains smoke fog and sulphur dioxide
takes place and when is it replenished? 21. Which of the following statements is wrong?
10. Depending upon the nature of pollutants, how can the (a) Ozone is not responsible for green house effect.
pollution be classified into different types ? (b) Ozone can oxidise sulphur dioxide present in the atmo-
sphere to sulphur trioxide.
11. How plant nutrients and pesticides acts as water pollutants?
(c) Ozone hole is thinning of ozone layer present in strato-
12. Fish do not always grow in warm as well as in cold water, sphere.
why?
(d) Ozone is produced in upper stratosphere by the action
13. On the basis of chemical reactions involved, explain how of UV rays on oxygen.
do chlorofluorocarbons cause thinning of ozone layer in 22. Which of the following statements is correct?
stratosphere.
(a) Ozone hole is a hole formed in stratosphere from which
14. How can lead poisoning be cured? ozone oozes out.
(b) Ozone hole is a hole formed in the troposphere from
Long Answer Questions which ozone oozes out.
15. What is the strategy for control of Environmental pollution? (c) Ozone hole is thinning of ozone layer of stratosphere
16. List industrial wastes which contaminate water. at some places.
Multiple Choice Questions (d) Ozone hole means vanishing of ozone layer around
the earth completely.
17. Dinitrogen and dioxygen are main constituents of air but
these do not react with each other to form oxides of nitrogen 23. Which among the following statements is false?
because __________. (a) Oil slick in sea water increases D.O. value.
(a) the reaction is endothermic and requires very high (b) The main reason for river water pollution is industrial
temperature. and domestic sewage discharge.
(b) the reaction can be initiated only in presence of a (c) Surface water contains a lot of organic matter mineral
catalyst. nutrients and radioactive materials.
(c) oxides of nitrogen are unstable. (d) Oil spill in sea water causes heavy damage to fishery.
(d) N2 and O2 are unreactive 24. Sewage containing organic waste should not be disposed
18. The pollutants which came directly in the air from sources in water bodies because it causes major water pollution.
are called primary pollutants. Primary pollutants are Fishes in such a polluted water die because of
sometimes converted into secondary pollutants. Which of (a) large number of mosquitoes
the following belongs to secondary air pollutants?
(b) increase in the amount of dissolved oxygen
(a) C O
(b) Hydrocarbon (c) decrease in the amount of dissolved oxygen in water
(c) Peroxyacetyl nitrate (d) clogging of gills by mud.
(d) NO
JEEMAIN.GURU
downloaded from jeemain.guru
1. The uppermost region of the atmosphere is called 11. Formation of photochemical smog takes place in
(a) ionosphere (b) stratosphere (a) winter during day time
(c) troposphere (d) exosphere (b) summer during morning time
2. Which of the following is the coldest region of atmosphere? (c) summer during day time
(a) thermosphere (b) mesosphere (d) winter during morning time
(c) troposphere (d) stratosphere 12. Which of the following statement is false?
3. The region which is greatly affected by air pollution is (a) London smog is oxidising in nature
(a) thermosphere (b) stratosphere (b) Photochemical smog causes irritation in eyes
(c) troposphere (d) mesosphere (c) London smog is a mixture of smoke and fog
4. The region containing water vapour is (d) Photochemical smog results in the formation of PAN
(a) thermosphere (b) stratosphere
13. The viable particulate among the following is
(c) troposphere (d) mesosphere
(a) fumes (b) algae
5. In which of the following regions hydrogen and helium are
found (c) smoke (d) mist
(a) stratosphere (b) mesosphere 14. The non-viable particulate among the following is
(c) exosphere (d) troposphere (a) dust (b) bacteria
6. The substance which is a primary pollutant? (c) moulds (d) fungi
(a) H2SO4 (b) CO 15. Which of the following acts as a sink for CO?
(c) PAN (d) Aldehydes (a) Plants
7. Which of the following is most abundant hydrocarbon (b) Haemoglobin
pollutant? (c) Microorganisms present in the soil
(a) Butane (b) Ethane
(d) Oceans
(c) Methane (d) Propane
16. Which forms the part of hazy fumes of photochemical smog?
8. The aromatic compounds present as particulates are
(a) SO2 (b) Nitrogen dioxide
(a) polycyclic aromatic hydrocarbons
(b) benzene (c) PAN formation (d) Aldehydes
(c) toluene 17. Depletion of ozone layer causes
(d) nitrobenzene (a) breast cancer (b) blood cancer
9. The biggest particulate matter is (c) lung cancer (d) skin cancer
(a) HNO3 droplets (b) soot 18. The gas responsible for ozone depletion :
(c) H2SO4 droplets (d) fly ash (a) NO and freons (b) SO2
10. Formation of London smog takes place in (c) CO2 (d) CO
(a) winter during day time 19. The reaction caused by U.V. radiations from sun produces
(b) summer during day time (a) ozone (b) carbon monoxide
(c) summer during morning time
(c) sulphur dioxide (d) fluorides
(d) winter during morning time
JEEMAIN.GURU
downloaded from jeemain.guru
500 Chemistry
20. Which of the following chemical, harmful to ozone, is 28. Water pollution is caused by
released by chlorofluoro carbon? (a) pesticides (b) fly ash
(a) Sulphur dioxide (b) Fluorine (c) auto exhausts (d) aeroplanes
(c) Chlorine (d) Nitrogen dioxide 29. Which causes death of fishes in water bodies polluted by
sewage?
21. Ozone hole refers to
(a) Foul smell (b) Pathogens
(a) increase in concentration of ozone
(c) Clogging of gills by silt (d) Decrease in D.O.
(b) hole in ozone layer 30. Phosphate pollution is caused by
(c) reduction in thickness of ozone layer in troposphere (a) sewage and agricultural fertilizers
(d) reduction in thickness of ozone layer in stratsophere (b) weathering of phosphate rocks only
22. Ozone layer of stratosphere requires protection from (c) agricultural fertilizers only
indiscriminate use of (d) phosphate rocks and sewage
(a) baloons 31. Sewage water is purified by
(b) pesticides (a) aquatic plants (b) micro-oganisms
(c) atomic explosions (c) light (d) fishes
(d) aerosols and high flying jets 32. Water is often treated with chlorine to
(a) remove hardness
23. Phosphate fertilizers when added to water leads to
(b) increase oxygen content
(a) increased growth of decomposers
(c) kill germs
(b) reduced algal growth
(d) remove suspended particles
(c) increased algal growth
33. Ozone is an important constituent of stratosphere because it
(d) nutrient enrichment (eutrophication)
(a) destroys bacteria which are harmful to human life
24. The type of pollution caused by spraying of DDT
(b) prevents the formation of smog over large cities
(a) air and soil (b) air and water (c) removes poisonous gases of the atmosphere by reacting
(c) air (d) air, water and soil with them
25. Pollution in large cities can be checked only by (d) absorbs ultraviolet radiation which is harmful to human
(a) shifting of factories out of the residential area life
(b) less use of insecticides 34. Which is the major air pollutant
(c) proper disposal of organic wastes, sewage and industrial (a) He (b) O2
effluents (c) CO2 (d) CO
(d) All the above 35. The ozone layer is present in
26. Sewage mostly constitutes (a) stratosphere (b) troposphere
(a) non-biodegradable pollutants (c) thermosphere (d) mesosphere
(b) biodegradable pollutants 36. The green house effect is caused by
(c) effluents (a) CO2 (b) NO2
(d) air pollutants (c) NO (d) CO
27. Chief source of soil and water pollution is 37. Surface water contains
(a) mining (b) agro industry (a) suspended impurity (b) salt + organic matter
(c) thermal power plant (d) All the above (c) only salt (d) organic matter
JEEMAIN.GURU
downloaded from jeemain.guru
1. The greenhouse effect is because of the 7. When rain is accompanied by a thunderstorm, the collected
[CBSE-PMT 1996] rain water will have a pH value
[AIEEE 2003]
(a) presence of gases, which in general are strong infrared (a) slightly lower than that of rain water without
absorbers, in the atmosphere thunderstorm
(b) presence of CO2 only in the atmosphere (b) slightly higher than that when the thunderstorm is not
(c) pressure of O3 and CH4 in the atmosphere there
(d) N2O and chlorofluorohydrocarbons in the atmosphere (c) uninfluenced by occurrence of thunderstorm
2. Which of the following is/are the hazardous pollutant(s) (d) which depends upon the amount of dust in air
present in automobile exhaust gases? [CBSE-PMT 1996] 8. The smog is essentially caused by the presence of
(i) N2 (ii) CO (a) Oxides of sulphur and nitrogen [AIEEE 2004]
(iii) CH4 (iv) Oxides of nitrogen (b) O2 and N2
(a) (ii) and (iii) (b) (i) and (ii)
(c) O2 and O3
(c) (ii) and (iv) (d) (i) and (iii)
(d) O3 and N2
3. Green chemistry means such reactions which :
9. Identify the wrong statement in the following: [AIEEE 2008]
(a) produce colour during reactions [CBSE-PMT 2008]
(b) reduce the use and production of hazardous chemicals (a) Chlorofluorocarbons are responsible for ozone layer
depletion
(c) are related to the depletion of ozone layer
(d) study the reactions in plants (b) Greenhouse effect is responsible for global warming
4. Which one of the following statement is not true ? (c) Ozone layer does not permit infrared radiation from the
[CBSE-PMT 2011] sun to reach the earth
(a) pH of drinking water should be between 5.5 – 9.5. (d) Acid rain is mostly because of oxides of nitrogen and
(b) Concentration of DO below 6 ppm is good for the sulphur
growth of fish. 10. Identify the incorrect statement from the following :
(c) Clean water would have a BOD value of less than 5 [AIEEE 2011RS]
ppm. (a) Ozone absorbs the intense ultraviolet radiation of the
(d) Oxides of sulphur, nitrogen and carbon are the most sun.
widespread air pollutant.
(b) Depletion of ozone layer is because of its chemical
5. Which one of the following statements regarding reactions with chlorofluoro alkanes.
photochemical smog is not correct? [CBSE-PMT 2012]
(c) Ozone absorbs infrared radiation.
(a) Carbon monoxide does not play any role in
(d) Oxides of nitrogen in the atmosphere can cause the
photochemical smog formation.
depletion of ozone layer.
(b) Photochemical smog is an oxidising agent in character.
11. What is DDT among the following ? [AIEEE 2012]
(c) Photochemical smog is formed through photochemical
(a) Greenhouse gas
reaction involving solar energy.
(b) A fertilizer
(d) Photochemical smog does not cause irritation in eyes
and throat. (c) Biodegradable pollutant
6. Frequent occurrence of water blooms in a lake indicates (d) Non-biodegradable pollutant
(a) nutrient deficiency [AIEEE 2003] 12. The gas leaked from a storage tank of the Union Carbide
plant in Bhopal gas tragedy was : [JEE M 2013]
(b) oxygen deficiency
(a) Methyl isocyanate (b) Methylamine
(c) excessive nutrient availability
(c) Ammonia (d) Phosgene
(d) absence of herbivores in the lake
JEEMAIN.GURU
downloaded from jeemain.guru
502 Chemistry
1. The substance which is not regarded as a pollutant? 9. Minamata disease is due to pollution of
(a) NO2 (b) CO2 (a) aresenic into the atmosphere
(c) O3 (d) Hydrocarbons (b) organic waste into drinking water
2. The greatest affinity for haemoglobin is shown by which of (c) oil spill in water
the following : (d) industrial waste mercury into fishing water
(a) NO (b) CO 10. BOD is connected with
(c) O2 (d) CO2 (a) microbes and organic matter
3. The substance having the largest concentration in acid rain? (b) organic matter
(a) H2CO3 (b) HNO3 (c) microbes
(c) HCl (d) H2SO4 (d) None of the above
4. Which of the following is not involved in the formation of 11. Eutrophication causes reduction in
photochemical smog? (a) dissolved oxygen (b) nutrients
(a) Hydrocarbon (b) NO (c) dissolved salts (d) All the above
(c) SO2 (d) O3 12. Which among the following statements is false?
5. The statement which is not true (a) Oil slick in sea water increases D.O. value
(a) NO2 does not play any role in photochemical smog (b) The main reason for river water pollution is industrial
(b) SO3 is more harmful air polluntant than SO2 and domestic sewage discharge
(c) SO2 dos not affect larynx (voice box) (c) Surface water contains a lot of organic matter mineral
(d) NO is more toxic to living tissues than NO2 nutrients and radioactive materials
6. The false statement among the followings : (d) Oil spill in sea water causes heavy damage to fishery
(a) The average residence time of NO is one month 13. Presence of which of the following fuel gas in the exhaust
(b) Limestone acts as a sink for SOx fumes shows incomplete combustion of fuel?
(c) SOx can be removed from flue gases by passing through (a) Sulphur dioxide
a solution of citrate ions (b) Carbon monoxide and water vapour
(d) Ammonia acts as a sink for NOx (c) Carbon monoxide
7. The statement which is not correct about control of (d) Nitrogen dioxide
particulate pollution 14. Which one of the following statements about ozone and
(a) In electrostatic precipitator, the particulates are made to ozone layer is true?
acquire positive charge which are then attracted by the (a) Ozone layer is beneficial to us because ozone cuts out
negative electrode and removed the ultraviolet radiation of the sun
(b) Gravity settling chamber removes larger particles from (b) The conversion of ozone to oxygen is an endothermic
the air reaction
(c) Cyclone collector removes fine particles in the diameter (c) Ozone has a triatomic linear molecule
range 5-20 microns (d) None of the above
(d) Wet scrubbers are used to wash away all types of
particulates
8. Which of the following statements about polar stratosphere
clouds (PSCs) is not correct?
(a) PSCs do not react with chlorine nitrate and HCl
(b) Type I clouds are formed at about –77ºC and contain
solid HNO3 . 3H2O
(c) Type II clouds are formed at about –85ºC and contain
some ice
(d) A tight whirlpool of wind called Polar Vortex is formed
which surrounds Antarctica
JEEMAIN.GURU
downloaded from jeemain.guru
EXERCISE 1 hn •
20. (c) CF2 Cl 2 ¾¾® CF2 Cl + Cl
1. Temperature increases in stratosphere and thermosphere,
• •
it decreases in troposphere and mesosphere. Cl + O 3 ¾
¾® Cl O + O 2
2. Soil micro–organism.
21. (d) Ozone hole is reduction in ozone layer in stratosphere.
3. Pollution of sea water due to discharge of wastes into it. 22. (d) Aerosols use CFC an flying jets release NO. Both causes
4. COD can be found in a few minutes whereas BOD requires depletion of ozone layer.
at least 5 days. 23. (d) Addition of phosphate fertilizers to water leads to
5. 1 ppm or 1 mg dm–3. Higher concentration is harmful to nutrient enrichment (eutrophication)
bones and teeth. 24. (d) DDT causes water, air and soil pollution.
6. Recycling, burning incineration and sewage treatment. 25. (d)
7. Sulphur dioxide 26. (c) Domestic sewage constitute biodegradable pollutants.
8. The lung disease caused by particulates of asbestos is 27. (d)
'asbestosis' and that caused by silica is 'silicosis'. 28. (a) Pesticides cause water pollution.
29. (d) Decrease in D.O causes death of fish
14. By feeding the patient with an aqueous solution of calcium
complex of EDTA. 30. (a) Phosphate pollution is caused by sewage and
agricultural fertilizers.
17. (a) 18. (c) 19. (d) 20. (a) 21. (a)
31. (b) Sewage water is purified by micro-organisms.
22. (c) 23. (a) 24. (c) 25. (d) 26. (c)
32. (c) Water is often treated with Cl2 to kill germs.
EXERCISE 2 33. (d) Ozone absorbs U.V. radiations harmful to human life.
1. (d) The uppermost region of atmosphere is exosphere. 34. (d) CO is major air pollutant.
2. (b) The coldest region is mesosphere 35. (a) Ozone layer is present in stratosphere.
(temp. –27ºC to –92ºC) 36. (a) CO2 causes green house effect.
3. (c) Air pollution greatly affect the troposphere. 37. (b) Surface water contains salts + organic matter.
4. (c) Troposphere contains water vapour. EXERCISE 3
5. (c) H2, He and ionic oxygen are present in exosphere. 1. (a) Green house gases such as CO2, ozone, methane, the
6. (b) CO is primary pollutant. chlorofluorocarbon compounds and water vapour form
7. (c) Most abundant hydrocarbon pollutant is methane. a thick cover around the earth which prevents the IR
8. (a) PAH (Poly Aromatic Hydrocarbon) rays emitted by the earth to escape. It gradually leads
to increase in temperature of atmosphere.
9. (d) Fly ash.
2. (c) CO and oxides of Nitrogen are poisnous gases present
10. (d) London smog is formed in morning during winter.
in automobile exhaust gases.
11. (b) Photochemical smog is formed in noon in summer.
3. (b) Green chemistry may be defined as the programme of
12. (a) London smog is reducing in nature. developing new chemical products and chemical
13. (b) Algae processes or making improvements in the already
14. (a) Dust existing compounds and processes so as to make less
15. (c) CO is converted into CO2 by microorganism present in harmful to human health and environment. This means
soil. the same as to reduce the use and production of
16. (b) NO2 forms a part of photochemical smog. hazardous chemicals.
i.e. correct answer is option (b).
17. (d) Depletion of ozone layer causes skin cancer.
18. (a) NO and freons are responsible for ozone depletion. 4. (b) The ideal value of D.O for growth of fishes is 8 mg/ l .
7mg /l is desirable range, below this value fishes get
¾® O + O ; O + O 2 ¾
19. (a) O 2 ¾ ¾® O 3 susceptible to disease. A value of 2 mg/ l or below is
lethal for fishes.
JEEMAIN.GURU
downloaded from jeemain.guru
504 Chemistry
5. (d) The oxidised hydrocarbons and ozone in presence of 11. (d) DDT is a non-biodegradable pollutant.
humidity cause photochemical smog. 12. (a) Methyl isocyanate, CH3 – N = C = O
Hydrocarbons + O2, NO2, NO, O, O3 ® Peroxides, EXERCISE 4
formaldehyde, peroxyacetylnitrate (PAN), acrolein etc.
1. (b) CO2 is generally not regarded as an pollutant.
It is oxidising in nature and causes irritation to eyes,
lungs, nose, asthamatic attack and damage plants. 2. (a) Haemoglobin has great affinity for NO.
6. (b) 3. (d) Acid rain contains H2SO4 > HNO3> HCl.
4. (c) Photochemical smog does not involve SO2.
7. (a) Normal rain water has pH 5.6 Thunderstorm results in
the formation NO and HNO3 which lowers the pH. 5. (b) SO3 is more harmful pollutant than SO2.
8. (a) Smog is caused by oxides of sulphur and nitrogen. 6. (a) The average residence time of NO is 4 days.
9. (c) Ozone layer acts as a shield and does not allow 7. (a) Particulates acquire negative charge and are attracted
ultraviolet radiation from sun to reach earth. It does by the positive electrode.
not prevent infra-red radiation from sun to reach earth. 8. (a) PSCs react with chlorine nitrate and HCl to give HOCl
Thus option (c) is wrong statement and so it is the and Cl2.
correct answer. 9. (d) Minamata is caused by Hg poisoning.
10. (c) The ozone layer, existing between 20 to 35 km above 10. (a) BOD is connected with microbes and organic matter
the earth’s surface, shield the earth from the harmful 11. (a) Eutrophication causes reduction in D.O
U. V. radiations from the sun.
12. (a) Oil slick in sea water decreases D.O value.
Depletion of ozone is caused by oxides of nitrogen
13. (c) Presence of CO in the exhaust fumes shows incomplete
N 2O + h u ¾ ¾® NO + N
combustion.
reactive nitric oxide
14. (a) Statement (a) is correct.
NO + O 3 ¾
¾® NO 2 + O2
qqq
O3 + h u ¾
¾® O 2 + O
NO 2 + O ¾
¾® NO + O 2
2 O3 + h u ¾
¾® 3 O 2 (Net reaction)
The presence of oxides of nitrogen increase the
decomposition of O3.
JEEMAIN.GURU
downloaded from jeemain.guru
15
The Solid State
molecules or ions) are closely packed and held together by strong Binding Electrostatic Shared Vander Waals' Electrostatic
forces attraction electrons Dipole-dipole between +ve
forces. ions and
negative
CRYSTALLINE SOLIDS : electrons
The constituent particles are arranged in definite geometrical Properties High melting Very high Low mpt Moderate to
pattern i.e. they have lattice structure. points mpt high mpt.
Hard & brittle Very hard Very soft Hard & Soft
AMORPHOUS SOLIDS : Semi Non Insulators good
They have random arrangement of the constituent particles Conductors Conductors Conductors
(amorphous - means without any form). Examples NaCl, CaF2 Diamond, H2O, CO2 Cu, Fe
Silica
DIF FERENCES BETWEEN CRYSTALLINE AND
CRYSTAL LATTICE :
AMORPHOUS SOLIDS ARE :
The three dimensional orderly arrangement of constituent particles
Crystalline Amorphous of a crystalline solid is known as Crystal lattice.
• Have lattice structure • Do not have lattice structure UNIT CELL :
• Have sharp melting point • No sharp mpt The smallest geometrical portion of the crystal lattice which can
be used as repetitive unit to build up the whole crystal is called
• They are anisotropic i.e. • They are isotropic i.e. their
unit cell.
their physical properties are physical properties are the
different along different same along all directions TYPES OF UNIT CELL :
(i) Simple or primitive : Unit cell in which the particles are
directions
present at the corners only
• They are symmetrical • They are non symmetrical.
JEEMAIN.GURU
downloaded from jeemain.guru
506 Chemistry
(ii) Face centred : In which the particles are present at the corners a
& at the centre of each of six faces. Atoms touch each other along edges. Hence r =
2
( r = radius of atom and a = edge length)
4
pr
Therefore P.F. = 3 3 = 0.52
( 2r )
(ii) Face centred cubic unit cell : Number of atoms per unit cell
(iii) Body centred : In which the particles are present at the corners
=4
and in the centre.
G B
A
H
(iv) End face centred : In which the particles are present at the F
corners and at the centre of two opposite faces.
E D
Atoms touch each other along the face diagonal. Hence r =
2a
(length of face diagonal = 2a )
4
1 1 F C
4. End face Centred 8 × 2× – 2 b
8 2 a
E a D
PACKING FRACTION : Atoms touch each other along the body diagonal. Hence
It is defined as the ratio of the volume of the unit cell that is
occupied by the spheres to the volume of the unit cell. 3a
r= (length of body diagonal = 3 a )
(i) Primitive cubic unit cell : Number of atoms per unit 4
cell = 1
4
G 2 ´ pr 3
B 3 = 0.68
Therefore P.F. = 3
æ 4r ö
H A çç ÷÷
è 3ø
(iv) Hexagonal primitive unit cell : Each corner atom is being
F shared by 6 other unit cells therefore their contribution to one
C
1
E D unit cell would be .
6
JEEMAIN.GURU
downloaded from jeemain.guru
1 1 MILLER INDICES :
Total number of atoms per unit cell ´ 12 + 3 + ´ 2 = 6 Reciprocals of Weiss indices and multiplying throughout by
6 2
smallest number to make integers are known Miller indices and
a = 2r represented by h, k and l and the plane as (hkl). For example, in
(112) plane h = 1, k = 1 and l = 2.
The distance between the parallel planes in a crystal is designated
as dhkl. For different cubic lattices the interplanar distances are
C a
given by d hkl =
h + k 2 + l2
2
è ø angles.
JEEMAIN.GURU
downloaded from jeemain.guru
508 Chemistry
CRYSTALLOGRAPHY AND X-RAY DIFFRACTION Now for maximum reflection condition (defined above)
(BRAGG'S EQUATION) : path difference = n × wavelength
When X-rays strike the parallel planes of the crystal at an angle q, 2d . sin q = nl
they are reflected from different planes. The resulting reflected This is Bragg's equation.
beam will be strong if all reflected rays are in phase. Now as SYMMETRY IN CRYSTAL SYSTEMS :
2p (i) Plane of symmetry : Which divides a crystal in two parts in
Phase difference = ´ path difference
l such a way that one part is the mirror image of the other.
If path difference is an integral multiple (say n) of wavelength, (ii) Axis of symmetry : It is a line about which the crystal may be
then phase difference becomes an integral multiple of 2p or 360° rotated such that it presents the same appearance more than
and hence the reflected rays will be in same phase once during complete revolution.
(iii) Centre of symmetry : It is a point such that any line drawn
Q’ through it intersects the surface of the crystal at equal
Q P’ distances in both directions.
ELEMENTS OF SYMMETRY :
P q O
Total number of planes, axes and centre of symmetries present in
q d a crystal are termed as elements of symmetry. A cubic crystal of
A B NaCl possesses 23 elements of symmetry.
X-ray reflection from crystals • Planes of symmetry = 3 + 6 = 9
Now from figure the path difference between waves reflected from • Axes of symmetry = 3 + 4 + 6 = 13
upper planes = AO + OB • Centre of symmetry = 1
From simple trignometry, if d is the distance between successive • Total number of symmetry elements = 23
OA SEVEN CRYSTAL SYSTEMS :
layers then sinq =
d There are about 230 crystal forms, which have been grouped into
OA = d sin q 14 types of space lattices called BRAVAIS LATTICES on the
Similarly OB = d sin q basis of their symmetry and 7 different crystal systems on the
Thus net path difference = OA + OB = 2d sin q basis of interfacial angles and axes.
c c c
b a
g
b a b a
b b
g g a b
a a
Simple Cubic Tetragonal Rhombohedral
JEEMAIN.GURU
downloaded from jeemain.guru
b a b a
b
g g
a a
Orthorhombic Monoclinic b
c c
b b a
a b (ii) Close packing in three dimensions : Following the
b g
g hexagonal close packing here, we have two layers.
a
a
Triclinic Hexagonal
Bravais showed from geometrical considerations that there
are only seven shapes in which unit cells can exist. c
c c c
These are
(i) Cubic a a a
a
(ii) Orthorhombic
c c c
(iii) Rhombohedral
(iv) Hexagonal
(v) Tetragonal
(vi) Monoclinic
(vii) Triclinic
On the basis of presence of particles there are four types For third layer there are two types of voids, marked a
of unit cells tetrahedral voids and marked c octahedral voids. If spheres
(i) Primitive or simple are placed over a, first layer is repeated and we have AB- AB
(ii) Face centred arrangement. This is known as hexagonal close packing
(iii) Body centred (hcp). If spheres for third layer are placed over c, a different
(iv) End centred
layer is formed and we have ABC-ABC arrangement. This is
He also showed that out of possible twenty eight unit cells. (Seven
knwon as cubic close packing (ccp).
shapes × four types in each shape = 28) only fourteen actually
Both hcp and ccp are equally efficient and space occupied
exist. These are called BRAVAIS LATTICES.
by spheres is 74.0%. The cubic close packing has face
CO-ORDINATION NUMBER : centered cubic (fcc) unit cell.
It is defined as the number of particles immediately adjacent to Following the square close packing in three dimensions,
each particle in the crystal lattice. we have AB, AB arrangement of spheres.
In simple cubic lattice C.N. is 6
In body centred lattice C.N. is 8 and
In face centred cubic lattice C.N. is 12.
High pressure increases C.N. and high temperature decreases
the C.N.
PACKING OF CONSTITUENT PARTICLES IN
CRYSTALS :
Generally the particles of larger size do the packing and particles
The resulting structure in this arrangement is referred to as
of smaller size occupy interstitial places
body-centred cube (bcc). In this arrangement only 68% of
(i) Close packing in two dimensions : It is of two types
(a) Square close packing : Space occupied by spheres is the available space is occupied by spheres and occur in
52.4% many solids.
INTERSTITIAL VOIDS :
The space left after hcp and ccp (74.0% in each case) is known as
interstitial voids. They are of two types:
(i) Tetrahedral voids : The vacant space touching four spheres
is called tetrahedral void. The radius ratio is
rvoid
= 0.225
rsphere
JEEMAIN.GURU
downloaded from jeemain.guru
510 Chemistry
rvoid
= 0.414
rsphere
(a) (b)
(a) (b)
(a) Eight tetrahedral voids per unit cell of ccp structure
Location of octahedral voids per unit cell of ccp or fcc lattice
(b) one tetrahedral void showing the geometry.
(a) at the body centre of the cube and
The number of tetrahedral voids is twice the number of (b) at the centre of each edge (only one such void is shown).
spheres (atoms). The number of octahedral voids is equal to the number of
(ii) Octahedral voids : The vacant space touching six spheres is spheres (atoms).
called octahedral void. The radius ratio is
Cations tend to get surrounded by the largest number of anions therefore the larger the rvoid ratio, the larger is the coordination
rsphere
number.
Limiting radius ratio(r+/r–) Shape Coordination number Example
0.155 – 0.225 Planar triangle 3 B2O3
0.225 – 0.414 Tetrahedral 4 ZnS
0.414 – 0.732 Square planar 4
0.414 – 0.732 Octahedral 6 NaCl
0.732 – 1.000 Body Centred Cubic 8 CsCl
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
512 Chemistry
F-Centres - Holes occupied by electrons are called F-Centres DONORS :
(Colour centres). The greater the number of F-centres the Impurities capable of donating electrons are known as donors
greater is the intensity of colour of solid and solids are e.g. P, As, Sb.
paramagnetic in nature. Due to F-centres
NaCl is yellow ACCEPTORS :
KCl is violet Impurities capable of accepting electrons are known as acceptors
LiCl is pink. e.g. B, Al, Ga.
Crystals showing schottky defect also show this defect. n-TYPE SEMI CONDUCTORS :
(ii) Metal excess due to interstitial cations : It is due to extra
Silicon doped with phosphorous is called n-type semi conductor.
positive ion and an electron occupying an interstitial position
The conductivity is due to presence of negative charge
A+ B– A+ B–
A+ e– (electrons).
B– A+ B– A+ Si Si Si
Crystals exhibiting Frenkel defect show this defect eg ZnO. +
(iii) Metal deficiency due to cation vacancy : It is due to absence Si P
of a metal ion from its lattice site and charge is balanced by –
ion having higher positive charge. Si Si Si
A+ B– O B–
B – A ++ B– A+ p-TYPE SEMI CONDUCTORS :
Transition metals exhibits this defect due to metal deficiency, Silicon doped with gallium is called p-type semi conductor. The
the compound obtained are non stoichiometric. e.g. it is conductivity is due to the presence of positive holes.
difficult to prepare ferrous oxide with the ideal composition
Si Si Si
FeO. What we actually obtain is Fe0.95O or FexO with x=0.93 +
to 0.96 Si Ga
(iv) Metal deficiency due to interstitial negative ion : It is due to
presence of negative ion in interstitial position and presence Si Si Si
of metal ion with extra charge.
Some typical 13-15 comounds are InSb, AlP and GaAs and some
A+ B– A+ B–
B – typical 12-16 compounds are ZnS, CdS, CdSe and HgTe.
B– A+ B– A++ These exhibit electrical and optical properties of great use in
This defect is not common electronic industry.
NON STOICHIOMETRIC DEFECT DUE TO PRESENCE PIEZOELECTRIC EFFECT AND PIEZOELECTRICITY :
OF FOREIGN ATOMS : The charge developed on the crystal due to mechanical stress is
In AgCl crystals two Ag+ ions may be missing while one Cd++ called piezoelectric effect and the current thus produced is called
occupies one of the vacant sites. piezo electricity.
Ag+ Cl– Ag+ Cl– PYROELECTRICITY :
Cl– Cd++ Cl– The electric current produced by heating on the faces of a crystal
FOOL'S GOLD : is called pyroelectricity.
Some samples of Iron pyrites shine like gold due to exchange of FERROELECTRIC EFFECT :
electrons between Fe2+ and Fe3+, which leads to metallic lustre. The reversal of direction of permanently lined up dipoles of piezo
Such samples are known as fool's gold.
electric crystal by applying electric field is called ferro electric
SEMI CONDUCTORS : effect.
Electronic conductors having electrical conductivity in the range Examples Rochelle Salt, KH2PO4 and Barium titanate BaTiO3.
of 104 – 10–7 ohm–1 cm–1 are known as semi-conductors. Examples
ANTIFERRO ELECTRIC SOLID :
Si, Ge, Sn (grey) Cu2O, SiC and GaAs.
When the dipoles in alternate lattices point are in opposite direction
INTRINSIC SEMI CONDUCTORS :
and net dipole moment is zero, the crystals are referred to as
Pure substances those are semi-conductors known as intrinsic
antiferro electric. Example is lead Zirconate PbZrO3.
semi conductors e.g. Si, Ge.
DIAMAGNETIC :
EXTRINSIC SEMI CONDUCTORS :
Their conductivity is due to the presence of impurities. They are The substances which are weakly repelled by magnetic fields e.g.
formed by doping e.g. Si doped with P. KCl, NaCl and TiO2. It is independent of temperature.
DOPING : PARAMAGNETIC :
It is defined as addition of impurities to a semiconductor to increase The substances which are attracted by magnetic field and loss
the conductivity. Doping of Si or Ge is carried out with P, As, Sb, magnetism in the absence of a magnetic field e.g. O2, Cu++, Fe+++,
B, Al or Ga. Na, K etc.
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
514 Chemistry
1. Sodium metal crystallises in a body centred cubic lattice with Sol. The arrangement of atoms shows a simple cubic cell.
the cell edge a = 4.29 Å. What is the radius of sodium atom.
1
Sol. In bcc the atoms touch along body diagonal Number of X atoms = ´ 8 = 1 (at corners)
8
3 ´ 4.29
\ 2r + 2r = 3 . a ; r = = 1.857 Å 1
4 Number of O atoms = ´12 = 3 (at edges)
2. Chromium metal crystallizes with a body centred cubic lattice. 4
The length of the unit cell edge is found to be 287 pm. Calculate Number of Na atoms = 1 (at centre)
the atomic radius. What would be the density of chromium Hence formula NaXO3
in g/cm3.
+ –
3 .a 3 ´ 287 6. A solid A B has NaCl type close packed structure. If the
Sol. In bcc lattice r = = = 124.24 pm anion has a radius of 250 pm; What should be the ideal
4 4
radius for the Cation? Can a cation C+ having radius 180 pm
Z´M + –
Density = N ´ a 3 be slipped into the tetrahedral void of the crystal A B ? Give
A
reasons for your answer.
2 ´ 51.99
r= = 7.30 g / ml + –
6.023 ´ 10 23 ( 287 ´ 10 -10 ) 3 Sol. Since A B has NaCl type close packed structure it must
3. Gold has closed packed structure which can be viewed as belong to a crystal system having coordination number 6.
spheres occupying 0.74 of the total volume. If the density of Hence limiting radius ratio
gold is 19.3 g/ml. Calculate the approximate radius of gold r+
ion in the solid (gold = 197 amu). = 0.414 - 0.732
Sol. Packing fraction = 0.74. It has fcc type cell. r-
So number of gold ions per cell = 4
r– = 250 pm ; r + ³ 0.414 ´ 250 = 103.5 pm
Z´M 4 ´ 197 Ideal radius for cation.
r= = = 19 .3 ;
NA ´ a3 a 3 ´ 6 .023 ´ 10 23 (II) Cation C+ having radius 180 pm cannot be slipped into
\ a = 4.07 ´10 -8 cm + – r+
the tetrahedral site of crystal A B because should be
For fcc cell, r-
2 .a 2 ´ 4.07 ´ 10 -8 r+
r= = = 1.439 ´10 -8 cm 0.225 – 0.414. In the given case
180
=
= 0.72 .
4 4 r 250-
4. A metal crystallizes into two cubic phases. (fcc and bcc)
7. In an ionic crystalline solid AB, r + = 0.74 Å and
whose unit cell lengths are 3.5 and 3.0 Å respectively.
r– = 1.84Å. The atomic weights of A and B are 70 and 40 amu
Calculate the ratio of densities of fcc and bcc.
respectively. Find (a) Coordination number of A & B (b)
Z´M Density in g/cc of solid.
Sol. r =
NA ´ a3
r+ 0.74
Sol. Given = = 0.402 < 0.414 therefore coordination
4´ M 2´ M r - 1.84
For fcc, r1 = ; For bcc, r2 =
N A (3.5 ´10-8 ) 3 N A (3.0 ´10 -8 )3 number = 4 (tetrahedral)
2r+ + 2r– = a
r1 4 (3.0 ´10 -8 ) 3
= = 1.259 \ a = 2(0.74 + 1.84) = 5.16Å
r 2 2 (3.8 ´10 -8 )3
5. A solid has a structure in which X atoms are located at the 4 ´ 110
= = 5.33 g / cc
cube corners of the unit cell. O atoms are located at the 6.023 ´ 10 23 (5.16 ´ 10-8 )3
centre of cube edges and Na atom at the cube centre. What
8. What is the concentration of cation vacancies when NaCl is
type of lattice is represented by this compound. Also suggest
a molecular formula for the compound. doped with 10–3 mole % of SrCl2.
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
516 Chemistry
Adding 1 on both sides
Z´ M 4 ´ 108
rK + + rCl - Hence density r = =
=
1.2 NA ´ a 3 6.023 ´ 10 23 (3.53 ´ 10- 8 )3
rCl - 0. 7 ...(ii)
= 16.3 g cm - 3
Dividing (ii) by (i)
22. LiI occurs as a cubical closest packing . If the edge length of
r +r
K+ Cl -
=
1.2
×
1 the unit cell is 624 pm, determine the ionic radii of Li + and
r +r 0.7 1 .5
Na + Cl - I - ions
a KCl / 2 1.2 a KCl 1 .2 Sol. The cubical closest packing has fcc unit cell. I - ions occupy
or = or = the corner and the face centers. These ions touch each other
a NaCl / 2 0.7 ´ 1.5 a NaCl 1 . 05
along the face diagonal of the cube. Hence
Z´ M 4r - =
Now since r = I
2 .a
NA ´ a3
a 624pm
3 or r- = = = 220.65 pm
I
r NaCl æa ö æ M NaCl ö 2 2 2(1.414)
We will have = çç KCl ÷÷ ç ÷
ç M ÷
r KCl è a NaCl ø è KCl ø Along the edge we have I - Li + I - arrangement where I -
æ 1.2 ö æ 58.5 ö
3 are at the corners and Li + at the centre of the edge
=ç ÷ ´ç ÷ = 1.172 (Octahedral void)
è 1.05 ø è 74.5 ø
\ 2r - +2r =a
-3 I Li+
19. The density of CsBr which has bcc structure is 4.4 g cm .
The unit cell has edge length a pm. Calculate the inter ionic a æ 624 ö
r = – rI- = ç - 220.65 ÷ pm = 91.35 pm
distance in crystals of CsBr (Atomic mass Cs = 133, Br = 80) Li+ 2 è 2 ø
é Z´ M ù 23. Calculate the packing fraction for Ca unit cell, given that Ca
3 2 ´ 213 êFormula r = ú
Sol. a = crystallises in face centred cube unit cell
4.4 ´ 6.023 ´10 23 êë N A ´ a 3 úû
Sol. The rank of fcc unit cell = 4
a = 5.438 × 10 - 8 cm 2.a
The atomic radius r =
For bcc lattice the interionic distance 4
(The atoms touch along face diagonal)
3 1.732 ´ 5.438 ´ 10- 8
r+ + r- = ×a= = 470.9 pm Volume of 4 atoms
2 2
3
20. If the radius of Cs + is 169 pm and that of Cl - is 181 pm. 4 3 4 æ 2 .a ö÷ 2 pa3
= 4 × p r = 4 × pç =
Predict the structure of CsCl. What is the coordination 3 3 çè 4 ÷ø 6
number of Cs + ion?
2 p a3 3
rc 169 Packing fraction = a = 0.74
Sol. = = 0.94 6
ra 181
24. The first order reflection of a beam of X -rays of wavelength
Since the value is greater than 0.732, the structure of CsCl is 1.54Å from the (100) plane of a crystal of the simple cubic
bcc. Its coordination number is 8. type occurs at an angle of 11.29. Calculate the length of the
21. The nearest neighbour Ag atoms in the silver crystal are unit cell (sin 11.29° = 0.1991)
2.5 × 10 - 8 cm. Presuming fcc structure of the crystal, what Sol. nl = 2 d sin q
will be the density of the silver? [At. wt. of Ag = 108 mol -1 ] 1 × 1.54 × 10 - 8 cm = 2 × d × sin11.29
Sol. We know that the nearest neighbour distance between the d = 3.68 × 10 - 8 cm
silver atoms is half of the face diagonal which is related to Further
2.a a
the edge length a by a
2 d= or 3.68 × 10 - 8 =
h 2 + k 2 + l2 12 + 0 2 + 0 2
2.a
= 2.5 × 10 - 8 cm or a = 3.53 × 10 - 8 cm
2 or a = 3.68 × 10 - 8 cm
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
518 Chemistry
25. For two ionic solids CaO and KI, identify the wrong 26. For a covalent solid, the units which occupy lattice points
statement amongst the following : are:
(a) The lattice energy of CaO is much large than that of KI (a) atoms (b) ions
(c) molecules (d) electrons
(b) KI is more soluble in water
27. Graphite is a
(c) KI has higher melting point (a) molecular solid (b) covalent solid
(d) CaO has higher melting point (c) ionic solid (d) metallic solid
1. Which of the following is not a crystalline solid? 10. A match box exhibits
(a) KCl (b) CsCl (a) cubic geometry
(c) Glass (d) Rhombic S (b) monoclinic geometry
2. Among solids, the highest melting point is exhibited by (c) tetragonal geometry
(a) Covalent solids (b) Ionic solids (d) orthorhombic geometry.
(c) Pseudo solids (d) Molecular solids
11. When molten zinc is cooled to solid state, it assumes hcp
3. The major binding force of diamond, silicon and quartz is
structure. Then the number of nearest neighbours of zinc
(a) electrostatic force
atom will be
(b) electrical attraction
(a) 4 (b) 6
(c) covalent bond force
(d) non-covalent bond force (c) 8 (d) 12
+
4. The maximum proportion of available volume that can be 12. Co-ordination number of Na in NaCl is
filled by hard spheres in diamond is (a) 4 (b) 3
(a) 0.52 (b) 0.34 (c) 6 (d) 5
(c) 0.32 (d) 0.68 13. A crystal lattice with alternate +ve and –ve ions has radius
5. The packing fraction for a body-centred cubic is ratio 0.524. Its co-ordination number is
(a) 0.42 (b) 0.53 (a) 4 (b) 3
(c) 0.68 (d) 0.82 (c) 6 (d) 12
6. In a solid AB having the NaCl type structure, ‘A’ atoms 14. How many unit cells are present in a cube-shaped ideal
occupy the corners of the cubic unit cell. If all the face- crystal of NaCl of mass 1.00 g?
centred atoms along one of the axes are removed, then the [Atomic masses : Na = 23, Cl = 35.5]
resultant stoichiometry of the solid is
(a) 2.57 × 1021 unit cells (b) 5.14 × 1021 unit cells
(a) AB2 (b) A2B 21
(c) A4B3 (d) A3B4 (c) 1.28 × 10 unit cells (d) 1.71 × 1021 unit cells
7. A substance AxBy crystallizes in a face centred cubic (fcc) 15. Which of the following is example of body centred
lattice in which atoms ‘A’ occupy each corner of the cube cube ?
and atoms ‘B’ occupy the centres of each face of the cube. (a) Mg (b) Zinc
Identify the correct composition of the substance AxBy (c) Copper (d) Sodium
(a) AB3 16. Which of the following describes the hexagonal close packed
(b) A4B3 arrangement of spheres?
(c) A3B (a) ABCABA (b) ABCABC
(d) Composition can’t be specified (c) ABABA (d) ABBABB
8. Crystals can be classified into basic crystal habits, equal to 17. A metallic crystal crystallizes into a lattice containing a
(a) 7 (b) 4 sequence of layers AB AB AB......Any packing of spheres
(c) 14 (d) 2 leaves out voids in the lattice. What percentage of volume
9. Tetragonal crystal system has the following unit cell of this lattice is empty space?
dimensions (a) 74% (b) 26%
(a) a = b = c, a = b = g = 90° (c) 50% (d) none of these.
(b) a = b ¹ c, a = b = g = 90° 18. In crystal structure of sodium chloride, the arrangement of
Cl– ions is
(c) a ¹ b ¹ c, a = b = g = 90° (a) fcc (b) bcc
(d) a = b c, = b = 90° = 120° (c) Both fcc and bcc (d) None of these.
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
520 Chemistry
44. If one end of a piece of a metal is heated the other end becomes 48. The existence of a substance in more than one solid
hot after some time. This is due to modifications is known as
(a) Energised electrons moving to the other part of the metal (a) Isomorphism
(b) resistance of the metal (b) Polymorphism
(c) mobility of atoms, in the metal
(c) Amorphism
(d) minor perturbation in the energy of atoms.
45. Which of the following is ferroelectric compound? (d) Allotropy
(a) BaTlO3 (b) K4[Fe(CN)6] 49. The second order Bragg diffraction of X-rays with l = 1.0Å
(c) Pb2O3 (d) None of these from a set of parallel planes in a metal occurs at an angle of
46. Which of the folliowing metal oxides is anti-ferromagnetic in 60°. The distance between the scattering planes in the crystal
nature? is
(a) MnO2 (b) TiO2 (a) 0.575Å (b) 1.00Å
(c) VO2 (d) CrO2
(c) 2.00Å (d) 1.15Å
47. Among the following which compound will show the highest
lattice energy? 50. Superconductors are derived from compounds of
(a) KF (b) NaF (a) p-block elements (b) lanthanides
(c) CsF (d) RbF (c) actinides (d) transition elements
1. If NaCl is doped with 10– 4 mol % of SrCl2, the concentration 7. A solid compound XY has NaCl structure. If the radius of the
of cation vacancies will be (NA = 6.02 × 1023 mol–1) cation is 100 pm, the radius of the anion (Y–) will be :
[CBSE-PMT 2007] [CBSE-PMT 2011 M]
16
(a) 6.02 × 10 mol –1 (b) 6.02 × 1017 mol–1 (a) 275.1 pm (b) 322.5 pm (c) 241.5 pm (d) 165.7 pm
14
(c) 6.02 × 10 mol –1 (d) 6.02 × 1015 mol–1 8. A metal crystallizes with a face-centered cubic lattice. The
2. The fraction of total volume occupied by the atoms present edge length of the unit cell is 408 pm. The diameter of the
in a simple cube is [CBSE-PMT 2007] metal atom is : [CBSE-PMT 2012]
(a) 288 pm (b) 408 pm
p p p p
(a) (b) (c) (d) (c) 144 pm (d) 204 pm
3 2 4 2 4 6
9. A metal has a fcc lattice. The edge length of the unit cell is 404
3. If ‘a’ stands for the edge length of the cubic systems : simple pm. The density of the metal is 2.72 g cm-3. The molar mass of
cubic, body centred cubic and face centred cubic, then the the metal is : (NA Avogadro’s constant = 6.02 × 1023 mol-1)
ratio of radii of the spheres in these systems will be [NEET 2013]
respectively, [CBSE-PMT 2008] (a) 30 g mol -1 (b) 27 g mol -1
JEEMAIN.GURU
downloaded from jeemain.guru
12 3 16 3
(a) pr (b) pr
3 3 M
X
20 3 24 3
(c) pr (d) pr
3 3
17. In a compound, atoms of element Y form ccp lattice and those
of element X occupy 2/3rd of tetrahedral voids. The formula
of the compound will be [AIEEE 2008]
(a) X4Y3 (b) X2Y3 (c) X2Y (d) X3Y4
18. Copper crystallises in fcc with a unit cell length of 361 pm.
(a) MX (b) MX2 (c) M2X (d) M5 X14
What is the radius of copper atom? [AIEEE 2009]
25. The arrangement of X–ions around A+ion in solid AX is
(a) 127 pm (b) 157 pm
given in the figure (not drawn to scale). If the radius of X– is
(c) 181 pm (d) 108 pm 250 pm, the radius of A+ is [JEE Advanced 2013]
19. The edge length of a face centered cubic cell of an ionic
substance is 508 pm. If the radius of the cation is 110 pm, the
radius of the anion is [AIEEE 2010] –
X
(a) 288 pm (b) 398 pm (c) 618 pm (d) 144 pm
20. Percentages of free space in cubic close packed structure A+
and in body centered packed structure are respectively
[AIEEE 2010]
(a) 30% and 26% (b) 26% and 32%
(c) 32% and 48% (d) 48% and 26% (a) 104 pm (c) 183 pm (b) 125 pm (d) 57 pm
JEEMAIN.GURU
downloaded from jeemain.guru
522 Chemistry
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
524 Chemistry
28. NH 4 Cl crystallises in a bcc lattice with edge length of unit 32. Al (at. wt 27) crystallizes in the cubic system with a cell edge
of 4.05 Å . Its density is 2.7 g per cm 3 . Determine the unit
-
cell equal to 387 pm. If the radius of the Cl ion is 181 pm, cell type calculate the radius of the Al atom
+ (a) fcc, 2.432 Å (b) bcc, 2.432 Å
the radius of N H 4 ions is (c) bcc, 1.432 Å (d) fcc, 1.432 Å
33. The ratio of inner planar distancess of three types of planes
(a) 366.3 pm (b) 154.1 pm (d100 , d110 , d111 ) for simple cubic lattice are
(c) 92.6 pm (d) None of these
1 1
(a) 1 : 1 : 1 (b) : :1
29. A metal crystallizes in 2 cubic phases fcc and bcc whose unit
2 3 3 2
cell lengths are 3.5 Å and 3.0Å respectively. The ratio of their
densities is (c) 3 : 2 :1 (d) 1 : 2 : 3
(a) 0.72 (b) 2.04 34. In mineral MX 2 , M 2 + does ccp and X - occupy the
(c) 1.46 (d) 3.12 tetrahedral voids. The number of cations and anions per unit
cell, the coordination number of cation and percent of
30. In a cubic closed packed structure of mixed oxides, the lattice tetrahedral voids occupied are
is made up of oxide ion, 20% of tetrahedral voids are occupied (a) 8, 4, 8, 100 % (b) 8, 4, 8, 50%
(c) 4, 8, 8, 50% (d) 4, 8, 8, 100%
by divalent X 2 + ions and 50% of the octahedral voids are
35. Iron crystallizes in several modifications. At about 911°C,
occupied by trivalent Y 3 + ions. The formula of the oxide is the bcc ' a ' form undergoes a trasition to fcc ' g ' form. If the
distance between the two nearest neighbours is the same in
(a) X.Y2O 4 (b) X 4 Y5O10 the two forms at the transition temperature, the ratio of the
(c) X 5 Y4 O10 (d) X 2 YO 4 density of iron in fcc form (r2 ) to that of iron of bcc form
(r1 ) at the transition temperature
31. The ranks of atoms in face centred cubic and hexagonal unit
cells respectively are r1 r1
(a) = 0.918 (b) = 0.718
(a) 6, 4 (b) 4, 6 r2 r2
(c) 1, 6 (d) 2, 6 r1 r1
(c) = 0.518 (d) = 0.318
r2 r2
JEEMAIN.GURU
downloaded from jeemain.guru
EXERCISE 1
14. (a) Number of unit cells = N A ´ Weight of subs tan ce
High Pressure M. Wt. ´ Z
¾¾¾¾¾
NaCl structure ¬¾¾¾¾¾ ® CsCl structure
1.
(CN 6 : 6) Heat to 760K (CN8 : 8) 6.023 ´ 10 23 ´ 1
= = 2.57 ´ 10 21 unit cells .
3. In the face-centred unit cell, there are eight tetrahedral voids. 58.5 ´ 4
Of these, half are occupied by silver cations. 15. (d) Na has Body centred cubic lattice.
4. Electrical conductivity increases with decrease of 16. (c) ABAB is hexagonal close packing.
temperature. 17. (b) In AB AB packing spheres occupy 74%. 26% is empty.
8. 128 pm. 18. (a) Arrangement of Cl– ions is fcc in NaCl
9. The formula of the compound will be = N3 M2 or M2N3. 19. (b) In bcc each atom has C. No. = 8.
18. (c) 19. (c) 20. (d) 21. (d) 22. (a) 20. (c) In CsI since Cs+ and I– have largest size.
23. (b) 24. (d) 25. (c) 26. (a) 27. (b) 21. (a) Potassium crystallises in BCC lattice.
22. (d) For octahedral r+ / r– = 0.414 – 0.732.
EXERCISE 2
23. (c) CsCl is body centred. Therefore 2r + + 2r – = 3.a body
1. (c)
Glass is amorphous solid. diagonal.
2. (a)
Covalent as in case of diamond.
3a
3. (c)
Covalent bond force (see text). \ r+ + r - = .
4. (b)
The volume to be filled by hard spheres in diamond is 2
0.34. 24. (c) Zn has hcp lattice.
5. (c) The p.f. for body centred cube = 0.68 (see text). 25. (c) In fluorite structure the C.No. of Ca++ is 8. See structure
6. (d) In NaCl structure we have particles at (8 corners + 6 faces) of simple ionic compounds.
one type. (12 edges + 1 in body) other type.
r+
A atoms are at eight corners. Removal of atoms along one 26. (b) Since C.No. is 6 it is octahedral and = 0.414 - 0.73 .
axis from face means removal of two A atoms. r-
27. (c) It is bcc hence, C. No. of each ion is 8.
1 1
\ Number of A atoms = ´8 + ´4 = 3
8 2 28. (c) Number of unit cells = N A ´ Wt. of subs tan ce
M. Wt. ´ Z
1
Number of B atoms = ´12 + 1 = 4 . \ A 3B 4 . 6.023 ´ 10 23 ´ 58.8
4 = = 1.5 ´10 23
58.8 ´ 4
1
7. (a) Number of A atoms = ´8 =1 Total number of molecules
8 29. (b) Number of unit cells =
(Z)
1
Number of B atoms = ´6 = 3 \Number of atoms = 12.08 ´ 1023 ´ 2 = 24.16 ´ 10 23
2
\ Formula AB3 (for bcc Z = 2)
8. (a) Seven crystal systems.
30. (b) r = Z ´ M = 2 ´ 100
9. (b) For tetragonal a = b ¹ c , a = b = g = 90° 3
NA ´ a 6.023 ´ 10 23
´ (400 ´ 10 -10 ) 3
JEEMAIN.GURU
downloaded from jeemain.guru
526 Chemistry
35. (c) AgBr exhibit Frenkel defect. 4. (d) The semiconductors formed by the introduction of
36. (c) KBr does not exhibit Frenkel defect. impurity atoms containing one elecron less than the
37. (d) No change in density (see text). parent atoms of insulators are termed as p-type
38. (b) From the given substances Li has high thermal & semiconductors. Therefore silicon containing 14
Electrical conductivity (due to metallic bond). electrons is to be doped with boron containing 13
39. (b) n-type, since electron is set free. electrons to give a p-type semi-conductor.
40. (d) Extrinsic semiconductor (see text).
5. (a) For bcc lattice body diagonal = a 3 .
41. (a) p-type semiconductors are formed by doping 14 group
elements with 13 group elements (valency 3). The distance between the two oppositely charged ions
42. (a) p-type semi-conductor. a
= 3
43. (b) It is the property of liquid crystal. 2
44. (a) It is due to movement of energised electrons 387 ´ 1.732
= = 335pm
(KE µ T). 2
45. (a) BaTlO3 (see text.) M+
46. (a) MnO2 (see text). 6. (c) is highest in CsF
47. (b) The smaller the size of cation and anion the more is X-
lattice energy Na+ has smaller size than others. \ correct choice : (c)
48. (b) Polymorphisms (see text). 7. (c) Radius ratio of NaCl like crystal
49. (d) nl = 2d sin q ; r+
= = 0.414
r-
æ 3ö 100
2 ´1Å = 2 ´ d sin 60 Þ d = 1.15Å ç sin 60 =
ç ÷ r- = = 241.5 pm
è 2 ÷ø 0.414
50. (a) Superconductors are derived from compound of p block 8. (a) For ccp 2 a = 4r
elements.
2 ´ 408
= 2r (2r = Diameter)
EXERCISE 3 2
1. (b) Since each Sr++ ion provides one cation vacancy, hence Diameter = 288.5
Concentration of cation vacancies = mole % of SrCl2 9. (b) Density is given by
added
Z´M
= 10–4 mole % d= ; where Z = number of formula units
-4 NA a 3
10
= ´ 6.023 ´ 1023 = 6.023 ´ 1017 mol–1 present in unit cell, which is 4 for fcc
100
2. (d) Number of atoms per unit cell = 1 a = edge length of unit cell. M = Molecular mass
a
Atoms touch each other along edges. Hence r = 4´M
2 2.72 =
( )
3
( r = radius of atom and a = edge length) 6.02 ´10 23 ´ 404 ´ 10 -10
4
pr
p
Therefore % fraction =
3 = (Q 1pm = 10 -10 cm)
3 6
(2 r )
3. (a) Following generalization can be easily derived for 2.72 ´ 6.02 ´ (404)3
various types of lattice arrangements in cubic cells M= = 26.99
4 ´107
between the edge length (a) of the cell and r the radius
of the sphere. = 27 gm mole–1
a 10. (a) In interstitial compounds small atoms like H, B & C
For simple cubic : a = 2r or r =
2 enter into the void sites between the packed atoms
For body centred cubic : of crystalline metal. They retain metallic conductivity
4 3 and are chemically inert.
a= r or r = a 11. (a) Diamond is like ZnS. In diamond cubic unit cell, there
3 4
are eight corner atoms, six face centered atoms and
For face centred cubic :
four more atoms inside the structure.
1
a = 2 2r or r = a Number of atoms present in a diamond cubic cell
2 2
Thus the ratio of radii of spheres for these will be 1 1
= 8´ + 6 ´ + 4 = 8
simple : bcc : fcc 8 2
a 3 1 (corners) (face (inside
= : a: a i.e. option (a) is correct answer.. centered) body)
2 4 2 2
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
528 Chemistry
r+ 3
11. (d) Calculate the ratio to get the limiting ratio value and d1 (a 2 )3 z1 æ 3 ö 4
r- 29. (c) = ´ =ç ÷ ´ = 1.46
d 2 (a1 )3 z 2 è 3.5 ø 2
consult the table. All are correct.
12. (c) Examine the nearest number of neighbours in (I) and (II). 30. (b) Sphere Tetrahedral void Octahedral void
The number is six which is octahedral. O 2- X 2+ Y 3+
13. (c) CsCl (8 : 8 coordination) transform to NaCl (6 : 6
coordination) on heating but reverse is not possible. O OO O
14. (b) The coulombic attractions between Cs + and F - ions is 2 ´ 20 50
+ 1
lowest due to larger size of Cs . 100 100
15. (a) One octahedral void is present at the body centre of the 1 0.4 0.5
cube and 12 octahedral voids are present on the centres 10 4 5
of the cube. Hence formula X 4 Y5O10
16. (a) The number of Fe 3+ ions replacing x Fe2+ ions = 2 x 31. (b) No. of particles in face centered cubic unit cell
3 1 1
2x = ´ 8 (corners) + ´ 6 (faces) = 4
vacancies of cations = x – = x /3 8 2
3 No. of particles in hexagonal unit cell
But x/3 = 1 – 0.94 = 0.06, x = 0.06 × 3 = 0.18 = 18% 1 1
17. (a) Statement (a) is correct. = ´ 12 (corners) + ´ 2(faces ) + 3 (in the body) = 6
6 2
18. (a) The first nearest neighbour of K+ ion will be 6 Br - ions Z´ M
at a distance of a/2 and the second nearest neighbours 32. (d) r = ,
No ´ a3
a 2
will be 12 K+ ions at a distance of. Z ´ 27
2 2.7 = \ Z=4
19. (b) CsCl has a bcc structure ions touching along body 6.02 ´ 10 ´ ( 4.05) 3 ´ 10 -24
23
JEEMAIN.GURU
downloaded from jeemain.guru
16
Solutions
SOLUTION : Soluble substances : Have solubility greater than
Homogeneous mixture of two or more non reacting components 1g per 100 ml
whose composition can be varied within certain limits is known as Insoluble substances : Have solubility less than
solution. 0.001 g per 100 ml
SOLUTE : Sparingly soluble substances : Have solubility less than 1g
The component which is present relatively in smaller proportion and more than 0.001 g per 100 ml.
in the solution is called solute.
(iii) Factors influencing solubility :
SOLVENT :
The component which is present in larger proportion in solution (a) Temperature : If the dissolution is endothermic the
is called solvent. solubility increases with temperature e.g. NaNO2, KNO3,
NaCl.
BINARY SOLUTION :
Containing two components only. If the dissolution is exothermic the solubility decreases
TYPES OF SOLUTIONS : with temperature e.g. Li2CO3, Na2CO3, Na2SO4, CeSO4
Depending upon the physical state of solute and solvent, the (b) Nature of solute/solvent.
solutions may be of the following types. SOLUBILITIES OF IONIC SOLIDS :
S.No. Solute Solvent Example The smaller the value of lattice energy and more the value of heat
1. Gas Gas gases in air of hydration more is the solubility of ionic compounds. Lattice
2. Gas Liquid Aerated Water energy depends upon force of attraction (F) between oppositely
3. Gas Solid Occluded hydrogen
qq'
4. Liquid Gas Moist air charged ions and is given by F = .
r 2D
5. Liquid Liquid Alcohol in water, Toluene + Benzene
6. Liquid Solid Mercury in Zinc amalgam q, q' are charges, r distance between charges, D is the dielectric
7. Solid Gas Smog constant of medium. Dielectric constant of water is 80, methanol
8. Solid Liquid Salt solution, Sugar solution 33.5, Benzene 2.3
9. Solid Solid Alloys Ionic solids dissolve more in a solvent having high dielectric
constant.
SOLUTIONS OF SOLIDS IN LIQUIDS :
(Solute = Solid and Solvent = Liquid) SOLUBILITIES OF MOLECULAR SOLIDS (NON
(i) Saturated solution : A solution which remains in contact IONIC SOLIDS) :
with excess of the solute is said to be saturated. Molecular solids containing polar groups (e.g. OH) are soluble in
(ii) Solubility : The amount of solute dissolved in 100 g of a polar solvents like water, methanol etc. Others are soluble in non
solvent to form a saturated solution at a given temperature is polar solvents.
termed as the solubility of solute.
JEEMAIN.GURU
downloaded from jeemain.guru
530 Chemistry
SOLUBILITY OF GASES : (v) Molality (m) : Number of moles of solute dissolved in 1000 g
It is generally expressed in terms of absorption coefficient which of the solvent.
is defined as the volume of gas, reduced to NTP, dissolved by Molality (m)
unit volume of solvent at particular temperature and 1 atmospheric wt. of solute ´1000
pressure of the gas. =
M. wt of solute ´ wt. of solvent in grams
Absorption co-efficients of some gases at 20°C.
(vi) Mole fraction : The ratio of the number of moles of one
Solvent Hydrogen Nitrogen Oxygen Carbon dioxide component to the total number of moles of solution. For
Water 0.017 0.015 0.028 0.88 components A & B.
Ethanol 0.080 0.130 0.143 3.00 nA nB
Benzene 0.060 0.104 0.165 xA = ; xB = ; x A + x B = 1 always.
nA + nB nA + nB
FACTORS INFLUENCING THE SOLUBILITY OF A
(vii) Mass fraction :
GAS :
(i) Nature of the gas : Easily liquifiable gases are more soluble. Mass of A
Mass fraction of A = ;
e.g. CO2 is more soluble than O2 and H2 Total mass of solution
(ii) Nature of solvent : Gases capable of forming ions in aqueous
solution are more soluble in water than in other solvents. eg. Mass of B
Mass fraction of B =
HCl, NH3 etc. Total mass of solution
(iii) Temperature : Solubility decreases with rise of temperature (viii) ppm (parts per million) : It is the mass of the solute present
at constant pressure. in million (106) parts by mass of the solution.
(iv) Pressure of the gas (Henry's Law) Mass of A ´10 6
Henry's law : The mass of a gas dissolved per unit volume of ppm A =
Mass of solution
solvent is proportional to the pressure of the gas at constant
Molality, mole fraction and mass fraction do not change
temperature. with temperature.
m µ P or (ix) Demal (D) : When one mole of solute is present in one litre
m = k.P where k is Henry's constant. of the solution at 0°C, it is known as one demal.
Henry's Law in terms of volume : The volume of a gas dissolved (x) Formality (f) : Number of formula mass in grams present in
in a solvent at a given temperature is independent of the pressure. one litre of solution.
Most gases obey Henry's law : SOME IMPORTANT RELATIONS :
(a) when pressure is not very high
(b) temperature is not very low md æ1 M ö
(i) M= or d = Mç + 2 ÷
(c) gas is not highly soluble M è m 100 ø
1+ m 2
(d) gas does not form any compound with solvent 1000
(e) gas does not undergo dissociation. 1000x 2
(ii) m =
EXPRESSION OF THE CONCENTRATION OF A x1M1
SOLUTION :
1000 dx 2
(i) Percentage : (iii) M =
(a) By weight - weight of solute per 100 g of solution. x1M1 + x 2 M 2
(b) By volume - weight of solute per 100 ml of solution.
Volume of solute per 100 ml of solution. m
(iv) Mole fraction ( x 2 ) =
(ii) Strength : Number of grams of solute dissolved per litre of 1000
m+
solution. (g/litre) M = molarity M1
Strength = Equivalent weight × Normality m = molality
(iii) Normality (N) : Number of gram equivalents of the solute
d = density of solution
dissolved per litre of the solution.
x1 = mole fraction of solvent
wt. of solute ´1000 x2 = mole fraction of solute
Normality (N) =
E. wt of solute ´ volume in mL M1 = molecular mass of solvent
(iv) Molarity (M) : Number of moles of the solute dissolved in M2 = molecular mass of solute
one litre of solution. Normality = n × Molarity
wt. of solute ´1000 Molecular Mass
Molarity (M) = where n =
M. wt of solute ´ volume in mL Equivalent mass
JEEMAIN.GURU
downloaded from jeemain.guru
Solutions 531
VAPOUR PRESSURE : when components are mixed to form the solution (III) DVmix = 0
It is defined as the pressure of the vapour in equilibrium with the i.e. no change in volume. In ideal solution the A–B intermolecular
liquid at that temperature interactions are the same as A–A and B–B inter-molecular
interactions. Strictly, there is no ideal solution. The following pairs
(i) Vapour pressure of a liquid increases with rise in temperature. almost behave as ideal solutions.
(ii) When intermolecular forces are weak, the liquid is more (a) benzene and toluene
volatile and has more vapour pressure. (b) ethyl bromide and ethyl chloride
VARIATION OF VAPOUR PRESSURE WITH (c) n-Heptane and n-hexane
TEMPERATURE : (d) chlorobenzene and bromobenzene
(e) ethylene chloride and ethylene bromide.
It is given by Clapeyron-Clausius Equation
For ideal solutions the vapour pressure of the solution always
P2 DH v é1 1 ù lies between the vapour pressure of the pure components and
log = ê - ú generally dilute solutions behave as ideal solutions.
P1 2.303R T
ë 1 T2û
NON IDEAL SOLUTIONS :
DHv = Enthalpy of vapourisation of liquid; R = gas constant; P2 =
vapour pressure at T2 and P1= vapour pressure at T1. Solutions which (I), do not obey Raoult's law, (II) DHmix ¹ 0 (III)
DVmix ¹ 0.
VAPOUR PRESSURE OF SOLUTION :
The vapour pressure of a solution is the sum of the partial vapour TYPES OF NON IDEAL SOLUTIONS :
pressures of the components of the solution. (Dalton's law) They are of two types
(i) Showing positive deviations : For such solutions (a) A–B
P = p A + p B + p C ......... etc . inter-molecular interactions are weaker than A–A and B–B
In general, the vapour pressure of a component in solution is less intermolecular interactions (b) DHmix is +ve (c) DVmix is +ve
than that of pure solvent. Examples :
Carbon tetrachloride + benzene
RAOULT'S LAW :
Carbon tetrachloride + chloroform
(i) The partial pressure of a volatile component of a solution is Carbon tetrachloride + Toluene
directly proportional to its mole fraction in solution at any
Acetone + Carbon disulphide
temperature.
Acetone + Ethyl alcohol
p A µ x A and p B µ x B and Acetone + Benzene
Methyl alcohol + Water
p A = p oA .x A , p B = p oB .x B Ethyl alcohol + Water
where pA = partial pressure of component A, (ii) Showing negative deviations : For such solutions (a) A–B
intermolecular interactions are stronger than A–A and B–B
p oA = vapour pressure of component A in pure form, intermolecular interactions (b) DHmix is –ve (c) DVmix is –ve.
xA = mole fraction of component A in solution. Examples :
Chloroform + Acetone
Also remember, p A = p ´ g A , where p = Total pressure Chloroform + Benzene
and gA = Mole fraction of component A in vapour phase Chloroform + Diethyl ether
(ii) Raoult's law for solution containing non-volatile Acetone + Aniline
solute : The relative lowering of vapour pressure of a solution HCl + Water
containing non volatile solute is equal to the mole fraction of HNO3 + Water
p oA - p A n AZEOTROPIC MIXTURE OR CONSTANT BOILING
non volatile solute = xB =
p oA n+N . MIXTURE :
A mixture of two or more components which like a pure chemical
For very dilute solution :
compound boils and distills over completely at the same
poA - pA n temperature without change in their chemical composition is called
Alternate formula = (Q n << N ) an azeotrope. Non ideal solutions form azeotropes.
poA N
AZEOTROPIC MIXTURE WITH MINIMUM BOILING
A = Volatile component of solution,
POINT :
B = non-volatile component of solution or the solute
n = moles of B, N = moles of A. It is formed by liquids showing positive deviation. An intermediate
composition of liquids having highest vapour pressure, hence
AN IDEAL SOLUTION : lowest boiling point gives this azeotrope. Such azeotropes have
The solution which (I) Obey Raoult's law at all temperatures and boiling points lower than either of the pure component e.g.
concentrations (II) DHmix = 0 i.e. no heat is evolved or absorbed Rectified spirit (ethanol 95.5% + H2O 4.50%) bpt 351.5 K.
JEEMAIN.GURU
downloaded from jeemain.guru
532 Chemistry
AZEOTROPIC MIXTURE WITH MAXIMUM BOILING These are
POINT : (i) Relative lowering of vapour pressure
It is formed by liquids showing negative deviation. An intermediate (ii) Osmotic pressure
composition of liquids having minimum vapour pressure, hence (iii) Elevation in boiling point
highest boiling point gives this azeotrope. Such azeotropes have (iv) Depression in freezing point
boiling points higher than either of the pure components e.g.
Water & HNO3 (HNO3 68% + H2O 32%) bpt 393.5K. RELATIVE LOWERING OF VAPOUR PRESSURE :
It is measured by Ostwald and Walker's method (Gas saturation
GRAPHICAL REPRESENTATION OF IDEAL AND
method)
NON IDEAL SOLUTIONS :
Ideal Solution po - p w2
= mole fraction of non volatile solute = w + w
po 1 2
2Cu + + + Fe (CN ) 46 - ¾
¾® Cu 2 [ Fe( CN ) 6 ] ¯
It is not suitable for non aqueous solution as it gets dissolved.
p = pA + pB 0
pA Another artificial semipermeable membrane is Ca3(PO4)2.
V.P.
pB
0
pA OSMOTIC PRESSURE (p) :
The hydrostatic pressure developed on the solution which just
pB prevents the osmosis of pure solvent into the solution through a
semipermeable membrane is called osmotic pressure.
xA = 0 xA = 1
xB = 1 Mole fraction xB = 0
p
Solvent
0
V.P. pA Solution
pB
0
p = p A + pB
pA Semipermeable
membrane
pB p = hrg
xA = 0 xA = 1
xB = 1 Mole fraction xB = 0
=hrg
COLLIGATIVE PROPERTIES : Or
Properties which depend upon the number of particles irrespective The minimum external pressure applied to the solution to just
of their nature (ions or molecules) are called colligative properties. stop the process of osmosis is known as osmotic pressure.
JEEMAIN.GURU
downloaded from jeemain.guru
Solutions 533
RELATION BETWEEN OSMOTIC PRESSURE (p) AND
patm p patm LOWERING OF VAPOUR PRESSURE :
Relative lowering of vapour pressure is directly proportional to
osmotic pressure
po - p p´M po - p æ M ö
o
= \ o
µ p ç since Constant ÷
p dRT p è dRT ø
SPM
OSMOLARITY :
Solution Solvent Osmotic behaviour of solutes undergoing association or
dissociation is equal to molarity × number of particles produced
Or per formula unit of solute known as osmolarity.
The minimum external pressure applied on solution to make its REVERSE OSMOSIS :
vapour pressure equal to that of solvent is known as osmotic When the external pressure applied on the solution is more than
pressure. osmotic pressure, the solvent flows from the solution to the pure
DETERMINATION OF OSMOTIC PRESSURE : solvent which is called reverse osmosis. Desalination of sea water
(i) Pfeffer's method is done by reverse osmosis to make it potable.
(ii) Berkeley and Hartley's method (most common) PLAMOLYSIS :
(iii) Morse and Frazer's method The flow of the fluid from the plant cell when placed in a hypertonic
(iv) Townsend's negative pressure method solution is called plamolysis. The plant cell undergoes shrinkage.
(v) De. Vries method EXO-OSMOSIS :
ISOTONIC SOLUTIONS : Outward osmotic flow of fluid from a cell through semipermeable
Solutions having the same osmotic pressure. 0.91% NaCl solution memberane e.g. grape in conc. NaCl solution.
is isotonic with human RBC's. ENDO-OSMOSIS :
HYPOTONIC SOLUTION : Inward osmotic flow of fluid from a cell through semipermeable
Solution having lower Osmotic pressure. membranes e.g. grape in water.
HYPERTONIC SOLUTION : SILICA GARDEN :
Solution having higher osmotic pressure. When coloured salts e.g. Copper Sulphate, Cobalt Nitrate,
Manganese Chloride, Nickel Chloride and Ferrous sulphate etc.
VAN'T HOFF'S THEORY OF DILUTE SOLUTIONS : are placed in Sodium silicate solution of density 1.1, a colloidal
Dilute solutions behave like gases and gas laws can be applied to and semipermeable shell of Silicates is formed round the crystal.
them. Inside this, there is strong solution of salt and outside weak
BOYLE-VAN'T HOFF LAW : solution of sodium silicate. Water permeates into the shell, pressure
rises and the shell bursts out, the salt solution escapes but
Osmotic pressure of a solution is directly proportional to its
immediately reacts with sodium silicate to form again
concentration at constant given temperature.
semipermeable shell of the metallic silicate. The process is repeated
1 again and again and projection of coloured silicates continues to
pµCµ
V grow.
JEEMAIN.GURU
downloaded from jeemain.guru
534 Chemistry
BOILING POINT AND ELEVATION IN BOILING Carbon tetrachloride 5.03
POINT : Chloroform 3.63
The temperature at which the vapour pressure of a liquid becomes Ethyl alcohol 1.20
equal to atmospheric pressure is known as the boiling point of the Ethyl ether 2.11
liquid.
Addition of non volatile solute in a solvent lowers the vapour
DETERMINATION OF MOLECULAR WEIGHT FROM
pressure and increases the boiling point. The increase in boiling BOILING POINT ELEVATION :
point is directly proportional to the molality of solution,
K b ´ w ´1000
Boiling point of M=
DTb ´ W
Solvent
Solution Kb = molal elevation constant,
1.013 bar
or 1Atm w = weight of solute,
nt W = weight of solvent,
olve n
S io DTb = Elevation in bpt.
lut
Vapour pressure
nt
K ´ w ´ 1000 solve
DTb µ m or DTb = K b ´ m = b id
M´W liqu tion
Kb = molal elevation constant or ebullioscopic constant. It is solu
nt
characteristic for given solvent. When olve
s
Vapour pressure
JEEMAIN.GURU
downloaded from jeemain.guru
Solutions 535
RT02 M A RT02 1
Kf = = Units of Kf = K . Kg mol–1 Colligative property µ , hence higher
1000 lf DH fusion ´ 1000 Molecular mass of solute
values are obtained for molecular masses in case of association.
R = gas constant,
Acetic acid in benzene associates and its observed molecular
T0 = normal freezing point, mass is 120.
lf = heat of fusion per gram of solvent.
O--H—O
Kf is freezing point constant for a given solvent.
MOLAL DEPRESSION CONSTANTS OF SOME CH3–C C–CH3
COMMON SOLVENTS :
O—H--O
Water 1.86 Naphthalene 6.90
Acetic acid
Acetic acid 3.90 Bromoform 14.40
Phenol 7.27 Cyclohexane 20.00 Benzoic acid in benzene associates and its observed molecular
mass is 244.
Benzene 5.12 Camphor 37.70
DETERMINATION OF MOLECULAR WEIGHT BY O--H—O
DEPRESSION IN FREEZING POINT :
C6H5–C C–C6H5
K ´ w ´1000
M= f O—H--O
DTf ´ W
Benzoic acid
Kf = Molal depression constant, w = weight of non-volatile solute,
DTf = depression in freezing point,W = weight of solvent KCl in water dissociates and its observed molecular mass
The method employed is known as Cryoscopic method. The is 37.25.
common methods are + –
KCl K + Cl
(i) The Beckmann method
These observed values are corrected by multiplying by Van't Hoff
(ii) The Rast Method
factor i.
RELATION BETWEEN OSMOTIC PRESSURE AND
VAN'T HOFF FACTOR (i ) :
OTHER COLLIGATIVE PROPERTIES :
Its value is obtained by any of the following expression
æ p o - p ö dRT
(i) p = ç A o A ÷´ Normal molecular mass
ç p ÷ M Relative lowering of vapour pressure (i) i=
è A ø B
Observed molecular mass
JEEMAIN.GURU
downloaded from jeemain.guru
536 Chemistry
RELATION BETWEEN RELATIVE LOWERING OF CONJUGATE SOLUTIONS :
VAPOUR PRESSURE AND MOLALITY OF SOLUTION: When two partially miscible liquids A and B are mixed with each
other, two layers are formed. First, Solution of A in B and Second,
pº -p m ´ M1 Solution of B in A. Such solutions co-existing together are called
=
pº 1000 conjugate solutions. For example solution of phenol and water.
