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Vol. XXIV No. 1 January 2015 chemistry, analytical chemistry and

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is very important. Many standards are available, each set for one type of
Chemistry Musing Problem Set 18 8
analysis in different concentration levels as well as materials. The same
Examiner’s Mind Class XI 11 concentration of impurities in different materials give different values of
concentration. It is also difficult to obtain different standards of different
You Asked, We Answered 19 concentrations to analyse every type of material, even slightly differing in
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Examiner’s Mind Class XII 71

Advanced Chemistry Bloc 81

Chemistry Olympiad Problems 86

Chemistry Musing Solution Set 17 90

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chemistry today | January ‘15 7

C hemistry Musing was started from August '13 issue of Chemistry Today with the suggestion of
Shri Mahabir Singh. The aim of Chemistry Musing is to augment the chances of bright students preparing
for JEE (Main and Advanced) / AIPMT / AIIMS / Other PMTs & PETs with additional study material.
In every issue of Chemistry Today, 10 challenging problems are proposed in various topics of JEE (Main
and Advanced) / AIPMT. The detailed solutions of these problems will be published in next issue of
Chemistry Today.
The readers who have solved five or more problems may send their solutions. The names of those who
send atleast five correct solutions will be published in the next issue.
We hope that our readers will enrich their problem solving skills through "Chemistry Musing" and stand in
better stead while facing the competitive exams.


jee main/PmTs 3. Although aldehydes and ketones also contain

a carbonyl group, like acid halides they do not
1. 1 M NaOH solution was slowly added to 1 L of undergo nucleophilic substitution reactions
210 g impure H2SO4 solution and the following because
plot was obtained. (a) they do not have electronegative chlorine
[H+] (mol/L)

(b) carbon atom of carbonyl group in aldehydes

2 and ketones is less electron deficient
1 (c) hydride ion and methylide ion are strong
1 2 3 bases and hence are poor leaving groups
Volume of NaOH
(d) none of the above.
added (L) 4. All the oxygen in a 0.5434 g sample of a pure
The percentage purity of H2SO4 sample is oxide of iron is removed by reduction in a
(a) 70 % (b) 80 % stream of H2. The loss in weight is 0.1210 g.
(c) 75 % (d) none of these. Hence, formula of the iron oxide is (Fe = 56)
(a) FeO (b) Fe2O3
2. Bromine, Br2 boils at 58.8 °C, while iodine (c) Fe3O4 (d) FeO2
monochloride, ICl boils at 97.4 °C. The main
reason ICl boils almost 40 °C higher than Br2 is Solution Senders of Chemistry Musing
that set 17
(a) the molecular weight of ICl is 162.4 while 1. Pijush Kanti roy (West Bengal)
that of Br2 is 159.8 2. agranipanda
(b) ICl is covalent compound, while Br2 is 3. Kashish arora (Haryana)
ionic 4. ronal Gaonkhowa (assam)

(c) London dispersion forces are stronger for set 16

ICl than that for Br2 1. Sayantan adhikary (West Bengal)
2. rajesh Kumar yadav (Kanpur)
(d) ICl is polar, while Br2 is non-polar.

8 chemistry today | January ‘15

5. An aliphatic organic compound containing biological activity is lost. Such a protein is called
C, H and N reacts with dilute HCl to produce denatured protein. In most of the cases, the process
formic acid. It is reduced to dimethylamine by of denaturation is irreversible but in some cases it
Pt or Ni, and undergoes addition reactions with may also be reversible.
chlorine and sulphur. The compound can be
7. Denaturation of proteins leads to loss of its
(a) CH3NC
biological activity by
(b) CH3CN
(a) formation of amino acids
(c) CH3NH2 (b) loss of primary structure
(d) a mixture of (a) and (b). (c) loss of both primary and secondary
jee advanced structures
(d) loss of both secondary and tertiary
6. Compound (A) C5H8O2 liberated CO2 on
reaction with sodium bicarbonate. It exhibits
8. Which of the following statements is incorrect
geometrical isomerism. It gave compound (B),
about denaturation of proteins?
C5H10O2 on hydrogenation. Compound (B) can
(a) The primary structure of the protein does
be separated into enantiomorphs. Structures of not change.
(A) and (B) respectively are (b) Globular proteins are converted into
(a) CH3 C CH COOH , fibrous proteins.
CH3 (c) Fibrous proteins are converted into
CH3 CH2 CH COOH globular proteins.
(d) The biological activity of the protein is
(b) CH3 CH C COOH ,
inTeger vaLUe
9. Total number of isomers possible for the
CH3 CH2 CH COOH complex ion [Cr(NH3)(OH)2Cl3]2– is
CH3 10. The rate constant of a reaction increases by 8%
(c) CH3 CH CH2 COOH , when its temperature is raised from 400 K to
410 K, while its equilibrium constant increases
CH3 CH3 CH C COOH by 3%. The sum of the activation energies of
CH3 the forward and reverse reactions is x × 103 cal,
x is
(d) CH3 C CH COOH , nn
A protein with a specific biological activity has
a unique three-dimensional structure called its
native shape. When a protein in its native form
is subjected to change of temperature or pH or is
exposed to heavy metal salts such as Hg2+, Pb2+,
etc., the native shape of the protein is destroyed and

10 chemistry today | January ‘15

The questions given in this column have been prepared strictly on the basis of NCERT Chemistry for Class XI.
This year JEE (Main & Advanced)/AIPMT/AIIMS/other PMTs have drawn their papers heavily from NCERT books.

section - i 5. An organic compound has C and H percentage

Only One Option Correct Type in the ratio 6 : 1 and C and O percentage in the
ratio 3 : 4. The compound is
This section contains 20 multiple choice questions. Each
(a) HCHO (b) CH3OH
question has four choices (a), (b), (c) and (d), out of which
(c) CH3CH2OH (d) (COOH)2
ONLY ONE is correct.
6. Which of the following mixtures cannot be
1. When 80 mL of 0.20 M HCl is mixed with prepared?
120 mL of 0.15 M KOH, the resulting solution (a) NaHCO3 + Na2CO3
is the same as a solution of (b) Na2CO3 + NaOH
(a) 0.16 M KCl and 0.02 M HCl (c) NaHCO3 + NaOH
(b) 0.08 M KCl (d) H2CO3 + NaHCO3
(c) 0.08 M KCl and 0.01 M KOH 7. If E1, E2, and E3 represent the kinetic energies of
(d) 0.08 M KCl and 0.01 M HCl. an electron and an alpha particle and a proton
2. In the dehydration reaction, respectively, each having same de-broglie
wavelength then
CH3CONH2  2 5
→ CH3C N (a) E1 > E3 > E2 (b) E2 > E3 > E1
the hybridisation state of carbon changes from (c) E1 > E2 > E3 (d) E1 = E2 = E3
(a) sp3 to sp2 (b) sp to sp 8. One mole N2O4(g) at 300 K is kept in a closed
(c) sp to sp (d) sp to sp3. container under one atmosphere. It is heated
3. The AsF5 molecule is trigonal pyramidal. to 600 K when 20% of N2O4(g) decomposes to
The hybrid orbitals used by the As atoms for NO2(g). The resultant pressure is
bonding are (a) 1.2 atm (b) 2.4 atm
(c) 2.0 atm (d) 1.0 atm
(a) dx2–y2, dz2, s, px, py (b) dxy, s, py, pz
(c) s, px, py, pz , dz2 (d) dx2–y2, s, px, py, pz 9. In Kjeldahl’s method for the estimation of N2,
potassium sulphate and copper sulphate are
4. Mg2C3 reacts with water forming propyne.
used. The function of them is
C34– has I. Potassium sulphate raises the of H2SO4
(a) two sigma and two pi bonds and thus, ensures complete reaction.
(b) three sigma and one pi bonds II. Copper sulphate acts as catalyst.
(c) two sigma and one pi bonds III. Potassium sulphate acts as catalyst and
(d) two sigma and three pi bonds. copper sulphate raises the of H2SO4.

chemistry today | January ‘15 11

Which of these is correct? 17. H3BO3 is
(a) Only III (b) Both I and II (a) monobasic and weak Lewis acid
(c) Only II (d) None of these. (b) monobasic and weak Bronsted acid
10. The signs for DH, DS and DG for the freezing of (c) monobasic and strong Lewis acid
liquid water at –10°C respectively are (d) tribasic and weak Bronsted acid.
(a) +, –, + (b) –, –, 0 18. A ∆ H2 O
→ B
 + C + D; D  → E.
(c) –, +, – (d) –, –, – Colourless salt Gas
11. To which orbit the electron in the hydrogen Gas ‘C’ turns solution ‘E’ milky. ‘B’ burns with
atom will jump on absorbing 12.1 eV of blue flame. ‘A’ also decolourises MnO4–/H+.
energy? A, B, C, D and E respectively are
(a) II orbit (b) III orbit (a) CaC2O4, CO, CO2, CaO, Ca(OH)2
(c) IV orbit (d) V orbit (b) CaC2O4, CO2, CO, CaO, Ca(OH)2
12. Which pair of elements belongs to same group? (c) CaCO3, CO, CO2, Ca(OH)2, CaO
(a) Elements with atomic no. 17 and 38. (d) CaOCl2, Cl2, O2, CaO, Ca(OH)2
(b) Elements with atomic no. 20 and 40. 19. Which of the following salts is sparingly soluble
(c) Elements with atomic no. 17 and 53. in water?
(d) Elements with atomic no. 11 and 33. (a) BeSO4 (b) MgSO4
13. The self ionisation constant for pure formic acid, (c) CaSO4 (d) BaSO4
K = [HCOOH2+][HCOO–] has been estimated 20. Which is most stable out of the following?
as 10–6 at room temperature. The density of (a) [Be(H2O)4]2+ (b) [Mg(H2O)4]2+
formic acid is 1.22 g cm–3. The percentage (c) [Ca(H2O)4]2+ (d) [Sr(H2O)4]2+
dissociation of formic acid is
section - ii
(a) 0.002 % (b) 0.004 %
One or More Options Correct Type
(c) 0.006 % (d) 0.008 %
14. The compound X (C5H8) reacts with This section contains 5 multiple choice questions. Each
ammoniacal AgNO3 to give a white precipitate question has four choices (a), (b), (c) and (d), out of which
and on oxidation with hot alkaline KMnO4 ONE or MORE are correct.
gives the acids, (CH3)2CHCOOH. Therefore, X 21. The dissociation of ammonium carbamate may
is be represented by the equation,
(a) CH2 CHCH CHCH3 NH2COONH4(s) 2NH3(g) + CO2(g)
(b) CH3(CH2)2C CH DH° for the forward reaction is negative. The
(c) (CH3)2CH C CH equilibrium will shift from right to left if there
(d) (CH3)2C C CH2 is
15. Le Chatelier’s principle is valid for (a) a decrease in pressure
(a) formation of molasses (b) an increase in temperature
(b) rectification of dilute alcohol (c) an increase in the concentration of ammonia
(c) manufacture of H2SO4 by Contact process (d) an increase in the concentration of carbon
(d) manufacture of acid by vinegar process. dioxide.
16. (C5H5)– is a/an 22. Which of the following statements is/are correct?
(a) non-aromatic compound (a) Alkali metals are better reducing agents
(b) anti-aromatic compound than alkaline earth metals.
(c) aromatic compound (b) SF6 is well known but SH6 is not known.
(d) sometimes behaves as an aromatic and (c) BCl3 is a stronger Lewis acid than BF3.
sometimes as a non-aromatic compound. (d) Boron forms B3+ ions.