CRITICA L SOLUTION TEM PERATURE O R
Where m = molality of solution CONSOLUTE TEMPERATURE :
M1 = Molecular weight of solvent On heating the conjugate solution the mutual solubility of A and
B increases. A temperature is reached when two phases disappear
RELATION BETWEEN WEIGHTS OF TWO
and one homogeneous phase is left. This temperature is known
IMMISCIBLE LIQUIDS IN THE DISTILLATE :
as Critical solution temperature or Consolute Temperature. It is
of two types :
w A pA ´ M A
= (i) Upper Consolute temperature : For example water-phenol
wB pB + p B
system.
where w = weight of liquid (ii) Lower Consolute temperature : In some cases it is also
possible to have a lower temperature of similar kind. For
p = partial pressure
example Trimethylamine-water is a lower consolute
M = Molecular weight temperature.
25 3
Moles fraction of Na2S2O3 = = 0.065
Moles of ethanol n B = = 0.543 46.1
46
JEEMAIN.GURU
downloaded from jeemain.guru
Solutions 537
(III) Number of moles of Na+ ions = 2 × 3 = 6
17.3555 - 17.2350 10 18
6 ´ 1000 or = ´
Molality of Na+ = = 7.73 m 17.3555 m 100
776
Number of moles of S2O32– ions = 3 1.8
0.006943 =
3 ´ 1000 m
Molality of S2O32– = = 3.86 m
776 \ m = 259.25
5. 0.080575 kg of Glauber's Salt is dissolved in water to obtain
1 dm3 of solution of density 1.0772 kgdm–3. Calculate the p o - ps w´M
(b) =
molarity, molality and mole fraction of Na2SO4 in solution. p o m´ w
Sol. Molecular mass of Glauber's salt = 322 g/mol = 0.322
kg mol–1 23.62 - Ps 1.5 ´ 18
or =
0.080575 23.62 60 ´ 50
Moles of Glauber's salt = = 0.2502
0.322
\ Ps = 23.407 mm Hg
Moles of Na2SO4 will be same i.e. 0.2502.
8. The vapour pressure of water at 20°C is 17.54 mm Hg. When
0.2502 20g of solute was added in 50 g water, the V.P. was found to
\ Molarity of solution = = 0.2502 M
1 lower by 0.30 mm Hg. Calculate M wt of solute.
Mass of 1 litre solution = V × d = 1 dm 3 × 1.0772 kg dm–3
= 1.0772 kg po - ps w´M
Sol. =
Mass of Na2SO4 = 0.2502 × 142 (M. wt of Na2SO4 = 142) p o m´ W
= 0.03552 kg
Mass of solvent = (1.0772 – 0.0355) Kg = 1.0417 kg 0.30 20 ´ 18
or =
0.2502 17.54 m ´ 50
Molality m = = 0.24 m
1.0417
\ m = 420.96
1041.7 9. Find the molality of a solution containing non volatile solute
Moles of solvent = = 57.87
18 if the vapour pressure is 2% below the vapour pressure of
pure water. (DHANBAD 1990)
0.2502
Mole fraction of Na2SO4 = = 4.3 ´ 10 -3
0.2502 + 57.87 p o - ps m´M
Sol. Apply o
=
6. How much concentrated H2SO4 of density 1.84 g cm–3 which p 1000
contains 98 mass percent of H2SO4 must be diluted to prepare
where m = molality of solution;
100 cm3 of the 20 mass percent H2SO4 of density 1.14 g cm–
3.
M = Molecular weight of solvent.
JEEMAIN.GURU
downloaded from jeemain.guru
538 Chemistry
11. The freezing point of a solution containing 50 cm3 of ethylene 15. A 1.2% solution (wt/volume) of NaCl is isotonic with 7.2%
glycol in 50 g of water is found to –34°C. Assuming ideal solution (wt/volume) of glucose. Calculate degree of
behaviour calculate the density of ethylene glycol. ionisation and Van't Hoff factor of NaCl.
Kf for water = 1.86 K kg mol–1 Sol. Since glucose is non electrolyte its osmotic pressure is
Sol. Ethylene glycol = 50 cm3
Weight of ethylene glycol = 50 × d
æ 7.2 ´ 1000 ö æ 7.2 ´ 1000 ö
Molecular weight of ethylene glycol = 62 g p1 = CRT = ç ÷ ´ 0.0821 ´ T çQ C = ÷
è 180 ´ 100 ø è 180 ´ 100 ø
Weight of water = 50 g
NaCl is electrolyte and let a be the degree of ionisation then
K ´ w ´ 1000 1.86 ´ 50 ´ d ´ 1000
DTf = f ; 34 = NaCl Na+ + Cl–
M´W 62 ´ 50
d = 1.133 g/cm3 1–a a a
12. Calculate the freezing point of an aqueous solution of non 1- a + a + a
electrolyte having an osmotic pressure 2.0 atm at 900 K. Van't Hoff's factor i = = 1+ a
1
Kf = 1.86 K mol–1 kg and S = 0.0821 litre atm K–1mol–1.
Osmotic pressure of NaCl is
Sol. p = CST where C = Molar concentration, p = 2 atm,
S = 0.0821 litre atm K–1 mol–1, T = 300 K æ 1.2 ´ 1000 ö
p2 = (1 + a) ç ÷ ´ 0.0821´ T
\ 2 = C × 0.0821 × 300 \ C =0.0812 mol lit–1 è 58.5 ´ 100 ø
DTf = Kf × molality
For isotonic solutions p1 = p 2
For dilute solutions molarity = molality
DTf = 1.86 × 0.0812 = 0.151 æ 7.2 ´ 1000 ö æ 1.2 ´ 1000 ö
ç ÷ ´ 0.0821´ T = ç ÷ ´ 0.0821´ T (1 + a)
Freezing point = T – DTf = 0 – 0.151 = –0.151°C è 180 ´ 100 ø è 58.5 ´ 100 ø
13. A decimolar solution of potassium ferrocyanide is 50%
dissociated at 300K. Calculate the osmotic pressure of the \ a = 0.95 and i = 1.95
solution. Given S = 8.314 JK–1 mol–1. 16. The degree of dissociation of Ca(NO3)2 in a dilute aqueous
solution containing 7g of salt per 100 g of water at 100°C is
0.1
Sol. Given C = 0.1 mol lit–1 = = 10 2 mol m -3 70%. Calculate the vapour pressure of solution.
10 -3
Sol. Ca(NO3)2 Ca++ + 2 NO3–
p = 102 ´ 8.314 ´ 300 Nm -2 1 – 0.7 0.7 2 × 0.7
But, K4 [Fe(CN)6] 4K+ + [Fe(CN)6]4– Van't Hoff factor i = 1 – 0.7 + 0.7 + 1.4 = 2.4
p o - ps w M 7 ´ 18
14. 0.85%, aqueous solution of NaNO3 is apparently 90% Now = ´ = = 0.0184
p o m W 68.33 ´ 100
dissociated at 27°C. Calculate the osmotic pressure.
(R = 0.0821 atm K–1 mol–1)
Sol. Molecular weight of NaNO3 = 85 po - ps
= 0.0184
po
Wt ´1000 0.85 ´ 1000
Molarity = = = 0.1 mol lit -1
M. wt ´ V 85 ´ 100 760 - ps
= 0.0184
NaNO3 solution is 90% dissociated 760
NaNO3 Na+ + NO3– \ ps = 746.01 mm Hg
1 – 0.9 0.9 0.9 17. To 500 cm3 of water 3.0 × 10–3 Kg of acetic acid is added. If
23% acetic acid is dissociated, what will be the depression in
Van't Hoff factor i = 1 – 0.9 + 0.9 + 0.9 = 1.9
freezing point? Kf and density of water are 1.86K kg–1 mol–1
\ p = 1.9 ´ 0.1 ´ 0.0821 ´ 300 = 4.68 atm and 0.997 g cm–3 respectively.
JEEMAIN.GURU
downloaded from jeemain.guru
Solutions 539
Sol. Mass of acetic acid = 3 × 10–3 kg = 3.0 g
x 2 ´1000
Molecular mass of acetic acid = 60 g now apply the formula m =
x1M1
Mass of Solvent = 500 × 0.997 = 498.5 g
CH3COOH CH3COO– + H+ 1000 ´ 0.012
m= ;
1 – 0.23 0.23 0.23 i = 1.23 0.988 ´ 78
3 ´ 1000 m = 0.156 mol kg -1
\ DTf = K f ´ molality ´ i = 1.86 ´ ´ 1.23 = 0.229
60 ´ 498.5
21. Addition of 0.643 g of a compound to 50 ml of benzene
18. Calculate the molality of a 1 litre solution of 93%
(density 0.879 g mol -1 ), lower the freezing point from 5.51°C
H 2SO 4 (mass/volume). The density of the solution is 1.84
g/ml to 5.03°C. If Kf for benzene is 5.12 kg mol -1 , Calculate the
molecular mass of the compound
93 ´ 1000
Sol. Molarity of 93% H 2SO 4 is = = 9.48
98 ´ 100 K f ´ w ´ 1000
Sol. Molecular mass =
The relation between M and m is as follows DTf ´ W
m´ d 5.12 ´ 0.643 ´ 1000
M= ; =
m M2 0.48 ´ 50 ´ 0.879
1+
1000 = 156.06 g/mol
m ´1.84 ( DTf = (5.51 – 5.03) = 0.48 and Mass of solvent
9.48 =
m ´ 98
1+ = V ´ d = 50 × 0.879)
1000 22. At 100°C benzene and toluene have vapour pressure of 1375
On solving and 558 torr, respectively. Assuming these two form an ideal
m = 10.30 solution calculate the composition of the solution that boils
19. What mass of non volatile solute urea ( NH 2 CONH 2 ) must at 1 atm and 100°C. What is the composition of vapour issuing
at these conditions.
be dissolved in 100 g of water in order to decrease the vapour
pressure of water by 25%. What will be the molality of the Sol. Let xAand xB be the mole fraction of benzene and toluene
solution? respectively
Sol. Let the mass of urea be w g o
then, P = x A p A + (1 - x A )p Bo
Now use the alternate formula
760 = x A × 1375 + (1 – x A ) 558
p0 - p n
= x A = 0.247
p N
Mole fraction of benzene in the vapour phase
100 - 75 W / 60 o
= x ApA 0.247 ´ 1375
75 100 / 18 = = = 0.447
P 760
6000 Mole fraction of toluene in solution
or w = = 111.11 g
54 (1 – 0.247) = 0.753
111.11´ 1000 Mole fraction of toluene in vapour
Molality of urea = (1 – 0.447) = 0.553
60 ´ 100
23. The vapour pressure of pure benzene at a certain temperature
= 18.5 mol kg -1 is 640 mm Hg. The non volatile solid weighing 2.175 g is
20. The vapour pressure of pure benzene at 25°C is 639.7 mm Hg added to 39.0 g of benzene. The vapour pressure of the
and the vapour pressure of a solution of a solute in benzene solution is 600 mm Hg. What is the molar mass of the solid
at the same temperature is 631.9 mm Hg. Calculate the molality substance?
of the solution. Sol. Apply the formula
o
Sol. From Raoult’s law p A = x A PA P° - P n
=
P N
631.9
\ x1 = = 0.988 640 - 600 2.175 / M
639.7 =
600 39 / 78
\ Mole fraction of solute = ( 1 – 0.988) = 0.012 = x 2
M = 65.25 g/mol
JEEMAIN.GURU
downloaded from jeemain.guru
540 Chemistry
24. A 0.1 molar solution of NaCl is found to be isotonic with 1%
NaCl Na + + Cl -
urea solution. Calculate
(a) degree of dissociation of sodium chloride. 1– a a a
(b) Van’t Hoff factor and 1- a + a + a
i= ; 1 + a = 1.87
-3 1
Assume density of 1% urea equal to 1 g cm
\ a = 0.87 or 87%
Sol. (a) NaCl Na + + Cl - 27. The freezing point of a solution containing 0.2 g of ethanoic
C(1 – a ) Ca Ca acid in 20 g of benzene is lowered by 0.45°C. Calculate the
Total concentration of species in solution degree of association of ethanoic acid in benzene. Assume
= C(1 + a ) = 0.1(1 + a )
ethanoic acid dimerises in the solvent benzene. Kf for
Osmotic pressure of NaCl
= 0.1 (1 + a ) RT
T benzene = 5.12 K mol -1 kg
Osmotic pressure of urea solution
K f ´ w ´ 1000 5.12 ´ 0.2 ´ 1000
1 Sol. M = = = 113.77
= RT
T DTf ´ W 0.45 ´ 20
60 ´ 0.1
Since two solutions are isotonic, then Van’t Hoff factor
1 Normal M.wt 60
0.1 (1 + a ) RT = RT
T i= = = 0.53
60 ´ 0.1 Observed M.wt 113.77
\ a = 0.667 2 CH 3COOH (CH3COOH)2
(b) Again Van’t Hoff's factor
a
C(1 + a) 1–a
i= = 1.667 2
C
25. What minimum weight of ethane -1, 2-diol must be mixed 1- a + a / 2
Van’t Hoff factor i = = 0.53
with 10 gallons of water to protect it from freezing at – 24°C? 1
Ethane 1, 2 - diol is an antifreeze addition
a
(1 gallon = 3.785 liters, Kf for H 2 O = 1.86 K mol -1 kg) or 1 – = 0.53
2
Sol. DTf = Kf × m (m = Molality) \ Degree of association a = 0.94 = 94%
28. The degree of dissociation of calcium nitrate in dilute solution
24 containing 7 g per 100 g of water at 100°C is 70%. Calculate
\ m= = 12.90
1.86 the vapour pressure of solution.
Freezing point of water = 0.0°C
\ 1 kg of water should contain 12.90 mole of Sol. Ca ( NO 3 ) 2 Ca + + + 2 NO 3-
ethane-1, 2-diol 1– a a 2a
10 gallons of water = 10 × 3.785 Moles at equilibrium
= 37.85 liters 1 – a + a + 2 a = 1 +2 a
Moles of ethane – 1, 2-diol in 37.85 liters = 1 + 2 × 0.7 = 2.4
= 12.9 × 37.85mol Again
JEEMAIN.GURU
downloaded from jeemain.guru
Solutions 541
JEEMAIN.GURU
downloaded from jeemain.guru
542 Chemistry
Multiple Choice Questions 24. Osmotic pressure of a sugar solution at 24°C is 2.5
20. When mercuric iodide is added to the aqueous solution of atmosphere. The concentration of the solution in gm mole
potassium iodide then per litre is
(a) freezing point is raised. (a) 10.25 (b) 1.025
(c) 102.5 (d) 0.1025
(b) freezing point is lowered.
25. A solution is obtained by dissolving 12 gm of urea (mol. wt.
(c) freezing point does not change.
60) in a litre of water. Another solution is obtained by
(d) boiling point does not change. dissolving 68.4 gm of cane sugar (mol. wt. 342) in a litre of
21. Which one of the following salts will have the same value of water at the same temperature. The lowering of vapour
van’t Hoff factor (i) as that of K4[Fe (CN)6]. pressure in the first solution is
(a) same as that of 2nd solution
(a) Al2(SO4)3 (b) NaCl (b) nearly one-fifth of the 2nd solution
(c) Al (NO3)3 (d) Na2SO4. (c) double that of 2nd solution
22. For a dilute solution, Raoult’s law states that (d) nearly five times that of 2nd solution
(a) the lowering of vapour pressure is equal to the mole 26. Freezing point of an aqueous solution is (–0.186)°C. Elevation
fraction of the solute of boiling point of the same solution is Kb = 0.512°C,
(b) the relative lowering of vapour pressure is equal to the Kf = 1.86°C, find the increase in boiling point.
mole fraction of the solute (a) 0.186°C (b) 0.0512°C
(c) the relative lowering of vapour pressure is proportional (c) 0.092°C (d) 0.2372°C.
to the amount of solute in solution 27. The relationship between osmotic pressure at 273 K when
(d) the vapour pressure of the solution is equal to the 10g glucose (P1), 10 g urea (P2), and 10g sucrose (P3) are
mole fraction of the solvent dissolved in 250 ml of water is
23. The normality of 10% (weight/volume) acetic acid is (a) P1 > P2 > P3 (b) P3 > P1 > P2
(a) 1 N (b) 10 N
(c) P2 > P1 > P3 (d) P2 > P3 > P1
(c) 1.7 N (d) 0.83 N
1. Which of the following modes of expressing concentration (a) more than the theoretical weight
is independent of temperature? (b) less than the theoretical weight
(a) Molarity (b) Formality (c) same as theoretical weight
(c) Normality (d) Molality (d) None of the above
2. The solubility of a gas in water depends on
7. What is the molarity of H2SO4 solution that has a density
(a) nature of the gas (b) temperature
1.84 gm/cc at 35°C and contains 98% H2SO4 by weight?
(c) pressure of the gas (d) All of these
(a) 4.18 M (b) 8.14 M
3. If one mole of a substance is present in 1 kg of solvent, then
its concentration is called (c) 18.4 M (d) 18 M
(a) Molar conc. (b) Molal conc. 8. The amount of oxalic acid (mol. wt. 63) required to prepare
(c) Normality (d) Strength wt/wt. 500 ml of its 0.10 N solution is
4. Equal volumes of 0.1 M HCl and 0.1M NaOH are mixed. The (a) 0.315 g (b) 3.150 g
concentration of the resulting solution will be (c) 6.300 g (d) 63.00 g
(a) 0.1 M (b) 0.05 M 9. The molarity of the solution containing 7.1 g of Na2SO4 in
(c) 0.2 M (d) 0.0 M 100 ml of aqueous solution is
5. When the solute is present in trace quantities the following (a) 2 M (b) 0.5 M
expression is used (c) 1 M (d) 0.05 M
(a) gram per million (b) milligram percent 10. A solution of CaCl2 is 0.5 mol/litre, then the moles of chloride
(c) microgram percent (d) parts per million ions in 500 ml. will be
6. For preparing 0.1 N solution of a compound from its impure (a) 0.25 (b) 0.50
sample of which the percentage purity is known, the weight
(c) 0.75 (d) 1.00
of the substance required will be
JEEMAIN.GURU
downloaded from jeemain.guru
Solutions 543
11. What will be the molality of a solution having 18 g of glucose 20. The vapour pressure of a solvent A is 0.80 atm. When a non-
(mol. wt. = 180) dissolved in 500 g of water? volatile substance B is added to this solvent its vapour
(a) 1 m (b) 0.5 m pressure drops to 0.6 atm. the mole fraction of B in the solution
(c) 0.2 m (d) 2 m is
12. 50 ml of 10N H2SO4, 25 ml of 12 N HCl and 40 ml of 5 N HNO3 (a) 0.25 (b) 0.50
were mixed together and the volume of the mixture was made (c) 0.75 (d) 0.90
1000 ml by adding water. The normality of the resulting 21. At a particular temperature, the vapour pressures of two
solution will be liquids A and B are respectively 120 and 180 mm of mercury.
(a) 1 N (b) 2 N If 2 moles of A and 3 moles of B are mixed to form an ideal
(c) 3 N (d) 4 N solution, the vapour pressure of the solution at the same
13. An aqueous solution of 6.3 g oxalic acid dihydrate is made temperature will be (in mm of mercury)
upto 250 ml. The volume of 0.1 N NaOH required to completely (a) 156 (b) 145
neutralize 10 ml of this solution is (c) 150 (d) 108
22. At room temperature, the mole fraction of a solute is 0.25 and
(a) 40 ml (b) 20 ml
the vapour pressure of a solvent is 0.80 atm. Then the lowering
(c) 10 ml (d) 4 ml
of vapour pressure is
14. 2.5 litre of 1 M NaOH solution are mixed with another 3 litre
(a) 0.75 (b) 0.60
of 0.5 M NaOH solution. Then the molarity of the resulting (c) 0.20 (d) 0.80
solution is 23. Which of the following is not correct for ideal solution?
(a) 0.80 M (b) 1.0 M (a) DSmixing = 0 (b) DVmixing = 0
(c) 0.73 M (d) 0.50 M (c) DHmixing = 0 (d) It obeys Raoult's law
15. 12g of urea is dissolved in 1 litre of water and 68.4 g of 24. Which of the following does not show positive deviation
sucrose is dissolved in 1 litre of water. The lowering of vapour from Raoult's law?
pressure of first case is (a) Benzene-Chloroform
(a) equal to second (b) greater than second (b) Benzene-Acetone
(c) less than second (d) double that of second (c) Benzene-Ethanol
16. Which of the following statement is correct if the (d) Benzene-Carbon tetrachloride
intermolecular forces in liquids A, B and C are in the order 25. Identify the mixture that shows positive deviation from
A < B < C? Raoult's law
(a) B evaporates more readily than A (a) CHCl3 + (CH3)2CO
(b) B evaporates less readily than C (b) (CH3)2CO + C6H5NH2
(c) A and B evaporates at the same rate (c) CHCl3 + C6H6
(d) A evaporates more readily than C (d) (CH3)2CO + CS2
26. Azeotropic mixture of HCl and H2O has
17. The aqueous solution that has the lowest vapour pressure
(a) 48% HCl (b) 22.2% HCl
at a given temperature is
(c) 36% HCl (d) 20.2% HCl
(a) 0.1 molal sodium phosphate 27. Which of the following is not a colligative property?
(b) 0.1 molal barium chloride (a) Depression in freezing point
(c) 0.1 molal glucose (b) Elevation of boiling point
(d) 0.1 molal acetic acid (c) Osmotic pressure
18. Vapour pressure of CCl4 at 25°C is 143 mm Hg. 0.5 g of a non- (d) Modification of refractive index
volatile solute (mol. wt. 65) is dissolved in 100 ml of CCl4. 28. Which of the following is a colligative property?
Find the vapour pressure of the solution. (Density of CCl4 = (a) Change in free energy (b) Change in pressure
1.58 g/cm3) (c) Heat of vapourisation (d) Osmotic pressure
29. Which of the following colligative properties can provide
(a) 141.93 mm Hg (b) 94.39 mm Hg
molar mass of proteins (or polymers or colloids) with greatest
(c) 199.34 mm Hg (d) 143.99 mm Hg precision?
19. The vapour pressure of solvent decreases by 10 mm of (a) Depression in freezing point
mercury when a non-volatile solute was added to the solvent. (b) Osmotic pressure
The mole fraction of the solute in the solution is 0.2. What (c) Relative lowering of vapour pressure
should be the mole fraction of the solvent if the decrease in (d) Elevation of boiling point
vapour pressure is to be 20 mm of mercury ? 30. Isotonic solutions have same
(a) 0.8 (b) 0.6 (a) molar concentration (b) molality
(c) 0.4 (d) 0.4 (c) normality (d) None of these
JEEMAIN.GURU
downloaded from jeemain.guru
544 Chemistry
31. When mango is placed in dilute aqueous solution of 42. If the solution boils at a temperature T1 and the solvent at a
hydrochloric acid, it temperature T2 the elevation of boiling point is given by
(a) shrinks (b) swells (a) T1 + T2 (b) T1 – T2
(c) bursts (d) Nothing happens (c) T2 – T1 (d) T1 + T2
32. As a result of osmosis, the volume of the solution
43. Which of the following will have highest boiling point at 1
(a) gradually decreases (b) gradually increases
atm pressure?
(c) is not affected (d) Any of the three
33. The relationship between osmotic pressure at 273 K when (a) 0.1 M NaCl (b) 0.1 M Sucrose
10g glucose (P1), 10 g urea (P2), and 10g sucrose (P3) are (c) 0.1 M BaCl2 (d) 0.1 M Glucose
dissolved in 250 ml of water is 44. A solution of 1 molal concentration of a solute will have
(a) P1 > P2 > P3 (b) P3 > P1 > P2 maximum boiling point elevation when the solvent is
(a) ethyl alcohol (b) acetone
(c) P2 > P1 > P3 (d) P2 > P3 > P1
(c) benzene (d) chloroform
34. 0.1 M NaCl and 0.1 M CH3COOH are kept in separate
45. The normal boiling point of water is 373 K (at 760 mm Hg).
containers. If their osmotic pressures are P 1 and P 2
Vapour pressure of water at 298 K is 23 mm Hg. If enthalpy of
respectively then what is the correct statement?
vaporisation is 40.656 kJ mol–1, the boiling point of water at
(a) P1 > P2 (b) P1 = P2
23 mm Hg pressure will be
(c) P1 < P2 (d) P1 = P2 = 0 atm.
35. What happen when isotonic solution of A (mol. wt. 342) and (a) 250 K (b) 294.4 K
B (mol. wt. 60) are put into communication through (c) 51.6 K (d) 12.5 K
semipermeable membrane? 46. If the elevation in boiling point of a solution of 10 gm of
(a) Transference of solvent from solution of A to that of B solute (mol. wt. = 100) in 100 gm of water is DTb, the
takes place ebullioscopic constant of water is
(b) Transference of solvent from solution of B to that of A (a) 10 (b) 10 DTb
takes place
(c) No transference of solvent from solution of A to that of DTb
(c) DT b (d)
B takes place 10
(d) Change in temperature of the solutions takes place 47. The rise in the boiling point of a solution containing 1.8 g of
36. Which among the following will show maximum osmotic glucose in 100 g of solvent is 0.1°C. The molal elevation
pressure? constant of the liquid is
(a) 1 M NaCl (b) 1 M MgCl2 (a) 0.01 K/m (b) 0.1 K/m
(c) 1 M (NH4)3PO4 (d) 1 M Na2SO4 (c) 1 K/m (d) 10 K/m
37. Isotonic solutions have 48. The boiling point of a solution of 0.11 g of a substance in 15
(a) same boiling point (b) same vapour pressure g of ether was found to be 0.1°C higher than that of pure
(c) same melting point (d) same osmotic pressure ether. The molecular weight of the substance will be (Kb =
38. An aqueous solution of sucrose, C12H22O11, containing 34.2 2.16°K kg mol–1)
g/ litre has an osmotic pressure of 2.38 atmospheres at 17°C. (a) 148 (b) 158
For an aqueous solution of glucose, C6H12O6 to be isotonic (c) 168 (d) 178
with this solution, it would have 49. The boiling point of 0.1 molal K4[Fe(CN)6] solution will be
(a) 34.2 g/lit of glucose (b) 17.1 g/lit of glucose (Given Kb for water = 0.52°K kg mol–1)
(c) 18.0 g/lit of glucose (d) 36.0 g/lit of glucose (a) 100.52°C (b) 100.104°C
39. The osmotic pressure of 5% (mass-volume) solution of cane (c) 100.26°C (d) 102.6°C
sugar at 150°C (mol. mass of sugar = 342) is 50. The freezing point of equimolal aqueous solution will be
(a) 4 atm (b) 5.07 atm highest for
(c) 3.55 atm (d) 2.45 atm (a) C6H5NH3+Cl– (b) Ca(NO3)2
40. A 1% aqueous solution (mass by volume) of a certain (c) La(NO3)2 (d) C6H12O6
substance is isotonic with a 3% solution of dextrose i.e. 51. If all the following four compounds were sold at the same
glucose (molar mass 180) at a given temperature. The molar price, which would be cheapest for preparing an antifreeze
mass of the substance is solution for a car radiator?
(a) 60 (b) 120 (a) CH3OH (b) C2H5OH
(c) 180 (d) 360 (c) C2H4(OH)2 (d) C3H5(OH)3
41. A 5% solution of cane sugar (mol. wt. = 342) is isotonic with 52. Which of the following 0.10 m aqueous solution will have
1% solution of substance X. The molecular weight of X is the lowest freezing point?
(a) 34.2 (b) 171.2 (a) Al2(SO4)3 (b) C6H10O5
(c) 68.4 (d) 136.8 (c) KI (d) C12H22O11
JEEMAIN.GURU
downloaded from jeemain.guru
Solutions 545
53. Which of the following aqueous solution will have highest 61. The van't Hoff factor for 0.1 M Ba(NO3)2 solution is 2.74.
depression in freezing point? The degree of dissociation is
(a) 0.1 M Urea (b) 0.1 M Sucrose (a) 91.3% (b) 87%
(c) 0.1 M AlCl3 (d) 0.1 M K4 [Fe(CN)6] (c) 100% (d) 74%
54. The depression in freezing point for 1 M urea, 1 M glucose 62. Formation of a solution from two components can be
and 1 M NaCl are in the ratio considered as
(a) 1 : 2 : 3 (b) 3 : 2 : 2 (i) pure solvent ® separated solvent molecules, DH1
(c) 1 : 1 : 2 (d) None of these
(ii) pure solute ® separated solute molecules, DH2
55. Which one of the following aqueous solutions will have the
lowest freezing point? (iii) separated solvent and solute molecules ®
(a) 0.1 molal solution of urea solution, DH3
(b) 0.1 molal solution of sucrose Solution so formed will be ideal if
(c) 0.1 molal solution of sodium chloride
(a) DHsoln = DH1 + DH 2 - DH3
(d) 0.1 molal solution of calcium chloride
56. The depression of freezing point is directly proportional to (b) DHsoln = DH1 - DH 2 - DH3
(a) mole fraction of the solution
(b) molarity of the solution (c) DHsoln = DH3 - DH1 - DH 2
(c) molality of the solution
(d) molarity of the solvent (d) DHsoln = DH1 + DH 2 + DH3
57. A 0.5 molal solution of ethylene glycol in water is used as 63. If liquids A and B form an ideal solution
coolant in a car. If the freezing point constant of water be
(a) the enthalpy of mixing is zero
1.86°C per mole, the mixture shall freeze at
(a) 0.93°C (b) –0.93°C (b) the entropy of mixing is zero
(c) 1.86°C (d) –1.86°C (c) the free energy of mixing is zero
58. An aqueous solution freezes at –0.186°C (Kf = 1.86, Kb = (d) the free energy as well as the entropy of mixing are each
0.512) what is the elevation in boiling point? zero
(a) 0.186 (b) 0.512
64. 25 ml of a solution of barium hydroxide on titration with a 0.1
(c) 0.86 (d) 0.0512
molar solution of hydrochloric acid gave a titre value of 35
59. The molal freezing point constant for water is 1.86°C/m.
Therefore, the freezing point of 0.1 M NaCl solution in water ml. The molarity of barium hydroxide solution was
is expected to be (a) 0.07 (b) 0.14
(a) –1.86°C (b) –0.186°C (c) 0.28 (d) 0.35
(c) –0.372°C (d) + 0.372°C 65. During depression of freezing point in a solution the
60. The molecular weight of benzoic acid in benzene as
following are in equilibrium
determined by depression in freezing point method
corresponds to (a) liquid solvent, solid solvent
(a) ionization of benzoic acid (b) liquid solvent, solid solute
(b) dimerization of benzoic acid (c) liquid solute, solid solute
(c) trimerization of benzoic acid (d) liquid solute, solid solvent
(d) solvation of benzoic acid
1. A 0.0020 m aqueous solution of an ionic compound (a) Addition of NaCl (b) Addition of Na 2SO4
Co(NH3)5(NO2)Cl freezes at – 0.00732 °C. Number of moles
of ions which 1 mol of ionic compound produces on being (c) Addition of 1.00 molal KI (d) Addition of water
dissolved in water will be (Kf = – 1.86°C/m) 3. A solution of sucrose (molar mass = 342 g mol–1) has been
[CBSE-PMT 2009] prepared by dissolving 68.5 g of sucrose in 1000 g of water.
The freezing point of the solution obtained will be
(a) 3 (b) 4 (c) 1 (d) 2
(Kf for water = 1.86 K kg mol–1). [CBSE-PMT 2010]
2. An aqueous solution is 1.00 molal in KI. Which change will
cause the vapour pressure of the solution to increase? (a) – 0.372°C (b) – 0.520°C
[CBSE-PMT 2010] (d) + 0.372°C (d) – 0.570°C
JEEMAIN.GURU
downloaded from jeemain.guru
546 Chemistry
4. 25.3 g of sodium carbonate, Na 2 CO3 is dissolved in enough 12. In mixture A and B components show -ve deviation as
water to make 250 mL of solution. If sodium carbonate (a) D Vmix > 0 [AIEEE 2002]
dissociates completely, molar concentration of sodium ions, (b) D Hmix < 0
Na + and carbonate ions, CO 32– are respectively (Molar mass (c) A – B interaction is weaker than A – A and B – B interaction
of Na2CO3 = 106 g mol–1) [CBSE-PMT 2010] (d) A – B interaction is stronger than A – A and B – B
(a) 0.955 M and 1.910 M (b) 1.910 M and 0.955 M interaction.
(c) 1.90 M and 1.910 M (d) 0.477 M and 0.477 M 13. A pressure cooker reduces cooking time for food because
[AIEEE 2003]
5. The freezing point depression constant for water is
– 1.86ºC m–1. If 5.00 g Na2SO4 is dissolved in 45.0 g H2O, the (a) boiling point of water involved in cooking is increased
freezing point is changed by – 3.82ºC. Calculate the van’t (b) the higher pressure inside the cooker crushes the food
Hoff factor for Na2SO4 [CBSE-PMT 2011] material
(a) 2.05 (b) 2.62 (c) 3.11 (d) 0.381 (c) cooking involves chemical changes helped by a rise in
temperature
6. The van’t Hoff factor i for a compound which undergoes
(d) heat is more evenly distributed in the cooking space
dissociation in one solvent and association in other solvent
is respectively : [CBSE-PMT 2011] 14. In a 0.2 molal aqueous solution of a weak acid HX the degree
of ionization is 0.3. Taking kf for water as 1.85, the freezing
(a) less than one and greater than one.
point of the solution will be nearest to [AIEEE 2003]
(b) less than one and less than one. (a) – 0.360º C (b) – 0.260º C
(c) greater than one and less than one. (c) + 0.480º C (d) – 0.480º C
(d) greater than one and greater than one. 15. Which one of the following aqueous solutions will exihibit
7. Mole fraction of the solute in a 1.00 molal aqueous solution is highest boiling point ? [AIEEE 2004]
[CBSE-PMT 2011] (a) 0.015 M urea (b) 0.01 M KNO3
(a) 0.1770 (b) 0.0177 (c) 0.01 M Na2SO4 (d) 0.015 M glucose
(c) 0.0344 (d) 1.7700 16. 6.02 × 1020 molecules of urea are present in 100 ml of its
solution. The concentration of urea solution is
8. A 0.1 molal aqueous solution of a weak acid is 30% ionized. If
[AIEEE 2004]
Kf for water is 1.86°C/m, the freezing point of the solution will
be : [CBSE-PMT 2011 M] (a) 0.02 M (b) 0.01 M
(a) – 0.18°C (b) – 0.54°C (c) 0.001 M (d) 0.1 M
(Avogadro constant, NA = 6.02 × 1023 mol–1)
(c) – 0.36°C (d) – 0.24°C
17. To neutralise completely 20 mL of 0.1 M aqueous solution of
9. 200 mL of an aqueous solution of a protein contains its 1.26 g.
phosphorous acid (H3PO3), the value of 0.1 M aqueous KOH
The osmotic pressure of this solution at 300 K is found to be
solution required is [AIEEE 2004]
2.57 × 10–3 bar. The molar mass of protein will be (R = 0.083 L
(a) 40 mL (b) 20 mL
bar mol–1 K–1) [CBSE-PMT 2011 M]
(c) 10 mL (d) 60 mL
(a) 51022 g mol–1 (b) 122044 g mol–1
18. For which of the following parameters the structural isomers
(c) 31011 g mol–1 (d) 61038 g mol–1 C2H5OH and CH3OCH3 would be expected to have the same
10. PA and PB are the vapour pressure of pure liquid components, values? [AIEEE 2004]
A and B, respectively of an ideal binary solution. If XA (Assume ideal behaviour)
represents the mole fraction of component A, the total pressure
(a) Boiling points
of the solution will be. [CBSE-PMT 2012]
(b) Vapour pressure at the same temperature
(a) PA + XA (PB – PA) (b) PA + XA (PA – PB)
(c) Heat of vapourization
(c) PB + XA (PB – PA) (d) PB + XA (PA – PB)
(d) Gaseous densities at the same temperature and pressure
11. Freezing point of an aqueous solution is 19. Which of the following liquid pairs shows a positive
(–0.186)°C. Elevation of boiling point of the same solution is deviation from Raoult’s law ? [AIEEE 2004]
Kb = 0.512°C,Kf = 1.86°C, find the increase in boiling point.
(a) Water - nitric acid
[AIEEE 2002]
(b) Benzene - methanol
(a) 0.186°C (b) 0.0512°C
(c) Water - hydrochloric acid
(c) 0.092°C (d) 0.2372°C.
(d) Acetone - chloroform
JEEMAIN.GURU
downloaded from jeemain.guru
Solutions 547
20. Which one of the following statements is FALSE? 28. A 5.25% solution of a substance is isotonic with a 1.5% solu-
[AIEEE 2004] tion of urea (molar mass = 60 g mol–1) in the same solvent. If the
(a) The correct order of osmotic pressure for 0.01 M densities of both the solutions are assumed to be equal to
aqueous solution of each compound is 1.0 g cm–3, molar mass of the substance will be [AIEEE 2007]
BaCl 2 > KCl > CH3COOH > Sucrose (a) 210.0 g mol–1 (b) 90.0 g mol–1
(b) The osmotic pressure (p) of a solution is given by the (c) 115.0 g mol–1 (d) 105.0 g mol–1.
equation p = MRT, where M is the molarity of the solution 29. At 80° C, the vapour pressure of pure liquid ‘A’ is 520 mm Hg
(c) Raoult’s law states that the vapour pressure of a and that of pure liquid ‘B’ is 1000 mm Hg. If a mixture solution
component over a solution is proportional to its mole of ‘A’ and ‘B’ boils at 80° C and 1 atm pressure, the amount of
fraction ‘A’ in the mixture is (1 atm = 760 mm Hg) [AIEEE 2008]
(d) Two sucrose solutions of same molality prepared in
(a) 52 mol percent (b) 34 mol percent
different solvents will have the same freezing point
depression (c) 48 mol percent (d) 50 mol percent
30. The vapour pressure of water at 20°C is 17.5 mm Hg. If 18 g of
21. If a is the degree of dissociation of Na 2SO 4 , the Vant
glucose (C6H12O6) is added to 178.2 g of water at 20°C, the
Hoff’s factor (i) used for calculating the molecular mass is
vapour pressure of the resulting solution will be [AIEEE 2008]
[AIEEE 2005]
(a) 1 – 2 a (b) 1 + 2 a (a) 17.325 mm Hg (b) 15.750 mm Hg
(c) 1 – a (d) 1 + a (c) 16.500 mm Hg (d) 17.500 mm Hg
22. Benzene and toluene form nearly ideal solution. At 20°C, the 31. A binary liquid solution is prepared by mixing n-heptane and
vapour pressure of benzene is 75 torr and that of toluene is ethanol. Which one of the following statements is correct
22 torr. The partial vapour pressure of benzene at 20°C for a regarding the behaviour of the solution? [AIEEE 2009]
solution containing 78 g of benzene and 46 g of toluene in (a) The solution is non-ideal, showing – ve deviation from
torr is [AIEEE 2005]
Raoult’s Law.
(a) 53.5 (b) 37.5
(b) The solution is non-ideal, showing + ve deviation from
(c) 25 (d) 50
Raoult’s Law.
23. Two solutions of a substance (non electrolyte) are mixed in
the following manner. 480 ml of 1.5 M first solution + 520 ml (c) n-heptane shows + ve deviation while ethanol shows
of 1.2 M second solution. What is the molarity of the final – ve deviation from Raoult’s Law.
mixture ? [AIEEE 2005] (d) The solution formed is an ideal solution.
(a) 2.70 M (b) 1.344 M 32. Two liquids X and Y form an ideal solution. At 300 K, vapour
(c) 1.50 M (d) 1.20 M pressure of the solution containing 1 mol of X and 3 mol of Y
24. Equimolar solutions in the same solvent have is 550 mm Hg. At the same temperature, if 1 mol of Y is further
[AIEEE 2005] added to this solution, vapour pressure of the solution
(a) different boiling and different freezing points
increases by 10 mm Hg. Vapour pressure ( in mm Hg) of X and
(b) same boiling and same freezing points
Y in their pure states will be, respectively: [AIEEE 2009]
(c) same freezing point but different boiling point
(d) same boiling point but different freezing point (a) 300 and 400 (b) 400 and 600
25. Density of a 2.05M solution of acetic acid in water is (c) 500 and 600 (d) 200 and 300
1.02 g/mL. The molality of the solution is [AIEEE 2006] 33. If sodium sulphate is considered to be completely dissociated
(a) 2.28 mol kg–1 (b) 0.44 mol kg–1 into cations and anions in aqueous solution, the change in
(c) 1.14 mol kg –1 (d) 3.28 mol kg–1
freezing point of water (DTf ), when 0.01 mol
26. 18 g of glucose (C6H12O6) is added to 178.2 g of water. The
of sodium sulphate is dissolved in 1 kg of water, is (Kf = 1.86
vapour pressure of water for this aqueous solution at 100ºC
is [AIEEE 2006] K kg mol–1) [AIEEE 2010]
(a) 76.00 Torr (b) 752.40 Torr (a) 0.372 K (b) 0.0558 K (c) 0.0744 K (d) 0.0186 K
(c) 759.00 Torr (d) 7.60 Torr 34. On mixing, heptane and octane form an ideal solution. At
27. A mixture of ethyl alcohol and propyl alcohol has a vapour 373 K, the vapour pressures of the two liquid components
pressure of 290 mm Hg at 300 K. The vapour pressure of (heptane and octane) are 105 kPa and 45 kPa respectively.
propyl alcohol is 200 mm Hg. If the mole fraction of ethyl Vapour pressure of the solution obtained by mixing 25.0 g of
alcohol is 0.6, its vapour pressure (in mm Hg) at the same heptane and 35 g of octane will be (molar mass of heptane
temperature will be [AIEEE 2007] = 100 g mol–1 and of octane = 114 g mol–1) [AIEEE 2010]
(a) 360 (b) 350 (c) 300 (d) 700 (a) 72.0 kPa (b) 36.1 kPa (c) 96.2 kPa (d) 144.5 kPa
JEEMAIN.GURU
downloaded from jeemain.guru
548 Chemistry
35. A 5% solution of cane sugar (molar mass 342) is isotonic with [IIT-JEE 2009]
1% of a solution of an unknown solute. The molar mass of
(a) 4.0× 10– 4 (b) 4.0 × 10–5
unknown solute in g/mol is : [AIEEE 2011RS]
(c) 5.0 × 10– 4 (d) 4.0 × 10–6
(a) 171.2 (b) 68.4 (c) 34.2 (d) 136.2
40. Dissolving 120 g of urea (mol. wt. 60) in 1000 g of water gave
36. Kf for water is 1.86 K kg mol–1. If your automobile radiator
a solution of density 1.15 g/mL. The molarity of the solution
holds 1.0 kg of water, how many grams of ethylene glycol
is [IIT-JEE 2011]
(C2H6 O2) must you add to get the freezing point of the
solution lowered to –2.8ºC ? [AIEEE 2012] (a) 1.78 M (b) 2.00 M (c) 2.05 M (d) 2.22 M
(a) 72 g (b) 93 g (c) 39 g (d) 27 g 41. The freezing point (in °C) of a solution containing 0.1 g
of K3[Fe(CN)6] (Mol. wt. 329) in 100 g of water (Kf = 1.86 K
37. The molarity of a solution obtained by mixing 750 mL of 0.5(M)
kg mol–1) is [IIT-JEE 2011]
HCl with 250 mL of 2(M) HCl will be : [JEE M 2013]
(a) –2.3 × 10–2 (b) –5.7 × 10–2
(a) 0.875 M (b) 1.00 M (c) 1.75 M (d) 0.975 M
(c) –5.7 × 10–3 (d) –1.2 × 10–2
38. When 20 g of naphthoic acid (C11H8O2) is dissolved in 50 g
of benzene (Kf = 1.72 K kg mol–1), a freezing point depression 42. For a dilute solution containing 2.5 g of a non-volatile non-
of 2 K is observed. The Van't Hoff factor (i) is [IIT-JEE 2007] electrolyte solute in 100 g of water, the elevation
in boiling point at 1 atm pressure is 2°C. Assuming
(a) 0.5 (b) 1 (c) 2 (d) 3
concentration of solute is much lower than the concentration
39. The Henry’s law constant for the solubility of N2 gas in water of solvent, the vapour pressure (mm of Hg) of the solution is
at 298 K is 1.0 × 105 atm. The mole fraction of N2 in air is 0.8. (take Kb = 0.76 K kg mol–1) [IIT-JEE 2012]
The number of moles of N 2 from air dissolved in
(a) 724 (b) 740 (c) 736 (d) 718
10 moles of water at 298 K and 5 atm pressure is
1. An X molal solution in carbon tetrachloride show the mole (a) 6.2 g (b) 8.5 g
fraction of solute equal to 0.23527 . The value of X is (c) 12.6 g (d) 14.0 g
(a) 1.55 (b) 1.82 6. At 30°C and 40°C the vapour pressure of a liquid are 0.025
(c) 2.00 (d) 2.16 and 0.050 atm respectively. Calculate the heat of vaporization
2. 3.0 molal sodium hydroxide solution has a density of of the liquid.
1.110 gm L-1 . The molarity of this solution is (a) 14.06 cal/mol (b) 13060 cal/mol
(a) 2.97 (b) 3.05 (c) 140.8 cal /mol (d) 2160 cal/ mol
(c) 3.65 (d) 4.11 7. The equilibrium vapour pressure of water vapour over a 0.20
mole sample of water (l) is 35 torr at 27°C. If the amount of the
3. For a solution of two liquids A and B it was proved that
liquid water is decreased to 0.10 mole, the equilibrium vapour
PS = x A (p°A - p°B ) + p°B . The resulting solution will be pressure of it would be
(a) Non -ideal (b) ideal (a) 17.5 torr (b) 35.0 torr
(c) semi-ideal (d) None of these (c) 51.5 torr (d) None of these
4. The vapour pressure of water at 50°C is 92.5 torr. What will 8. A flask is partially evacuated to 400 torr pressure of air. A
be the vapour pressure of solution which consists of 1 mole small amount of benzene is introduced into the flask in order
of nonvolatile solute in 100 g of water at 50°C that some liquid will remain after equilibrium has been
(a) 906 .5 torr (b) 94.2 torr established. The vapour pressure of benzene at 25°C is 220
torr. . What is the total pressure in the flask at equilibrium at
(c) 91.8 torr (d) 90.8 torr.
25°C ?
5. When 200g of 10% solution was cooled part of the solute
(a) 120 torr (b) 510 torr
precipitated and the concentration of solution become 6% .
The mass of the precipitated solute is (c) 620 torr (d) 480 torr
JEEMAIN.GURU
downloaded from jeemain.guru
Solutions 549
9. Which of the following solutions will have the highest 15. Consider the following statements
boiling point?
1. Isotonic solutions have the same molar concentration at
(a) 0.5 molal BaCl2 a given temperature
(b) 1.0 molal KBr 2. The molal elevation constant Kb is a characteristic of a
(c) 1.8 × 1024 glucose molecules per litre. solvent, and is independent of the solute added
3. The freezing point of a 0.1 M aqueous KCl solution is
(d) 100 g powdered glucose in one litre water
more than that of a 0.1 M aqueous AlCl3 solution.
10. Two 1-litre flask A and B are connected to each other by a
Which of these statements is correct?
valve which is closed. Flask A has benzene in equilibrium
with its vapours at 30°C. The flask B, is evacuated, and the (a) 1 and 2 (b) 2 and 3
valve is opened. Which of the following is true. If temperature (c) 1 and 3 (d) 1, 2 and 3
is kept constant.’ 16. The vapour pressure of pure liquid is 70 torr at 300 K. It forms
(a) Some of the benzene molecules would move to flask B an ideal solution with another liquid Y. The mole fraction of Y
from flask A. in the solution is 0.2 and total pressure of solution is 84 torr
at 300 K. The vapour pressure of pure liquid Y at 27° C
(b) Vapour pressure will be half the initial value.
(a) 70 torr (b) 560 torr
(c) The vapour pressure remains unchanged
(c) 140 torr (d) 154 torr
(d) Some more of the liquid benzene in flask A would
17. The molecular mass of a solute cannot be calculated by which
evaporate.
of the following?
11. The vapour pressure of ethanol and methanol are 42.0 mm
and 88.5 mm Hg respectively . An ideal solution is formed at WB ´ RT po WB MA
the same temperature by mixing 46.0 g of ethanol with 16.0 g (a) M B = (b) M B =
pV (po - p)WA
of methanol. What is the mole fraction of methanol vapour ?
(a) 0.467 (b) 0.502 DTb WB ´ 1000 K b WB ´1000
(c) 0.513 (d) 0.556 (c) M B = (d) M B =
K b WA DTb ´ WA
12. Which of the following solutions will have the maximum
lowering of vapour pressure at 300 K 18. At certain hill station pure water boils at 99.725 ° C. If K b for
(a) 1 M CaCl2 (b) 1 M NaCl water is 0.513 ° C kg mol-1 , the boiling point of 0.69 m solution
(c) 1 M Phenol (d) 1 M sucrose of urea will be
13. Two Aqueous solutions S1 and S2 are separated by a (a) 103 °C (b) 100.079 °C
semipermeable membrane . Solution S1 has got a greater (c) 100.359 °C (d) unpredictable
vapour pressure than solution S2 . Water will be flowing 19. Two elements A and B form compounds of formula AB2 and
(b) from S2 to S1 lowers F. pt. by 2.3° C whereas 1.0 g of AB4 lowers F. pt. by
(c) in both the directions 1.3° C. The K f for benzene is 5.4. The atomic masses of A
(d) in either direction depending upon the nature of the and B are
solute (a) 25, 42 (b) 42, 25
14. What is the degree of dissociation of sodium chloride, if the (c) 52, 48 (d) 48, 52
molar mass determined by a cryoscopic method was found to
20. The heat of vaporisation of benzene is 7353 cal mol -1 . The
be 31.80 g mol-1 [ Atomic mass Na = 23 g mol–1 Cl = 35.5 g mol–
1] ? approximate bpt. of benzene is
JEEMAIN.GURU
downloaded from jeemain.guru
550 Chemistry
21. The vapour pressure of a solution of the liquids A 23. How many grams of sucrose (M. wt. 342) must be dissolved
(p° = 80 mm Hg and x A = 0.4) and B (p°= 120 mm Hg and in 100 g water to produce a solution with a 105.0°C difference
between the freezing point & the boiling point temperature ?
x B = 0.6) is found to be 100 mm Hg. It shows that the (a) 460 g (b) 342 g
solution exhibits (c) 72 g (d) 34.2 g
(a) positive deviation from ideal behaviour 24. Coolent used in car radiator is aqueous solution of ethylene
glycol. In order to prevent the solution from freezing at – 0.3
(b) negative deviation from ideal behaviour
°C. How much ethylene glycol must be added to 5 kg of
(c) ideal behaviour
-1
(d) positive deviation for lower conc. and negative for higher water ? ( K f = 1.86 K kg mol )
conc. (a) 50 kg (b) 55 g
(c) 45 g (d) 40 g
1 1 25. The total vapour pressure of a solution of components A
22. Plot of Vs ( x A mole fraction of A in liquid state
xA YA and B is 600 torr. The mole fraction of component A in liquid
and vapour phase are 0.70 and 0.35 respectively. The vapour
and YA in vapour state) is linear whose slope and intercept
pressure of pure A and B are
respectively are given (a) 300 torr, 130 torr (b) 1300 torr, 300 torr
(c) 300 torr, 1300 torr (d) 300 torr, 300 torr
p oB - p oA
(a) p oB / p oA , 26. A current of dry air is passed through a solution of 2.64 g of
p oB a non volatile solute in 30.0 g of ether and then through pure
ether. The loss in weight of solution was 0.645 g and of the
p oA - p oB ether 0.0345 g. The molecular weight of the solid is
(b) p oA - p oB ,
p oB (a) 122 g (b) 12.2 g
(c) 244 g (d) 135 g
27. An ideal solution of 1 mol A and 2 mol B has vapour pressure
p oB - p oA
(c) p oB - p oA , 250 torr at 50° C. If 1 mole of A is added to the solution, the V.
p oB P. of solution becomes 300 torr. What will be the V. P. if 1 mole
of B is added to the solution instead of 1 mole of A
p oA - p oB (a) 150 torr (b) 225 torr
(d) p oB / p oA ,
p oB (c) 275 torr (d) 175 torr
JEEMAIN.GURU
downloaded from jeemain.guru
Solutions 551
EXERCISE 1
50 ´ 10 + 25 ´ 12 + 40 ´ 5
= = 1N
7. (a) 0×322 mol/kg. 1000
(b) 373×165 K.
(c) 0×137 mm Hg. 13. (a) Normality of oxalic acid = 6.3 ´ 1000 = 0.4
63 ´ 250
8. 177×38 g mol–1
N1V1 = N2V2; 0.1 ×V1 = 0.4 × 10. \ V1 = 40 ml
9. (i) They will shrink due to plasmolysis.
14. (c) M3V3 = M1V1 + M2V2
(ii) They will swell and may even burst.
\ M3 × 5.5 = 2.5 × 1 + 3 × 0.5. \ M3 = 0.727.
14. Sucrose < NaCl < Glucose
12
20. (a) 21. (a) 22. (c) 23. (c) 24. (d) 15. (a) Moles of urea = = 0.2
60
25. (a) 26. (b) 27. (c)
68.4
EXERCISE 2 Moles of sucrose = = 0. 2
342
1. (d) Molality involves weight of solute and solvent, hence it Both are non electrolyte hence lowering of V.P. will be
is independent of temperature. same.
2. (d) All are correct. See Henry's law. 16. (d) Lesser the intermolecular forces, the more the volatile
3. (b) If one mole of solute is present in 1 Kg of solvent the character.
conc. is 1 m. 17. (a) 0.1 m Na3PO4 = 0.4 m (Van't Hoff factor i = 4)
4. (b) Solution will be neutral. Concentration of each will be \ Lowering of vapour pressure will be maximum.
0.05 M since volume got doubled. 18. (a) Relative lowering of V.P. = mole fraction of Solute
5. (d) For very dil. solution the concentration is expressed in
p o - ps
ppm. = x2
po
6. (a) Since the compound is impure more than theoretical
weight is required. 143 - p s 0.5 / 65
= ; p s = 141.93 mm Hg
143 158 / 154
Wt ´1000 98 ´ 1000
7. (c) M = = ´1.84 = 18.4
M. Wt ´ V 98 ´100 19. (b) Dp = x ; Dp = x 2 ; 10 = 0.2 ;
2
po Dp ' x '2 20 x '2
Wt ´ 1000 Wt ´1000
8. (b) M = ; 0.10 = ;
E.wt. ´ V 63 ´ 500 \ x '2 = 0.4, x '1 = 1– 0.4 = 0.6
sum of mole fractions is always 1
Wt = 3.150 g
20. (a) 0.80 - 0.6 = x B ; x B = 0.25
9. (b) M = Wt ´ 1000 ; M = 7.1 ´ 1000 = 0.5M 0.80
M.Wt . ´ V 142 ´ 100
21. (a) Vapour pressure of solution = PA + PB
10. (b) CaCl2 Ca++ + 2Cl–. 120 ´ 2 180 ´ 3
= p oA x A + p oB x B = + = 156 mm Hg
Moles of CaCl2 in 500 ml = 0.25 and Cl– = 0.50. 5 5
Wt. ´1000g Dp
11. (c) Apply m = 22. (c) = xB; \ Dp = 0.25 ´ 0.80 = 0.20
M.Wt ´ Wt. of Solvent po
N1V1 + N 2 V2 + N 3 V3 23. (a) DSmixing ¹ 0 for ideal solution. On mixing two solutions
12. (a) N =
Total volume the entropy increases.
JEEMAIN.GURU
downloaded from jeemain.guru
552 Chemistry
24. (a) Benzene + chloroform, show negative deviation.
P2 DH v æ T2 - T1 ö
25. (d) CH3COCH3 + CS2 45. (b) Clapeyron Clausius equation log = ç ÷.
P1 2.303R è T1T2 ø
26. (d) Azeotrope of HCl + H2O contains 20.2% HCl.
27. (d) Modification of refractive index is not a colligative 760 40656 æ 373 - T1 ö
log = ç ÷
property. 23 2.303 ´ 8.314 çè 373T1 ÷ø
28. (d) Osmotic pressure.
29. (b) Osmotic pressure. T1 = 294.4K
30. (a) Isotonic solutions have same molar concentration at K b ´ w ´ 1000 DTb ´ 100 ´ 100
given temperature provided the Van't Hoff factor (i) is 46. (c) DTb = ; \Kb = = DTb
M´W 10 ´ 1000
same
31. (b) Mango swells due to osmosis. 0.1 ´ 180 ´ 100
47. (c) K b = =1 K/ m
32. (b) Increases 1.8 ´1000
JEEMAIN.GURU
downloaded from jeemain.guru
Solutions 553
EXERCISE 3
WB
1. (d) DTf = 0 – (0.00732°C) = 0.00732 11. (b) DTb = K b ´1000 ;
M B ´ WA
DTf = i × Kf × m
DT f 0.00732 WB
i= = = 1.97 » 2 DTf = K f ´1000 ;
K f ´m 1.86 ´ 0.002 M B ´ WA
2. (d) When the aqueous solution of one molal KI is diluted
with water, concentration decreases, therefore the DTb K b DTb 0.512
= = = = 0.0512°C .
vapour pressure of the resulting solution increases. DTf Kf - 0.186 1.86
1000W2 1.86×1000×68.5
3. (a) DT f = K f = = 0.372 12. (b) [DH mix < 0]
M 2W1 342×1000
13. (a) On increasing pressure, the temperature is also increased.
Tf = T °f –DTf
Tf = – 0.372°C Thus in pressure cooker due to increase in pressure the
b.p. of water increases.
25.3 1000
4. (b) Concentration of Na 2CO3 = ´ = 0.955 M 14. (d) DTf = Kf × m × i ;
106 250
DTf = 1.85 × 0.2 × 1.3 = 0.480º C
+
[Na ] = 2 × 0.955 = 1.91 M
\ Tf = 0 - 0.480 = -0.480o C
é CO32– ù = 0.955 M
ë û
+ -
5. (b) Given Kf = – 1.86ºC m–1, mass of solute = 5.00 g, ( HX H + X , i = 1.3)
1- 0.3 0. 3 0.3
mass of solvent = 45.0 g and DTf = – 3.82°C
DTf = i × Kf .m
i = 1 - 0.3 + 0.3 + 0.3 = 1.3
5 ´ 1000
3.82 = i × 1.86 ×
142 ´ 45 15. (c) DTb = K b ´ m ´ i .
\ i = 2.62 (Molecular mass of Na2SO4 = 142 g)
6. (c) If compound dissociates in solvent i > 1 and on The value of i for Na 2SO 4 = 3,
association i < 1.
7. (b) 1 molal solution means 1 mole of solute dissolved in for KNO3 = 2, for urea = 1 and for glucose = 1
1000 gm solvent.
\ nsolute = 1 wsolvent = 1000 gm 6.02 ´ 10 20 ´ 1000
16. (b) M = = 0.01M
6.02 ´ 10 23 ´ 100
1000
\ nsolvent = = 55.56
18 17. (a) N1V1 = N 2 V2 (H 3PO 3 is dibasic \ M = 2N)
1 20 ´ 0.2 = 0.1´ V
xsolute = = 0.0177
1 + 55.56 \ V = 40 ml
8. (d) Given a = 30% i.e., 0.3
18. (d) Gaseous densities of ethanol and dimethyl ether would
HA ¾¾ ® H+ + A–
be same at same temperature and pressure. The heat of
1–a a a
vaporisation, V.P. and b.pt. will differ due to H - bonding
1 – 0.3 0.3 0.3
i = 1 – 0.3 + 0.3 + 0.3 in ethanol.
i = 1.3 19. (b) A mixture of benzene and methanol show positive
DTf = 1.3 × 1.86 × 0.1 = 0.2418 deviation from Raoult’s law
Tf = 0 – 0.2418 = – 0.2418 °C
20. (d) DTf = K f ´ m ´ i . Since Kf has different values for
WRT 1.26 ´ 0.083 ´ 300
9. (d) M = = different solvents, hence even if the m is the same DTf
pV 2.57 ´10-3 ´ 200 ´ 10 -3
will be different
31.374 ´ 10 6
= = 61038 g
514 2Na + SO 4-
21. (b) Na 2SO 4 2a
10. (d) p = pAxA + pBxB 1-a a
= pAxA + pB (1 – xA)
Þ pAxA + pB – pBxA 1 - a + 2a + a
Vant. Hoff’s factor i = = 1 + 2a
Þ pB+ xA (pA – pB) 1
JEEMAIN.GURU
downloaded from jeemain.guru
554 Chemistry
22. (d) Given 28. (a) Osmotic pressure (p) of isotonic solutions are equal.
Vapour pressure of benzene= 75 torr For solution of unknown substance C1(concentration).
Vapour pressure of toluene = 22 torr 5.25 / M
mass of benzene in = 78g C1 =
V
78 Where M represents molar mass.
hence moles of benzene = = 1mole
78 1.5 / 60
For solution of urea, C2 (concentration) =
(mol.wt of benzene = 78) V
mass of toluene in solution = 46g Given, p1 = p2 Q p = CRT
46 5.25 / M 1.5 / 60
\ C1RT = C2RT or C1 = C2 or =
hence moles of toluene = = 0.5 mole V V
92
\ M = 210 g/mol
now partial pressure of benzene = Pbo .X b 29. (d) At 1 atmospheric pressure the boiling point of mixture
is 80°C.
1 1 2 At boiling point the vapour pressure of mixture, pT = 1
= 75 × = 50 torr = 75 × = 78 × atmosphere = 760 mm Hg.
1 + 0.5 1.5 3
Using the relation,
23. (b) From the molarity equation.
pT = p A° x A + p B° xB , we get
M1V1 + M2V2 = MV
pT = 520 x A + 1000(1 - x A )
M1V1 +M V2
2
M= where V = V1 + V2 {Q pAo = 520 mm Hg ,
V
JEEMAIN.GURU
downloaded from jeemain.guru
Solutions 555
JEEMAIN.GURU
downloaded from jeemain.guru
556 Chemistry
JEEMAIN.GURU
downloaded from jeemain.guru
Solutions 557
DTb ´ WB ´1000 1 po 1 æ po ö
17. (c) M B = is wrong. The correct form is or, = Ao . + çç 1 - Ao ÷÷
K b ´ WA xA p B yA è pB ø
K b ´ WB ´1000
MB = p oA 1 po - po
DTb ´ WA = . + B o A
p oB yA pB
18. (b) DTb = K b × m = 0.513 × 0.69 = 0.3539° C
This is equation of straight line.
\ bpt. of solution = 99.725° C + 0.3539° C
= 100.079° C p oA p oB - p oA
Slope = , Intercept =
19. (a) Let the masses of A and B be a and b. The mass of AB2 p oB p oB
will be (a + 2b) g mol -1 and AB4 will be (a + 4b) g mol -1 23. (c) B. pt. = 100 + D T b = 100 + K b m
F. pt. = 0 – D Tf = 0 – Kf m
5.1´1´1000
For AB2, 2.3 = ............ (I)
(a + 2b) ´ 20 Tb – Tf = 100 + K b m – (– K f m)
105 = 100 + 0.51 m + 1.86 m
5.1´1´1000
For AB4, 1.3 = ............ (II) 5
(a + 4b) ´ 20 \ m= = 2.11
2.37
On solving (I) and (II),
Weight of sucrose to be dissolved in 100 g water
a = 25.49 and b = 42.64
2.11´ 342 ´ 100
D H evp = = 72 g
-1 -1 1000
20. (a) Trouton’s rule is = 21 cal. K mol
Tb
24. (b) DTf = 0.3° C
7353
Tb = = 350.1 K = 77.1° C K f ´ WB ´ 1000
21 DTf = 0.3° C =
M B ´ WA
o o
21. (b) Ptotal = p A ´ x A + p B ´ x B
1.86 ´ WB ´ 1000
= 80.0 × 0.4 + 120.0 × 0.6 = 104 mm Hg =
62 ´ 5000
The observed Ptotal is 100 mm Hg which is less than
\ WB = 50 g
104 mm Hg. Hence the solution shows negative deviation.
The amount used should be more than 50 g.
o
22. (c) p A = pA ´ x A = Total pressure × yA 25. (c) XA = 0.70 \ X B = 0.30;
p B = poB ´ x B = Total pressure × yB YA = 0.35 \ YB = 0.65
Where x and y represent mole fraction in liquid and vapour
600 ´ 0.35
phase respectively. p A = 600 × 0.35 \ = p oA
0.70
p oB x B yB p oA = 300 torr
\ = , \
p oB xA yA
600 ´ 0.65
p B = 600 × 0.65 \ = p oB
1 - yA 0.30
poB (1 - x A )
=
poA x A yA
\ p oB = 1300 torr
JEEMAIN.GURU
downloaded from jeemain.guru
558 Chemistry
26. (a) Ostwald and Walker’s method When 1 mole of A is added
2 1 2 1
po - ps W2 W2 / m xA = = and x B = =
= = 4 2 4 2
po W1 + W2 W2 / m + W1 / M
1 o 1
W1 = loss of weight of solution, \ p oA . + p B . = 300
2 2
W2 = loss of weight of solvent
\ p oA + p oB = 600 ............. (ii)
0.0345 2.64 / m From (i) and (ii),
\ =
0.645 + 0.0345 2.64 / m + 30 / 74
p oB = 150 and p oA = 450
m = 122 g
When 1 mole of B is added
o o
27. (b) V. P. of solution P = p A x A + pB xB
1 3
xA = , xB =
1 2 4 4
or 250 = p oA . + p oB .
3 3 3 1
\ P = 150 × + 450 × = 225
4 4
p oA + 2 p oB = 750 ............... (i)
JEEMAIN.GURU
downloaded from jeemain.guru
17
Electrochemistry
ELECTROLYTES AND ELECTROLYSIS : Z is a constant known as Electrochemical equivalent
A substance which decomposes as a result of the passage of When I = 1 amp., t = 1 sec. then Q = 1 coulomb, then W = Z.
electric current is called an electrolyte and phenomenon of Thus Electrochemical equivalent is the amount of the
decomposition by electricity is called electrolysis. substance deposited or liberated by 1 ampere current
passing for 1 second (i.e. 1 coulomb, I × t = Q)
ELECTROLYTIC CELL :
(II) Second law : When the same quantity of electricity is passed
The apparatus used to carry out electrolysis is known as
through different electrolytes, the amounts of the products
electrolytic cell. The main features of electrolytic cell are :
obtained at the electrodes are directly proportional to their
Feature Cathode Anode chemical equivalents or equivalent weights. Thus
Sign Negative since attached to Positive since attached to Mass of A Eq. wt of A m1 E1 Z1Q Z1
negative end of external positive end of external = ; = = =
battery battery
Mass of B Eq. wt of B m 2 E 2 Z 2 Q Z 2
Direction of into the cell out of the cell Hence electrochemical equivalent µ Equivalent wt.
movement of
electrons ONE FARADAY :
Direction of Cations Anions E µ Z; E = FZ F = Known as Faraday's constant
movement of ions
Half-Reaction Reduction Oxidation One Faraday is the quantity of charge carried by one mole of
electrons
OXIDATION :
Loss of electrons is called oxidation. IF = 1.6023 ´ 10 -19 ´ 6.023 ´ 10 23 = 96500 Coulombs
¾® O 2 + 4H + + 4e -
2H 2 O ¾ AMOUNT OF THE SUBSTANCE 'm' LIBERATED OR
DEPOSITED AT AN ELECTRODE :
REDUCTION :
Gain of electrons is called reduction. Eq . wt of the Sub . ´ I ´ t Eq. wt ´ Q
m= =
96500 96500
2 H 2 O + 2e - ¾
¾® H 2 + 2OH -
Ex.1: Three electrolytic cells A, B and C containing electrolytes
FARADAY'S LAWS OF ELECTROLYSIS : AlCl3, CuSO4 and AgNO3 respectively were connected in
(I) First law : The amount of the substance deposited or series. A steady current of 1.287 ampere was passed through
liberated at an electrode is directly proportional to the the cells for a definite time. After electrolysis 2.158 g of
quantity of electricity passed through an electrolyte silver were deposited at the cathode of cell. Calculate.
W µ I´ t = I´ t ´ Z = Q´ Z (I) total charge passed during electrolysis.
I = Current strength in amp., t = time in sec., (II) time period for which the current is passed
Q = Quantity of charge (coulombs) (III) Mass of aluminium deposited at cathode of cell A
(IV) Mass of Copper deposited at cathode of cell B
JEEMAIN.GURU
downloaded from jeemain.guru
560 Chemistry
Eq. of Zn++ deposited =
Eq. wt ´ total charge (Q)
Sol.: (I) Amt. deposited =
96500 i´ t 1.70 ´ 90 ´ 230
= = 3.646 ´ 10 -3
96500 100 ´ 96500
107.9
2.158 = ´ total charge Meq. of Zn++ deposited = 3.646
96500
Initial Meq of Zn++ = 300 × 0.160× 2 = 96
2.158 ´ 96500 (Q M × 2 = N for Zn++)
\Q = = 1930 C
107.9 Meq. of Zn++ left in solution 96 – 3.646 = 92.354
1930 C 92.354
(II) Charge = Current × time; \ time = = 1499.6 s [ ZnSO 4 ] = = 0.154M
1.287 A 2 ´ 300
31.75 ´ 2.158 3. Chemical property No change in chemical property there is chemical change
(IV) Mass of copper deposited = = 0.635 g 4. Resistance Resistance is offered Resistance is offered by
107.9 by atomic Kernels interionic attractions,
viscosity of solvent
Ex.2 : The same quantity of electrical charge that deposited
5. Temperature decreases with increase increases with increase of
0.583 g of Ag was passed through solution of gold salt and of temperature temperature
0.355 gold was deposited. Find the oxidation state of gold in 6. Magnitude generally high generally low
the solution. 7. Solvation No solvation Ions are solvated
Sol.: Au n + + ne- ¾
¾® Au FACTORS AFFECTING ELECTROLYTIC
CONDUCTION :
197 Please refer to the properties discussed above viz. viscosity,
Eq. wt. of Au =
n temperature, solvation of ions etc.
m1 E1 0.583 107.9 OHM'S LAW :
= ; = ; The potential difference across the conductor is directly
m 2 E 2 0.355 197
proportional to the current flowing through it.
n
Potential difference µ current
\ n = 3, \ Oxidation state of gold = 3
V µ I; V = RI
Ex.3: Calculate the quantity of electricity that would be
where R is a constant and known as resistance of the conductor
required to reduce 12.3 g of nitrobenzene to aniline if current
efficiency is 50%. If the potential drop across the cell is 3.0 V
R=
volt, how much energy will be consumed. I
Law is applicable to metallic as well as electrolytic conductors. R
Sol.: C 6 H 5 NO 2 + 6H + + 6e - ¾
¾® C 6 H 5 NH 2 + 2H 2 O
is expressed in Ohms also designated as W.
M 123 RESISTANCE (R) :
Eq. wt of nitrobenzene = =
6 6 It offers obstruction to the passage of electric current. It is directly
proportional to the length (l) and inversely proportional to the
E´i´t 123 i ´ t ´ 50 æ 2 ´ 50 ö
W= Þ 12.3 = ´ çi = ÷ area of cross section (a) of the conductor.
96500 6 100 ´ 96500 è 100 ø
l l
(given current efficiency is 50 %) Rµ
= r´
a a
Q = i × t = 115800 coulombs where r is a constant, called resistivity or specific resistance.
Now energy used = Q × V = 115800 × 3 = 347.4 kJ
when l = 1 cm and a = 1 cm2 then r = R
Ex.4: A current of 1.70 amp. is passed through 300 ml of 0.160 M
solution of ZnSO4 for 230 sec with a current efficiency of SPECIFIC RESISTANCE (r) :
90%. Find the molarity of Zn++ after the deposition of Zn The resistance offered by 1 cm3 of the conductor is known as
assuming no change in volume during electrolysis. specific resistance.
1.70 ´ 90 R.a Ohm ´ cm 2
Sol. i = amp. Units of r = = = Ohm cm or W cm
100 l cm
JEEMAIN.GURU
downloaded from jeemain.guru
Electrochemistry 561
CONDUCTANCE (C) : RELATION BETWEEN EQUIVALENT CONDUCTIVITY
It is ease of flow of electric current through the conductor ( L eq ) AND SPECIFIC CONDUCTIVITY ( k)
and reciprocal of resistance R.
k ´ 1000 k ´ 1000
C=
1
units ohm–1, mhos or W–1 L eq = k ´ V = =
R Normality of solution N
SPECIFIC CONDUCTIVITY k (KAPPA) : where V is the volume in cm3 or ml containing 1 gev. of the
It is the reciprocal of specific resistance. electrolyte.
UNITS OF EQUIVALENT CONDUCTIVITY :
1 l l æl ö Ohm–1 cm2 eq–1 or W–1 cm2 eq–1 or S cm2 eq–1
k= = = C ´ = C ´ cell constant ç = cell constant ÷
r R.a a èa ø EFFECT OF DILUTION ON EQUIVALENT
Hence specific conductivity k (Kappa) = Conductance × cell CONDUCTIVITY :
constant Since the degree of dissociation of the electrolyte increases with
Units k = Ohm–1 cm–1 = W–1 cm–1 = S cm–1 (W–1 = S, Seimens) dilution, the equivalent conductivity also increases. The increase
is more in case of weak electrolytes than strong electrolytes.
EFFECT OF DILUTION ON CONDUCTANCE :
The equivalent conductivity increases and specific conductivity
The number of current carrying particles or ions per ml decrease
decreases with dilution.
on dilution and specific conductivity, being the conductance of
IMPORTANCE OF EQUIVALENT CONDUCTIVITY :
one centimetre cube of solution, decreases with dilution.
It helps to compare the conductivity of different electrolytes,
CELL CONSTANT AND ITS DETERMINATION : since solutions of different electrolytes having 1 gram equivalent
l each in the same volume will have the same total charge of
The quantity is known as cell constant. Its direct measurement electricity. One mole of NaCl yields ions carrying 2 faradays of
a
electricity and one mole of Na2SO4 yields ions carrying 4 faradays
is very difficult. It is measured by using standard solution of KCl
of electricity. But 1 gram equivalent of each will produce ions
whose conductivity is known at different concentrations and
carrying 2 faradays of electricity
temperatures. Specific conductance of KCl solutions :
Concentration Specific conductance (W–1 cm–1) at Mol wt. of Na 2SO 4
(Equivalent wt. of Na2SO4 = ).
0°C 18°C 25°C 2
0.1M 0.007154 0.011192 0.012886 Hence conductivity of different electrolytes can only be compared
0.01M 0.0007751 0.0012227 0.0014114 if their solutions have equivalent concentrations.
MOLAR CONDUCTIVITY (Lm) :
Specific conductance
Hence cell constant = Measured conductance The conductivity of all the ions produced when 1 mole of an
electrolyte is dissolved in V ml of solution is known as molar
Ex.5: Specific conductance of a decinormal solution of KCl at conductivity.
18°C is 0.0112 Ohm–1 cm–1. The resistance of the cell or
containing the solution at 18°C was found to be 55 Ohm. 'The conductance of a solution containing one gram-mole of
What is the cell constant. electrolyte placed between two large electrodes one centimeter
apart'.
Specific conductance
Sol. Cell constant = RELATION BETWEEN MOLAR CONDUCTIVITY (Lm)
Measured conductance
AND SPECIFIC CONDUCTIVITY ( k) :
0.0112
= 0.616 cm -1 k ´ 1000
= Lm = k ´ V =
1 M
55 where V is the volume in cm3 or ml containing 1 mole of the
electrolyte.
EQUIVALENT CONDUCTIVITY ( L eq ) :
UNITS OF MOLAR CONDUCTIVITY (Lm) :
The conductivity of all the ions produced when 1 gram equivalent Ohm–1 cm2 mol–1 or W–1 cm2 mol–1 or S cm2 mol–1
of an electrolyte is dissolved in V ml of solution is known as
equivalent conductivity EFFECT OF DILUTION ON MOLAR CONDUCTIVITY:
or Since the degree of dissociation of electrolyte increases with
'The conductance of a solution containing 1 gm. equivalent of dilution, L m also increases but less in case of strong electrolytes
electrolyte placed between two large electrodes one centimetre and more in case of weak electrolytes.
apart'.
JEEMAIN.GURU
downloaded from jeemain.guru
562 Chemistry
DEBYE-HUCKEL ONSAGAR EQUATION : 1
Sol. Conductance of solution C = ohm–1
Relation between molar conductivity L m at a particular 45
¥
concentration and molar conductivity L m at infinite dilution l 2.3
is given by Cell constant = = 0.6052
a 3.8
L m = L ¥m - b C Specific conductance
where b is constant. It depends upon nature of solvent and
1
temperature. = 0.6052 ´ = 0.01345 Ohm-1cm-1
45
FACTORS AFFECTING THE MOLAR
0.01345 ´1000
CONDUCTIVITY Lm : L eq = = 26.90 Ohm -1cm 2 eq -1
1
(I) Nature of electrolyte : The strong electrolytes like KNO3,
KCl, NH4NO3, HCl, H2SO4, NaOH, KOH etc are completely 2
ionised in aqueous solution and have high values of Lm. N
Ex.7: The specific conductance of an solution of KCl at
The weak electrolytes are ionised to lesser extent in aqueous 50
solution and have lower values of Lm. 25°C is 0.002765 mho. If the resistance of a cell containing
(II) Concentration of the solution : The concentrated solutions this solution is 400 ohms, what is the cell constant.
of strong electolytes have significant inter-ionic attractions,
which reduce the speed of ions and lower the value of Lm. Sol.: Cell constant=
0.002765
= 0.002765 ´ Resistance
The dilution decreases such attractions and increases the Conductance
value of L m. The limiting value L m( L¥m the molar = 0.002765 ´ 400 = 1.106
conductivity at zero concentration or at infinite dilution) KOHLRAUSCH'S LAW :
can be obtained by extrapolating the graph.