12 chemistry today | January ‘15

23. A gas described by van der Waals equation hydrogen atoms. Rotation around C C single bond
(a) behaves similar to an ideal gas in the limit results into infinite number of spatial arrangements
of large molar volumes called conformational isomers.
(b) behaves similar to an ideal gas in the limit Repulsive interaction between the electron clouds
of large pressures which affects the stability of a conformation is
(c) is characterised by van der Waals called torsional strain. Magnitude of torsional strain
coefficients that are dependent on identity depends upon the angle of rotation around C C
of the gas bond called dihedral angle.
(d) none of the above is correct. 26. Which of the following statements is correct?
24. Which of the following are correct? (a) Ethane has two conformations of which
1. O3
staggered conformation is more stable than
(a) the eclipsed conformation.
2. Zn, H2O
H H (b) Ethane has an infinite number of
OHC CH2CH2CH2 CHO conformations of which eclipsed
O conformation is more stable than the
C6H5C OOH staggered conformation.
(b) H H
CH2Cl2 (c) Ethane has an infinite number of
H H O conformations of which staggered
KMnO4 conformation has the maximum energy.
(c) HH (d) Ethane has an infinite number of
Cold dilute alkaline
H H solution conformations of which the staggered
HO OH conformation is possessed by majority of
(d) –
OH , heat the molecules at room temperature.
O O 27. In the following structures, which two forms

O CCH2CH2CH2C O – are staggered conformation of ethane?
25. The correct statement(s) concerning the H
structures E, F and G is (are)
(E) (F) (G) H
(a) E, F and G are resonance structures. (1) (2)
(b) E, F and E, G are tautomers. H
(c) F and G are geometrical isomers. H H
(d) F and G are diastereomers. H H
section - iii H H H
Paragraph Type
(3) (4)
This section contains 2 paragraphs each describing
theory, experiment, data, etc. Six questions relate to two (a) 1 and 4 (b) 2 and 3
paragraphs with three questions on each paragraph. (c) 1 and 2 (d) 1 and 3
Each question of a paragraph has only one correct 28. The dihedral angle between the hydrogen atoms
answer among the four choices (a), (b), (c) and (d).
of two methyl groups in staggered conformation
Paragraph for Questions 26 to 28 of ethane is
Ethane molecule contains a carbon–carbon single (a) 120° (b) 60°
bond with each carbon atom attached to three (c) 90° (d) 180°

chemistry today | January ‘15 13

Paragraph for Questions 29 to 31 section - iV
In case of mechanical work if the pressure is not Matching List Type
constant at every stage of compression, but it This section contains 3 multiple choice questions. Each
changes in number of finite steps, work done on the question has matching lists. The codes for the lists have
gas will be summed over all the steps and will be choices (a), (b), (c) and (d), out of which ONLY one is
equal to –SPDV. correct.
If the pressure is not constant but changes
32. Match the change of pressure or temperature
during the process such that it is always
given in List I with the description given in
infinitesimally greater than the pressure of the
List II and select the correct answer using the
gas, then, at each stage of compression, the
code given below the lists :
volume decreases by an infinitesimal amount, dV.
List I List II
In such a case we can calculate the work done on P. P is increased 1. Solubility of KCl in
the gas by the relation, H2O is increased.
Vf Q. P is decreased 2. Solubility of gas in
w = − ∫ Pex dV H2O is increased.
Vi R. T is increased 3. Dissociation of PCl5
Such processes are called reversible processes. is increased.
Processes other than reversible processes are known S. T is decreased 4. Exothermic reaction
as irreversible processes. moves in forward
29. The work done during the expansion of a gas
from a volume of 4 dm3 to 6 dm3 against a
(a) 4 2 1 3
constant external pressure of 3 atm is (1 L atm
(b) 2 3 1 4
= 101.3 J)
(c) 3 1 2 4
(a) – 6 J (b) – 608 J (d) 2 3 4 1
(c) + 304 J (d) – 304 J
33. Match the name of the compound given in
30. One mole of an ideal gas is allowed to expand List I with its formula given in List II and select
freely and adiabatically into vacuum until its the correct answer using the code given below
volume has doubled. The expression which is the lists :
not true about the given statement is List I List II
(a) DH = 0 (b) DS = 0 P. Borax 1. SiC
(c) DU = 0 (d) W = 0 Q. Carborundum 2. Na2B4O7.10H2O
R. Borazine 3. Na2SiO3
31. 1.0 mol of a monoatomic ideal gas is expanded
S. Water glass 4. B3N3H6
from state (1) to state (2) as shown in the
(a) 2 1 4 3
Calculate the work done for the expansion of
(b) 3 1 2 4
gas from state (1) to (c) 1 4 2 3
2.0 State (1)
state (2) at 298 K. (d) 4 2 1 3
(a) –1786.2 J

34. Match the reactants and reagents given in

(b) 1717.46 J List I with the final products given in List II and
1.0 State (2)
(c) 1.71746 J select the correct answer using the code given
(d) –1717.46 J V(L) below the lists :

14 chemistry today | January ‘15

List I List II 39. Assertion : Singlet carbene has a linear
R H structure.
P. R C C R 1. C C Reason : The carbon atom in singlet carbene is
PtO2 or (C6H5)3P]3 H R

Q. R C C R 2. RCH2CH2R 40. Assertion : The lower the concentration of D.O.

Li-NH3, C2H5OH
the more polluted is the water.
Reason : Oxygen is consumed by microbes for
Pd/CaCO3 R R the decomposition of organic matter present in
R. R C C R 3. C C
H H water.
O section - Vi
BH3,THF Integer Value Correct Type
S. R C C R 4. RCH2CR
This section contains 10 questions. The answer to each
P Q R S question is a single digit integer, ranging from 0 to 9
(a) 1 3 2 4 (both inclusive).
(b) 2 1 4 3 41. In a constant volume calorimeter, 3.5 g of a gas
(c) 2 1 3 4 with molecular weight 28 was burnt in excess
(d) 1 2 3 4 oxygen at 298.0 K. The temperature of the
calorimeter was found to increase from 298.0 K
section - V
to 298.45 K due to the combustion process.
Assertion-Reason Type
Given that the heat capacity of the calorimeter is
In the following questions, a statement of assertion is 2.5 kJ K–1, the numerical value for the enthalpy
followed by a statement of reason. Mark the correct of combustion of the gas in kJ mol–1 is
choice as : 42. A 4 : 1 molar mixture of He and CH4 is contained
(a) If both assertion and reason are true and reason is in a vessel at 10 atm pressure. Due to a hole in
the correct explanation of assertion. the vessel the gas leaks out. The ratio of rate of
(b) If both assertion and reason are true but reason is diffusion of He to that of CH4 is
not the correct explanation of assertion.
(c) If assertion is true but reason is false. 43. A hydrocarbon W(C6H10) gave a white
(d) If both assertion and reason are false. precipitate with ammoniacal silver nitrate.
Oxidation of W with hot alkaline KMnO4 gave
35. Assertion : N2 and NO+ both are diamagnetic 2,2-dimethylpropanoic acid. The number of
substances. sp2 hybridised C-atoms in W is
Reason : NO+ is isoelectronic with N2.
44. The silver salt of an alkyne contains 67.08 % of
36. Assertion : Helium shows only +ve deviations silver. If no other functional group is present,
from ideal behaviour. then number of carbon atoms in alkyne is
Reason : Helium is an inert gas.
45. Among the following, the number of underlined
37. Assertion : The O O bond length in H2O2 is elements having +6 oxidation state is
shorter than that of O2F2. PO43–, H2S2O8, H2SO5, OF2, Cr2O72–, CrO5
Reason : H2O2 is an ionic compound. 46. Compounds X and Y are obtained by the
38. Assertion : Glycerol can be purified by reaction of Cl2 with cold and dil. NaOH and
distillation under reduced pressure. compounds X and Z are formed with hot and
Reason : Liquid organic compounds are conc. NaOH. The oxidation state of the cation
purified by distillation. in Y is

chemistry today | January ‘15 15

47. X has exceptional outer electronic configuration 3. (c) : AsF5 has sp3d hybridisation with trigonal
as 4d10 5s0. Period to which it belongs is bipyramid geometry in which one ‘dz2’ one ‘s’
48. Emission transitions in the Paschen series end and three ‘p’ orbitals are involved.
at orbit n = 3 and start from orbit n and can be 4. (a) : Mg2C3 + 4H2O CH3 C CH
represented as