At infinite dilution the molar conductivity of an electrolyte is the
L¥m sum of the ionic conductivities of the cations and anions. e.g. for
KCl AxBy.
Lm
CH3 COOH
( )
L ¥m (A x By ) = xl¥ A+ + yl¥ B- ( )
It is important to note that the source of cations (A+) and anions
C (B–) may be electrolyte itself or any other electrolyte.
¥ ¥
In case of weak electrolytes, the degree of ionisation Thus L¥m (CH3COOH) = l CH3COO- + l H +
increases which increases the value of Lm. The limiting value
L¥m cannot be obtained by extrapolating the graph. The ¥ ¥ ¥
(II) L m (Al2 (SO4 )3 ) = 2l Al3+ + 3lSO24-
limiting value, L¥m , for weak electrolytes is obtained by APPLICATIONS OF KOHLRAUSCH'S LAW :
Kohlrausch law. (I) Calculation of molar conductivities of weak electrolytes at
(III) Temperature : The increase of temperature decreases inter- infinite dilution.
ionic attractions, solvation of ions, viscosity and increases Ex.8:Calculate the degree of dissociation of 0.01 M NH4OH
kinetic energy of ions and their speed. Thus Lm increases solution when its molar conductivity is 9.4 Ohm–1 cm2 mol–
with temperature. 1. The molar conductivities at infinite dilution of NaCl, NH Cl
4
(IV) Viscosity of solvent : The higher the value of viscosity the and NaOH are 126, 130 and 217 Ohm–1 cm2 mol –1
lower is the value of Lm. respectively.
(V) Dielectric constant of solvent : The higher the value of
Sol. Lm (NaCl) = lNa+ + lCl- = 126 Ohm cm mol ( I)
¥ ¥ ¥ -1 2 -1
dielectric constant of solvent, the more is the value of Lm.
The former decreases interionic attractions.
L¥m (NH4Cl) = l¥NH+ + lCl
¥ -1
- = 130 Ohm cm mol
2 -1 (II)
DEGREE OF DISSOCIATION (a) : 4
JEEMAIN.GURU
downloaded from jeemain.guru
Electrochemistry 563
(II) Calculation of the solubility of sparingly soluble salts:
speed
Very small amount of sparingly soluble salts like AgCl or Ionic Mobility U =
potential gradient
BaSO4 is present in their saturated solutions in completely
ionised form. Their L eq equal to k V can be regarded as POTENTIAL GRADIENT :
Potential difference applied at the electrodes divided by the
L¥eq at infinite dilution. According to Kohlrausch law its distance between the electrodes is known as Potential gradient.
value is given by GALVANIC CELL, ELECTROCHEMICAL CELL OR
VOLTAIC CELL :
kV = L ¥eq = l ¥a + l ¥c
A device which converts chemical energy into electrical energy
Hence knowing the value of k (Kappa), V can be known is called Galvanic, Electrochemical or voltaic cell. Main features
which is the volume containing 1 gev of substance and of the cell are
solubility can be known. General representation of an electrochemical cell
(III) Calculation of degree of ionisation :
e
Lcm Molar conductivity at particular concentration
a= =
L¥
n+ n+
m
Molar conductivity at infinite dilution M(s) | M (aq) (1M, 1 atm, 298 K) | | M (aq) (1M, 1 atm, 298 K) | M’(s)
Anode Oxidation Salt Reduction Cathode
(IV) Calculation of absolute ionic mobilities : half cell bridge half cell
The ionic mobility ( U ¥ ) and ionic conductance ( l¥ ) at
Cathode Anode
infinite dilution are related to each other as below Sign Positive due to Negative due
consumption of electrons to release of electrons
l¥ l¥
U¥ = = (IF = 96500 coulombs) Reaction Reduction Oxidation
F 96500 Movement Into the cell Out of cell
of electrons
IONIC MOBILITY :
Other features of the electrochemical cell are :
The distance travelled by an ion per second under a potential (i) There is no evolution of heat
gradient of 1 volt per cm is known as ionic mobility.
(ii) The solutions remain neutral on both side
(iii) The reaction and flow of electrons stops after some time.
– +
+ –
– + –
– +
– +
–
– +
M ® M n+ + n e M n+ + ne - ® M
Anode Cathode
1. Assembly It is a combination of two half cells, It is a single cell containing the same electrodes
containing the same or different present in the same electrolyte.
electrodes in the same or different electrolytes.
2. Nature of electrodes Anode is negative, Cathode is positive Anode is positive, Cathode is negative
3. Movement of From anode to cathode in Electrons enter through cathode and
electrons external circuit leave through anode.
4. Energy It converts chemical energy It converts electrical energy into chemical
into electrical energy, produced energy. Energy is supplied to the electrolytic
as a result of redox reaction. solution to bring about the redox reaction.
5. Spontaneity Cell reaction is spontaneous. Cell reaction is non-spontaneous.
6. Salt bridge Salt bridge is required. No salt-bridge is required.
JEEMAIN.GURU
downloaded from jeemain.guru
564 Chemistry
DANIELL CELL : Cr3+/Cr Cr 3+ + 3e - ¾
¾® Cr –0.74
An electrochemical cell of Zinc and copper metals is known as
Daniell Cell. It is represented as Fe3+/Fe Fe3+ + 3e - ¾
¾® Fe –0.41
Cd++/Cd Cd + + + 2e - ¾
¾® Cd –0.40
Zn plate Voltmeter Cu plate
Ni + + + 2e - ¾
Anode Cathode Ni++/Ni
Salt ¾® Ni –0.25
bridge
0.1 M 0.1 M Sn++/Sn Sn + + + 2e - ¾
¾® Sn –0.14
ZnSO4 CuSO 4
1 1
H+/ H 2 H + + e- ¾
¾® H 2 0.00
2 2
Zn (s) | Zn++ (aq.) | | Cu2+ (aqs.) | Cu (s)
Cu++/Cu Cu + + + 2e - ¾
¾® Cu 0.34
¾® Zn 2+ + 2e -
LHS oxidation : Zn ¾
1 1
I2 / I I2 + e- ¾
¾® I 0.54
RHS reduction : Cu 2+ + 2e - ¾
¾® Cu 2 2
Overall reaction :
Ag+/Ag Ag + + e - ¾
¾® Ag 0.80
2+ 2+
Zn + Cu (aq) ¾¾
® Zn (aq) + Cu
Hg++/Hg Hg + + + 2e - ¾
¾® Hg 0.85
By convention cathode is represented on the RHS and anode
on the LHS. Two vertical lines represent the salt bridge.
1 1
Br2 / Br - Br2 + e - ¾
¾® Br - 1.09
FUNCTION OF SALT BRIDGE : 2 2
(I) Completes the circuit and allows the flow of current (II) It
1
maintain the electrical neutrality on both sides. Salt-bridge Cr2 O 72- / Cr 3+ 1
Cr2 O72- + 7H + + 3e - ¾¾
7
® Cr 3+ + H 2 O 1.33
generally contains solution of strong electrolyte such as KNO3, 2 2 2
KCl etc. KCl is preferred because the transport numbers of K+
1 1
and Cl– are almost same. Cl 2 / Cl - Cl 2 + e - ¾
¾® Cl - 1.36
2 2
ELECTRODE POTENTIAL :
When an electrode is in contact with the solution of its own ions in MnO -4 / Mn + + MnO 4- + 8H + + 5e - ¾
¾® Mn + + + 4H 2 O 1.51
a half cell, it has a tendency to lose or gain electrons which is known
as electrode potential. It is expressed in volts. H2O2/H2O H 2 O 2 + 2H + + 2e - ¾
¾® 2H 2 O 1.77
Some standard electrode potentials (E° Red) at 298K (ECS)
1 1
Couple Half-Reaction E° Volts F2 / F - F2 + e - ¾
¾® F - 2.87
2 2
Li+/Li Li + + e - ¾
¾® Li –3.05
Hg +2 + / 2Hg Hg 2+ + + 2e - ¾
¾® 2Hg 0.79
M+/M M + + e- ¾
¾® M –2.94
NO 3- / NO, H 2 O NO 3- + 4H + + 3e - ¾
¾® NO + 2H 2 O 0.97
(K, Rb or Cs)
Ba++/Ba Ba + + + 2e - ¾
¾® Ba –2.90 Au3+/Au Au 3+ + 3e - ¾
¾® Au 1.42
OXIDATION POTENTIAL :
Sr++/Sr Sr + + + 2e - ¾
¾® Sr –2.89
The tendency to lose electrons in above case is known as
Ca++/Ca Ca + + + 2e - ¾
¾® Ca –2.76 Oxidation potential.
Oxidation potential of a half-cell is inversely proportional to
Na+/Na Na + + e - ¾
¾® Na –2.71 the concentration of ions in the solution.
REDUCTION POTENTIAL :
Mg++/Mg Mg + + + 2e - ¾
¾® Mg –2.38
The tendency to gain electrons in above case is known as
1 1 reduction potential.
H2 / H- H 2 + e- ¾
¾® H - –2.23 It is not possible to determine the absolute value of electrode
2 2
potential. For this a reference electrode is required. The
Al3+/Al Al3+ + 3e - ¾
¾® Al –1.67 electrode potential is only the difference of potentials between
two electrodes that we can measure by combining them to give
Zn++/Zn Zn + + + 2e - ¾
¾® Zn –0.76 a complete cell.
JEEMAIN.GURU
downloaded from jeemain.guru
Electrochemistry 565
Reduction :
STANDARD REDUCTION POTENTIAL ( Eo ):
Mn+ /M
Hg 2 Cl 2 (s) ® Hg 22 + + 2Cl -
According to latest convention the electrode potential is always
represented as reduction potential. If its value is negative, it means Hg 22+ + 2e - ® 2Hg(l)
electrode has oxidation potential. The standard conditions are 1 Overall reaction :
molal solution, 298K temperature and 1 atm. pressure. According
2Hg(l) + 2Cl
– –
to IUPAC convention, the reduction potential alone be called as Hg2Cl2(s) +2e E ºRe d = 0.2422 V
the electrode potential unless it is specifically mentioned. (iii) Silver-silver salt electrode
REFERENCE ELECTRODE : Half cell is Ag, AgCl(s), Cl– (KCl or HCl)
The following electrodes are used as reference electrodes for Oxidation :
determining the standard reduction potentials.
Ag ®Ag+ + e-
(i) Standard hydrogen electrode (SHE) : Standard hydrogen
Ag + + Cl - ® AgCl(s)
electrode (SHE) also known as Normal Hydrogen Electrode
(NHE), consists of platinum wire, carrying platinum foil
coated with finely divided platinum black. The wire is sealed Ag + Cl - ® AgCl(s) + e -
into a glass tube, placed in a beaker containing 1M HCl. The
hydrogen gas at 1 atm pressure is bubbled through the Reduction :
solution at 298K. Half cell is Pt, H2(1 atm)/H+ (1M)
AgCl(s) ® Ag + + Cl -
In SHE, at the surface of platinum, either of the following
reactions can take place Ag + + e - ® Ag
AgCl(s) + e - ® Ag + Cl -
EoRed = 0.2225 V
H2(g) at
1 bar ELECTROMOTIVE FORCE (EMF) OF A CELL :
It is the difference between the electrode potentials of two half-
cells and cause of flow of current from electrode at higher
potential to electrode at lower potential. It is also the measure of
free energy change. Standard EMF of a cell
E ocell = E ocathode - E oanode = E oright - E oleft
1.00 MH
+ Finely divided
platinum coated
ELECTROCHEMICAL SERIES :
on platinum foil It is the arrangement of electrodes in the increasing order of their
o
+ - Standard Reduction potential E M n + / M .
2H (aq) + 2e ® H 2 (g) Reduction
APPLICATIONS OF ELECTROCHEMICAL SERIES :
H 2 (g) ¾¾ ® 2H + (aq) + 2e - Oxidation
(I) The lower the value of E°, the greater the tendency to form
The electrode potential of SHE has been fixed as zero.
cation
All other single electrode potentials are referred to as
potentials on hydrogen scale. M – ne ¾ ¾® M n +
Drawbacks of SHE (II) Replacement (or evolution) of H2 from hydro acids by metals.
1. It is difficult to maintain H2 at 1 atm. pressure.
Metals placed below hydrogen in E.C.S. can not replace
2. It is difficult to maintain H+ ion concentration at 1M
hydrogen from dil. acids but metals placed above hydrogen
3. The platinum electrode is easily poisoned by traces of
can replace hydrogen from dil. acids.
impurities.
Hence calomel and silver chloride electrodes are Ca + H 2SO 4 ¾
¾® CaSO 4 + H 2
conveniently used as reference electrodes.
possible
(ii) Calomel electrode (Hg, Hg2Cl2, KCl)
Half cell is Hg, Hg2Cl2(s) KCl(solution) (Ca + 2H + ® Ca + + + H 2 )
Oxidation :
Cu + H 2SO 4 ¾
¾® CuSO 4 + H 2
2Hg(l) ® Hg 22+ + 2e - not possible
Hg 22 + + 2 Cl -
® Hg 2 Cl 2 (Cu + 2H + ® Cu + + + H 2 )
(III) Metals placed above hydrogen evolve H2 with H2O or steam,
2Hg (l) + 2Cl ® Hg 2 Cl 2 (s) + 2e - but metals placed below hydrogen cannot.
JEEMAIN.GURU
downloaded from jeemain.guru
566 Chemistry
(IV) Oxides of metals placed above hydrogen are not reduced
by H2 but oxides of iron and metals placed below iron are Ag(s) + Br - (aq) ® AgBr(s) + e -
reduced by H2
SnO, PbO, Fe3O4, CuO are reduced with H2 AgBr(s) + e - ¾¾
® Ag(s) + Br - (aq)
CaO, MgO, K2O are not reduced with H2 Cl–(aq) / Hg2Cl2(s) / Hg (Pt) :
(V) Oxides of Ag and metals below Ag are decomposed
2Hg(l) + 2Cl- ® Hg 2 Cl2 (s) + 2e -
2HgO ¾
¾® 2Hg + O 2
Hg 2 Cl 2 (s) + 2e - ¾¾
® 2Hg(l) + 2Cl - (aq)
2 Ag 2 O ¾
¾® 4Ag + O 2
OH–(aq) / Cu(OH)2(s) / Cu :
(VI) Reducing character decreases down the series.
(VII) Reactivity decreases down the series. Cu(s) + 2OH - (aq) ® Cu(OH) 2 + 2e -
(VIII)Feasibility of redox reaction : A redox reaction can occur if
the species losing the electrons lie above that which gains Cu(OH) 2 (s) + 2e - ¾¾
® Cu(s) + 2OH - (aq)
the electrons.
(IX) Determination of emf : Emf is the difference of reduction SO--
4 (aq) / PbSO 4 (s) / Pb :
potentials of two half cells.
Eemf = ERHS – ELHS
Pb(s) + SO 4-- (aq) ® PbSO 4 (s) + 2e -
If the value of e.m.f. is positive the reaction can take place
spontaneously, otherwise not.
PbSO 4 (s) + 2e- ¾¾
® Pb(s) + SO --
4 (aq)
FUNCTIONING OF ELECTROCHEMICAL CELL :
With the passage of time the electrode potential of the cathode (IV) Redox electrodes half cells : An inert metal such as platinum
decreases and that of anode increases the difference becomes wire dipped in a solution of ions of the same metal in different
zero, the driving force of emf becomes zero and reaction stops. oxidation states
TYPES OF ELECTRODES AND HALF-CELLS : Fe3+(aq), Fe2+(aq) / Pt : Fe 2+ (aq) ® Fe3+ (aq) + e-
(I) Gas electrodes or gas Ion half cells :
Half-cell Reaction Fe3+ (aq) + e - ¾¾
® Fe 2 + (aq)
Oxidation
Sn4+(aq), Sn2+(aq) / Pt: Sn 2+ (aq) ® Sn 4+ (aq) + 2e-
H + (aq) / H 2 (g) / Pt : H 2 (g ) 2H+ + 2e–
2.303RT 1
Ag + + e - ¾
¾® Ag E M n + / M = E oM n + / M - log
nF [M n + ]
Cu++(aq) / Cu : Cu ® Cu ++ + 2e-
2.303 ´ 8.314 ´ 298 1
Cu + + + 2e - ¾
¾® Cu E M n + / M = E oM n + / M - log
n ´ 96500 [M n + ]
(III) Metal-metal insoluble Salt-Salt anion :
Cl–(aq) / AgCl / Ag:
0.059 1
E M n + /M = E oM n+ /M - log n +
Ag(s) + Cl – (aq) ® AgCl(s) + e - n [M ]
AgCl(s) + e - ¾¾
® Ag(s) + Cl - (aq) If we write the elcetrode reaction, in general, as
Br–(aq) / AgBr / Ag : Oxidised state + ne– Reduced State
JEEMAIN.GURU
downloaded from jeemain.guru
Electrochemistry 567
The potential of electrode is given by RELATIONSHIP BETWEEN FREE ENERGY CHANGE
AND EQUILIBRIUM CONSTANT :
RT [Reduced state]
E cell = E cell
o
- 2.303 log
nF [Oxidised state] DGo = -2.303RT log Kc
aA + bB ¾
¾® cC + dD Zn, Zn + + (c1 ) | | Zn + + (c 2 ); Zn c 2 > c1
2.303 c 0.0591 c
2.303RT [C]c [D]d E cell = RT log 2 = log 2
E cell = E cell
o
- log nF c1 n c1
nF [A]a [B]b
Concentration of solids and liquids is taken as unity, APPLICATIONS OF THE CONCENTRATION CELLS :
concentration of ions Mol L–1 and concentration of gases as (I) Determination of valency
partial pressures in Atmosphere. (II) Determination of solubility of sparingly soluble salts.
NERNST EQUATION AND EQUILIBRIUM (III) Determination of transition point.
CONSTANT (Kc) : OVERVOLTAGE :
When Ecell drops to zero the concentration of ions will be The difference between the voltage at which a gas is actually
equilibrium concentrations. We have for general cell reaction evolved and theoretical value at which it ought to have been
evolved during electrolysis is known as overvoltage.
aA + bB cC + dD
REVERSIBLE CELL :
2.303RT [C] [D] c d When the cell reaction can be stopped or reversed by applying
E cell = E cell
o
- log an emf exactly equal to or infinitesimally greater than that of the
nF [A]a [B]b
cell, it is called reversible cell.
Examples of reversible electrodes
2.303RT
E ocell = log K c [Since at equilibrium Ecell = 0] 1. Metal-metal ion electrode : Metal rod dipped into a solution
nF
of its own ions.
0.0591 + –
E ocell = log Kc at 298K. M M +e
n The negative electrode (electrode reaction involving
RELATION BETWEEN ELECTRICAL ENERGY AND oxidation) increases M+ ions in solution
FREE ENERGY (DG) : The positive electrode (electrode reaction involving
reduction) decreases M+ ions in solution.
If n is the number of electrons liberated (or taken up) in a particular
Thus, electrode is reversible with respect to M+ ions
cell reaction, then n faradays (nF) of electricity will be generated
in the complete reaction. If E is the EMF of the cell, then 2. Gas electrodes :
(a) Hydrogen electrode : Pt, H2(g), H+
Electrical energy supplied by the cell = nFE
Reaction
According to Gibbs and Helmholtz, the decrease of free energy
1 H (g) H+ + e–
(–DG) of the reaction occuring in the cell is equal to electrical 2 2
energy The electrode is reversible with respect to H+ ions
Hence, –DG = nFE (b) Chlorine electrode : Pt, Cl2(g), Cl–
Reaction
The standard free energy and E ocell are related as
1 – –
Cl (g) + e Cl (aq)
2 2
DG = o
- nFE ocell The electrode is reversible with respect to Cl– ion.
JEEMAIN.GURU
downloaded from jeemain.guru
568 Chemistry
(c) Metal - Metal Salt Ion Electrode : (I) Electrolysis of aqueous NaOH :
¾® Na + + OH -
i) Calomel Electrode
NaOH ¾ Completely dissociated
Hg, Hg2Cl2(s) ; KCl(solution)
Oxidation : ¾® H + + OH - Slightly dissociated
H 2O ¾
2Hg(l )
2+
Hg 2 + 2e
– At cathode : 2 H + + 2e - ¾
¾® 2H ¾
¾® H 2
2+ –
Hg 2 + 2Cl Hg2Cl2(s) At anode : 2OH - - 2e - ¾ ¾® H 2 O + O; O + O ¾
¾® O 2
2Hg + 2Cl
–
Hg2Cl2(s) + 2e
– Current is carried by Na+ and OH– ions.
(II) Electrolysis of aqueous H2SO4
Oxidation decreases concentration of chloride ions.
¾® 2H + + SO 24 -
H 2SO 4 ¾ Completely dissociated
Reduction :
2+ – ¾® H + + OH -
H 2O ¾ Slightly dissociated
Hg2Cl2(s) Hg + 2e
–
2
At cathode : 2H + + 2e - ¾
¾® 2H ¾
¾® H 2
2Hg(l )
2+
Hg + 2e
2
At anode : 2OH - - 2e - ¾
¾® 2OH ¾
¾® H 2 O + O;
2Hg(l ) + 2Cl
– –
Hg2 Cl2(s) + 2e
O+O¾
¾® O 2
Reduction increases the concentration of chloride ions
(III) Electrolysis of aqueous NaCl
The electrode is reversible with respect to Cl– ions.
ii) Silver-Silver Chloride Electrode : Ag, AgCl(s), Cl–(KCl ¾® Na + + Cl -
NaCl ¾ Completely dissociated
or HCl)
¾® H + + OH -
H 2O ¾ Slightly dissociated
Oxidation :
+ – At cathode : 2 H + + 2e - ¾
¾® 2H ¾
¾® H 2
Ag Ag + e
+
Ag + Cl
–
AgCl(s) At anode : 2Cl - - 2e - ¾
¾® 2Cl ¾ ¾® Cl 2
– Although the oxidation potential of OH– is more than Cl–
Ag + Cl AgCl(s)+ e– yet Cl2 is formed at anode due to overvoltage.
Oxidation decreases the concentration of Cl– ions. (IV) Electrolysis of aqueous CuSO4 using Pt electrodes
Reduction : ¾® Cu + + + SO -4 -
CuSO 4 ¾
+ –
AgCl(s) Ag + Cl ¾® H + + OH -
H 2O ¾
+ –
Ag + e Ag At cathode Cu + + + 2e - ¾
¾® Cu
– –
AgCl(s) + e Ag + Cl At anode 2OH - - 2e - ¾
¾® 2OH ¾
¾® H 2 O + O;
Reduction increases the concentration of Cl– O+O¾ ¾® O 2
(d) Oxidation - Reduction Electrodes : Such electrodes (V) Electrolysis of CuSO4 solution using copper electrodes
are set up by inserting unattackable metal (eg Platinum)
into a solution of ions in different oxidation states. The ¾® Cu + + + SO -4 - ;
CuSO 4 ¾ ¾® H + + OH -
H 2O ¾
metal acquires a potential due to tendency of ions in
one oxidation state to change into another stable
At Cathode Cu + + + 2e - ¾
¾® Cu
oxidation state. At Anode ¾® Cu + + + 2e -
Cu ¾
Electrode reaction :
Oxidation potential Cu > OH - > SO 4- -
n+ – (n+m)+ - 3. 4 -1.23 - 2.01
M – me M
2+ – 3+
Fe – e Fe FACTORS GOVERNING THE DISCHARGE
2+ – 4+
Sn – 2e Sn POTENTIAL :
(I) Position in the electrochemical series
IRREVERSIBLE CELL : (II) Concentration of ions in the solution
When the cell reaction cannot be stopped or reversed it is called (III) Nature of electrodes
irreversible cell e.g. cell of Zn and Ag electrodes immersed in Discharge potential of some ions
solution of H2SO4.
Criteria of the formation of products in Electrolysis - Li + < K + < Na + < Ca + + < Mg + + < Al + + < Zn + + < Fe + +
JEEMAIN.GURU
downloaded from jeemain.guru
Electrochemistry 569
TRANSPORT NUMBER : (b) Nickel-cadmium storage cell
The fraction of the total current carried by each ion is called its Anode - Cadmium
transport number. Cathode - metal grid containing NiO2
The amount of electricity carried by a particular ion µ speed of Electrolyte - KOH solution
particular ion. Anode Reaction Cd ( s ) + 2OH - ® Cd(OH) 2 ( s ) + 2e -
Transport number of the cation nc Cathode Reaction :
=
Current carried by the cation
=
Uc
NiO 2 ( s ) + 2H 2 O ( l ) + 2e - ® Ni ( OH )2 ( s ) + 2OH - ( aq )
Total current U c + Ua
Net Reaction :
Ua Cd ( s ) + NiO2 ( s ) + 2H 2 O ( l )
Transport number of anion na =
Uc + Ua
® Cd(OH)2 ( s ) + Ni(OH)2 ( s )
Uc = speed of cation and Ua = speed of anion.
Cell potential = 1.4 V.
Further na + nc = 1
FUEL CELLS :
SOME COMMERCIAL CELLS AND THEIR TYPES :
They convert chemical energy into electrical energy and the
They are broadly classified into two groups. reactants are continuously fed and products are removed.
(I) Primary cells : They cannot be recharged and used again. (a) Hydrogen-Oxygen-Fuel Cell : Electrodes are made of porous
Examples are graphite impregnated with catalyst (Pt, Ag or a metal oxide).
(a) Dry cell or Leclanche cell : Particulars are
Anode - Zinc Container H2O
Cathode - graphite rod surrounded by MnO2 powder Anode Cathode
Electrolyte - paste of NH4Cl + ZnCl2
Aqueous electrolyte
Cathode Reaction : MnO2 + NH +4 + e– ¾¾® MnO(OH) + NH3
Anode Reaction : Zn – 2e - ¾
¾® Zn + +
H2 O2
Zn 2 + + 2 NH 3 ¾
¾®[ Zn ( NH 3 ) 2 ]2+
Cell potential 1.25V to 1.5V
(b) Mercury Cell :
Anode - Zn-Hg amalgam
Cathode - paste of (HgO + C) Fuel cell using H2 and O2 produces electricity.
Electrolyte - moist paste of KOH-ZnO
Cathode Reaction : Electrolyte-aqueous solution of KOH or NaOH
- -
HgO(s) + H 2 O( l ) + 2e ¾¾
® Hg(l) + 2OH Oxygen and hydrogen are continuously fed into the cell.
Oxidation (half-cell reaction) :
Anode Reaction : Zn + 2OH - ¾¾
® ZnO + H 2 O(l) + 2e - Reaction : H 2 + 2OH - ¾
¾® 2H 2 O + 2e -
® ZnO(s) + Hg(l)
Net Reaction : Zn(Hg) + HgO(s) ¾¾ Reduction (half-cell reaction) :
cell potential = 1.30 volt O 2 + 2H 2 O + 4e - ¾
¾® 4OH -
(II) Secondary cells : It can be recharged and can be used again
and again. Examples Net Reaction : 2H 2 + O 2 ¾
¾® 2H 2 O
(a) Lead storage battery : EMF of the cell 1 volt.
Anode - Spongy lead (b) Hydrocarbon-oxygen fuel cell : Based upon the combustion
Cathode - grid of lead packed with PbO2 of hydrocarbons such as methane, ethane propane etc.
Electrolyte - 38% H2SO4 by mass Oxidation (half cell reaction) :
Anode Reaction : Pb + SO 4- - ¾
¾® PbSO 4 + 2e - C 3 H 8 + 20 OH - ¾¾
® 3CO 2 + 14H 2 O + 20e -
Cathode Reaction : Reduction (half cell reaction) :
( O 2 + 2 H 2 O + 4e - ¾
¾® 4OH - ) ´ 5
PbO 2 + SO 4- - + 4H + + 2e - ¾
¾® PbSO 4 + 2H 2 O
Net Reaction : Net Reaction C 3 H 8 + 5O 2 ¾
¾® 3CO 2 + 4 H 2 O
Pb + PbO 2 + 4H + + 2SO 4- - ¾
¾® 2PbSO 4 + 2H 2 O ADVANTAGES OF FUEL CELLS :
When recharged the cell reactions are reversed. I. Pollution free II. High efficiency
JEEMAIN.GURU
downloaded from jeemain.guru
570 Chemistry
THERMODYNAMIC EFFICIENCY OF FUEL CELLS : 1
Net Reaction, Fe + 2H + + ¾® Fe + + + H 2 O
O2 ¾
-DG -nFEocell 2
h= =
DH DH
1
For H2–O2 fuel cells it is 95%. At surface 2Fe + + + O 2 + 2H 2 O ¾
¾® Fe 2 O 3 + 4H +
2
CORROSION :
Slow formation of undesirable compounds such as oxides, Fe 2 O 3 + xH 2 O ¾
¾® Fe 2 O 3 .xH 2 O
sulphides or Carbonates at the surface of metals by reaction with
moisture and other atmospheric gases is known as corrosion. Net reaction at surface
FACTORS AFFECTING THE CORROSION : 1
2Fe + + + O 2 + ( x + 2)H 2 O ¾
¾® Fe 2 O 3 xH 2 O+ 4H +
(I) Reactivity of metals 2 Rust
(II) Presence of moisture and atmospheric gases like CO2, SO2
etc. PREVENTION OF CORROSION :
(III) Presence of impurities (I) Barrier protection : By painting, coating, electroplating
(IV) Strains in the metal (II) Sacrificial protection : By galvanization, Sherardising
(V) Presence of electrolyte (III) Electrical protection
RUSTING OF IRON-ELECTROCHEMICAL THEORY : (IV) Use of anti rust compounds.
An electrochemical cell known as corrosion cell is developed at
CALCULATION OF POTENTIAL OF INTERMEDIATE
the surface of iron.
Anode ® Pure iron
REACTION :
Cathode ® Impure Surface When two half-reactions having potential E1 and E2 which are
Electrolyte : combined to yield a third half reaction having potential E3. Then
E3 is given by
CO 2 + H 2 O ¾
¾® H 2 CO 3 H + + HCO 3-
SO 2 + H 2 O ¾
¾® H 2SO 3 H + + HSO 3- n1E1 + n 2 E 2
E3 =
n
Anode Reaction ¾® Fe + + + 2e -
Fe ¾
Remember : The cell potentials are not thermodynamic functions
Cathode Reaction 2 H + + 2e - ¾
¾® 2H
and should not be added.
1
2H + O2 ¾
¾® H 2 O
2
JEEMAIN.GURU
downloaded from jeemain.guru
Electrochemistry 571
JEEMAIN.GURU
downloaded from jeemain.guru
572 Chemistry
1. Which of the following is the use of electrolysis? 6. A current of 2.0 A passed for 5 hours through a molten metal
(a) Electrorefining (b) Electroplating salt deposits 22.2 g of metal (At wt. = 177). The oxidation
(c) Both (a) and (b) (d) Neither (a) nor (b) state of the metal in the metal salt is
2. Which of the following will form the cathode with respect to
(a) +1 (b) +2
iron anode in an electrolytic cell?
(a) Mg (b) Al (c) +3 (d) +4
(c) Cu (d) Zn 7. A 5 ampere current is passed through a solution of zinc
3. The number of coulombs required for the deposition of sulphate for 40 minutes. Find the amount of zinc deposited
107.870 g of silver is at the cathode
(a) 96500 (b) 48250 (a) 40.65 g (b) 4.065 g
(c) 193000 (d) 10000
(c) 0.4065 g (d) 65.04 g
4. An electrolytic cell contains a solution of Ag2SO4 and has
platinum electrodes. A current is passed until 1.6 gm of O2 8. On passing a current of 1.0 ampere for 16 min and 5 sec
has been liberated at anode. The amount of silver deposited through one litre solution of CuCl2, all copper of the solution
at cathode would be was deposited at cathode. The strength of CuCl2 solution
(a) 107.88 gm (b) 1.6 gm was (Molar mass of Cu = 63.5, Faraday constant = 96500 C
(c) 0.8 gm (d) 21.60 gm mol–1).
5. 1.08 g of pure silver was converted into silver nitrate and its (a) 0.07 M (b) 0.2 N
solution was taken in a beaker. It was electrolysed using
platinum cathode and silver anode. 0.01 Faraday of electricity (c) 0.005 M (d) 0.02 N
was passed using 0.15 volt above the decomposition 9. In a solution of CuSO4 how much time will be required to
potential of silver. The silver content of the beaker after the precipitate 2 g copper by 0.5 ampere current ?
above shall be (a) 12157.48 sec (b) 102 sec
(a) 0 g (b) 0.108 g (c) 510 sec (d) 642 sec
(c) 1.08 g (d) None of these
JEEMAIN.GURU
downloaded from jeemain.guru
Electrochemistry 573
10. What is the amount of chlorine evolved when 2 amperes of 21. The unit of equivalent conductivity is
current is passed for 30 minutes in an aqueous solution of (a) ohm cm
NaCl? (b) ohm–1 cm+2 (g equivalent)–1
(a) 66 g (b) 1.32 g (c) ohm cm2 (g equivalent)
(c) 33 g (d) 99 g (d) S cm–2
11. When 9.65 coulombs of electricity is passed through a 22. The conductivity of a saturated solution of BaSO 4
solution of silver nitrate (atomic mass of Ag = 108 is 3.06 × 10–6 ohm–1 cm–1 and its equivalent conductance is
g mol–1), the amount of silver deposited is
1.53 ohm–1 cm2 equiv–1. The Ksp for BaSO4 will be
(a) 16.2 mg (b) 21.2 mg
(a) 4 × 10–12 (b) 2.5 × 10–9
(c) 10.8 mg (d) 6.4 mg –13
12. The charge required to deposit 9 g of Al from Al3+ solution (c) 2.5 × 10 (d) 4 × 10–6
is (At. wt. of Al = 27.0) 23. The resistance of 0.1 N solution of a salt is found to be 2.5×
(a) 3216.3 C (b) 96500 C 103 ohm . The equivalent conductance of the solution is
(c) 9650 C (d) 32163 C (cell constant = 1.15 cm–1)
13. The quantity of electricity needed to deposit 127.08 g of (a) 4.6 (b) 5.6
copper is (c) 6.6 (d) 7.6
(a) 1 Faraday (b) 4 Coulombs 24. Specific conductance of 0.1 M sodium chloride solution is
(c) 4 Faraday (d) 1 Ampere 1.06 × 10 –2 ohm –1 cm –1 . Its molar conductance in
14. Silver is monovalent and has atomic mass of 108. Copper is ohm–1 cm2 mol–1 is
divalent and has an atomic mass of 63.6. The same electric (a) 1.06 × 102 (b) 1.06 × 103
current is passed for the same length of time through a (c) 1.06 × 10 4 (d) 5.3 × 102
silver coulometer and a copper coulometer. If 27.0 g of silver 25. Molar conductivity of a solution is 1.26 × 102 W–1 cm2 mol–1.
is deposited, then the corresponding amount of copper Its molarity is 0.01. Its specific conductivity will be
deposited is (a) 1.26 × 10–5 (b) 1.26 × 10–3
(a) 63.60 g (b) 31.80 g (c) 1.26 × 10 –4 (d) 0.0063
(c) 15.90 g (d) 7.95 g
26. Molar ionic conductivities of a two-bivalent electrolytes
15. By passing 0.1 Faraday of electricity through fused sodium
chloride, the amount of chlorine liberated is x 2+ and y 2- are 57 and 73 respectively. The molar
(a) 35.45 g (b) 70.9 g conductivity of the solution formed by them will be
(c) 3.545 g (d) 17.77 g (a) 130 S cm2 mol–1 (b) 65 S cm2 mol–1
16. The unit of specific conductivity is 2 –1
(c) 260 S cm mol (d) 187 S cm2 mol–1
(a) ohm cm–1 (b) ohm cm–2
27. The equivalent conductivity of 0.1 M weak acid is 100 times
(c) ohm–1 cm (d) ohm–1 cm–1
less than that at infinite dilution. The degree of dissociation
17. The cell constant of a given cell is 0.47 cm–1. The resistance
of a solution placed in this cell is measured to be 31.6 ohm. of weak acid will be
The conductivity of the solution (in S cm–1 where S has (a) 100 (b) 10
usual meaning) is (c) 0.01 (d) 0.001
(a) 0.15 (b) 1.5 28. An electrochemical cell is set up as follows :
(c) 0.015 (d) 150 Pt (H2, 1 atm)/0.1 M HCl/0.1 M acetic acid/(H2, 1 atm) Pt
18. The specific conductivity of N/10 KCl solution at 20°C is EMF of this cell will not be zero because
0.212 ohm–1 cm–1 and the resistance of the cell containing (a) the temperature is constant
this solution at 20°C is 55 ohm. The cell constant is (b) the pH of 0.1 M HCl and 0.1 M acetic acid is not the
(a) 4.616 cm–1 (b) 11.66 cm–1 same
(c) 2.173 cm–1 (d) 3.324 cm–1 (c) acids used in the two compartments are different
19. The resistance of 1 N solution of acetic acid is 250 ohm, (d) EMF of a cell depends on molarities of the acids used
when measured in a cell of cell constant 1.15 cm–1. The 29. Which one of the following reaction occurs at the cathode?
equivalent conductance (in ohm–1 cm2 equiv–1) of 1 N acetic
(a) 2OH - ¾ ¾® H 2 O + O + 2e -
acid will be
(a) 4.6 (b) 9.2 ¾® Ag + + e -
(b) Ag ¾
(c) 18.4 (d) 0.023
(c) Fe 2 + ¾
¾® Fe 3+ + e -
20. The equivalent conductance at infinite dilution of a weak
acid such as HF (d) Cu 2 + + 2e - ¾
¾® Cu
(a) can be determined by extrapolation of measurements of 30. Which of the following statements is true for an
dilute solutions of HCl, HBr and HI electrochemical cell?
(b) can be determined by measurement of very dilute HF
(a) Reduction occurs at H2 electrode
solutions
(b) H2 is cathode and Cu is anode
(c) can be determined from measurements of dilute
solutions of NaF, NaCl and HCl (c) H2 is anode and Cu is cathode
(d) is an undefined quantity (d) Oxidation occurs at Cu electrode
JEEMAIN.GURU
downloaded from jeemain.guru
574 Chemistry
31. On the basis of the information available from the reaction 39. The standard electrode potential (E°) for OCl– /Cl– and
1
Cl - / Cl 2 respectively are 0.94 V and –1.36 V. The E° value
4 2
Al + O 2 ¾¾® Al 2 O 3 , D G = - 827 kJmol - 1 of O , the
3 3 2 2
minimum e.m.f. required to carry out electrolysis of Al2O3 is 1
(F = 96500 C mol–1) for OCl - / Cl 2 will be
2
(a) 4.28 V (b) 6.42 V (a) –0.42 V (b) –2.20 V
(c) 8.56 V (d) 2.14 V (c) 0.52 V (d) 1.04 V
32. In the electrochemical reaction 40. The standard reduction potential for Fe 2+ / Fe and
Sn2+/ Sn electrodes are –0.44 and –0.14 volt respectively.
2Fe3+ + Zn ¾ ¾® Zn 2+ + 2Fe 2+ , For the cell reaction
on increasing the concentration of Fe2+
(a) increases cell emf Fe 2+ + Sn ¾
¾® Fe + Sn 2+
(b) increases the current flow the standard emf will be
(a) +0.30 V (b) –0.58 V
(c) decreases the cell emf
(c) +0.58 V (d) –0.30 V
(d) alters the pH of the solution
41. The emf of the cell
33. In the cell reaction
Ni / Ni 2+ (1.0 M ) | | Au 3+ (1.0 M) / Au is [E° for Ni2+ / Ni = –
+ 2+
Cu(s) + 2Ag (aq) ¾¾
® Cu (aq) + 2Ag(s) , 0.25 V; E° for Au3+ / Au = 1.5 V]
Eo 0.46 V. By doubling the concentration of Cu2+, Eocell (a) +1.25 V (b) +1.75 V
cell =
will become (c) –1.25 V (d) –1.75 V
(a) doubled 42. An unknown metal M displaces nickel from nickel (II)
sulphate solution but does not displace manganese from
(b) halved
manganese sulphate solution. Which order represents the
(c) increases but less than double
correct order of reducing power?
(d) decreases by a small fraction (a) Mn > Ni > M (b) Ni > Mn > M
34. If salt bridge is removed from two half-cells the voltage (c) Mn > M > Ni (d) M > Ni > Mn
(a) drops to zero (b) does not change 43. Electrode potentials (E° red ) of four elements A, B, C, D are
(c) increases gradually (d) increases rapidly
–1.36, –0.32, 0, –1.26 V respectively. The decreasing reactivity
35. In a salt bridge KCl is used because order of these elements is
(a) it is an electrolyte (a) A, D, B and C (b) C, B, D and A
(b) it is good conductor of electricity (c) B, D, C and A (d) C, A, D and B
(c) the transport number of K+ and Cl– ions are nearly same 44. Chlorine cannot displace
or both have same ionic mobility (a) Fluorine from NaF (b) Iodine from NaI
(d) it is ionic compound (c) Bromine from NaBr (d) None of these
36. The reference electrode is made by using 45. Standard potentials (E°) for some half-reactions are given
(a) ZnCl2 (b) CuSO4 below :
(c) HgCl2 (d) Hg2Cl2 (I) Sn 4 + + 2e ¾¾
® Sn 2 + ; E° = +0.15V
37. The standard hydrogen electrode potential is zero, because
(a) there is no potential difference between the electrode (II) 2Hg 2 + + 2e ¾
¾® Hg 22+ ; E° = 0.92 V
and the solution
(III) PbO 2 + 4H + + 2e ¾
¾® Pb 2+ + 2 H 2 O;
(b) hydrogen ions acquire electrons from a platinum
electrode E° = +1.45V
(c) it has been measured accurately based on the above, information which one of the following
(d) it has been defined that way statements is correct?
38. The standard reduction potentials E° for the half reactions (a) Sn4+ is a stronger oxidising agent than Pb4+
are as (b) Sn2+ is a stronger reducing agent than Hg22+
(c) Pb2+ is a stronger oxidising agent than Pb4+
¾® Zn 2+ + 2e - ; E° = 0.76 V
Zn ¾ (d) Pb2+ is a stronger reducing agent than Sn2+
46. The oxidation potentails of A and B are +2.37 and +1.66 V
¾® Fe 2+ + 2e - ; E° = 0.41V
Fe ¾ respectively. In chemical reactions
(a) A will be replaced by B
The EMF for the cell reaction will be
(b) A will replace B
(a) –0.3 V (b) 0.35 V
(c) A will not replace B
(c) 1.17 V (d) –1.17 V (d) A and B will not replace each other
JEEMAIN.GURU
downloaded from jeemain.guru
Electrochemistry 575
47. Electrode potential data are given below : 53. The e.m.f. of a Daniell cell at 298 K is E1
Fe +3 (aq) + e - ¾¾
® Fe +2 (aq); E° = +0.77 V ZnSO 4 CuSO 4
Zn Cu
(0.01M) (1.0 M)
3+ -
Al (aq) + 3e ¾¾
® Al (s) ; E° = – 1.66 V
When the concentration of ZnSO4 is 1.0 M and that of CuSO4
Br2 (aq) + 2e - ¾¾
® 2Br - (aq); E° = + 1.08V
is 0.01 M, the e.m.f. changed to E2. What is the relationship
between E1 and E2?
Based on the data, the reducing power of Fe2+, Al and Br–
(a) E1 < E2 (b) E1 = E2
will increase in the order
(c) E2 = 0 ¹ E1 (d) E1 > E2
(a) Br– < Fe2+ < Al (b) Fe2+ < Al < Br–
54. The metal that cannot displace hydrogen from dilute
(c) Al < Br– < Fe2+ (d) Al < Fe2+ < Br–
hydrochloric acid is
48. Choose the correct statement from the following which is
related to the electrochemical series (a) aluminium (b) Iron
(a) Electrochemical series is not the arrangement of metals (c) copper (d) zinc
and ions according to their reactivity 55. Which reaction is not feasible?
(b) The metal ions at the top of the electrochemical series (a) 2 KI + Br2 ¾
¾® 2KBr + I 2
are highly electronegative
(c) Strongly electropositive metals can displace weakly (b) 2 KBr + I 2 ¾
¾® 2KI + Br2
electropositive metals from their salt solution
(d) All metals above hydrogen in the series do not displace (c) 2KBr + Cl 2 ¾
¾® 2KCl + Br2
hydrogen from dilute acids
49. The standard reduction potentials of four elements are given (d) 2H 2 O + 2F2 ¾
¾® 4HF + O 2
below. Which of the following will be the most suitable
reducing agent? 56. Which of the following will form a cell with the highest
I = –3.04 V II = – 1.90 V voltage?
III = 0 V IV = 1.90 V (a) 1 M Ag + ,1 M Co 2+ (b) 2 M Ag + , 2 M Co 2+
(a) III (b) II
(c) I (d) IV (c) 0.1 M Ag + , 2 M Co 2+ (d) 2 M Ag + , 0.1 M Co 2+
50. The standard reduction potentials at 298K for the following
half reactions are given against each 57. E° of a cell aA + bB ¾
¾® cC + dD is
Fe3+ (aq) + e Fe2+ (aq) ; 0.770 V 58. The standard EMF for the cell reaction,
JEEMAIN.GURU
downloaded from jeemain.guru
576 Chemistry
61. For the cell reaction, 70. Which of the following reaction occurs at the cathode during
the charging of lead storage battery?
® Zn ( C 2 ) + Cu ( s )
2+
Cu 2+ [C1 (aq)] + Zn(s) ¾¾
(a) Pb 2+ + 2e - ¾
¾® Pb
of an electrochemical cell, the change in free energy, DG at a
given temperature is a function of (b) Pb 2 + + SO 24 - ¾
¾® PbSO 4
æ C2 ö ¾® Pb 2+ + 2e -
(c) Pb ¾
(a) ln (C1) (b) ln çç C ÷÷
è 1ø ¾® 2PbO 2 + 4H + + SO 24- + 2e -
(d) PbSO 4 + 2H 2 O ¾
(c) ln (C1 + C2) (d) ln (C2) 71. Reaction that takes place at graphite anode in dry cell is
62. The relationship between standard reduction potential of a (a) Zn 2 + + 2e - ¾¾
® Zn(s)
cell and equilibrium constant is shown by
® Zn 2 + + 2e -
(b) Zn(s) ¾¾
n 0.059
(a) E ocell = log k c
o
(b) E cell = log k c (c) Mn 2 + + 2e - ¾¾
0.059 n ® Mn(s)
log k c ® Mn + + e - + 1.5V
(d) Mn(s) ¾¾
(c) E ocell = 0.059 n log k c (d) E cell =
o
n 72. Which one of the following cells can convert chemical energy
63. E° for the cell, of H2 and O2 directly into electrical energy?
(a) Mercury cell (b) Daniell cell
Zn | Zn 2+ (aq) | | Cu 2+ (aq)| Cu is 1.10 V at 25°C. The (c) Fuel cell (d) Lead storage cell
equilibrium constant for the cell reaction 73. Hydrogen-Oxygen fuel cells are used in space craft to supply
(a) power for heat and light (b) power for pressure
Zn + Cu 2+ (aq) Cu + Zn 2+ (aq) (c) oxygen (d) water
is of the order of 74. As lead storage battery is charged
(a) 10–37 (b) 1037 (a) lead dioxide dissolves
(c) 10 –17 (d) 1017 (b) sulphuric acid is regenerated
64. The standard EMF of Daniell cell is 1.10 volt. The maximum (c) lead electrode becomes coated with lead sulphate
electrical work obtained from the Daniell cell is (d) the concentration of sulphuric acid decreases
(a) 212.3 kJ (b) 175.4 kJ 75. The thermodynamic efficiency of cell is given by
(c) 106.15 kJ (d) 53.07 kJ (a) DH/DG (b) nFE/DG
65. The emf of Daniell cell is 1.1 volt. If the value of Faraday is (c) nFE/DH (d) nFE
96500 coulombs per mole, the change in free energy in kJ is 76. The electroplating with chromium is undertaken because
(a) 212.30 (b) –212.30 (a) electrolysis of chromium is easier
(c) 106.15 (d) –106.15 (b) chromium can form alloys with other metals
66. Pure water does not conduct electricity because it (c) chromium gives protective and decorative coating to
the base metal
(a) has low boiling point (b) is almost unionised
(d) of the high reactivity of metallic chormium
(c) is neutral (d) is readily decomposed
77. Prevention of corrosion of iron by Zn coating is called
67. At cathode, the electrolysis of aqueous Na2SO4 gives
(a) galvanization (b) cathodic protection
(a) Na (b) H2
(c) electrolysis (d) photoelectrolysis
(c) SO3 (d) SO2
78. Which of the following statements is correct?
68. At anode in the electrolysis of fused NaCl
(a) Oxidation number of oxygen in KO2 is +1
(a) Na+ is oxidized (b) Cl– is oxidized (b) The specific conductance of an electrolyte solution
(c) Cl is reduced (d) Na is reduced decreases with increase in dilution
69. In electrolysis of NaCl when Pt electrode is taken then H2 is (c) Sn2+ oxidises Fe3+
liberated at cathode while with Hg cathode, it forms sodium (d) Zn/ZnSO4 is a reference electrode
amalgam 79. In the electrolytic cell, flow of electrons is from
(a) Hg is more inert than Pt (a) cathode to anode in solution
(b) More voltage is required to reduce H+ at Hg than at Pt (b) cathode to anode through external supply
(c) Na is dissolved in Hg while it does not dissolve in Pt (c) cathode to anode through internal supply
(d) Conc. of H+ ions is larger when Pt electrode is taken (d) anode to cathode through internal supply
JEEMAIN.GURU
downloaded from jeemain.guru
Electrochemistry 577
1. Zn gives H2 gas with H2SO4 and HCl but not with HNO3 M
because [CBSE-PMT 2002] 9. The equivalent conductance of solution of a weak
32
(a) Zn acts as an oxidising agent when it reacts with HNO3 2
monobasic acid is 8.0 mho cm and at infinite dilution is 400
(b) HNO3 is weaker acid than H2SO4 and HCl mho cm2. The dissociation constant of this acid is:
(c) in electrochemical series, Zn is above hydrogen
[CBSE-PMT 2009]
(d) NO3– is reduced in preference to hydronium ion
(a) 1.25 × 10–6 (b) 6.25 × 10–4
2. The efficiency of a fuel cell is given by [CBSE-PMT 2007]
(c) 1.25 × 10–4 (d) 1.25 × 10–5
DG DS DH
(a) DG (b) (c) (d) 10. For the reduction of silver ions with copper metal, the standard
DS D H DG DG cell potential was found to be + 0.46 V at 25°C.
3. The equilibrium constant of the reaction: The value of standard Gibbs energy, D G° will be
Cu( s) + 2Ag+ (aq)
Cu 2+ (aq) + 2Ag( s) ;
(F = 96500 C mol –1 ) [CBSE-PMT 2010]
E° = 0.46 V at 298 K is [CBSE-PMT 2007]
(a) – 89.0 kJ (b) – 89.0 J (c) – 44.5 kJ (d) – 98.0 kJ
(a) 2.0 × 1010 (b) 4.0 × 1010 (c) 4.0 × 1015 (d) 2.4 × 1010
4. On the basis of the following E° values, the strongest oxidizing 11. An increase in equivalent conductance of a strong electrolyte
agent is : [CBSE-PMT 2008] with dilution is mainly due to: [CBSE-PMT 2010]
[Fe(CN)6]4– ® [Fe(CN)6]3– + e– ; E° = – 0.35 V (a) increase in ionic mobility of ions
Fe2+ ® Fe3+ + e–; E° = – 0.77 V (b) 100% ionisation of electrolyte at normal dilution
(a) [Fe(CN)6]4– (b) Fe2+ (c) increase in both i.e. number of ions and ionic mobility of
(c) Fe3+ (d) [Fe(CN)6]3– ions
5. Kohlrausch’s law states that at : [CBSE-PMT 2008] (d) increase in number of ions
(a) finite dilution, each ion makes definite contribution to 12. Which of the following expressions correctly represents the
equivalent conductance of an electrolyte, whatever be equivalent conductance at infinite dilution of Al2(SO4)3,
the nature of the other ion of the electrolyte.
° 2-
(b) infinite dilution each ion makes definite contribution to Given that L °Al3+ and LSO are the equivalent
4
equivalent conductance of an electrolyte depending on
the nature of the other ion of the electrolyte. conductances at infinite dilution of the respective ions?
(c) infinite dilution, each ion makes definite contribution to [CBSE-PMT 2010]
conductance of an electrolyte whatever be the nature of
(b) 2L°Al3+ + 3LSO
° 2-
1 ° 1
the other ion of the electrolyte. (a) L 3+ + L° 2-
3 Al 2 SO4 4
(d) infinite dilution, each ion makes definite contribution to
æ ° 2- ö ´ 6
equivalent conductance of an electrolyte, whatever be (c) L°Al3+ + LSO
° 2- (d) èL °Al3+ + LSO
4 4 ø
the nature of the other ion of the electrolyte.
6. Standard free energies of formation (in kJ/mol) at 298 K are 13. Consider the following relations for emf of a electrochemical
– 237.2, – 394.4 and – 8.2 for H2O(l), CO2(g) and pentane (g), cell: [CBSE-PMT 2010]
respectively. The value E°cell for the pentane-oxygen fuel cell (i) emf of cell = (Oxidation potential of anode) –
is : [CBSE-PMT 2008] (Reduction potential of cathode)
(a) 1.968 V (b) 2.0968 V (c) 1.0968 V (d) 0.0968 V (ii) emf of cell = (Oxidation potential of anode) + (Reduction
7. Given: [CBSE-PMT 2009] potential of cathode)
(i) Cu2+ + 2e– ® Cu, Eo = 0.337 V (iii) emf of cell = (Reduction potential of anode) + (Reduction
(ii) Cu2+ + e– ® Cu+, Eo = 0.153 V potential of cathode)
Electrode potential, Eo for the reaction, (iv) emf of cell = (Oxidation potential of anode) – (Oxidation
Cu + + e– ® Cu, will be : potential of cathode)
(a) 0.90 V (b) 0.30 V (c) 0.38 V (d) 0.52 V
Which of the above relations are correct?
8. Al2O3 is reduced by electrolysis at low potentials and high
currents. If 4.0 × 104 amperes of current is passed through (a) (ii) and (iv) (b) (iii) and (i)
molten Al 2 O 3 for 6 hours, what mass of aluminium is (c) (i) and (ii) (d) (iii) and (iv)
produced? (Assume 100% current efficiency. At. mass of 14. Standard electrode potential of three metals X, Y and Z are
Al = 27 g mol–1) [CBSE-PMT 2009] – 1.2 V, + 0.5 V and – 3.0 V, respectively. The reducing power
(a) 8.1 × 104 g (b) 2.4 × 105 g of these metals will be : [CBSE-PMT 2011]
(c) 1.3 × 104 g (d) 9.0 × 103 g (a) Y > Z > X (b) X > Y > Z (c) Z > X > Y (d) X > Y > Z
JEEMAIN.GURU
downloaded from jeemain.guru
578 Chemistry
15. The electrode potentials for [CBSE-PMT 2011] 23. At 25°C molar conductance of 0.1 molar aqueous solution
Cu2+(aq) + e– ¾¾ ® Cu+(aq) of ammonium hydroxide is 9.54 ohm-1 cm2mol-1 and at
and Cu+(aq) + e– ¾¾ ® Cu(s) infinite dilution its molar conductance is 238 ohm-1cm2 mol-1.
are + 0.15 V and + 0.50, respectively. The value of The degree or ionisation of ammonium hydroxide at the
E°Cu 2+ / Cu will be : same concentration and temperature is : [NEET 2013]
(a) 20.800% (b) 4.008%
(a) 0.500 V (b) 0.325 V (c) 0.650 V (d) 0.150 V
(c) 40.800% (d) 2.080%
16. Standard electrode potential for Sn4+ / Sn2+ couple is + 0.15 V
24. A button cell used in watches functions as following
and that for the Cr3+ / Cr couple is – 0.74 V. These two couples
in their standard state are connected to make a cell. The cell Zn(s) + Ag2O(s) + H2O(l)
potential will be : [CBSE-PMT 2011] 2Ag(s) + Zn2+(aq) + 2OH–(aq)
(a) + 1.19 V (b) + 0.89 V (c) + 0.18 V (d) + 1.83 V If half cell potentials are :
17. If the E°cell for a given reaction has a negative value, then Zn2+(aq) + 2e– ® Zn(s); Eo = – 0.76 V
which of the following gives the correct relationships for the Ag 2 O(s) + H 2 O (l) + 2e – ® 2Ag(s) + 2OH – (aq);
values of DG° and Keq ? [CBSE-PMT 2011] Eo = 0.34 V
(a) DG° > 0 ; Keq > 1 (b) DG° < 0 ; Keq > 1 The cell potential will be : [NEET 2013]
(c) DG° < 0 ; Keq < 1 (d) DG° > 0 ; Keq < 1 (a) 0.42 V (b) 0.84 V
18. A solution contains Fe2+, Fe3+ and I– ions. This solution (c) 1.34 V (d) 1.10 V
was treated with iodine at 35°C. E° for Fe3+ / Fe2+ is + 0.77 V 25. Conductivity (unit Siemen’s S) is directly proportional to
and E° for I2/2I– = 0.536 V. The favourable redox reaction is : area of the vessel and the concentration of the solution in it
(a) I2 will be reduced to I– [CBSE-PMT 2011 M] and is inversely proportional to the length of the vessel
(b) There will be no redox reaction then the unit of the constant of proportionality is
(c) I– will be oxidised to I2 [AIEEE 2002]
(d) Fe2+ will be oxidised to Fe3+ (a) Sm mol–1 (b) Sm2 mol–1
19. Limiting molar conductivity of NH4OH [CBSE-PMT 2012 S] (c) S–2m2 mol (d) S2m2 mol–2.
(i.e., L° ) is equal to :
26. EMF of a cell in terms of reduction potential of its left and
m(NH4OH right electrodes is [AIEEE 2002]
(a) E = Eleft - Eright (b) E = Eleft + Eright
(a) L°m( NH Cl) + L°m( NaCl) -L°m NaOH (c) E = Eright - Eleft (d) E = -(Eright + Eleft).
4 ( )
27. If f denotes reduction potential, then which is true?
(b) L°m( NaOH ) + L°m( NaCl) -L°m( NH Cl) [AIEEE 2002]
4
(a) E°cell = f right – f left (b) E°cell = f left + f right
(c) L°m( NH 4OH ) + L °m( NH 4Cl) -L°m( HCl)
(c) E°cell = f left – f right (d) E°cell = – ( f left + f right).
(d) L°m( NH 4Cl) + L°m( NaOH)-L°m( NaCl) 28. What will be the emf for the given cell
Pt | H2 (P1) | H+ (aq) | | H2 (P2) | Pt [AIEEE 2002]
20. Standard reduction potentials of the half reactions are given P P
RT RT
below : [CBSE-PMT 2012 M] (a) log 1 (b) log 1
F2(g) + 2e– ® 2F– (aq); E° = + 2.85 V f P2 2f P2
Cl2(g) + 2e– ® 2Cl–(aq); E° = + 1.36 V RT P
Br2(l) + 2e– ® 2Br–(aq); E° = + 1.06 V (c) log 2 (d) None of these.
f P1
I2(s) + 2e– ® 2I–(aq); E° = + 0.53 V
The strongest oxidising and reducing agents respectively 29. Which of the following reaction is possible at anode?
are : [AIEEE 2002]
(a) F2 and I– (b) Br2 and Cl– (a) 2 Cr3+ + 7H2O ® Cr2O72– + 14H+
(c) Cl2 and Br – (d) Cl2 and I2 (b) F2 ® 2F –
21. Molar conductivities ( L° m ) at infinite dilution of NaCl, HCl (c) (1/2) O2 + 2H+ ® H2O
and CH3COONa are 126.4, 425.9 and 91.0 S cm2 mol–1 (d) None of these.
respectively. L°m for CH3COOH will be : 30. For a cell reaction involving a two-electron change, the
[CBSE-PMT 2012 M] standard e.m.f. of the cell is found to be 0.295 V at 25ºC. The
(a) 425.5 S cm2 mol–1 (b) 180.5 S cm2 mol–1 equilibrium constant of the reaction at 25ºC will be
(c) 290.8 S cm2 mol–1 (d) 390.5 S cm2 mol–1 (a) 29.5 × 10–2 (b) 10 [AIEEE 2003]
22. A hydrogen gas electrode is made by dipping platinum (c) 1 × 1010 (d) 1 × 10–10
wire in a solution of HCl of pH = 10 and by passing hydrogen 31. Standard reduction electrode potentials of three metals A, B
gas around the platinum wire at one atm pressure. The & C are respectively + 0.5 V, – 3.0 V & –1.2 V. The reducing
oxidation potential of electrode would be ? [NEET 2013] powers of these metals are [AIEEE 2003]
(a) 0.59 V (b) 0.118 V (a) A > B > C (b) C > B > A
(c) 1.18 V (d) 0.059 V (c) A > C > B (d) B > C > A
JEEMAIN.GURU
downloaded from jeemain.guru
Electrochemistry 579
32. When during electrolysis of a solution of AgNO3 9650 41. Aluminium oxide may be electrolysed at 1000°C
coulombs of charge pass through the electroplating bath, to furnish aluminium metal (At. Mass = 27 amu; 1 Faraday =
the mass of silver deposited on the cathode will be 96,500 Coulombs). The cathode reaction is–
(a) 10.8 g (b) 21.6 g [AIEEE 2003]
(c) 108 g (d) 1.08 g Al3+ + 3e- ® Al
33. For the redox reaction : [AIEEE 2003] To prepare 5.12 kg of aluminium metal by this method we
Zn(s) + Cu 2+ (0.1 M) ® Zn 2+ (1 M) + Cu (s) require [AIEEE 2005]
º
taking place in a cell, E cell is 1.10 volt. Ecell for the cell will (a) 5.49 × 101 C of electricity
4
(b) 5.49 × 10 C of electricity
be æç 2.303 RT = 0.0591 ö÷
è F ø 7
(c) 1.83 × 10 C of electricity
(a) 1.80 volt (b) 1.07 volt
(c) 0.82 volt (d) 2.14 volt (d) 5.49 × 10 7 C of electricity
34. Several blocks of magnesium are fixed to the bottom of a
ship to [AIEEE 2003] Electrolyte: KCl KNO3 HCl NaOAc NaCl
42.
(a) make the ship lighter 2
^¥ (S cm mol ) : 149.9
–1
145 426.2 91 126.5
(b) prevent action of water and salt
(c) prevent puncturing by under-sea rocks Calculate L ¥
HOAC using appropriate molar conductances
(d) keep away the sharks
35. In a hydrogen-oxygen fuel cell, combustion of hydrogen of the electrolytes listed above at infinite dilution in H 2 O
occurs to [AIEEE 2004] at 25°C [AIEEE 2005]
(a) produce high purity water (a) 217.5 (b) 390.7
(b) create potential difference between two electrodes
(c) 552.7 (d) 517.2
(c) generte heat
o o
(d) remove adsorbed oxygen from electron surfaces 43. The molar conductivities L NaOAc and L HCl at infinite
36. Consider the following Eº values [AIEEE 2004]
dilution in water at 25ºC are 91.0 and 426.2 S cm2/mol
Eº = +0.77V ; E º Sn 2+ / Sn = -0.14V o
Fe3+ /Fe2 + respectively. To calculate L HOAc , the additional value
Under standard conditions the potential for the reaction required is [AIEEE 2006]
Sn (s) + 2Fe3+ (aq) ® 2Fe 2+ (aq) + Sn 2+ (aq) is o o
(a) L NaOH (b) L NaCl
(a) 0.91 V (b) 1.40 V
o o
(c) 1.68 V (d) 0.63 V (c) LH (d) L KCl
2O
37. The standard e.m.f. of a cell involving one electron change
is found to be 0.591 V at 25ºC. The equilibrium constant of 44. Resistance of a conductivity cell filled with a solution of an
the reaction will be electrolyte of concentration 0.1 M is 100 W. The conductivity
(F = 96,500 C mol–1; R = 8.314 JK–1 mol–1) [AIEEE 2004] of this solution is 1.29 S m–1. Resistance of the same cell
(a) 1.0 × 1010 (b) 1.0 × 105 when filled with 0.2 M of the same solution is 520 W. The
(c) 1.0 × 101 (d) 1.0 × 1030 molar conductivity of 0.02 M solution of electrolyte will be
38. The limiting molar conductivities L º for NaCl, KBr and KCl [AIEEE 2006]
are 126, 152 and 150 S cm2 mol–1 respectively. The L º for (a) 1.24 × 10–4 S m2 mol–1 (b) 12.4 × 10–4 S m2 mol–1
NaBr is [AIEEE 2004] (c) 124 × 10–4 S m2 mol–1 (d) 1240 × 10–4 S m2 mol–1
(a) 278 S cm2 mol–1 (b) 176 S cm2 mol–1 45. The equivalent conductances of two strong electrolytes at
(c) 128 S cm2 mol–1 (d) 302 S cm2 mol–1 infinite dilution in H2O (where ions move freely through a
39. The E º values for Cr, Mn, Fe and Co are – 0.41, + solution) at 25°C are given below : [AIEEE 2007]
M 3+ / M 2 +
1.57, + 0.77 and + 1.97V respectively. For which one of these LoCH3COONa = 91.0 S cm2 / equiv.
metals the change in oxidation state from +2 to +3 is easiest?
L o HCl = 426.2 S cm 2 / equiv.
(a) Fe (b) Mn [AIEEE 2004]
(c) Cr (d) Co What additional information/ quantity one needs to calcu-
40. The highest electrical conductivity of the following aqueous late L o of an aqueous solution of acetic acid?
solutions is of [AIEEE 2005] (a) L o of chloroacetic acid (ClCH2COOH)
(a) 0.1 M difluoroacetic acid
(b) L o of NaCl
(b) 0.1 M fluoroacetic acid
(c) 0.1 M chloroacetic acid (c) L o of CH3COOK
(d) 0.1 M acetic acid (d) the limiting equivalent coductance of H + (l° ).
H+
JEEMAIN.GURU
downloaded from jeemain.guru
580 Chemistry
54. Resistance of 0.2 M solution of an electrolyte is 50 W. The
46. The cell, Zn | Zn 2+ (1 M) || Cu 2+ (1 M) | Cu ( E °cell = 1.10 v)
specific conductance of the solution is 1.3 S m–1. If resistance
was allowed to be completely discharged at 298 K. The of the 0.4 M solution of the same electrolyte is 260 W, its molar
æ [Zn 2+ ] ö conductivity is : [AIEEE 2011RS]
relative concentration of Zn2+ to Cu2+ çç 2+ ÷
÷ is (a) 6.25 × 10–4 S m2 mol–1 (b) 625 × 10–4 S m2 mol–1
è [Cu ] ø (c) 62.5 S m2 mol–1 (d) 6250 S m2 mol–1
[AIEEE 2007] 55. The standard reduction potentials for Zn 2+ /Zn,
(a) 9.65 × 104 (b) antilog (24.08) Ni2+/Ni and Fe2+/Fe are –0.76,–0.23 and –0.44 V respectively.
(c) 37.3 (d) 1037.3. The reaction X + Y 2 + ¾¾ ® X 2+ + Y will be spontaneous
47. Given Eº = –0.72 V, Eº 2+ = – 0.42 V. The when : [AIEEE 2012]
Cr 3+ / Cr Fe / Fe (a) X = Ni, Y = Fe (b) X = Ni, Y = Zn
potential for the cell (c) X= Fe, Y = Zn (d) X= Zn, Y = Ni
Cr|Cr3+ (0.1M)|| Fe2 + (0.01 M)| Fe is [AIEEE 2008]
(a) 0.26 V (b) 0.336 V (c) – 0.339 (d) 0.26 V 56. Given : E° 3+ = -0.74 V; E° - = 1.51 V
Cr / Cr MnO4 / Mn 2 +
48. In a fuel cell methanol is used as fuel and oxygen gas is used
as an oxidizer. The reaction is E° 2- 3+ = 1.33 V; E° - = 1.36 V
Cr2O7 / Cr Cl / Cl
CH 3OH(l ) + 3/2O 2 (g) ¾¾ ® CO 2 (g) + 2H 2 O(l ) Based on the data given above, strongest oxidising agent
At 298 K standard Gibb’s energies of formation for CH3OH(l), will be : [JEE M 2013]
H2O(l) and and CO2 (g) are –166.2 –237.2 and –394.4 kJ mol–1 (a) Cl (b) Cr3+
respectively. If standard enthalpy of combustion of methonal (c) Mn2+ (d) MnO4 –
is – 726 kJ mol–1, efficiency of the fuel cell will be: 57. Four successive members of the first row transition elements
[AIEEE 2009] are listed below with atomic numbers. Which one of them is
(a) 87% (b) 90% (c) 97% (d) 80% expected to have the highest E° 3+ 2+ value ?
49. Given: M /M
[JEE M 2013]
E° 3+ = –0.036V, (a) Cr(Z = 24) (b) Mn(Z = 25)
Fe / Fe
(c) Fe(Z = 26) (d) Co(Z = 27)
E° = –0.439V
Fe2+ / Fe 58. Electrolysis of dilute aqueous NaCl solution was carried out
The value of standard electrode potential for the change, by passing 10 milli ampere current. The time required to liber-
ate 0.01 mol of H2 gas at the cathode is (1 Faraday = 96500
Fe3+ ( aq ) + e – ¾¾
® Fe 2+ ( aq ) will be: [AIEEE 2009]
C mol–1)
(a) 0.385 V (b) 0.770 V (c) –0.270 V (d) –0.072 V [IIT-JEE 2008S]
50. The Gibbs energy for the decomposition of Al2O3 at 500°C is (a) 9.65 × 104 sec (b) 19.3 × 104 sec
as follows : (c) 28.95 × 104 sec (d) 38.6 × 104 sec
2 4 59. AgNO3(aq.) was added to an aqueous KCl solution gradually
Al2 O3 ® Al + O2 , D r G = + 966 kJ mol -1 and the conductivity of the solution was measured. The plot
3 3
The potential difference needed for electrolytic reduction of of conductance ( L ) versus the volume of AgNO3 is
Al2O3 at 500°C is at least [AIEEE 2010] [IIT-JEE 2011]
(a) 4.5 V (b) 3.0 V
(c) 2.5 V (d) 5.0 V
51. The correct order of E ° 2+ values with negative sign for
M /M
the four successive elements Cr, Mn, Fe and Co is
[AIEEE 2010]
(a) Mn > Cr > Fe > Co (b) Cr < Fe > Mn > Co
(c) Fe > Mn > Cr > Co (d) Cr > Mn > Fe > Co
52. The reduction potential of hydrogen half-cell will be negative
if : [AIEEE 2011]
(a) p(H2) = 1 atm and [H+] = 2.0 M
(b) p(H2) = 1 atm and [H+] = 1.0 M
(c) p(H2) = 2 atm and [H+] = 1.0 M
(d) p(H2) = 2 atm and [H+] = 2.0 M
53. Consider the following cell reaction: [AIEEE 2011]
2Fe( s) + O2 ( g) + 4H+ (aq) ® 2Fe2+ (aq) + 2H2O(l);E° = 1.67V
At [Fe2+] = 10–3 M, p(O2) = 0.1 atm and pH = 3, the cell
potential at 25ºC is (a) (P) (b) (Q)
(a) 1.47 V (b) 1.77 V (c) 1.87 V (d) 1.57 V (c) (R) (d) (S)
JEEMAIN.GURU
downloaded from jeemain.guru
Electrochemistry 581
1. Which of the following solutions of KCl will have the highest 7. What is the reaction taking place at the anode when an
value of specific conductance? aqueous solution of copper sulphate is electrolysed using
(a) 1.0 N (b) 0.1 N Pt–electrodes (inert) ?
(c) 1.0 ×10–2N (d) 1.0 ×10–3N (a) Cu 2 + + 2e - ® Cu
2. Which of the following statements is not correct? (b) 2 H + + 2 e - ® H 2
(a) The equivalent conductance of an electrolyte increases
(c) 2H 2 O ® O 2 + 4H + + 4e -
on dilution.
(b) The equivalent conductance of an electrolyte decreases (d) 2SO 24 - ® S 2 O 82 - + 2e -
on dilution 8. The specific conductance at 298 K of AgCl is
(c) The degree of ionization of a weak electrolyte is given -1 -1
1.826 × 10–6 ohm cm . The ionic conductances of Ag+
by a = l c / l 0 , where l c and l 0 are equivalent
conductances at concentration c and zero respectively and Cl– are 61.92 and 76.34 respectively. What is the solubility
(d) In case of a weak electrolyte on dilution,, specific of AgCl in water ?
conductance decreases but its equivalent conductance (a) 1.1´10 -2 g -1 (b) 1.9 ´ 10 -3 g L-1
increases
3. Which of the following statements is wrong ? (c) 2.1´ 10 -5 g L-1 (d) 2.1´ 10 -6 g L-1
(a) Electrolysis of an aqueous sodium hydroxide solution 9. The potential of a hydrogen electrode at pH=10 is
liberates H2 gas at the cathode and O2 gas at the anode. (a) 0.59 V (b) zero volt
(b) Electrolysis of dil. H2SO4 liberates H2(g) at cathode (c) –0.59 V (d) 0.059 V
10. Equivalent conductance at infinite dilution, l° of NH4Cl,
and O2 (g) at the anode
NaOH and NaCl are 128.0, 217.8 and 109.3 ohm–1 cm2 eq–1
(c) DG°= nFE° for a spontaneous reaction
respectively. The equivalent conductance of 0.01 N NH4OH
0.059 is 9.30 ohm–1 cm2 eq–1, then the degree of ionization of
(d) E=E° - log Q , Where Q = reaction quotient.
n NH4OH at this temperature would be
4. In the electrolysis of CuCl2 solution, the mass of the cathode (a) 0.04 (b) 0.1
increased by 3.2g. What occured at the copper anode ? (c) 0.39 (d) 0.62
(a) 0.12 litre of Cl2 was liberated 11. What is the standard cell potential E° for an electrochemical
cell in which the following reaction takes place
(b) 0.56 litre of O2 was liberated spontaneously ?
(c) 0.1 mol Cu2+ passed into the solution.
Cl2 (g) + 2Br - ® Br2 (aq) + 2Cl- DG° = -50.6 kJ
(d) 0.05 mol of Cu2+ passed into the solution.
(a) 1.2 V (b) 0.53 V
5. Copper can be deposited from acidified copper sulphate (c) 0.26 V (d) –0.53 V
and alkaline copper cyanide both. If the same current is 12. When electric current is passed through acidified water, 112
passed for the definite time, which of the following is correct? ml of hydrogen gas at STP collected at the cathode in 965
(a) The amount of copper deposited from acidic copper seconds. The current passed in amperes is
sulphate will be higher (a) 1.0 (b) 0.5
(b) The amount of copper deposited from alkaline copper (c) 0.1 (d) 2.0
-
cyanide will be more. 13. If the half cell reaction is A + e ® A- has a large negative
(c) The same amount of Cu will be deposited reduction potential , it follows that.
(d) No Cu will be deposited (a) A is readily reduced (b) A is ready oxidised
6. The EMF of the cell Tl/Tl+ (0.001M) || Cu2+ (0.01M) /Cu is (c) A- is readily reduced (d) A- is readily oxidised
0.83. The cell EMF can be increased by 14. The electrochemical equivalent of silver is 0.001180 g. When
(a) Increasing the concentration of Tl+ ions. an electric current of 0.5 amp is passed through an aqueous
silver nitrate solution for 200 sec., the amount of silver
(b) Increasing the concentration of Cu2+ ions. deposited is
(c) Increasing the concentration of Tl + and Cu2+ ions. (a) 1.1180 g (b) 0.1180 g
(d) None of these (c) 5.590 g (d) 0.5598 g
JEEMAIN.GURU
downloaded from jeemain.guru
582 Chemistry
15. A gas X at 1 atm is bubbled through a solution containing a 21. The mathematical expression for law of independent
mixture of 1 M Y– and M Z– at 25°C. If the reduction potential migration of ions and Ostwald’s dilution law are given by
of Z > Y > X, then,
(a) Y will oxidize X and not Z (a) L = Lom - BC½ (b) L o = F( U + + U - )
(b) Y will oxidize Z and not X
(c) Y will oxidize both X and Z Lo 1 Lmc
(c) Lom = n+ l + + n- l- (d) L = o +
(d) Y will reduce both X and Z m L m K a (L om )2
16. For the electrochemical cell, M | M + || X - | X, 22. The variation of equivalent conductance of a weak electrolyte
o – with (concentration)½ is represented as
E o M + / M = 0.44V and E (X/X ) = 0.33V..