1 1 :C C  C :

: :
frequency υ = 3.29 × 1015 (Hz)  2 − 2  .  
3 n  It has two s and two p bonds.
The value of n if the transition is observed at
5. (a) : % ratio of C : H = 6 : 1 and C : O = 3 : 4
1285 nm is
\ % at. wt. ratio of C : H : O = 6 : 1 : 8
49. When excess NaOH solution is added to Pb2+ 6 40
salt a clear solution (Y) is obtained. When H2O2 \ % C = × 100 = 40 , = 3.33
15 12
is added to (Y) a black ppt., (Z) is obtained. The 1 6.66
change in oxidation state of Pb is % H = × 100 = 6.66 , = 6.66
15 1
50. 1 mole of NO2 and 2 moles of CO are introduced 8 53.3
in a 1 litre closed vessel to get the following % O = × 100 = 53.3 , = 3.33
15 16
equilibrium. \ Simplest ratio of C : H : O = 1 : 2 : 1
NO2(g) + CO(g) NO(g) + CO2(g) i.e., CH2O so, the compound is HCHO.
At equilibrium point 25% of the initial amount 6. (c) : NaHCO3 is acidic and decomposed by
of CO(g) was reacted, then Kc for the above NaOH forming Na2CO3
reaction is 1/x. The value of x is NaHCO3 + NaOH → Na2CO3 + H2O
solutions Acid Base

1. (c) : 80 mL of 0.20 M HCl = 80 × 0.2 7. (a)

= 16 millimoles 8. (b) : N2O4(g) 2NO2(g)
120 mL of 0.15 M KOH = 120 × 0.15 Initial 1 0
At equilibrium (1 – 0.2) 2 × 0.2
= 18 millimoles
Total moles at equilibrium = (1 – 0.2 + 0.4) = 1.2
As M1V1 < M2V2
(HCl) (KOH) pV = nRT
Thus, resulting solution is basic containing KCl p2V2 n2 RT2
and unreacted KOH, p1V1 n1RT1
KOH + HCl → KCl + H2O p2 × V 1.2 × R × 600
M2V2 − M1V1 18 − 16 1×V 1 × R × 300
[KOH]unreacted = = p2 = 2.4 atm
V1 + V2 200
= 0.01 M 9. (b) 10. (d)
KCl formed = HCl used 11. (b) : Energy of electron in the nth orbit of
= 16 millimoles 13.6
H-atom is, En = − 2 eV
= 16 × 10–3 mol in 200 mL or n
0.2 L solution \ E1 = – 13.6 eV (as n = 1)
16 × 10−3 After absorbing 12.1 eV, the energy will be
\ [KCl] = = 0.08 M = – 13.6 eV + 12.1 eV = – 1.5 eV
0. 2 L
O 13.6
Thus, − 2
= − 1.5 eV ⇒ n2 = 9 or n = 3
2. (c) : CH3 C NH2 CH3 C N n
2 sp sp Thus, electron will jump to III orbit.

16 chemistry today | January ‘15

12. (c) : Elements with atomic no. 17 (Cl) and 53 At large molar volumes,
(I) are present in the same group. a
P + 2 ≈ P and Vm − b ≈ Vm
13. (b) : Given density of formic acid = 1.22 g cm–3 Vm
\ Weight of formic acid in 1 litre solution thus, behaves as an ideal gas and van der Waals
= 1.22 × 103 g coefficients a and b are dependent upon the
1.22 × 103 nature of gas.
Thus, [HCOOH] = = 26.5 M 24. (a, b, c, d)
Since in case of auto-ionisation, 25. (b, c, d) : E and F; and also E and G differ in
[HCOOH2+] = [HCOO–] and position of atom (H), so these are tautomers
[HCOO–][HCOOH2+] = 10–6 (not resonating structures). F and G are
[HCOO–] = 10–3 geometrical isomers. Geometrical isomers are
Now, % dissociation of HCOOH also diastereomers.
[HCOO− ] 10−3 26. (d) 27. (c) 28. (b)
= × 100 = × 100 = 0.004 %
[HCOOH] 26.5 29. (b) : Work done = –Pext × DV = –3(6 – 4) L atm
= –6 L atm = –6 × 101.3 J = –608 J
14. (c)
30. (b) : Pext = 0 \ W = –PextDV = 0
15. (c) : Le Chatelier’s principle makes a qualitative
For adiabatic process, q = 0 \ DU = W = 0
prediction about the effects of change in
For ideal gas, U = f (T)
conditions on equilibrium. Only manufacture
of H2SO4 (Contact process) involves reversible As dU = 0, \ dT = 0
reaction, 2SO2 + O2 2SO3. dH = d(U + PV) = dU + d(RT)
= dU + RdT = 0 + 0 = 0
16. (c) : H – For isothermal process,

DST = R ln ≠0
Cyclopentadienyl anion (planar)
(C5H5)–, 6-electrons 31. (d) : The given diagram represents isothermal
(aromatic) expansion of the ideal gas from pressure
17. (a) 2.0 atm to 1.0 atm at 298 K.
18. (a) : ‘A’ decolourises MnO4–/H+ thus, ‘A’ is P
CaC2O4. w = −2.303 nRT log 1
CaC2O4 → CO + CO2 + CaO
(A) (B) (C) (D) = −2.303 × 1 mol × 8.314 J K −1mol −1 ×
‘B’ burns with blue flame. 2
298 K × log
CaO + H2O → Ca(OH)2 1
(D) (E) = –2.303 × 8.314 × 298 × 0.3010 J
Ca(OH)2 + CO2 CaCO3 +H2O = –1717.46 J
(E) Milky 32. (b) 33. (a) 34. (c) 35. (b)
19. (c) 36. (b) : In helium atom (small in size), the
20. (a) : Smaller the size of cation, larger is the intermolecular forces of attraction can be
degree of hydration, hence, larger is the stability neglected, so that van der Waals equation
of hydrated ion. becomes P(V – b) = RT or PV = RT + Pb.
21. (b, c, d) 22. (a, b, c) 37. (d) : The O O bond length in H2O2 is
23. (a, c) : van der Waals equation is given as longer than in O2F2 and H2O2 is a covalent
 n2 a 
 P +  (V − nb) = nRT 38. (b) : Glycerol decomposes at its normal boiling
 V2  point.

chemistry today | January ‘15 17

39. (d) : Singlet carbene has a bent structure and 45. (4) : PO43– → x + 4(–2) = –3, ⇒ x = +5
the carbon is sp2 hybridised. H2S2O8 → 2(+1) + 2x + 2(–1) + 6(–2) = 0
40. (a) ⇒ x = +6 (two oxygen atoms with peroxide
41. (9) : Given, Cv = 2.5 kJ K–1 = 2500 J K–1 linkage).
DT = T2 – T1 = 298.45 – 298 = 0.45 K H2SO5 → 2(+1) + x + 2(–1) + 3(–2) = 0
DH due to combustion of 3.5 g of gas ⇒ x = +6 (two oxygen atoms with peroxide
= Cv × DT linkage).
= 2500 × 0.45 = 1125 J OF2 → x + 2(–1) = 0, ⇒ x = +2
Given, molecular weight of gas = 28 Cr2O72– → 2x + 7(–2) = –2, ⇒ x = +6
1 mol of gas = 28 g CrO5 → x + 4(–1) + (–2) = 0, ⇒ x = +6
Hence, DH due to combustion of 1 mole of gas (four oxygen atoms with peroxide linkage).
1125 46. (1) : Cl2 + 2NaOH NaCl + NaClO + H2O
= × 28 = 9000 J mol −1 (cold, dil.) (X) (Y)
3. 5
\ DH in kJ mol–1 = 9 kJ mol–1 3Cl2 + 6NaOH 5NaCl + NaClO3 + 3H2O
(hot) (X) (Z)
42. (8) : In a 4 : 1 molar ratio of He and CH4, In Y, i.e., NaClO, the cation is Na+,
4 \ The oxidation state of Na is +1.
the partial pressure of He = × 10 = 8 atm
5 47. (5) : The exceptional outer electronic
and the partial pressure of CH4 configuration suggests that the expected
1 configuration of X is 4d8 5s2. Thus it belongs to
= × 10 = 2 atm
5 5th period.
According to Graham’s law of effusion,
c 3.0 × 108 m s −1
rHe P MCH 8 16 48. (5) : υ = =
= He × 4
= × = 8 :1 = 8 λ 1285 × 10−9 m
rCH PCH MHe 2 4
4 4 1 1 
= 3.29 × 1015  3 − 2 
43. (0) : 3 n 
white ppt. indicates 1 1 3.0 × 108 1
or, = − ×
the presence of 2 −9
Hot alkaline [O]
triple bond at the
n 9 1285 × 10 3.29 × 1015
terminal position 1
(CH3)3C COOH = 0.111 – 0.071 = 0.04 =
2,2-Dimethylpropanoic acid or n2 = 25 or n = 5.
Thus, the structural formula of W is 49. (2) : Pb2+ + excess NaOH [Pb(OH)4]2–
sp3 (Y) soluble
CH3 H2O2 +4
sp3 sp3 sp sp PbO2
CH3 C C CH (Z) black ppt.
CH3 50. (3) : NO2(g) + CO(g) NO(g) + CO2(g)
Initial moles 1 2 0 0
At equil. (1–0.5) (2–0.5) 0.5 0.5
44. (4) : Let the structure of silver salt of alkyne be At equilibrium 0.5 mole of CO(g) was reacted.
R C C Ag As volume of the reaction vessel is one litre, so
The mass of silver salt which contains 108 g at equilibrium,
100 [NO2] = 0.5 M, [CO] = 1.5 M
of Ag = × 108 = 161.0
67.08 [NO] = [CO2] = 0.5 M
Thus, R + 12 + 12 + 108 = 161 [NO][CO2 ] 0.5 × 0.5 1
⇒ Kc = = =
R = 29 or R = C2H5 [NO2 ][CO] 0.5 × 1.5 3
So, number of carbon atoms in alkyne = 4. nn