From this data one can deduce that
(a) M+X®M++X– is the spontaneous reaction
(b) M++X–®M+X is the spontaneous reaction (a) l (b) l
(c) Ecell = 0.77 V
(d) Ecell = - 0.77 V Öc Öc
17. Standard electrode potential data are useful for understanding
the suitability of an oxidant in a redox titration. Some half cell
reactions and their standard potentials are given below:
(c) l (d) l
MnO -4 (aq.) + 8H + (aq.) + 5e - ® Mn 2 + (aq.) + 4H 2 O(l)
Öc Öc
E° = 1.51 V
23. The ionic mobility of ions at infinite dilution is related to
Cr2 O 72 - (aq.) + 14H + (aq.) + 6e - ® 2Cr 3+ (aq.) + 7H 2 O(l) ionic conductance by
E° = 1.38 V (a) L o = Fk (b) L o F = U++U–
Fe3+ (aq.) + e - ® Fe2 + (aq.) E° = 0.77 V (c) L o = U++ U– (d) L o = F(U++ U–)
24. The variation of equivalent conductance of strong
Cl2 (g) + 2e- ® 2Cl- (aq.) E° = 1.40 V electrolyte with (concentration)½ is represented by
Identify the only incorrect statement regarding the
quantitative estimation of aqueous Fe(NO3)2
(a) MnO-4 can be used in aqueous HCl
(a) l (b) l
(b) Cr2O72 - can be used in aqueous HCl c c
JEEMAIN.GURU
downloaded from jeemain.guru
Electrochemistry 583
For the galvanic cell involving the above reactions. Which 34. Absolute ionic mobility is the speed of ion under the electric
of the following is not correct ? field of and its dimension
(a) Molar concentration of the cation in the cathodic
compartment changes faster than that of the cation in (a) 5 V across a distance of 5 cm, m 2 v -1s -1
the anodic compartment. -1 -1
(b) 10 V across a distance of 5 cm, mv s
2+
(b) E cell increase when Cd solution is diluted.
(c) 5 V across a distance of 10 cm, m 2 v - 2 s -1
(c) Twice as many electrons pass through the cadmium
electrode as through silver electrode. (d) None of these
35. Given the cell reactions
(d) E cell decreases when Ag + solution is diluted.
MX(s) + e - ¾¾
® M(s) + X - (aq), E ° = 0.207V
28. Conductance of 0.1 M KCl (conductivity = X Ohm-1cm -1 ) and M + (aq ) + e - ¾
¾® M (s ) , E° = 0.799 V
filled in a conductivity cell is Y Ohm-1 . If the conductance The solubility of MX (s) at 298 K is
-1
of 0.1 M NaOH filled in the same cell is Z Ohm-1 , the molar (a) 1. 10 -5 mol L-1 (b) 1.0 × 10 - 4 mol L
conductance of NaOH will be (c) 1.0 ´ 10 -10 mol L-1 (d) 1.0 ´ 10 -9 mol L-1
(a) 10 3 XZ (b) 10 4 XZ 36. Electrolysis is carried out in three cells
Y Y
(A) 1.0 M CuSO 4 Pt electrode
XZ XZ
(d) 10 (d) 0.1
Y Y (B) 1.0 M CuSO 4 copper electrodes
29. In electrolytic reduction of a nitroarene with 50% current (C) 1.0 M KCl Pt electrodes
efficiency 20.50 g of the compound is reduced by 2 × 96500 C If volume of electrolytic solution is maintained constant in
of electric charge. The molar mass of the compound is each of the cell, which is correct set of pH changes in (A), (B)
(a) 123.0 g (b) 61.5 g and (C) cell respectively ?
(c) 10.2 g (d) 20.5 g (a) decrease in all the three
30. On electrolysing K 2SO 4 solution using inert electrodes, (b) increase in all the three
(c) decrease, constant, increase
1.68 L (STP) of gases was obtained. How many moles of MnO -4
(d) increase, constant, increase
could be reduced to Mn 2 + by the same quantity of 37. The reversible reduction potential of pure water is – 0.414 V
electricity ? under 1 atm H 2 pressure. If the reduction is considered to
(a) 0.02 (b) 0.15
(c) 0.20 (d) 0.10 be 2 H + + 2e ¾
¾® H 2 . Calculate the [H+ ] of pure water
31. The standard reduction potential for Cu 2+ /Cu is + 0.34. (a) 1.02 ´ 10 -7 (b) 1.02 ´ 10 -9
Calculate the reduction potential at pH = 14 for the above
(c) 2.01 ´ 10 - 7 (d) 2.01 ´ 10 -9
couple. (Ksp Cu (OH) 2 = 1 × 10 -19 )
(a) – 0.22 V (b) + 0.22 V 38. 1. 0 L each of a buffer containing 1 mole NH 3 and 1 mol of
(c) – 0.44 V (d) + 0.44 V
NH +4 were placed in the cathodic and anodic half-cells and
32. A 1.0 M with respect to each of the metal halides AX 3 , BX 2 ,
965 C of electricity was passed. If anodic and cathodic half
CX 3 and DX 2 is electrolysed using platinum electrodes. If cells reactions involve oxidation and reduction of water only
E oA3+ / A = 1.50 V, E oB2 / B = 0.3 V, E Co 3+ / C = -0.74 V, as
E oD 2 / D = -2.37 V. The correct sequence in which the ¾® 4H + + O 2 - 4e - ;
2H 2 O ¾
various metals are deposited at the cathode is ¾® H 2 + 2OH -
2 H 2 O + 2e ¾
(a) A, B, C, D (d) A, B, C
Then pH of
(c) D, C, B, A (b) C, B, A
33. Electrolysis of NaCl solution with inert electrodes for certain (a) cathodic solution will increase
(b) anodic solution will decrease
period of time gave 600 cm 3 of 1.0 M NaOH in the electrolytic (c) both the solutions will remain practically constant
cell. During the same period 31.80 g of copper was deposited
(d) both the solutions will increase
in a copper voltmeter in series with the electrolytic cell. What
39. The pH of 0.5 L of 1.0 M NaCl after the electrolysis for 965
is the percent current efficiency in the electrolytic cell ? (At.
wt. of Cu = 63. 6) seconds using 5.0 A current (100% efficiency) is
(a) 40 (b) 25 (a) 1.0 (b) 13.0
(c) 60 (d) 50 (c) 12.7 (d) 1.3
JEEMAIN.GURU
downloaded from jeemain.guru
584 Chemistry
40. The emf of a particular voltaic cell with the cell reaction 44. A lead storage battery containing 5.0 L of (1N) H 2SO 4
Hg 22+ + H2 2Hg + 2H +
solution is operated for 9. 65 × 10 5 s with a steady current
is 0.65 V. The maximum electrical work of this cell when 0.5 g
of 100 mA. Assuming volume of the solution remaining
of H 2 is consumed.
constant, normality of H 2SO 4 will
(a) – 3.12 × 10 4 J (b) –1.25´105 J (a) remain unchanged (b) increases by 0.20
(c) 25.0 ´ 10 6 J (d) None (c) increase by unity (d) decrease by 0.40
41. 48250 C of electricity was required to deposit all the copper
45. The emf of the cell Pt Cl 2 (g) ( p1 atm)/ Cl - (aq) (1M)/ Cl 2 (g)
present in 0.5 L of CuSO 4 solution using inert electrodes.
(p 2 atm) Pt will be positive when
The molarity of solution was (Assume volume constant)
(a) 0.50 M (b) 2.50 M (a) p1 = p 2 (b) p1 < p 2
(c) 0.25 M (d) 1.00 M
42. At 298 K, the conductivity of saturated solution of AgCl in (c) p1 > p 2 (d) None of these
-6 46. The equilibrium constant for the disproportionation reaction
water is 2.6 × 10 Scm-1 . Its solubility product at 298 K
+
2+
(given l¥ (Ag + ) = 63.0 Scm2 mol-1 , l¥ (Cl - ) = 67.0 ¾® Cu (s) + Cu (ag)
2C u (aq) ¾
JEEMAIN.GURU
downloaded from jeemain.guru
Electrochemistry 585
EXERCISE 1 E´i´ t
10. (b) Apply m =
1. Iron ions. 96500
2. No, we cannot use nickel spatula to stir a solution of CuSO4.
7. (a) Standard electrode potential = 0.46V E´Q
11. (c) Apply m = where Q = coulombs
(b) Ecell = 0×37 V. 96500
8. 2×886 × 10–3 cm. E´Q 27
17. (a) 18. (d) 19. (c) 20. (d) 21. (c) 12. (b) Apply m = . E. wt of Al = =9.
96500 3
22. (c) 23. (d) 24. (b)
127.08
EXERCISE 2 13. (c) geq of copper to be deposited is = =4
31.75
1. (c) Electrorefining and electroplating are done by 1F deposits 1 geq, 4F will deposit 4 geq.
electrolysis.
WA WB W
2. (c) In cell the cathode is of higher reduction potential. 14. (d) = ; 27 = Cu ; \ WCu = 7.95g
3. (a) Amount of substance deposited EA EB 108 31.8
15. (c) 0.1 F will liberate 0.1 gev of Cl2 = 3.545 g
= m = E. wt ´ Q ; 16. (d) Ohm–1 cm–1
96500
1 0.47
107.870 17. (c) k = ´ Cell constant = = 0.01487
107.870 = ´ Q; R 31.6
96500
\ Q = 96500C 18. (b) Cell constant = k ´ R
= 0.212 ohm -1 cm -1 ´ 55 ohm
4. (d) WA = WB ; 1.6 = Wt. of Ag
EA EB 8 108 = 11.66 cm -1
\ Wt. of Ag = 21.6 g Cell constant 1.15
19. (a) k = =
5. (a) Ag + + e - ¾ R 250
¾® Ag
1F 108 g 1.15 1000
L eq = ´ = 4.6
1 F = 1 mole of electrons = 96500 C 250 1
0.01F = 1.08 g Ag; Ag left = 1.08 – 1.08 = 0
20. (c) Kohlrausch Law. Leq (NaF)+ Leq (HCl)– Leq (NaCl) =
6. (c) m = E.Wt ´ Q ;
96500 Leq (HF)
21. (b) Ohm–1 cm2 geq–1
m ´ 96500 22.2 ´ 96500
\ E. wt = = = 60.3
Q 2 ´ 5 ´ 60 ´ 60 k ´ 1000 3.06 ´ 10-6 ´ 1000
22. (d) Solubility = = = 2 × 10–3
L eq 1.53
At wt . 177
Oxidation state = = =3 Ksp = S2 = 4 × 10–6
Eq. wt. 60.3
23. (a) Specific conductance = Conductance × Cell constant
7. (b) m = E ´ Q = 32.68 ´ 5 ´ 40 ´ 60 = 4.065 g
96500 96500 1
k= ´1.15 ;
2.5 ´103
31.75 ´ 1´ 965 .3175
8. (c) m = = 0.3175 g = = 0.005 moles in
96500 63 1.15 1000
L eq = ´ = 4.6
one litre. \ 0.005 M. 2.5 ´ 10 3 0.1
E´i´ t 31.75 ´ .5 ´ t
9. (a) m = ;2= , \ t = 12157.48 sec . k ´ 1000 1.06 ´ 10-2 ´ 1000
96500 96500 24. (a) L m = = = 1.06 ´ 10 2
M 0.1
JEEMAIN.GURU
downloaded from jeemain.guru
586 Chemistry
47. (a) Fe Al Br
L m ´ M 1.26 ´ 10 -2 ´ 0.01
25. (b) k = = = 1.26 ´ 10 -3 0.77 –1.66 1.08 E°Red
1000 1000 –0.77 1.66 –1.08 E°Oxi
26. (a) L¥m = 57 + 73 = 130 S cm 2 mol -1 X 2+ Y 2 - Hence Reducing power Al > Fe > Br
48. (c) On the basis of ECS strongly electropositive metals can
x displace less electropositive metals from their salt
Lcm solutions.
27. (c) Degree of dissociation = ¥ = 100 = 0.01 . 49. (c) I has the highest oxidation potential hence most reducing.
Lm x
50. (a) Since oxidation potential of Zn is highest hence strongest
28. (b) It is an example of concentration cell, Ecell cannot be zero reducing agent.
since [H+] are different (HCl is strong and CH3COOH
51. (d) The reduction potential of NO3- ion is more than H+
weak acid).
29. (d) Reduction occurs at cathode. ion. (see ECS).
30. (c) Consult ECS. Reduction potential of Cu is more 52. (c) Gold having higher E oRed and oxidises Fe ¾
than H2. ¾® Fe + + .
53. (d) Cell reaction Zn + Cu + + ¾ ¾® Zn + + + Cu
31. (d) 4 2 DG = –827 kJ mol–1
¾® Al 2 O 3 ;
Al + O 2 ¾ 0.059 0.01
3 3 o
E1 = E cell - log
2 1.0
æ2 ö o
Number of electrons involved is 4 ç ´ 6 = 4 ÷ \ E1 = (E cell + 0.059) V
è 3 ø
o 0.059 1.0
E 2 = E cell - log
827000 2 0.01
DGo = –nFE o or = Eo
4 ´ 96500 o
\ E 2 = (Ecell - 0.059) V E1 > E2.
o
\ E = 2.14V 54. (c) Copper is below in ECS hence cannot displace hydrogen
2+ 2 from HCl.
RT ln[Fe ] é 2+ ù
32. (c) Nernst equation Ecell = E ocell - Zn HCl H+ + Cl–
nF [Fe3+ ]2 ë û
2H + 2e ® H2
+ –
increasing [Fe2+] will decrease the Ecell. Cu ® Cu++ + 2e–
33. (d) Emf will decrease. not possible. Hence evolution of H2 is not possible.
34. (a) Salt bridge allows the flow of current by completing 55. (b) I2 is less reactive than Br2.
circuit. No current will flow and voltage will drop to zero, 56. (d) Oxidation potential of Co is more than Ag, hence cell
if salt bridge is removed. reaction will be
35. (c)
Co + 2 Ag + ¾
¾® Co 2 + + 2 Ag
36. (d) Calomel electrode is used as reference electrode.
37. (d) Though it is not zero but has been fixed as zero. o RT ln [Co 2 + ] , the lesser the value of
E cell = E cell -
38. (b) E ocell = E ored (Zn) + E oxi
o
(Fe) = 0.76 - 0.41 = 0.35V nF [Ag + ]2
2+
39. (a) OCl - ¾
¾® Cl - ; E° = 0.94 V (I) the factor [Co ] greater will be value of Ecell. .
[ Ag + ]2
1
Cl - ¾
¾® Cl 2 + e - ; E° = 1.36 V (II)
2 o RT [C]c [D]d
57. (b) E cell = E cell - ln .
nF [A]a [B]b
- 1
Add (I) + (II) OCl ¾¾® Cl 2 ; E° = 0.94 – 1.36 = –0.42 V
2 RT [C]c [D]d
Hence E ocell = E cell + ln
40. (d) E ocell = E oRe d (Fe) + E oxi
o
(Sn) = –0.44 + 0.14 = –0.30V nF [A]a [B]b
58. (a) Since concentration of ions is the same hence
41. (b) E ocell = E oRe d (Au) + E oxi
o
(Ni) = 1.5 + 0.25 = 1.75V
Ecell = E o cell.
42. (c) Oxidation potential of M is more than Ni and less than
Mn. Hence reducing power Mn > M > Ni 59. (a) The Half cell reaction is Zn + + + 2e - ¾
¾® Zn .
43. (a) The greater the oxidation potential greater is reactivity o 0.059 1
E cell = E cell - log
A > D > B > C. 2 [Zn ++ ]
44. (a) Chlorine is less reactive than fluorine.
45. (b) Follow ECS, more the reduction potential, the stronger = - 0.763 - 0.059 log 1 = -0.822 V
the oxidising power and vice versa. 2 0.01
46. (b) Follow ECS, A will replace B. Eoxi = 0.822 V
JEEMAIN.GURU
downloaded from jeemain.guru
Electrochemistry 587
60. (d) 2 H + + 2e - ¾
¾® H 2 o 0.0591
3. (c) As Ecell = log Kc
n
0.059 1
E Red = E oRe d - log + 2 ; 0.0591
n [H ] \ 0.46 = log Kc
2
0.059 1 2 ´ 0.46
E Re d = 0 - log ; ERed = –0.059 V,,
2 (0.1) 2 \ log K c = = 15.57
0.0591
Eoxi = 0.059 V. or Kc = Antilog 15.57 = 3.7 × 1015 » 4 × 1015
RT C 4. (c) From the given data we find Fe 3+ is strongest
o
61. (b) E cell = E cell - ln 2 and DG = –nFE°cell oxidising agent. More the positive value of E°, more is
nF C1
the tendency to get oxidized. Thus correct option is
C (c).
Hence DG is a function of ln 2 . 5. (d) Kohlrausch’s Law states that at infinite dilution, each
C1
ion migrates independent of its co-ion and contributes
0.059 to the total equivalent conductance of an electrolyte a
o
62. (b) At equilibrium Ecell = 0. E cell = log K C definite share which depends only on its own nature.
n
From this definition we can see that option (d) is the
o 0.059 1.10 ´ 2 correct answer.
63. (b) E cell = log K C or = log K C
6. (c) Writing the equation for pentane-oxygen fuel cell at
2 0.059
respective electrodes and overall reaction, we get
\ K C = 1.9 ´ 1037 At Anode:
64. (a) DG = –nF E°cell = –2 × 96500 × 1.1 J = 212.3 kJ. C5 H12 + 10H 2 O ® 5CO 2 + 32H + + 32e -
65. (a) Q Change in free energy = maximum electrical work done (pentane)
66. (b) Water is weak electrolyte and remains almost unionised.
At Cathode:
67. (b) Cathode Anode
Aqs. soln. of Na2SO4 2 Na+ SO4– – 8O 2 + 32H + + 32e - ® 16H 2O
Ionisation of H2O ® H+ OH– Overall :C5H12 + 8O2 ® 5CO 2 + 6H 2O
+ - 1 Calculation of DG° for the above reaction
E°Red of H is more hence H + e ¾ ¾® H 2
2 DG° = [5×(–394.4) + 6× (–237.2)]
68. (b) Cl– is oxidised to Cl2 at anode. – [–8.2]
69. (b) 70. (d) 71. (b) 72. (c) = – 1972.0 – 1423.2 + 8.2 = – 3387.0 kJ
73. (b) H2 – O2 fuel cell supply power for pressure. = – 3387000 Joules.
74. (b) H2SO4 regenerated follow text. From the equation we find n = 32
-nFE ° and substituting
75. (c) Thermodynamic efficiency is given by Using the relation, DG° = – nFEcell
DH
76. (c) various values, we get
77. (a) Galvanization ° (F = 96500C)
– 3387000 = –32×96500× Ecell
78. (b) Specific conductance decreases with dilution
(follow text). 3387000
° =
or Ecell
79. (d) In electrolytic cell the flow of electrons is from anode to 32 ´ 96500
cathode through internal supply.
3387000 3387
EXERCISE 3 = or V = 1.0968 V
3088000 3088
1. (d) Zinc gives H2 gas with dil H2SO4/HCl but not with HNO3 Thus option (c) is correct answer.
because in HNO3, NO3– ion is reduced and give NH4NO3, 7. (d) Cu2+ + 2e– ® Cu; DGo = – nEoF
N2O, NO and NO2 (based upon the concentration of = – 2 × F × 0.337
HNO3) = – 0.674 F ....(i)
4Zn+10HNO 3 ¾¾ ® 4Zn(NO 3 ) 2 +NH 4 NO 3 +3H 2 O Cu+ ® Cu2+ + e– ; DGo = – nEoF
= – 1 × F × – 0.153
Zn is on the top position of hydrogen in electrochemical
= 0.153 F ....(ii)
series. So Zn displaces H2 from dilute H2SO4 and HCl
On adding eqn (i) & (ii)
with liberation of H2.
Cu+ + e– ® Cu ;
Zn + H2SO4 ® ZnSO4 + H2
DGo = – 0.521 F = – nEoF;
DG Here n = 1 \ Eo = + 0.52 V
2. (b) Efficiency of a fuel cell (h ) =
DH
JEEMAIN.GURU
downloaded from jeemain.guru
588 Chemistry
8. (a) Q Q = i × t 16. (b) Given ESn +4 = + 0.15 V
Sn +2
\ Q = 4.0 × 104 × 6 × 60 × 60 C
= 8.64 × 10 8 C E Cr+ 3 Cr = – 0.74 V
3+ -
Al + 3e ¾¾
® Al
3´96500C 27g E °cell = E °ox + E °red
[3 × 96500 C liberates = 27 g of Al] = 0.74 + 0.15
\ 96500 C liberates 9 g of Al = 0.89 V
9 17. (d) Standard Gibbs free energy is given as DG° = – nE°F
8.64 × 108 C liberates = ´ 8.64 ´ 108 g Al
96500 If E°cell < 0 i.e., – ve
= 8.1 × 104 g of Al DG° > 0
9. (d) Degree of dissociation Further DG° = – RT ln Keq
L 8.0 \ DG° > 0 and Keq < 0
a= = = 2 ´ 10-2 18. (c) Given Fe+3/Fe2+ = + 0.77 V
L ¥ 400
and I2/2I– = 0.536V
2 (e– + Fe+3 ¾¾ ® Fe+2) E° = 0.77 V
ca 2 1
( )
2
Ka = » ca 2 = ´ 2 ´ 10 -2 2I – ¾¾ ® I2 + 2e – E° = – 0.536 V
(1 - a ) 32
2Fe+3 + 2I– ¾¾ ® 2Fe+2 + I2
= 1.25 ´ 10-5 E° = E°ox + E°red
10. (a) Cu + 2 Ag+ (aq) ¾¾
® Cu 2+ (aq ) + 2 Ag (s ) = 0.77 – 0.536
= 0.164 V
Here, n = 2 , E°cell = + 0.46 V \ Since value of E° is + ve reaction will take place.
JEEMAIN.GURU
downloaded from jeemain.guru
Electrochemistry 589
LM 9.54 0.059
23. (b) a = L ¥ = = 0.04008 = 4.008 %. 37. (a) Ecell = log K c
M 238 n
24. (d) E°Cell = E°OP + E°RP
0.591 = 0.059 log K c or 10 = log K c \ K c = 1´1010
= 0.76 + 0.314 = 1.10 V
25. (b) S =
K m 2 mol
\ K = Sm 2 mol-1
( )
38. (c) L o NaCl = l o Na + + lCl- ....(i)
3
m´m
26. (c) Ecell = Reduction potential of cathode (right)
Lo KBr = lo ( K ) + l ( Br )
+ o -
....(ii)
- reduction potential of anode (left)
= Eright - Eleft. L o KCl = l o ( K ) + l ( Cl )
+ -
....(iii)
27. (a) Ecell = Eright (cathode) - Eleft (anode). (i) + (ii) - (iii)
28. (d) If p1 > p2 then E cell =
2.303
nF
p
RT log 1
p2
(
L o NaBr = l o Na + + lo Br - ) ( )
29. (a) 2Cr 3+ + 7H 2 O ® Cr2 O 72- + 14H + = 126 + 152 - 150 = 128 S cm 2 mol -1
O.S. of Cr changes from + 3 to + 6 by loss of electrons. 39. (c) The given values show that Cr has maximum oxidation
At anode oxidation takes place. potential, therefore its oxidation will be easiest. (Change
30. (c) The equilibrium constant is related to the standard emf the sign to get the oxidation values)
of cell by the expression 40. (a) Thus difluoro acetic acid being strongest acid will furnish
maximum number of ions showing highest electrical
n 2
log K = Eº cell ´ = 0.295 ´ conductivity. The decreasing acidic strength of the
0.059 0.059
carboxylic acides given is difluoro acetic acid >
590 fluoro acetic acid > chloro acetic acid > acetic acid.
log K = = 10 or K = 1 × 1010
59 41. (d) 1 mole of e– = 1F = 96500 C
31. (d) A B C 27g of Al is deposited by 3 × 96500 C
+ 0.5C –3.0V –1.2V 5120 g of Al will be deposited by
The higher the negative value of reduction potential, 3 ´ 96500 ´ 5120
the more is the reducing power. Hence B > C > A. = = 5.49 ´ 10 7 C
27
9650 1
32. (a) No. of moles of silver = = moles 42. (b) L ¥
96500 10 HCl = 426.2 (i)
JEEMAIN.GURU
downloaded from jeemain.guru
590 Chemistry
45. (b) According to Kohlrausch’s law, molar conductivity of 49. (b) Given
weak electrolyte acetic acid (CH3COOH) can be
Fe3+ + 3e - ® Fe ,
calculated as follows:
… (i)
(
LoCH3COOH = LoCH3COONa + L oHCl - Lo NaCl ) E°
Fe3+ / Fe
= –0.036 V
JEEMAIN.GURU
downloaded from jeemain.guru
Electrochemistry 591
53. (d) Here n = 4, and [H+] = 10– 3 (as pH = 3) Q=I×t
Applying Nernst equation Q 1930 C
t= = = 19.3´10 4 sec
2+ 2 I 10 ´10-3 A
0.059 [Fe ]
E = Eº – log + 4
n [H ] ( pO2 ) 59. (d) AgNO 3 ( aq ) + KCl( aq ) ¾¾
® AgCl( s ) + KNO 3 ( aq )
Conductivity of the solution is almost compensated
0.059 (10-3 )2
= 1.67 - log due to formation of KNO3(aq). However, after end
4 (10-3 ) 4 ´ 0.1 point, conductivity increases more rapidly due to
addition of excess AgNO3 solution.
0.059
= 1.67 - log107 = 1.67 – 0.103 = 1.567
4 EXERCISE 4
1 l 1. (a) The specific conductance increases with concentration.
54. (a) k= ´
R A The number of ions per cm -3 increase with increase of
1 l concentration.
1.3 = ´ 2. (a) The equivalent conductance increase with dilution, since
50 A
interionic attractions decrease with dilution
l
= 65m-1 3. (c) The correct-relation is DG° = -nFE°
A 4. (d) The amount. of copper deposited at cathode by
k ´ 1000 3.2
L= reduction of Cu 2+ ions is = 0.05 moles. The same
molarity 63
[molarity is in moles/litre but 1000 is used to convert
liter into cm3] amount 0.05 mole of Cu 2+ must pass into solution from
anode by oxidation
æ 1 ö 5. (c) Cu(CN) 2 in basic medium forms a complex which
çè ´ 65 m -1 ÷ ´ 1000 cm3
260 ø 2 ++
= maintains the constant supply of Cu ions
0.4 moles
1
6. (b) The oxidation potential µ and
650 m -1 1 Concentration of ions
= ´ m3
260 ´ 4 mol 1000 reduction potential µ concentration of ions. The cell
= 6.25 × 10–4 S m2 mol–1 voltage can be increased by decreasing the concentration
55. (d) For a spontaneous reaction DG must be –ve of ions around anode or by increasing the concentration
Since DG = – nFE° of ions around cathode
Hence for DG to be -ve DE° has to be positive. Which 7. (c) Electrodialysis of aqueous solution of
is possible when X = Zn, Y = Ni CuSO 4 Cu ++ + SO --
4
Zn + Ni++ ¾¾ ® Zn++ + Ni
Around anode we have SO 4- - and H 2 O . The oxidation
E° + E°
Zn / Zn +2
Ni / Ni= 0.76 + (–0.23)
2+
Potential of H 2 O(1.23V) is lower than oxidation
= +0.53 (positive)
56. (d) Higher the value of standard reduction potential, potential of SO 4-- (2.0V)
stronger is the oxidising agent, hence MnO4– is the \ 2H 2 O ® O2 + 4H + + 4e-
strongest oxidising agent.
57. (d) E°
Cr 3+ / Cr 2 + = – 0.41 V ( ) ( )
8. (b) L ¥m (AgCl) = l ¥ Ag + + l ¥ Cl - = 61.92 + 76.34 = 138.26
JEEMAIN.GURU
downloaded from jeemain.guru
592 Chemistry
18. (a) The reaction is 2Tl(s) + Sn4+ ® 2Tl+ + Sn2+
10. (a) Λ ¥ ¥ ¥ ¥
eq (NH 4 OH) = Λ eq (NH 4 Cl) + Λ eq (NaOH) - Λ eq (NaCl)
The cell is Tl(s) | Tl+(1.0M) | | Sn4+(1.0M) | Sn2+(1.0M) 1Pt
–0.34 V +0.13V
= 129.8 + 217.8 - 109.3 = 238.3 ohm -1cm 2 eq -1
0.0592 [Tl + ]2 [Sn 2 + ]
L eq 9.30 E = 0.13 - ( -0.34) - log
a= = = 0.04 or 4% 2 [Sn 4 + ]
L¥aq 238.3
= 0.47 V – 0.0296 log (10)2 [Tl+ conc. increases tenfold)
= 0.47 – 0.0592 = 0.411V
11. (c) DG ° = -nFE°; E° = -DG ° ; 19. (b) Unit of ionic mobility is cm2 s–1 volt–1
nF 20. (b) Reciprocal of resistance is conductance. We can add
the conductance and not resistance. Hence
-(-50.61kJ)
E° = = 0.26V
2 ´ 96500 ´10-3 1 1 1
= + + .........
r r r
2 ´ 112g
12. (a) 112 ml of H2 at STP = (Since 22400 ml at STP= 21. (c) At infinite dilution each ion makes a definite contribution
22400 towards molar conductance which is given by
M.wt)
Lom = V+ l + + V- l -
Eq.wt ´ i ´ t 22. (a) The equivalent conductance of weak electrolytes
Amount deposiled =
96500 increase with dilution ( c ).
2 ´ 112 1 ´ 965 ´ i 23. (d) The relation between ionic mobility and ionic
\ = ; l°
22400 96500 conductance is U º =
F
i = 1 amp
Where Uº is ionic mobility and lº ionic conductance
13. (a) A + e- ® A- has large negative potential . It means A- is \ Lo = F (U+ + U- )
readily oxidised the reaction proceeds towards left hand 24. (a) In case of equivalent conductance of strong electrolyte
side there is little increase with dilution.
14. (b) The electrochemical equivalent is the amount deposited 25. (a) The greater the ionic mobility, the greater the molar
by one coulomb of electricity conductance. The ionic mobility of HCl is greater than
that of NaCl.
coulomb of electricity = 0.5 ´ 200 = 100o C
0.059
\ Amount deposited = 0.001180´100 = 0.1180g 26. (b) DE = E° - log [H + ]2
2
15. (a) The given order of reduction potentials (or tendencies)
0.059
is Z > Y > X. A spontaneous reaction will have the = 1.30 - log (10 -2 ) 2
following characteristics 2
Z reduced and Y oxidised = 1.418 V
Z reduced and X oxidised 27. (c) Cd(s) + 2 Ag + (aq) ¾
¾® Cd 2 + (aq) + Ag (s),
Y reduced and X oxidised
Hence, Y will oxidise X and not Z. 0.059 [Cd 2 + ]
E cell = E °cell – log
16. (b) For, M + + X - ¾ o 2 [Ag + ]2
¾® M + X , E cell = 0.44 – 0.33 = 0.11V is
positive, hence reaction is spontaneous. 28. (b) Conductivity (X) = conductance (c) × cell constant
Eocell being +ve, DG ° will be -ve and hence the above 29. (a) Ar NO 2 + 6H + + 6e - ¾
¾® ArNH 2 + 2H 2 O
JEEMAIN.GURU
downloaded from jeemain.guru
Electrochemistry 593
31.8 Cathode : 2H 2 O + 2e - ¾
¾® H 2 + 2OH -
geq of Cu deposited = = 1 .0
63.6 / 2
1´ 5 ´ 965
Moles of OH - formed = Z × i × t = = 0.05
0.6 ´100 96500
\ Current efficiency = = 60 %
1
0.05
34. (d) Ionic mobility is the velocity of an ion under a potential [OH - ] = = 1 ´ 10 -1
0 .5
gradient of 1Vm -1 .
[H + ] = 10 -13 pH = 13
- -
35. (a) MX(s) + e ¾
¾® M(s) + X (aq); E° = 0.207 V .......(i)
40. (a) Wmax = – n.FE;
+ - ......(ii)
M ( aq ) + e ¾
¾® M (s ); E ° = 0 .799 V Wmax = – 2 × 96500 × 0.65 = – 1.25 ´ 10 5 J
From (i) – (ii),
0.5g H 2 = 0.25 mole.
¾® Ms+ (aq) + Xs- (aq);
MX(s) ¾
Hence Wmax = – 1.25 ´ 10 5 ´ 0.25 = –3.12 ´ 10 4 J
JEEMAIN.GURU
downloaded from jeemain.guru
594 Chemistry
JEEMAIN.GURU
downloaded from jeemain.guru
18
Chemical Kinetics
CHEMICAL KINETICS : rinst d[P]
Deals with rate, mechanism and factors affecting the chemical dt =slope
Concentration of reactants
reactions.
RATE OF REACTION : d[P]
It is defined as the change in concentration of a reactant or a dt
product in a particular interval of time. The change in concentration [P1]
of a substance say A is represented by D[A] D[P]
D[A] = [Final concentration – Initial concentration] [P2] rav D[P] {[P2]–[P1]}
For a reactant : Final concentration < Initial concentration Dt Dt (t2 – t1)
Thus D[A] will have negative sign
For a product : Final concentration > Initial concentration
Thus D[A] will have positive sign t Time t1 t2
Average rate in terms of products (b)
D[A ] Total change in concentration Instantaneous and average rate of a reaction
= = The minus sign indicates the decrease in concentration and plus
Dt Total change in time sign increase in concentration. The above expressions give the
D[ A ] average rate of reaction.
Average rate in terms of reactants = - FEATURES OF THE RATE OF REACTION :
Dt
The negative sign in the expression make the rate positive. Hence (I) Rate of reaction is proportional to the concentration of the
rate of a reaction is never negative. reactants
Consider the decomposition of N2O5 (II) Rate of a reaction is always a positive quantity
(III) Rate of a reaction is determined by measuring the
2 N 2 O 5 (g ) ¾
¾® 4 NO 2 (g ) + O 2 (g )
concentration of a reactant or a product as a function of time
1 DN 2 O 5 1 DNO 2 DO 2 (IV) Property related to concentration is selected e.g. volume,
Rate = - . = =
2 Dt 4 Dt Dt pressure, thermal or electrical conductivity, colour change,
pH, etc.
[R]0 UNITS OF RATE OF REACTION :
Mol L–1 time–1 and for gaseous reaction atm time–1
INSTANTANEOUS RATE :
Concentration of reactants
JEEMAIN.GURU
downloaded from jeemain.guru
596 Chemistry
RELATION BETWEEN AVERAGE AND Increase in temperature or decrease in the activation energy
INSTANTANEOUS RATE: will increase the rate of reaction and exponential increase in
Instantaneous rate = Average rate as Dt approaches to zero the rate constant
Dx ö At temperature T1 the equation (ii) is
Instantaneous rate = æç
dx
÷ =
è Dt ø Dt ®0 dt - Ea
lnk1 = + log A (iii)
FACTORS AFFECTING THE RATE OF REACTION : RT1
(i) Nature of the reactants : Reactions involving lesser bond and at temperature T2
rearrangement proceed much faster than those which involve
larger bond rearrangement. - Ea
(ii) Temperature : In most cases the rate of reaction in a lnk2 = + log A (iv)
RT2
homogeneous system is approximately doubled or even
tripled by an increase in temperature of 10°C. Since A is constant for a given reaction
(iii) Concentration of reactants : At fixed temperature and in Subtracting (iii) from (iv)
absence of catalyst, the rate increases with increased
Ea E
concentration of reactants. lnk2 – lnk1 = - a
(iv) Surface area : The more the surface area, the more is the RT1 RT2
rate of reaction.
(v) Positive catalyst : Increases the rate by lowering the energy k Ea é T2 - T1 ù
log 2 = ê ú
of activation. k1 2.303R ë T1T2 û
(vi) Presence of light : Photochemical reactions are influenced
by radiations of specific wavelength. Knowing the value of slope Ea can be calculated.
THE RATE CONSTANT : (b) Catalyst : Presence of positive catalyst lowers the energy of
acitvation and hence influences the rate constant.
Consider a reaction A + B ¾ ¾® Products .
UNITS OF RATE CONSTANT :
At a particular temperature rate is given by
Units depend upon the order of a reaction
dx units = (Concentration)1 – n . time–1
r= µ C A .C B = kCA .C B
dt = (Mol L–1)1–n . time–1
where k is rate constant, velocity constant or specific reaction where n = order of reaction
rate. When CA = CB = 1 then k= r (rate) Units of rate constant for zero order reaction
In general rate constant may be defined as the rate of the
= Mol L–1 time–1
reaction when the concentration of each of the reactants is
unity. It is characteristic of a particular reaction. Units of rate constant for first order reaction = time–1
FACTORS INFLUENCING RATE CONSTANT : CHARACTERISTICS OF RATE CONSTANT :
(a) Temperature : Variation of rate constant with temperature (I) The value of k is different for different reactions.
is given by (II) At fixed temperature the value of k is constant.
Arrhenius equation : k = Ae - E a / RT (i) (III) It is independent of concentration but depends on
A = Constant known as frequency factor temperature.
Ea = Energy of activation. Both A and Ea are characteristic of (IV) The larger the value of k the faster is the reaction and vice
a particular reaction. versa.
e - E a / RT = known as Boltzmann factor
THE DIFFERENCE BETWEEN RATE CONSTANT AND
Taking natural logarithm of (i) RATE OF REACTION :
Rate Constant Rate of reaction
- Ea
lnk = + log A (ii) (a) It is equal to rate of (a) It is the change in
RT
reaction when the concentration of reactants or
1 concentration of reacting products per unit time.
The plot of lnk vs gives a straight line
T species is unity
(b) Units depends on order of –1 –1
Intercept (b) Units are Mol L Sec
–1 –n
reaction = (Mol L )1 time–1
–Ea (n = Order of reaction)
Slope =
lnk R (c) It depends upon (c) It depends upon
temperature temperature and concentration
1
T
JEEMAIN.GURU
downloaded from jeemain.guru
dx
( Rate) = [ A ] x [ B] y ; HOOBr + HBr ¾
¾® 2HOBr Molecularity two
dt
( HOBr + HBr ¾
¾® H 2 O + Br2 ) ´ 2 Molecularity two
Order w.r.t. A is x, Order w.r.t. B is y
Overall order is x + y
4HBr + O 2 ¾
¾® 2H 2 O + 2Br2 Molecularity five
JEEMAIN.GURU
downloaded from jeemain.guru
598 Chemistry
PSEUDO UNIMOLECULAR REACTIONS : The half-life period of the first order reaction is independent
Reactions like hydrolysis of an ester or cane sugar, which though of the initial concentration of reacting substances.
bimolecular and yet following the kinetics of first order are called The time taken for the completion of any fraction of the
pseudo unimolecular reactions. reaction is independent of the initial concentration.
First order growth kinetics : It is used in population growth
CH 3COOC 2 H 5 + H 2 O CH 3COOH + C 2 H 5 OH
and bacteria multiplication
dx
= k[CH 3 COOC 2 H 5 ] 2.303 a+x
k= log
dt t a
C12 H 22 O11 + H 2 O C 6 H12 O 6 + C 6 H12 O 6 where a is initial population and (a + x) population after time
t.
dx (2) Second order reaction : The reaction rate is determined by
= k[C12 H 22 O11 ] .
dt the variation of two concentration terms. They are of two
In above reactions the rate is independent of concentration types
of H2O being present in excess. Hence [H2O] is constant. (a) 2A ¾
¾® Products
DIFFERENCES BETWEEN ORDER AND
MOLECULARITY OF REACTION : Rate µ [A]2
1 a 2.303 a (c) A + B + C ¾
¾® Products
k = .ln = log
t (a - x) t a-x Rate µ [A][B][C]
This is called the kinetic equation of a first order reaction.
Units of k = time–1 eg h–1, m–1 or s–1 x ( 2a - x )
Consider the type (a) k =
Half-life period (t1/2). The time taken for the completion of 2 t a 2 (a - x ) 2
half of the reaction is known as half-life period. When Unit of k = (mol L–1)–2 s–1 = mol–2 L2 s–1
t = t1 / 2 , x = a / 2 . When t = t1/2, x = a/2
0.693 3 1
t1/ 2 = Half-life period (t1/2) = (Q t1/ 2 µ )
2
k 2ka a2
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
600 Chemistry
1
For II order slope = ; k can be calculated
Zero order k
dx dx
dt dt 1
For III order slope = ; k can be calculated
I order 2k
(3) Use of differential rate equations.
(a – x) (a – x)
(4) Use of integral rate equations – hit and trial method
(5) Ostwald's isolation method.
Examples of reactions of different order :
(a) Reactions of zero order :
dx dx
hn
dt dt (I) H 2 (g ) + Cl 2 (g ) ¾¾® 2HCl (g )
II order III order
MO
(II) 2NH 3 (g) ¾¾¾
® N 2 (g) + 3H 2 (g)
hn
2 3
(a – x) (a – x) Au
(III) 2HI(g) ¾¾¾ ® H 2 (g) + I 2 (g)
(b) Making use of integrated form of rate expression : (b) Reactions of Ist order :
(I) 2 N 2O5 ¾
¾® 4 NO 2 + O 2
(II) 2H2 O2 ¾¾
® 2H2 O + O2
t t I order
Zero order
(III) NH 4 NO 2 ¾
¾® N 2 + 2H 2 O
x Log (a – x) (IV) SO 2 Cl 2 ¾
¾® SO 2 + Cl 2
x
(V) (CH 3 ) 3 CO . OC(CH 3 ) 3 ¾¾® 2CH 3COCH 3 + C 2 H 6
x
Zero order t = COOH
k
(VI) O2N NO2
a
For first order kt = 2.303 log
a-x
2.303 2.303
or t= log a - log(a - x) NO2
k k
O2N NO2
+ CO2
-2.303 ® CH 3COONa + C 2 H 5 OH
For I order slope = ; k can be calculated
k
(V) NO + O 3 ¾
¾® NO 2 + O 2
JEEMAIN.GURU
downloaded from jeemain.guru
(VII) Fe 3+ + 3I - ¾
¾® FeI 3
GRAPHICAL REPRESENTATION OF EXOTHERMIC
REACTION :
(e) Reactions of fractional order :
(I) H 2 + Br2 ¾
¾® 2HBr A(Reactant) ® B (Product)
E a(F.R.) + DH = E a(B.R.)
Rate = k[H 2 ][Br2 ]1/ 2 Order = 1.5
DH = - ve
(II) CO + Cl 2 ¾
¾® COCl 2 where F.R. = Forward reaction and B.R. = Backward reaction
Rate = k[CO] [Cl 2 ]
2 1/ 2
Order = 2.5
Threshold energy
(III) COCl 2 ¾
¾® CO + Cl 2
JEEMAIN.GURU
downloaded from jeemain.guru
602 Chemistry
GRAPHICAL REPRESENTATION OF THE EFFECT OF QUANTUM EFFICIENCY OR QUANTUM YIELD :
TEMPERATURE ON RATE OF REACTION : Number of moles reacting per Einstein of the light absorbed. It is
Fraction of the molecules having energy equal to activation expressed as
energy is shown by shaded portion. The fraction of such Number of molecules reacting in a given time
molecules become almost double for 10°C rise of temperature f=
Number of quanta of light absorbed in the same time
and the rate of reaction almost doubles for 10°C rise of
temperature. Number of moles reacting in a given time
f=
Number of Einsteins absorbed in the same time
T1 T2>T1
CHEMILUMINESCENE :
T2 Emission of light in a chemical reaction at ordinary temperature is
DN called chemiluminescence.
N
FLUORESCENCE :
The absorption of energy and instantaneous re-emitting of the
energy is called fluorescence.
Energy
PHOSPHORESCENCE :
The continuous glow of some substances even after the cutting
PHOTOCHEMICAL REACTIONS : of source of light is called phosphorescene e.g. ZnS.
Reactions which take place by the absorption of radiations of BIOLUMINESCENCE :
suitable wavelength e.g. The phenomenon of chemiluminescence exhibited by certain
light living organisms is called bioluminescence e.g. light emission by
H 2 (g ) + Cl 2 (g ) ¾¾¾® 2HCl (g )
fire flies.
Photosynthesis of carbohydrates in plants takes place in presence
EFFECT OF CATALYST ON REACTION RATES :
of chlorophyll and sunlight.
A catalysed reaction provides a new pathway or a mechanism by
light
6CO 2 + 6H 2 O ¾¾¾® C 6 H12 O 6 + 6O 2 which the potential energy barrier between the reactants and
products is lowered. The graphical representation is as follows :
FREE ENEREGY CHANGE IN PHOTOCHEMICAL
REACTIONS : Activated Complex
The free energy change of a photochemical reaction may not be
negative. In the synthesis of carbohydrates and formation of Ea Ea
HCl, DG is +ve.
PHOTOSENSITISATION : Ea(c)
E
Certain molecules absorb light energy and transfer it to another Ea (c)
molecule which may undergo a reaction. The process is called Reactants
DH
photosensitisation and the substance doing so is called
photosensitizer e.g. chlorophyll acts as photosensitizer in Products
photosynthesis. Progress of Reaction
VISION : (I) DH (enthalpy) of reaction remains the same for catalysed as
The isomerisation of retina by absorbing photon of light in the well as uncatalysed reaction.
retina of eye and reconversion to original form by releasing energy (II) Energy of activation is lowered considerably for catalysed
is known as vision. forward and backward reactions.
Study of kinetics of some reactions :
GROTHUS-DRAPER LAW :
(I) Hydrolysis of an ester
Only those rays which are absorbed by the substance are effective
CH3COOC2H5 + H2O CH3COOH + C2H5OH
in producing a chemical change. A part of light is reflected and
transmittted also. It is biomolecular and 1 order. The rate constant is given by
JEEMAIN.GURU
downloaded from jeemain.guru
(a - x ) µ rt - r¥ a
The value of k = t.a (a - x)
Sol. 2 N 2 O 5 ¾
¾® 2 N 2 O 4 + O 2 \ k = 2.35 ´10-5 sec-1
a -x x x/2
JEEMAIN.GURU
downloaded from jeemain.guru
604 Chemistry
9 ´10 -3 = [0.05]m [0.15]n (III) 11. When the initial concentration is changed from 0.50 to 1.0
mole lit–1, the time of half completion for a certain reaction is
Divide II by I, found to change from 50 sec. to 25 sec. Calculate the order
of reaction.
JEEMAIN.GURU
downloaded from jeemain.guru
n -1
Sol. k = 2.303 log a
Sol. T1 = æç a 2 ö÷ t a-x
T2 çè a1 ÷ø
2.303 5.0
n -1 6= log
50 æ 1.0 ö t 0.05
=ç ÷ 2 = (2)n – 1 or 21 = (2)n – 1
25 è 0.5 ø 2.303
t= log100 = 46.06 sec.
\ 1 = n – 1. Hence n = 1 + 1 = 2. Reaction is of second order. 6 min -1
12. Find the 3/4 th life (t 3/4) of a first order reaction. The rate
16. For the reaction, 2A + B + C ® A 2 B + C , rate law has been
constant k = 7.4 ´ 10 -5 sec-1
determined to be rate = k[A][B] 2. If the rate constant
2.303 a 2.303 1 k = 2.0 ´ 10 -6 mol L sec , what will be initial rate
–2 2 –1
Sol. t 3 = log = log
4
k a-x k 1-
3 of the reaction with [A] = 0.1 mol L–1 and [B] = 0.2 mol L–1
4 and [C] = 0.8 mol L–1.
2.303 Sol. For 2A + B + C ® A 2 B + C
t3 = log 4 = 1.84 ´104 sec
4
7.4 ´ 10-5 Rate = k[A][B]2
13. For a reaction it takes 10 min. for the initial concentration of = 2.0 ´10 -6 ´ 0.1´ [0.2]2
2.0 mol L–1 to become 1.0 mol L–1 and another 10 min to
become 0.50 mol L–1. Calculate the rate constant of the = 8.0 ´ 10 -9 mol L-1 s -1
reaction. 17. At some temperature, the rate constant for
Sol. The time taken for the concentration to fall to half the decomposition of HI on the surface of gold is 0.08 mol L –
1 s–1
concentration is constant in both the cases. Hence the
reaction is of first order 2HI (g) ® H 2 (g ) + I 2 (g)
0.693 0.693 what is the order of the reaction. How long will it
\ k= = = 0.0693 min -1
t½ 10 take for the concentration of HI to drop from 1.50 M to 0.30
M.
14. The rate of reaction 2 NO + Cl 2 ® 2 NOCl is doubled when
Sol. From the unit of k, the reaction is of zero order.
concentration of Cl2 is doubled and it becomes 8 times
when concentration of both NO and Cl2 are doubled. Deduce C0 - C
k=
the order of reaction. 2t
Sol. Rate is doubled when [Cl2] is doubled
1.5 - 0.30 1.2
Rate w.r.t. Cl2 = k[Cl2]1 0.08 = or t=
2t 0.08 ´ 2
Rate becomes 8 times when concentration of both NO and
Cl2 is doubled \ t = 7.5 s
Rate = k[Cl2 ][NO]x 18. The following data were obtained at a certain temperature
for the decomposition of ammonia in contact with tungsten
8 = k[2][2]x p (mm Hg) 50 100 200
\x=2 t½ 3.64 1.82 0.90
Find the order of the reaction.
Rate law is Rate = K[Cl 2 ][ NO]2
n -1 n -1
( t½)1 æ a1 ö 3.64 æ 100 ö
Total order 1 + 2 = 3 Sol. =ç ÷ or =ç ÷
15. A reaction that is of the first order with respect to ( t½) 2 çè a 2 ÷ø 1.82 è 50 ø
reactant A has a rate constant of 6 min–1. If we start with [A]
= 5.0 mol L–1 when would [A] reach the value of 0.05 mol L–1. 2 = (2) n -1 or n -1 = 1
\n = 2
JEEMAIN.GURU
downloaded from jeemain.guru
606 Chemistry
JEEMAIN.GURU
downloaded from jeemain.guru
2k1 3 d[ A] 2 d[ A]
(a) [ NO 2 ]2 (a) - (b) -
k2 2 dt 3 dt
(b) 2k1[ NO 2 ]2 - 2k 2 [ N 2 O 4 ] 1 d[ A ] d[ A ]
(c) - (d) + 2
3 dt dt
(c) 2k1[ NO 2 ]2 - k 2 [ N 2 O 4 ] 4. Consider the chemical reaction,
(d) (2k1 – k2) [NO2]
N 2 (g ) + 3H 2 (g ) ¾¾® 2 NH 3 (g ) . The rate of this reaction
2. The rate of the reaction intermediates can be determined by
the study of can be expressed in terms of time derivative of concentration
of N2 (g), H2 (g) or NH3 (g). Identify the correct relationship
(a) catalyst effects
amongst the rate expressions
(b) concentration of the reactants
JEEMAIN.GURU
downloaded from jeemain.guru
608 Chemistry
13. In Arrhenius plot, intercept is equal to
-d[ N 2 ] -1 d[H 2 ] 1 d[ NH 3 ]
(a) Rate = = =
dt 3 dt 2 dt Ea
(a) - (b) ln A
R
-d[ N 2 ] d[ H 2 ] d[ NH 3 ]
(b) Rate = = -3 =2 (c) ln k (b) log10a
dt dt dt
14. A chemical reaction was carried out at 300 K and 280 K. The
d[ N 2 ] 1 d[H 2 ] 1 d[ NH 3 ] rate constants were found to be k1 and k2 respectively. then
(c) Rate = = =
dt 3 dt 2 dt (a) k1 = 4k1 (b) k2 = 2k1
(c) k2 = 0.25 k1 (d) k2 = 0.5 k1
d[ N 2 ] d[ H 2 ] d[ NH 3 ]
(d) Rate = - =- = 15. The decomposition of a substance follows first order kinetics.
dt dt dt
Its concentration is reduced to 1/8th of its initial value in 24
5. The rate of a gaseous reaction is given by the expression minutes. The rate constant of the decomposition process is
k(A)(B). If the volume of the reaction vessel is suddenly
reduced to 1/4 of the initial vol. the reaction rate relative to 0.692
(a) 1/24 min–1 (b) min -1
the original rate will be 24
1 1
2.303 æ1ö 2.303 æ8ö
log ç ÷ min -1 log ç ÷ min -1
(a) (b)
16 8 (c) (d)
24 è8ø 24 è1ø
(c) 8 (d) 16
6. The units for the rate constant of first order reaction is 16. The rate of chemical reaction is doubled for every 10°C rise
in temperature because of
(a) s –1 (b) mol L–1 s–1
(c) mol s –1 (d) L mol–1 s–1 (a) increase in the activation energy
7. The rate constant of reaction depends upon (b) decrease in the activation energy
(a) temperature (b) pressure (c) increase in the number of molecular collisions
(c) volume (d) All the these (d) increase in the number of activated molecules
8. The rate constant of a reaction is 10.8 × 10 –5 17. The temperature coefficient of most of the reactions lies
mol dm–3 s–1. The order of the reaction is between
(a) zero (b) 1 (a) 1 and 3 (b) 2 and 3
(c) 2 (d) 3 (c) 1 and 4 (d) 2 and 4
9. If concentration of reactants is increased by 'x', then k 18. The velocity of a reaction is doubled for every 10°C rise in
becomes temp. If the temp. is raised to 50°C the reaction velocity
k k increases by about
(a) ln (b) (a) 12 times (b) 16 times
x x
(c) k + x (d) k (c) 32 times (d) 50 times
10. Rate constant in the case of first order reaction is
19. For the reaction A ¾ ¾® B , the rate law expression is : rate
(a) inversely proportional to the concentration units
= k [A]. Which of the following statements is incorrect?
(b) independent of concentration units
(a) The reaction follows first order kinetics
(c) directly proportional to the concentration units
(b) The t1/2 of reaction depends on initial concentration of
(d) inversely proportional to the square of the concentration
reactants
units
11. The Arrhenius equation expressing the effect of temperature (c) k is constant for the reaction at a constant temperature
on the rate constant of the reaction is (d) The rate law provides a simple way of predicting the
conc. of reactants and products at any time after the
Ea
(a) k = e - E a / RT (b) k = start of the reaction.
RT
20. For a reaction of type A + B ¾¾® products , it is observed
Ea
(c) k = log e (d) k = Ae - E a / RT that doubling concentration of A causes the reaction rate to
RT
be four times, but doubling amount of B does not affect the
12. For the following homogeneous reaction, rate. The rate equation is
k
A + B ¾¾ ®C k
(a) Rate = k [A] [B] (b) Rate = [A]2
the unit of rate constant is 4
(a) sec –1 (b) sec–1 mol L–1 (c) Rate = k [A]2 [B] (d) Rate = k [A]2 [B]2
(c) sec–1 mol–1 L (d) sec–1 mol–2 L2
JEEMAIN.GURU
downloaded from jeemain.guru
25. For the reaction A + B ¾ ¾® C , it is found that doubling 34. The reaction L ¾ ¾® M is started with 10.0 g of L. After 30
the concentration of A increases the rate 4 times, and and 90 minutes 5.0 g and 1.25 g of L respectively are left. The
doubling the concentration of B doubles the reaction rate. order of the reaction is
What is the overall order of the reaction? (a) 0 (b) 1
(a) 3/2 (b) 4 (c) 2 (d) 3
(c) 1 (d) 3 35. If initial concentration is reduced to 1/4th in a zero order
26. For a first-order reaction, the half life period is independent reaction, the time taken for half the rection to complete
of (a) remains same (b) becomes 4 times
(a) initial concentration (c) becomes one-fourth (d) doubles
(b) cube root of initial concentration 36. A first order reaction is half-completed in 45 minutes. How
(c) first power of final concentration long does it need for 99.9% of the reaction to be completed?
(d) square root of final concentration (a) 20 hours (b) 10 hours
27. For a first order reaction, the plot of log K against 1/T is a
straight line. The slope of the line is equal to 1
(c) 7 hours (d) 5 hours
2
Ea 2.303
(a) - (b) - E R 37. A reaction which is of first order w.r.t. reactant A, has a rate
R a constant 6 min–1. If we start with [A] = 0.5 mol L–1, when
-E a would [A] reach the value of 0.05 mol L–1
Ea
(c) - (d) 2.303R (a) 0.384 min (b) 0.15 min
2.303
(c) 3 min (d) 3.84 min
28. For a first order reaction, a plot of log (a – x) against time is 38. The rate constant for the reaction
a straight line with a negative slope equal to
-k 2 N 2O5 ¾ ¾® 4 NO 2 + O 2 , is 3.0 × 10–5 sec–1. If the rate is
(a) (b) – 2.303 k 2.40 × 10–5 mol litre–1 sec–1, then the concentration of N2O5
2.303
(in mol litre–1) is
2.303 Ea (a) 1.4 (b) 1.2
(c) (d) - 2.303 R (c) 0.04 (d) 0.8
k
JEEMAIN.GURU
downloaded from jeemain.guru
610 Chemistry
39. The reaction, 47. According to the collision theory of reaction rates, the rate
1 of reaction increases with temperature due to
N 2 O 5 (ln CCl 4 ) ¾¾® 2 NO 2 + O 2 (g) (a) greater number of collision
2
(b) higher velocity of reacting molecules
is first order in N2O5 with rate constant 6.2 × 10–4 s–1. What
(c) greater number of molecules having the activation
is the value of rate of reaction when [N2O5] = 1.25 mol L–1? energy
(a) 7.75 × 10–4 mol L–1 s–1 (b) 6.35 × 10–3 mol L–1 s–1 (d) decrease in the activation energy
(c) 5.15 × 10–5 mol L–1 s–1 (d) 3.85 × 10–4 mol L–1 s–1 48. Which of the following has been used to explain the subject
40. The time taken for 90% of a first order reaction to complete of chemical kinetics
is approximately (a) Collision theory of bimolecular reactions
(a) 1.1 times that of half-life (b) The activated complex theory
(b) 2.2 times that of half-life (c) Arrhenius equation
(c) 3.3 times that of half-life (d) All of these
(d) 4.4 times that of half-life 49. Which of the following statements is incorrect?
41. The rate of a certain reaction at different time intervals are (a) Activation energy for the forward reaction equals to
as follows activation energy for the reverse reaction
Time Rate (b) For a reversible reaction, an increase in temperature
0 sec. 1.8×10–2 mol l–1 s–1 increases the reaction rate for both the forward and the
10sec. 1.82×10–2 mol l–1 s–1 backward reaction
(c) The larger the initial reactant concentration for a second
20 sec. 1.79×10–2 mol l–1 s–1
order reaction, the shorter is its half-life.
The reaction is of
(d) When Dt is infinitesimally small, the average rate equals
(a) zero order (b) first order the instantaneous rate
(c) second order (d) third order 50. Activation energy of a chemical reaction can be determined
42. A substance initial concentration (a) reacts according to by
zero order kinetics. What will be the time for the reaction to (a) evaluating rate constant at standard temperature
go to completion (b) evaluating velocities of reaction at two different
a k temperatures
(a) (b) (c) evaluating rate constants at two different temperatures
k a
(d) changing concentration of reactants
a 2k 51. A catalyst increases rate of reaction by
(c) (d) (a) decreasing enthalpy
2k a
(b) decreasing internal energy
43. The hypothetical reaction A 2 + B 2 ¾
¾® 2AB ; follows (c) decreasing activation energy
(d) increasing activation energy
Fast
the following mechanism A 2 ¾¾¾® A + A , 52. The activation energy for a simple chemical reaction A ® B
Fast is Ea in forward direction. The activation energy for reverse
A + B 2 ¾¾¾® AB + B , A + B ¾¾
¾® AB .
Slow
reaction
The order of the overall reaction is (a) is always less than Ea
(a) 0 (b) 1 (b) can be less than or more than Ea
(c) 2 (d) 3/2 (c) is always double of Ea
44. The reaction (d) is negative of Ea
2N2O5 2N2O4 + O2 is 53. A graph plotted between log k Vs 1/T for calculating
activation energy is shown by
(a) bimolecular and of second order
(b) unimolecular and of first order
(c) bimolecular and of first order log k
log k
(d) bimolecular and of zero order (a) (b)
45. The given reaction
2FeCl 3 + SnCl 2 ¾
¾® 2 FeCl 2 + SnCl 4 1/T 1/T
is an example of
(a) first order reaction (b) second order reaction
(c) third order reaction (d) None of these log k
log k
46. Collision theory is applicable to
(c) (d)
(a) first order reactions (b) zero order reactions
(c) bimolecular reactions (d) intra-molecular reactions
1/T
1/T
JEEMAIN.GURU
downloaded from jeemain.guru
(b) the energy evolved when activated complex is formed = A . e - E a Activation energy (Ea) of the reaction can be
calculated by plotting
(c) minimum amount of energy needed to overcome the
potential barrier 1 1
(a) k vs. log T (b) log k vs
(d) the energy needed to form one mole of the product T
55. The activation energy for a hypothetical 1
reaction, A ® Product, is 12.49 kcal/mole. If temperature is (c) log k vs. log T (d) k vs. T
raised from 295 to 305, the rate of reaction increased by
59. The reaction A ® B follows first order kinetics. The time
(a) 60% (b) 100% taken for 0.8 mole of A to produce 0.6 mole of B is 1 hour.
(c) 50% (d) 20% What is the time taken for conversion of 0.9 mole of A to
produce 0.675 mole of B?
56. In a reaction, the threshold energy is equal to
(a) 0.5 hour (b) 0.25 hour
(a) activation energy + normal energy of reactants (c) 2 hours (d) 1 hour
(b) activation energy - normal energy of reactants 60. According to the adsorption theory of catalysis, the speed
(c) normal energy of reactants - activation energy of the reaction increases because
(a) in the process of adsorption, the activation energy of
(d) average kinetic energy of molecules of reactants
the molecules becomes large
57. When two reactants A and B are mixed to give products C (b) adsorption produces heat which increases the speed of
and D, the reaction quotient, 'Q', at the initial stages of the the reaction
reaction (c) adsorption lowers the activation energy of the reaction
(a) is zero (b) decreases with time (d) the concentration of product molecules at the active
(c) is independent of time (d) increases with time centres of the catalyst becomes high due to adsorption.
JEEMAIN.GURU
downloaded from jeemain.guru
612 Chemistry
These kinetic data were obtained for given reaction (a) 6.25 × 10–3 mol L–1s–1 and 6.25 × 10–3 mol L–1s–1
concentrations. (b) 1.25 × 10–2 mol L–1s–1 and 3.125 × 10–3 mol L–1s–1
(c) 6.25 × 10–3 mol L–1s–1 and 3.125 × 10–3 mol L–1s–1
Initial Initial rate, (d) 1.25 × 10–2 mol L–1s–1 and 6.25 × 10–3 mol L–1s–1
Concentrations, M disappearance of
11. For an endothermic reaction, energy of activation is Ea and
Br2, Ms–1
[CH3 COCH3] [Br2] [H+] enthalpy of reaction of DH (both of these in kJ/mol). Minimum
0.30 0.05 0.05 5.7×10–5 value of Ea will be. [CBSE-PMT 2010]
0.30 0.10 0.05 5.7 × 10–5
0.30 0.10 0.10 1.2 × 10–4 (a) less than DH (b) equal to DH
0.40 0.05 0.20 3.1 × 10–4 (c) more than DH (d) equal to zero
Based on given data, the rate equations is:[CBSE-PMT 2008] 12. During the kinetic study of the reaction, 2A + B ® C + D,
following results were obtained:
(a) Rate = k[CH3COCH3][H+]
(b) Rate = k [CH3COCH3][Br2]
Run [A](mol L–1 ) [B](mol L–1 ) Initial rate of
(c) Rate = k [CH3COCH3] [Br2] [H+]2
formation of
(d) Rate = k [CH3COCH3][Br2] [H+] –1 –1
D (mol L min )
6. For the reaction, N2 + 3H2 ® 2NH3, [CBSE-PMT 2009] –3
I 0.1 0.1 6.0 × 10
d [ NH3 ] – d [H2 ] II 0.3 0.2 7.2 × 10
–2
= 2 × 10–4 mol L–1 s–1 , the value of
dt dt III 0.3 0.4 2.88 × 10
–1
would be : –2
IV 0.4 0.1 2.40 × 10
(a) 4 × 10–4 mol L–1 s–1 (b) 6 × 10–4 mol L–1 s–1
(c) 1 × 10–4 mol L–1 s–1 (d) 3 × 10–4 mol L–1 s–1 Based on the above data which one of the following is correct?
7. In the reaction [CBSE-PMT 2009] [CBSE-PMT 2010]
(a) rate = k [A]2 [B] (b) rate = k[A] [B]
BrO3– (aq) + 5Br - ( aq ) + 6H + ( aq) ® 3Br2 (l ) + 3H 2O(l )
2 2
The rate of appearance of bromine (Br2) is related to rate of (c) rate = k [A] [B] (d) rate = k [A] [B]2
disappearance of bromide ions as following: 13. The rate of the reaction 2NO + Cl 2 ¾¾ ® 2NOCl is given
by the rate equation rate = k [NO]2 [Cl2] [CBSE-PMT 2010]
d[Br2 ] 5 d[Br – ] d[Br2 ] 5 d[Br – ] The value of the rate constant can be increased by:
(a) =– (b) =
dt 3 dt dt 3 dt (a) increasing the concentration of NO.
(b) increasing the temperature.
d[Br2 ] 3 d[Br – ] d[Br2 ] 3 d [Br – ] (c) increasing the concentration of the Cl2
(c) = (d) =-
dt 5 dt dt 5 dt (d) doing all of these
8. Half life period of a first-order reaction is 1386 seconds. The 14. Which one of the following statements for the order of a
specific rate constant of the reaction is : [CBSE-PMT 2009] reaction is incorrect ? [CBSE-PMT 2011]
(a) 0.5 × 10–2 s–1 (b) 0.5 × 10–3 s–1 (a) Order can be determined only experimentally.
–2 –1 (b) Order is not influenced by stoichiometric coefficient of
(c) 5.0 × 10 s (d) 5.0 × 10–3 s–1
the reactants.
9. For the reaction A + B ¾¾ ® products, it is observed that: (c) Order of reaction is sum of power to the concentration
[CBSE-PMT 2009] terms of reactants to express the rate of reaction.
(d) Order of reaction is always whole number.
(1) On doubling the initial concentration of A only, the rate
15. The rate of the reaction 2N2O5 ® 4NO2 + 2O2 can be written
of reaction is also doubled and
in three ways : [CBSE-PMT 2011 M]
(2) On doubling the initial concentrations of both A and B,
- d[N 2O5 ]
there is a change by a factor of 8 in the rate of the reaction. = k [N 2O5 ]
dt
The rate of this reaction is given by:
(a) rate = k [A] [B]2 (b) rate = k [A]2 [B]2 d[NO 2 ]
= k ¢ [N 2 O5 ]
(c) rate = k [A] [B] (d) rate = k [A]2 [B] dt
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
614 Chemistry
30. Consider an endothermic reaction X ® Y with the activation (c) the energy above which all the colliding molecules will
energies E b and E f for the backward and forward reactions, react
(d) the energy below which colliding molecules will not
respectively. In general [AIEEE 2005]
react
(a) there is no definite relation between E b and E f 36. The following mechanism has been proposed for the
(b) E b = E f reaction of NO with Br2 to form NOBr :
(c) E b > E f NO(g) + Br2(g) NOBr2(g)
(d) E b < E f NOBr 2 ( g ) + NO (g ) ¾
¾® 2 NOBr ( g )
31. A reaction involving two different reactants can never be If the second step is the rate determining step, the order of
[AIEEE 2005] the reaction with respect to NO(g) is [AIEEE 2006]
(a) bimolecular reaction (a) 3 (b) 2
(b) second order reaction
(c) first order reaction (c) 1 (d) 0
(d) unimolecular reaction 37. The energies of activation for forward and reverse reactions
32. A schematic plot of ln k eq versus inverse of temperature for A2 + B2 2AB are 180 kJ mol–1 and 200 kJ mol–1
respectively. The presence of a catalyst lowers the activation
for a reaction is shown below [AIEEE 2005]
energy of both (forward and reverse) reactions by 100 kJ
6.0 mol–1. The enthalpy change of the reaction (A2 + B2 ® 2AB)
in the presence of a catalyst will be (in kJ mol–1)
In keq
[AIEEE 2007]
(a) 20 (b) 300 (c) 120 (d) 280
2.0 38. Consider the reaction, 2A + B ® products. When
1.5 ´10 -3 1 (k -1 ) 2.0 ´10 -3 concentration of B alone was doubled, the half-life did not
T change. When the concentration of A alone was doubled, the
The reaction must be rate increased by two times. The unit of rate constant for this
(a) highly spontaneous at ordinary temperature reaction is [AIEEE 2007]
(b) one with negligible enthalpy change (a) s –1 (b) L mol–1 s–1
(c) endothermic
(c) no unit (d) mol L–1 s–1.
(d) exothermic
33. t1/4 can be taken as the time taken for the concentration of a 39. A radioactive element gets spilled over the floor of a room. Its
half-life period is 30 days. If the initial velocity is ten times the
3
reactant to drop to of its initial value. If the rate constant permissible value, after how many days will it be safe to enter
4
the room? [AIEEE 2007]
for a first order reaction is K, the t1/4 can be written as
[AIEEE 2005] (a) 100 days (b) 1000 days
(a) 0.75/k (b) 0.69/k (c) 300 days (d) 10 days.
(c) 0.29/k (d) 0.10/k
1
34. A reaction was found to be second order with respect to the 40. For a reaction A ® 2B, rate of disappearance of ‘A’ is
concentration of carbon monoxide. If the concentration of 2
carbon monoxide is doubled, with everything else kept the related to the rate of appearance of ‘B’ by the expression
same, the rate of reaction will [AIEEE 2006] [AIEEE 2008]
(a) increase by a factor of 4
d[A] 1 d[B]
(b) double (a) – = (b) – d[A] = 1 d[B]
(c) remain unchanged dt 2 dt
dt 4 dt
(d) triple
35. Rate of a reaction can be expressed by Arrhenius equation d[A] d[B]
(c) d[A ] d[B]
– =
(d) – =4
as : [AIEEE 2006] dt dt dt dt
k = A e–E/RT
41. The half life period of a first order chemical reaction is 6.93
In this equation, E represents
minutes. The time required for the completion of 99% of the
(a) the total energy of the reacting molecules at a
temperature, T chemical reaction will be (log 2 = 0.301) [AIEEE 2009]
(b) the fraction of molecules with energy greater than the (a) 23.03 minutes (b) 46.06 minutes
activation energy of the reaction (c) 460.6 minutes (d) 230.03 minutes
JEEMAIN.GURU
downloaded from jeemain.guru
42. The time for half life period of a certain reaction 47. The rate of a reaction doubles when its temperature changes
A ¾¾ ® Products is 1 hour. When the initial concentration from 300 K to 310 K. Activation energy of such a reaction will
of the reactant ‘A’, is 2.0 mol L–1, how much time does it take be : (R = 8.314 JK–1 mol–1 and log 2 = 0.301) [JEE Main 2013]
for its concentration to come from 0.50 to 0.25 mol L–1 if it is (a) 53.6 kJ mol –1 (b) 48.6 kJ mol–1
a zero order reaction ? [AIEEE 2010] (c) 58.5 kJ mol –1 (d) 60.5 kJ mol–1
(a) 4 h (b) 0.5 h (c) 0.25 h (d) 1 h 48. Consider a reaction aG + bH ® Products. When
43. Consider the reaction : concentration of both the reactants G and H is doubled, the
rate increases by eight times. However, when concentration
Cl2 (aq ) + H 2S( aq ) ® S( s) + 2H + ( aq) + 2Cl - ( aq) of G is doubled keeping the concentration of H fixed, the rate
is doubled. The overall order of the reaction is
The rate equation for this reaction is
[IIT-JEE 2007]
rate = k[Cl2 ][H 2S] (a) 0 (b) 1
Which of these mechanisms is/are consistent with this rate (c) 2 (d) 3
equation? [AIEEE 2010] 49. Under the same reaction conditions, initial concentration of
1.386 mol dm–3 of a substance becomes half in 40 seconds
A. Cl2 + H 2S ® H + + Cl - + Cl+ + HS- (slow)
and 20 seconds through first order and zero order kinetics,
Cl + + HS- ® H + + Cl - + S (fast) respectively. Ratio (k1/k0) of the rate constant for first order
(k1) and zero order (k0) of the reaction is [IIT-JEE 2008]
B. H 2S H + + HS- (fast equilibrium) (a) 0.5 mol–1 dm3 (b) 1.0 mol dm–3
(c) 1.5 mol dm –3 (d) 2.0 mol–1 dm3
Cl2 + HS- ® 2Cl - + H + + S (Slow) 50. For a first order reaction A®P, the temperature (T) dependent
(a) B only (b) Both A and B rate constant (k) was found to follow the equation
(c) Neither A nor B (d) A only 1
log k = – (2000) + 6.0 . The pre-exponential factor A and
44. A reactant (A) froms two products : [AIEEE 2011RS] T
k the activation energy Ea, respectively, are [IIT-JEE 2009]
A ¾¾
1 ® B,
Activation Energy Ea1
(a) 1.0 × 106 s–1 and 9.2 kJ mol–1
k2
A ¾¾® C, Activation Energy Ea2 (b) 6.0 s–1 and 16.6 kJ mol–1
(c) 1.0 × 106 s–1 and 16.6 kJ mol–1
If Ea2 = 2 Ea1, then k1 and k2 are related as : (d) 1.0 × 106 s–1 and 38.3 kJ mol–1
51. Plots showing the variation of the rate constant (k) with
(a) k2 = k1e Ea1 / RT (b) k2 = k1e Ea2 / RT
temperature (T) are given below. The plot that follows
(c) k1 = Ak2 e Ea1 / RT (d) k1 = 2k2 e Ea2 / RT Arrhenius equation is [IIT-JEE 2010]
45. The rate of a chemical reaction doubles for every 10°C rise of
temperature. If the temperature is raised by 50°C, the rate of
the reaction increases by about : [AIEEE 2011]
(a) 10 times (b) 24 times (c) 32 times (d) 64 times (a) (b)
46. For a first order reaction (A) ® products the concentration of
A changes from 0.1 M to 0.025 M in 40 minutes.
The rate of reaction when the concentration of A is 0.01 M is :
[AIEEE 2012]
(a) 1.73 × 10–5 M/min (b) 3.47 × 10–4 M/min (c) (d)
(c) 3.47 × 10–5 M/min (d) 1.73 × 10–4 M/min
JEEMAIN.GURU
downloaded from jeemain.guru
616 Chemistry
1. Two substances R and S decompose in solution Rate in terms of N2. Rate in terms of H2
independently, both following first order kinetics. The rate
(mol L–1sec–1 ) (mol L–1sec–1 )
constant of R is twice that of S. In an experiment, the solution
initially contained 0.5 millimoles of R and 0.25 millimoles of (a) 2×10–4 2×10–4
S. The molarities of R and S will be equal just at the end of (b) 3×10–4 1×10–4
time equal to (c) 1×10–4 3×10–4
(a) twice the half life of R (b) twice the half life of S (d) 2×10–1 2×10–3
(c) the half life of S (d) the half life of R 8. The rate constant , the activation energy and the Arrhenius
2. For a reaction, the rate constant at particular temperature parameter of a chemical reaction at 25°C are 3×10–4 s–
has a value of 2.0 × 10–3 mol lit-1s -1 . The order of the reaction
1,104.4kJ /mol and 6×1014 s–1 respectively. The value of the
is rate constant as T ® ¥ is
(a) –1 (b) 0 (a) 2.0×1018 s–1 (b) 6.0×1014 s–1
(c) 1 (d) 2 (c) Infinity (d) 3.6×1030 s–1
3. For the gas phase decomposition A ® 2B, the rate 9. A substance ‘A’ decomposes in solution following first order
constant is 6.93 × 10–3 min–1 at 300 K. The percentage of a kinetics. Flask I contains l L of a 1M solution of A and flask
remaining at the end of 300 minutes is II contains 100 ml of a 0.6 M solution. After 8 hours the
concentration of A in flask I has become 0.25. What will be
(a) 75 (b) 50
the time taken for concentration of A in flask II to become
(c) 25 (d) 12.5 0.3M ?
4. For a first order reaction t 0.75 is 1368 seconds, therefore, (a) 0.4 h
the specific rate constant in sec–1 is (b) 2.4 h
(c) 4.0 h
(a) 10–3 (b) 10–2 (d) Can’t be calculated since rate constant is not given
(c) 10–9 (d) 10–5 10. A reaction rate constant is given by
5. Consider the following reactions at 300 K k = 1.2 ´ 1014 e-25000/RT sec-1 . It means
(a) log k versus log T will give a straight line with a slope as
X ¾¾ ¾
¾® Y (uncatalysed reaction)
–25000
catalyst
X ¾¾¾
¾® Y (catalysed reaction) (b) log k versus T will give a straight line with slope as
25000
The energy of activation is lowered by 0.314 KJ mol -1 for (c) log k versus log 1/T will give a straight line with slope as
the catalysed reaction. The rate of reaction is –25000
(a) 38 times (d) log k versus 1/T will give a straight line
(b) 15 times 11. Consider a general chemical change 2A + 3B ® products.
(c) 25 times The rate with respect to A is r1 and that with respect to B is
(d) 22 times that of uncatalysed reaction. r2. The rates r1 and r2 are related as
6. For a reaction A ® B , the rate increases by a factor of 2.25 (a) 3 r1=2r2 (b) r1 = r2
when the concentration of A is increased by 1.5. What is the (c) 2r1 = 3r2 (d) r12 = 2r22
order of the reaction?
12. In case of first order reaction,the ratio of the time required for
(a) 3 (b) 0
99.9% completion to 50% completion is
(c) 2 (d) 1 (a) 2 (b) 5
7. The reactions rate N 2 (g) + 3H 2 (g) ® 2 NH 3 (g) was (c) 10 (d) None of these
13. For the exothermic reaction A + B ® C + D, DH is the heat
measured d[ NH 3 ] = 2 ´ 10 - 4 mol sec –1 . The rates of of reaction and Ea is the energy of activation. The energy of
dt
activation for the formation of A + B will be
reactions expressed in terms of N2 and H2 are (a) Ea (b) DH
(c) Ea + DH (d) DH – Ea
JEEMAIN.GURU
downloaded from jeemain.guru
(c) [N2O4] (d) [N2O4] 26. In acidic medium the rate of reaction between BrO3 - and
JEEMAIN.GURU
downloaded from jeemain.guru
618 Chemistry
34. For a zero order reaction, the plot of conc. Vs time is linear
28. The activation energy of the reaction A ¾ ¾® X is 12.49
with
kcal mol–1. If temperature is raised to 305 K from 295 K, the
(a) –ve slope and non zero intercept
reaction rate increases by
(b) +ve slope and zero intercept
(a) » 50 % (b) » 60 %
(c) –ve slope and zero intercept
(c) » 100 % (d) unpredictable.