18 chemistry today | January ‘15

Y U ASKED Physical properties
Reddish brown liquid

WE ANSWERED Acidity (pH)

Viscosity (cSt)
20–100 at 40°C
Do you have a question that you just can’t get Starts boiling below
Boiling curve
answered? 100°C
Use the vast expertise of our mtg team to get to the Auto ignition Approximately above
temperature 500°C
bottom of the question. From the serious to the silly,
Specific gravity
the controversial to the trivial, the team will tackle 1.070–1.090 at 25°C
the questions, easy and tough.
Vapour pressure Similar to water
The best questions and their solutions will be printed
Odour Pleasant-smoky aroma
in this column each month.
Chemically, pyroligneous acid consists of a
Q1. Establish Born-Haber cycle for LiCl crystal water, water-soluble organic compounds and
and also calculate lattice energy with the water-insoluble organic compounds.
help of Born-Haber cycle. The principal components of pyroligneous
– Parth Savaliya acid are acetic acid, acetone and methanol.
Ans. Born-Haber cycle for LiCl is shown as : It was once used as a commercial source for
H°lattice = ? –
acetic acid. In addition, the ‘wood vinegar’
LiCl(s) Li(+g) + Cl(g)
often contains 80-90% water along with some
200 organic compounds. Some important
H°f (–410) HIP
° Heg
(+520) (–350) applications of pyroligneous acid are in the
1 field of agriculture, swine and poultry culture
H°sub (+161) + –
2 H°d (+122)
Li(s) + –Cl Li(g) + Cl(g) and floriculture.
2 2(g)
(Enthalpy changes are given in kJ mol–1) Q3. Why is SiCl4 a weaker Lewis acid than SiF4?
– Rajat Gupta, Mumbai
DH°f = DH°sub + DH°d + DH°IP + DH°eg + DH°lattice Ans. Unlike carbon, silicon atom being large in size
–410 = +161 + 122 + 520 + (–350) + DH°lattice can expand its covalency beyond 4.
Lewis acid-base reaction of SiF4 with two F–
DH°lattice = – 863 kJ mol–1
ions is shown as :
Q2. What is pyroligneous acid? F F F 2–
– Rehan Rizvi, Vaishali, Bihar
Si F + 2F– F Si F
Ans. Pyroligneous acid, also called wood vinegar, F F F F
is the crude condensate produced from the
Acidic strength increases in the order :
distillation of smoke generated in the process
SiI4 < SiBr4 < SiCl4 < SiF4
of making charcoal. The word ‘pyroligneous’ due to increase in the electron-withdrawing
comes from ‘pyrolysis’ involving wood and power of the halogen from I to F.
‘lignin’ as one of the components in wood. This order is reverse of that for BX3.
Physical properties of pyroligneous acid are nn

chemistry today | January ‘15 19

Dear students, this is the last part of p-block elements. Hope you will enjoy reading it. Wish you all a very happy new year.
Stay well, keep yourself healthy. Take care!!
*Arunava Sarkar

Important Reactions of SO2 It is in fact an indirect way of reduction. This is also

SO2 is both oxidising and reducing in nature. believed to occur.
Because in SO2, oxidation state of sulphur is +4 and
Cl2 + H2O 2HCl + [O] A possible
it can either increase or decrease it. Here are some combination
important reactions which depict both oxidising SO2 + 2H2O H2SO4 + 2[H]
and reducing nature of SO2.
From the previous demonstration,
In SO2, sulphur has an oxidation number of +4
0 –2 (1) + (2) + (3) ⇒
which can either decrease (mainly S, S(in H2S)) or Cl2 + SO2 + 2H2O 2HCl + H2SO4
increase (H2SO4). So, SO2 can act both as oxidising Two products
and reducing agent. are both acids

Reducing Nature of SO2 This is an example where both the products are
SO2(g) + 2H2O(l) H2SO4 + 2[H] acids.
This nascent hydrogen is responsible for the Example 2 : SO2 is passed through acidified KMnO4
reducing property of SO2. Moreover, this is also solution.
responsible for the bleaching action of SO2. Now first objective is to produce nascent oxygen.
Coloured substance +[H] Decolourised 1. 2KMnO4 + 3H2SO4
However, this bleaching is temporary as when the K2SO4 + 2MnSO4 + 3H2O + 5[O]
decolourised substance is kept in open air, it gets 2. SO2 + H2O + [O] H2SO4
oxidised and gains its previous colour infact its own (1) + [(2) × 5] ⇒
colour. +7 +4
How SO2 carries out the reduction process? 2KMnO4 + 5SO2 + 2H2O
Pink violet
Example 1 : SO2 is passed through Cl2 water. +2 +6
Where is the K2SO4 + 2MnSO4 + 2H2SO4
1. Cl2 + H2O HCl + HOCl Colourless
use of nascent
2. HOCl HCl + [O] hydrogen? How
3. SO2 + [O] + H2O H2SO4 There is a notable point here that though it is said
is it showing
the reducing that ‘acidified KMnO4 solution’ but at the final
SO2 is oxidised. Where does property of SO2? balanced reaction there is no acid at the left hand
this nascent oxygen come from?
From Cl2? Yes, so, Cl2 is reduced!! side. Why is this?
* Institute of Chemistry (IOC)- Asansol, Durgapur, Dhanbad, Burdwan, Kolkata, Jamshedpur, Bokaro, Patna 09732313208

20 chemistry today | January ‘15

Example 3 : In the similar fashion, it is said that What happens when SO2 is passed through
the orange colour of K2Cr2O7 is decolourised when lime water?
SO2 is passed through it. Ans.: SO2 + Ca(OH)2 CaSO3 + H2O
K2Cr2O7 + H2SO4 + 3SO2 Insoluble in water
Orange CaSO3 + H2O + SO2 Ca(HSO3)2
K2SO4 + Cr2(SO4)3 + H2O Soluble in water
Green € Addition reactions of SO2:
Example 4 : What happens when SO2 is passed charcoal
– SO2 + Cl2 SO2Cl2
through ferric sulphate solution?
Sulphuryl chloride
Now, here a little bit change in the strategy is
required. As the salt already contains sulphate – SO2 + PCl5 SOCl2 + POCl3
Thionyl Phosphoryl
unit so its reaction with H2SO4 cannot be written. chloride chloride
So here direct and normal reduction process is
Oxoacids of Sulphur
As obvious, the most important is H2SO4.
1. SO2 + 2H2O H2SO4 + 2[H]
Industrially H2SO4 is prepared through Contact
2. Fe2(SO4)3 + 2[H] 2FeSO4 + H2SO4
process. Look at the following aspects :
(1) + (2) ⇒
€ Optimum temperature → 720 K
SO2 + Fe2(SO4)3 + 2H2O 2FeSO4 + 2H2SO4 € Optimum pressure → 2 bar
Oxidising Nature of SO2 € Removal of impurities
As already said, SO2 is oxidising in nature also. Structure of H2SO4 is as follows :
The following reactions demonstrate that. O
+4 –2 0
1. SO2 + 2H2S 2H2O + 3S  S
and it also shows H-bonding in between the
Reduction molecules :
2. When SO2 is passed through SnCl2 solution O HO O
added with dil. HCl, then SnCl4 is produced. HO S
+2 +4 HO O HO O
2SnCl2 + 4HCl + SO2 2SnCl4 + 2H2O + S
This is why H2SO4 has high density and high boiling
0 +4 +1 +2 point.
3. 4K + 3SO2 K2SO3 + K2S2O3
0 +4 +2 +2 –2 H2SO4 is a strong oxidising agent. For example,
3Fe + SO2 2FeO + FeS H2SO4  H2O + SO2 + [O]
Add to Your Knowledge C + 2[O] CO2
What happens when in the potassium iodate Some Important Reactions of H2SO4
solution SO2 gas is passed?
COOH conc. H2SO4
Ans.: 1. 2KIO3 + 5SO2 + 4H2O 1. (i) CO + CO2 + H2O
2KHSO4 + I2 + 3H2SO4 COOH
conc. H2SO4
2. I2 + SO2 + 2H2O 2HI + H2SO4 (ii) HCOOH CO + H2O
(1) + (2) ⇒ conc. H2SO4
2KIO3 + 6SO2 + 6H2O (iii) C12H22O11 12C + 11H2O
2HI + 4H2SO4 + 2KHSO4 All the above reactions depict that H2SO4 is a
dehydrating agent.

chemistry today | January ‘15 21

2. (i) K4[Fe(CN)6] + 3H2SO4(dil.) € H2S2O8 : Same logic.
2K2SO4 + FeSO4 + 6HCN O O
(ii) K4[Fe(CN)6] + 6H2SO4 (conc.) + 6H2O
2K2SO4 + 3(NH4)2SO4 + FeSO4 + 6CO
Add to Your Knowledge
Exception to the above strategy will be H2S2O3
€ K4[Fe(CN)6]  FeC2 + 4KCN + N2
which is
€ K4[Fe(CN)6] strong  Fe + 4KCN + (CN)2 S
S [This can also be anticipated as the
Pseudo HO O normal strategy will violate symmetry.]
€ 3KClO3 + 3H2SO4 
3KHSO4 + HClO4 GROup 17 elemeNtS
+ 2ClO2 + H2O Some common sources of halogen elements :
Structures of other oxoacids can be drawn with the
following strategy :
€ Cryolite : Na3AlF6
€ With S atom put a single bonded —OH € Fluorspar : CaF2
group and double bonded oxygen at first.
€ Fluorapatite : CaF2·3Ca3(PO4)2
€ Then, if required increase O group as well
as —OH group. Chlorine
€ Rock salt : NaCl
€ Check the oxidation number obtained
through the calculation with that obtained € Carnallite : KCl·MgCl2·6H2O
through the structure. Bromine
€ From NaBr, KBr of sea water
€ H2SO3 : S
HO +4 € Coppice under the sea (some algaes infact)
OH € Caliche or chile saltpetre which is mainly
O sodium nitrate containing iodine in the form
H2SO5 : of sodium iodate (NaIO3). Amount of iodine
€ S
O O O H present is very less, nearly 0.2%.
OH ‘Halogen’ means salt forming elements or salt formers.
It won’t be +8. See here
‘Halo’ = sea salts, ‘genes’ = producing. Halogens are
O O quite reactive, fluorine being the most reactive
€ H2S2O6 : HO S S OH Step 1 is called ‘super halogen’. Fluorine is thirteenth
most abundant element on the earth’s crust.
O O Astatine (At) is that halogen which is radioactive
No more ‘O’ left. in nature.
O O In general, colour of the halogen elements :
Therefore, HO S S OH Step 2 – F2 gas is light yellow.
– Cl2 gas is yellow-green.
O O – Br2 (both in gaseous and liquid state) is dark
€ H2S2O7 : From the above structure red brown.
O O – I2 (gas) is violet. I2 (solid) is black.
Different colours are due to absorption of different
HO S O S OH wavelengths of light and promotion of electron to
O O different energy levels.

22 chemistry today | January ‘15

Different Oxidation States € Enthalpy of bond dissociation : Due to
Fluorine does not have vacant d-orbitals, it cannot smaller size, fluorine atoms in F2 molecule
extend its oxidation state. It only shows –1 oxidation experience greater amount of repulsion force
state. which naturally helps to dissociate the bond
F(9) → 1s2, 2s2, 2p5 between fluorine atoms. Overall order is :
Cl2 > Br2 > F2 > I2.
€ Halogens are coloured. They absorb the
Only can accept here. energy of a certain wavelength and release its
No tendency of loosing electrons. complementary colour.
However, for the other members (except astatine) For example, fluorine, due to absorption of
the available oxidation states are (available to each violet light emits pale yellow. Reverse is true for
of them) : –1, +1, +3, +5, +7. I2. For the similar kind of reason, Br2 is reddish
brown and Cl2 is greenish yellow.
–1 is of course the main oxidation state.
Cl(17) → 10[Ne] 3s2 3p5 Chemical Reactivity in the light of Oxidising power
(+1) Halogens are electronegative and hence oxidising
in nature. Fluorine being the most electronegative
Releases this one electron to get + 1.
is the most oxidising indeed. Overall the anion
formation process for halogens is as below :
Cl(17)  10[Ne] 3s2 3p5 1
(+3) 1 ∆ BD H ° ∆ eg H °
X2( g ) 2→ X( g ) → X −( g )
Releases one one electron each to get overall
half-filled state as (BD = Bond Dissociation)
and in aqueous solution, finally
Cl(17)  10[Ne] 3s2 3p5 ∆ hyd H °
(+5) X(−g ) 
→ X(−aq)
Releases all five electrons to get Fluorine has large negative value of DhydH° as it
stable ns2 (i.e. 3s2 here) state.
is strongest H-bonding forming agent. Moreover,
Cl(17)  10[Ne] 3s2 3p5 standard reduction potential values of the halogens
are as below :
Releases all electrons to get nearest noble F2 + 2e– → 2F– ; E° = +2.87 V
gas/fully-filled electronic configuration. Cl2 + 2e– → 2Cl– ; E° = +1.36 V
Few important points regarding some common Br2 + 2e– → 2Br– ; E° = +1.09 V
properties of halogen elements : I2 + 2e– → 2I– ; E° = +0.54 V
€ Ionization enthalpy order is : F > Cl > Br > I Some Common evidences of Oxidising power of
€ Electron gain enthalpy order is as follows : Halogens
Cl (–349) > F (–333) > Br (–325) > I (–296)
€ It oxidises even oxygen.
Order is according to the more negative to less +1
negative. F2 + O 2 discharge
€ With the increase in the size, van der Waals liquid air low pressure

force of attraction increases which results € F2 reacts with water to give O2 and O3 both.
into the increase in melting and boiling 2F2 (g) + 2H2O(l) O2(g) + 4HF(aq)
points from fluorine to iodine. This is pertinent {4H+(aq) + 4F–(aq)}
to say that at normal temperature, F2 and Cl2 3F2(g) + 3H2O(l) O3(g) + 6HF(aq)
are gases whereas Br2 is liquid and I2 is solid. {6H+(aq) + 6F–(aq)}

chemistry today | January ‘15 23

0 –2 –1 +2 preparation
€ 2F2(g) + 2NaOH 2NaF + H2O + OF2
OF2 is known as oxygen difluoride. Here, oxygen Preparation of F2 is not that easy due to its
atom is sp3 hybridised. unconventional behaviour. However, following
methods are there in order to prepare fluorine.
Structure is . . ..
€ Moissan method
1p O
14 103°
€ Dennis method
12 € Whytlaw and Gray method
Structure of O2F2 is O m F moissan method
F O 8 pm
15 € Electrolytic cell : Electrolytic cell here is a
O2F2 is known as dioxygen difluoride. O2F2 is U-tube made of Pt-Ir alloy. Two mouths of
quite unstable. However, both OF2 and O2F2 the U-tube is closed with two corks made
can be used as strong fluorinating agents. of fluorspar (CaF2). Through these mouths,
Cl2 electrodes made of Pt-Ir alloy again, are inserted
Cl2 is oxidising because in its aqueous solution, it through the cork.
can generate nascent oxygen. € Electrolyte : KHF2 dissolved in anhydrous HF.
Cl2 + H2O HCl + HOCl € Reactions involved :
Hypochlorous acid HF + KF KHF2
HOCl HCl + [O] KHF2 K+ + HF2–
This nascent oxygen is responsible for the HF2– HF + F –
oxidising power as well as bleaching action of Cl2. Cathode reactions : 2K+ + 2e– 2K
– –
Few examples showing the oxidising properties of 2K + 2HF2 2KF + H2↑ + 2F
Cl2 : Anode reaction : 2F– F2 + 2e–
Overall : 2KHF2(l) F2(g) + H2(g) + 2KF
Example 1 : Cl2 + H2O 2HCl + [O] … (1)
2FeSO4 + H2SO4 + [O] Fe2(SO4)3 + H2O Q. What happens when in cold NaOH solution,
(1) + (2) ⇒ … (2) F2 gas is passed?
2FeSO4 + Cl2 + H2SO4 2HCl + Fe2(SO4)3 Ans.: In the cold, aqueous NaOH if F2 gas is passed,
then OF2 is produced.
Example 2 : Cl2 + H2O 2HCl + [O] ... (1) 2NaOH + 2F2 OF2 + 2NaF + H2O
I2 + 5[O] I2O5 ... (2) Now, in OF2, oxidation number of oxygen is
I2O5 + H2O 2HIO3 ... (3) +2. It is a powerful oxidising agent. When OF2
[(1)× 5] + (2) + (3) ⇒ reacts with water at normal temperature, it
5Cl2 + 5H2O + I2 + 5[O] + I2O5 + H2O gives HF and O2.
10HCl + 5[O] + I2O5 + 2HIO3 Oxidation

⇒ 5Cl2 + I2 + 6H2O 2HIO3 + 10HCl +2 –2 0

OF2 + H2O O2 + 2HF
After this, in case of Br2 or I2, oxidising power is
highly reduced. Reduction
Reaction between Br2 and H2O is still possible as Here, both O2+ and O2– go to O 2. This reaction
shown below : is known as comproportionation reaction.
Br2 + H2O 2HBr + [O]
Q. Prove that, oxidising power of F2 is more than
But the reaction between I2 and H2O is non-
(i) KClO3, (ii) K2SO4, and (iii) K2CO3.
spontaneous and in acidic solution rather, reverse Ans.:
reaction is found to occur. +5 0 +7 –1
(i) KClO3 + F2 + H2O KClO4 + 2HF
4I–(aq) + 4H+(aq) + O2(g) 2I2(s) + 2H2O(l)
Potassium perchlorate

24 chemistry today | January ‘15

+6 0 +7 –1 Ans.: In a conical flask KMnO4 crystal is taken and
(ii) 2K2SO4 + F2 K2S2O8 + 2KF dropwise conc. HCl is added into it. Cl2 gas is
2KMnO4 + 16HCl
+4 +5 –1
(iii) 2K2CO3 + F2 K2C2O6 + 2KF 2KCl + 2MnCl2 + 8H2O + 5Cl2↑
Potassium Q. What happens when a mixture of NaCl, MnO2
percarbonate and conc. H2SO4 is heated?
Q. What happens when NH4F is heated? Ans.: 2NaCl + 2H2SO4 2NaHSO4 + 2HCl
Ans.: 2NH4F NH3 + (NH4)HF2 MnO2 + H2SO4 + 2HCl
Ammonium MnSO4 + Cl2↑ + 2H2O
2NaCl + MnO2 + 3H2SO4
Q. How can you identify fluoride salt? 2NaHSO4 + MnSO4 + Cl2↑ + 2H2O
SiO2/conc. H2SO4
Ans.: Fluoride salt SiF4(g) Q. What do you mean by ‘available chlorine’ from