(d) + ve slope and non zero intercept
29. For the reaction A + B ¾ ¾® C + D. The variation of the 35. The half life decomposition of gaseous CH3CHO at constant
concentration of the products is given by the curve
temperature but at initial pressure of 364 mm and 170 mm of
Hg were 410 sec, and 880 sec respectively. The order of the
Y
reaction is
Z
(a) 1.0 (b) 3.0
Conc (c) 2.0 (d) 1.5
36. The racemisation of a - pinene is first order reaction. In the
W
X gas the specific reaction rate was found to be 2.2 ´ 10 -5 mm
Time
Hg–1 at 457.6 K and 3.07 ´ 10 -3 mm Hg–1 at 510.1 K. The
(a) Z (b) Y energy of activation is
-3
(c) W (d) X (a) K (510.1 – 457.6) ln (3.07 × 10 / 2.2 ´ 10 -5 )
30. A gaseous reaction
1 (b) 3. 048 ´10 -3
X 2 (g) ¾
¾® Y + Z(g)
2
There is increase in pressure from 100 mm Hg to 120 mm Hg (c) ln 2. 2 ´10 -5 ´ 457.6 k cal.
in 5 minutes. The rate of disappearance of X 2 is (d) (510 .1 ´ 457 .6 / 52 .5) R ln (307)/2.2) cal.
(a) 8 mm Hg min -1 (b) 2 mm Hg min -1 37. The half life of the first order reaction
(i) A + B ¾¾® X (slow) (ii) X ¾ ¾® AB (fast) pressure at the end of 20 minutes is 120 mm Hg
(a) 80 min (b) 120 min
The progress of the reaction can be best described by
(c) 20 min (d) 40 min
JEEMAIN.GURU
downloaded from jeemain.guru
k1 14. (c) The rate constant doubles for 10º C rise in temperature.
1. (b) 2 NO2 N2O4,
k2 For 20º C rise, the rate constant will be 4 times
\ k1 = 4k2 or k2 = 0.25 K1
For forward reaction rate = - 1 dNO2 = dN2 O4
2 dt dt
2.303 a 2.303 1 2.303
15. (d) k = log = log = log 8
= k1[NO 2 ] 2 t a-x 24 1 24
8
For backward reaction
16. (d) With temperature the number of activated molecules
dN 2 O 4 1 dNO 2
Rate = - = = k 2 [N 2 O 4 ] . increase.
dt 2 dt
17. (b) Between 2 and 3.
Rate of disappearance of NO2 = (Rate of disapperance of 18. (c) There are 5 tens hence (2)5 = 32.
NO2 – Rate of appearence of NO2)
19. (b) For 1st order rection t 1/2 independent of initial
= 2k1[NO2]2 – 2k2[N2O4].
concentration.
2. (b) By concentration of reactants.
20. (c) Let the rate law equation be r = k[A]x[B]y................(1)
3. (b) 3A ® 2B
when A = 2A, 4r = k[2A]x[B]y........................(2)
Rate of reaction - 1 dA = 1 dB or - 2 dA = dB
4r k[2A]x [B] y
3 dt 2 dt 3 dt dt Divide(2) by (1) =
r k[A]x [B] y
4. (a) N 2 (g ) + 3H 2 (g ) ¾
¾® 2 NH 3 (g )
\ 4 = (2)x, Hence x = 2
Rate = -
dN 2 1 dH 2 1 dNH 3 when B = 2B, r = k[A]x [2B]y.........................(3)
=- =
dt 3 dt 2 dt
r k[A]x [2B] y
5. (d) If volume is reduced to 1/4th concentration will \ 1 = Divide (3) by (1) = (2)y \ y = 0
be increased 4 times hence reaction rate will r k[A]x [B]y
increase by 16. Rate = k[A][B].
\ Rate = k[A]2[B]0
New rate = k[4A][4B] = 16k[A][B]
JEEMAIN.GURU
downloaded from jeemain.guru
620 Chemistry
21. (a) Let the rate law be r =k [A]x[B]y
1
34. (b) After every 30 minutes the amount is reduced to
x y 2
0.10 [0.024] [0.035]
Divide (3) by (1) =
0.10 [0.012] x [0.035] y therefore t1/2 is 30 minutes. In 90 minutes the amount is
\ 1 = [2]x, x = 0 1 1
reduced to i.e. . Here n = 3. True for 1st order reaction.
8 2n
0.80 [0.024] x [0.070] y
Divide (2) by (3) = a
0.10 [0.024]x [0.035] y 1 1
35. (c) t = for zero order, t = and t1 = , \ t1 = 2t
k 4k 2k
\ 8 = (2)y , y = 3
Hence rate equation, R = k[A]0[B]3 =k[B]3 0.693 2.303 100
36. (c) k = further t = ´ 45 log
45 0.693 100 - 99.9
22. (b) O 3 ¾Fast
¾
Slow
¾® O 2 + O; O + O 3 ¾¾¾® 2O 2
2.303 ´ 45 ´ 3 1
= = 7 hours .
[O ][O] 0.693 2
k= 2 (I), Rate = k' [O3][O] put [O] from (I)
[O 3 ]
2.303 a 2.303 0 .5
37. (a) t = log = log = 0.384 min .
k '[O3 ]k[O3 ] k a-x
= k[O3 ]2 [O2 ]-1
6 0.05
r=
[O2 ] 38. (d) Rate = k [N2O5] ;
Note intermediates are never represented in rate law 2.4 ´10 -5 = 3.0 ´ 10 -5 [ N 2 O 5 ]
equation.
23. (b) 1st order reaction. \ [ N 2 O 5 ] = 0 .8
24. (d) Rate = k [A]0 39. (a) Rate = k [N2O5]
\ Rate = k for zero order. = 6.2 ×10–4×1.25 = 7.75 × 10–4 mol L–1s–1
25. (d) Order with respect to A is 2 and B is 1.
2.303 100
\ Order of reaction = 2+1 = 3 40. (c) t 90% = log (I)
k 100 - 90
26. (a) t1/2 for 1st order is independent of initial concentration.
2.303 100
Ea t 50% = log (II)
27. (d) k = Ae - Ea / RT log k = log A – .
1 k 100 - 50
2.303R T
t log10
-E a Dividing 90% = \ t 90% = 3.3t 50%
Equation of straight line slope = . t 50% log 2
2.303R
41. (a) Since rate is constant throughout. It is zero order.
2.303 a
28. (a) t = log 42. (a) For zero order reaction tcompletion = a/k.
k a-x
43. (d) A 2 + B 2 ¾
¾® 2AB ; A 2 ¾
¾® A + A ( Fast );
2.303 2.303
or t = log a - log(a - x)
k k A + B2 ¾
¾® AB + B (Slow )
29. (d) Order of reaction is independent of given factors.
Rate law = k[A][B 2 ] put value of [A] from Ist reaction
30. (b) For zero order the rate does not change with
concentration. since A is intermediate k[A 2 ] = A
31. (c) t1/2 µ aº. t1/2 is independent of initial concentration.
32. (b) The order of a chemical reaction is given by \ Rate law equation = K k[A 2 ][B2 ]
concentration of reactants appearing in the lowest step.
1 3
\ Order = +1 =
1
33. (a) t1 / 2 µ a1- n
2 2
t1 / 2 µ hence n = 4.
a3 44. (c) It is bimolecular first order reaction since Rate µ [N2O5]
JEEMAIN.GURU
downloaded from jeemain.guru
-E a 2.303 a
Straight line Slope = k= log
2.303R t a- x
JEEMAIN.GURU
downloaded from jeemain.guru
622 Chemistry
2000 1000 M to 0.20 M but the rate has changed from 1.2× 10 –4 to
- -
or 10 ´ 10 .e
15 T 15
= 10 .e T 3.1×10–4. This is due to change in concentration of
CH3COCH3 from 0.30 M to 0.40 M. Thus the rate is
2000 1000 directly proportional to [CH3 COCH3]. We now get
- -
T T
or 10.e =e
rate = k [CH3COCH3]1[Br2]0[H+]1
2000 1000 = k [CH3COCH3][H+].
or ln 10 - =-
T T 6. (d) Rate of disappearance of H2 = rate of formation of
NH3.
2000 1000
or ln 10 = - 1 d[H2 ] 1 d[NH3 ]
T T – =
3 dt 2 dt
1000
or 2.303 log 10 = – d[H 2 ] 3 d[NH3 ] 3 –4
T Þ = = × 2×10
dt 2 dt 2
or 2.303 ×1×T=1000 [\ log 10= 1]
= 3×10 –4 mol L–1s –1
1000
or T = K 7. (d) Rate of disappearance of Br–
2.303
= rate of appearance of Br2
5. (a) Rewriting the given data for the reaction
1 d[Br – ] 1 d[Br2 ]
H+ Þ– =
CH 3COCH 3 ( aq ) + Br2 ( aq ) ¾¾® 5 dt 3 dt
CH3COCH 2 Br(aq) + H + (aq) + Br - ( aq) 1 d[Br2 ] 1 d[Br – ]
Þ =-
3 dt 5 dt
S. Initial concent Initial concentr Initial concentr Rate of
d[Br2 ] 3 d[Br – ]
No. -ration of -ation of Br2 -ation of H + disappearance Þ =-
dt 5 dt
CH3 COCH3 in M in M of Br2 in Ms -1
in M d dx 8. (b) For a first order reaction
i.e. - [Br2 ]or
dt dt
0.693 0.693
1 0.30 0.05 0.05 5.7 ´ 10-5 t1/2 = ; k= = 0.5 × 10–3s–1
k 1386
2 0.30 0.10 0.05 5.7 ´ 10-5
3 0.30 0.10 0.10 1.2 ´ 10-4 9. (a) When concentration A is doubled, rate is doubled.
4 0.40 0.05 0.20 3.1 ´ 10-4 Hence order with respect to A is one.
When concentrations of both A and B are doubled,
rate increases by 8 times hence order with respect to B
Actually this reaction is autocatalyzed and involves
is 2.
complex calculation for concentration terms.
\ rate = k [A]1 [B]2
We can look at the above results in a simple way to
find the dependence of reaction rate (i.e., rate of Total order = 1 + 2 = 3
disappearance of Br2).
10. (b) N 2 O5 (g) ¾¾
® 2NO2 (g) + 1/2 O 2 (g)
From data (1) and (2) in which concentration of
CH3COCH3 and H+ remain unchanged and only the
[ N2 O5 ] = + [ NO2 ] = 2 [O2 ]
concentration of Br2 is doubled, there is no change in d 1d d
–
rate of reaction. It means the rate of reaction is dt 2 dt dt
independent of concentration of Br2.
[ NO2 ] = 1.25 ´ 10-2 mol L–1s–1 and
d
Again from (2) and (3) in which (CH3CO CH3) and (Br2)
dt
remain constant but H+ increases from 0.05 M to 0.10
i.e. doubled, the rate of reaction changes from 5.7×10–5
[O2 ] = 3.125 ´ 10-3 mol L–1s–1
d
to 1.2 × 10–4 (or 12 × 10–5), thus it also becomes almost
dt
doubled. It shows that rate of reaction is directly
proportional to [H+]. From (3) and (4), the rate should 11. (b)
have doubled due to increase in conc of [H+] from 0.10
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
624 Chemistry
32. (d) The graphs show that reaction is exothermic. 39. (a) Since initial velocity is ten times the permissible value
\ A0 = 10A
-DH
log k = +I
RT 0.693 0.693
l= =
For exothermic reaction DH < 0 or t1/ 2 30
[ A0 ]
keeping concentration of B constant.
2
\ Order of reaction = 1 + 1 = 2 and units of second or k = = = 1 mol lit –1 hr–1
2 t1/ 2 2 ´1
order reaction are L mol–1 sec–1.
JEEMAIN.GURU
downloaded from jeemain.guru
43. (d) Since the slow step is the rate determining step hence Rate = k[A] = 3.47 × 10–2 × 0.01
if we consider option (A) we find
= 3.47 × 10–4 M/min
Rate = k [ Cl2 ][ H 2S] 47. (a) Activation energy can be calculated from the equation
Now if we consider option (B) we find log k2 -Ea æç 1 1ö
= çç - ÷÷÷÷
log k1 2.303R è T2 T1 ø
Rate = k [ Cl2 ] éë HS ùû
-
...(i)
For equation, k
Given 2 = 2 ; T2 = 310 K ; T1 = 300 K
H+ + HS–
H S k1
2
é H + ù é HS- ù -Ea æ 1 1 ÷ö
= log 2 = çç - ÷
K = ë ûë 2.303´8.314 èç 310 300 ÷ø
û
H 2S
Ea = 53598.6 J/mol = 53.6 kJ/mol.
- K [ H 2S ] 48. (d) Overall order = sum of orders w.r.t each reactant.
or éë HS ùû =
H+ Let the order be x and y for G and H respectively
Ea1 / RT 0.693
k1 = k2 A ´ e and k1 =
t1/ 2
45. (c) Since for every 10ºC rise in temperature rate doubles Substituting various given values, we get
for 50ºC rise in temperature increase in reaction rate
= 25 = 32 times 1.386 mol litre –1
k0 = ... (i)
2 ´ 20 sec
JEEMAIN.GURU
downloaded from jeemain.guru
626 Chemistry
0.693
and k1 =
40sec
... (ii) 4. (a) k = 2.303 log 100 On solving we get . k = 10–3
1386 100 - 75
Dividing (ii) by (i), we get
5. (c) k un cat = A e E uncat / RT ......... (i)
k1 0.693 2´ 20 0.693
= ´ k cat = A e E cat / RT ......... (ii)
1.386 mol dm-3
40 = = 0.5
k0 1.386
Let the Ea for uncatalysed reaction be A then for catalysed
= 0.5 mol–1 dm3
reaction it will be (A - 8.314 ´ 103 ) cal/mole
Thus the correct answer is (a).
Dividing (ii) by (i),
Ea
50. (d) log k = log A - …(1) 3
2.303RT k cat e ( A -8.314´10 ) / RT
8.314´10 3
/ RT
= =e
k un cat e A / RT
1
Also given log k = 6.0 - (2000) …(2)
T k cat
= e 3.33 = 28 (take log then antilog)
On comparing equations, (1) and (2) k un cat
log A = 6.0 Þ A = 106 s–1
6. (c) Let the rate law equation be
Ea
and 2.303 R = 2000 ; r = k[A]x ...................(i)
25000 1
\ T = 2 t 1 / 2 . 2t1/2 is half life of S and twice the half - log k = log 1.2 × 10 -
14
.
R T
life of R
2. (c) Units of k = (Mol lit–1) time –1 ; Hence n = 1 order
0.693 Logk
3. (d) For first order t½ = = 100 min ; 300 = 100 × n
-3
6.93 ´10
1/T
100 Equation of straight line
Percentage left = = 12.5%
( 2) 3
2500
slope = -
R
JEEMAIN.GURU
downloaded from jeemain.guru
11. (a) For the change 2A + 3B ® products 17. (d) N 2 O 4 2NO 2 . Decomposition of N2O4 is first
order and its concentration will will decrease with time.
1 d[ A ] 1 d[ B] 1 1
- =- , r1 = r2 ; 3r1 = 2r2
2 dt 3 dt 2 3 18. (b) For zero order
2.303 100 Co - C t
12. (c) t 99.9% = log k=
k 100 - 99.9 t
-5
Rate = k[A][B]2 = k(0.60)(0.80)2 .......................(i)
kC 3.8 ´ 10
The fractional yield of C = =
k av 1.64 ´ 10 - 4 when p c = 0.20 atm p A is reduced to 0.40 and
pB = 0.40 (See stoichiometric representation)
= 0.2317 = 23.17 %
Rate = k[0.40] [0.40]2..............................(ii)
2.303 [A]0 2.303 800
16. (c) k = log = log = 1.386 ´ 10 4 s -1 0.40 ´ 0.40 ´ 0.40 1
t [A]t 2 ´ 10 4 50 \ (ii) divide by (i) = =
0.60 ´ 0.80 ´ 0.80 6
JEEMAIN.GURU
downloaded from jeemain.guru
628 Chemistry
26. (a) The rate law equation contains [H + ]2 , term. The rate k2 E a (T2 - T1 )
36. (d) ln =
k1 R T2 ´ T1
will change with change in pH and new rate will be [2]2
= 4 times the old rate 3.07 ´10-3 E a (510.1 - 457.6)
ln =
Ea 2.2 ´10 -5 R 510.1´ 457.6
1
27. (b) log k = log A – .
2.303 T \ Ea = (510.1 × 457.6) / 52.5 × R ln 307/2.2 cal.
The value of k increases with the increase of temperature.
37. (c) CH 3CHO (g ) ¾
¾® CH 4 (g) + CO (g)
28. (c) Generally the rate of reactions is doubled by 10°C rise in
temperature i.e. the increase is » 100 %.
When t = 0 p0 0 0
29. (b) The curve Y shows the increase in concentration of
products with time. When t = t p0 - p p p
30. (a) The increase in pressure shows the increase in conc. of Z.
120 - 100 \ p 0 - p + p + p = 120 mm Hg
Rate of appearance of Z = = 4 mm Hg min -1
5
or, p 0 + p = 120 mm Hg;
Rate of disappearance of X 2 = 2 × rate of appearance of
p = 120 – 80 = 40 mm Hg
Z = 2 × 4 mm Hg min -1 = 8 mm Hg min -1
31. (c) A dip in the curve shows the formation of X (reaction 1 p0 1 80 1
k= ln = ln = ln 2
taking place in two steps). Since the reaction is exothermic t p -p
0 20 80 - 40 20
Ea of X must be less.
ln2
K 310 Again, t1 / 2 =
32. (b) Temperature coefficient = = 2.3 k
K 300
ln2
K 310 = 2.3 K 300 \ t1 / 2 = ´ 20 = 20 min.
ln2
1
33. (c) t1 / 2 µ
6 ´ 10 -7
where n is the order of reaction
( p) n -1 38. (b) [H + ] = = 1.2 ´ 10 -2 M
-3
0.05 ´ 10
n -1 n -1
2 æ 50 ö 1 æ1ö
=ç ÷ or =ç ÷ DX DX 1.2 ´ 10 -2 M
4 è 100 ø 2 è2ø Rate r = ; Dt = =
Dt r 6 ´ 105 M s -1
\ n=2
-8
C0 - C \ T = 2 ´ 10 s
34. (a) For zero order reaction k = or C = C0 – kt
t
k 2 E 2 + k 1 E1
The equation has negative slope and non zero intercept. 39. (c) Ea =
k 2 + k1
n -1
t1 / 2 (1) é p (2) ù
35. (c)
t1 / 2 (2) êë p (1) úû
= , 1.0 ´10 - 2 ´ 60 + 3.0 ´10 - 2 ´ 70
=
1.0 ´10 - 2 + 3.0 ´10 - 2
n -1
880 é 364 ù Ea = 67.5 k J mol -1
= ê ú ;
410 ë 170 û
[2.14]1 = [2.1]n -1
JEEMAIN.GURU
downloaded from jeemain.guru
19
Surface Chemistry
Thomas Graham divided the solids into two types. TYPES OF COLLOIDAL SYSTEMS :
CRYSTALLOIDS : Dispersed Dispersion Name Examples
The substances whose solution readily diffuse through a phase medium
parchment membrane eg sugars, salts, acid and base. Gas Liquid Foam Shaving Cream,
COLLOIDS : Soda Water froth
The substance whose solution diffused at very slow rate through Gas Solid Solid foam Pumice stone,
a parchment membrane eg glue, gelatin, gum arabic etc. corck, foam rubber
Later on it was found that crystalloids and colloids differed only Liquid Gas Aerosol Mist , cloud, fog
in their size of particles. They can be interconverted, hence Liquid Liquid Emulsion Hair cream, milk
colloidal is a state.
Liquid Solid Gel Cheese, butter
On the basis of the size of particles we have
Solid Gas Smoke Occluded gases,
1nm 100nm dust soot in air
1Å 10Å 1000Å 10,000Å Solid Liquid Sol Colloidal gold
Solid Solid Solid sol alloys
JEEMAIN.GURU
downloaded from jeemain.guru
630 Chemistry
CHARACTERISTICS OF LYOPHILIC AND LYOPHOBIC AgNO + Tannic acid ® Ag Sol
SOLS :
AuCl3 + Tannic acid ® Au Sol
Property Lyophilic Sol Lyophobic Sol (iv) Hydrolysis - Ferric hydroxide sol is prepared by pouring
1 . Preparation Can be prepared easily Prepared by special methods dilute solution of ferric chloride into boiling water
2 . Charge May or may not carry Always carry positive or
any charge negative charge. FeCl3 + 3H 2 O ¾¾
® Fe(OH)3 + 3HCl
3. Solvation Sol particles are Not solvated. Red Sol
(Positive in nature)
heavily hydrated
4. Precipitation High concentration Precipitated by low Sols of chromium and aluminium can also be prepared
of the electrolytes concentration by this method.
required to cause . of electrolytes.
precipitation
(v) Change of solvent - When ethanolic solution of sulphur is
5. Viscosity Very high Same as that of dispersion added to an excess of water, the sol of sulphur is obtained.
medium. This is physical method.
6. Surface tension Low Same as that of dispersion (b) Dispersion methods :
medium. Here lumps of the substances broken down to colloidal size
7. Reversibility Reversible Irreversible
in presence of dispersion medium and suitable stabilizer.
8. Migration in May or may Always migrate in electric
(i) Mechanical dispersion - In this method colloid mill, ball mill
electric field not migrate field. or ultrasonic disintegrator are used.
9 . Tyndall effect No Yes (ii) Bredig’s arc method (electrical disintegration). An arc is
10. Stability More stable Less stable struck between two metal electrodes of silver, gold or platinum
CLASSIFICATION ON THE BASIS OF SIZE OF SOL held at the surface of cold water containing traces of alkali
when sol of metal is obtained.
PARTICLES :
(i) Multimolecular colloids - In this case the colloidal particles Electrodes
consists of aggregates of atoms or small molecules with
diameters of less than 1nm eg gold sol, sulphur sol.
(ii) Macromolecular colloids - In this case dispersed particles
are of colloidal size and are called macromolecules, usually
Dispersion
polymers such as starch, cellulose, proteins or synthetic medium
polymers etc. Ice-bath
(iii) Associated colloids - At low concentrations they behave as
electrolytes and at higher concentrations as colloids. They
are also known as micelles. Soaps and detergents are the
Bredig’s Arc method
examples. The micelles may contain about 100 molecules or
more. (iii) By peptization - The dispersal of freshly precipitated
PREPARATION OF COLLOIDAL SOLUTIONS : substance into colloidal solution by the addition of some
Lyophobic sols and lyophilic sols are prepared by different electrolyte having one ion common is known as peptization.
methods. The electrolyte used is called peptizing agent e.g.
Preparation of lyophobic sols - The methods employed are : (i) Ferric hydroxide Fe(OH)3 is peptized by ferric chloride
(a) Condensation methods (b) Dispersion methods. giving sol. of [Fe(OH)3]Fe3+
(a) Condensation methods : (ii) Silver chloride AgCl is peptized by HCl giving negative
In these methods small ions or molecules are induced to combine sol of [AgCl]Cl–
together to form aggregates of colloidal size and chemical or (iii) Cadmium sulphide CdS is peptized by H2S giving
physical methods may be employed. negative sol of [CdS]S– –
(iv) Cellulose nitrate is peptized by a mixture of ethanol and
Chemical methods :
water. The product obtained is called “colloidon”.
(i) Double decomposition - An arsenic sulphide (As2S3) sol is
prepared by passing H2S through cold solution of As2O3 till PURIFICATION OF COLLOIDAL SOLUTIONS :
yellow colour deepens to its maximum The removal of the particles of electrolytes from sols is known as
purification of sols. It can be achieved by any of the following
As 2 O 3 + 3H 2S ® As 2S3 (Sol ) + 3H 2 O
methods.
(ii) Oxidation - A sol of sulphur is prepared by passing H2S into a) Dialysis b) Electrodialysis c) Ultra Filtration
solution of SO2 Dialysis : A mixture containing colloidal particles and particles of
2H 2S + SO 2 ® 2 H 2 O + S ¯ true solution is placed in a parchment bag. The bag is hanged in
water vessel through which it is continously flowing. The particles
(iii) Reduction - Sols of gold, platinum and silver are prepared of true solution come out of membrane leaving behind colloidal
by reduction of their compounds in water using, solution.
formaldehyde or hydrazine or tannic acid
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
632 Chemistry
Zeta potential - The potential difference developed between Factors affecting Brownian movement
the two layers is known as zeta potential or electric kinetic (i) Size of particles - Small particles execute more rapid, brisk
potential. and vigrous motion than larger particles.
(ii) Temperature - It is increases with temperature.
- + - Importance
- - (i) Stability of colloidal solution
+ +
+ + +
(ii) Confirmation of kinetic theory
- Positive -
-
(iii) Determination of avogadro number
- + sol
+
+ +
Brownian movement is due to the bombardment of the
+ - particles of the dispersion medium on the particles of
-
- + - dispersed phase.
(iii) Electrophoresis - The movement of sol particles under an COAGULATION, PRECIPITATION
applied electric potential is called electrophoresis or OR FLOCCULATION:
cataphoresis. The phenomenon helps in The settling down of the discharged sol particles is called
Reservoir coagulation or precipitation of the sol. It can be achieved by
(i) Electrophoresis
(ii) Addition of electrolytes
Anode Cathode (iii) By boiling
(iv) Mixing two sols of opposite charge
(v) By persistant dialysis
HARDY SCHULZE RULE :
Initial level
It states that the precipitating effect of an ion increases with the
Water valency of the ion.
(dispersion Colloidal For precipitating a negative sol the precipitating power of cations
medium) solution follow the order
Al 3+ > Ba 2 + > Na +
For precipitating a positive sol the precipitating power of anions
follow the order
Stop cock
[Fe(CN)6 ]4 - > PO34- > SO24 - > Cl-
Electrophoresis Blood is positively charged sol (pH=7.4) and is coagulated by
alum, Al2(SO4)3 or FeCl3. These salts lower the pH and denaturate
(a) removing suspended impurities
globular proteins.
(b) removing smoke from chimney gases
(c) electroplating of rubber FLOCCULATION VALUE :
(d) painting metals with colloidal pigments The minimum concentration in millimoles per litre required to cause
(e) coagulation of sols the precipitation of a sol in 2 hours. The smaller the flocculation
(f) determination of charge value, the higher is the precipitating power of an ion.
(iv) Electro-osmosis - The movement of the dispersion medium PROTECTIVE ACTION OF LYOPHILIC SOLS :
under the influence of applied electric potential is known as The lyophobic sols are less stable than lyophilic sols. The lyophilic
electro osmosis. The phenomenon helps in sols are thus used to protect the lyophobic sols. This property of
(a) Removing water from peat lyophilic sols is known as protective action of lyophilic sols. A
(b) Dewatering of moist clay little gelatin stabilises As2S3 sol.
(c) Drying dye pastes.
GOLD NUMBER :
(v) Kinetic properties - Brownian movement - The zig - zag
movement of colloidal particles in the dispersion medium is The number of milligrams of a hydrophilic colloid that will just
called Brownian movement. prevent the precipitation of 10 ml of a gold sol on the addition of
1 ml of 10% sodium chloride solution is known as gold number.
The smaller the value of gold number of lyophilic sol, the greater
is the protective action.
Gold number of some lyophilic sols.
1. Gelatin 0.005 - 0.01
2. Caseinate 0.01
3. Haemoglobin 0.03
4. Gum arabic 0.15
5. Sodium Oleate 0.4
Brownian movement 6. Potato starch 25
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
634 Chemistry
(e) Artificial rains - Clouds are aerosols (water dispersed (ii) Heterogeneous catalysis - When the catalyst is in
in air). Aggregates of particles of water cause the rain a different phase than that of reactants and products the
fall which can be artificially achieved by throwing process is known as heterogeneous catalysis eg.
electrified sand or AgI on clouds and cause the artificial (a) Formation of ammonia by Haber’s process
rain. AgI has similar crystal structure as that of ice. N 2 + 3H 2 + [Fe] ® 2 NH3 + [Fe]
(f) Leather tanning - Skin of animals is positively charged gas gas solid gas solid
colloidal system. Extract of barks, wood leaves is (b) Formation of sulphur trioxide (contact process for
negatively charged colloidal solution of tannin. When sulphuric acid)
latter is applied on the surface of skin (leather) it becomes
2SO2 + O2 + [Pt] ® 2SO3 + [Pt]
hard and does not putrefy. gas gas solid gas solid
(g) In warfare - Animal charcoal is used in gas masks to
(c) In solution decomposition of hydrogen peroxide by
adsorb poisonous gases. Smoke screens are titanium
MnO2 or Pt
oxide particles dispersed in air.
2H 2 O 2 + [Pt ] ® 2H 2 O+ O 2 + [Pt ]
(2) In everyday life - Blood, milk, butter, cheese, clothes, shoes liquid solid
all are colloidal system.
(3) In medicines - Colloidal medicines are easily adsorbed and CLASSIFICATION OF CATALYSTS :
assimilated, hence are widely used. Colloidal antimony is According to their mode of action they have been classified into
effective medicine for kalazar. Blood is coagulated by FeCl3. four groups.
Colloidal sols of Ag (argyrol and protargol) are used as eye (i) Positive Catalysts - They always accelerate the speed of a
lotions. chemical reaction eg.
(a) Decomposition of potassium chlorate in presence of
(4) In nature - Blue colour of sky, tails of comets are due to
manganese dioxide
scattering of light.
2KClO + [MnO 2 ] ® 2KCl + O 2 + [MnO 2 ]
Formation of deltas in rivers is due to coagulation of
negatively charged sand particles by Na +, Mg2+ etc present (b) Manufacture of ammonia in presence of iron
in sea water. N 2 + 3H 2 + [ Fe] ¾
¾® 2 NH 3 + [ Fe ]
(ii) Negative Catalysts :
CATALYSIS They always retard the speed of chemical reaction eg
CATALYST : (a) Oxidation of chloroform in presence of ethanol
A substance which when added in very small amount to a chemical ®
4CHCl3 + 3O 2 + [C 2 H 5OH] ®
reaction change the speed of that reaction without itself
undergoing any chemical change is known as catalyst and the 4COCl 2 + 2Cl 2 + 2H 2 O + [ C 2 H 5 OH ]
phenomenon is known as catalysis. (b) Decomposition of hydrogen peroxide in presence of
dilute acids or glycerol
TYPES OF CATALYSIS :
2H 2O 2 + [H 3PO 4 ] ® 2H 2 O + O 2 + [H 3 PO 4 ]
The catalysis may be of two types
(i) Homogeneous Catalysis - When catalyst, reactants and the (iii) Auto catalyst - In this case one of the products act as a
products all are present in one phase, the process is known catalyst eg.
as homogeneous catalysis eg. Oxidation of oxalic acid by acidic permangnate
(a) Oxidation of sulphur dioxide to sulphur trioxide with
nitric oxide 2KMnO 4 + 3H 2SO 4 ® 2MnSO 4 + K 2SO 4 + 3H 2O + 5O
JEEMAIN.GURU
downloaded from jeemain.guru
2 N 2 + 3H 2 ¾¾ ¾
Fe / Mo
¾® 2 NH 3 2SO 2 + O 2 + [ NO] ® 2SO 3 + [ NO]
(vi) Catalyst poisoning - The substance which destroys the Intermediate mechanism
activity of a catalyst is called a poison and process is called O2 + 2NO ® 2NO 2
catalytic poisoning eg. Catalyst Intermediate
pt
2SO 2 + O 2 ¾¾ ¾ ¾ ¾
¾® 2SO 3 [SO 2 + NO 2 ® SO 3 + NO] ´ 2
poisoned by As 2O 3
2SO 2 + O 2 + [2NO] ® 2SO 3 + 2[ NO]
pt
2H 2 + O 2 ¾¾ ¾ ¾
¾® 2H 2 O
poisoned by CO Catalytic oxidation of hydrochloric acid by atmospheric
oxygen in presence of cupric chloride (Deacon’s process)
CHARACTERISTICS OF CATALYST :
CuCl
The following are some important features for a catalyst or HCl + O 2 ¾¾¾2 ® 2Cl 2 + 2H 2 O
catalysis. Mechanism - (2CuCl2 ® Cu2Cl2 + Cl2) × 2
(i) Small quantity - Generally small amount of a catalyst is 2Cu 2Cl 2 + O 2 ® 2Cu 2 .OCl 2
required but sometimes the large quantity of catalyst is Intermediate
effective eg anhydrous AlCl3 in Friedel Craft’s reaction is
needed upto 30%. (Cu 2 OCl 2 + 2HCl ® 2CuCl 2 + H 2 O) ´ 2
(ii) Unchangeabiliy - Although there is no change in the chemical 4HCl + O 2 + [4CuCl 2 ] ® 2Cl 2 + 2H 2 O + [4CuCl 2 ]
compostion and mass, there may be a change in physical Limitations of intermediate theory-
state of catalyst eg granular MnO2 changes to fine powder (a) Action of promoters and poisons.
in decomposition of potassium chlorate (b) Participation of catalyst in chemical reaction.
(iii) Specific action of catalyst - From the same reactants the (ii) Adsorption theory - By the adsorption of the reactants at the
different products are obtained with different catalysts eg. surface of a catalyst, their concentrations are increased. The
(a) C 2 H 5 OH ¾Al
¾2¾
O3
¾® C 2 H 4 + H 2 O ( Dehydratio n ) rate being directly proportional to concentration, is increased.
D (iii) Modern theory - It is the combination of intermediate theory
C2H5OH ¾¾¾
hot
® CH3CHO + H 2 (Dehydrogenation) and adsorption theory. At the surface of a catalyst there are
Cu,300ºC residual or free valencies and reactant molecules are retained
at the surface in distorted or strained positions. These
(b) 4 NH 3 + 3O 2 ¾Cu
¾® 2 N 2 + 6H 2 O molecules then react vigrously to give products and make
500º C
space for other reactant molecules. The greater the surface
Pt
4 NH 3 + 5O 2 ¾¾® 4 NO + 6 H 2 O area of the catalyst, the more is its activity. Further catalysts
800º C
with rough surface, having greater number of corners, peaks,
(iv) Initiation of reaction - In general a catalyst does not start a cracks have more active centres and more effective e.g. finely
chemical reaction, but there are reactions initiated by catalysts divided nickel or platinum
eg.
Active spot
H 2 + O 2 ¾Room
¾ ¾Temp
¾¾.® No reaction
Pt Black Ni
2H 2 + O 2 ¾¾ ¾¾® 2 H 2 O
(v) Equilibrium - A catalyst does not affect the state of Ni Ni Active spot Ni
equilibrium, it simply helps to attain it quickly.
Ni Ni Active spot Ni Ni Ni Ni
(vi) Optimum temperature - The rate of reaction is maximum at a
particular temperature which is fixed for every reaction. Ni Ni Ni Ni Ni Ni
(vii) Physical state of catalyst - Finely divided catalyst gives better
yield in a short period than lumps.
(viii) Activation energy - A positive catalyst lowers the activation ACTION OF PROMOTERS :
energy of a chemical reaction. It can be assumed that a loose compound is formed between the
catalyst and the promoter which possesses an increased capacity
THEORY OF CATALYSIS : of adsorption.
There are following main theories Action of catalytic poison - It may be due to the preferential
(i) Intermediate theory adsorption of poison on the active spots of the catalyst thus
(ii) Adsorption theory reducing the number of free active spots for reacting molecules.
(iii) Modern theory
JEEMAIN.GURU
downloaded from jeemain.guru
636 Chemistry
ACID BASE CATALYSIS :
A large number of reactions catalysed by acids or bases are known
ADSORPTION
eg. ADSOPRTION :
(a) Hydrolysis of an ester in presence of an acid Adsorption is the phenomenon of higher concentration of
H+
molecular species at the surface than in the bulk of a solid or
CH 3COOC 2 H 5 + H 2 O ¾¾
¾® CH 3COOH + C 2 H 5 OH
liquid. Forces involved are van der waal’s forces.
(b) Cyanides are hydrolysed by acids or alkalis The unbalanced or residual forces acting along the surface of a
solid or liquid attract the moleculs of other species when brought
H+ +H O
RCN + H2O ¾¾¾
®RCONH2 ¾¾¾
2 ¾
®RCOOH + NH3 into their contact. These molecules remain at surface and do not
-
or OH
go into bulk, hence making the concentration more at surface.
Such reactions are called acid base catalysis and H+ or OH–
ADSORBATE :
ions act as catalyst.
The substance that concentrates at the surface is called adsorbate.
MODERN CONCEPT OF ACID BASE CATALYSIS:
ADSORBENT :
According to this concept
(i) A reaction which is catalysed by an acid is also catalysed by Adsorbent is the solid or liquid at whose surface the concentration
all substances having tendency to lose protons (H+) occurs.
(ii) A reaction which is catalysed by a base is also catalysed by ABSORPTION :
all substances having a tendency to gain protons. Absorption is the phenomenon of uniform distribution of a
ENZYMES OR BIOLOGICAL CATALYSTS : substance throughout the body of a solid or liquid. For eg water
Many complex chemical reactions like oxidation, reduction or vapour is absorbed by a sponge or anhydrous CaCl2 while it is
hydrolysis take place in presence of enzymes which are highly adsorbed by silicagel. The pressure of gases (SO2, Cl2, NH3)
complex, nitrogenous non living organic substances. They are pressure decreases when treated with powdered charcoal in a
highly specific in nature eg. closed vessel due to adsorption of gas on charcoal surface.
(a) Starch is catalysed by diastase maltose is formed and then SORPTION :
maltose by maltase
Adsorption and absorption go hand in hand thus making it tough
Diastase
2(C 6 H10 O5 ) n + n H 2 O ¾¾ ¾¾® n C12 H 22 O11 to distinguish between them. The general term sorption was
Maltose introduced by McBain to include both processes.
Maltase
CHARACTERISTICS OF ADSORPTION :
C12H 22O11 + H 2O ¾¾¾¾
® 2C6H12O6
(i) It is a surface phenomenon.
Glucose
(ii) It is a spontaneous process.
(b) Urea is converted into ammonium carbonate by Urease (iii) Adsorption is accompanied by evolution of heat as the
H 2 N.CO.NH 2 + 2 H 2 O ¾¾ ¾
Urease
¾®( NH 4 ) 2 CO 3 residual forces acting along the surface of adsorbent
decrease.
MECHANISM OF ENZYME ACTION : Heat evolved on adsorption of 1 mole of a gas is molar heat
Enzyme can increase the rate of biochemical reactions by 106 to of adsorption.
1012 times. They are highly selective and specific and act on
(iv) Adsorption is accompanied by decrease in enthalpy. i.e. D H
certain molecules called substrates and leave the rest of the system
= -ve
unaffected (LOCK AND KEY THEORY). Michaelis and Menten
proposed the following mechanism for enzyme catalysis (v) Adsorption is accompanied by decrease in entropy i.e. TDG
is negative.
E + S ES ¾
¾® P + E
Enzyme Substrate Activated Complex Product Enzyme Also, DG = DH - TDS. As D H is negative and so is DS,
Þ DG is negative. But experimentally DH becomes less
CHARACTERISITCS OF ENZYME CATALYSIS :
negative as the adsorption progresses and ultimately
1. Enzymes are most efficient catalysts.
becomes zero as the equilibrium is reached.
2. Enzymes are very selective and specific.
Adsorption of gases at the surface of metals like Ni, Pt, Pd
3. Enzymes require optimum condition of temperature and pH etc is called Occlusion.
of the medium.
4. Enzymes are easily poisoned by addition of other substances PHYSICAL ADSORPTION :
particularly heavy metal ions (Hg2+ or Ag+) It is also called van der Waal’s adsorption which involves weak
5. Activity of enzymes is increased by activators (certain metal forces, physical in nature, with small heat of adsorption. For
ions Co2+, Mn2+, Na+, Cu++ etc) or coenzymes. example adsorption of H2 or O2 on charcoal.
JEEMAIN.GURU
downloaded from jeemain.guru
x/m
Ps
Often adsorption involves combination of two types of P
adsorption
At low pressure, x/m µ p 1 or x/m = kp 1 where
POINTS OF DISTINCTION BETWEEN PHYSICAL
k = constant
AND CHEMICAL ADSORPTION :
At high pressure, beyond saturation x/m is independent of p
Physical Chemical and x/m µ pº.
(i) Forces van der waals Chemical bonds At intermediate pressures, x/m µ p1/n where n > 1
(ii) Temperature at low temperature at high temperature
x 1
(iii) Layer multimolecular monomolecular or log = log k + log p where k = constant.
m n
(iv) Pressure increases with decrease with P. Infact
JEEMAIN.GURU
downloaded from jeemain.guru
638 Chemistry
(v) Surface area - Larger specific area (surface area per g of ACTIVATION OF ADSORBENT :
adsorbent) means greater adsorption. Activation or increasing the power of adsorption can be achieved
(vi) Heat of adsorption - Energy released when 1g mole of a gas in different ways.
is adsorbed on solid surface is called heat of adsorption.
Adsorption is an exothemic process similar to condensation. (i) by increasing surface area
Heat of adsorption is small as attractive forces between gas (ii) by making surface rough.
molecules and solid surface are due to weak van der waal’s Small size of particles makes the interparticle space too small
forces. to allow penetration of gas molecules and thus may decrease
ADSORPTION OF SOLUTES FROM SOLUTIONS: the extent of adsorption.
Porous and finely divided solid substances can also adsorb APPLICATIONS :
dissolved substances from solution eg activated charcoal adsorbs (i) High vacuum can be generated if a partially evacuated vessel
dye stuffs. When solution of acetic acid is shaken with activated is connected to a container of activated charcoal cooled with
charcoal, part of acid is removed by adsorption and concentration
liquid air. This is due to adsorption of gas molecules in vessel.
of the soluion is decreased. Some precipitates act as adsorbents.
For e.g. Mg(OH)2 when precipitated in the presence of dyestuff (ii) Gas masks contain activated charcoal or adsorbents to
magnesium forms a blue lake. Adsorption from solution follows remove poisonous gases and thus purify the air.
same principles as that for adsorption of gases by solids. Thus (iii) Heterogenous catalysis (see chapter on catalysis)
(i) Some adsorbents specifically adsorb some solute more (iv) Chromatographic analysis is based on principle of selective
effectively than others. adsorption. Mixture of gases can also be separated by
(ii) Increase in surface area causes increase in adsorption. selective adsorption of gases by liquids (gas
(iii) Adsorption increases with temperature. chromatography).
(iv) It involves establishment of equilibrium between the amount (v) Colouring matter can be removed from solutions by animal
adsorbed and the concentration of solute in solution. charcoal which adsorbs the colouring matter.
Freundlich isotherm using concentration can be written as: (vi) Froth floatation process which involves adsorption of mineral
particles wetted with oil is used to free low grade sulphide
x ores (PbS, ZnS, Cu2S) from silica.
= k × c1/n
m not in AIEEE syllabus but given for additional information.
where x = mass of solute adsorbed.
m = mass of adsorbent DISTRIBUTION LAW
c = equilibrium concentration of solution.
NERNST DISTRIBUTION LAW OR PARTITION LAW:
x 1
log = log k + log c is a straight line. When a solute is shaken with two immiscible liquids, having
m n
solubility in both, the solute distributes itself between the two
LANGMUIR’S ADSORPTION ISOTHERM : liquids in such a way that the ratio of its concentrations in two
Langmuir exploited theoretical considerations based on kinetic liquids is constant at a given temperature, provided the molecular
theory of gases to derive an adsorption isotherm. If w is mass of state of the solute remains the same in both the liquids.
gas adsorbed per unit mass of adsorbent and p is the pressure of
the gas then Solute X
p 1 æ Bö C1
= + ç ÷p where A and B are constant A
w A èAø
B X C2
p/w q
B 1 Concentiation of X in A C1
slope = , intercept = = a constant or = KD
A A Concentiation of X in B C2
p
COMPETING ADSORPTION : (Where KD = distribution coefficient or partition coefficient or
Different adsorbates compete among themselves to adsorb on distribution ratio)
the adsorbent. Strongly adsorbable substance can displace a Distribution of Succinic acid between ether and water illustrates
weakly adsorbable substance. For e.g. Cl2 and NH3 can replace the consistancy of the ratio of concentrations in each layer
O2 and N2 already adsorbed on charcoal. Moisture is also strongly C1 in ether C2 in water C1 /C2
adsorbed by silica though it is present in small proportion in air
and charcoal adsorbs polluting gases present in air in small 0.013 0.069 0.188
amounts. 0.022 0.119 0.184
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
640 Chemistry
1. If the solubility of iodine in water is 0.8 g/l at 25º C, calculate 3. The solubility of pure oxygen in water at 20º C and 1.00 atm
the solubility of I2 in CCl4. The kD of iodine in between CCl4
pressure is 1.38 ´ 10 -3 mole/litre. Calculate the concentration
and water is 85 in favour of CCl4 at 25º C.
of O2 (mole/litre) at 20º C and partial pressure of 0.21 atm.
[I 2 ]in CCl 4 layer Sol. Calculation of Henry’s constant
Sol. k D = = Let the solubility of I2 in CCl4 be
[I 2 ]in water layer
Conc. of O 2 1.38 ´10 -3
a g/litre kH or k = mole / litre
pressure of O 2 1.00 atm
a
85 = mole / litre
0.8 = 1.38 ´ 10 - 3
atm
a = 68 g litre–1 Calculation of concentration of O2
2. Succinic acid has normal molecular weight in water. Succinic
mole / litre
acid was allowed to distribute in water and benzene by C = kP = 1.38 ´ 10 - 3 ´ 0.21 atm
atm
shaking. The concentiation of acid in water and benzene
are C1 and C2 having values. = 2.9 × 10–4 mole/litre
(i) (ii) (iii) 4. The distribution coefficient of an alkaloid between
C1 g/100 ml 0.150 0.195 0.289 chloroform and water is 20 in favour of chloroform. Compare
the weights of the alkaloid remaining in aqueous solution
C2 g/100 ml 2.420 4.120 9.600
when 100 ml containing 1 gram has been shaken with (a)
Find the molecular weight of acid in benzene 100 ml chloroform and (b) two successive 50 ml portion.
Sol. Calculating the value of kD by applying the relation C1/C2
C water 1
and C1/ÖC2 Sol. K = =
C chloroform 20
C1 0.152 C1 0.150
In (i) = = 0.062 ; = = 0.096 (a) When 100 ml is used in one lot, the amount unextracted is
C 2 2.420 C2 2.420
æ KV ö
X1 = 1 ´ ç ÷
C1 0.195 C1 0.195 è KV + v ø
In (ii) = = 0.047 ; = = 0.096
C 2 4.120 C2 4.120
æ 1 / 20 ´ 100 ö 5
= 1´ ç ÷= = 0.0476 g
è 1 / 20 ´ 100 + 100 ø 105
C1 0.289 C1 0.289
In (iii) = = 0.030 ; = = 0.093 (b) When 50 ml chloroform is used in each of two stages the
C 2 9.600 C2 9.600 amount unextracted is
Since constant value of K D is obtained by relation 2 2
C1/ÖC2 hence succinic acid forms a dimer in benzene æ 1 / 20 ´ 100 ö æ 5 ö
X 2 = 1´ ç ÷ = ç ÷ = 0.0083 g
è 1 / 20 ´ 100 + 50 ø è 55 ø
Therefore its molecular weight in benzene = 2 × 118 = 236
JEEMAIN.GURU
downloaded from jeemain.guru
Very Short Answer Questions 19. Which one of the following in not a colloidal solution?
(a) Smoke (b) Ink
1. Which of the following is adsorbed most preferably:
(c) Blood (d) Air
O2, NH3, CO?
2. Can crystalloid be brought into colloidal state? Give one 20. Which of the following statements is not true about the oil-
example. in-water type emulsion?
3. Why are colloids good adsorbents? (a) On addition of small amount of water, no separate layer
4. Write the names of two gases which are adsorbed by of water appears
transition metals such as nickel and cobalt. (b) On addition of oil, separate layer of oil is formed
5. Can a gas mixed with another gas form a colloidal solution? (c) Addition of an electrolyte causes the conductivity of
Give reasons. the emulsion to increase
6. Account for the following: (d) Addition of small amount of oil soluble dye renders the
(a) Ferric hydroxide sol is positively charged. entire emulsion coloured.
(b) The extent of physical adsorption decreases with rise
21. Suspensions are
in temperature.
(a) Visible to naked eye
(c) A delta is formed at the point where river enters the sea.
(b) Not visible by any means
7. Detergents with straight chain hydrocarbons are preferred
(c) Invisible under electron microscope
to branched chain hydrocarbons. Explain.
(d) Invisible through microscope
8. Smoke is passed through charged plates before allowing it
to pass through chimneys in industries. 22. Which of the following terms is not related with colloids ?
9. Comment on sign of DH, DS and DG for adsorption process. (a) Brownian movement
10. What is demulsification? Name two demulsifiers. (b) Dialysis
11. Out of NH3 and CO2, which gas will be absorbed more readily (c) Ultrafiltration
on the surface of activated charcoal and why? (d) Wavelength
12. What is meant by chemisorption? 23. A colloid always :
13. Explain the following terms : (a) Contains two phases
(i) Electrophoresis (b) Is a true solution
(ii) Dialysis (c) Contains three phases
(iii) Tyndall effect. (d) Contains only water soluble particles
14. What is meant by coagulation of colloidal solution? 24. When a colloidal solution is observed under an
Describe briefly and three methods by which coagulation of ultramicroscope, we can see
lyophobic sols can be carried out. (a) Light scattered by colloidal particles
15. Explain the following terms giving a suitable example for each: (b) Size of the particle
(i) Aerosol (c) Shape of the particle
(ii) Emulsion (d) Relative size
(iii) Micelle 25. One desires to prepare a positively charged sol of silver
16. Write the dispersed phase and dispersion medium of the iodide. This can be achieved by
following colloidal systems: (a) adding small amount of AgNO3 solution to KI solution
(i) Smoke in slight excess
(ii) Milk (b) adding small amount of KI solution to AgNO3 solution
17. What are lyophilic and lyophobic colloids? Which of these in slight excess
sols can be easily coagulated on the addition of small (c) mixing equal volumes of equimolar solutions of AgNO3
amounts of electrolytes? and KI
Multiple Choice Questions (d) None of these
26. Cod Liver oil is
18. Which one of the following statements is incorrect in the (a) fat dispersed in water (b) water dispersed in fat
case of heterogeneous catalysis ?
(c) water dispersed in oil (d) fat dispersed in fat.
(a) The catalyst lowers the energy of activation
27. Colloid of which one of the following can be prepared by
(b) The catalyst actually forms a compound with the
electrical dispersion method as well as reduction method ?
reactant
(a) Sulphur (b) Ferric hydroxide
(c) The surface of the catalyst plays a very important role
(c) Arsenious sulphide (d) Gold
(d) There is no change in the energy of activation.
JEEMAIN.GURU
downloaded from jeemain.guru
642 Chemistry
1. The size of colloidal particles is between 13. When H 2 S gas is passed thr ough nitric acid, the
(a) 10-7 - 10-9 cm (b) 10-9 - 10-11 cm product is
-5
(c) 10 - 10 cm-7 (d) 10-2 - 10-3 cm (a) Rhombic S (b) Prismatic S
2. The size of colloidal particles is of the order (c) Amorphous S (d) Monoclinic S
(a) > 0.1 m (b) 1mm to 0.2m 14. Colloid of which one of the following can be prepared by
(c) < 1 mm (d) > 10 mm electrical dispersion method as well as reduction method ?
3. Butter is a colloid formed when (a) Sulphur (b) Ferric hydroxide
(a) fat is dispersed in water (c) Arsenious sulphide (d) Gold
(b) fat globules are dispersed in water 15. The formation of colloid from suspension is
(c) water is dispersed in fat (a) Peptisation (b) Condensation
(d) None of the these (c) Sedimentation (d) Fragmentation
4. Milk is a colloid in which 16. Which one of the following substances is not used for
(a) A liquid is dispersed in liquid preparing lyophillic sols ?
(b) A solid is dispersed in liquid (a) Starch (b) Gum
(c) A gas is dispersed in liquid (c) Gelatin (d) Metal sulphide
(d) some sugar is dispersed in water 17. Blood may be purified by
5. Cod Liver oil is (a) Dialysis (b) Electro osmosis
(a) Fat dispersed in water (b) Water dispersed in fat (c) Coagulation (d) Filtration
(c) Water dispersed in oil (d) Fat dispersed in fat. 18. The cause of Brownian movement is
6. Cloud or fog is a colloidal system in which the dispersed (a) Heat changes in liquid state
phase and the dispersion medium are
(b) Convectional currents
(a) Gas, Liquid (b) Liquid, gas
(c) The impact of molecules of the dispersion medium on
(c) Liquid, liquid (d) Solid, Liquid
the colloidal particles.
7. Which one among the following sols is hydrophobic ?
(d) Attractive forces between the colloidal particles and
(a) Gum (b) Gelatin
molecules of dispersion medium.
(c) Starch (d) Sulphur
19. Brownian movement is found in
8. Which of the following constitutes irreversible colloidal
(a) Colloidal solution (b) Suspension
system in water as dispersion medium?
(c) Saturated solution (d) Unsaturated solution
(a) Clay (b) Platinum
20. Random motion of colloidal particles is known as
(c) Fe(OH)3 (d) All of these
9. Which of the following is a lyophillic colloid ? (a) Dialysis (b) Brownian movement
(a) Milk (b) Gum (c) Electroosmosis (d) Tyndall effect
(c) Fog (d) Blood 21. Milk can be preserved by adding a few drops of
10. Surface tension of lyophillic sols is (a) Formic acid solution (b) Formaldehyde solution
(a) lower than that of H2O (c) Acetic acid solution (d) Acetaldehyde solution.
(b) more than that of H2O 22. In which of the following Tyndall effect is not
(c) equal to that of H2O observed ?
(d) can either lower or more than H2O. (a) Suspensions (b) Emulsions
11. Peptization denotes (c) Sugar solution (d) Gold sol
(a) Digestion of food 23. Point out the false statement
(b) Hydrolysis of proteins (a) Brownian movement and Tyndall effect are shown by
(c) Breaking and dispersion into the colloidal state colloidal systems.
(d) Precipitation of solid from colloidal dispersion (b) Gold number is a measure of the protective power of a
12. Colloidal gold is prepared by lyophillic colloid
(a) Mechanical dispersion (b) Peptisation (c) The colloidal solution of a liquid in liquid is called gel
(c) Bredig’s Arc method (d) Hydrolysis (d) Hardy - Schulze rule is related with coagulation.
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
644 Chemistry
45. Which of the following statements about a catalyst is/are 57. Which one of the following is an incorrect statement for
true ? physisorption ?
(a) A catalyst accelerates the reaction by bringing down the (a) It is reversible process
free energy of activation (b) It requires less heat of absorption
(b) A catalyst also takes part in the reaction mechanism (c) it requires activation energy
(c) A catalyst makes the reaction more feasible by making (d) It takes place at low temperature
the DGº more negative 58. Which is adsorbed in maximum amount by activated charcoal
(d) A catalyst makes the equilibrium constant of the reaction ?
more favourable for the forward reaction. (a) N2 (b) CO2
46. The role of a catalyst in a reversible reaction is to (c) Cl2 (d) O2
(a) Increase the rate of forward reaction 59. Which among the following statements is false?
(b) Decrease the rate of backward reaction (a) Increase of pressure increases the amount of adsorption
(c) alter the equilibrium constant of the reaction (b) Increase of temperature may decrease the amount of
(d) Allow the equilibrium to be achieved quickly adsorption.
47. Which of the following kind of catalysis can be explained by (c) The adsorption may be monolayered or multilayered
the adsorption theory ? (d) Particle size of the adsorbent will not affect the amount
(a) Homogeneous catalysis of adsorption.
(b) Acid - base catalysis 60. Rate of physisorption increases with
(c) Heterogeneous catalysis (a) decrease in temperature (b) increase in temperature
(d) Enzyme catalysis (c) decrease in pressure (d) decrease in surface area
48. A biological catalyst is essentially 61. Distribution law was given by
(a) An enzyme (b) A carbohydrate (a) Van’t Hoff (b) Henry
(c) An amino acid (d) A nitrogenous base (c) Nernst (d) Ostwald
49. In Zeigler - Natta polymerisation of ethylene, the active species 62. When is the Distribution Law applicable?
is (a) Temperature remains constant
(a) AlCl3 (b) Et3Al (b) Dilute solutions are employed
(c) Two solvents are mutually insoluble
(c) CH2CH2 (d) Ti3+
(d) All of these
50. Adsorbed acetic acid on activated charcoal is:
63. The relation between pressure and solubility of a gas was
(a) Adsorber (b) Absorber given by
(c) Adsorbent (d) Adsorbate (a) Henry (b) Nernst
51. Which of the following is less than zero during adsorption. (c) Both (a) and (b) (d) Neither (a) nor (b)
(a) D G (b) D S 64. The solubility of iodine in water is 0.35 g/ litre at 25°C. If
(c) D H (d) All of these distribution coefficient of iodine between CS2 and water is
52. The heats of adsorption in physisorption lie in the range (in 600, the solubility of iodine in CS2 in g/ litre will be
kJ/mol) (a) 210 (b) 510
(a) 40 - 400 (b) 40 - 100 (c) 195 (d) 250
(c) 10 - 40 (d) 1 - 10 S1
65. Partition coefficient, K = is valid
53. In physical adsorption, gas molecules are bound on the solid S2
surface by (a) when dissociation takes place
(a) Chemical forces (b) Electrostatic forces (b) when association takes place
(c) Gravitational forces (d) van der waal’s forces (c) when there is a complex formation
54. How many layers are adsorbed in chemical adsorption ? (d) in case of normal distribution
(a) One (b) Two 66. When a solute is shaken with two immiscible liquid, it
(c) Many (d) Zero associates in one of the liquids. The distribution constant is
55. In physical adsorption, the forces associated are given by
(a) ionic (b) covalent C1 C1
(a) (b)
(c) van der Waal (d) H - bonding C2 C 2 (1 - a )
56. Adsorption due to strong chemical forces is called
S1 C1
(a) Chemisorption (b) Physiosorption (c) (d)
S2 n C2
(c) Reversible adsorption (d) Both (b) and (c)
JEEMAIN.GURU
downloaded from jeemain.guru
1. The Langmuir adsorption isotherm is deduced by using the 3. In Freundlich Adsorption isotherm, the value of 1/n is :
assumption [CBSE-PMT 2007] (a) between 0 and 1 in all cases [CBSE-PMT 2012S]
(b) between 2 and 4 in all cases
(a) the adsorption sites are equivalent in their ability to adsorb
(c) 1 in case of physical adsorption
the particles
(d) 1 in case of chemisorption
(b) the heat of adsorption varies with coverage 4. Which one of the following, statements is incorrect about
(c) the adsorbed molecules interact with each other enzyme catalysis? [CBSE-PMT 2012S]
(d) the adsorption takes place in multilayers. (a) Enzymes are mostly proteinous in nature.
(b) Enzyme action is specific.
2. If x is amount of adsorbate and m is amount of adsorbent,
(c) Enzymes are denaturated by ultraviolet rays and at high
which of the following relations is not related to adsorption
temperature.
process ? [CBSE-PMT 2011] (d) Enzymes are least reactive at optimum temperature.
(a) x / m = f (p) at constant T. 5. The protecting power of lyophilic colloidal sol is expressed in
(b) x / m = f (T) at constant p. terms of : [CBSE-PMT 2012S]
(c) p = f (T) at constant (x / m). (a) coagulation value
(b) gold number
x (c) critical miscelle concentration
(d) p T
m (d) oxidation number
JEEMAIN.GURU
downloaded from jeemain.guru
646 Chemistry
6. Which of the following is not the property of hydrophilic 10. Gold numbers of protective colloids A, B, C and D are 0.50,
solutions ? 0.01, 0.10 and 0.005, respectively. The correct order of their
(a) High concentration of dispersed phase can be easily protective powers is [AIEEE 2008]
obtained (a) D < A < C < B (b) C < B < D < A
(b) Coagulation is reversible (c) A < C < B < D (d) B < D < A < C
11. Which of the following statements is incorrect regarding
(c) Viscosity and surface tension are nearly the same as
physisorptions? [AIEEE 2009]
that of water.
(a) More easily liquefiable gases are adsorbed readily.
(d) The charge of the particle depends on the pH of the
(b) Under high pressure it results into multimolecular layer
medium and it may be positive, negative or zero. on adsorbent surface.
7. Which one of the following characteristics is not correct for (c) Enthalpy of adsorption ( DH adsorption) is low and positive.
physical adsorption ? [AIEEE 2003] (d) It occurs because of van der Waal’s forces.
(a) Adsorption increases with increase in temperature 12. According to Freundlich adsorption isotherm which of the
(b) Adsorption is spontaneous following is correct? [AIEEE 2012]
(c) Both enthalpy and entropy of adsorption are negative x
(d) Adsorption on solids is reversible (a) µ p°
m
8. The disperse phase in colloidal iron (III) hydroxide and
x
colloidal gold is positively and negatively charged, (b) µ p1
respectively. Which of the following statements is NOT m
correct ? [AIEEE 2005] x
(a) Coagulation in both sols can be brought about by (c) µ p1/n
m
electrophoresis
(d) All the above are correct for different ranges of pressure
(b) Mixing the sols has no effect 13. The coagulating power of electrolytes having ions Na+, Al3+
(c) Sodium sulphate solution causes coagulation in both and Ba2+ for arsenic sulphide sol increases in the order :
sols [JEE M 2013]
(d) Magnesium chloride solution coagulates, the gold sol (a) Al3+ < Ba2+ < Na+ (b) Na+ < Ba2+ < Al3+
more readily than the iron (III) hydroxide sol (c) Ba2+ < Na+ < Al3+ (d) Al3+ < Na+ < Ba2+
9. In Langmuir's model of adsorption of a gas on a solid surface 14. Among the following, the surfactant that will form micelles in
[AIEEE 2006] aqueous solution at the lowest molar concentration at ambient
(a) the mass of gas striking a given area of surface is condition is : - [IIT-JEE 2009S]
proportional to the pressure of the gas (a) CH3(CH2)15N+(CH3)3Br– (b) CH3(CH2)11OSO–3 Na+
(c) CH3(CH2)6COO–Na+ (d) CH3(CH2)11N+(CH3)3Br–
(b) the mass of gas striking a given area of surface is
15. Among the electrolytes Na 2 SO4, CaCl 2, Al 2 (SO4 )3 and
independent of the pressure of the gas
NH4Cl, the most effective coagulating agent for Sb2S3 sol is
(c) the rate of dissociation of adsorbed molecules from [IIT-JEE 2009S]
the surface does not depend on the surface covered (a) Na2SO4 (b) CaCl2
(d) the adsorption at a single site on the surface may (c) Al2(SO4)3 (d) NH4Cl
involve multiple molecules at the same time
1. For the adsorption of a gas on a solid, the plot of 3. Adsorption is accompanied by the evolution of heat. So
log(x/m) versus log p is linear with slope equal to according to Le-Chatelier principle the amount of substance
(a) k (b) log k adsorbed should
(c) n (d) 1/n (a) increase with decrease in temperature
(where, p= pressure of gas, m = mass of the adsorbent, (b) increase with increase in temperature
x = mass of the gas adsorbed) (c) decrease with decrease in temperature
2. Which of the following gas molecules have maximum value (d) decrease with increase in temperature
of enthalpy of physisorption? 4. At low pressure, the fraction of the surface covered follows
(a) C2H6 (b) Ne (a) zero-order reaction (b) second-order reaction
(c) H2O (d) H2 (c) first-order reaction (d) fractional order
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
648 Chemistry
17. (a) Blood is purified by dialysis. 41. (c) Alum. coagulates mud particles and helps in purifying
water.
18. (c) It is due to impact of molecules of dispersion medium on
the colloidal particles. 42. (b) In auto catalysis one of the products act as catalyst
43. (d) In acid hydrolysis of methyl acetate all are present in one
19. (a) Brownian movement is exhibited by colloidal system.
phase (liquid)
JEEMAIN.GURU
downloaded from jeemain.guru
55. (c) In physical adsorption the forces between adsorbate and 74. (a) Pallison process is not based on distribution law.
adsorbent are weak van der waal’s forces. 75. (b) The concentration of the solute in both the solvents must
56. (a) Chemisorption involves strong chemical forces. be kept low and not high.
57. (c) Physical adsorption does not require any activation 76. (c) Let the amount of iodine in water be a gm., C1 = 5g in x ml
energy. of CS2, C2 = 5 – a g in x ml of H2O. Then
58. (b) The gases having higher values for critical temperature 5-a
= 420, \= 0.0118
are easily liquified and are adsorbed to the greater extent. a
59. (d) Statement (d) is wrong (see text) EXERCISE 3
1 1. (a) Langmuir adsorption isotherm is based on the
60. (a) Physical adsorption µ . assumption that every adsorption site is equivalent
Temperature
and the ability of a particle to bind there is independent
61. (c) The distribution law was given by Nernst. of whether nearby sites are occupied or not.
62. (d) All the conditons are correct. 2. (d)
63. (a) Henry gave the relation between pressure and solubility 3. (a) According to Freundlich Adsorption isotherm
of a gas as, solubility a pressure. 1
x
64. (a) Let the solubility of iodine in CS2 be a then = KP n
m
S1 a 1
= KD , = 600 , \ a = 210 at low pressure =1
S2 0.35 n
x
S \ µ P1
65. (d) K D = 1 is valid only when their is no association or m
S2
dissociation of solute dissolved and no change of 1
at high pressure =0
temperature. There is no complex formation. n
x
C1 µ P°
66. (d) In case when solute associate, k D = m
n C2 i.e., the value of n varies between 0 to 1
67. (d) All the statements are correct. 4. (d) Enzymes are most reactive at optimum temperature. The
optimum temperature for enzyme activity lies between
C1 1.843 0.127 1.843 / 100
68. (b) k D = , C1 = and C 2 = ,\ k D = = 7.25 40°C to 60°C.
C2 100 50 0.127 / 50
5. (b) The lyophobic sols are less stable than lyophilic sols.
1.843 0.127 The lyophilic sols are thus used to protect the
1= and C 2 = ,
100 50 lyophobic sols. This property of lyophilic sols is known
as protective action of lyophilic sols which is
1.843 /100
\ kD = = 7.25 represented by gold number.
0.127 / 50
6. (c) See properties of hydrophilic sols.
C
69. (b) At equilibrium stage 1 = k D ; where C1 & C2 are the 7. (a) As adsorption is an exothermic process.
C2
concentrations of the solute in the upper and lower layer. \ Rise in temperature will decrease adsorption.
JEEMAIN.GURU
downloaded from jeemain.guru
650 Chemistry
8. (b) When oppositely charged sols are mixed their charges 14. (b)
are neutralised. Both sols may be partially or completely 15. (c) As Sb2S3 is a negative sol, so Al2(SO4)3 will be the
precipitated.
most effective coagulant due to higher positive charge
9. (a) According to Langmuir's model of adsorption of a gas
on a soild surface the mass of gas adsorbed(x)per gram on Al (Al3+) – Hardy-Schulze rule.
of the adsorbent (m) is directly proportional to the EXERCISE 4
pressure of the gas (p) at constant temperature i.e.
x x 1
µp 1. (d) Freundlich equation is log = log K + P where
m m n
10. (c) For a protective colloid lesser the value of gold number 1
= slope .
more will be the protective power. Thus the correct n
order of protective power of A, B, C and D is 2. (c) The more the liquefiable nature of a gas, the more is the
Þ (A) < (C) < (B) < (D) enthalpy of adsorption. Water is more liquefiable.
Gold number 0.50 0.10 0.01 0.005 3. (a) The extent of adsorption increases with decrease in
temperature.
Hence (c) is the correct answer
4. (c) At low pressure the extent of adsorption is directly
11. (c) Adsorption is an exothermic process, hence DH will
proportional to pressure which follows first order kinetics.
always be negative.
5. (d) At high pressure the extent of adsorption follows zero
12. (d) The Freundlich adsorption isotherm is mathematically order kinetics.
represented as 6. (c) Adsorption increases with decrease in temperature.
x 7. (b) DG = DH – TDS. Adsorption is spontaneous process DG
= kP1/n
m should be negative. Hence DH – TDS should be negative.
At high pressure 1/n = 0. Hence, x / m µ P° 8. (d) All statements are correct
At low pressure 1/n = 1 Hence, x/m µ P1 9. (a) CMC is the concentration at which micellization starts
13. (b) According to Hardy Schulze rule, greater the charge i.e. surfactant molecules aggregate.
on cation, greater is its coagulating power for negatively 10. (b) At isoelectric point there is no migration of dispersed
charged sol (As2 S3 ), hence the correct order of phase in an electric field.
coagulating power : Na+ < Ba2+ < Al3+ 11. (b) Peptisation is disintegration of colloidal aggregate.
JEEMAIN.GURU
downloaded from jeemain.guru
20
General Principles
& Processes of
Isolation of Elements
METALLURGY : CONCENTRATION OR DRESSING :
The science and technology of isolation of pure metals from their The process of the removal of gangue or matrix from the ore is
ores and preparing them for practical use. The process includes. known as concentration. It is achieved by
(i) Mining - getting the ore out of ground. (i) Hand picking
(ii) Concentration - preparing for further treatment. (ii) Gravity separation (hydraulic -washing )
(iii) Reduction - to obtain the metals in zero oxidation state. (iii) Magnetic separation
(iv) Refining - to obtain the pure metal. (iv) Electrostatic separation
(v) Mixing with other metals - to form an alloy. (v) Froth flotation process -for sulphide ores.
MINERALS : (vi) Leaching
Most metals are found in nature in the form of solid inorganic Froth flotation process - Finely divided ore is mixed with oil (pine
compounds called minerals. Names of minerals are based on the oil, eucalyptus oil or camphor oil) and agitated with water
location of their discovery, the person who discovered them or containing a detergent (foaming agent). When air is bubbled
some characteristics of the mineral. through the mixture, the air bubbeles are stabilised by the detergent
.These adsorb mineral particles wetted with oil and rise to the
ORE : surface. The earthy matter wetted by water settles down at the
The mineral from which the metal can be extracted economically. bottom.
Hence all minerals can not be classified as ores. The most Collectors - Which increase the non wettability of ore particles
important ores are oxide,sulphide and carbonate minerals. e.g. pine oil, xanthates and fatty acids.
GANGUE OR MATRIX : Froth stabiliser -Which stabilise the froth e.g. cresoles and aniline.
The unwanted rocky,earthy or sandy materials almost always Depressants - Depressants prevent the formation of froth eg
associated with the ores as impurities are called gangue or matrix. NaCN, when added to ore containing ZnS and PbS form a complex
FLUX AND SLAG : with ZnS as Na 2 [ Zn (CN )4 ] and prevent it from forming froth.
Flux is a substance added to the ores before heating which PbS is then easily separated from ZnS.
combines chemically with earthy impurities (gangue) and form a Leaching- Leaching is the selective dissolution of the desired
fusible mass known as slag . mineral leaving behind the impurities in a suitable dissolving agent
Flux can be Acidic e.g. SiO2 (silica), Na2 B4O7 .10H 2O (borax); eg bauxite when treated with strong solution of
Basic e.g. CaO, MgO ; or Neutral - neutral compounds, and they NaOH, Al 2O 3 dissolves leaving behind Fe 2O 3 .SiO 2 .
decrease the melting point and make the order conducting in an
Al2O3 + 6NaOH ® 2Na 3AlO3 + 3H 2O
electrolytic cell e.g. CaF2 , Na3 AlF6 , KF etc.
Slag consists mostly of molten silicates ,aluminates, phosphates, Na 3 AlO 3 + 3H 2 O ® 3 NaOH + Al(OH )3
fluorides and another inorganic materials. The formation of slag is 2Al(OH )3 ® Al 2 O 3 + 3H 2 O
known as slagging .
JEEMAIN.GURU
downloaded from jeemain.guru
652 Chemistry
Leaching is also employed in Ag ore and native gold. (iii) Self reduction -Cu, Pb and Mg are obtained by self
reduction in roasting.
Ag2S + 4NaCN® 2Na[Ag(CN)2 ] + Na2S
3
4Au + 8KCN + 2H2O + O2 ® 4K[Au(CN)2 ] + 4KOH Cu 2S + O2 ® Cu 2O + SO2
2
CALCINATION : Cu 2S + 2Cu 2O ® 6Cu + SO 2
It is the heating of the ore in a suitable furnace in absence of air 2PbS + 3O 2 ® 2PbO + 2SO 2
much below its melting point to cause decomposition and PbS + 2PbO ® 3Pb + SO 2
elimination of volatile products.
(iv) Electrolytic reduction -Oxides of very active metals like
PbCO 3 ® PbO + CO 2 alkali or alkaline earth are not easily reduced by chemical
The process is generally applied to hydrated oxide or carbonate reducing agents e.g. Na, Mg, Al etc. They are obtained
ores. by electrolytic reduction.
Fusion
ROASTING : ® 2Na + + 2Cl -
2NaCl ¾¾¾¾
It is the heating of the concentrated ore in a suitable furnace At anode : 2Cl - - 2e - ® Cl 2
strongly in presence of air with or without certain substances
below the melting point which causes chemical reaction to expel At Cathode : 2Na + + 2e- ® 2Na
volatile impurities eg oxides of S, As and Sb. (v) Amalgamation process - Ag and Au are obtained by
leaching process using solution of KCN or NaCN to
2ZnS + 3O 2 ® 2ZnO + 2SO 2 form argento cyanide or aurocyanide . Ag and Au is
2MoS 2 + 7O 2 ® 2MoO 3 + 4SO 2 precipitated by adding Zn dust.
REDUCTION : 2Na[Ag(CN )2 ] + Zn ® Na 2 [Zn(CN )4 ] + 2Ag
After calcination or roasting, the metal oxides are reduced and 2K[Au(CN )2 ] + Zn ® K 2 [Zn(CN )4 ]+ 2Au
impurities are removed as slag. Reduction and slagging take place Soluble complex
together.
(a) Removal of impurities as slag - For acidic impurities viz. REFINING :
SiO 2 , P2 O5 basic flux is added. The methods employed for the refining of metals are
SiO 2 + CaO ® CaSiO 3 (i) Liquation -Impurities present must be less fusible than the
metal to be purified . Impure metal is placed on the slopping
For basic impurities like MnO acidic flux is added.
hearth of reverberatory furnace at a temperature just above
MnO + SiO 2 ® MnSiO3 the melting point of the metal . The pure metal flows down
(b) Reduction of oxides - leaving behind the impurities . Sn ,Pb, Bi are purified by this
(i) Decomposition of oxides by heating - For thermally method.
unstable oxide. (ii) Distillation - Zn and Hg are purified by distillation under
HgS + O 2 ® Hg + SO 2 reduced pressure provided the impurities are non volatile.
Hg is obtained from its sulphide ore cinnabar directly in (iii) Fractional crystallisation - (Zone refining ).
the roasting step.
(ii) Chemical Reduction -
• Reduction by carbon - Sn from oxide ore cassiterite Molten zone
SnO2 is obtained by heating with coke.
SnO 2 + C ® Sn + 2CO Recrystallized metal Metal rod
Zn from sulphide ore Zinc blende (ZnS).
Roasting Circular heater
2ZnS + 3O 2 ¾¾ ¾¾® 2ZnO + 2SO 2
ZnO + C ® Zn + CO
Impure metal rod is heated with the help of circular heater at
Iron is obtained from oxide ore haematite ( Fe2O3 ). one end. The metal melts and on cooling the pure metal gets
Fe 2 O 3 + 3C ® 2Fe + 3CO solidified while impurities pass on into the molten zone. The
• Reduction by H2 and CO- process is repeated twice or thrice to get the pure metal.
(iv) Polling -The molten metal is stirred with green poles of wood,
MoO 3 + 3H 2 ® Mo + 3H 2 O
which liberates gas like methane. The latter reduces any oxide
CuO + CO ® Cu + CO 2
present in the metal eg CuO in the blister copper is reduced
• Reduction by other metals e.g. Al and Mg - to copper.
Cr2 O 3 + 2Al ® 2Cr + Al 2 O 3 (v) Electrolytic refining- The blocks of impure metal form the
3Mn 3 O 4 + 8Al ® 4Al 2 O3 + 9Mn anode and pure metal form the cathode. Aqueous
Rb 2 O 3 + 3Mg ® 3MgO + 2Rb
JEEMAIN.GURU
downloaded from jeemain.guru
General Principles
General Principles & Processes of Isolation of Elements 653
solution of appropriate salt is then electrolised. On oxidised and carried away by blast air .
electrolysis at a suitable voltage the pure metal is deposited (viii)Desilverisation of lead -Lead obtained from galena (PbS)
at cathode. contains impurities of silver, removal of which is called
desilverisation .The processes employed are
At anode M - ne- ® M n + (a) Parke’s process -Lead containing silver is melted in iron
At cathode M n + + ne- ® M pots and 1% Zn is added then cooled. Zn -Ag alloy
solidifies and being light floats over molten lead and
Cu, Sn, Ag, Pb, Cr, Ni are refined by this process. removed .
(vi) Vapour phase refining - Metal is removed as volatile ( Pb and Ag ) + Zn ® ( Zn - Ag ) alloy + Pb
compound which is then decomposed by heating to get pure
(b) Pattison’s process -Lead containing less than 2.5% of
metal. e.g.
Ag melts at lower temperature than lead. Thus when an
(a) Mond’s process - Ni is purified by this process. alloy of Pb-Ag containing more lead is melted then
allowed to cool slowly, pure lead separates.
Ni(s ) + 4CO(g) ¾¾¾ ¾¾® Ni (CO) 4 (g)
300 -350K
450- 470K (ix) Chromatographic methods - It is based on the preferential
Ni(CO) 4 (g) ¾¾ ¾¾¾® Ni(s) + 4CO(g) adsorption of different compunds on an adsorbent. The
(b) Van Arkel process-Zr, Hf , Si,Ti and Be are refined by mixture is put in the liquid or gaseous medium which is moved
this process. through the adsorbent. The different compounds are
adsorbed at different levels on adsorbent in column
Zr s + 2 I 2 g ® ZrI 4 g chromatography and recoverd by using suitable solvent
ZrI4(g ) On hot
Zr(s) + 2 I 2(g) (eluent). The common adsorbent as Al2O3 or SiO2 (silica).
filament The least adsorbed component is recoverd first. The method
(vii) Cupellation - This is the method of purifying silver containing is very useful for purification of elements available in minute
lead as impurity. Impure silver is heated in a shallow (Cupel) quantities.
which is made of bone ash under blast of air. Lead is easily
Flow meter
Detector
Mixture of
compounds
C
O
L
U Oven
Stationary Coloured
M
N phase bands
Flow injector
Pump
Solvent
tank (a) (b)
Industrial method Laboratory method
Schematic diagrams showing column chromatography
There are several chromatographic techniques such as gas chromatography, paper chromatography, etc.
METAL SOURCE MAIN METHOD OFEXTRACTION
Metal Occurrence (ore) Common method of extraction
Li Spodumene LiAl (SiO 3 ) 2 Electrolysis of fused LiCl with KCl .
K Carnallite KCl MgCl2 . 6H2O ; Kaenite KCl MgSO4 3H2O, Electrolysis of fused KCl with CaCl 2 added to it.
Sylvine KCl ; Nitre KNO3 ; Feldspar K2O Al2O3 6SiO2 ;
Mical KH2Al3(SO4)3 ;
JEEMAIN.GURU
downloaded from jeemain.guru
654 Chemistry
JEEMAIN.GURU
downloaded from jeemain.guru
General Principles
General Principles & Processes of Isolation of Elements 655
Pt Native; Sperrylite PtAs 2 : Thermal decomposition of (NH 4 )2 Pt.Cl 6
(NH 4 )2 PtCl 6 ® Pt + 2 NH 4 Cl + 2Cl 2 .
Au Bismuth aurite BiAu; Sylvanite (Au Ag) Te2 Cyanide process:
2K éë Au ( CN ) 2 ùû + Zn ® K 2 éë Zn ( CN ) 4 ùû + 2Au.
JEEMAIN.GURU
downloaded from jeemain.guru
656 Chemistry
(v) Thermit - It is mixture of Fe2O3 (3 parts ) and Al powder (e) Metals obtained by precipitation method are - Ag ,Au
(f) Metals obtained by reduction with Co, Fe
(1part) when ignited with the help of barium peroxide, Fe2O3
(g) Metals obtained by reduction with water gas are - Ni
is reduced to iron and an enormous amount of heat is
produced due to exothermic nature of the reaction. (xv) Alloys -Alloys contain more than one element and have the
characteristics of metals.
Fe2 O3 + 2Al ® Al2 O3 + 2Fe + 2500o C · Pure metals and alloys have different physical properties.
The molten is utilised for welding and the process is known · Solution alloys are homogeneous mixtures and they are of
as thermit welding known as Goldschmidt Alumino thermic two types
process. (a) Subtitutional alloys (Solute atoms take the positions of
(vi) Refractory materials - The substance capable of solvent atom)
withstanding at very high temperature without undergoing (b) Interstitial alloys (Solute atoms occupy interstitial sites)
any deformation is called refractory material. · Heterogeneous alloys - Components are not dispersed
Acidic refractories -silica, quartz and sand stone uniformally e.g. pearlite steel .
Basic refractories - lime ,dolomite and magnesite RELATIVE ABUNDANCE :
Neutral refractories - chromite, bone ash and graphite. Abundance of elements in the earth’s crust (by weight)
(vii) Matte or regulus - Artificially obtained sulphides are known O > Si > Al > Fe > Ca > Na > K > Mg > H > Ti > Cl > F
as matte or regulus e.g. Cu 2S in extraction of copper..
Abundance of elements in the earth’s crust (in terms of number of
(viii)Sulphating roasting - It is partial oxidising roasting. Roasting atoms per 100 atoms)
of galena gives mixture of lead oxide and lead sulphate O > Si > Al > H > Na > Ca > Fe > Mg >
2 PbS + 3O 2 ® 2 PbO + 2SO 2 > K > Ti > C > Mn > S > F > Cl > Cr
PbS + 2O 2 ® 2 PbSO 4 THERMODYNAMIC PRINCIPLES OF METALLURY :
Theory of metallurgical transformations can be interpreted by
(ix) Chlorinating roasting- Silver ores mixed with common salt
Gibb’s free energy change at any specified temp.
when heated in presence of air, the chloride is obtained.
DG = DH - TDS or DGº = - RT lnK
Ag 2S + 2 NaCl ® 2AgCl + Na 2S
where, DH = enthalpy change and
(x) Bessemerisation -The oxidation of impurities by passing the
DS = entropy change
hot blast of air through molten metal in bessemer converter
is called bessemerisation . Pig iron and copper are purified K = equilibrium constt. at temp. T
by this method. The reducing agent is oxidised and metal oxide is reduced. The
(xi) Sintering-The conversion of small pieces of a substances role of reducing agent is to provide DGº negative.
into larger one by partial fusion is known as sintering. During reduction the metal oxide decomposes.
(xii)Pulverisation- The conversion of large pieces of a substance
M x O(s) ¾¾® xM (Solid or liquid) +12 O 2 (g)
into small fine pieces or powder is known as pulverisation.
(xiii)Anodizing-The process of forming an oxide coating on metal The reducing agent (C or CO) is oxidised
surface by making it an anode by electrolytic method in called 1
anodizing. C(s) + O 2 (g) ¾¾
® CO(g)
2
(xiv)Mode of extraction of some metals- 1
CO(g) + O 2 (g) ¾¾
® CO 2 (g)
(a) Metals obtained by electrolytic reduction are - Li, Na, K, 2
Mg, Ca , Al, Sr, Ba
C(s) + O 2 (g) ¾¾
® CO 2 (g)
(b) Metals obtained by reduction of oxides by carbon are -
Zn from ZnO, Sn from SnO2. If net DG of two possible reactions (Reduction/Oxidation) is
negative, the overall reaction will occur.
(c) Metals obtained by reduction of oxides by thermite
process, (Alumino thermic process) are Cr from Cr 2O3, H.J.T. Elligham diagram (plots of DG Vs T) provides a sound basis
Mn from Mn3O4. for considering the choice of reducing agent in the reduction of
oxides.
(d) Metals obtained by air reduction method are - Hg from
HgS, Pb from PbS.
JEEMAIN.GURU
downloaded from jeemain.guru
General Principles
General Principles & Processes of Isolation of Elements 657
Note: Although thermodynamically feasible the magnesium metal,
is not used for the reduction of aluminas. The temperature required
would be so high and the process would be technologically difficult
and uneconomic.
EXTRACTION OF IRON FROM ITS OXIDES:
The two simple reactions are
1
(i) ® Fe(s / l) + O 2 (g); DG(FeO, Fe)
FeO (s) ¾¾
2
1
(ii) C(s) + O (g) ® CO(g); DG(C, CO)
2 2
Adding the two reactions, we get
FeO(s) + C(s) ® Fe(s/l) + CO(g)
DG(FeO, Fe) + DG (C, CO) = DG
The resultant DG is –ve above 1073K (approx).
If the metal is obtained in liquid state the reduction becomes easier.
Fig. Gibbs energy (DGº) vs T plots (schematic) for formation of (entropy increases and DG decreases).
some oxides (Ellingham diagram) LIMITATIONS OF ELLINGHAM DIAGRAM :
When alumina is reduced by magnesium, the two equations are 1. It fails to predict the kinetics of reduction processes i.e. how
(i) ® 2Al2 O 3 (ii) 2 Mg + O 2 ¾¾
4 Al + 3O 2 ¾¾ ® 2MgO fast it could be
2. When the reactant/product are solid DG° cannot be
DG becomes ZERO at the point of intersection of the Al2O3 and
interpreted by the equation DG° = – RT log K
MgO curves (marked “A”). Above this point the magnesium can
reduce alumina.
JEEMAIN.GURU
downloaded from jeemain.guru
658 Chemistry
Very Short/Short Answer Questions 14. Explain the role of each of the following:
1. Write the names of two oxides which cannot be reduced with (i) NaCN in the extraction of silver.
carbon but can be reduced with aluminium powder to get the (ii) SiO2 in the extraction of copper.
corresponding metals. 15. (a) Which solution is used for the leaching of silver metal
2. Why are metal carbonates and sulphides first converted into in the presence of air in the metallurgy of silver?
corresponding oxides for finally obtaining the corresponding (b) Out of C and CO, which is a better reducing agent at the
metals? lower temperature range in the blast furnace to extract
3. Copper and silver lie below in the electrochemical series and iron from the oxide ore?
yet they are found in the combined state as sulphides in 16. (a) Which of the following ores can be concentrated by
nature. Comment. froth floatation method and why?
4. Indicate the temperature at which carbon can be used as a Fe2O3, ZnS, Al2O3
reducing agent for FeO.
(b) What is the role of silica in the metallurgy of Copper?
5. What is the metal extracted from malachite and azurite? Give
one important use of the metal.
Multiple Choice Questions
6. Name two metals each of which can be obtained 17. The metal always found in the free states is
(a) by thermite process (a) Au (b) Ag
(b) by electrolytic reduction (c) Cu (d) Na
(c) refined by liquation, and
18. Bronze is a mixture of
(d) refined by electrolysis.
(a) Pb + Sn (b) Cu + Sn
7. Name the type of reduction processes by which the following
metals are obtained from their oxides: (c) Cu + Zn (d) Pb + Zn
(a) Metal x which is low in the reactivity series. 19. Which reagent is used in Bayer’s process?
(b) Metal y which is in the middle of the reactivity series. (a) Na2CO3 (b) Carbon
(c) Metal z which is high up in the reactivity series.
(c) NaOH (d) Silica
8. What method for concentration of ore is preferred in each of
20. Matrix is defined as –
the following cases and why:
(a) The ore has higher density particles interspersed with a (a) the unwanted foreign material present in the ore
large bulk of low density impurities. (b) the flux added to remove the unwanted impurities from
(b) The ore consists of copper sulphide intermixed with ore
clay particles. (c) the slag formed as a result of the reaction of flux with
9. At a site, low grade copper ores are available and zinc and gangue
iron scraps are also available. Which of the two scraps will (d) the material used in the reduction of metal oxide to
be more suitable for reducing the leached copper ore and metal
why? 21. The process to heat the ore in the presence of excess supply
10. Although thermodynamically feasible, in practice, of air below its melting point is called –
magnesium metal is not used in for the reduction of alumina (a) roasting (b) calcination
in the metallurgy of aluminium. Why?
(c) smelting (d) liquation
11. Differentiate between a mineral and an ore.
22. Thomas slag is
12. Describe the principle controlling each of the following
processes: (a) Ca3(PO4)2
(i) Zone refining of metals (b) CaSiO3
(ii) Electrolytic refining of metals (c) Mixture of (a) and (b)
13. Which methods are usually employed for purifying the (d) FeSiO3
following metals? 23. Blister copper is
(i) Nickel
(a) Impure Cu (b) Cu alloy
(ii) Germanium
(c) Pure Cu (d) Cu having 1% impurity
JEEMAIN.GURU
downloaded from jeemain.guru
General Principles
General Principles & Processes of Isolation of Elements 659
24. Which of the following fluxes is used to remove acidic Codes:
impurities in metallurgical process? (a) I-C, II-A, III-D, IV-B
(a) Silica (b) I-D,II-B,III-C,IV-A
(b) Lime stone (c) I-C,II-B,III-D, IV-A
(c) Sodium chloride (d) I-D,II-A,III-C,IV-B
(d) Sodium carbonate 26. In forth flotation process many chemicals (frother , collector,
25. Match list I with list II and select the correct answer using activator, and depressant) are used . Which is called a frother:
the codes given below the lists: (a) CuSO 4 (b) NaCN+ alkali
List I List II
(c) Pine oil (d) Potassium xanthate.
I. Cyanide process A. Ultrapure Ge
II. Floatation process B. Pine oil
III. Electrolytic reduction C. Extraction of Al
IV. Zone refining D. Extraction of Au
1. An example of an oxide ore is 9. Which of the following fluxes is used to remove acidic
(a) bauxite (b) malachite impurities in metallurgical process?
(c) zinc blende (d) feldspar (a) Silica (b) Lime stone
2. The natural materials from which an element can be extracted (c) Sodium chloride (d) Sodium carbonate
economically are called 10. Cryolite is
(a) ores (b) minerals
(a) Na 3AlF6 and used in the electrolysis of alumina for
(c) gangue (d) None of these
3. The impurities associated with mineral used in decreasing electrical conductivity
metallurgy are called collectively? (b) Na 3AlF6 and used in the electrolysis of alumina for
(a) Slag (b) Flux lowering the melting point of alumina
(c) Gangue (d) Ore
(c) Na 3AlF6 and used in the electrolytic purification of
4. The most abundant metal on the surface of the earth is
alumina
(a) Fe (b) Al
(c) Ca (d) Na (d) Na 3AlF6 and used in the electrolysis of alumina
5. The most abundant element in the earth’s crust (by weight) 11. Flux is used to
is
(a) remove all impurities from ores
(a) Si (b) Al
(b) reduce metal oxide
(c) O (d) Fe
(c) remove silica
6. During smelting an additional substance is added which
combines with impurities to form a fusible product. It is known (d) remove silica and undesirable metal oxide
as 12. Cassiterite is concentrated by
(a) slag (b) mud (a) levigation
(c) gangue (d) flux (b) electromagnetic separation
7. When a metal is to be extracted from its ore and the gangue (c) floatation
associated with the ore is silica, then (d) liquefaction
(a) an acidic flux is needed 13. Froth floatation process is used for the metallurgy of
(b) a basic flux is needed
(a) chloride ores (b) amalgams
(c) both acidic and basic fluxes are needed
(c) oxide ores (d) sulphide ores
(d) Neither of them is needed
14. Electromagnetic separation is used in the concentration of
8. A basic lining is given to a furnace by using
(a) calcined dolomite (b) lime stone (a) copper pyrites (b) bauxite
(c) haematite (d) silica (c) cassiterite (d) cinnabar
JEEMAIN.GURU
downloaded from jeemain.guru
660 Chemistry
15. For which ore of the metal, froth floatation method is used 29. Use of electrolysis is
for concentration? (a) Electroplating (b) Electrorefining
(a) Horn silver (b) Bauxite (c) Both (a) and (b) (d) Neither (a) nor (b)
(c) Cinnabar (d) Heamatite 30. In electrorefining of copper some gold is deposited as
16. Which of the following metal is leached by cyanide process (a) anode mud (b) cathode mud
(a) Ag (b) Na (c) electrolyte (d) None of these
(c) Al (d) Cu 31. Purification of silicon element used in semiconductors is
17. Which one of the following ores is not concentrated by done by
(a) zone refining (b) heating
froth floatation process?
(c) froth floatation (d) heating in vacuum
(a) Copper pyrites (b) Pyrargyrite
32. Silver containing lead as an impurity is removed by
(c) Pyrolusite (d) Zinc blende
(a) poling (b) cupellation
18. Calcination is used in metallurgy for removal of?
(c) lavigation (d) distillation
(a) Water and sulphide (b) Water and CO2
33. Nickel is purified by thermal decomposition of its
(c) CO2 and H 2S (d) H 2 O and H 2S (a) hydride (b) chloride
19. Which of the following reactions is an example for calcination (c) azide (d) carbonyl
process ? 34. The chief source of iodine, in which it is present as sodium
(a) 2Ag + 2HCl + (O ) ® 2AgCl + H 2 O iodate, is
(a) Carnallite (b) Sea weeds
(b) 2Zn + O 2 ® 2 ZnO (c) Caliche
(d) Iodine never exists as sodium iodate.
(c) 2ZnS + 3O 2 ® 2ZnO + 2SO 2
35. Malachite is an ore of
(d) MgCO3 ® MgO + CO 2 (a) iron (b) copper
20. Heating of ore in the absence of air below its melting point is (c) mercury (d) zinc
called 36. The important oxide ore of iron is
(a) leaching (b) roasting (a) siderite (b) haematite
(c) smelting (d) calcination (c) pyrites (d) bauxite
21. Heating pyrites to remove sulphur is called 37. In the commercial electrochemical process for aluminium
(a) smelting (b) calcination extraction the electrolyte used is
(c) liquation (d) roasting
22. The process of converting hydrated alumina into (a) Al(OH )3 in NaOH solution
anhydrous alumina is called (b) An aqueous solution of Al 2 (SO 4 )3
(a) roasting (b) smelting
(c) dressing (d) calcination (c) A molten mixture of Al2 O 3 and Na 3 AlF6
23. Mac Arthur process is used for
(a) Ag (b) Fe (d) A molten mixture of Al 2 O 3 and Al(OH )3
(c) Cl (d) O2 38. Cassiterite is an ore of
24. In Goldschmidt aluminothermic process, reducting agent is (a) Mn (b) Ni
used
(c) Sb (d) Sn
(a) coke (b) Al powder
39. Which of the following element is extracted commercially by
(c) Na (d) Ca
the electrolysis of an aqueous solution of its compound?
25. Aluminothermic process is used for metallurgy of
(a) Pb (b) Ag (a) Chlorine (b) Bromine
(c) Al (d) None of these (c) Sodium (d) Aluminium
26. Which metal can’t be obtained from electrolysis? 40. Galena is an ore of
(a) Ca (b) Mg (a) Pb (b) Hg
(c) Cr (d) Al (c) Zn (d) Zn
27. Which of the following metals is obtained by 41. Which one of the following element does not exits in the
electrolytic reduction process? native form?
(a) Fe (b) Cu (a) Au (b) Pt
(c) Ag (d) Al (c) Fe (d) S
28. The common method of extraction of metals from oxide ores 42. The most electropositive metals are isolated from their ores by
is (a) high temperature reduction with carbon
(a) reduction with carbon
(b) self reduction
(b) reduction with hydrogen
(c) thermal decomposition
(c) reduction with aluminium
(d) electrolytic method (d) electrolysis of fused ionic salts
JEEMAIN.GURU
downloaded from jeemain.guru
General Principles
General Principles & Processes of Isolation of Elements 661
43. The metal always found in the free states is 49. Match list I with list II and select the correct answer using
(a) Au (b) Ag the codes given below the lists:
(c) Cu (d) Na List I List II
44. Pyrolusite is a/an I. Cyanide process A. Ultrapure Ge
(a) oxide ore (b) sulphide ore II. Floatation process B. Pine oil
(c) carbide ore (d) Not an ore III. Electrolytic reduction C. Extraction of Al
45. Which of the following metals is extracted by the IV. Zone refining D. Extraction of Au
electrometallurgical method ? Codes:
(a) Cu (b) Fe (a) I-C, II-A, III-D, IV-B (b) I-D,II-B,III-C,IV-A
(c) Na (d) Ag (c) I-C,II-B,III-D, IV-A (d) I-D,II-A,III-C,IV-B
46. Among the following statements the incorrect one is 50. Which of the following condition favours the reduction of
a metal oxide to metal?
(a) Calamine and siderite are carbonates
(a) DH = +ve, TDS = + ve at low temperature
(b) Argentite and cuprite are oxides
(b) DH = +ve, TDS = – ve at any temperature
(c) Zinc blende and iron pyrites are sulphides (c) DH = –ve, TDS = – ve at high temperature
(d) Malachite and azurite are ores of copper. (d) DH = –ve, TDS = + ve at any temperature
47. When an aqueous solution of sodium chloride is electrolysed 51. Ellingham diagram normally consists of plots of
using platinum electrodes, the ion (a) DSº vs T (b) D fGº vs DSº
discharged at the electrodes are (c) DGº vs T (d) DHº vs DT
(a) sodium and hydrogen (b) sodium and chloride 52. A coupled reaction is takes place as follow–
(c) hydrogen and chloride (d) hydroxyl and chloride A + B ––––® C + D, D Gº = + x kj
48. In the extraction of iron , slag is produced.Slag is D + E ––––® F D Gº = – y kj
(a) CO (b) FeSiO3 for the spontaneity of reaction A + B + E –––® C+F,
which of the following is correct?
(c) MgSiO 3 (d) CaSiO 3 (a) 2x = y (b) x < y
(c) x > y (d) x = (y)× TDS
1. Which of the following statements, about the advantage of (a) Manganese (b) Carbon
roasting of sulphide ore before reduction is not true?
[CBSE-PMT 2007] (c) Silicon (d) Phosphorus
4. Which of the following pairs of metals is purified by van
(a) The DG of of the sulphide is greater than those for CS2 Arkel method ? [CBSE-PMT 2011]
and H2S. (a) Ga and In (b) Zr and Ti
(b) The DG of is negative for roasting of sulphide ore to oxide. (c) Ag and Au (d) Ni and Fe
5. The following reactions take place in the blast furnace in the
(c) Roasting of the sulphide to the oxide is thermodynamically
feasible. preparation of impure iron. Identify the reaction pertaining to
the formation of the slag. [CBSE-PMT 2011 M]
(d) Carbon and hydrogen are suitable reducing agents for
reduction of metal sulphides. (a) Fe2O3(s) + 3 CO(g) ®2 Fe (l) + 3 CO2 (g)
2. Sulphide ores of metals are usually concentrated by froth (b) CaCO3 (s) ®CaO (s) + CO2 (g)
flotation process. Which one of the following sulphide ores (c) CaO (s) + SiO2(s) ® CaSiO3(s)
offer an exception and is concentrated by chemical leaching?
(d) 2C(s) + O2 (g) ®2 CO(g)
[CBSE-PMT 2007]
6. Aluminium is extracted from alumina (Al2O3 ) by electrolysis
(a) Galena (b) Copper pyrite
of a molten mixture of : [CBSE-PMT 2012 S]
(c) Sphalerite (d) Argentite
(a) Al2O3 + HF + NaAlF4 (b) Al2O3 + CaF2 + NaAlF4
3. Which of the following elements is present as the impurity to
the maximum extent in the pig iron ? [CBSE-PMT 2011] (c) Al2O3 + Na3AlF6 + CaF2 (d) Al2O3 + KF + Na3AlF6
JEEMAIN.GURU
downloaded from jeemain.guru
662 Chemistry
7. Which one of the following is a mineral of iron ? (c) Metal sulphides are less stable than the corresponding
[CBSE-PMT 2012 S] oxides
(a) Malachite (b) Cassiterite (d) CO2 is more volatile than CS2
(c) Pyrolusite (d) Magnetite 12. Pb and Sn are extracted from their chief ore by
8. In the extraction of copper from its sulphide ore, the metal is [IIT-JEE 2004S]
finally obtained by the reduction of cuprous oxide with : (a) carbon reduction and self reduction.
(a) Copper (I) sulphide (Cu2S) [CBSE-PMT 2012 S] (b) self reduction and carbon reduction.
(b) Sulphur dioxide (SO2) (c) electrolysis and self reduction.
(c) Iron sulphide (FeS) (d) self reduction and electrolysis.
(d) Carbon monoxide (CO) 13. Extraction of zinc from zinc blende is achieved by
9. Which one of the following ores is best concentrated by (a) electrolytic reduction [IIT-JEE 2007]
froth-flotation method ? [AIEEE 2004] (b) roasting followed by reduction with carbon
(a) Galena (b) Cassiterite (c) roasting followed by reduction with another metal
(c) Magnetite (d) Malachite (d) roasting followed by self-reduction
10. Heating mixture of Cu 2 O and Cu 2 S will give 14. In the cyanide extraction process of silver from argentite ore,
[AIEEE 2005] the oxidising and reducing agents used are [IIT-JEE 2012]
(a) Cu2SO3 (b) CuO + CuS (a) O2 and CO respectively
(c) Cu + SO3 (d) Cu + SO2 (b) O2 and Zn dust respectively
11. Which of the following factors is of no significance for (c) HNO3 and Zn dust respectively
roasting sulphide ores to the oxides and not subjecting the (d) HNO3 and CO respectively
sulphide ores to carbon reduction directly? [AIEEE 2008] 15. Sulfide ores are common for the metals
(a) Metal sulphides are thermodynamically more stable than (JEE Advanced 2013)
CS2 (a) Ag, Cu and Pb (c) Ag, Mg and Pb
(b) CO2 is thermodynamically more stable than CS2 (b) Ag, Cu and Sn (d) Al, Cu and Pb
1. Which process represents the change, (a) absorbance of ultraviolet light- and reemission of white light
Ti + 2I 2 ® TiI 4 ® Ti + 2I 2 (b) shock cooling by contact with a shower of molten lead.
(a) Cupellation (b) Van Arkel (c) X-ray method
(c) Polling (d) Zone Refining (d) smelting.
2. In froth flotation process many chemicals (frother , collector, 6. Among the following groups of oxides, the group containing
activator, and depressant) are used . Which of the folloiwng oxides that cannot be reduced by carbon to give the
is a frother:
respective metals is
(a) CuSO 4 (b) NaCN+ alkali
(a) Cu 2 O, SnO 2 (b) Fe 2O 3 , ZnO
(c) Pine oil (d) Potassium xanthate.
3. Froth flotation process is based on (c) CaO, K 2O (d) PbO, Fe3O 4
(a) wetting properties of ore particle
7. The electrolytic reduction technique is used in the extraction of
(b) specific gravity of ore particles
(c) magnetic properties of ore particles (a) highly electronegative elements
(d) electrical properties of ore particles . (b) highly electropositive elements
4. In the electrolysis of alumina, cryolite is added to: (c) metalloids
(a) lower the melting point of alumina and to increase the (d) transition metals.
electrical conductivity
8. In electro-refining of metal the impure metal is made the
(b) minimise the anode effect
anode and a strip of pure metal, the cathode, during the
(c) remove impurities from alumina
electrolysis of an aqueous solution of a complex metal salt.
(d) None of these
This method cannot be used for refining of
5. In the metallurgy of Zn the Zn dust obtained from roasting
and reduction of zinc sulphide contains some ZnO. It is (a) silver (b) copper
removed by (c) aluminium (d) sodium
JEEMAIN.GURU
downloaded from jeemain.guru
General Principles
General Principles & Processes of Isolation of Elements 663
9. In the froth flotation process of concentration of ores, the 18. D G° Vs T plot in the Ellingham’s diagram slopes downward
ore particles float because they: for the reaction
(a) are light
1 1
(b) are insoluble (a) Mg + O 2 ® MgO (b) 2Ag + O 2 ® Ag 2O
2 2
(c) have the surface which is not wetted easily
(d) have a constant electrical charge 1 1
(c) C + O2 ® CO (d) CO + O 2 ® CO 2
10. Thomas slag is 2 2
(a) calcium silicate 19. Which of the following reactions taking place in the bast
(b) calcium phosphate furnace during extraction of iron is endothermic?
(c) tricalcium phosphate and calcium silicate (a) CaCO3 ® CaO + CO 2
(d) calcium ammonium phosphate
(b) 2C + O2 ® 2CO
11. Extraction of Ag from commercial lead is possible by
(a) Parke’s process (b) Clarke’s process (c) C + O 2 ® CO 2
(c) Pattinson’s process (d) Electrolytic process
(d) Fe 2O3 + 3CO ® 2Fe + 3CO 2
12. Iron is obtained on large scale from Fe2O3 by
20. Consider the following reactions at 1000°C
(a) Reduction with CO (b) Reduction with Al
1
(c) Calcination (d) Passing H2 A. Zn(s) + O 2 (g) ® ZnO(s); DG° = -360 kJ mol-1
13. After partial roasting the sulphide of copper is reduced by 2
(a) cyanide process (b) electrolysis
1
(c) reduction with carbon (d) self reduction B. C(gr) + O 2 (g) ® CO(g); DG° = -460 kJ mol –1
2
14. Before introducing FeO in blast furnace , it is converted to
Choose the correct statement at 1000°C
Fe2O3 by roasting so that
(a) zinc can be oxidised by carbon monoxide.
(a) it may not be removed as slag with silica
(b) zinc oxide can be reduced by graphite
(b) it may not evaporate in the furnace
(c) carbon monoxide can be reduced by zinc.
(c) presence of it may increase the m.pt. of charge (d) both statements (a) and (b) are true
(d) None of these. 21. The substance not likely to contain CaCO3 is
15. The phenomenon of removing layers of basic oxides from (a) calcined gypsum (b) sea shells
metals before electroplating is called (c) dolomite (d) a marble statue
(a) galvanising (b) anodising 22. The value of Df Gº for formation of Cr2 O3 is – 540 kJmol–1 and
(c) pickling (d) poling. that of Al2O3 is – 827 kJ mol–1 What is the value of DrG° for
16. Aluminothermic process is used for the extraction of metals the reaction?
, whose oxides are
4 2 2 4
(a) fusible Al(s) + Cr2 O 3 (s) ® Al 2 O3 (s) + Cr(s).
3 3 3 3
(b) not easily reduced by carbon
(c) not easily reduced by hydrogen (a) – 574 kJ mol –1
(b) –287kJ mol–1
(c) + 574 kJ mol –1
(d) +287kJ mol–1
(d) strongly basic.
23. Which of the following statement is not correct about
17. When the sample of copper with zinc impurity is to be purified
Ellingham diagram?
by electrolysis, the appropriate electrodes are
cathode anode (a) D G increases with an increase in temperature
(a) pure zinc pure copper (b) It consists of plots of DfGº Vs T for formation of
oxides
(b) impure sample pure copper
(c) A coupling reaction can be well expressed by this
(c) impure zinc impure sample diagram
(d) pure copper impure sample. (d) It express the kinetics of the reduction process
JEEMAIN.GURU
downloaded from jeemain.guru
664 Chemistry
EXERCISE 1 15. (c) Cinnabar is sulphide ore (HgS). Hence purified by froth
floatation process.
1. Manganese oxide (MnO2) and chromium oxide (Cr2O3). 16. (a) Ag is leached by cyanide process (see text).
2. Reduction of oxides is easier 17. (c) Pyrolusite is MnO2. Hence not concentrated by froth
3. This is due to high polarising power of Cu and Ag ions floatation process.
4. Carbon can be used as a reducing agent above 1123 K. 18. (b) Calcination is used for removal of volatile impurities and
5. Copper is extracted from malachite and azurite. decompose carbonates.
19. (d) Decomposition of carbonates and hydrated oxides.
6. (a) Chromium and manganese
20. (d) It is definition of calcination (see text).
(b) Sodium and mangnesium
21. (d) Pyrites are sulphur ores and are converted into oxide by
(c) Tin and lead
roasting.
(d) Copper and silver
22. (d) Al2O 3.2H 2O ® Al 2O3 + 2H 2O is calcination.
7. (a) x is obtained by heating metal oxide alone.
23. (a) Mac Arthur process is used for Ag and Au (see text).
(b) y is obtained by the reducing its oxide with carbon. 24. (b) In Goldschmidt aluminothermic process reducing agent
(c) z is obtained by electrolytic reduction. is Al powder.
25. (d)
10. Because magnesium is a more costlier metal than aluminium
26. (c) Chromium is obtained by reduction with Al.
17. (a) 18. (b) 19. (c) 20. (a) 21. (a) 27. (d) Al is obtained by electrolytic reduction of Al2O3 in
presence of cryolite (see text).
22. (c) 23. (d) 24. (b) 25. (b) 26. (c) 28. (a) The common method for the extraction of metal from oxide
EXERCISE 2 ore is by reduction with carbon.
29. (c) Electrolysis is used for electroplating and
1. (a) Bauxite ore of aluminium is Al 2 O3 .2H 2 O . electrorefining both.
2. (a) Ores (see text). 30. (a) Gold is deposited as anode mud (see refining of copper).
3. (c) Impurities associated with minerals are called gangue or 31. (a) Silicon is purified by zone refining . Metals of high purity
matrix. are always purified by zone refining.
4. (b) Al, see text. 32. (b) Silver containing lead is purified by cupellation (see text).
5. (c) O, see text. 33. (d) Ni is purified by Mond’s process by decomposition of
6. (d) Flux is added which combines with impurities to form Ni(CO)4.
slag.
34. (c) Caliche is crude chilesaltpetre (NaNO3) and contains
7. (b) Since silica is acidic impurity the flux must be basic.
NaIO3, source of iodine.
CaO + SiO2 ® CaSiO3
8. (a) Dolomite on calcination gives CaO.MgO which provides 35. (b) Malachite is an ore of copper Cu ( OH ) 2 .CuCO3 .
basic lining in furnace. 36. (b) Important ore of iron is Haematite Fe 2 O3 .
9. (b) To remove acidic impurities basic flux is added which
37. (c)
is CaCO3 .
38. (d)
Cassiterite is an ore of Sn also known as tin stone SnO2.
10. (b) Na 3 AlF6 is cryolite and used in the electrolysis of 39. (a)
Cl2 is obtained by electrolysis of (aqueous) NaCl.
alumina to lower the melting point and increase electrical 40. (a)
Galena is an ore of lead. It is PbS.
conductivity. 41. (c)
Fe does not exist native.
11. (d) Flux removes acidic or basic impurities e.g. silica and 42. (d)
Most electropositive metals are obtained by electrolysis
other metal oxides etc. of their fused ionic salts.
12. (b) Cassiterite contains the magnetic impurities of FeSO 4 43. (a) Gold being least reactive found native.
and concentrated by electromagnetic separation. 44. (a) MnO2 is pyrolusite (oxide ore).
13. (d) Froth floatation process is used for the concentration of 45. (c) Na is obtained by elctrolytic reduction being
sulphide ores. electropositive in nature.
14. (c)
46. (b) Cuprite is Cu2O and Argentite is Ag 2 S .
JEEMAIN.GURU
downloaded from jeemain.guru
General Principles
General Principles & Processes of Isolation of Elements 665
5. (c) In blast furnace at about 1270 K, calcium carbonate is
47. (c) almost completely decomposed to give CaO which acts
as a flux and combines with SiO2 present as impurity
(gangue) in the ore to form calcium silicate (fusible
slag)
(At cathode) (At anode) CaO(s) (basic flux) + SiO2 (s) (acidic flux) ¾¾ ®
CaSiO3 (s) (slag)
Reduction potential of H is more than Na. 6. (c) Fused alumina (Al2O3) is a bad conductor of electricity.
Therefore, cryolite (Na3AlF6) and fluorspar (CaF2) are
48. (d) Slag formed in the extraction of iron is CaSiO3 .
added to purified alumina which not only make alumina
49. (b) Cyanide process is for gold (I-D); floatation process - a good conductor of electricity but also reduce the
pine oil (II-B); Electrolytic reduction - Al (III-C); Zone melting point of the mixture to around 1140 K.
refining -Ge (IV-A).
7. (d) Fe3O4 – Magnetite
50. (d)
CuCO3 · Cu(OH)2 – Malachite
51. (c) Ellingham diagram normally consists of plots of DfGº
Vs T for the formation of oxides of elements. Pyrolusite – MnO2 and Cassiterite – SnO2.
52. (d) For a spontaneous reaction , D Gº must be negative 8. (a) Cuprous oxide formed during roasting of cuprous
and it can be possible only in this case when x < y sulphide is mixed with few amount of cuprous sulphide
and heated in a reverberatory furnace to get metallic
EXERCISE 3
copper.
1. (d) The sulphide ore is roasted to oxide before reduction
because the DGof of most of the sulphides are greater 2Cu 2O + Cu 2S ® 6Cu + SO2
than those of CS2 and H2S, therefore neither C nor H 9. (a) Galena is PbS and purified by froth floatation method
can reduce metal sulphide to metal. Further, the standard 10. (d) During bessemerisation, cuprous sulphide
free energies of formation of oxide are much less than
is oxidised which combines with remaining cuprous
those of SO2. Hence oxidation of metal sulphides to
sulphide to form free copper metal
metal oxide is thermodynamically favourable.
2. (d) Leaching is the selective dissolution of the desired 2Cu 2 O + Cu 2S ¾
¾® 6Cu + SO 2
mineral leaving behind the impurities in a suitable
dissolving agent e.g., 11. (c) The reduction of metal sulphides by carbon reduction
process is not spontaneous because DG for such a
Argentitie or Silver glance, Ag2S is an ore of silver.
process is positive. The reduction of metal oxide by
Silver is extracted from argentite by the mac-Arthur
carbon reduction process is spontaneous as DG for
and Forest process (leaching process).
such a process is negative. From this we find that on
Ag 2S + 4NaCN ® 2Na[Ag ( CN )2 ] + Na 2S thermodynamic considerations CO2 is more stable than
CS2 and the metal sulphides are more stable than
4Au + 8KCN + 2H 2O + O 2 ® 4K[Au ( CN ) 2 ] + 4KOH corresponding oxides.
3. (b) Pig iron or cast iron contains 3 – 5% carbon and varying In view of above the factor listed in choice (c) is incorrect
amounts of Mn, Si, P and S which makes the iron hard and so is of no significance.
and brittle. 12. (b) PbO & PbSO4 get reduced by PbS itself which is already
4. (b) Zr and Ti are purified by van Arkel method. present in mixture so because the reduction took place
870K by itself, hence is known as self reduction.
Zr( s ) + 2I 2 ( g ) ¾¾¾® ZrI 4 ( g )
D
2PbO + PbS ¾¾
® 3Pb + SO 2
2075K
ZrI4 ( g ) ¾¾¾¾¾¾¾ ® Zr(s ) + 2I 2 ( g )
Tugsten filament
D
PbSO 4 + PbS ¾¾
® 2Pb + 2SO 2
523K
Ti(s) + 2I2(s) ¾¾¾ ® TiI4(g) 13. (b) Extraction of Zn from ZnS (Zinc blende) is achieved by
1700K roasting followed by reduction with carbon.
2ZnS + 3O2 ¾¾
® 2ZnO + 2SO2
Ti(s) + 2I2(g)
Pure titanium ZnO + C ¾¾
® Zn + CO
JEEMAIN.GURU
downloaded from jeemain.guru
666 Chemistry
14. (b) The reactions involved in cyanide extraction process 10. (c) Tricalcium phosphate and calcium silicate is Thomas slag
are : 11. (a) See Parke’s process
12. (a) Fe2O3 + 3CO ® 2Fe + 3CO2 ( in blast furnace)
Ag 2 S + 4NaCN ® 2Na [Ag(CN)2] + Na2S
(argentite) 13. (d) 2CuO + CuS ® 3Cu + SO 2 (Self - reduction)
14. (a) FeO is capable forming slag with SiO2
4Na2S + 5O 2 + 2H2O ® 2Na2SO4 + 4NaOH + 2S
Oxiding SiO 2 + FeO ® FeSiO 3
agent
15. (c) Pickling is removel of basic oxide layers on metals before
electroplating.
2Na[Ag(CN)2] + Zn ® Na2 [Zn(CN)4] + 2 Ag ¯ 16. (b) When reduction by carbon is not satisfactory in case of
(reducing
agent) metals having high m.pt., aluminothermic process is used
.
15 (a) Silver, copper and lead are commonly found in earth's
17. (d) Pure metal always deposits at cathode.
crust as Ag2S (silver glance), CuFeS2 (copper pyrites)
18. (c) 19. (a) 20. (b)
and PbS (galena)
21. (a) Gypsum is CaSO4.2H2O
EXERCISE 4 22. (b) The two equation are:
1. (b) The given reaction is the method named as Van Arkel for 4 2
the purification of titanium Al(s) + O 2 (g) ® Al2 O3 (s), D f Gº = -827kJ mol -1
3 3
2. (c) Froth reduces the surface tension of water and the
… (1)
solution forms froth.
3. (a) Froth flotation process is based on wetting properties of 4 2
Cr(s) + O 2 (g) ® Cr2 O3 (s), D f Gº = -540kJ mol -1
ore particles. 3 3
4. (a) Cryolite lowers the m.p of alumina and increases the … (2)
electrical conductivity Subtracting equation (ii) from equation (i) we have,
5. (d) See metallurgy of Zn 4 2
6. (c) Ca and K are strong reducing agents, hence their oxides Al(s) + Cr2 O 3 (s),
3 3
cannot be reduced with carbon
7. (b) Highly electropositive elements are obtained by 2 4
® Al2 O3 (s) + Cr(s), D r G° = -287kJ mol -1
electrolytic reduction. 3 3
8. (d) Na reacts vigorously with water (exothermic process ) 23. (d) Ellingham diagrams are based on thermodynamic con-
9. (c) The surface of particles not wetted hence they float at cepts. It does not tell anything about the kinetics of the
the surface reduction process.
JEEMAIN.GURU
downloaded from jeemain.guru
21A
JEEMAIN.GURU
downloaded from jeemain.guru
668 Chemistry
14. Electronegativity : The electronegativity decreases from 2. Phosphine :
nitrogen to bismuth. a) Any metal phosphide + H 2O ® PH3
15. Catenation : They exhibit the property of catenation but
due to weak M–M bond to less extent than 14 group Ca 3P2 + 6H 2O ® 3Ca (OH) 2 + 2PH 3
elements.
b) P4 + 3KOH + 3H 2O ® PH 3 + 3KH 2 PO 2
Bond C–C N–N P–P As–As
kJ/mol 353.3 163.7 201.6 147.4 c) PH 4 I + NaOH ® NaI + H 2O + PH 3
16. Reactivity : Elemental nitrogen is higly unreactive largely 3. Other hydrides :
because of its strong triple bond. (almost as inert as noble
(a) Zn 3M 2 (s) + 6HCl ® 2MH 3 (g) + 3ZnCl 2 (aq)
gases).
While phosphorus is extremely reactive and kept in water. It M = As, Sb, Bi
is inflamable and can be ignited at 45ºC. It shows green (b) Halides : All the elements of this group form trihalides
luminiscence or glow in dark on account of its slow of th e type MX 3 and except nitrogen all form
oxidation. Th is glow phenomenon is known as pentahalides of the type MX5
phosphorescence. MX3 M = N, P, As, Sb, Bi and X = F, Cl, Br or I
17. Multiple bond formation : Only nitrogen has a tendency to MX5
form pp—pp multiple bonds. Others forms dp–pp multiple when X = F, M can be P, As, Sb and Bi
bonds easily. when X = Cl, M can be P, As and Sb
COMPOUNDS OF GROUP 15 ELEMENTS : when X = Br, M can be P
a) Hydrides : All the elements of this group form hydrides of NF3 is a colourless, odourless gas and the most stable
the type MH3 which are covalent and pyramidal in shape. of this series. It has low reactivity.
Some properties follow the order which are NCl3 is a yellow oily liquid that reacts with water to form
NH3 > PH3 > AsH3 > SbH3 > BiH3 ammonia and hypochlorous acid.
Ammonia Phosphine Arsine Stabene Bismuthene NI3 is shock sensitive and decomposes explosively
1. Ease of formation when touched.
2. Stability Hydrolysis :
3. Basic character NCl3 + 3H 2O ® NH 3 + 3HOCl
4. Solubility
PCl3 + 3H 2O ® H3PO3 + 3HCl
5. Bond angle (NH3 107.5º ; PH3 92º, AsH3 91, SbH3 90º)
6. Strength of M – H bond 2AsCl 3 + 3H 2 O ® As 2O 3 + 6HCl
7. Dipole moment SbCl 3 + H 2 O ® SbOCl + 2HCl
8. Decomposition temperature
Some properties follow the order BiCl 3 + H 2O ® BiOCl + 2HCl
NH3 < PH3 < AsH3 < SbH3 < BiH3 * Ease of hydrolysis BiCl3 > SbCl3 > AsCl3 > PCl3 > NCl3
1. Reducing character * Trihalides except BiF3 are covalent in nature
2. Covalent character * Trihalides have pyramidal structure.
3. Poisonous character (c) Pentahalides : As nitrogen does not contain-vacant d-
4. Rate of combustion orbitals in the second shell and cannot expand its
Boiling points : BiH3 > SbH3 > NH3 > AsH3 > PH3 outer shell hence it does not form pentahalides.
Preparation of hydrides : Some hydrides can be prepared as * The hybridisation in pentahalides is sp3d (trigonal
follows : bipyramidal)
1. Ammonia : * Thermally less stable than trihalides
(a) Any ammonium salt + metal oxide or * Act as Lewis acids PCl5 + Cl - ® [PCl -6 ]
D
hydroxide ¾¾® NH3 * On complete hydrolysis they produce acids
eg. NH 4 Cl + Ca (OH ) 2 ® CaCl 2 + H 2 O + NH 3 PCl5 + 4H 2 O ® H 3PO 4 + 5HCl
2 NH 4 NO 2 + K 2 O ® 2 NH 3 + 2KNO 2 + H 2 O (d) Oxides : All the elements of this group form oxides of
or (NH4)3PO4, NH4NO3, (NH4)2SO4, the type M2O3 and M2O5. either by direct combination
(NH4)2SO3, (NH4)2S or (NH4)2 (C2O4) with O2 or indirectly.
(b) Any nitride + H 2 O ® NH 3 Oxides of N N2O5 , N2O4 , N2O3 , NO, N2O
strongly acidic
14243
BN + 3H 2 O ® H 3 BO 3 + NH 3 neutral
JEEMAIN.GURU
downloaded from jeemain.guru
Oxides of As As 2 O 5 As 2 O 3 Uses :
Amphoteric i) For manufacturing of nitric acid
ii) For detection of Oxygen
Oxides of Sb Sb 2 O 5 Sb 2 O 3 iii) For manufacturing of sulphuric acid as catalyst (Lead
Amphoteric chamber process)
Bi 2O 5 Bi 2 O3 Structure :
Oxides of Bi . .. .-. +.
Basic :N =O
..¬¾® N
.. =O:
N2O (dinitrogen oxide or nitrous oxide) known as laughing NO2 (nitrogen dioxide)
gas Preparation :
Preparation :
i) 2NO + O 2 ® 2 NO 2
(i) Priestley’s method :
ii) 2Pb ( NO 3 ) 2 ® 2PbO + 4 NO 2 + O 2
2 NO + H 2 O + Fe ® N 2O + Fe(OH) 2
(Common method)
(ii) Bertholet’s (common method) :
iii) Cu + 4HNO3 (conc.) ® Cu( NO3 )2 + 2H2O + 2NO2
D
NH 4 NO 3 ¾¾® N 2 O + 2 H 2 O Properties : Highly toxic, paramagnetic, reddish brown gas
(iii) 2NaNO3 + ( NH 4 ) 2 SO 4 ® N 2O + 2H 2O + Na 2SO 4 with choking odour, acidic
Reactions :
Properties :
Colourless, fairly unreactive, pleasing odour, sweet taste, i) 2NO 2 + H 2O ® HNO 2 + HNO 3 (Hence it is mixed
supports combustion. It is neutral. anhydride of HNO2 and HNO3)
D
2 N 2 O( g ) ¾¾® 2 N 2 (g ) + O 2 ( g ) ii) 2NO 2 N 2O4
brown colourless, solid / liquid, acidic
.-. + .. .. + .. -
.. = N =O
Structure : Linear N .. ¬
¾® N º N — O
.. : hn
iii) NO 2 ¾¾® NO + O
Uses : Mixed with oxygen it is used as anaesthetic iv) It is combustible and supports the combustion of
NO (nitrogen oxide or nitric oxide) : burning P, Mg or charcoal. Burning S or candle is
Preparation : extinguished.
Common method v) It is oxidising and reducing in nature
2NaNO2 + 2FeSO 4 + 3H 2SO4 Uses :
i) For Manufacturing of HNO3
® Fe 2(SO 4 )3 + 2NaHSO 4 + 2H 2O + 2NO
ii) As Catalyst in lead chamber process for Sulphuric acid
(i) D
N 2 (g ) + O 2 ( g ) ¾¾® 2 NO (g ) (commercial) Structure :
(ii) 3Cu (s) + 8HNO 3 (dil) ® 3Cu ( NO 3 ) 2 + 4H 2 O + 2 NO
(Lab method)
D , Pt N2O3 (dinitrogen trioxide) Nitrogen sesquioxide
(iii) 4NH3 + 5O2 ¾¾¾¾¾
750°C,6atm
® 4NO + 6H 2O
253K
Common method : 2NO + N 2 O 4 ¾¾¾ ® 2N 2 O 3
(Ostwald’s process)
Properties : Colourless, paramagnetic, slightly toxic gas, Preparation : NO + NO 2 ® N 2 O 3
blue in liquid state. It is combustible and supports Properties : It is blue solid, acidic
combustion. It is neutral.
N 2O 3 + H 2O ® 2HNO 2
D
FeSO 4 + NO ® FeSO 4 .NO ¾¾® FeSO 4 + NO Hence it is anhydride of HNO2
dark brown pure gas
Absorbed by sulphuric acid
D N 2 O 3 + 2H 2SO 4 ® 2 NO[HSO 4 ]2 + H 2 O
[Fe (H 2 O) 6 ]SO 4 + NO ® [Fe(H 2 O)5 NO]SO 4 ¾¾®
Hydrated nitrosyl Nitroso
complex sulphuric acid
:
:
JEEMAIN.GURU
downloaded from jeemain.guru
670 Chemistry
N2O5 (dinitrogen pentaoxide) (d) Oxyacids of N and P : Both form a number of oxy acids
Preparation : which are as follows :
i) 2HNO 3 + P2O 5 ® N 2 O5 + 2HPO 3 (common method) Oxidation Basicity
90º C number
ii) 4AgNO 3 + 2Cl 2 ¾¾¾® 4AgCl + 2 N 2 O 5 + O 2
1. Hyponitrous acid H2N2O2 +1
iii) N 2 O 4 + O 3 ® N 2 O 5 + O 2
2. Nitroxylic acid H4N2O4 +2
Properties : Colourless crystalline solid and sublimes
3. Nitrous acid HNO2 +3
N 2O 5 + H 2 O ® 2HNO 3
4. Nitric acid HNO3 +5
It is anhydride of nitric acid
5. Peroxy nitric acid HNO4 +5
N 2 O 5 + 2NaOH ® 2 NaNO3 + H 2 O
6. Hydronitrous acid H2NO2 +2
N 2 O 5 + H 2O 2 ® HNO 4 + HNO 3
7. Hypophosphorous acid H3PO2 +1 1
Pernitric acid
O:
O
.
O:
O
.
..
O NITROGEN :
|| Discovered by Daniel Rutherford. Abundance in air is 78.15% by
P volume. It occurs in combined state as saltpetre (KNO3) and Chile
O O Saltpetre (NaNO3). It is also known as Azote (without life)
O Preparation :
Structure : O=P P=O
O i) NH 4+ + NO 2- ® N 2 + 2H 2 O
P
O || O ii) 2 NH 3 + 3CuO ® N 2 + 3H 2 O + 3Cu
O iii) 8 NH 3 + 3Cl 2 ® N 2 + 6 NH 4 Cl
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
672 Chemistry
Oxidation of compounds : Conc. HCl). eg.:
2HNO 3 ® H 2O + 2 NO 2 + O , SO 2 + H 2 O + O ® H 2SO 4 HNO 3 + 3HCl ® NOCl + 2 H 2 O + 2Cl
nascent
H 2S + O ® H 2 O + S , 2HBr + O ® H 2O + Br2 chlorine
..
H O H O
ï .. .. .. ..
2HNO3 + 8H ® N 2 O + 5H 2O ý secondary reactions O N
.. O
.. N
2HNO3 + 10H ® N 2 + 6H 2 O ï
.. .
O
.. .
O
ï
.
..
.
2HNO3 + 16H ® 2NH3 + 6H 2O ïþ Uses : In the manufacture of fertilizers ii) For purification of silver
and gold iii) In the manufacture of explosives iv) oxidising reagent
Factors affecting the secondary reactions v) As nitrating reagent
i) Nature of the metal ii) Concentration of the acid NITROUS ACID (HNO2) :
iii) Temperature iv) Presence of impurities Preparation :
Action of nitric acid on zinc under different conditions
(i) Cold and very dil. acid evolves ammonia which reacts with (i) Ba ( NO 2 ) 2 + H 2SO 4 (dil.) ® BaSO 4 ¯ +2HNO 2
HNO3 forming ammonium nitrate (ii) 2NaNO 2 + H 2SO 4 ® Na 2SO 4 + 2HNO 2
4Zn + 10HNO 3 ® 4Zn( NO3 ) 2 + 3H 2 O + NH 4 NO3
(iii) N 2O 3 + H 2O ® 2HNO 2
(ii) Cold and dil HNO3
(iv) NH 3 + 3H 2O 2 ® HNO 2 + 4H 2 O
4Zn + 10HNO 3 ® 4Zn ( NO 3 ) 2 + 5H 2O + N 2 O
Properties : It has slight bluish colour in solution may be due to
(iii) Cold and moderately conc.
anhydride N2O3. It is very unstable.
3Zn + 8HNO 3 ® 3Zn( NO3 ) 2 + 4H 2O + 2 NO (i) Decomposition :
(iv) Cold and concentrated
3HNO 2 ® 2 NO + HNO 3 + H 2 O (auto oxidation)
Zn + 4HNO 3 ® Zn( NO3 ) 2 + 2H 2O + 2NO 2
(ii) Action of heat :
Action of nitric acid on Copper under different conditions
2HNO 2 ® H 2O + N 2 O3 ® NO 2 + NO
(i) Cold and dil.
4Cu + 10HNO 3 ® 4Cu( NO3 ) 2 + 5H 2O + N 2O (iii) Oxidising nature : 2HNO 2 ® 2 NO + H 2O + O
(ii) Cold and moderately concentrated H + + HNO 2 + e - ® H 2 O + NO (electron acceptor)
3Cu + 8HNO 3 ® 3Cu ( NO 3 ) 2 + 4H 2O + 2NO
(iv) Reducing nature : HNO 2 + O ® HNO 3
(iii) Cold and concentrated
Cu + 4HNO 3 ® Cu( NO3 ) 2 + 2H 2O + 2 NO 2 H 2 O + HNO 2 ® HNO 3 + 2H + + 2e - (electron donor)
(iv) Hot and conc. (v) Reaction with ammonia :
5Cu + 12HNO 3 ® 5Cu ( NO 3 ) 2 + 6H 2O + N 2 NH 3 + HNO 2 ® NH 4 NO 2 ® N 2 + 2H 2O
Metals like Mg and Mn give hydrogen with dil. HNO3 (vi) Formation of diazonium compounds :
Mg + 2HNO 3 ® Mg( NO3 ) 2 + H 2 C 6 H 5 NH 2 HCl + HNO 2 ® C6 H 5 N = NCl + 2H 2O
Uses : In the manufacture of azo dyes.
Mn + 2HNO 3 ® Mn ( NO 3 ) 2 + H 2
Structure : It is a tautomeric mixture of the following forms
Passivity : Metals like, Fe, Cr, Ni, Al or Co become inactive or ..
passive due to stable oxide layers. O
..
.. .. .. ..
Noble Metals like Pt, Pd, Os, Ir and Au do not react with nitric H O
.. N O
.. H N
.. .
acid. They react with aqua regia (1 vol. Conc. HNO3 + 3 vol. O
.
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
674 Chemistry
ORTHOPHOSPHORIC ACID (H3PO4) : FERTILIZERS :
Preparation : Fertilizers are the chemical substances which are added to soil in
(i) P4 O10 + 6 H 2 O ® 4H 3 PO 4 order to make up the deficiency of nutrients required by plants.
Nutrients are classified as
(ii) D
Red P + 5HNO 3 ¾¾® H 3 PO 4 + H 2 O + 5 NO 2 (i) Primary nutrients : which are consumed in large quantities
(iii) Ca 3 (PO 4 ) 2 + 3H 2SO 4 ® 3CaSO 4 + 2H 3 PO 4 eg. Nitrogen, Phosphorous and Potassium
(ii) Secondary nutrients : Calcium and Magnesium
(iv) PCl 5 + 4 H 2 O ® H 3 PO 4 + 5HCl
(iii) Micro nutrients : which are required in minute quantities
Properties : Colourless syrupy liquid eg. Copper, Zinc, Manganese, Boron, Molybdenum, chlorine
(i) Action of heat : and Iron
250 º C
2H 3 PO 4 ¾¾ ¾
¾® H 4 P2 O 7 + H 2 O ¾¾ ¾®
316º C TYPES OF FERTILIZERS :
Pyrophosph oric (i) Nitrogenous fertilizers : These provide nitrogen to the
acid
plants. They are
® 2 HPO 3 + H 2 O (a) Urea :
meta phosphoric 200 Atm.
acid 2 NH 3 + CO 2 ¾¾ ¾ ¾® H 2 NCOONH 4
(ii) It is tribasic and ionises in three steps 2H 2 NCOONH 4 ® H 2 N.CONH 2 + H 2O
H 3 PO 4 ® H + + H 2 PO -4 (Readily) It contains about 47% N2
(b) Ammonium sulphate (Sindri fertilizer) :
H 2 PO 4- ® H + + HPO -4 - (Weakly) NH 3 + H 2 O ® NH 4 OH
JEEMAIN.GURU
downloaded from jeemain.guru
Very Short/Short Answer Questions 19. If you touch concentrated HNO3 with your finger and
immediately wash it with water, then the skin at the place
1. On being slowly passed through water, PH3 forms bubbles where it came into contact with HNO3 becomes yellow. This
but NH3 dissolves. Why is it so? is because of :
2. What is the difference between the nature of pi-bonds present (a) the formation of Xanthoprotein
in H3PO3 and HNO3? (b) the absorption of HNO3 by skin
3. NO2 is coloured but its dimer is colourless. Why? (c) the blood absorbing HNO3
4. N atom possesses 5 valence electrons but does not form (d) the absorption of yellow/brown NO2 gas
20. PCl5 is possible but NCl5 does not exist :
NCl5. Why?
(a) in N, d-sub-shell is absent
5. NF3 is an exothermic compound but NCl3 is an endothermic (b) ionization energy of N is very high
compound. Explain. (c) it does not like Cl
6. What is laughing gas? How is it prepared? (d) none of these
7. PCl5 is ionic in nature in the solid state. Why? 21. The boiling points of the following hydrides follow the order
8. In trimethylamine, nitrogen has a pyramidal geometry of
whereas in trisilylamine N(SiH3)3 it has a planar geometry? (a) SbH 3 > NH 3 > AsH 3 > PH 3
9. Molecular nitrogen N2 is not particularly reactive. Explain. (b) NH 3 > AsH 3 > PH 3 > SbH 3
10. NH3 is more basic than PH3. Explain.
(c) SbH 3 > AsH 3 > PH 3 > NH 3
11. Present a comparative account of proton affinities of NH3
and PH3. (d) NH 3 > PH 3 > AsH 3 > SbH 3
12. Which of the following is/are not known and why: PCl3, 22. Which of the following statements is not correct for
AsCl3, SbCl3, NCl5, BiCl5 nitrogen ?
(a) Its electronegativity is very high
13. Both PCl+4 and SiCl4 have tetrahedral structures. Explain.
(b) d-orbitals are available for bonding
Long Answer Questions (c) It is a typical non-metal
(d) Its molecular size is small
14. In what ways nitrogen differs in its chemical behaviour from 23. The structural formula of hypophosphorous acid is
that of its heavier congeners? O O
15. Discuss the pattern of variation in the oxidation states of P P P
to Bi (a) H (b) H
OH OH
H OH
Multiple Choice Questions O O
16. Which one of the following statements is true for HNO2 ? P P
(c) HO (d) H
(a) It can not act as reducing agent OH OOH
(b) It can not act as oxidising agent OH OH
24. Producer gas is a mixture of :
(c) It can not act both as oxidant reductant
(a) CO and N 2 (b) CO 2 and H 2
(d) It is stable only in aqueous solution.
17. Of the following which is paramagnetic and has three (c) N 2 and O 2 (d) CH 4 and N 2
electron bond in its structure 25. Which of the following oxides of nitrogen is a coloured
(a) N2O (b) NO gas?
(a) N2O (b) NO
(c) N2O3 (d) N2O5
(c) N2O5 (d) NO2
18. With respect to protonic acids, which of the following 26. Which is the most thermodynamically stable allotropic form
statements is correct ? of phosphorus?
(a) PH3 is more basic than NH3 (a) Red (b) White
(b) PH3 is less basic than NH3 (c) Black (d) Yellow
(c) PH3 is equally basic as NH3 27. The number of P – O – P bonds in cyclic metaphosphoric
acid is
(d) PH3 is amphoteric while NH3 is basic.
(a) zero (b) two (c) three (d) four
JEEMAIN.GURU
downloaded from jeemain.guru
676 Chemistry
1. Which one of the following elements is most metallic ? 13. The one which does not form pentachloride is
(a) P (b) As (a) nitrogen (b) phosphorus
(c) Sb (d) Bi (c) arsenic (d) antimony
2. In NH3 and PH3 the common is 14. Which of the following compounds does not exist?
(a) odour (b) combustibility (a) AsCl5 (b) SbCl3
(c) basic nature (d) None of these (c) BiCl5 (d) SbCl5
3. Which element from group 15 gives most basic compound 15. What is hybridization of P in PCl5 ?
with hydrogen (a) sp3 (b) sp3d 2
(a) Nitrogen (b) Bismuth
(c) sp3d (d) sp2
(c) Arsenic (d) Phosphorus
16. Nitrous oxide is
4. Ionic radii (in Å) of As3+, Sb3+ and Bi3+ follow the order
(a) soluble in cold water (b) soluble in hot water
(a) As3+ > Sb3+ > Bi3+ (b) Sb3+ > Bi3+ >As3+
3+ 3+
(c) Bi > As > Sb 3+ (d) Bi3+ > Sb3+ > As3+ (c) acidic in nature (d) None of these
5. The three important oxidation states of phosphorus are 17. Which of the following oxides of nitrogen reacts with FeSO4
(a) –3, +3 and +5 (b) –3, +3 and –5 to form a dark brown compound
(c) –3, +3 and +2 (d) –3, +3 and +4 (a) N2O (b) NO
6. The basic character of hydrides of the group 15 elements (c) NO2 (d) N2O3
decreases in the order 18. Which of the following oxides is the most acidic?
(a) SbH3 > PH3 > AsH3 > NH3 (a) N2O5 (b) P2O5
(b) NH3 > SbH3 > PH3 > AsH3 (c) As2O 5 (d) Sb2O5
(c) NH3 > PH3 > AsH3 > SbH3 19. In the reaction
(d) SbH3 > AsH3 > PH3 > NH3 4HNO 3 + P4 O10 ® 4HPO 3 + X , the product X is
7. The stability of the hydrides follows the order
(a) NH3 > PH3 > AsH3 > SbH3 (a) N2O5 (b) N2O3
(b) NH3 < PH3 < AsH3 < SbH3 (c) NO2 (d) H2O
(c) PH3 > NH3 > AsH3 > SbH3 20. Which oxide of nitrogen is obtained on heating ammonium
(d) AsH3 > NH3 > PH3 > SbH3 nitrate at 250ºC ?
8. In nitrogen family, the H-M-H bond angle in the hydrides (a) Nitric oxide (b) Nitrous oxide
gradually becomes closer to 90º on going from N to Sb. This (c) Nitrogen dioxide (d) Dinitrogen tetraoxide
shows that gradually
(a) the basic strength of the hydrides increases 21. Which of the following can be used as an anaesthesia ?
(b) almost pure p-orbitals are used for M-H bonding (a) N2O (b) NO
(c) the bond energies of M-H bonds increases (c) NCl3 (d) NO2
(d) the bond pairs of electrons become nearer to the central
atom 22. The brown ring test for NO -2 and NO 3- is due to the
9. The boiling points of the following hydrides follow the order formation of complex ion with a formula
(a) SbH3 > NH3 > AsH3 > PH3 (a) [Fe(H2O)6]2+ (b) [Fe(NO)(CN)5]2+
(b) NH3 > PH3 > AsH3 > SbH3 (c) [Fe(H2O)5NO] 2+ (d) [Fe(H2O)(NO)5]2+
(c) NH3 > AsH3 > PH3 > SbH3 23. A deep brown gas is formed by mixing two colourless gases
(d) SbH3 > AsH3 > NH3 > PH3 which are
10. Which of the following has highest dipole moment? (a) NO2 and O2 (b) N2O and NO
(a) NH3 (b) PH3 (c) NO and O2 (d) NH3 and HCl
(c) AsH3 (d) SbH3 24. Which one of the following oxides of nitrogen is blue solid ?
11. The correct sequence of decrease in the bond angle of the (a) NO (b) N2O3
following hydrides is
(c) N2O (d) N2O5
(a) NH3 > PH3 > AsH3 > SbH3
25. Of the following compounds, the most acidic is
(b) NH3 > AsH3 > PH3 > SbH3
(a) As 2O30 (b) P2O5
(c) SbH3 > AsH3 > PH3 > NH3
(d) PH3 > NH3 > AsH3 > SbH3 (c) Sb2O3 (d) Bi2O3
12. Among the trihalides of nitrogen which one is most basic ? 26. Which of the following is a cyclic phosphate ?
(a) NF3 (b) NCl3 (a) H3P3O10 (b) H6P4O13
(c) NI3 (d) NBr3 (c) H5P5O15 (d) H7P5O16
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
678 Chemistry
53. BCl3 is a planar molecule whereas NCl3 is pyramidal because 63. The nitride ion in lithium nitride is composed of
(a) BCl3 has no lone pair of electrons but NCl3 has a lone (a) 7 Protons + 10 electrons (b) 10 Protons + 10 electrons
pair of electrons (c) 7 Protons + 7 electrons (d) 10 Protons + 7 electrons
(b) B—Cl bond is more polar than N—Cl bond 64. Which of the following leaves no residue on heating ?
(c) nitrogen atom is smaller than boron atom (a) Pb(NO3)2 (b) NH4NO3
(d) N—Cl bond is more covalent than B—Cl bond (c) Cu(NO3)2 (d) NaNO3
54. The electronic configuration of an elements is 1s2 2s2 2p6 65. Which of the following molecules is linear ?
3s2 3p6 3d10 4s2 4p3. Its properties would be similar to which (a) SO2 (b) NO +2
(c) NO 2 - (d) SCl2
of the following elements ?
(a) Boron (b) Oxygen 66. A metal X on heating in nitrogen gas gives Y. Y on treatment
(c) Nitrogen (d) Chlorine with H2O gives a colourless gas which when passed through
55. Which of the following has least covalent P—H bond ? CuSO4 solution gives a blue colour. Y is
(a) Mg(NO3)2 (b) Mg3N2
(a) PH3 (b) P2 H 62+ (c) NH3 (d) MgO
67. Which one of the following molecules will have bonds of
(c) P2 H 5+ (d) PH +4 unequal lengths ?
56. Among the followng species, identify the isostructural pairs (a) NF3 (b) BF3
(c) PF5 (d) SF6
NF3 , NO 3- , BF3 , H 3 O + , HN 3 68. In which of the following the bond angle is maximum ?
(a) [ NF3 , NO 3- ] and [BF3 , H 3 O + ] (a) NH3 (b) NH +4
(c) PCl3 (d) SCl2
(b) [ NF3 , HN 3} and [ NO3- , BF3 ]
69. One of the oxidants used with liquid propellants is
+
(c) [ NF3 , H 3O ] and [ NO3- , BF3 ] (a) ammonium perchlorate (b) nitrocellulose
(c) sulphuric acid (d) nItrogen tetroxide (N2O4)
(d) [ NF3 , H 3O + ] and [HN 3 , BF3 ] 70. The aqueous solution/liquid that absorbs nitric oxide to a
considerable extent is
57. In PO 34- ion, the formal charge on each oxygen atom and (a) lead nitrate (b) nitric acid
P—O bond order respectively are (c) ferrous sulphate (d) sodium hydroxide
(a) –0.75, 1.25 (b) –3, 1.25 71. Which one of the following arrangements of molecules is
(c) –0.75, 1.0 (d) –0.75, 0.6 correct on the basis of their dipole moments ?
58. In nitroprusside ion, the iron and NO exist as Fe++ and NO+ (a) BF3 > NF3 > NH3 (b) NF3 > BF3 > NH3
(c) NH3 > BF3 > NF3 (d) NH3 > NF3 > BF3
rather than Fe+++ and NO. These forms can be differentiated
72. Sodium hexametaphosphate is known as
by
(a) calgon (b) permutit
(a) estimating the concentration of iron
(c) natalite (d) nitrolim
(b) measuring the concentration of CN - 73. The oxidation number of As in H 2 AsO -4 is
(c) measuring the solid state magnetic moment (a) +6 (b) +5
(d) thermally decomposing the compound (c) –7 (d) +9
59. Nitrogen atom has an atomic number of 7 and oxygen has an 74. Which of the following compounds is explosive in nature ?
atomic number 8. The total number of electrons in a nitrate (a) Phosphorus trichloride (b) Nitrogen trichloride
ion will be (c) Hyponitrous acid (d) Nitrosyl chloride
(a) 8 (b) 16 75. Among the 15th group elements, as we move from nitrogen
(c) 32 (d) 64 to bismuth, the pentavalency becomes less pronounced and
60. If HNO3 changes into N2O, the oxidation number is changed trivalency becomes more pronounced due to
by (a) Non metallic character (b) Inert pair effect
(a) 2 (b) 6 (c) High electronegativity (d) Large ionization energy
(c) 0 (d) +4
61. The hybridized state of N in R2NH is 76. In NO 3- ion, the number of bond pair and lone pair of
(a) sp3 (b) sp2 electrons on nitrogen atom are
(c) sp (d) dsp 2 (a) 2,2 (b) 3, 1
(c) 1, 3 (d) 4, 0
62. The hybridization of atomic orbitals of nitrogen in NO +2 , 77. Pentavalence in phosphorus is more stable when compared
to that of nitrogen even though they belong to same group.
NO 3- and NH +4 are
This is due to
(a) sp, sp3 and sp2 respectively (a) dissimilar electronic configuration
(b) sp, sp2 and sp3 respectively (b) due to presence of vacant d-orbitals
(c) sp2, sp and sp3 respectively (c) reactivity of phosphorus
(d) sp2, sp3 and sp respectively (d) inert nature of nitrogen
JEEMAIN.GURU
downloaded from jeemain.guru
1. Which of the following is a nitric acid anhydride? 11. H3PO2 is the molecular formula of an acid of phosphorus. Its
(a) NO (b) NO2 [CBSE PMT 1988] name and basicity respectively are [CBSE PMT 1992]
(c) N2O5 (d) N2O3. (a) Phosphorus acid and two
2. Which of the following metal evolves hydrogen on reacting (b) Hypophosphorous acid and two
with cold dilute HNO3 ? [CBSE PMT 1989] (c) Hypophosphorous acid and one
(a) Mg (b) Al (d) Hypophosphoric acid and two
(c) Fe (d) Cu. 12. Which of the following fertilizers has the highest nitrogen
3. Each of the following is true about white and red phosphorus percentage ? [CBSE PMT 1993]
except that they [CBSE PMT 1989] (a) Ammonium sulphate
(a) Are both soluble in CS2 (b) Calcium cyanamide
(b) Can be oxidised by heating in air (c) Urea
(c) Consist of the same kind of atoms (d) Ammonium nitrate
(d) Can be converted into one another 13. Which of the following oxides will be the least acidic?
4. When orthophosphoric acid is heated to 600°C, the product (a) As4O 6 (b) As 4O10 [CBSE PMT 1996]
formed is [CBSE PMT 1989]
(c) P4O10 (d) P4O6
(a) PH3 (b) P2O5
14. Which of the following oxy-acids has the maximum number
(c) H3PO3 (d) HPO3
of hydrogens directly attached to phosphorus?
5. Which of the following statements is not correct for nitrogen?
(a) H4P2O7 (b) H3PO2 [CBSE PMT 1999]
[CBSE PMT 1990]
(c) H3PO3 (d) H3PO4
(a) Its electronegativity is very high
15. Nitrogen forms N2, but phosphorus is converted into P4 from
(b) d-orbitals are available for bonding
P, the reason is [CBSE PMT 2001]
(c) It is a typical non-metal
(a) Triple bond is present between phosphorus atom
(d) Its molecular size is small
(b) pp – pp bonding is strong
6. P2O5 is heated with water to give [CBSE PMT 1991]
(c) pp – pp bonding is weak
(a) Hypophosphorous acid
(d) Multiple bond is formed easily
(b) Phosphorous acid
(c) Hypophosphoric acid 16. Oxidation states of P in H4 P2O5 , H4 P2O6 , and H4 P2O7 ,
(d) Orthophosphoric acid are respectively: [CBSE-PMT 2010]
7. PCl3 reacts with water to form [CBSE PMT 1991] (a) + 3, + 5, + 4 (b) + 5, + 3, + 4
(a) PH3 (b) H3PO3, HCl (c) + 5, + 4, + 3 (d) + 3, + 4, + 5
(c) POCl3 (d) H3PO4 17. In which of the following compounds, nitrogen exhibits
8. PH4I + NaOH forms [CBSE PMT 1991] highest oxidation state ? [CBSE-PMT 2012 S]
(a) PH3 (b) NH3 (a) N2H4 (b) NH3
(c) P4O6 (d) P4O10 (c) N3H (d) NH2OH
9. Pure nitrogen is prepared in the laboratory by heating a 18. Which of the following statements is not valid for oxoacids
mixture of [CBSE PMT 1991] of phosphorus? [CBSE-PMT 2012 S]
(a) NH4OH + NaCl (b) NH4 NO3 + NaCl (a) Orthophosphoric acid is used in the manufacture of triple
(c) NH4 Cl + NaOH (d) NH4 Cl + NaNO2. superphosphate.
10. Sugarcane on reaction with nitric acid gives (b) Hypophosphorous acid is a diprotic acid.
(a) CO2 and SO2 [CBSE PMT 1992] (c) All oxoacids contain tetrahedral four coordinated
(b) (COOH)2 phosphorus.
(c) 2 HCOOH (two moles) (d) All oxoacids contain atleast one P = O and one P — OH
(d) No reaction. group.
JEEMAIN.GURU
downloaded from jeemain.guru
680 Chemistry
19. In case of nitrogen, NCl3 is possible but not NCl5 while in 24. The decreasing values of bond angles from NH3 (106º) to
case of phosphorous, PCl3 as well as PCl5 are possible. It is SbH3 (101º) down group-15 of the periodic table is due to
due to [AIEEE 2002] (a) decreasing lp-bp repulsion [AIEEE 2006]
(a) availability of vacant d orbitals in P but not in N (b) decreasing electronegativity
(b) lower electronegativity of P than N (c) increasing bp-bp repulsion
(c) lower tendency of H-bond formation in P than N (d) increasing p-orbital character in sp3
(d) occurrence of P in solid while N in gaseous state at room 25. Regular use of which of the the following fertilizers increases
temperature.
the acidity of soil? [AIEEE 2007]
20. Number of sigma bonds in P4O10 is [AIEEE 2002]
(a) Ammonium sulphate
(a) 6 (b) 7
(b) Potassium nitrate
(c) 17 (d) 16.
(c) Urea
21. What may be expected to happen when phosphine gas is
(d) Superphosphate of lime.
mixed with chlorine gas ? [AIEEE 2003]
(a) PCl3 and HCl are formed and the mixture warms up 26. The reaction of P4 with X leads selectively to P4O6. The X is
(b) PCl5 and HCl are formed and the mixture cools down (a) Dry O2 [IIT-JEE 2009]
(c) PH3 . Cl2 is formed with warming up (b) A mixture of O2 and N2
(d) The mixture only cools down (c) Moist O2
22. Which one of the following substances has the highest (d) O2 in the presence of aqueous NaOH
proton affinity? [AIEEE 2003] 27. Extra pure N2 can be obtained by heating [IIT-JEE 2011]
(a) H2S (b) NH3 (a) NH3 with CuO (b) NH4NO3
(c) PH3 (d) H2O (c) (NH4)2Cr2O7 (d) Ba(N3)2
23. The number of hydrogen atom(s) attached to phosphorus 28. Concentrated nitric acid, upon long standing, turns yellow
atom in hypophosphorous acid is [AIEEE 2005] brown due to the formation of [JEE Advanced 2013]
(a) three (b) one (a) NO (b) NO2
(c) two (d) zero (c) N2O (d) N2O4
1. Phosphine on reaction with hydrobromic acid gives 5. The nitrate which when heated gives off a gas or a mixture of
(a) PBr3 (b) PH4Br gases which cannot relight a glowing splinter is
(c) PBr5 (d) P2H4 (a) sodium nitrate (b) ammonium nitrate
2. An inorganic compound producing organic compound on (c) lead nitrate (d) potassium nitrate
heating is 6. Liquid ammonia bottles are opened after cooling them in ice
(a) sodamide for sometime. It is because liquid NH3
(b) ammonium cyanate (a) Brings tears to the eyes
(c) sodalime (b) Has a high vapour pressure
(d) potassium cyanide (c) Is a corrosive liquid
3. Which is not correct for N2O ? (d) Is a mild explosive
(a) It is laughing gas and is used as anaesthetic agent. 7. Ammonia is generally manufactured for fertilizers by the
(b) It is nitrous oxide reaction
(c) It is not a linear molecule. (a) 2 NH 4 Cl + Ca (OH ) 2 ® CaCl 2 + 2H 2 O + 2 NH 3
(d) It is least reactive of all the oxides of nitrogen
(b) By passing an electric discharge in a mixture of N 2 and
4. An important method of fixation of atmospheric N2 is
H2
(a) Fisher- Tropsch’s process
(c) By passing a mixture of N2 and H2 under high pressure
(b) Haber’s process
and moderate temperature over a catalyst
(c) Frasch’s process
(d) None of these
(d) Solvay’s process
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
682 Chemistry
EXERCISE 1 14. (c) Due to inert pair effect the lower O.S. is more common at
the bottom of group
1. This is because PH3 is much weaker base than NH3.
NH3 dissolves in water forming NH4OH. 1
15. (c) Hybridisation in PCl5 = (5 + 5 + 0 - 0) = 5 sp3d
NH + H O NH + + OH– 2
3 2 4
2. In H3PO3, there is pp – dp bond whereas in HNO3 there is 16. (a) N2O is soluble in cold and not in hot water
pp – pp bond. pp – pp bond in HNO3 is stronger than pp – 17. (b) FeSO 4 + NO ® FeSO 4 .NO
dp bond in H3PO3.