If a platinum wire with a drop of water at its tip, bleaching powder?
Ans.: Bleaching powder is Ca(OCl)Cl. When
is held in the silicon tetrafluoride gas, then the
bleaching powder reacts with HCl then we get
water drop becomes opaque as wax and this is
chlorine from it. From a 100 part (as per weight)
due to the production of solid silicic acid.
sample of bleaching powder, part of chlorine
e.g., CaF2 + H2SO4 CaSO4 + 2HF
(as per weight) that is obtained is known as
4HF + SiO2 SiF4 + 2H2O
available chlorine. In general, commercially
3SiF4 + 4H2O 2H2SiF6 + Si(OH)4 available bleaching powder has 35% or 37% as
Hydrofluorosilicic acid
available chlorine.
Q. Why the bond dissociation energy of F2 is only
Q. What happens when chlorine reacts with
36 kcal mol–1?
(i) dilute and cold NaOH
Ans.: Size of fluorine atom is very small. F2 molecule
(ii) conc. and hot NaOH?
has a covalent radius of 64 pm. This is why the Ans.: (i) Dilute and cold NaOH reacts with Cl2 to
lone pairs of fluorine atoms strongly repel each give NaCl and NaOCl.
other and make the F — F bond quite weak. 2NaOH + Cl2 NaCl + NaOCl + H2O
Preparation (ii) Conc. and hot NaOH reacts with Cl2 to
Cl2 give NaCl and NaClO3 (sodium chlorate).
In the laboratory, mixture of conc. HCl and MnO2 6NaOH + 3Cl2 5NaCl + NaClO3 + 3H2O
is heated to give Cl2 gas. Q. What happens when chlorine reacts with
1. 2MnO2 + 8HCl 2MnCl3 + Cl2 + 4H2O (i) lime water, (ii) hot lime, (iii) dry lime,
2. 2MnCl3 2MnCl2 + Cl2 (iv) white hot lime?
(1) + (2) ⇒ Ans.: (i) 2Ca(OH)2 + 2Cl2
2MnO2 + 8HCl 2MnCl2 + 2Cl2 + 4H2O CaCl2 + Ca(OCl)2 + 2H2O
⇒ MnO2 + 4HCl MnCl2 + Cl2 + 2H2O hypochlorite
Produced Cl2 has some water vapours and HCl (ii) 6Ca(OH)2 + 6Cl2
gas in it. At first it is passed through water so that 5CaCl2 + Ca(ClO3)2 + 6H2O
HCl vapours get dissolved and then passed through chlorate
conc. H2SO4 to dry it. (iii) Ca(OH)2 + Cl2 40°C-50°C
Q. How can you get Cl2 gas at ordinary (dry) Ca(OCl)Cl + H2O
temperature? (iv) 2CaO + 2Cl2 2CaCl2 + O2↑

chemistry today | January ‘15 25

Q. What happens when chlorine reacts with AgNO3 + HCl AgCl↓ + HNO3
(i) little amount of NH3 AgNO3 + HOCl AgClO + HNO3
(ii) large amount of NH3? 3AgClO 2AgCl + AgClO3
Ans.: (i) With little amount of NH3, an explosive
Q. What happens when Cl2 reacts with
liquid NCl3 is produced.
3Cl2 + NH3 NCl3 + 3HCl↑ (i) Na2SO3 (ii) Na2S2O3?
(ii) With large amount of NH3, ammonium Ans.:
+4 0 +6 –1
chloride and N2 are produced. (i) Na2SO3 + Cl2 + H2O Na2SO4 + 2HCl
8NH3 + 3Cl2 6NH4Cl + N2↑ +2 0
Q. What happens when dry chlorine gas is passed (ii) Na2S2O3 + 5H2O + 4Cl2
over slightly hot silver nitrate? +6 –1
Na2SO4 + H2SO4 + 8HCl
Ans.: In the reaction, white silver chloride, nitrogen
pentoxide and O2 gas are produced. Cl2 is an oxidising agent in both the reactions.
4AgNO3 + 2Cl2 4AgCl + 2N2O5 + O2 Q. Give an example where Cl2 is used as a reducing
Q. What happens when the mixture of calcium agent.
phosphate and carbon is heated with CO and 0 0 +1 –1
Ans.: F2 + Cl2 2ClF
300°C 0 0 +3–1
Ans.: Ca3(PO4)2 + 6CO + 6Cl2 or 3F2 + Cl2 2ClF3
3CaCl2 + 2POCl3 + 6CO2
Q. What happens when Cl2 reacts with
Q. What happens when excess Cl2 is passed (i) potassium manganate
through the iodine suspended in water?
(ii) potassium ferrocyanide?
Ans.: Here, iodine is oxidised to HIO3 and Cl2 is
+6 0 +7 –1
reduced to HCl. Ans.: (i) 2K2MnO4 + Cl2 2KMnO4 + 2KCl
I2 + 5Cl2 + 6H2O 2HIO3 + 10HCl
Solution will turn pink.
Q. What happens when Cl2 is passed through +2
KOH solution? (ii) 2K4[Fe(CN)6] + Cl2
Ans.: 3Cl2 + 6KOH KClO3 + 5KCl + 3H2O 2K3[Fe(CN)6] + 2KCl
Q. What happens when excess amount of silver
Q. What happens when chlorine reacts separately
nitrate is added to the Cl2 water?
with (i) CO, (ii) NO, (iii) SO2? Are they
Ans.: H2O + Cl2 HCl + HOCl
oxidation-reduction reactions?
In chlorine water, both hydrochloric acid and
+2 0 +4 –1
hypochlorous acid are present. So, the following Ans.: (i) CO + Cl2 COCl2
observations are there.
+2 0 +3 –1
(a) HCl will react with AgNO3 to give white (ii) 2NO + Cl2 2NOCl
ppt. of AgCl. +4 0 +6 –1
(b) Excess AgNO3 will react with HOCl to (iii) SO2 + Cl2 SO2Cl2
give silver hypochlorite. Silver hypochlorite, All the above reactions are oxidation-reduction
in disproportionation reaction gives silver as well as addition reactions.
chlorate which is soluble in water.
(c) No amount of Cl2 gas will remain till the Q. Explain the following observation :
end with the formation of HNO3, solution will “A wet blue litmus paper turns red at first with
remain acidic. Cl2 but later gets decolourised.”

26 chemistry today | January ‘15

chemistry today | January ‘15 27
Ans.: Cl2 + H2O HCl + HOCl Q. How can you prepare Br2 from carnallite?
Ans.: Though the formula of carnallite is
This helps the blue litmus paper to turn red. KCl·MgCl2·6H2O but around 1% MgBr2 is
HOCl HCl + [O] present in that. Dissolve carnallite in water and
make it dense through heating, KCl precipitates
This helps to decolourise. out. Filtering the solution, the filtrate thus
Q. Convert : CS2 CCl4 obtained contains mainly MgCl2 and MgBr2.
I2 This filtrate is known as Bittern. Pass Cl2
Ans.: CS2 + 3Cl2 CCl4 + S2Cl2 through this. Br2 vapours are produced. These
Sulphur are collected and get converted to liquid form
on condensation.
Q. What happens when HCl reacts with MgBr2 + Cl2 MgCl2 + Br2↑
K2Cr2O7? Q. What happens when Br2 reacts with
Ans.: K2Cr2O7 + 14HCl (i) cold, dilute NaOH solution
2KCl + 2CrCl3 + 3Cl2 + 7H2O (ii) hot, conc. NaOH solution?
Q. What happens when aqueous solution of Ans.: (i) Br2 + 2NaOH NaBr + NaOBr + H2O
bleaching powder is added to the hot lead (ii) 3Br2 + 6NaOH
acetate solution? 5NaBr + NaBrO3 + 3H2O
Ans.: (CH3COO)2Pb + Ca(OCl)Cl + H2O Q. Give an example which shows bromine is
PbO2  + 2CH3COOH + CaCl2 oxidising in nature.
Brown –2 –1 0
Ans.: H2S + Br2 2HBr + S 
Q. In the laboratory, Cl2 is produced when a
mixture of MnO2 and conc. HCl is heated. I2
Before heating, with the emergence of little Cl2 Q. How can you prepare I2 in laboratory?
a brown colour is also produced. What is that? Ans.: 2KI + MnO2 + 3H2SO4
Ans.: 2MnO2 + 8HCl 2MnCl3 + Cl2 + 4H2O MnSO4 + 2KHSO4 + 2H2O + I2
 Q. Give examples of oxidising and reducing
2MnCl3 2MnCl2+ Cl2
nature of I2.
Br2 Ans.: Oxidising nature :
–2 0 –1 0
Q. In laboratory, how can you prepare pure Br2? H2S + I2 2HI + S
Ans.: (1) In retort, take the mixture of KBr, MnO2 Reducing nature :
and conc. H2SO4. Heat it. Br2 vapours come out 0 +5
and in contact with the flask get condensed and I2 + 10HNO3 2HIO3 + 10NO2 + 4H2O
liquified. GROup 18 elemeNtS
2KBr + MnO2 + 3H2SO4
He, Ne, Ar, Kr, Xe and Rn — these are called ‘noble
MnSO4 + 2KHSO4 + 2H2O + Br2↑
gases’. Earlier they were better known as ‘inert
(2) This Br2 contains the following impurities,
gases’ as it was not into the light that though very
(i) water vapours (ii) Cl2 (iii) I2.
small, still they can react, at least some of them (like
Now mix KBr and ZnO with liquid Br2 and
heat it.
2KBr + Cl2 2KCl + Br2 A few important points for group 18 elements will
2ZnO + 2I2 2ZnI2 + O2 be as below :
O2 does not react with Br2. Use conc. H2SO4 to € They have stable outer electronic configuration
remove water vapours. as ns2 np6. [He has 1s2 configuration.]