18. (a) In N2O5 nitrogen is present in the highest O.S. and it is
3. NO2 has unpaired electron and due to this, it has brown most electronegative in nature than others
colour. N2O4 does not have unpaired electron and thus it is
19. (a) See preparation of N2O5
colourless.
20. (b) N2O (see text)
4. N atom does not have d-orbitals and thus it cannot have all
21. (a) N2O is used as anaesthetic
five valence electrons as unpaired.
22. (c) [Fe(H2O)5NO]2+ ion is formed
5. F is highly electronegative and N – F bond energy is higher
than N – Cl bond energy. 23. (c) 2NO + O 2 ® 2 NO 2 brown
6. N2O is laughing gas prepared by heating NH4NO 3 . 24. (b) N2O3 is blue solid
D 25. (b) P2O5 ;P is electronegative and present in highest O.S. of
NH 4 NO3 ¾¾® N 2 O + 2H 2 O
5, hence P2O5 is most acidic
7. PCl5 is ionic in the solid state because it exists as [PCl4]+
26. (c) H5P5O15 (HPO3)5. It is metaphosphoric acid which is a
[PCl6]–.
cyclic phosphate.
16. (d) 17. (b) 18. (b) 19. (a) 20. (a)
27. (b) See structures of oxy acids of phosphorous
21. (a) 22. (b) 23. (a) 24. (a) 25. (d)
28. (b) H4P2O5 is pyrophosphorous acid it contains P–O–P
26. (c) 27. (c) bond
EXERCISE 2 29. (c) H3PO4 is tribasic
30. (a) Hypophosphorous acid is H3PO2 in which O.S. of P is
1. (d) Metallic character increases down the group, Bi is most +1
metallic
31. (c) See structure of metaphosphoric acid.
2. (c) Basic nature
32. (c) One s and two p
3. (a) Nitrogen; NH3 is most basic .. ..
4. (d) Ionic radii increases down the group 33. (b) It is N º N
5. (a) –3, +3, +5 (see text) 34. (c) Nitrogen can form NCl3, N2O5 Ca3N2 and not NCl5 since
6. (c) it has no d atomic orbitals in valence shell
7. (a) 35. (c) CaC2 + N 2 ® (CaCN 2 + C)
8. (b) With the decrease in the electronegativity of central atom Calcium cyanamide
the bond angle decreases
D
9. (a) 36. (d) (NH 4 ) 2Cr2 O 7 ¾¾
® Cr2 O3 + 4H 2 O + N 2
10. (a) Dipole moment decreases with decrease in 37. (d) The cause of inert nature of N2 is the presence of triple
electronegativity of central metal atom .. ..
11. (a) bond N º N
12. (c) The lesser the electronegativity of halogen in NX3 the 38. (b) NH3 is not used as anaesthetic
more is the basic character. N can donate more electrons 39. (c) Ammonia is dried over CaO. Others will react with it
in that case. 40. (b) Ammonia has pyramidal shape with sp3 hybridisation.
13. (a) Nitrogen does not contain vacant d orbitals in valence NH
41. (c) P4 O10 + 2 H 2 O ¾
¾® 4HPO 3 ¾¾¾
3 ® NH PO
4 3
shell hence cannot extend its coordination number more basic
Acidic meta phosphoric meta ammonium
than 3 acid phosphate
JEEMAIN.GURU
downloaded from jeemain.guru
54. (c) The valence shell electronic configuration is 4s24p3 67. (c) PF5 has trigonal pyramidal shape in which axial and
similar to nitrogen 2s2p3 equitorial bonds have different lengths
55. (b) For this calculate the formal charge distributed on each 68. (b) Bond angle in NH +4 is 109º28' due to sp3 hybridisation
P–H bond which is given by = Total charge . and symmetrical structure
No. of P - H bonds 69. (d) N2O4 is used as an oxidant with liquid propellants
The more the formal charge the lesser is the covalent 70. (c) FeSO 4 + NO ® FeSO 4 .NO
character. 71. (d) NH3 > NF3 > BF3. NH3 and NF3 have pyramidal shape.
In BF3 is planar.
+2 +1 +1 d–
P2 H 26 + = = +0.33 ; P2 H 5+ = = +0.2 ; PH 4+ = = +0.25 .. F
6 5 4 N N d+
B F
Hence lowest covalent character of P–H bond is d+H H H d– F
d– F F
F m=0
d–
in P2 H 62+
72. (a) It is calgon (Sodium hexametaphosphate)
56. (c) In NF3 and H3O+ the hybridisation is sp3 and both are
73. (b) H 2 AsO -4 2(1) + x +4(–2)= –1 , \ x = +5
pyramidal. In NO 3- and BF3 the hybridisation is sp2 and
74. (b) NCl3 is explosive in nature.
both are planar 75. (b) Inert pair effect (follow text)
JEEMAIN.GURU
downloaded from jeemain.guru
684 Chemistry
.. 12. (c) Urea (46.6%N). % of N in other compound are :
– O
..
( NH 4 ) 2 SO 4 = 21.2%;
..
76. (d) O
.. N .. , Bond pairs = 4, lone pair = 0
O..
CaCN 2 = 35.0% and NH 4 NO 3 = 35.0%
..
77. (b) Phosphorous can achieve coordination number 5 due to 13. (a) As the O.N of the central atom of the compounds
vacant d atomic orbitals in valence shell which is not increases acidic strength of that compound also
possible in nitrogen increases and on moving from top to bottom in groups
acidic strength of oxides also decrease due to decreasing
EXERCISE 3 electronegativity in groups.
1. (c) N 2 O 5 + H 2 O ¾¾® 2 HNO 3 +5 +3 +5 +3
2. (a) Magnesium and manganese are the metals that produce P4O10 > P4O6 > As 4O10 > As 4O6
hydrogen with dilute nitric acid 14. (b)
Mg + 2HNO3 ¾ ¾® Mg (NO3)2 + H2 OH OH
3. (a) Both white and red phosphorus are not soluble in CS2
(a) H4P2O7 ÞO P O P O
only white P is soluble.
OH OH
600°C
4. (d) 2H 3 PO 4 ¾¾¾¾ ® 2HPO 3 Pyrophosphoric acid
ortho phosphoric -2H 2 O meta phosphoric
acid acid O
5. (b) In case of nitrogen, d-orbitals are not available. P
(b) H3PO2 Þ OH H
6. (d) P2O5 have great affinity for water. The final product is H
orthophosphoric acid. Hypophosphorous acid
2H2O O
P4O10 4HPO3
Metaphosphoric (c) H3PO3 Þ HO – P – OH
acid H
2H2O
Phosphorous acid
2H 2O
4H3PO4 2H4P2O7 O
orthophosphoric Pyrophosphoric
acid acid (d) H3PO4 Þ HO – P – OH
OH
7. (b) PCl3 + 3H 2 O ® H 3PO 3 + 3HCl orthophosphoric acid
8. (a) PH 4 I + NaOH ® NaI + PH 3 + H 2 O 15. (c) Nitrogen form N2 (i.e. N º N) but phosphorus form P4,
because in P2, pp — pp bonding is present which is a
9. (d) Pure nitrogen in the lab can be obtained by heating
weaker bonding.
ammonium nitrate. Ammonium nitrate is not a stable
16. (d)
compound it dissociate to give nitrogen.
17. (c) Compound Oxidation number of nitrogen
Heat
NH 4 Cl + NaNO 2 ¾¾¾® NH 4 NO 2 N2H4 = –2
NH3 = –3
Heat
¾¾¾® N 2 + 2 H 2 O. N3H = –1/3
10. (b) Cane sugar is oxidised to oxalic acid NH2OH = –1
(2HNO 3 ¾¾
® H 2 O + 2NO 2 + O)18
O
C12 H 22 O11 + 18[O] ¾
¾® 6 (COOH) 2
Cane sugar From HNO3 Oxalic acid 18. (b) H P H Hypophosphorous acid (H3PO2) is a
+ 5H 2O. O
H
C12H22O11 + 36HNO3 ¾¾®
6(COOH)2 + 36NO2 + 23H2O monobasic acid. i.e., it has only one ionisable hydrogen
atom or one OH is present.
11. (c) H3 PO2 is named as hypophosphorous acid. As it 19. (a) 7N = 1s2 2s2 2p3; 2 2 6
15P = 1s 2s 2p 3s 3p
2 3
contains only one P – OH group, its basicity is one. In phosphorous the 3 d- orbitals are available.
JEEMAIN.GURU
downloaded from jeemain.guru
||
O
O P compound
|| O
O 3. (c) N2O has linear structure ( see structure)
4. (b) By Haber’s Process atmospheric nitrogen is converted
21. (a) PH 3 + 3Cl 2 ¾
¾® PCl 3 + 3HCl into NH3.
.. 5. (b) NH 4 NO3 ® N 2O + 2H 2O.
22. (b) Among the given compounds, the NH 3 is most basic.
N2O is non combustible an d non supporter of
Hence has highest proton affinity
combustion. Other nitrates give O2 which supports
H combustion.
|
23. (c) Hypophosphorous acid H - O - P ® O 6. (b) Liquid ammonia has high vapour pressure which is
| lowered down by cooling, otherwise the liquid will bump.
H
7. (c) By Haber’s process
Two H-atoms are attached to P atom. 8. (d) The oxides of nitrogen being acidic in nature are soluble
24 (b) The bond angle decreases on moving down the group in KOH which is an alkali.
due to decrease in bond pair-bond pair repulsion. 9. (b) (NH 4 ) 2 Cr2 O 7 ® N 2 + Cr2O 3 + 4H 2O
NH3 PH3 AsH3 SbH3 BiH3 green
107º 94º 92º 91º 90º
10. (b) Red P does not react with NaOH to give PH3.
This can also be explained by the fact that as the size of
11. (d) PH3 is not obtained when metaphosphoric acid is heated.
central atom increases sp3 hybrid orbital becomes more
12. (a) The combustibility of PH3 is due to presence of P2H4.
distinct with increasing size of central atom i.e. pure
The pure PH3 is not combustible.
p-orbitals are utilized in M–H bonding.
25. (a) (NH4)2SO4 + 2H2O¾¾ ® 2H2SO4 + NH4OH 13. (c) BiCl 3 + H 2O ® BiOCl + 2HCl . BiOCl gives white ppt.
H2SO4 being strong acid increases the acidity of soil. In which is used as white pigment, under the name of pearl
case of potassium nitrate and superphosphate of lime on white.
hydrolysis strong base also form along with strong acid 14. (a) CaCN 2 + 3H 2O ® CaCO3 + 2NH3
on hydrolysis results into neutralisation.
15. (c) NO2 is paramagnetic and readily dimerises to N2O4 which
In presence of N 2
26. (b) P4 + 3O 2 ¾¾¾¾¾¾¾® P4 O 6 is diamagnetic.
16. (b) PI 3 + 3H 2 O ® H 3 PO 3 + 3HI
Here N2 acts as a diluent and thus retards further
Dibasic acid Monobasic acid
oxidation. Reaction of P4 under other three conditions.
2O
17. (b) 20% nitrogen means if 20 g N then M.wt = 100
(a) P4 + 3O 2 ¾¾
® P4 O 6 ¾¾¾
2® P O
4 10
(c) In moist air, P4O6 is hydrolysed to form H3PO3 if 14 g N then M.wt = 100 ´ 14 = 70
20
P4 O 6 + 6H 2 O ¾¾
® 4H 3 PO 3
At least one N atom must be present in the molecule.
(d) In presence of NaOH,
18. (b) TNT when mixed with NH4NO3 , gives blasting mixture.
P4 + 3OH - + 3H 2O ¾¾
® PH 3 + 3H 2 PO 2- 19. (c) 2NH3 + OCl– ® NH2.NH2 + H2O + Cl–
27. (d) Very pure N2 can be obtainted by thermal decomposition Pt . gauge
20. (a) 4NH 3 + 5O 2 ¾¾¾¾® 4NO + 6H 2 O
of sodium or barium azide. Ba(N 3 ) 2 ¾¾
® Ba + 3N 2
28. (b) The slow decomposition of HNO3 is represented by the 21. (b) CuSO 4 + 4NH 3 ® [Cu( NH 3 ) 4 ] SO 4
eqn.
4HNO3 ® 4NO2 + 2H2O + O2 Blue complex due to Cu(NH3 )2 +
4
(yellow-brown)
22. (b) 4NH 3 + 5O 2 ® 4NO + 6H 2O
JEEMAIN.GURU
downloaded from jeemain.guru
686 Chemistry
24. (a) Except (a) all other properties are shown by white
23. (d) NH 3 N d- phosphorous.
25. (b) The conversion of atmospheric nitrogen to nitrogen
d+
H H d+ compounds is known as fixation of nitrogen.
Hd+
26. (c) P2O 5 + 2HNO 3 ® N 2O 5 + 2HPO 3
JEEMAIN.GURU
downloaded from jeemain.guru
21B
The p-Block Elements-
Oxygen Family
GENERAL CHARACTERISTICS : 6. Oxidation state
The elements oxygen, sulphur, selenium, tellurium and polonium O S Se Te Po
belong to group VIA or 16 group of periodic table. –1,–2 –2 to +6 –2 to +6 –2 to +6 –2 to +6
These elements are known as chalcogens i.e. ore forming elements. In OF2 the oxidation state of oxygen is +2
1. Electronic configuration 7. Ionisation energy - They possess a large amount of ionisation
Elements At.No. Electronic Confg. Valence shell energy which decrease gradually from O to Po due to increase
electronic confg. in size of atoms and increase in screening effect.
8. Electron affinity - They have high electron affinity which
Oxygen 8 [He]2s2 p 4 2s 2 2p 4
decrease from O to Po. As the size of the atom increases the
Sulphur 16 [Ne]3s 2 3p4 3s 2 3p 4 extra added electron feels lesser attraction by nucleus and
electron affinity decreases.
Selenium 34 [Ar]4s2 4p 4 4s 2 4p 4 9. Electronegativity - It decreases down the group due to
decrease in the effective nuclear charge down the group.
Tellurium 52 [Kr]5s 2 5p 4 5s 2 5p 4 10. Catenation - The tendency to form chains of identical atoms
is known as catenation. It follows the order
Polonium 84 [Xe]6s 2 6p 4 6s 2 6p 4
S-S > Se - Se > O- O > Te - Te
The oxygen differs from the rest of the elements due to its (i)
small size (ii) higher electronegativity (iii) absence of d atomic 226 172 142 126 kJ/mole
orbitals in valence shell (iv) tendency to form multiple The higher the bond strength, the higher is the catenation.
bonding. 11. Atomicity - Oxygen is diatomic, sulphur and selenium octa
2. Metallic and non metallic character atomic with puckered ring structure
O S Se Te Po S
144244
3 1442443 S S S S S
Non metals Metalloids S S , S
S S S
S S
Metal (Radio active) t1/2 138.4 days
3. Abundance O > S > Se > Te > Po Ring S6
Oxygen is the most abundant element. It constitutes 46.6% 12. Allotropy - All the elements exhibit allotropy
of earth’s crust, 21% of air and 89.1% of ocean by weight. · Oxygen - O2 dioxygen and O3 ozone
Sulphur forms about 0.052% of earth’s crust. · Sulphur - Rhombic (or a ) sulphur S8
4. Density - Increases down the group regularly.
Monoclinic (or b ) sulphur S8
5. Melting point and boiling point - Both show a regular increase
down the group due to increase in molecular weight and Van (most stable)
der Waal’s forces of attraction. Plastic (or l ) sulphur open chain
Colloidal (or d ) sulphur
JEEMAIN.GURU
downloaded from jeemain.guru
688 Chemistry
The SR changes to SM above 95.4ºC. lewis acid character
· Selenium Rhombic Se8 SF4 + F2 ® SF6
Monoclinic Se8 They have trigonal bipyramidal shape with sp 3d
Grey hybridiation.
Grey is the most stable consisting of regularly arranged Cl Cl
spirals of Se atoms.
· Tellurium Non metallic
Te
Metallic (more stable)
· Polonium a and b both metallic
Cl Cl
13. Atomic radii - Increases regularly from O to Po.
(c) Dihalides - The dihalides eg SCl2, OF2, TeBr 2 are sp3,
14. Ionic radii - Increases regularly from O to Po hybridised and have distorted bond angles due to
15. Atomic volume - Increase regularly from O to Po. electron pair repulsions
16. Multiple bond formation - The tendency of these elements SCl2 OF2 TeBr2
to form multiple bonds to C and N decreases down the group 104º 101.5º 98º
eg S = C = S is moderately stable.
Se = C = Se decomposes readily and
Te = C = Te not known
COMPOUNDS OF SIX GROUP ELEMENTS : S
Cl
(i) Hydrides - All these elements form stable hydrides of the
type H2M either by directly combining with hydrogen or by
the action of acids on metal sulphides, Selenides and Cl
tellurides (d) Dimeric monohalides - The dimeric monohalides are
given by sulphur and selenium eg S2F2, S2Cl2, Se2Cl2
2H 2 + O 2 2H 2 O S2Br2, Se2Br2. These are slowly hydrolysed and undergo
FeS + H 2SO 4 ® H 2S + FeSO 4 disproportionation.
2S2Cl 2 + 2H 2O ® 4HCl + SO 2 + 3S
Na 2Se + H 2SO 4 ® H 2Se + Na 2SO 4
H2O is a liquid due to hydrogen bonding. Others are 2Se 2 Cl 2 ® SeCl 4 + 3Se
colourless gases with unpleasant smell. Cl
H2O > H2S > H2Se > H2Te
104.5º 92.5º 91º 90º S
(all sp3 hybridised) 104º
¬ Stability, volatile character (from H2S to H2Te) S
® Poisonous nature, acidic character, raducing character..
The weakening of M – H bond with the increase in the size of Cl
M (not the electronegativity) explains the acid character of The monohalides have structure similar to H2O2 with
hydrides. distorted bond angle of sp3 hybridisation
(ii) Halides - All these elements form a number of halides. The (iii) Oxides - Ozone is considered as oxide of oxygen O. Oxides
halides of oxygen are not very stable eg OF2, Cl2O7, I2O5 etc of other elements are as follows
(a) Hexahalides - These are formed by fluorine only (not Element Mono Oxide Dioxide Tri Oxide
by Cl, Br, I) where elements exhibit maximum valency of S SO SO2 SO3
+6. SF6, SeF6, TeF6 are colourless gases with sp3d2 Se - SeO2 SeO3
hybridisation and octahedral structure. These are covalent Te TeO TeO2 TeO3
in nature. Due to bigger size of Cl, Br and I the coordination
number of 6 is not achieved. Po PoO PoO2 -
F SO2 is a gas having sp2 hybridisation and V-shape.
F F S S S
S O 119.5 O O O O O
2
SO3. is a gas, sp hybridised and planar in nature.
F F
O O O
F
(b) Tetrahalides - With the exception of SBr4, SI4 and SeI4 S S S
all tetrahalides are known. SF4 is gaseous, SeF4 is liquid
and TeF4 is solid. SCl4 is unstable liquid. These have O O O O O O
JEEMAIN.GURU
downloaded from jeemain.guru
:
O
: :
:
98º O
: :
O O
O O O O
: :
: :
: :
: :
Se 125º Se Se Se H – O – S – O– H or H – O – S – S– H
90º
O O
S
: : O
: :
SeO3 has tetrameric cyclic structure
:
:
O O O O
Se
O O O O (iii)Pyrosulphuric acid H2S2O7 HO – S – O – S – OH
Se Se
O O O O O O
3. Thionic acid series
Se
:
:
O O
: :: :
O O
Oxy acids - Sulphur forms four series of oxy acids
: :
: :
(i) Dithionic acid H2S2O6 HO – S – S – OH
Name Formula Structure
1. Sulphurous acid series O O
: :: :
(ii) Polythionic acid H2SnO6
:
:
(i) Sulpurous acid H2SO3
O O
S HO – S – S n – S – OH
: :
: :
HO OH
O O
:O : (n=3, 4, 5, 6)
(ii) Thiosulphurous acid 4. Peroxy acid series
(i) Peroxomonosulphuric acid
S H2SO5
H2S2O2 HO OH
S O
O HO – S – O – OH
O
(iii)Hyposulphurous acid H2S2O4 HO – S – S – OH
(Caro’s Acid)
O (ii) Peroxodisulphuric acid H2S2O8
O
O O
(iv) Pyrosulphurous acid H2S2O5 HO – S – S – OH HO – S – O – O – S – OH
O O O O
(Marshall’s acid)
Oxy acids of selenium - Selenous acid H2SeO3, Selenic acid
H2SeO4
JEEMAIN.GURU
downloaded from jeemain.guru
690 Chemistry
Oxy acids of Tellurium Tellurous acid H2TeO3; Telluric acid (4) Manufacture of KMnO4 and artificial silk.
H2TeO4 Tests:-
OZONE (O3) : (1) Turns starch iodine paper blue.
Discovered by Van Marum by passing electric discharge through (2) Tailing of Hg. Mercury loses its meniscus in contact with O3
air, named by Schonbien (azo - I smell) and Sorret established the and sticks to the surface of glass due to formation of Hg2O
formula O3 as allotrope of oxygen (3) Clean silver foil blackened by O3
It is formed in atmosphere by action of UV rays on O2. It is also (4) It turns benzidene paper brown and tetramethyl base violet
+
formed by (i) slow oxidation of phosphorous in air (ii) Reaction of +
O
O
fluorine with water at low temperature (iii) Electrolysis of water Structure – –
(iv) SO2 reacts with H2O2 O O O O
Preparation lab method : By passing silent electric discharge Oxidation state of O is +1 and –1
through cold, dry oxygen in ozoniser Oxides: Oxides are the binary compounds of oxygen with metals
3O2 2O3 + 284.5 kJ and non metals. Based on their oxygen content they have been
classified as
The ozonisers used are
(1) Normal oxides - Oxides containing oxygen according to
1. Siemen’s ozoniser 2. Brodie’s ozoniser normal oxidation number of M eg. H2O, MgO, Al2O3.
Manufacture. For the manufacture of ozonised air Siemen and (2) Polyoxides - These contain more oxygen than normal
Halske’s ozoniser is employed. oxidation number of M and M – O and O – O bonds. They
Electrolytic method. When acidified water, using high current are further classified as
density and Pt. anode, is electrolysed 95% O3 is obtained at anode
rest being O2. (i) Peroxides - They contain O22- ion, produce hydrogen
Properties - Pale blue gas, dark blue liquid and violet black solid peroxide with dil. acids and O2 with concentrated acids
with characteristic strong smell, slightly soluble in water but more eg BaO2, Na2O2
soluble in turpentine oil, glacial acetic acid and carbon tetrachloride. ( dil.)
Decomposition BaO 2 + H 2SO 4 ¾¾¾® BaSO 4 + H 2 O 2
573K (Conc )
2O3 ¾¾¾ ® 3O 2 DH = 284 kJ / mole 2 BaO 2 + 2H 2SO 4 ¾¾ ¾
¾® 2BaSO 4 + 2H 2 O + O 2
Oxidising action (ii) Super oxides - They contain O 2– ion. With water they
O 3 ® O 2 + O (nascent oxygen hence powerfully oxidising) give hydrogen peroxide and oxygen
PbS + 4O ® PbSO 4 2KO 2 + 2H 2 O ® 2KOH + H 2O 2 + O 2
H 2S + O ® H 2 O + S (iii)Dioxides - They give chlorine with conc HCl and oxygen
with Conc H2SO4 eg MnO2, PbO2 etc.
2FeSO 4 + H 2SO 4 + O ® Fe 2 (SO 4 ) 3 + H 2O
2MnO 2 + 4HCl(Conc) ® MnCl 2 + 2H 2 O + Cl 2
2K 4 [Fe(CN) 6 ] + H 2 O + O ® 2K 3[Fe(CN) 6 ] + 2KOH
2MnO 2 + 2H 2SO 4 (Conc) ® 2MnSO 4 + 2H 2 O + O 2
2I 2 + 9O ® I 4O9 [I2 , P,S, As] + O3 ® ic acid
(iv) Suboxides - They contain lower percentage of oxygen
Reducing action eg N2O, C3O2
H 2 O 2 + O 3 ® H 2O + 2O 2 BaO 2 + O 3 ® BaO + 2O 2 They have M – M and M – O bonds. For example O
= C = C = C = O (carbon suboxide)
NaOCl + O 3 ® NaCl + 2O 2
(v) Mixed oxides - Formed by the combination of two simple
Alkaline oxides eg Red lead, Pb3O 4 (PbO 2.2PbO), Fe 3O 4
K 3 [ Fe( CN ) 6 ] ¾¾ ¾¾® K 4 [ Fe( CN ) 6 ]
(FeO+Fe2O3)
O Classification on the basis of chemicals behaviour
Addition reactions CH 2 = CH 2 + O3 ® H 2C CH2 (i) Acidic oxides - Oxides of non metals which give acids
when dissolved in water are called acidic oxides eg.
O O CO2, NO2, P2O5, SO2, SO3, Cl2O7 etc.
Ozonide
CO 2 + H 2 O ® H 2CO 3 carbonic acid
Uses:- The metallic oxides of high oxidation state eg Mn2O7,
(1) Bleaching ivory, oils, flour etc. V2O5 and CrO3
(2) As germicide and disinfectant, for sterilising water (ii) Basic oxides
(3) For improving atmosphere in crowded places (a) Ionic in nature. Oxides of alkali and alkaline earth
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
692 Chemistry
discharge tube As2O3 is precipitated as As2S3 by passing H2S
Atomic oxygen : O2 ¾¾¾¾¾¾ ® O + O DH = 489.6kJ
1 mm pressure As 2 O 3 + 3H 2S ® As 2S3 + 3H 2 O
Isotopes O16 O17 O18 PbSO4 is insoluble in water and settles down on
10000: 1: 8 dilution and filtered off.
NO and NO 2 are removed by heating with
SULPHUR :
Occurence - It occurs free in volcanic regions. In combined state ( NH 4 ) 2 SO 4
it occurs as ( NH 4 ) 2 SO 4 + NO + NO 2 ® 3H 2 O + H 2SO 4 + 2 N 2
(i) Gypsum CaSO4.2H2O
(f) Concentration - The sulphuric acid is concentrated
(ii) S-Celesite SrSO4 by evaporation
(iii) Galena PbS (2) Contact process - The steps involved are
(iv) Zinc blende ZnS (i) Production of SO2 - It is produced by burning sulphur
(v) Copper pyrites Cu2SFe2S3 and iron pyrites and purified by treating with steam to
(vi) Iron pyrites FeS2 remove dust particles. The arsenic is removed by ferric
Properties - Ordinary sulphur is pale yellow, insoluble in water hydroxide, water vapour removed by conc H2SO4. The
but dissolves in CS2, C6H6 and turpentine gases are filtered through coke filters and purity is tested
Allotrophic forms - Its important allotrophic forms are by Tyndal box.
Crystalline - Rhombic, monoclinic (ii) Conversion of SO2 to SO3 - It is done in contact or
Amorphous - Plastic, milk of sulphur, colloidal sulphur. catalyst chamber after being preheated to 450ºC.
COMPOUNDS OF SULPHUR : 2SO 2 + O 2 == 2SO 3 + x cal
1. Sulphuric acid - It is also known as oil of vitriol and king of 450° - 500ºC 1.6 to 1.7 atm Pressure
chemicals. Catalyst - Formerly platinised asbestose was used which
Manufactures of sulphuric acid is costly and easily poisoned. Now a days V2O5 is used.
(1) Lead chamber process - The various steps involved are (iii)SO3 is absorbed by conc H2SO4 and then water is added
(a) Production of SO2 : By burning S or iron pyrites. to produce the acid of desired concentration
D
S + O 2 ¾¾® SO 2 H 2SO 4 + SO 3 ® H 2S 2O 7
(oleium or pyrosulphuric acid)
4FeS2 + 11O2 ® 2Fe2O3 + 8SO2
H 2S 2O 7 + H 2O ® 2H 2SO 4
(b) Production of catalyst - Oxides of nitrogen
If SO3 is absorbed by water it liberates large amount of
2 NaNO3 + H 2SO 4 ® Na 2SO 4 + 2HNO 3
heat producing acid fog.
2HNO 3 ® H 2O + NO + NO 2 + O 2 Properties - Its specific gravity is 1.8 and it is 98% by weight
(c) Reaction in lead chamber normality is 36N.
Chemical properties
SO 2 + NO 2 ® SO 3 + NO
(i) Action of heat H 2SO 4 ® H 2O + SO 2 + O
SO 3 + H 2 O ® H 2SO 4
Hence it acts as oxidising agent
2NO + O 2 ® 2 NO 2 (used again) Non metals are oxidised to their oxides
Gay-Lussac Tower : The residual gases (mainly air + oxides C + 2O ® CO 2 S + 2O ® SO 2
of nitrogen) from lead chambers + conc. H2SO4 from glover
tower give nitrated acid. 2P + 5O ® P2O 5
2H 2SO 4 + NO + O 2 ® 2 NO.HSO 4 + H 2 O 2KI + 2H 2SO 4 ® K 2SO 4 + SO 2 + I 2 + 2H 2 O
Glover Tower : The nitrated acid from Gay-Lussac tower is 2KBr + 2H 2SO 4 ® K 2SO 4 + SO 2 + Br2 + 2H 2 O
denitrated in this tower.
(ii) Displacement reactions - It displaces volatile acids from
2 NO.HSO 4 + H 2 O ® 2H 2SO 4 + NO + NO 2 their salts.
Nitroso Na 2S + H 2SO 4 ® H 2S + Na 2SO 4
sulphuric acid
(d) Conditions - Temperature 50ºC, excess of steam, lead NaCl + H 2SO 4 ® HCl + NaHSO 4
chamber since lead is not attacked H2SO4. NaNO3 + H 2SO 4 ® HNO 3 + NaHSO 4
(e) Purification - The acid obtained contains the
impurities of PbSO4, AS2O3, NO and NO2 which are Ca 3 (PO 4 ) 2 + 3H 2SO 4 ® 2H 3PO 4 + 3CaSO 4
removed as follows
JEEMAIN.GURU
downloaded from jeemain.guru
HO.SO 2 .OH + 2PCl5 ® Cl.SO 2 .Cl + 2POCl 3 + 2HCl (ii) As oxidising agent
Sulphuryl 2H 2S + SO 2 ® 2H 2 O + 3S ¯
Chloride
(v) Sulphonation of aromatic compounds SO 2 + 2Mg ( burning ) ® 2MgO + S ¯
C6 H6 + H 2SO4 ® C6 H5 .SO2 OH + H2O 3Fe + SO 2 ® 2FeO + FeS
Benzene
sulphonic acid PbO 2 + SO 2 ® PbSO 4
(vi) Precipitation - Barium and lead are precipitated as (iii)Burning of potassium - Potassium burns in SO2 giving
sulphates sulphate and thiosulphate
BaCl 2 + H 2SO 4 ® BaSO 4 + 2HCl 4K + 3SO 2 ® K 2SO3 + K 2S2O3
Pb( NO 3 ) 2 + H 2SO 4 ® PbSO 4 + 2HNO 3 (iv) Bleaching action - Its bleaching action is due to
Hence these are gravimetrically estimated reduction
Fuming sulphuric acid [H2SO4.SO3] SO 2 + 2H 2O ® H 2SO 4 + 2H
With ammonia it forms (NH4)2 SO4 hence NH3 can not
Structure : It is sp2 hybridised and has V- shape.
be dried over H2SO4
Uses - It is used as oxidising, dehydrating agent and for the
S S S
preparation of dyes, drugs, explosives, volatile acids etc.
Structure - It has tetrahedral structure O 120º O O O or O O
120º
O O S- in excited state
S S
HO OH or HO OH
O O sp2
hybridisation
S- in doubly excited state s bond from sp2 -p overlap
one p bond from pp-pp bond overlap
other p bond from pp-dp overlap
SULPHUR TRIOXIDE (SO3) :
sp3 hybridisation These orbitals form two Preparation
p-bonds with two oxygen (i) By heating conc H2SO4 with P2O5
SULPHUR DIOXIDE (SO2) H 2SO 4 + P2 O 5 ® SO 3 + 2HPO 3
Preparation (ii) Manufacture : It is done by contact process
D
(i) By heating sulphur in air S + O 2 ¾¾® SO 2 2SO 2 + O 2 == 2SO 3
JEEMAIN.GURU
downloaded from jeemain.guru
694 Chemistry
Properties - It dissolves in water with loud hissing sound and (ii) Reducing nature
evolution of heat 2KMnO 4 + 3H 2SO 4 + 5H 2S ® K
Chemical properties
K 2SO 4 + 2MnSO 4 + 8H 2 O + 5S
1. Action of heat 2SO 3 == 2SO 2 + O 2
K 2Cr2 O 7 + 4H 2SO 4 + 3H 2S ®
2. Water SO 3 + H 2 O == H 2SO 4 K 2 Cr2O7 + 4H 2SO4 + 3H 2S ® K 2SO4 + Cr2(SO 4 )3 + 7H 2O + 3S
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
696 Chemistry
4. A group 16 element exists in monoatomic state in the metallic 19. There is S – S bond in
lattice. It also exists in two crystalline forms. The metals is (a) H2S2O7 (b) H2S2O8
(a) Po (b) S (c) H2S2O6 (d) H2SO5
(c) Se (d) Te 20. Oleum is chemically known as
5. Atomicity of sulphur in rhombic sulphur is (a) H2SO3 (b) H2SO5
(a) 1 (b) 2 (c) H2S2O7 (d) H2S2O8
(c) 8 (d) 6 21. S - S bond is present in
6. Which of the following hydrides has the lowest boiling point
? (a) S2 O 27 - (b) S3O9
(a) H2O (b) H2S (c) S2 O 24 - (d) S2 O32 -
(c) H2Se (d) H2Te
7. Which of the following hydrides is most acidic ? 22. Which of the following has pp- dp bonding ?
(a) H2Te (b) H2Se
(a) NO 3- (b) SO 32 -
(c) H2O (d) H2S
8. Which of the following hydrides shows the highest boiling (c) BO 33- (d) CO 32-
point ?
23. Caro’s acid is
(a) H2O (b) H2S
(c) H2Se (d) H2Te (a) H2SO3 (b) H3S2O5
9. Electronegativity of oxygen is more than sulphur yet H2S is (c) H2SO5 (d) H2S2O8
acidic while water is neutral. This is because 24. H2S reacts with O2 to form
(a) water is highly associated compound (a) H2O + S (b) H2O + SO2
(b) molecular mass of H2S is more than H2O (c) H2O + SO3 (d) H2SO4 + S
(c) H2S is gas while H2O is a liquid 25. Which is the best oxidising agent among the following ?
(d) H–S bond is weaker than H–O bond (a) S (b) O
10. What is the hybridization of S in SF4 ? (c) Se (d) Te
(a) sp 3d 2 (b) sp 3 d 26. On heating KClO3 we get
(c) sp d3 3 (d) sp 3 (a) KClO2 + O2 (b) KCl + O2
11. The shape of the molecule SF3Cl3 is (c) KCl + O3 (d) KCl + O2 + O3
(a) trigonal bipyramidal (b) cubic 27. Oxygen molecule is
(c) octahedral (d) tetrahedral (a) diamagnetic with no-unpaired electron(s)
12. States of hybridization of P in PF5 and S in SF6 are (b) diamagnetic with two unpaired electrons
respectively? (c) paramagnetic with two unpaired electrons
(a) sp 3d2,sp 3d (b) sp3d,sp 3d 2 (d) paramagnetic with no unpaired electron(s)
3
(c) sp ,sp d 3 (d) sp2,d 3 28. The number of electrons that are paired in oxygen molecule
are
13. Which of the following is not tetrahedral ?
(a) 16 (b) 12
(a) SCl4 (b) SO 24 - (c) 14 (d) 7
29. Which of the following is incorrect ?
(c) Ni(CO)4 (d) NiCl 24 - (a) O2 is weaker oxidant than O3
14. In OF2 molecule, the total number of bond pairs and lone pairs (b) O2 has larger bond length than O3
of electrons present respectively are (c) Both O2 and O3 are paramagnetic
(a) 2, 6 (b) 2, 8 (d) O2 is linear and O3 is angular in shape
(c) 2, 10 (d) 2, 9 30. Which of the following species possesses the highest bond
15. The type of hybridization in water molecule is order ?
(a) sp (b) sp 2 (a) O2 (b) O +2
(c) sp 3 (d) None of these
16. Hybridization of S in SO3 is (c) O 2– (d) O 22 –
(a) sp 2 (b) sp 3
(c) sp d2 (d) sp 3d 2 31. In the species O2, O +2 , O 2– and O 22 – , the correct decreasing
17. Permonosulphuric acid is known as order of bond strength is
(a) Marshall’s acid (b) Caro’s acid (a) O 2 > O 2+ > O 2– > O 22 -
(c) Sulphuric acid (d) None of these
18. S – S bond is not present in (b) O 2+ > O 2 > O 2– > O 22 -
(a) S2 O 24 - (b) S2 O52 - (c) O 22- > O 2- > O 2+ > O 2
(c) S2 O32 - (d) S2 O 27 - (d) O -2 > O 22- > O 2 > O +2
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
698 Chemistry
1. Hypo is used in photography to [CBSE-PMT1988] 11. By passing H 2S gas in acidified KMnO4 solution, we get
(a) Reduce AgBr grains to metallic silver [CBSE-PMT 1995]
(b) Convert metallic silver to silver salt (a) S (b) K2S
(c) Remove undecomposed silver bromide as a soluble (c) MnO2 (d) K2SO3
complex 12. Oxidation of thiosulphate by iodine gives
(d) Remove reduced silver [CBSE-PMT 1996]
2. Oxygen will directly react with each of the following elements (a) tetrathionate ion (b) sulphide ion
except [CBSE-PMT 1989] (c) sulphate ion (d) sulphite ion
13. During its reactions, ozone [CBSE-PMT 1999]
(a) P (b) Cl (c) Na (d) S.
(a) can only combine with hydrogen atoms
3. The gases respectively absorbed by alkaline pyrogallol and (b) accepts electrons
oil of cinnamon are [CBSE-PMT 1989] (c) loses electrons
(a) O3, CH4 (b) O2, O3 (c) SO2,CH4 (d) N2O, O3. (d) shows the role of electrons to be irrelevant
4. It is possible to obtain oxygen from air by fractional distillation 14. Which of the following is the most basic oxide?
because [CBSE-PMT 1989] (a) Sb2O3 (b) Bi2O3 [CBSE-PMT 2006]
(a) oxygen is in a different group of the periodic table from (c) SeO2 (d) Al2O3
nitrogen 15. Which one of the following compounds is a peroxide ?
(b) oxygen is more reactive than nitrogen [CBSE-PMT 2010]
(c) oxygen has higher b.p. than nitrogen (a) KO 2 (b) BaO2
(d) oxygen has a lower density than nitrogen.
5. Which would quickly absorb oxygen ? (c) MnO 2 (d) NO 2
[CBSE-PMT1991, 92] 16. Match List - I (substances) with List - II (processes) employed
(a) Alkaline solution of pyrogallol in the manufacture of the substances and select the correct
(b) Conc. H2SO4 option. [CBSE-PMT 2010]
(c) Lime water List - I List - II
(d) Alkaline solution of CuSO4 Substances Processes
6. Oleum is [CBSE-PMT 1991] (A) Sulphuric acid (i) Haber’s process
(a) Castor Oil (b) Oil of vitriol (B) Steel (ii) Bessemer’s
(c) Fuming H2SO4 (d) None of them process
7. A certain compound (X) when treated with copper sulphate
(C) Sodium hydroxide (iii) Leblanc process
solution yields a brown precipitate. On adding hypo solution,
(D) Ammonia (iv) Contact process
the precipitate turns white. The compound is
(a) K2CO3 (b) KI [CBSE-PMT 1994] Options:
(c) KBr (d) K3PO4 (A) (B) (C) (D)
8. Polyanion formation is maximum in [CBSE-PMT 1994] (a) (iv) (ii) (iii) (i)
(a) Nitrogen (b) Oxygen (b) (i) (iv) (ii) (iii)
(c) Sulphur (d) Boron (c) (i) (ii) (iii) (iv)
9. The acid which has a peroxy linkage is [CBSE-PMT 1994] (d) (iv) (iii) (ii) (i)
(a) Sulphurous acid (b) Pyrosulphuric acid 17. Which of the following oxide is amphoteric ?
(c) Dithionic acid (d) Caro’s acid [CBSE-PMT 2011 M]
10. About 20 km above the earth, there is an ozone layer. Which (a) SnO2 (b) CaO (c) SiO2 (d) CO2
one of the following statements about ozone and ozone layer
18. Sulphur trioxide can be obtained by which of the following
is true? [CBSE-PMT 1995]
reaction : [CBSE-PMT 2012 S]
(a) ozone has a triatomic linear molecule
(b) Fe 2 ( SO4 )3 ¾¾
Δ Δ
(b) it is harmful as it stops useful radiation (a) CaSO 4 + C ¾¾ ® ®
(c) it is beneficial to us as it stops U.V radiation
Δ Δ
(d) conversion of O3 to O2 is an endothermic reaction (c) S + H 2SO 4 ¾¾ ® (d) H 2SO 4 + PCl5 ¾¾ ®
JEEMAIN.GURU
downloaded from jeemain.guru
1. When SO2 gas is passed through an acidified solution of 7. Which reaction represents the oxidizing behaviour of H2SO4
K2Cr2O7 (a) 2PCl 5 + H 2SO 4 ® 2POCl 3 + 2HCl + SO 2Cl 2
(a) the solution becomes blue
(b) 2NaOH + H 2SO 4 ® Na 2SO 4 + 2H 2O
(b) the solution becomes colourless
(c) SO2 is reduced (c) NaCl + H 2SO 4 ® NaHSO 4 + HCl
(d) green Cr2(SO4)3 is formed
(d) 2HI + H 2SO 4 ® I 2 + SO 2 + 2H 2 O
2. FeCl3 solution on reaction with SO2 changes to
(a) FeCl2 (b) Fe2(SO4)3 8. Which characteristic is not correct about H2SO4 ?
(c) Fe2(SO3)3 (d) FeSO4 (a) Reducing agent (b) Oxidising agent
3. A considerable part of the harmful ultraviolet radiation of the (c) Sulphonating agent (d) Highly viscous
sun does not reach the surface of the earth . This is because 9. Which of the following is a saline oxide ?
high above the earth’s atmosphere there is a layer of (a) Na2O2 (b) BaO2
(a) CO2 (b) hydrogen (c) Na2O (d) Fe2O3
(c) ozone (d) ammonia 10. In the manufacture of H2SO4 the nitrated acid from the Gay -
4. On passing H2S through acidified FeCl3 solution FeCl3 is Lussac’s tower is chemically
converted into (a) H2SO4.NO2 (b) H2SO4.NO
(a) FeCl2 (b) Fe2( SO4)3 (c) H2SO4. 2NO (d) HSO4. NO
(c) FeS (d) FeSO4 11. Potassium chlorate on heating with conc H2SO4 gives
5. H2SO4 is added while preparing a standard solution of (a) chlorine dioxide (b) HClO4
Mohr’s salt to prevent (c) KHSO4 (d) All of these
(a) hydration (b) reduction 12. Sulphur forms the chlorides S2Cl2 and SCl2. The equivalent
(c) hydrolysis (d) complex formation mass of sulphur in SCl2 is 16g /mol . Therefore the equivalent
6. Concentrated H2SO4 is not used to prepare HBr from KBr mass of sulphur in S2Cl2 is
because it (a) 32 g / mol (b) 16 g /mol
(a) oxidizes HBr (c) 64 g/mol (d) 8 g/ mol
(b) reduces HBr 13. Reagent used to distinguish H2O2 and O3 is
(c) causes disproportionation of HBr (a) PbS (b) starch and iodine
(d) reacts too slowly with KBr (c) KMnO4 (d) bleaching powder
JEEMAIN.GURU
downloaded from jeemain.guru
700 Chemistry
14. Which of the following does not react with AgCl 22. Which of the following statements is correct :
(a) Na2S2O3 (b) NH4OH (a) Ozone is a resonance hybrid of oxygen
(c) NaNO3 (d) Na2CO3 (b) Ozone is an isomer of oxygen
15. When KBr is treated with conc. H2SO4 reddish brown gas is
(c) Ozone has no relationship with oxygen
evolved . The gas is
(a) Br2 (b) Br2 + HBr (d) Ozone is an allotropic modification of oxygen
(c) NO2 (d) H2O2 23. The crystals of ferrous sulphate on heating give :
16. One gas bleaches the colour of the flowers by reduction (a) FeO + SO 2 + H 2 O
while the other by oxidation. The gases are
(a) CO and CO2 (b) H2S and Br2 (b) FeO + SO 3 + H 2SO 4 + H 2O
(c) SO2 and Cl2 (d) NH3 and SO3
17. Which oxide is of different type than others (c) Fe 2 O 3 + SO 2 + H 2SO 4 + H 2O
(a) MnO2 (b) PbO2
(d) Fe 2O 3 + H 2SO 4 + H 2 O
(c) TiO2 (d) Na2O2
18. In which reaction does SO2 act as oxidising agent 24. In the upper layers of atmosphere ozone is formed by the
(a) Acidified KMnO4 (b) Acidified K2Cr2O7 (a) action of ultraviolet rays on oxygen
(c) Acidified C2H5OH (d) H2S (b) action of electric discharge on oxygen molecules
19. Hydrogen sulphide reacts with lead acetate forming a black
(c) combination of oxygen molecules
compound which reacts with H2 O2 to form another
compound . The colour of the compound is (d) None of these
(a) black (b) yellow 25. When sugar is treated with conc. sulphuric acid, the sugar is
(c) white (d) pink charred. In this process, sugar is
20. Hydrolysis of one mole of peroxodisulphuric acid produces (a) reduced (b) oxidized
(a) two moles of sulphuric acid (c) sulphonated (d) dehydrated
(b) two moles of peroxomonosulphuric acid
(c) one mole of sulphuric acid and one mole of 26. H 2SO 4 and H 2SO 3 can be distinguished by the addition
peroxomonosulphuric acid of :
(d) one mole of sulphuric acid, on e mole of
peroxomonosulphuric acid and one mole of hydrogen (a) magnesium powder (b) NaHSO 4 solution
peroxide.
(c) FeCl3 solution (d) litmus solution
21. Oxygen gas can be prepared from solid KMnO4 by :
27. Yellow ammonium sulphide is
(a) treating the solid with H 2 gas
(a) ( NH 4 ) 2 S8 (b) ( NH 4 ) 2 S
(b) strongly heating the solid
(c) dissolving the solid in dil. H 2SO 4 (c) ( NH 4 ) 2 S x (d) ( NH 4 ) 2 S 4
(d) dissolving solid in dil. HCl
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
702 Chemistry
31. (b)
56. (d) K 4 [Fe(CN)6 ] + 6H 2SO4 + 6H 2O ®
32. (c) Oxides of alkali and alkaline earth metals are basic Al2O3
is amphoteric hence acidic in comparision to others. 2K 2SO 4 + FeSO 4 + 6CO + 3 ( NH 4 ) SO4
2
33. (b) ZnO is amphoteric (see oxides).
57. (b) H2O2 > O3 > O2
34. (c) 2Na 2 O 2 + 2H 2O ® 4 NaOH + O 2 B. O. is 1, 1.5 and 2 respectively.
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
704 Chemistry
15. (a) 2KBr + 3H 2SO 4 ® 2KHSO 4 + SO 2 + Br2 + 2H 2 O D
21. (b) 2KMnO 4 ¾¾® K 2 MnO4 + 4MnO 2 + O 2
16. (c) SO2 bleaches by reduction and Cl 2 by oxidation
17. (d) N2O2 is peroxide while others are dioxides 22. (d) Ozone is an allotrope of oxygen.
18. (d) SO 2 + 2H 2S ® 2H 2O + 3S. 23. (c) FeSO 4 . 7H 2 O ® FeSO 4 + 7H 2 O
The O.S of S changes from – 2 to 0 by loss of electrons.
D
Hence SO2 is oxidising 2FeSO 4 ¾¾® Fe 2O 3 + SO 2 + SO 3
19. (c) (CH 3COO) 2 Pb + H 2S ® PbS + 2CH 3COOH UV
24. (a) 3O 2 ¾¾
¾® 2O 3
PbS + 4H 2O 2 ® PbSO 4 + 4H 2O
White
25. (d) C12 H 22O11 ¾H SO 4
¾2 ¾¾ ® 12C + 11H 2 O
D black
O O
20. (c) HO S O O S OH + H2O 26. (c) FeCl 3 acts as oxidant and H 2SO 3 as reductant.
peroxodisulphuric acid
O O O
O S OH + H O HO S O OH + HO S OH
O O O
JEEMAIN.GURU
downloaded from jeemain.guru
21C
The p-Block Elements -
Halogens
GENERAL CHARACTERISTICS : 7. Oxidation State -
The group 17 of periodic table consists of five elements fluorine, F2 Cl2 Br2 I2 At
chlorine, bromine, iodine and astatine and are known as -1 -1 to + 6 -1 to +6 -1 to +7 -1,+1,+5
halogens (sea salt forming elements). Astatine is artificially 8. Bond energy and bond length - The bond length increases
prepared by radioactive element. from fluorine to iodine
1. Electronic configuration - F-F Cl-Cl Br-Br I-I
Element Symbol At No. Valence shell Bond length (Å) 1.42 1.99 2.28 2.67
electronic configration Bond energy (kJ mol-1) 158.8 242.6 192.8 151.1
Due to small size the interelectronic repulsions between non
Fluorine F 9 [ He] 2s 2 2 p5 bonding electrons are high in case of fluorine which results
in weakening of F-F bond.
Chlorine Cl 17 [ Ne] 3s 2 3 p5 9. Density - It increases down the group in a regular fashion
and follows the order F > Cl > Br > I
Bromine Br 35 [ Ar ] 3d 10 , 4s 2 4 p 5
(i) Atomic radii (ii) Ionic radii
Iodine I 53 [ Kr ] 4d10 , 5s 2 5 p5 (iii) atomic volume (iv) density
(v) Electronegativity (vi) Oxidising power
Astatine At 85 [ Xe ] 4 f 14 , 3d10 , 6s 2 6 p5 (vii) Reactivity (viii) Affinity for hydrogen
(ix) Reduction potential
2. Physical State - Intermolecular forces in halogens are weak
(x) Solubility, all follow the above given order.
and increase down the group. Thus F2, Cl2 are gases, Br2
10. Ionisation potential - The ionisation potential of halogens
volatite liquid and I2 volatile solid.
is very high and value decreases down the group. Thus
3. Atomicity - All halogens are diatomic in nature. iodine also forms I+ and I3+ and forms compounds like ICl,
4. Abundance - Being very reactive in nature they are not ICN, IPO4. In molten state these compounds conduct
found free in nature. Their presence in earth’s crust follows electricity and show ionic character.
the order. 11. Electron affinity - The halogens have the high values for
F2 > Cl2 > Br2 > I2 > At electron affinity following the order.
5. Colour - They absorb light in the visible range forming excited Cl > F > Br > I
states and thus they are coloured in nature. Due to small size of fluorine (hence high electron density)
the extra electron to be added feels more electron - electron
F2 Cl2 Br2 I2
repulsion. Therefore fluorine has less value for electron
Pale yellow yellowish green reddish brown deep violet affinity than chlorine.
6. Metallic Character - All the elements are non metals and 12. Solubility - Halogens are soluble in water which follow the
metallic character increases down the group. order
JEEMAIN.GURU
downloaded from jeemain.guru
706 Chemistry
F2 > Cl2 > Br2 > I2 HF and HCl can be obtained by heating fluorides and
The solubility of iodine in water is enhanced in presence of chlorides with conc. H2SO4
KI CaF2 + H2SO4 ® CaSO4 + 2HF
2 NaCl + H2SO4 ® Na2SO4 + 2HCl
KI + I2 KI3 K+ + I3- HBr and HI are strong reducing agents in nature and reduce
In organic solvents like CS2, CHCl3 and CCl4 the Cl2, Br 2 conc. H2SO4 and cannot be prepared by this method.
and I2 are more soluble and give coloured solutions. Thus 2HBr (or 2HI) + H2SO4 ® Br2 (or I2) + 2H2O + SO2
Cl 2 gives yellow, Br 2 gives brown and I 2 gives violet Hence they are prepared by hydrolysis of phosphorous
solution. halides
13. Properties of halide ions (X-) - Some properties of halide PX3 + 3H2O ® H3PO3 + 3HX (X = Br, I)
ions follow the following order Properties - HF is a low boiling liquid due to intermolecular
F– > Cl– > Br– > I– hydrogen bonding, while HCl, HBr, HI are gases. The bpt follows
¬ Basic character the trend HF > HI > HBr > HCl
¬ Reducing character Some other properties observe the following trend :
¬ Heat of hydration HI > HBr > HCl > HF
14. Nature of bonds with other elements - Halogens with metals ¬ Acid Strength
of low ionisation potentials form ionic bonds. The ionic ¬ Reducing character
character follows the order ¬ Bond length
M - F > M - Cl > M - Br > M - I
Trend for following properties : HI < HBr < HCl < HF
The more the ionic character, the more is the mp and bp of
Thermal stability ®
halides .
Halogens with metals of high ionisation potentials Dipole moment ®
(transition metals) and non metals form covalent bond. Bond strength ®
Stability ®
COMPOUNDS OF HALOGENS :
Itching of glass : Glass contains silica which reacts with HF.
1. Hydracids (HX) - All halogens directly combine with
hydrogen to form HX known as hydracid. SiO 2 + 4HF ® SiF4 + 2H 2 O + 2HF ® H 2SiF6
H2 + X2 ® 2HX Hydro fluorosilicic acid
2. Oxy acids - All form oxy acids of the type HOX, HXO2, HXO3 and HXO4 as shown below
Name O. N. of X Fluorine Chlorine Bromine Iodine Salt’s name
Hypohalous acid, HXO +1 HOF HOCl HOBr HOI Hypohalite
Halous acid, HXO2 +3 - HClO2 - - Halite
Halic acid, HXO3 +5 - HClO3 HBrO3 HIO3 Halate
Perhalic acid, HXO4 +7 - HClO4 HBrO4 HIO4 Perhalate
Trend for following properties
HXO4 > HXO3 > HXO2 > HXO 2X – + XO3–
3 – OX
¬ Thermal stability Rate of disproportionation
¬ Acid strength
IO - > BrO - > ClO -
Oxidising nature ®
The conjugate bases obtained from above acids are The structure of HClO and HFO are
O O
XO – , XO2– , XO3– and XO4– . Their stability increases with
H F H Cl
the increase of oxygen atoms due to greater chances of 97° 103°
dispersal of negative charge. The more is the stability of Bleaching powder CaOCl2 is a mixed salt of HOCl and
conjugate base, the more is the acid character. HCl
(ii) Halic acids - HClO3 and HBrO3 exist in aqueous solution
XO4– > XO3– > XO2– > XO –
and HIO3 is a white solid. The stability follows the order
(i) Hypohalous acids (HOX) - They are formed in aqueous
HIO3 > HBrO3 > HClO3 ® Acid strength
solution by disproportionation of halogens
They are strong oxidising in nature
X2 + H2O HOX + HX
Acid character and thermal stability follows the order XO3– + 5X – + 6H + ® 3X 2 + 3H 2O
HClO > HBrO > HIO Their salts, NaClO3 is a powerful weed killer and KClO3
Hypohalites disproportionate in aqs. solution to halides (Berthelot’s salt) is used in fire works and matches as
and halates. oxidising agent.
JEEMAIN.GURU
downloaded from jeemain.guru
..
..
O Iodine Cation - Iodine also forms I+ and I3+ cations due to less
(c) Chloric acid (d) Perchloric acid ionisation energy as (CH3COO)3I, I (ClO4)3 and IPO4 have been
(HClO3) (HClO4) isolated.
H H Pseudohalogens and pseudohalides - The substances behaving
O O like halogens are known as pseudohalides.
Some examples are
Cl Cl Pseudo halogen Pseudohalide ion
..
X
X X X 2F – - 2e – ® F2 (At anode)
X
JEEMAIN.GURU
downloaded from jeemain.guru
708 Chemistry
(2) Whytlaw Gray’s method - Electrolysis of fused KHF2 is (7) With NH 3 - 2 NH 3 + 3F2 ® N 2 + 6HF and some NF3
carried out in Cu cell (electrically heated) which serves
( not explosive)
the purpose of cathode, Anode is of graphite
(3) Modern method - Electrolysis of fused mixture of KF (8) With H2S - H 2S + 4F2 ® SF6 + 2HF
and HF is carried out in steel vessel (cathode). Anode is (9) With hydrocarbons - It reacts with hydrocarbons
of graphite violently eg CH4
Properties - It is pale greenish yellow gas can be condensed to CH 4 + 4F2 ® 4HF + CF4
pale yellow liquid and then pale yellow solid. It is very reactive.
Hence fluorination is carried out in presence of N2 (it
(1) Most active - It directly combines with metals and non dilutes F2) and calalyst copper gauge.
metals eg Al, Mg, C, P, S, As, Sb, Br2, I2 etc to from
Uses
fluorides, Cu and Hg form a protective coating of
(1) Fluoro derivatives are solvents, lubricants, refrigerants,
fluoride.
fire extinguishers, fungicides, germicides, dyes and
(2) Reaction with Xe - With Xenon it forms three definite plastics etc.
halides
(2) For separation of U235 by forming UF6 from natural
XeF2, XeF4 and XeF6 having the following structure uranium
F (3) Preparation of Teflon (C2F4)n
FREONS :
:
: Xe
:
XeF2 hybridisation sp3d Chlorofluoro compounds of methane and ethane are known as
freons. They are extremely, unreactive, non corrosive, easily
F
liquefiable compounds. Freon-12 (CCl2F2) is most common and
Linear symmetrical prepared as
D
3CCl 4 + 2SbF3 ¾¾® 3CCl 2 F2 + 2SbCl 3
F F They are used as refrigerants and propellants .
Magic acid - FSO3H SbF5 is strongest acid and known as magic
XeF4 hybridisation sp3d2 Xe acid.
Chlorine :
F F It was discovered by Scheele by heating HCl acid (muriatic acid)
with MnO2 and named it oxymuriatic gas. Davy established its
nature and called it chlorine.
Square planar Occurrence - Being very reactive does not occur free in nature. It
is widely distributed as chlorides. Common salt NaCl is most
F important chloride present in sea water and as rock salt.
F F Preparation - By oxidation of Conc HCl
XeF6 sp3d3 hybridisation Xe MnO2 + 4HCl ® MnCl 2 + 2H 2 O + Cl 2
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
710 Chemistry
Properties - Bromine is a heavy dark brown liquid gives irritating Manufacture -
vapour. Density 3.2g/ml bpt 58.5ºC and fpt- 7ºC. It is soluble in (i) From sea weeds
water and gives bromine water about 3.6% at 20º C. D
Saturated solution of bromine on cooling gives bromine hydrate 2 NaI + MnO 2 + 3H 2SO 4 ¾¾®
Br2.8H2O.
Chemical properties - ® 2 NaHSO 4 + MnSO 4 + 2H 2 O + I 2
(i) Combination with hydrogen - (ii) From Caliche -
Pt at room temp . 2 NaIO3 + 5NaHSO 3 ®
H 2 + Br2 ¾¾¾ ¾¾¾® 2HBr
or at 200º C
® 2 Na 2SO 4 + 3NaHSO 4 + H 2O + I 2
(ii) Oxidising nature - Under ordinary conditions it does Exact amount of NaHSO3is to be added since it reacts
not react with water but in presence of an oxidisable with I2, if present in excess.
substance it gives HBr.
NaHSO 3 + I 2 + H 2O ® NaHSO 4 + 2HI
Br2 + H 2O ® 2HBr + O
Purification - It contains the impurities of Cl2, Br 2 and H2O.
Thus it oxidises SO2 to H2SO4
Cl2 and Br 2 are removed by distillation with KI.
SO 2 + H 2 + O ® H 2SO 4 2KI + Cl 2 ® 2KCl + I 2
Sodium sulphite to sulphate
2KI + Br2 ® 2KBr + I 2
Na 2SO 3 + O ® Na 2SO 4
Water is removed by distillation over concentrated H2SO4. Further
Thiosulphite to sulphate
it is purified by sublimation.
Na 2S2 O 3 + O ® Na 2SO 4 + S Properties - It is black (dark violet) shining solid with metallic
Arsenite to arsenate lustre. It sublimes on heating (mpt 114ºC). It is metallic in character
Na 3AsO3 + O ® Na 3AsO 4 and forms I+ and I3+ ions.
Hydrogen sulphide to sulphur Chemical properties -
(i) Solubility - It is slightly soluble in water but dissolves
H 2S + O ® H 2 O + S
in presence of KI
(iii)Reaction with alkali
KI + I2 KI3
(a) In cold 2NaOH + Br2 ® NaBr + NaBrO + H 2O
(ii) Combination with elements -
(b) In hot 6 NaOH + 3Br2 ® 5NaBr + NaBrO3 + 3H 2O Pt
H 2 + I 2 ¾¾® 2 HI
(iv) Displacement reaction - 2KI + Br2 ® 2KBr + I 2 D
JEEMAIN.GURU
downloaded from jeemain.guru
2+
_ _ Hydrogen halide Composition Boiling
solution contains Ca , C l and OC l ions. point ºC
Uses
H2F2 36% 120
(i) It is used as disinfectant and germicide
(ii) For the manufacture chloroform HCl 20.4% 110
(iii) For the sterlisation of drinking water HBr 47.0% 126
(iv) For making unshrinkable wool
HI 57.0% 127
(v) For bleaching cotton, wood pulp.
JEEMAIN.GURU
downloaded from jeemain.guru
712 Chemistry
JEEMAIN.GURU
downloaded from jeemain.guru
1. Among F, Cl, Br and I the lowest ionization potential will be 15. Hydrochloric acid at 25ºC is
of (a) ionic and liquid (b) covalent and liquid
(a) fluorine (b) chlorine (c) ionic and gas (d) None of these
(c) bromine (d) iodine 16. Which of the following is most volatile ?
2. The electron affinity of the halogens follows the order (a) HI (b) HBr
(a) F > Cl > Br > I (b) F < Cl < Br < I (c) HCl (d) HF
(c) F < Cl > Br > I (d) F < Cl < Br > I 17. Which of the following sets gives the correct arrangement of
3. The electronegativity follows the order the compounds involved based on their bond strengths ?
(a) F > O > Cl > Br (b) F > Cl > Br > O (a) HF > HCl > HBr > HI (b) HI > HBr > HCl > HF
(c) O > F > Cl > Br (d) Cl > F > O > Br (c) HF > HBr > HCl > HI (d) HCl > HF > HBr > HI
4. The bond energies of F2 , Cl2, Br2 and I2 are 155, 244, 193 and
18. At room temperature, HCl is a gas while HF is a low boiling
151 kJ mol–1 respectively. The weakest bond will be in
liquid. This is because
(a) Br2 (b) Cl2
(a) H- F bond is covalent (b) H- F bond is ionic
(c) F2 (d) I2
(c) HF has metallic bond (d) HF has hydrogen bond
5. The correct order of reactivity of halogens with alkalies is
(a) F > Cl > Br > I (b) F < Cl > Br < I 19. Which of the following has the highest bond strength?
(c) F < Cl < Br < I (d) F < Cl < Br > I (a) HI (b) HCl
6. The correct order of increasing oxidising power is (c) HF (d) HBr
(a) F2 > Br2 > Cl2 > I2 20. Which of the following is the strongest acid ?
(b) F2 < Cl2 < Br2 < I2 (a) HOCl (b) HOClO2
(c) Cl2> Br2 > F2 > I2 (c) HOClO3 (d) HOClO
(d) I2 < Br2 < Cl2 < F2 21. The geometry of ClO3- according to valence shell electron
7. Which of the following halogen does not exhibit positive
oxidation state in its compounds? pair repulsion (VSEPR) theory will be
(a) Cl (b) Br (a) planar triangle (b) pyramidal
(c) I (d) F (c) tetrahedral (d) square planar
8. The halogen that is most easily reduced is 22. Oxidation state of chlorine in hypochlorous acid is
(a) F2 (b) Cl2 (a) + 1 (b) + 2
(c) Br2 (d) I2 (c) – 1 (d) – 2
9. The bond energies of F2 , Cl2, Br2 and I2 are 37, 58, 46 and 36 23. The correct decreasing order of acidic character is
kcal mol–1 respectively. The strongest bond is present in (a) HClO > HBrO > HIO (b) HIO > HBrO > HClO
(a) Br2 (b) I2 (c) HBrO > HIO > HClO (d) HClO > HIO > HBrO
(c) Cl2 (d) F2 24. The element which never acts as reducing agent in a
10. Which one of the following order is correct for the bond chemical reaction is
energies of halogen molecules ? (a) O (b) Li
(a) I2 > Cl2 > Br2 (b) Br2 > Cl2 > I2 (c) F (d) C
(c) I2 > Br2 > Cl2 (d) Cl2 > Br2 > I2 25. Unlike other halogens, fluorine does not show higher
11. Which one of the following elements shows different oxidation states because
oxidation states ? (a) it is highly electronegative
(a) Sodium (b) Fluorine (b) it has no d- orbitals
(c) Chlorine (d) Potassium
(c) its atomic radius is very small
12. Which of the following halogens exhibit only one oxidation
(d) the F– ion is stable and isoelectronic with neon
state in its compounds ?
26. An element M has an atomic mass 19 and atomic number 9.
(a) Bromine (b) Chlorine
Its ion is represented by
(c) Fluorine (d) Iodine
13. Which has the highest bond energy ? (a) M+ (b) M2 +
(c) M – (d) M2 –
(a) F2 (b) Cl2
(c) Br2 (d) I2 27. Which one of the following halogen liberates oxygen when
14. Which is the weakest out of HF, HCl, HBr and HI? passed through hot concentrated KOH solution ?
(a) HF (b) HCl (a) I2 (b) Cl2
(c) HBr (d) HI (c) Br2 (d) F2
JEEMAIN.GURU
downloaded from jeemain.guru
714 Chemistry
28. One mole of fluorine is reacted with two moles of hot and 40. The reaction of KMnO4 and HCl results in
concentrated KOH. The products formed are KF, H2O and (a) oxidation of Mn in KMnO4 and production of Cl2
O2. The molar ratio of KF, H2O and O2 respectively is (b) reduction of Mn in KMnO4 and production of H2
(a) 1 : 1 : 2 (b) 2 : 1 : 0.5 (c) oxidation of Mn in KMnO4 and production of H2
(c) 1 : 2 : 1 (d) 2 : 1 : 2 (d) reduction of Mn in KMnO4 and production of Cl2
41. Chlorine acts as a bleaching agent only in
29. Fluorine oxidizes HSO -4 to (a) dry air (b) sunlight
(c) moisture (d) oxygen
(a) S2 O32 - (b) S2 O82 -
42. In the reaction
(c) S4 O 26 - (d) SO 2 - -
3Br2 + 6CO 32 - + 3H 2 O ¾
¾® 5Br + BrO 3 + 6HCO 3
30. Chlorine cannot displace (a) bromine is oxidised and carbonate is reduced
(a) Fluorine from NaF (b) bromine is both oxidised and reduced
(b) Iodine from NaI (c) bromine is reduced and water is oxidised
(c) Bromine from NaBr (d) bromine is neither oxidised nor reduced
(d) None of these 43. The solubility of I2 increases in water in presence of
31. Cl2 gas is dried over (a) KI (b) H2SO4
(a) CaO (b) NaOH (c) KMnO4 (d) H2S
(c) KOH (d) conc. H2SO4 44. Oxidation of thiosulphate with iodine gives
32. The outer electronic structure of 3s2 3p5 is possessed by (a) sulphate ion (b) sulphite ion
(a) O (b) Cl (c) tetrathionate ion (d) sulphide ion
(c) Br (d) Ar 45. Which of the following cann ot work as oxidizing
agent ?
33. Chlorine acts as a bleaching agent only in the presence of
(a) O2 (b) KMnO4
(a) dry air (b) moisture
(c) H2O2 (d) I–
(c) sunlight (d) None of these 46. On boiling an aqueous solution of KClO3 with I2 the products
34. When chlorine reacts with cold and dilute solution of sodium obtained are
hydroxide, the products obtained are (a) KIO3+Cl2 (b) KCl+I2O5
(a) Cl– + ClO– (b) Cl– + ClO -2 (c) KIO4+Cl2 (d) No reaction takes place
47. When KI and CuSO4 solutions are mixed, it gives
(c) Cl– + ClO3- (d) Cl– + ClO -4 (a) K2SO4 + I2 (b) Cu2I2 + K2SO4
(c) CuI2 + K2SO4 (d) Na2SO4 + I2
35. In the reaction
48. When I2 is passed through KCl, KF and KBr solutions
2Br + X2 ® Br2 ,2X- ,X2 is (a) Cl2 and Br 2 are evolved
(a) Cl2 (b) Br2 (b) Cl2 is evolved
(c) I2 (d) N2 (c) Cl2, Br 2 and F2 are evolved
36. Chlorine is liberated when we heat (d) None of these
(a) KMnO4 + NaCl (b) K2Cr2O7 + MnO2 49. Sea weeds are an important source of
(c) Pb(NO3)2 + MnO2 (d) K2Cr2O7 + HCl (a) iodine (b) bromine
37. Which of the following is correct about the reaction? (c) chlorine (d) Both (a) and (b)
50. Which of the following elements exhibits the most basic
heat
3NaClO ¾¾¾ ® NaClO3 + 2NaCl properties ?
(a) It is disproportionation reaction (a) F (b) Cl
(b) Oxidation number of Cl decreases as well as increases in (c) Br (d) I
this reaction 51. Which of the following is used as an antiseptic?
(c) This reaction is used for the manufacture of halates (a) I (b) Br
(d) All of these (c) Cl (d) F
52. In the presence of cobalt chloride (CoCl2), bleaching powder
38. Which of the following is used in the preparation of chlorine ?
decomposes to form
(a) Only MnO2 (b) Only KMnO4
(a) CaCO3 and O3 (b) ClO2 and CaO
(c) Both MnO2 and KMnO4 (d) Either MnO2 or KMnO4 (c) Cl2O and CaO (d) CaCl2 and O2
39. A greenish yellow gas reacts with an alkali metal hydroxide 53. In the reaction
to form a halate which can be used in fire works safety
matches. The gas and halate respectively are ® H 2+ NO 3 + F - base is
HNO 3 + HF ¾¾
(a) Br2 KBrO3 (b) Cl2, KClO3 (a) HF (b) HNO3
(c) I2, NaIO3 (d) Cl2, NaClO3 (c) HF and HNO3 (d) None of these
JEEMAIN.GURU
downloaded from jeemain.guru
1. Which among the following is paramagnetic ? 7. Which is the best description of the behaviour of bromine in
(a) Cl 2 O (b) ClO2 [CBSE-PMT 1994] the reaction given below ? [ CBSE-PMT2004]
(c) Cl 2O 7 (d) Cl 2O 6 H 2 O + Br2 ® HOBr + HBr
2. Which one of the following oxides of chlorine is obtained by (a) Proton acceptor only
passing dry chlorine over silver chlorate at 90°C ? (b) Both oxidized and reduced
[CBSE-PMT 1994] (c) Oxidized only
(d) Reduced only
(a) Cl2 O (b) ClO3
8. Which one of the following orders correctly represents the
(c) ClO2 (d) ClO4 increasing acid strengths of the given acids?
3. The formula for calcium chlorite is [CBSE-PMT 1994] [CBSE-PMT 2007]
(a) Ca(ClO )
4 2 (b) Ca(ClO )
3 2
(a) HOClO < HOCl < HOClO3 < HOClO2
(b) HOClO2 < HOClO3 < HOClO < HOCl
(c) CaClO 2 (d) Ca(ClO 2 ) 2
(c) HOClO3 < HOClO2 < HOClO < HOCl
4. Regarding F– and Cl– which of the following statements is/
(d) HOCl < HOClO < HOClO2 < HOClO3
are correct? [ CBSE-PMT1996]
(i) Cl– can give up an electron more easily than F– 9. Which one of the following arrangements does not give the
(ii) Cl– is a better reducing agent than F– correct picture of the trends indicated against it ?
(iii) Cl– is smaller in size than F– [CBSE-PMT 2008]
(iv) F– can be oxidized more readily than Cl– (a) F2 > Cl2 > Br2 > I2 : Oxidizing power
(a) (i) and (ii) (b) (i), (ii) and (iv) (b) F2 > Cl2 > Br2 > I2 : Electron gain enthalpy
(c) (iii) and (iv) (d) only (i) (c) F2 > Cl2 > Br2 > I2 : Bond dissociation energy
5. Which one is the correct order of the size of iodine species? (d) F2 > Cl2 > Br2 > I2 : Electronegativity.
[CBSE-PMT 1997] 10. In the case of alkali metals, the covalent character decreases
(a) I > I+ > I– (b) I > I– > I+ in the order: [CBSE-PMT 2009]
(c) I+ > I– > I (d) I– > I > I+
(a) MF > MCl > MBr > MI
6. Which of the following statements is not true ?
[CBSE-PMT 2003] (b) MF > MCl > MI > MBr
(a) HF is a stronger acid than HCl (c) MI > MBr > MCl > MF
(b) Among halide ions, iodide is the most powerful reducing (d) MCl > MI > MBr > MF
agent 11. Among the following which is the strongest oxidising agent?
(c) Fluorine is the only halogen that does not show a variable [CBSE-PMT 2009]
oxidation state (a) Br2 (b) I2
(d) HOCl is a stronger acid than HOBr (c) Cl2 (d) F2
JEEMAIN.GURU
downloaded from jeemain.guru
716 Chemistry
12. The correct order of increasing bond angles in the following 16. Which among the following factors is the most important in
species are : [CBSE-PMT 2010] making fluorine the strongest oxidizing halogen ?
(a) Hydration enthalpy [AIEEE 2004]
(a) Cl 2 O < ClO 2 < ClO 2– (b) ClO2 < Cl 2O < ClO 2–
(b) Ionization enthalpy
(c) Cl 2O < ClO 2– < ClO2 (d) ClO 2– < Cl2 O < ClO2 (c) Electron affinity
13. Which is the strongest acid in the following : [NEET 2013] (d) Bond dissociation energy
(a) HClO3 (b) HClO4 17. Among the properties (a) reducing (b) oxidising (c)
(c) H2SO3 (d) H2SO4 complexing, the set of properties shown by CN– ion towards
14. Which of the following is a polar molecule ? [NEET 2013] metal species is [AIEEE 2004]
(a) SF4 (b) SiF4 (a) c, a (b) b, c
(c) XeF4 (d) BF3 (c) a, b (d) a, b, c
15. Concentrated hydrochloric acid when kept in open air 18. The correct order of the thermal stability of hydrogen halides
sometimes produces a cloud of white fumes. The explanation (H–X) is [AIEEE 2005]
for it is that [AIEEE 2003] (a) HI > HCl < HF > HBr
(a) oxygen in air reacts with the emitted HCl gas to form a (b) HCl< HF > HBr < HI
cloud of chlorine gas (c) HF > HCl < HBr > HI
(b) strong affinity of HCl gas for moisture in air results in (d) HI < HBr > HCl < HF
forming of droplets of liquid solution which appears like a 19. Identify the incorrect statement among the following.
cloudy smoke. [AIEEE 2007]
(c) due to strong affinity for water, concentrated (a) Br2 reacts with hot and strong NaOH solution to give
hydrochloric acid pulls moisture of air towards itself. NaBr and H2O.
This moisture forms droplets of water and hence the
(b) Ozone reacts with SO2 to give SO3.
cloud.
(c) Silicon reacts with NaOH(aq) in the presence of air to
(d) concentrated hydrochloric acid emits strongly smelling
give Na2SiO3 and H2O.
HCl gas all the time.
(d) Cl2 reacts with excess of NH3 to give N2 and HCl.
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
718 Chemistry
:
:
:
2. This is because A – X bond in interhalogens in weaker than
:
the X – X bond in halogens. 22. (a) In HClO the O.S of Cl is + ve (+1)
3. CaOCl2 + H2SO4 ¾¾ ® CaSO4 + H2O + Cl2. 23. (a) Since the electronegativity of halogens follow the order
4. It is most electronegative and is smallest in its atomic size, Cl > Br > I the strength of acids follow the order HClO >
and has relatively less bond energy. HBr > HIO
5. HF reacts with silica (SiO2) present in glass and forms water 24. (c) Fluorine has highest reduction potential hence it is
soluble acid. strongest oxidising agent in nature
SiO2 + 4HF ¾¾ ® SiF + 2H O
4 2
25. (b) Due to absence of d atomic orbitals the fluorine does
not exhibit higher O.S.
SiF4 + 2HF ¾¾
® H SiF
2 4 26. (c) The element is F and ion is represented by M–
(Water soluble)
27. (d) F2 reacts with KOH to give O2 and O3 (see text)
6. F being the most electronegative element does not show
28. (b) 2F2 + 4KOH ® 4KF + O 2 + 2H 2 O for 1 mole of F2 the molar
positive oxidation states.
7. (i) Cl – Cl > Br – Br > F – F > I – I ratio.
(ii) HI > HBr > HCl > HF F2 KOH KF O2 H2O
(iii) M – F > M– Cl > M – Br > M – I 1
(iv) BrO4– > ClO4– > IO4– 1 2 2 1
2
15. (a) 16. (a) 17. (d) 18. (b) 19. (c) 20. (c)
21. (d) 22. (b) 23. (d) 24. (d) 25. (a) 26. (c) 29. (b) HSO -4 - e ® HSO 4 ® H 2S 2 O8 ® S2 O8 2 -
27. (b) 30. (a) Chlorine cannot displace F from NaF. The reactivity
EXERCISE 2 follows the order F > Cl > Br > I
31. (d) Cl2 will react with CaO, NaOH and KOH (See text). It will
1. (d) Ionisation potential decreases down the group. not react with conc. H2SO4 hence can be dried over it.
2. (c) Since fluorine has small size the electron affinity of Cl is 32. (b) 3s2 3p5 is electronic configuration of Cl
more than F 33. (b) In presence of moisture only, chlorine will give O;
3. (a) Follow text
Cl 2 + H 2O ® HCl + HOCl
4. (d) The lesser the bond energy, the weaker is the bond
5. (a) (See text) Reactivity follows the order F > Cl > Br > I 34. (a) 2NaOH + Cl2 ® NaCl + NaOCl + H 2 O
6. (d) See text
7. (d) Fluorine exhibit -ve oxidation state hence Cl- and OCl-
8. (a) Since F2 is most oxidising, it is easily reduced _ _
35. (a) 2Br + Cl 2 ® Br2 + 2Cl Chlorine is more oxidising is
9. (c) The more the bond energy the stronger is the bond
10. (d) See text nature
11. (c) Chlorine shows O.S. from –1,+1 to +7, whereas others 36. (d) K 2 Cr2 O 7 + Conc HCl ® Cl 2 See text
show O.S. as Na® +1 ; K® +1 ; F® –1
+1 +5 -1
12. (c) Fluorine always –1 37. (d) NaClO ® NaClO3 + 2NaCl All statements are correct
13. (b) See text
as evident from the reaction
14. (a) HF, due to intermolecular H-bonding is weakest among
38. (d) MnO2 or KMnO4 with conc HCl give Cl2 (see text)
HX acids
15. (d) HCl acid at 25º C is a gas and polar in nature 39. (b) 3Cl 2 + 6KOH ® KClO3 + 5KCl + 3H 2O
16. (c) Volatile character HCl > HBr >HI > HF KClO3 is used in fire works and safety matches and Cl2
17. (a) See text is greenish yellow gas
18. (d) Due to hydrogen bonding HF is a liquid +7 +2
19. (c) Follow text 40. (d) 2 KMnO 4 + 16HCl ® 2 MnCl 2 + 2KCl + 8H 2 O + 5Cl 2
20. (c) Oxy acids having higher + O.S for halogen are
O.S of Mn changes from +7 to +2 hence reduction occurs
more stronger in nature . Hence the order
and Cl2 is formed.
HClO4 > HClO3 > HClO2 > HClO
JEEMAIN.GURU
downloaded from jeemain.guru
50. (d) Basic character increases down the group In case of oxyacids of similar element as the oxidation
number of the central atom increases, strength of acid
51. (a) Iodine is used as an antiseptic
also increases.
52. (d) 2CaOCl 2 ¾CoCl
¾¾ ¾ 2 ® 2CaCl + O (see text )
2 2 9. (b, c) From the given options we find option (a) is correct.
The oxidising power of halogens follow the order
+
F2 > Cl2 > Br2 > I2. Option (b) is incorrect because it in
53. (b) In HNO3 + HF ® H 2 NO3 + F- HNO3 accepts H+ hence
not the correct order of electron gain enthalpy of
it is a base halogens.
54. (a) NaClO is a salt of strong base and weak acid hence on The correct order is Cl2 > F2 > Br 2 > I2. The low value of
hydrolysis the solution will be most basic, therefore F2 than Cl2 is due to its small size.
maximum pH. Option (c) is incorrect. The correct order of bond
55. (d) Interhalogen compounds are not highly volatile dissociation energies of halogens is
56. (c) I – F is most polar. The more the electronegativity Cl2 > Br2 > F2 > I2.
difference, the more is polar character of bond Option (d) is correct. It is the correct order of
57. (b) 2KClO3 ® 2KCl + 3O 2 electronegativity values of halogens. Thus option (b)
and (c) are incorrect.
1
58. (a) ICl7. The hybridisation is (7 + 7 + 0 - 0) = 7 (sp3d3 ) 10. (c) MI > MBr > MCl > MF. As the size of the anion decreases
2 covalent character also decreases.
59. (a) When atomic orbitals present in the same principle energy 11. (d) Since all the halogens have a strong tendency to accept
level overlap, a strong bond is formed. In case of F and electrons. Therefore halogens act as strong oxidising
B, atomic orbitals are from second principle energy levels. agents and their oxidising power decreases from fluorine
60. (a) Fluorosis is caused due to reaction of Ca with excess of to iodine.
fluoride in the body 12. (c) The correct order of increasing bond angle is
61. (c) The strength of H- bonding follows the order Cl2 O < ClO 2- < ClO 2
F>O>N
Cl2O2 ClO2 2
ClO2 2
EXERCISE 3 ..
O . Cl . .
..
..
Cl
1. (b) ClO2 contains 7 + 12 i.e. 19 electrons (valence) which is
an odd number, i.e. there is (are) free electron(s). Hence it . . 110° . . . . 118°
Cl Cl .O. O O O
..
..
..
..
..
..
..
..
.. ..
..
is paramagnetic in nature.
..
–
* In ClO2 there are 2 lone pairs of electrons present on
2. (c) Pure ClO2 is obtained by passing dry Cl2 over AgClO3 at
90°C. the central chlorine atom. Therefore the bond angle in
90°C ClO2– is less than 118° which is the bond angle in ClO2
2AgClO 3 + Cl 2 (dry ) ¾¾¾® 2AgCl + 2ClO 2 + O 2
which has less number of electrons on central chlorine
3. (d) Calcium chlorite is Ca (ClO2 ) 2 atom.
JEEMAIN.GURU
downloaded from jeemain.guru
720 Chemistry
13. (b) HClO4 is the strongest acid amongst all because the
11. (b) 6CaOCl 2 ® Ca (ClO3 ) 2 + 5CaCl 2
oxidation state or Cl is maximum (+7).
14. (a) SF4 has 4 bond pairs and 1 lone pair of electrons, sp3d (disproportionation or auto oxidation)
12. (d) All the factors are responsible for the greater reactivity
F of F2
| F
hybridisation leads to irregular shape S and
| 13. (c) SO 2 + Cl 2 ® SO 2 Cl 2
F Sulphuryl chloride
F
resultant m ¹ 0. 14. (b) NaF + HF ® NaHF2
15. (a) 4HCl + O 2 ® 2Cl 2 + 2H 2 O 15. (d) The reactivity of halogens follows the order
cloud of white fumes F2 > Cl 2 > Br2 > I 2 Hence I2 cannot replace Br 2 from
16. (d) The fluorine has low dissociation energy of F - F bond KBr.
and reaction of atomic fluorine is exothermic in nature
16. (a) In ClO -4 the Cl is present in its highest O.S of +7 hence
17. (a) CN - ion acts good complexing as well as reducing it can undergo reduction and not oxidation
agent.
17. (a) KF + HF ® KHF2
18. (c) The H–X bond strength decreases from HF to HI. i.e.
HF > HCl > HBr > HI. Thus HF is most stable while HI is 18. (b) 2KI + Cl 2 ® 2KCl + I 2
least stable. This is evident from their decomposition
I 2 + CCl 4 ® Violet Colour
reactions. The decreasing stability of the hydrogen halide
is also reflected in the values of dissociation energy of Note: The excess of Cl2 should be avoided. The layer
the H–X bond may become colourless due to conversion of I 2 to HIO 3
9. (c) 2KClO3 + 4HCl ® 2KCl + Cl 2 + 2ClO 2 + 2H 2O 27. (b) Except ionisation potential other factors are true to explain
The mixture of (Cl 2 + ClO 2 ) is known as ‘euchlorine”. the oxidising (strong) behaviour of F2 .
10 (b) 2CaO + 2Cl 2 ® CaCl 2 + Ca (ClO) 2 28. (b) 2KMnO 4 + 16HCl ® 2KCl + 2MnCl 2 + 8H 2 O + 5Cl 2
JEEMAIN.GURU
downloaded from jeemain.guru
21D
The p-Block Elements-
Noble Gases
INTRODUCTION : 6. Melting and boiling points- Due to the increase in magnitude
The group 18 of the periodic table consists of colourless, odourless of Van der waals forces, the mpt and bpt increases from He
gases at room temperature, isolated by William Ramsay and lord to Rn.
Rayleigh in 1898 from air. They realized that a sample of nitrogen 7. Atomic radii- The atomic radii increases from He to Rn and
formed synthetically had a different density than obtained from air it corresponds to the vander waals radii.
after removing oxygen, water vapour and carbon dioxide. The 8. Critical temperature/critical pressure- The critical
sample from air was heavier and it was found to contain 1.0% temperature (Tc) and Critical pressure (Pc) of noble gases
mixture of inert gases by volume (except Rn). Radon was obtained increase down the group
by radioactive disintegration of radium.
Element He Ne Ar Kr Ye Rn
Helium is second most abundant element in the universe.
Argon is the most abundant of all the inert gases in the Tc(K) 5.1 44.3 150.6 211.0 256.4 373.5
atmosphere. Pc(Atm) 2.26 26.86 47.99 54.3 58.2 62.4
GENERAL CHARACTERISTICS : 9. Density- The density of noble gases increases down the
1. Electronic configuration : group.
Element Sym bol At No. Valence shell electronic confg. 10. Heat of vaporisation - They have very low values of heat of
vaporisation due to weak van der waals forces of attraction.
Helium He 2 1s 2
The value increases down the group.
Neon Ne 10 [He] 2s 22p 6
11. Solubility in water- They are slightly soluble in water and
Argon Ar 18 [Ne] 3s 23p 6
solubility increases from He te Rn.
Kr yp to n Kr 36 [Ar] 3d104s 24p 6
12. Liquefication - It is extremely difficult to liquefy inert gases
Xenon Xe 54 [Kr] 4d10, 5s 25p 6 due to weak van der waals forces of attraction among their
Radon Rn 86 [Xe] 4f14, 3d10, 6s26p 6 molecules. Hence they possess low value of critical
temperature also.
2. Physical state - They are all gases under ordinary conditions
of temperature and pressure. 13. Ionisation energy- All noble gases possess very stable (ns2
3. Presence - Except Radon all occur in atmosphere in dry air and ns2p6) electronic configuration. Therefore, ionisation
10% by volume. Main commercial source of helium is natural energy of noble gases is very high and decreases down the
gas . group.
4. Abundance- In 1.0% air the abundance follows the order 14. Electron affinity- Due to the presence of stable electronic
configuration they have no tendency to accept additional
Ar> Ne>He>Kr> Xe
electron. Therefore electron affinity is almost zero.
5. Atomicity- The Cp/Cv =1.67 shows their monoatomic nature.
JEEMAIN.GURU
downloaded from jeemain.guru
722 Chemistry
15. Polarizability- The polarizability increases with the size and SEPARATION OF RARE GASES BY DEWAR’S
hence follows the order. METHOD:
He< Ne< Ar< Kr< Xe It is as follows
16. Adsorption by charcoal- Except helium all are adsorbed by [He, Ne, Ar, Kr, and Xe] + Coconut charcoal at 171K
coconut charcoal at low temperature. The extent of
adsorption increases down the group.
DISCOVERY : He, Ne unadsorbed Ar, Kr, Xe Absorbed
+ charcoal at 93K +Coconut charcoal
(i) Argon- It was isolated by Rayleigh and confirmed by at liquid air temperature
Ramsay, from air (free from O2, moisture and CO2). Due to its
Ne He Ar Kr, Xe
inertness the gas was named as argon (meaning lazy). diffused Remain in first
Adsorbed unadsorbled
(ii) Helium- It was observed in the spectrum of the sun hence in another Charcoal
Charcoal Temperature
name helium, from helios, which means sun, by Lockyer raised to 183K
and Frankland. Ramsay obtained it from gases occluded in
Kr Xe
uranium minerals. evolved remains
adsorbed
(iii) Neon, Krypton and Xenon- These were obtained by
fractional distillation of liquid air under reduced pressure.
These were named as neon means “new” krypton means From liquid air - The difference in the boiling points of
“hidden” and Xenon means “stranger or foreigner”. various constituents of liquid air make possible their
separation by fractional distillation.
(iv) Radon- Spectroscopically was noticed by Dorn and isolated
by disintegration of radium by Rutherford and Soddy. Element He Ne N2 Ar O2 Kr Xe
B.pt (K) 4 27 77 87 90 121 124
Ra 226 ¾
¾® Rn 222 + He 4
88 86 2 HELIUM FROM OTHER SOURCES:
ISOLATION OF RARE GASES : He is also obtained by heating mineral clavite to 1273K . The gas
The following methods are employed for the isolation of Rare evolved is collected over potash solution to free from any CO2.
gas mixture. It may also be obtained from mineral by heating with dil.H2SO4
or KHSO4.
(i) Ramsay and Rayleigh’s first method-
Properties- The noble gases are inert in nature because of their
Air (dry and free from CO2)
completely filled s and p subshells. In 1962 the first compound of
D D noble gases was prepared. It is hexa fluoroplatinate prepared by
¾¾® 2Cu + O 2 ¾
¾® CuO ¾¾®
Cu Mg Bartlett.
Residual gas - mixture of inert gases. Now many compounds of Xe and Kr are known with fluorine and
(ii) Ramsay and Rayleigh’s second method oxygen.
No compounds of He, Ne or Ar exist, except under very special
discharge NaOH conditions (very unstable, not neutral compounds)
Air + O 2 ¾¾¾¾® N 2 + O 2 ® 2NO ¾¾¾® 2NO 2
6000 -8000V Rn is known to react with fluorine but its radio activity makes the
2NO + O 2 ® 2NO 2 study of its compounds difficult and dangerous. Kr forms one
(CO2 and NO2 are absorbed by NaOH and O2 if any is stable neutral molecule, KrF2. A, Kr- N bond has also been
removed by alkaline pyrogallol) reported, stable only below –50º C.
(iii) Fischer and Ringe’s method- Xe forms several compounds with fluorine and oxygen and Xe-N
and Xe-C bonds have been reported.
90%CaC2 D
R Air 10%CaCl ¾¾® CaC2 + N 2 ® [CaCN 2 + C ] 673K
Xe + F2 ¾¾¾® XeF2 673K
Xe + 2F2 ¾¾¾® XeF4
2 373K Nitrolium (C is graphite)
5- 6Atm
2 :1
C + O 2 ® CO 2 1: 5
JEEMAIN.GURU
downloaded from jeemain.guru
..
XeF2 hybridization sp3d Xe Linear
..
oxygen dilutant) for divers. Mixture of O2 and He is used in
the treatment of asthma. It is also used for inflating the tyres
..
F of aeroplanes.
.. (2) Neon - When an electric current is passed through a sample
F F
of the gas, it has a characteristic orange - red glow. Neon
XeF4 hybridization sp3d2 Xe square planar lighting is used for advertising. The noble gases argon
F .. F (purple), Xenon (blue green) and Krypton (pale violet) are
also used in “neon” lighting.
F
F .. F (3) Argon - It is used primarily to create an inert atmosphere in
XeF6 Hybribisation sp3d3 Xe light bulbs, welding and fluorescent bulbs. It is also used in
geiger counters, as it becomes ionised in the presence of
F F radiation. The ratio of 40K to 40Ar can be used to date the
F
Pentagonal pyramidal or distorted octahedral age of rocks since argon is obtained by radioactive decay
XeO3 is the anhydride of Xenic acid H2XeO4 - The structures of of an isotope of potassium.
oxyfluorides and oxides of Xenon are as follows. (4) Krypton - The light emitted by Krypton in an electric
O discharge tube is used for runway and approach lights in
..
F F airports.
Xe Xe (5) Xenon - It is used in electrical flash bulbs for high speed
.. O O photography.
F F
O (6) Radon - In radiotherapy of cancer.
XeOF4 XeO3
CLATHRATES :
Square pyramidal trigonal pyramidal
A number of organic and inorganic compounds having noble
(sp3d2) (sp3)
gases trapped into the cavities of crystal lattices are called
enclosure or clathrate compounds. They are known as cage
F
compounds also.
Xe = O The substance having cavities in crystal lattices is called the
host and atom of noble gases entraped in it is called the guest
F which are held by Van der waals forces of attraction. The clathrates
XeOF2 are non stoichiometric compounds. When clathrates are heated
T – shaped or dissolved the guest atom escapes from the host.
(sp3d)
He and Ne do not form clathrates due to their small size.
F Types of Clathrates - They are of two types.
(i) Gas hydrates - Solid water having entraped Ar, Kr, or Xe
Xe Xe
(ii) Quinol Clathrates - Quinol having entraped Ar, Kr, and Xe
F
Uses of Clathrates
XeO2F2 XeO4
See-Saw (i) Separation of noble gases - Since Ne does not form a
Tetrahedral
(sp3d) clathrate with Quinol it is separated from Ar, Kr and Xe. The
(sp3)
latter form a clathrate with quinol.
(ii) Xe- 133 clathrate is a source of g- radiations
F F
Xe F (iii) Kr - 85 clathrate is a source of b - radiations
F F (iv) As an anaesthetic - Xe clathrate is used for this
– (v) For transporting isotopes of noble gases.
XeF5
Pentagonal planar
3 3
(sp d )
JEEMAIN.GURU
downloaded from jeemain.guru
724 Chemistry
Very Short/Short Answer Questions 14. In XeF2, XeF4, XeF6 the number of lone pairs on Xe are
1. Why do noble gases form compounds with fluorine and respectively
oxygen only? (a) 2, 3, 1 (b) 1, 2, 3 (c) 4, 1, 2 (d) 3, 2, 1.
2. Which compound led to the discovery of noble gas 15. Total number of lone pair of electrons in XeOF4 is
compounds. (a) 0 (b) 1 (c) 2 (d) 3
3. Among the noble gases, Xe forms maximum noble gas 16. Which of the following is least polarisable ?
compounds with fluorine. Why is it so? (a) Ne (b) He (c) Xe (d) Kr
4. Why do boiling points of noble gases increases from helium 17. End-product of the hydrolysis of XeF6 is
to radon? (a) XeF4O (b) XeF2O2 (c) XeO3 (d) XeO3 –
5. Neon is generally used for warning signals. Why? 18. For advertisement, the coloured discharge tubes contain :
6. Give equations for the following : (a) He (b) Ne (c) Ar (d) Kr
(i) XeF2 + H2O ¾¾ ® 19. Which one of the following noble gases is not found in the
(ii) XeF6 + H2O ¾¾ ® atmosphere?
(iii) XeF6 + PF5 ¾¾ ® (a) Rn (b) Kr (c) Ne (d) Ar
(iv) XeF6 + NaF ¾¾ ® 20. Noble gases are group of elements which exhibit
7. How is XeO3 prepared? Write chemical equation. (a) high chemical activity
8. Solubility of noble gases in water increases as we more down (b) low chemical activity
the group. Explain. (c) minimum electronegativity
9. Why noble gases have low boiling point? (d) paramagnetic properties
10. Xenon does not form fluorides, such as XeF3 and XeF5. 21. Which one of the following statements regarding helium is
Why? incorrect ?
(a) It is used to produce an d sustain powerful
Multiple Choice Questions
superconducting magnets.
11. Which of the following fluorides of xenon is impossible?
(b) It is used as a cryogenic agent for carrying out experiments
(a) XeF2 (b) XeF3 (c) XeF4 (d) XeF6
at low temperatures.
12. The structure of XeF6 is (c) It is used to fill gas balloons instead of hydrogen because
(a) distorted octahedral (b) pyramidal it is lighter and non-inflammable.
(c) tetrahedral (d) None of these (d) It is used in gas-cooled nuclear reactors.
13. Which of the following statements is false ? 22. Which inert gas show abnormal behaviour on liquefaction
(a) Radon is obtained from the decay of radium (a) Xe (b) He (c) Ar (d) Kr
(b) Helium is inert gas 23. The ease of liquefaction of noble gases increases in the order
(c) Xenon is the most reactive among the rare gases (a) He < Ne < Ar < Kr < Xe (b) Xe < Kr < Ne < Ar < He
(d) The most abundant rare gas found in the atmosphere is (c) Kr < Xe < He < Ne < Ar (d) Ar < Kr < Xe < Ne < He
helium
1. The last member of the family of inert gases is (a) Neon (b) Radon
(a) argon (b) radon (c) Argon (d) Helium
(c) xenon (d) neon 4. Number of unpaired electrons in inert gas is
2. Which of the following is the correct sequence of the noble (a) zero (b) 8
gases in their group in the periodic table? (c) 4 (d) 18
(a) Ar, He, Kr, Ne, Rn, Xe (b) He, Ar, Ne, Kr, Xe, Rn 5. In the following four elements, the ionisation potential of
(c) He, Ne, Kr, Ar, Xe, Rn (d) He, Ne, Ar, Kr, Xe, Rn which one is the highest ?
3. Which of the following noble gases do not have an octet of (a) Oxygen (b) Argon
electrons in its outermost shell? (c) Barium (d) Cesium
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
726 Chemistry
35. Sea divers go deep in the sea water with a mixture of which 37. In the clathrates of xenon with water, the nature of bonding
of the following gases between xenon and water molecule is
(a) O2 and He (b) O2 and Ar (a) covalent
(c) O2 and CO2 (d) CO2 and Ar (b) hydrogen bonding
36. Which of the following is the life saving mixture for an (c) co-ordinate
asthmas patient ? (d) dipole-induced dipole interaction
(a) Mixture of helium and oxygen 38. Which of the following cannot be formed ?
(b) Mixture of neon and oxygen (a) He2+ (b) He+
(c) Mixture of xenon and nitrogen (c) He (d) He2
(d) Mixture of argon and oxygen
1. Noble gases do not react with other elements because (c) It is used to fill gas balloons instead of hydrogen because
(a) they are mono atomic [CBSE PMT 1994] it is lighter and non-inflammable
(b) they are found in abundance (d) It is used in gas-cooled nuclear reactors
(c) the size of their atoms is very small 5. Which one of the following reactions of xenon compounds
(d) they are completely paired up and stable electron shells is not feasible? [AIEEE 2009]
2. Which of the following statements is false ? (a) 3XeF4 + 6H 2 O ¾¾ ® 2Xe + XeO 3 +12HF +1.5O 2
[CBSE PMT 1994] (b) 2XeF2 + 2H 2 O ¾¾ ® 2Xe + 4HF + O 2
(a) Radon is obtained from the decay of radium
(c) XeF6 + RbF ¾¾ ® Rb[XeF7 ]
(b) Helium is inert gas
(c) Xenon is the most reactive among the rare gases (d) XeO3 + 6HF ¾¾ ® XeF6 + 3H 2 O
(d) The most abundant rare gas found in the atmosphere is 6. Which of the following has maximum number of lone pairs
helium associated with Xe ? [AIEEE 2011 RS]
3. XeF2 is isostructural with : [NEET 2013] (a) XeF4 (b) XeF6
(a) ICl2– (b) SbCl3 (c) XeF2 (d) XeO3
(c) BaCl2 (d) TeF2 7. Total number of lone pair of electrons in XeOF4 is
4. Which one of the following statement regarding helium is (a) 0 (b) 1 [IIT-JEE 2004]
incorrect ? [AIEEE 2004] (c) 2 (d) 3
(a) It is used to produce and sustain powerful 8. The shape of XeO2F2 molecule is [IIT-JEE 2012]
superconducting magnets (a) trigonal bipyramidal (b) square planar
(b) It is used as a cryogenic agent for carrying out (c) tetrahedral (d) see-saw
experiments at low temperatures
1. Density of nitrogen gas prepared from air is slightly greater 4. If two liters of air is passed repeatedly over heated copper
than that of nitrogen prepared by chemical reaction from a and heated Mg till no further reduction in volume takes place
compound of nitrogen due to the presence of the volume finally obtained will be approximately
(a) argon (a) 200 mL (b) 20 mL
(b) carbon dioxide (c) zero (d) 10 mL
(c) some N3 molecules analogous to O3 5. The atomic weight of noble gases is obtained by using the
(d) greater amount of N2 molecules derived from N-15 relationship
isotope (a) Atomic weight = equivalent weight × valency
2. A radioactive element X decays to give two inert gases X is (b) Atomic weight = equivalent weight/ valency
(c) At. weight = valency/ equivalent weight
(a) 238 (b) 226
92 U 88 Ra (d) 2 × V.D. = molecular weight = atomic weight
(c) Both (a) and (b) (d) Neither (a) nor (b) 6. Compounds formed when the noble gases get entrapped in
3. Coconut charcoal at 100°C adsorbs a mixture of the cavities of crystal lattices of certain organic and inorganic
(a) He and Kr (b) Ar, Kr and Xe compounds are known as
(c) Kr and Xe (d) He and Ne (a) Interstitial compounds (b) Clathrates
(c) Hydrates (d) Picrates
JEEMAIN.GURU
downloaded from jeemain.guru
EXERCISE 1 11. (d) Due to weak van der Waal’s forces, He has lowest boiling
point
2. Formation of O2+ [PtF6]–
led to the discovery of first noble
12. (d) Xe forms maximum compounds hence it is most reactive
gas compound Xe[PtF6].
13. (d) The larger the size the more is the polarisiability
5. Neon lights are visible from distance even in fog and mist
14. (a) Atomic number Xe is 54. Xe reacts with F2 and forms
and hence neon is generally used for warning signals. many compounds
6. (i) 2XeF2 + 2H2O ¾¾ ® 2Xe + 4HF + O2 15. (b) Noble gases exhibit low chemical activity
(ii) XeF6 + 3H2O ¾¾ ® XeO3 + 6HF 16. (c) Solubility increases from He to Rn
(iii) XeF6 + PF5 ¾¾ ® [XeF5]+ [PF6]– 17. (d) He was observed in the spectrum of the sun
(iv) XeF6 + NaF ¾¾ ® Na+ [XeF7]–
18. (b) XeF4 + H 2O ® 2HF + XeOF2
7. XeO3 is prepared by hydrolysis of XeF6 or XeF4.
Hydrolysis 19. (a) No compound of He as yet been reported
XeF6 + 3H2O ¾¾¾¾ ¾ ® XeO3 + 6HF
20. (a) No compound of Ar as yet been reported with F2
6XeF4 + 12H2O ® 4Xe + 2XeO3 + 24HF + 3O2
11. (b) 12. (a) 13. (d) 14. (d) 15. (b) 16. (b) 21. (c) 2XeF6 + SiO 2 ® SiF4 + 2XeOF4
17. (c) 18. (b) 19. (a) 20. (b) 21. (c) 22. (b) 22. (c) XeF6 + 3H 2 O ® 6HF + XeO 3
23. (a)
1
23. (d) Hybridisation in XeF4 = (8 + 4 + 0 - 0) = 6 sp3d 2
EXERCISE 2 2
1. (b) Radon is the last member of family 24. (b) XeOF4 square pyramidal
2. (d) He, Ne, Ar, Kr, Xe, Rn 25. (c) Hybridisation of XeF2 is sp3d
3. (d) Electronic configuration of He is 1s2 26. (b) XeF4 is planar (see text)
4. (a) Inert gases do not contain unpaired electrons 27 (a) In XeO3 the hybridisation is sp3
5. (b) Ionization potential of inert gases is highest in periodic 28. (a) XeF2 and IF2- both are linear and have hybridisation
table due to stable electronic configuration.
sp 3 d
6. (d)
7. (a) Ionisation energy decreases as we move away from F
nucleus due to less electrostatic attraction between
electrons and nucleus 29. (a) XeF2 has Xe structure hence number of lone pair
8. (a) The smaller the size the least is the polarisability
F
9. (c) The differentiating electron enter in s subshell in case of
of electrons 3
He, hence it is s- block element. Its electronic
configuration l s2 makes it inert in nature hence it is 30. (d) XeF4 is square planar (A-3) ; XeF6 is distorted octahedral
placed with inert gases. (B-1); XeO3 trigonal pyramidal (C-4) and XeO4 is
tetrahedral (D-2).
10. (c) Ar is the most abundant in atmosphere
JEEMAIN.GURU
downloaded from jeemain.guru
728 Chemistry
31. (c) Hybridisation of XeF4 is sp3d2 and structure is square F
planar F
32. (a) XeF2 XeF4 XeF6
Valence electrons of Xe 8 8 8
XeF6 : F Xe F
Electrons involved 2 4 6
in bond formation
Lone pairs left 3 2 1 F F
33. (c) Hybridisation in each case is XeF4sp3d2, XeF2sp3d,
34. (c) Coloured discharge tubes mainly contain Neon
35. (a) Breathing mixture is (O2 + He) Xe
36. (a) Mixture of (He + O2) is used for asthma patient
37. (d) In clathrates the forces are dipole - induced dipole XeO3 : O O
interaction O
1 1p
38. (d) He2 Bond order = (2 - 2) = 0 Hence cannot be formed.
2 Hence XeF2 has maximum no. of lone pairs of electrons.
EXERCISE 3 7. (b) In XeOF4, Xenon is sp3d2 hybridised and has one lone
1. (d) On account of highly stable ns2np6 configuration in the pair.
valence shell. These elements have no tendency either 8. (d) XeO2F2 has trigonal bipyramidal geometry, but due to
to lose gain or share electrons with atoms of other presence of lone pair of electrons on equitorial position,
elements i.e., their combining capacity or valency is zero. its actual shape is see-saw.
Further all the orbitals in the atoms of these elements are F
doubly occupied i.e electrons are not available for O
sharing. Xe
2. (d) The most abundant rare gas found in the atmosphere is
argon and not helium. O
F
3. (a) F ¾ Xe ¾ F sp3d and Linear EXERCISE 4
1. (a) Air contains about 1% inert gases, mainly Ar. (At.wt
– sp3d and Linear
Cl ¾ I ¾ Cl 40) The atomic wt of N2 is 28
4. (c) Helium is heavier than hydrogen although it is non- 226
inflammable
2. (b) 88 Ra ®86 Rn 222 + 2 He 4 . Both are inert gases
5. (d) The products of the concerned reaction react each 3. (b) Coconut charcoal at 100°C absorbs Ar, Kr and Xe
other forming back the reactants. air
4. (b) Cu and Mg ¾¾ ¾ ¾ ¾¾® CuO, MgO and Mg3N2
® XeO3 + 6HF .
XeF6 + 3H 2 O ¾¾ mainly N 2 and O 2
Xe 13. (d) 22 Ti = 1s 2 , 2s 2 p 6 , 3s 2 p 6 d 2 , 4s 2 ; Ti 4+ = 1s 2 , 2s 2 p 6 , 3s 2 p 6
14. (c) He does not form clathrates due to small size and low
XeF4 : F F molecular weight. Ne also does not form clathrates for
the same reason
2 p
JEEMAIN.GURU
downloaded from jeemain.guru
22
The d & f Block Elements
GENERAL CHARACTERISTICS : Zn ,Cd, Hg ,the end members of first three series have their
1. Transition elements :- Elements where the last orbitals filled general electronic configuration (n - 1)d 10 ns 2 . These do not
are the d orbitals known as transition elements. They have
been placed in the middle of the periodic table between show properties of transition elements to any appreciable
electropositive s-block and electronegative p-block elements. extent and are called non-typical transition elements.
3. Classification - Transition elements consist of the following
2. General Electronic Configuration :- Transition metals have four series
the electronic configuration (n - 1)d1-10 ns0 - 2 . When
3d series 21 Sc to 30 Zn 3d1-10 4s1- 2
electrons fill orbitals, ns-orbital is filled first than (n - 1) d- 4d series 39 Y to 48Cd 4d 1-105s0 - 2
orbital.When losing during oxidation ,ns electrons are lost 5d series 57 La 72 Hf to 80 Hg 5d1-10 6s1- 2
first than (n-1)d electrons. 6d series 89 Ac 104 Rf to 111Rg
JEEMAIN.GURU
downloaded from jeemain.guru
730 Chemistry
5. Physical properties of transition elements-
(i) Metallic character- Transition metals can lose valence
9 Ir Au
electrons and form cations M ® M+n + ne - They have 5d
simple hcp, ccp and bcc lattices characteristic of true metals. Pt
Except Hg they are solids at room temperature and are Os
dense ( d = 5 g / cm 3 in general, in case of osmium 22.6g/
–1
Pd
kJ mol
8
cm3 ), lustrous, malleable, ductile thermal and electrical Hf W Fe Co
Ta Re Cu 3d
conductors.
–2
There is gradual decrease in electropositive character from Ni
1E1 × 10
left to right Mn Ag
Rh 4d
(ii) Melting and boiling point - Due to strong metallic 7 Mo Ru
Tc
bond , they have high mpts and bpts. The mpts of these Zr Nb
elements rise to a maximum and then fall with the increase Ti
in atomic number the manganese and technitium show Cr
V
abnormal values as shown by graph) Sc
6
W
Transition elements
3500
Re First ionization energies of 3d-4d- and 5d-
Ta transition series
3000
Mo Os
Tc
Ir
2500 Nb (iv) Electrode potential ( E 0 ) ( E 0 M n+ M ) is governed by
Ru
three factors
Melting Point (K)
Zr Cr Rh
2000 Ti
V Pt (a) Heat of sublimation
Hf Fe
Y Pd (b) Heat of ionisation
(c) Heat of hydration
)
Co Ni
ies eries
1500
s)
Sc Cu
serie
s
Mn
For the 3d transition metals the E 0 M 2 + / M values are
(4d
Au
Ag
(5d
ser
1000
La V Cr Mn Fe Co Ni Cu
(3d
Zn
-1.18 -0.91 -1.18 -0.44 -0.28 -0.25 0.35
500 (Volts)
Cd The irregular trend is due to variation in ionization energies
and sublimation energies. Except copper
Hg 3d elements are good reducing agents but weaker than s-
1 2 3 4 5 6 7 8 9 10 11 12
block elements.
(v) Oxidation states -In different types of compounds ,
Periodic Groups
Melting point of Transition metals transition metals exhibit different oxidation states. The
highest oxidation state is exhibited in fluorides and oxides.
(iii) Ionisation energy- The ionisation energy increases with
In lower oxidation state the compounds formed are ionic
the increase in the atomic number but not in regular manner.
and in higher oxidation state they are covalent in nature.
The ionisation energies of 5d elements are higher than
Osmium exhibit +8 O.S. (highest)often but Ru exhibit +8
those of 4 d and 3d elements due to greater effective nuclear
oxidation state rarely. Transition metals also show oxidation
charge which in turn is due to poor shielding of nucleus by
states +1 and zero.
4f electrons.
Fe3+ is more stable than Fe2+. Hence Fe2+ act as reducing
Formation of Ni ++ requries 2.49 kJ mol-1 and formation agent Cr3+ is more stabe than Cr2+. Hence Cr2+ act as
Pt ++ requries 2.66 kJ mol -1 . Hence Ni (II) compounds reducing. Mn2+ is more stable than Mn 3+ Hence Mn3+ act
are thermodynamically more stable than Pt (II) Compounds. as oxidising agent
(vi) Atomic and Ionic radii - The values for atomic radii and
Formation of Ni 4 + requires 11.29 kJ mol-1 and ionic radii are in between the values for s and p-block
elements. In 3d transition series the ionic radii for
formation of Pt 4 + requires 9.36 kJ mol-1 . Hence Pt
M 2 + ion decreases upto the middle of the period then
(IV) compounds are relatively more stable than nickel (IV)
becomes almost constant (see table)
compounds. Thus K 2 PtCl6 is well known where as the Due to lanthanide contraction the second and third member
corresponding nickel compound is not known. (Ionisation of each group have atomic redii close to each other (Zr.160
energy graph is sketched here for ready reference) pm ,Hf 159pm)
JEEMAIN.GURU
downloaded from jeemain.guru
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Atomic radii (pm) 144 132 122 117 117 117 116 115 117 125
I. E. kJ mol–1 631 656 650 652 717 762 758 736 745 906
Oxidation State +3 (+2) +2 +2 +2 +2 +2 +2 +1 +2
+3 +3 +3 (+3) +3 +3 (+3) +2
+5 (+5) (+6)
+6 +7
Element Y Zr Nb Mo Tc Ru Ph Pd Ag Cd
Atomic radii 180 160 160 146 136 134 134 137 144 154
(pm)
I.E. (kJ mol–1) 616 674 664 685 703 711 720 804 731 876
Oxidation State +3 (+3) (+2) (+2) +4 +2 +3 +2 +1 +2
+4 (+3) +3 (+5) +3 +4 (+3) (+2)
(+4) +4 +7 +4 (+6) +4 (+3)
+5 +5 (+5)
+6 (+6)
(+7)
(+8)
Element La Hf Ta W Re Os Ir Pt Au Hg
Atomic radii (pm) 187 159 146 139 137 135 136 138 144 157
I.E. (kJ mol–1) 541 760 760 770 759 840 900 870 889 1007
Oxidation State +3 (+3) (+2) +2 +3 (+2) (+2) +2 +1 +1
+4 (+3) (+3) +4 (+3) +3 (+3) +3 +2
(+4) +4 +5 +4 +4 +4
+5 +5 +6 +6 (+6) (+5)
+6 +7 +8 (+6)
(vii)Density - d-block elements have high density because of their small atomic sizes and strong metallic bonding.
Density Sc Ti V Cr Mn Fe Co Ni Cu Zn
g/ml 3.0 4.54 6.10 7.19 7.40 7.87 8.70 8.90 8.92 7.13
(viii)Atomic volume - Atomic volume decreases along the Colour of a complex depends on the metal, its oxidation
period due to decrease in size. state and its ligands. e.g.
(ix) Reactivily -d-block elements are less reactive due to high 2+
ionisation energies. Some are almost inert and known as é Cu ( H 2O ) ù is Pale blue
ë 4û
noble metals, e.g. Au, Pt, Ru, Rh, Os, Ir etc.
2+
(x) Complex formation - They are well known to form a large éCu ( NH3 ) ù is Dark blue
ë 4û
number of complex compounds mainly due to
(i) Small atomic size and higher nuclear charge. CuSO 4 .5H 2 O is blue in colour and anhydrous CuSO4 is
(ii) Presence of partly filled or vacant orbitals colourless. In absence of ligands all d orbitals are degenerate
eg. K 4 [Fe (CN )6 ] (same energy) and the possbility of d-d excitation is no
(xi) Coloured ions - The colour exhibited by transition metal more. In presence of ligand d and d have higher
x 2 -y2 z2
ions is due to the presence of unpaired electrons in d- energy, d-d transition take place by absorption of light,
orbitals which permits the d-d excitation of electrons. hence the colour.
JEEMAIN.GURU
downloaded from jeemain.guru
732 Chemistry
(xii) Magnetic properties -They are 2. Extraction - It is extracted from haematite Fe2 O3 in a blast
(i) Paramagnetic- This is due to the presence of unpaired
furnace by reduction with carbon and carbon monoxide. The
electrons in d-orbitals. Paramagnetic character increases
steps inolved are-
with the number of unpaired electrons.
(ii) Diamagnetic - Diamagnetic substances are repelled (a) Concentration - The crushed ore is agitated with water
and then concentrated by electromagnetic method.
by an applied magnetic field.
(iii) Ferromagnetism - In this case permanent magnetic (b) Roasting or Calcination- To remove volatile substances
moment is acquired by substance e.g. Fe. Magnetic and organic matter. FeO changes to Fe2 O3
moment is given by
S + O 2 ® SO2
= n(n + 2 ) B.M. where n = number of unpaired 4As + 3O2 ® 2As2 O3
electrons and B.M. = Bohr magneton (unit of magnetic
moment) FeCO 3 ® FeO + CO 2
(xiii)Catalytic properties - The transition metals and their 4FeS 2 + 11O 2 ® 2Fe 2 O 3 + 8SO 2
compounds behave as catalyst due to 4FeO + O 2 ® 2Fe 2 O 3
(a) The presenc of partly filled d-orbitals and exhibiting (c) Smelting - Roasted or calcinated ore is mixed with lime
various oxidation states. stone and coke and fed into blast furnace. Reactions taking
(b) Their formation of intermediate complex with reactants place in the blast furnace.
and thus lowering the energy of activation (i) Lower region C + O 2 ® CO 2 + 97, 000 cal.
(c) Their rough surface area provides active sites for
adsorption of reactant molecules. eg. (ii) Middle region
Iron in the preparation of NH 3 (Habers process) CO2 + C ® 2CO - 39000 cal.
Finely divided nickel for hydrogenation CaCO3 ® CaO + CO2 - heat
Pt or V 2 O5 in the preparation of H 2 SO4 CaO + SiO 2 ® CaSiO3 (Slag )
(Contact process)
Fe 2 O 3 + 3CO ® 2Fe + 3CO 2
Pt in the preparation of nitric acid (Ostwald’s process)
Fe 2 O 3 + CO ® 2FeO + CO 2
(xiv)Formation of alloys -d block elements have a strong (iii) Upper region Fe3O 4 + CO ® 3FeO + CO 2
tendency to form alloys since their atomic sizes are very FeO + C ® Fe + CO
similar and in the crystal lattice one metal can be readily The gases leaving the furnace contain CO and used to heat
replaced by another. Alloys so formed are hard, have high incoming air blast.The two layers in the blast furnace are-
m.pts. The metals Mo, W, Cr, Ni, and V are used for the
Upper layer - Molten Iron - It is poured out in moulds and
production of stainless steel and alloy steel.
known as PIG IRON or CAST IRON.It contains 3-5% carbon
Amalgam is an alloy formed by mercury with other metals.
and varying amounts of Mn, Si, P and S which make the
Iron and platinum do not form any alloy with mercury. iron hard and brittle.
(xv) Interstitial compounds - The empty space persent in a
crystal lattice is known as interstitial place. The non metal Lower layer - Molten CaSiO 3 ( slag )
atoms due to their small size (eg H, B, N, C etc.) when 3. Wrought -Iron -It is obtained by heating cast iron with haematite.
occupy such place the resulting compound is known The impurities are oxidised.
interstitial compound. Such compounds are hard and rigid Fe 2 O 3 + 3C ® 2Fe + 3CO
e.g. cast iron and steel.
(xvi)Non stoichiometric compounds -The compounds not 2Fe 2 O 3 + 3Si ® 4Fe + 3SiO 2
having the elements in the exact ratio as shown by the
Fe 2O3 + 3Mn ® 2FeO + 3MnO
moleculer formula are known as non stoichiometric
compouds e.g., FeO, CuO etc. In FeO the Fe : O is approx. MnO + SiO 2 ® MnSiO 3 ( slag )
0.94 : 1 and not exactly 1:1. It containes carbon 0.2-0.5% and traces of P and Si. It is pure
form of Iron and soft , malleable, ductile. It is used to make
IRON [Fe, At.No.26, [Ar]3d 4s ]
6 1
magnets in electric cranes and dynamos, railway carriage
Being reactive in nature it does not occur in free state. couplings being corrosion resistant.
1. Ores of Iron- 4. Steel - It contains carbon 0.1-1.5%and manufactured by
Haematite Fe2 O3 following methods.
Magnetite Fe3 O4 (a) Bessemer process - Molten pig iron is heated in large pear
shaped furnace lined with silica bricks at 1873K when
Limonite or hydrated ferric oxide Fe 2 O3 .3H 2 O
impurities such as Mn, Si, C burn off. When all carbon is
Iron pyrites FeS 2 completely burn off the requisite amount of carbon is added.
Siderite FeCO3 Bessemer converter is lined with lime (CaO) or magnesia
(MgO) when pig iron contains high percentage of
copper pyrites CuFeS2
phosphorous.
JEEMAIN.GURU
downloaded from jeemain.guru
(8) Some chemical properties of Iron- (9) Passivity - The inertness exhibited by metals under conditions
(i) Red hot iron burns in O2 giving sparks when chemical activity is to be expected is called passivity.Iron
becomes passive with conc. HNO3 , Chromic acid ,
3Fe + 2O 2 ® Fe3O 4
(ii) When steam is passed over red hot iron, hydrogen is conc. H2SO4 and KMnO4 etc. It is due to the formation of a
liberated and megnetic oxide of iron (ferroso ferric oxide) is thin layer of oxide at the surface of iron.
formed- (10) Compounds of Iron :
3Fe + 4H 2 O ® Fe3O 4 + 4H 2 (1) Ferric chloride -
(i) It is FeCl3 .6H 2 O
(iii) Action of dil. H 2SO4 -
(ii) Preparation - (i) By passing dry chlorine over heated iron,
Fe + H 2SO 4 ® FeSO 4 + H 2 anhydrous ferric chloride is obtained
(iv) Hot and conc. H 2SO 4 - 2Fe + 3Cl2 ® 2FeCl3 ® Fe 2 Cl6
Fe + 2H 2SO 4 ® FeSO 4 + SO 2 + H 2 O (iii) By the action of hydrochloric acid on ferric hydroxide or
ferric oxide
(v) Action of dil. HNO3 -
Fe ( OH )3 + 3HCl ® 2FeCl 3 + 3H 2 O
4Fe + 10HNO 3 ® 4Fe ( NO3 )2 + NH 4 NO3 + 3H 2O Fe 2 O 3 + 6HCl ® 2FeCl 3 + 3H 2 O
JEEMAIN.GURU
downloaded from jeemain.guru
734 Chemistry
It is soluble in water , alcohol and ether. FeCl3 .6H 2 O is yellow.. · Reducing nature - It is strong reducing is nature.
Its aqueous solution is acidic. Sublimes at 300ºC, covalent and 2 KMnO 4 + 3H 2 SO 4 ® K 2 SO 4 + 2MnSO 4 + 3H 2 O + 5O
dissociates above 973K first into FeCl3 then FeCl 2 and Cl2 2 FeSO 4 + H 2 SO 4 + O ® Fe 2 (SO 4 )3 + H 2 O
e.g. · Addition compound with NO which is dark brown
973K 973K
Fe2Cl6 2 FeCl3 2 FeCl2 + Cl2 D
above FeSO 4 + NO ® FeSO 4 .NO ¾¾® FeSO 4 + NO
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
736 Chemistry
Compounds of copper : Cuprous chloride - Copper (I) chloride ( CuCl or Cu 2 Cl 2 )
Copper Sulphate CuSO 4 .5H2O (Blue vitriol or nila thotha) - Preparation -
Preparation - (i). By dissolving Cu (II) oxide or carbonate in (i) It can be prepared from Cu alone or in combination
dilute H 2SO4 . with CuO,CuCl2 , CuSO4 by action of concentrated
CuO + H 2SO 4 ® CuSO 4 + H 2 O hydrochloric acid.
CuCO3 + H 2 SO4 ® CuSO 4 + CO 2 + H 2 O 2Cu + 2HCl + O ® Cu 2 Cl2 + H 2O
Manufacture -Form scrap copper CuO + Cu + 2HCl ® Cu 2 Cl 2 + H 2 O
2Cu + 2H 2SO4 ( dil, hot ) + O2 ( air ) ® 2CuSO 4 + 2H 2 O CuCl2 + Cu ® Cu 2 Cl2
(vi) Structure of CuSO 4 .5H 2 O - Uses - In gas analysis for absorbing C 2 H 2 and CO. In
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
738 Chemistry
· Dissolves in dilute and concentrated nitric acid GOLD
3Ag + 4HNO 3 ( dil.) ® 3AgNO 3 + 2H 2 O + NO Occurrence - It occurs free as Reef gold, Vein gold or auriferous
quartz. Some improtant ores are
Ag + 2HNO 3 ( conc. ) ® AgNO 3 + H 2 O + NO 2
(i) Claverite AuI2 ,
· Dissolves in alkalicyanide
(ii) Sylvanite ( Ag.Cu ) Te 2
4Ag + 8KCN + 2H 2 O + O 2 ® 4K éë Ag ( CN )2 ùû + 4KOH
(iii) Auriferous pyrites. These are sulphide ores of Cu, Ag, lead
· Dissolves in conc. sulphuric acid (not in dil. sulphuric acid) which contain gold.
2Ag + 2 H 2SO 4 ® Ag 2SO 4 + 2H 2 O + SO 2 Extraction - By cyanide or Mac Arther Forest cyanide process
Uses- For making ornaments (80%Ag+20%Cu), electroplating, -
preparation of mirrors. (i) Concentration - Sulphides and tellurides are concentrated
Fineness- It is the amount of silver present in 1000 parts of silver by froth floatation process.
alloy. 925 fine silver means an alloy of 92.5% silver and 7.5%copper. (ii) Roasting - The concentrated ore is roasted to remove
Compounds of silver - oxidisable impurities of Te, As and S.
Silver nitrate or Lunar caustic AgNO3 : (iii) Formation of complex- NaCN solution is sprayed over
the crushed ore and the gold with air, forming complex ion
Preparation - By the action of dilute nitric acid on silver.
in solution.
3Ag + 4HNO3 ® 3AgNO3 + NO + 2H 2O
4Au + 8NaCN + 2H 2 O + O 2 ®
Properties - It is colourless crystalline solid, soluble in water. It leaves
black deposit when rubbed on the skin due to formation of finely
4Na éë Au ( CN )2 ùû + 4NaOH
divided silver.
· Action of heat - solution
2AgNO3 ® 2AgNO2 + O2 The gold is then recovered as a solid by reduction.
D 2Na éë Au ( CN )2 ùû + Zn ® Na 2 éë Zn ( CN ) 4 ùû + 2Au
2AgNO3
¾¾ ®2Ag + 2NO2 + O2
Strong
(iv) Parting - Removal of impurities of Ag and Cu from gold is
· Tollen’s reagent - The ammonical silver nitrate solution is
known as parting.Impure gold is boiled with conc. H 2SO4
known as Tollen’s reagent.
when Ag and Cu dissolve and Au remains unaffected.
2AgNO 3 + 2 NH 4 OH ® Ag 2 O ¯ + 2 NH 4 N O 3 + H 2 O
(v) Purification - By electrolytic method using gold chloride
Ag 2 O + 4 NH 4 OH ® 2 é Ag ( NH 3 )2 ù OH + 3H 2 O 2.5-6.0% and conc. HCl.
ë û
· Reaction with aqueous solution of certain compounds. · Plattner chlorine extraction process - From auriferous pyrites.
The moistened auriferous pyrites is saturated with chlorine,
NaCl leached with water then treated with FeSO4 or H 2S which
¾¾¾® AgCl(white precipitate)
precipitates gold. Auriferous pyrites (moistened)
¾¾¾® AgBr(pale yellow)
NaBr
+Cl2 ® AuCl3
¾® AgI (yellow)
NaI
¾¾
AuCl3 + 3FeSO4 ® Au + FeCl3 + Fe 2(SO 4 )3
® Ag2CrO4 (red )
K CrO
¾¾2¾¾
4
2AuCl3 + 3H 2S ® 2Au + 6HCl + 3S
¾¾¾¾® AgCNS (white)
NaCNS
Impurities of Ag and Cu are removed by parting (as above).
¾¾¾¾® Ag3 PO 4 (yellow)
Na3 PO 4
Properties - Pure gold is soft, hardened by Ag or Cu.
AgNO3 Fineness of gold - It is expressed in terms of carats. Pure gold is
® Ag2 S2 O3 ¾¾2¾® Ag2 S (black)
Na S O H O
¾¾2¾2¾
¾3
24 carats. 22 carats mean it contains 22 parts by
¾¾¾® AgCN ¾¾¾® K [Ag(CN )2 ]
KCN KCN
weight of gold and 2 parts by weight of other metals generally
Na S copper.
¾¾2¾® Ag2 S
It is very inert and not attacked by oxygen ,water and acids.
Cu
¾¾® Ag deposited · It is attacked by aqua regia (3 conc. HCl + 1 conc. HNO3 )
I 2 (excess )
¾¾¾ ¾
¾® AgI + HIO3 + HNO3
3HCl + HNO 3 ® NOCl + 2H 2 O + 2Cl
Uses - For silvering mirror ,electroplating, in medicines, for the Au + 3Cl ® AuCl3
preparation of silver halides used in photography. Particularly
· It is attacked by chlorine also.
AgBr which is most sensitive to light.
2Au + 3Cl2 ® 2AuCl3
2AgBr ® 2Ag + Br2
JEEMAIN.GURU
downloaded from jeemain.guru
· AuCl3 auric chloride forms red crystals. Soluble in water and · Chemical properties -
(i) Action with acids
decomposed on heating. Zn + H 2SO4 ( dilute ) ® ZnSO4 + H 2
AuCl3 ® AuCl + Cl 2 4Zn + 5H 2SO 4 ( 20%H 2SO4 ) ® 4ZnSO 4 + H 2S + 4H 2 O
light yellow powder 3Zn + 4H 2SO4 ( 20%H 2SO 4 ) ® 3ZnSO 4 + S + 4H 2 O
ZINC (Zn) : Zn + 2H 2SO4 ( hot and conc.) ® ZnSO 4 + SO2 + 2H 2 O
Zinc - It is not found free in nature.The principal ores are - 4Zn + 10HNO3 ( cold and dilute ) ® 4Zn ( NO3 )2 + NH 4 NO3 + 3H 2 O
(i) Zinc blende (sphalerite) ZnS
3Zn + 8HNO 3 (mode. conc. ) ¾
¾® 3Zn (NO )3 + 2 NO + 4H 2 O
(ii) Zincite or Red zinc oxide ZnO
Zn + 4HNO 3 (conc. hot ) ¾
¾® ZnNO 3 + 2 NO 2 + 2 H 2 O
(iii) Franklinite ZnO.Fe 2O3
Zn + 2 NaOH ¾ ¾® Na 2 ZnO 2 + H 2
(iv) Calamine or Zinc spar ZnCO3 · Displacement reactions
(v) Willemite 2ZnO.SiO2 Zn + CuSO 4 ® ZnSO4 + Cu ¯
Extraction - It is extracted by reduction process from ZnS (Zinc Zn + Pb ( NO3 )2 ® Zn ( NO3 ) 2 + Pb
blende).
Concentration - The ore is concentrated by froth flotation Zn + 2Na éë Ag ( CN )2 ùû ® Na 2 éë Zn ( CN ) 4 ùû + 2Ag
process.
Roasting - The concentrated Zinc blende is roasted in a current Zn + 2Na éë Au ( CN )2 ùû ® Na 2 éë Zn ( CN ) 4 ùû + 2Au
of air.
· With non metals
2ZnS + 3O2 ® 2ZnO + 2SO2
Zn + Cl 2 ® ZnCl 2
( SO2 is utilised for the manufacturing of H 2SO4 ) Zn + S ® ZnS
If calamine ore is used, it is calcined. · It is powerful reducing in nature.
ZnCO3 ® ZnO + CO2 Fe 2 ( SO 4 )3 + Zn ® 2FeSO 4 + ZnSO 4
Reduction - The ZnO is reduced by mixing with carbon and Uses- Galvanising, sherardizing, in Parke’s process for
heating in fire clay retort. desilverisation of lead , for extraction of Ag and Au
(Cyanide proces). Zinc compounds are used in paints, filling
ZnO + C ® Zn + CO rubber etc.
Purification - Zinc so obtained contains the impurities of Fe, Compounds of Zn
Pb, Cd, As or Sb. It is purified by ZnO - Zinc oxide, Philospher’s wool, zinc white or chinese white.
(a) Distillation or buring
(b) Electrolytic method Preparation - (i) Zn + air ¾¾¾¾ ® ZnO
D
Anode impure ( Zn ) Zn - 2e- ® Zn ++ (ii) ZnCO3 ¾¾ ® ZnO + CO2
D
Cathode pure ( Zn ) Zn ++ + 2e ® Zn (iii) Zn ( NO3 )2 ¾¾ ® ZnO + NO 2 + O 2
Properties - It is white powder becomes yellow on heating but
Electrolyte - Acidic solution of ZnSO4 .
again white on cooling. It sublimes at 673K.
(c) Liquation - Molten Zn is allowed to flow down on sloping · With alkali - It forms zincate.
hearth when non fusible impurities are left behind.
ZnO + 2NaOH + H 2O ® Na 2 éë Zn (OH )4 ùû
Electrolytic method - Pure ZnSO4 is electrolysed when Zn is
deposited on aluminium cathode. It is scrapped off and melted Sodium Zincate
to obtain 99.95% pure metal. · Reduction ZnO + H 2 ® Zn + H 2 O
· Zinc dust -It is prepared by atomising molten zinc with
ZnO + C ® Zn + CO
blast of air.
· Dissolves in acids to form corresponding salts.
· Granulated Zinc - It is prepared by pouring molten Zinc
into cold water. ZnO + H 2SO4 ® ZnSO 4 + H 2 O
Properities- It is bulish white metal, stable in air. Uses - As a white paint , in medicines, glaze in ceramics and filler
· In moist air a protective covering of basic zinc carbonate is in rubber industry.
ZnSO 4 .7H 2O (White vitriol) -
formed at its surface 2ZnCO3 .3Zn ( OH ) 2 .H 2O
· Action of heat -When heated to 500ºC it catches fire with Preparation - By the action of dil. H 2SO4 on Zinc metal, ZnO
bluish white flames forming ZnO which is very light and or ZnCO3
called philospher’s wool.
( Zn, ZnO or ZnCO 3 ) + dil. H 2 SO 4 ® ZnSO 4 .7H 2 O
JEEMAIN.GURU
downloaded from jeemain.guru
740 Chemistry
Properties - Colourless, crystalline compound, highly soluble
· It forms mercuric oxide at 300o C .
in water.
Action of heat - 2Hg + O 2 ® 2HgO
373K 723K
ZnSO4 .7H 2 O ¾¾¾® ZnSO4 .H 2 O + 6H 2 O ¾¾¾® ZnSO 4 anhydrous
· Dilute acids have no +action
ZnO SO 2 +onOmercury
2 except dil. HNO3 .
6 Hg + 8HNO 3 ® 3Hg 2 (NO 3 )2 + 2 NO + 4H 2 O
H 2 O + 6H 2O ¾¾¾® ZnSO 4 ( anhydrous ) Strong
¾¾¾
D
® ZnO + SO 2 + O 2
· With concentrated acids
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
742 Chemistry
In alkaline medium -
Hot concentrated solution of ( Na 2Cr2 O7 ) Potassium
2KMnO 4 + 2KOH ® 2K 2 MnO 4 + H 2 O + O dichromate is less soluble and seperates out on
or MnO -4 + e - ® MnO24 - crystallisation.
In neutral medium - Properties - It is garnet red prismatic (orange) crystalline
compound having melting point 398°C. Soluble in water.
2KMnO4 + H 2 O ® 2KOH + 2MnO2 + 3O Chemical properties -
or MnO -4 + 2H 2 O + 3e - ® MnO2 + 4OH - (i) Action of heat -
In alkaline medium it oxides potassium iodide to potassium iodate 4K 2 Cr2 O 7 ® 4K 2 CrO 4 + 2Cr2 O3 + 3O 2
and nitro toluene to nitro benzoic acid. Chromic oxide
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
744 Chemistry
(vii) Melting and boiling point - Lanthanides have high (x) Ionisation energies - The ionisation energy values of
melting and boiling points but there is no regular trend. lanthanides are not very high due to their large size
(viii) Density - Lanthanides have densities varying and are comparable with those of alkaline earth metals.
(xi) Complex compound - Due to having large ionic size
from 6.77 to 9.74 g cm -3 . But there is no definite trend they have little tendency to form complexes.
for these values. (xii) Reactivity - Due to their low values of ionisation
energies the lanthanides are very reactive.
(ix) TheElement electronegatively values of lanthanides
(xiii) Alloys - They form alloy especially with iron e.g. MISCH
are almost same as that of s-block elements.
METAL rare earths 94 - 95% iron 5% and
Lanthanides form ionic compounds.
S , C , Ca and Al in traces .
Atomic Name Symbol Electronic Oxidation Density Melting Boiling M 3+ radii
number configuration states (g/ml) point (K) point (K) (pm)
57 Lanthanum La [Xe]4 f 5d 6s
0 1 2 +3 6.17 1193 3742 106
JEEMAIN.GURU
downloaded from jeemain.guru
Very Short/Short Answer Questions 16. Complete the following chemical equations:
1. Why is HCl not used to acidify a permanganate solution in (i) MnO-4 ( aq ) + S2O32 - ( aq ) + H 2 O ( l ) ®
volumetric estimations of ferrous ion (Fe2+) or oxalate ion
(C2O42–)? (ii) Cr2 O72- ( aq ) + Fe 2+ ( aq ) + H + ( aq ) ®
2. Why does V2O5 act as catalyst?
3. What is the oxidation state of chromium in (a) potassium 17. State reason for the following :
dichromate (b) potassium chromate? (i) Cu (I) ion is not stable in an aqueous solution.
4. The d-electronic configuration of Co2+ and Cu2+ is d7 and d9 (ii) Unlike Cr3+, Mn2+, Fe3+ and the subsequent other M2+
respectively. Which one of these ions will be more ions of the 3d series of elements, the 4d and the 5d
paramagnetic? series metals generally do not form stable cationic
5. Lanthanum (Z = 57), gadolinium (Z = 64) and lutetium (Z = species.
71) are extra-ordinarily stable in + 3 oxidation state. Explain. 18. How would you account for the following:
6. Why KMnO4 is used in clearing surgical instruments in (i) Among lanthan oids, Ln (III) compounds are
hospitals? predominant, However, occasionally in solutions or in
7. Write chemical equation for the conversion of: solid compounds, + 2 and + 4 ions are also obtained.
(a) Chromite ore to sodium chromate
(ii) The E° for copper is positive (0.34 V). Copper
(b) Pyrolusite to potassium manganate M 2 + /M
(c) Potassium permanganate to manganese dioxide is the only metal in the first series of transition elements
8. There is only a very small increase in IE of an element in a showing this behaviour.
transition series (or d-block elements) when we move along (iii) The metallic radii of the third (5d) series of transition
the period as compared to s and p-block elements. Explain, metals are nearly the same as those of the correspond-
why. ing members of the second series.
9. Among lanthanides, why are ions like Sm2 +, Eu2+ and Yb2+ 19. (a) Which metal in the first transition series (3d series)
in aqueous solutions good reducing agents but an aqueous exhibits + 1 oxidation state most frequently and why?
solution of Ce4+ is a good oxidising agent? Explain. (b) Which of the following cations are coloured in aque-
10. (a) Which oxidation state of Mn is most stable and why? ous solutions and why?
(b) Which transition element show highest oxidation state
Sc3+, V3+, Ti4+, Mn2+
and in which compound?
(At. nos. Sc = 21, V = 23, Ti = 22, Mn = 25)
(c) Which is the densest transition element?
11. Which of the following oxides is basic, amphoteric and acidic Long Answer Questions
oxide: Sc2O3, MnO, FeO, Cu2O, MnO2, CuO, TiO2, Mn2O7,
CrO3. Cr2O3 20. The sums of first and second ionisation energies and those
12. A substance is found to have a magnetic moment of 4×89 of third and fourth ionisation energies of nickel and platinum
BM. How many unpaired electrons does it contain? are given below:
Element IE1 + IE2 (kJ mol–1) IE3 + IE4 (kJ mol–1)
13. Write the IUPAC name of éëCo ( NH3 )5 Cl ùû Cl 2 . [Atomic no. Ni 2×49 8×80
of Co = 27] Pt 2×66 6×70
14. Compare the chemistry of the actinoids with that of Taking these values in account, write
lanthanoids with reference to (a) the most common oxidation states of Ni and Pt and its
(i) electronic configuration reason.
(ii) oxidation states (b) the name of the metal (Ni or Pt) which can form
(iii) chemical reactivity compounds is + 4 oxidation state more easily and why?
15. Write the structures and names of all the stereoisomers of 21. Explain the following:
the following compounds: (a) Transition elements show similarity in properties along
the period as well as down the group (i.e., horizontal as
(i) é Co ( en ) ù Cl3 well as vertical similarities).
ë 3û
(b) In transition series, it is observed that melting point
(ii) é Pt ( NH3 ) Cl2 ù first increases and then starts decreasing.
ë 2 û
(c) Copper is a transition element but not sodium.
(iii) éë Fe ( NH3 ) 4 Cl 2 ùû Cl (d) Zinc atom is bigger than copper atom.
(e) Transition metals have low reactivity.
JEEMAIN.GURU
downloaded from jeemain.guru
746 Chemistry
22. (a) Describe with the help of chemical equations the 26. Cuprous compounds such as CuCl, CuCN and CuSCN are
preparation of potassium dichromate from chromite ore. the only salts stable in water due to
(b) Give balanced chemical equations for what happens (a) high hydration energy of Cu+ ions
when acidified potassium dichromate solution reacts
(b) their inherent tendency not do disproportionate
with
(i) ferrous sulphate solution. (c) diamagnetic nature
(ii) hydrogen sulphide gas. (d) insolubility in water
(c) Draw the structure of Cr2O72–. 27. The addition of excess of aqueous HNO3 to a solution
containing [Cu(NH3)4]2+ produces
Multiple Choice Questions (a) Cu+
23. Which element belongs to d-block ? (b) [Cu(H2O)4]2+
(a) Na (b) Ca (c) Cu(OH)2
(c) Cu (d) Ar (d) Cu(NO3)2
24. (n - 1)d 10ns 2 is the general electronic configuration of 28. An extremely hot copper wire reacts with steam to give
(a) Fe, Co, Ni (b) Cu, Ag, Au (a) CuO (b) Cu 2O
(c) Zn, Cd, Hg (d) Se, Y, La (c) Cu 2 O 2 (d) CuO2 .
25. Which of the following is not property of the transition 29. Which is not amphoteric ?
elements?
(a) Al 3+ (b) Cr 3 +
(a) Colour (b) Paramagnetism
(c) Fixed valency (d) None of these (c) Fe 3+ (d) Zn 2+
1. How many ‘d’ electrons are present in Cr 2 + ion? (b) All three are colourless
(a) 4 (b) 5 (c) All three are coloured
(c) 6 (d) 3 (d) Only Ni 2 + is coloured an d Zn 2+ and Cr 3+ are
2. Which of the following ions having following electronic colourless
structure would have maximum magnetic moment?
7. (n - 1)d 10ns 2 is the general electronic configuration of
(a) 1s 2 2 s 2 2 p 6 3s 2 3 p 6 3d 3 (b) 1s 2 2s 2 2 p 6 3s 2 3 p 6 3d 5
(a) Fe, Co, Ni (b) Cu, Ag, Au
2 2 6 2 6 7 2
(c) 1s 2s 2 p 3s 3 p 3d (d) 1s 2s 2 p 3s 3 p 3d 2 6 2 6 9 (c) Zn, Cd, Hg (d) Se, Y, La
8. Common oxidation state of scandium, a transition element
3. Which of the following element does not belong to first
transition series? is/are [Ar.No.of Sc = 21]
(a) Fe (b) V (a) +4 (b) +1
(c) Ag (d) Cu (c) +2 and +3 (d) +4 and +1
4. The transition metals have a less tendency to form ions 9. Which of the following is not correct about transition metals?
due to (a) Their melting and boiling points are high
(a) high ionisation energy (b) Their compounds are generally coloured
(b) low heat of hydration of ions (c) They can form ionic or covalent compounds
(c) high heat of sublimation (d) They do not exhibit varialbe valency
(d) All of these 10. Which of the following has maximum unpaired
5. Which of the following oxides of manganese is amphoteric? electrons?
(a) Scandium (b) Chromium
(a) MnO 2 (b) Mn 2O3
(c) Manganese (d) Iron
(c) Mn 2O7 (d) MnO 11. The last electron in d-block elements goes to
(a) (n-1) d (b) nd
6. Of the ions Zn 2+ , Ni 2+ and Cr 3+ (c) np (d) (n-1) s
( At.Nos Zn = 30, Ni = 28,Cr = 24) 12. Which of the following ions is coloured?
(a) Cu + (b) Cu 2+
(a) Only Zn 2+ is colourless and Ni 2 + and Cr 3+ are
coloured (c) Ti4+ (d) V5+
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
748 Chemistry
39. Corrosion of iron can be prevented by coating the surface 52. The oxidation number of Fe in Fe3O 4 is
with
(a) +2 (b) +3
(a) Zn (b) Sn
(c) 8/3 (d) 2/3
(c) Ni (d) Any of these
53. The iron obtained from blast funace is
40. Which of the following compound is called Turnbull’s blue?
(a) pig iron (b) silver
(a) Ferricyanide (b) Ferrous ferricyanide
(c) soft iron (d) steel
(c) Ferrous cyanide (d) Ferri-ferrocyanide
54. Which of the following gives blood red colour with
41. In an octahedral crystal field splitting the number of orbitals
KCNS?
pushed down in energy is
(a) 3 (b) 2 (a) Cu 2+ (b) Fe3+
(c) 5 (d) zero
(c) Al3+ (d) Zn 2 +
42. Which one of the following pairs of ions have the same
55. The protection of steel by chrome plating is due to
electronic configuration?
(a) cathodic protection
(a) Cr3+ ,Fe3+ (b) Fe3+ , Mn 2+ (b) anodic protection
(c) covering of steel surface
(c) Fe3+ , Co3+ (d) Sc3+ ,Cr3+ (d) formation of alloy with iron
43. Bonding in ferric chloride is 56. The nature of an aqueous solution of FeCl 2 is
(a) covalent (b) ionic (a) acidic (b) basic
(c) co-ordinate (d) None of these (c) amphoteric (d) neutral
44. Which one of the following elements constitutes a major 57. Which one of the following is the correct configuration of
impurity of pig iron?
Fe3+ ( Z = 26 ) ?
(a) Silicon (b) Oxygen
(c) Sulphur (d) Graphite (a) [Ar ]4s 2 3d 6 (b) [Ar ]4s 2 3d 3
45. A compound of a metal ion M x + ( Z = 24 ) has a spin (c) [Ar ]3d 5 (d) [Ar ]4s 2 3d 4
only magnetic moment of 15 Bohr Magnetons. The number 58. The number of ions formed on dissolving one molecule of
of unpaired electrons in the compound are FeSO 4 ( NH 4 )2 SO 4 .6H 2O
(a) 2 (b) 4
(Mohr’s salt) is/are
(c) 5 (d) 3
(a) 6 (b) 3
46. Which of the following configuration is correct for iron?
(c) 5 (d) 4
(a) 1s 2 2s 2 2 p 6 3s 2 3 p 6 3d 5 59. If steel is heated to a temperature well below red heat and is
then cooled slowly the process is called
(b) 1s 2 2s 2 2 p 6 3s 2 3 p 6 4s 2 3d 5 (a) tempering (b) hardening
(c) softening (d) annealing
(c) 1s 2 2s 2 2 p 6 3s 2 3 p 6 4s 2 3d 7
60. Which of the following is obtained when Fe reacts with
(d) 1s 2 2s 2 2 p 6 3s 2 3 p 6 4s 2 3d 6 dil. HNO3 ?
47. Stainless steel contains (a) N 2O (b) NO
(a) Fe + Cr + Cu (b) Fe + C + Ni
(c) NO2 (d) None of these
(c) Fe + Cr + Ni + C (d) Fe + Ni + Cu 61. Wrought iron, pig iron and steel differ in properties due to
48. Which of the following is not an element? (a) carbon content (b) malleability
(a) Graphite (b) Diamond (c) conductivity (d) softness
(c) 22-Carat gold (d) Rhombic sulphur 62. Green vitriol is
49. Which of the following elements does not exist in the native
(a) FeSO 4 .7H 2O (b) ZnSO 4 .7H 2O
form?
(a) Au (b) Pt (c) CaSO 4 .2H 2O (d) CuSO 4 .5H2O
(c) Fe (d) S 63. Which of the following is not an ore of iron?
50. In the extraction of iron, slag is produced which is (a) Limonite (b) Magnetite
(a) CO (b) FeSiO3 (c) Casiterite (d) All of these
64. Corrosion is basically a
(c) MgSiO3 (d) CaSiO3
(a) altered reaction in presence of H2O
51. The nature of an aqueous solutionof FeCl3 is (b) electrochemical phenomenon
(a) acidic (b) basic (c) interaction
(c) amphoteric (d) neutral (d) union between light metal and heavy metal
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
750 Chemistry
87. AgCl is soluble in NH4OH solution. The solubility is due to 98. Acidified solution of chromic acid on treatment with
the formation of H 2O2 gives blue colour which is due to
(a) AgOH (b) Ag 2O (a) CrO3 + H 2O + O2 (b) CrO5 + H 2O
+ (c) H 2Cr2O7 + H 2O + O2 (d) None of these
(c) éë Ag ( NH3 )2 ùû (d) NH 4Cl
99. In the extraction of zinc, the formation of blue flame is due
88. The compound that is soluble in water is the burning of
(a) AgF (b) AgCl (a) ZnO (b) C
(c) AgBr (d) AgI (c) Zn (d) CO
89. In the metallurgy of which of the following cupellation 100. Which of the following compounds turns black on
process is used? addition of NH 4OH ?
(a) Copper (b) Silver
(a) PbCl2 (b) Hg2Cl2
(c) Iron (d) Aluminium
90. When potassium ferrocyanide crystals are heated with (c) HgCl 2 (d) AgCl
conc. H 2SO 4 the gas evolved is 101. Mercury is the only metal which is liquid at 0°C. This is due
to its
(a) SO2 (b) NH3 (a) very high ionisation energy and weak metallic bond
(c) CO2 (d) CO (b) low ionisation potential
91. In the extraction of silver, Ag 2S is dissolved in (c) high atomic weight
(d) high vapour pressure
(a) HCl (b) HNO3
102. Which one of the following is false for Hg?
(c) KCN (d) H2SO4 (a) It can evolve hydrogen from H2S
92. Parke’s process is used (b) It is metal
(a) to extract Ag using NaCN (c) It has high specific heat
(b) to extract Cu using CuFeS2 (d) It is less reactive than hydrogen.
(c) to extract Ag from argentiferrous lead 103. Mercury sticks to the surface of the glass when it comes in
(d) to extract Ag by forming amalgam contact with
93. In the equation (a) Hg2O (b) HNO3
(c) O3 (d) grease
-
4M + 8CN - + 2H 2O + O2 ® 4 éë M (CN )2 ùû + 4OH - 104. Which compound is volatile on heating?
(a) MgCl2 (b) Hg Cl2
Identify the metal M. It is (c) ZnCl2 (d) None of these
(a) copper (b) iron 105. Which ion is detected by Nessler’s reagent?
(c) gold (c) zinc
(a) NH +4 (b) MnO-4
94. A metal which is not affected by conc. H 2SO 4 , HNO3
or alkalies forms an compound X This compound X can be (c) PO34- (d) CrO24 -
used to give a complex which finds its application for tonning 106. Mercurous ion is represented as
in photography. The metal is (a) Hg 22 + (b) Hg 2 +
(a) Au (b) Ag
(c) Hg (d) Cu (c) Hg + Hg 2 + (d) 3Hg3+
95. Which of the following is not the characteristic of zinc? 107. Nessler’s reagent is
(a) It is a volatile metal (a) potassium iodide in mercuric iodide
(b) It dissolves in alkali forming sodium zincate (b) TiCl 4
(c) It is brittle at very high temperatures
(d) Zinc dust is used as reducing agent (c) anhydrous AlCl3
96. Galvanization of iron denotes coating with (d) Al 2O3 / Cr2O3
(a) Al (b) Sn 108. The equivalent weight of KMnO4 (formula weight = M )
(c) Cd (d) Zn when it is used as an oxidant in neutral medium is
97. When Zn is treated with excess of NaOH, the product
M
obtained is (a) M (b)
2
(a) Zn (OH )2 (b) ZnOH
M M
(c) (d)
(c) Na 2 ZnO2 (d) None of these 3 5
JEEMAIN.GURU
downloaded from jeemain.guru
JEEMAIN.GURU
downloaded from jeemain.guru
752 Chemistry
1. Which one of the following ions is the most stable in aqueous 11. Acidified K2Cr2O7 solution turns green when Na2SO3 is
solution? [CBSE-PMT 2007] added to it. This is due to the formation of :
(a) V3+ (b) Ti3+ (c) Mn 3+ (d) Cr3+ [CBSE-PMT 2011]
(At.No. Ti = 22, V = 23, Cr = 24, Mn = 25) (a) Cr2(SO4)3 (b) CrO42– (c) Cr2(SO3)3 (d) CrSO4
2. Identify the incorrect statement among the following : 12. Which of the statements is not true? [CBSE-PMT 2012]
[CBSE-PMT 2007] (a) On passing H2S through acidified K2Cr2O7 solution, a
(a) Lanthanoid contraction is the accumulation of successive milky colour is observed.
shrinkages. (b) Na 2Cr 2 O7 is preferred over K2 Cr 2O7 in volumetric
(b) As a result of lanthanoid contraction, the properties of analysis.
4d series of the transition elements have no similarities (c) K2Cr2O7 solution in acidic medium is orange.
with the 5d series of elements. (d) K2Cr2O7 solution becomes yellow on increasing the pH
(c) Shielding power of 4f electrons is quite weak. beyond 7.
(d) There is a decrease in the radii of the atoms or ions as 13. Which one of the following does not correctly represent the
one proceeds from La to Lu. correct order of the property indicated against it?
3. The correct order of decreasing second ionisation enthalpy [CBSE-PMT 2012]
of Ti (22), V(23), Cr(24) and Mn (25) is : [CBSE-PMT 2008] (a) Ti < V < Cr < Mn : increasing number of oxidation states
(a) Cr > Mn > V > Ti (b) V > Mn > Cr > Ti (b) Ti3+ < V3+ < Cr3+ < Mn3+ : increasing magnetic moment
(c) Mn > Cr > Ti > V (d) Ti > V > Cr > Mn (c) Ti < V < Cr < Mn : increasing melting points
4. Which one of the elements with the following outer orbital (d) Ti < V < Mn < Cr : increasing 2nd ionization enthalpy
configurations may exhibit the largest number of oxidation 14. Four successive members of the first series of the transition
states? [CBSE-PMT 2009] metals are listed below. For which one of them the standard
(a) 3d 54s1 (b) 3d 54s2 (c) 3d 24s2 (d) 3d 34s2
5. Out of TiF62– , CoF63– , Cu2Cl2 and NiCl2– 4 (Z of Ti = 22,
( º
)
potential E M 2 + / M value has a positive sign?