28 chemistry today | January ‘15

€ They are monatomic in nature as they do not Chemical properties and Chemical Reactions of
even undergo reactions among themselves. Noble Gases
€ Ionisation enthalpy is very high. This is due to It is known that noble gases are chemically inert and
the stable electronic configuration. As we move they do not show spontaneous reactivity. However,
down the group, due to the increase in the it was found that when xenon is allowed to react
atomic radii and thus strong shielding effect, with a powerful oxidising agent like PtF6, it gives
ionisation enthalpy decreases. In kJ mol–1 unit,
the compound XePtF6.
the values of the ionisation enthalpies of noble
278 K
gases are : He → 2371, Ne → 2080, Ar → 1522, Xe + PtF6 Xe+[PtF6]–
Kr → 1350, Xe → 1169.2, Rn → 1036.
Later on, many other xenon compounds were also
€ As noble gases do not form molecules, their
prepared like
van der Waals radii can be calculated which are
definitely greater than the covalent radii of the Xe(g) + F2(g) 1 bar XeF2(s)
other elements. Excess

€ Noble gases have completely filled electronic 600°C

Xe(g) + 2F2(g) XeF4(s)
configuration and thus reluctant to accept 6.5–7 bar

electrons. Hence, they have positive electron Ratio 1 : 5

gain enthalpy. Xe(g) + 3F2(g) 60–70 bar
€ As the atoms of the noble gases are held Ratio 1 : 18
together by weak van der Waals forces, hence or 1 : 20

they have low melting and boiling points. With When XeF4 reacts with O2F2 at 140-145 K, then
the increase in the size of the atoms, extent of also XeF6 is prepared as below :
van der Waals forces of attraction increases. So, 140–145 K
melting and boiling points also increase. XeF4 + O2F2 XeF6 + O2
€ Though to a very small extent, but inert gases
are soluble in water. Your favourite mtG Books/magazines available in
With the increase in the polarisability of the WeSt BeNGAl at
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chemistry today | January ‘15 29

Reactions of Xenon fluorides with Water 2s bp with two F + 2s bp with two O
€ XeF2 : XeF2 reacts slowly with water to give O2 + 2 bp with O
and Xe along with HF. Not considered in hybridisation
2XeF2(s) + 2H2O(l) → 2Xe(g) + 4HF(aq) + O2(g) 3
+ 1 lp = sp d
€ XeF4 : XeF4 reacts violently and rapidly with So, structure will be see-saw (AB4L) type
water to give an explosive substance XeO3 or
xenon trioxide. [Why fluorine atoms on the axial
: Xe
6XeF4(s) + 12H2O(l) → 4Xe(g) + 2XeO3(s) positions?Follow Bent’s rule]
+ 24HF(aq) + 3O2(g) F
€ XeF6 : XeF6 in the similar manner, with H2O
reacts violently and gives the explosive solid Question from Students’ mind
XeO3. How to find out whether oxygen atoms are
XeF6(s) + 3H2O(l) → XeO3(s) + 6HF(aq) double bonded or not?
Some Common Structures involving Noble Gases Ans.: How many valence e–s in Xe?
€ XeOF4 : 8e–s of Xe + double bonded O’s 2e–s + No. of valence e–s in Xe = 8
4e–s of F = 14e–s = 7e– pairs. Now, out of this how many e–s are given to F.
4s bp with four F +1s bp with O For example, in XeOF4, for four fluorine atoms
+1p bp with O we need four electrons.
e–s given to F = 4
Not considered in hybridisation +
3 2 Now, how many left in Xe?
1 lp = sp d
e–s left in Xe = 4
Therefore, it will be square pyramidal.
e–s required to form double bond in oxygen = 2
(AB5L type)
O As Xe has four e–s left, then it will form double
F F bond.
F F Recommended structures for practice

XeO3, XeO4, XeO3F2, XeO2F4, XeF2, XeF4, XeF6,

€ XeO2F2 : 8e–s of Xe + 4e–s from two double
bonded O + 2e–s from two F = 14e–s = 7e– pairs XeOF2.

30 chemistry today | January ‘15

Maximize your chance of success, and high
rank in JEE (Main and Advanced) /BITSAT
by reading this column. This specially
designed column is updated year after year
by a panel of highly qualified teaching
experts well-tuned to the requirements of
these Entrance Tests.

Organic Compounds Containing Oxygen |

UNIT-7 Organic Compounds Containing Nitrogen

Organic cOmpOunds cOntaining (c) 3,3-dimethyl-1-cyclohexanol

Oxygen (d) 1,1-dimethyl-3-cyclohexanol.
(AIEEE 2004)
l Preparations, Properties, Reactions and Uses
l Alcohols, Phenols and Ethers ‰ Structure

Aldehydes and Ketones

l 142 pm
O 96 pm
l Carboxylic Acids H
C 108.9° H
tips tO remember H
€ Bond angle is slightly less than tetrahedral
‰ Alcohols are the hydroxy derivatives of alkanes angle (109°28′) due to the repulsion between
having general formula CnH2n + 1OH. two lone pairs of electrons of O-atom.
‰ In common system, alcohols are named as alkyl ‰ Preparation
alcohols. From alkyl halides
€ In IUPAC system, alcohols are called aq. KOH
‘alkanols’, by replacing ‘-e’ of alkane by RX ROH
Moist AgOH
‘-ol’. Alkyl halide
or aq. K2CO3
From alkenes
Common name : n-Propyl alcohol conc. H2SO4/H2O
IUPAC name : Propan-1-ol (Markovnikov's)
(i) B2H6 in THF
(ii) H2O2, OH –
1. The IUPAC name of the compound
(i) Hg(OAc)2 in THF-H2O
is (ii) NaBH4, OH –
HO From amines
(a) 3,3-dimethyl-1-hydroxycyclohexane RNH2
NaNO2/dil. HCl
ROH + N2 + H2O
(b) 1,1-dimethyl-3-hydroxycyclohexane 1° Amine

chemistry today | January ‘15 31

From ethers ‰ Physical Properties
H2O/dil. H2SO4 € Physical state : The lower members upto
2ROH C11 are colourless mobile liquids. Higher
members are wax like solids.
(i) RMgX/Dry ether € Odour : The lower members have a
(ii) H2O/H +
1° Alcohol
characteristic smell (alcoholic) and a
burning taste while solid members are
From carbonyl compounds almost colourless and tasteless.
H2/Pt or Pd or Ni € Solubility : The solubility in water is due to
reagent Reduction

RCH2OH hydrogen bonding.

RCHO 1° Alcohol
NaBH4 or LiAlH4 or − The solubility in water decreases with
R or Na/C2H5OH R2CHOH rise of molecular mass.

C O or − Among the isomeric alcohols, the

Carbonyl (i) RMgX/Dry ether R3COH solubility increases with increase in
compounds (ii) H2O/H + 3° Alcohol
branching. 1° < 2° < 3°
From acids and their derivatives € Boiling points : Increase gradually with
increase of carbon chain as van der Waals
(i) LiAlH4 or B2H6/ether
RCOOH RCH2OH forces increase.
Carboxylic acid (ii) H3O +
− Decrease with increase of branching
H2O/H + or OH
– in carbon chain due to decrease in
RCOOH + ROH van der Waals forces with decrease in
aq. NaOH surface area. 1° > 2° > 3°.
RCOOR (Saponification)
LiAlH4 or
RCH2OH + ROH • The boiling points of alcohols are higher
as compared to the corresponding alkanes,
LiAlH4 ethers and alkyl halides due to intermolecular
(RCO)2O ether
Acid anhydride hydrogen bonding.

LiAlH4 ‰ Chemical Properties
Acid chloride € Acidic nature : It is due to the polar nature
of O H bond.
€ Reducing nature of different reagents − They are weaker acids than water as
Functional LiAlH4/ NaBH4/ B2H6/ H2/ water is a better proton donor than
Group Product Ether EtOH THF Metal alcohol. Also, an alkoxide ion is a
CHO CH2OH better proton acceptor than hydroxide
ion, which suggests that alkoxides are
stronger bases.
− They act as Bronsted bases as well. It
Ru–C) is due to the presence of unshared
electron pairs on oxygen, which makes
them proton acceptors.
(RCO)2O RCH2OH − An electron releasing group increases
CO2R CH2OH electron density on oxygen tending to
decrease the polarity of O H bond
and thus decreases the acid strength.

32 chemistry today | January ‘15

chemistry today | January ‘15 33
‰ Chemical Reactions € Oxidising nature of different reagents
€ Reactions involving cleavage of O H Reagent Purpose
bond (Alcohols act as nucleophiles.)
Na or K
Chromic acid, 1° alcohol to carboxylic
RO Na + H2 H2CrO4 acid.
Mg or Ca
(RO)2 Ca + H2

Al Pyridinium 1° alcohol to aldehyde and

(RO)3 Al + H2 chlorochromate 2° alcohol to ketone without
(PCC) affecting double bond.

RO M + H2

RO Na + NH3 CrO3/H2SO4 2° alcohol to ketone.
Jones reagent 1° alcohol to aldehyde

(chromic acid and 2° alcohol to ketone,
RO OCR + HCl in aqueous without affecting double
(RCO)2O/H +
RO OCR + RCOOH acetone) bond.
RO MgX + RH MnO2 It selectively oxidises allylic
R2SO4 and benzylic 1° and 2°
alcohols to give aldehyde
Conc. H2SO4

RO SO2OH + H2O and ketones respectively.


Conc. HNO3
RO NO2 + H2O
€ Reactions involving cleavage of C O KEY POINT
bond (Alcohols act as electrophiles.) • Reactivity of alcohols involving cleavage of
HX/Anhyd. ZnCl2 C OH bond is 3° > 2° > 1°.
R X + H2O
 • Reactivity of alcohols towards esterification is
PX3 CH3OH > primary > secondary > tertiary.
R X + H3PO3
PX5 • Reactivity of acids towards esterification is
Red P/X2
R X + H3PO3

€ Dehydration of alcohols
RCl + SO2 + HCl Conc. H2SO4
Pyridine C2H5OH 443 K
CH2 CH2 + H2O
Conc. H2SO4
C C + H 2O
443 K or € Mechanism
R OH Conc. H3PO4
C C + H 2O
.. + fast +
350°C H C C O
.. H + H H C C O
.. H
Al2O3, 633 K
RNH2 633 K
2 Protonated alcohol
ROH/Al2O3 slow
R3N 633 K
[O] [O] H H +
KMnO4/H + or OH – H H
or K2Cr2O7/H Formation of carbocation
or CrO3C5H5NHCl
RCHO − It follows the order of stability of
Cu/573 K
RCHO or RCOR or C C 3° alcohols > 2° alcohols > 1° alcohols

34 chemistry today | January ‘15

− It always occurs in accordance with the change, i.e., it remains orange, the
Saytzeff rule i.e., the more substituted alcohol is 3°.
alkene is the major product. € Victor Meyer’s test : In this test,
− It often gives alkenes derived from − Alcohol is reacted with conc. HI or red
rearranged carbocations. P and I2 to form the corresponding
‰ Distinction between 1°, 2° and 3° alcohols alkyl iodide.
€ Lucas test : An equimolar mixture of conc. − Alkyl iodide is treated with silver nitrite
HCl and anhy. ZnCl2 (Lucas reagent) is to form corresponding nitroalkane.
added to an unknown alcohol at room − Nitroalkane is treated with nitrous acid
temperature. (NaNO2 + H2SO4) and the solution is
− If cloudiness appears immediately made alkaline by addition of excess of
(within 5 minutes), the alcohol is 3°. caustic soda.
− If cloudiness appears after 5 minutes, • 1° alcohols → a blood red colour.
the alcohol is 2°. • 2° alcohols → a blue colour.
− If the solution remains clear, i.e., no • 3° alcohols → no colour.
cloudiness is formed, the alcohol is 1°. KEY POINT
SELF CHECK • Benzyl and allyl alcohols react as rapidly as
tertiary alcohols with Lucas reagent because
2. From amongst the following alcohols the one
their cations are resonance stabilised and
that would react fastest with conc. HCl and
stable as 3° carbocations.
anhydrous ZnCl2 , is
(a) 1-butanol ‰ Uses : Alcohols are used
(b) 2-butanol € as solvents for oils, fats, paints, varnishes
(c) 2-methylpropan-2-ol and celluloid.
(d) 2-methylpropanol. € for the manufacture of formaldehyde (used
(AIEEE 2010) for the manufacture of formaldehyde
€ Catalytic dehydrogenation : It involves the resins) and formalin (used as a preservative
passing of vapours of alcohol over reduced for biological specimens).
copper at 573 K. € as fuel.
− 1° alcohols give aldehydes (dehydro- € as antifreeze for automobile radiators.
genation). € in the preparation of dyes, medicines and
− 2° alcohols give ketones (dehydro- perfumes.
genation). pHenOLs
− 3° alcohols give alkenes (dehydration).
€ Dichromate test : ‰ Phenols are the compounds in which hydroxy
( OH) group is directly linked to aromatic
Oxidising agent : K2Cr2O7 + H2SO4.
ring having formula C6H5OH.
− If carboxylic acid with same number
of carbon atoms as in the alcohol is ‰ In substituted compounds, the terms ortho(1,2-
formed and the colour of the solution disubstituted), meta(1,3-disubstituted) and
changes from orange to green, the para(1,4-disubstituted) are used in the common
alcohol is 1°. names.
− If ketone with same number of carbon 1
atoms as in the alcohol is formed 2
and the colour of the solution also 3
changes from orange to green, the NO2
alcohol is 2°. Common name : m-Nitrophenol
− If the colour of the solution does not IUPAC name : 3-Nitrophenol

chemistry today | January ‘15 35

‰ Structure € C O bond length is slightly less than that
136 pm
in alcohol due to partial double bond

O character of C O bond and sp2-hybridised
109° state of C-atom to which O-atom is
sp2-hybridised attached.
‰ Preparation
From benzenesulphonic acid From haloarenes (Dow's process)
623 K,
dil. HCl 320 atm
NaOH NaOH dil. HCl + NaOH
–H2O 573-623 K, –NaCl –NaCl –NaCl, –H2O
–Na2SO3, –H2O
From cumene
From diazonium salt
+ OH CH3 – CH – CH3
N2Cl –
1. O2
dil. H2SO4, 
+ H2 O 2. H+, H2O
–N2, –HCl
From phenylmagnesium bromide
Raschig's process
MgBr OMgBr 700 K
dry ether H+
C6H5Cl + H2O
+ O2 (steam)
H 2O

From sod. salt of salicylic acid CuCl2/FeCl3 1

C6H6 + HCl + 2 O2
OH ONa 500 K
NaOH/CaO, dil. HCl
From benzene
–Na2CO3, –H2O –NaCl C6H6 + O2

‰ Physical Properties ‰ Chemical Properties

€ Physical state : Phenols are colourless € Acidic nature : Phenols are weakly acidic
crystalline solids or liquids. in nature due to polar O H bond directly
€ Odour : They have characteristic phenolic attached to sp2-hybridised C-atom.
odours. − They turn blue litmus red and react
with alkali metals and alkalies to form
€ Solubility : Like alcohols, phenols are
their salts.
soluble in water due to the formation of
− Phenol is weaker acid than carboxylic
hydrogen bonding with water.
acid. It does not react with sodium
− Phenols are less soluble than alcohols
carbonate (Na2CO3) and sodium
due to large hydrocarbon (benzene
bicarbonate (NaHCO3).
ring) part. − Phenols are more acidic than alcohols
− Phenols are soluble in alcohols, ethers which can be explained on the basis of
and also in NaOH. resonance.
€ Boiling points : Much higher than the − Electron withdrawing groups increase
corresponding aromatic hydrocarbons and the acidic strength of phenols.
haloarenes due to intermolecular hydrogen − Electron releasing groups decrease the
bonding. acidic strength of phenols.

36 chemistry today | January ‘15

‰ Chemical Reactions
Zn Na or
ZnO +  NaOH

H2 O + anhyd. ZnCl2 PCl5
+ POCl3 + HCl

HCl + or (CH3CO)2O, H+ Na2Cr2O7
Br Br 3Br2 (aq.)
3HBr +
Br (i) CO2, 400 K, 4-7 atm
(white ppt.) (ii) H+

OH OH (Kolbe's reaction)
Br Br2 in CS2
+ OH
273 K
(minor) H2
(major) Ni/533 K

NO2 Phenol ONa OH
dil. HNO3

Reimer-Tiemann reaction
298 K CHCl3 H+
(major) H2O
NO2 aq. NaOH
(minor) 340 K
O2N NO2 conc. HNO3
conc. H2SO4
CCl4 H
aq. NaOH H2 O
340 K
(Picric acid)

+ CH3Cl
anhyd. AlCl3 (i) CH3COCl
(o-Cresol) (ii) anhyd. AlCl3
(p-Cresol) (minor)
(Fries rearrangement)
SO3H conc. OCOC6H5
(o-product) (p-product) aq. NaOH
+ NaCl + H2O
at 298 K at 373 K

chemistry today | January ‘15 37

SELF CHECK € in the manufacture of phenol-formaldehyde
plastics such as bakelite.
3. Phenol is heated with a solution of mixture of
€ in the manufacture of drugs like aspirin,
KBr and KBrO3. The major product obtained
salol, phenacetin, etc.
in the above reaction is
(a) 2-bromophenol etHers
(b) 3-bromophenol ‰ Ethers are the compounds having general
(c) 4-bromophenol formula CnH2n+2O (where n >1 ).
(d) 2, 4, 6-tribromophenol. ‰ Common names of ethers are derived from the
(AIEEE 2011) names of alkyl/aryl groups written as separate
4. The major product obtained on interaction words in alphabetical order and adding the
of phenol with sodium hydroxide and carbon word ‘ether’ at the end.
dioxide is € In IUPAC system ethers are named as
(a) benzoic acid (b) salicylaldehyde alkoxyalkanes. The smaller alkyl group
(c) salicylic acid (d) phthalic acid. plus oxygen is called alkoxy substituent,
(AIEEE 2009) while the larger alkyl group is called
‰ Test for Phenols alkane.
€ Ferric chloride test : Phenol gives violet CH3 O CH2CH2CH3
colour with neutral FeCl3 solution. Common name : Methyl n-propyl ether
IUPAC name : 1-Methoxypropane
€ Bromine water test : Phenol gives white
ppt. with Br2-water due to the formation of ‰ Structure
2, 4, 6-tribromophenol. 141 pm

€ Liebermann’s nitroso test : Phenol on H O H
reaction with NaNO2 and conc. H2SO4 gives H C 111.7° C H
deep green or blue colour which changes H H
into red on dilution with water. sp3-hybridised

€ Phthalic anhydride test : Phenol reacts € The bond angle is slightly greater than
with phthalic anhydride in presence of the tetrahedral angle due to the repulsive
conc. H2SO4 and gives phenolphthalein interaction between the two bulky ( R)
which gives pink colour with alkali. groups.
€ Ammonia or sodium hypochlorite test : € The C O bond length (141 pm) is almost
Phenol gives blue colour. the same as in alcohols.
€ Coupling reaction : Phenol gives orange KEY POINT
azo dye with diazonium salt in weakly basic
• As the size of alkyl groups in ethers increases,
solution. van der Waals repulsion increases and hence
‰ Uses : Phenols are used bond angle also increases.
€ in industry.
€ as antiseptics in soaps, lotions and
€ in the manufacture of azo dyes,
phenolphthalein, etc.
€ in the preparation of picric acid used as an
explosive and for dyeing silk and wool.

38 chemistry today | January ‘15

‰ Preparation of comparable molecular masses
From alcohols by dehydration
due to weak van der Waals forces of
conc. H2SO4, 413 K attraction.
or Al2O3, 523 K € Polarity : Ethers are polar in nature.
From alkyl halide € Density : Ethers have low density. All ethers
–NaX Ether are lighter than water.
‰ Chemical Reactions
(Williamson synthesis)

2RX + Ag2O(dry)
From Grignard reagent 373 K
Dry ether conc. HCl R +
–MgX2 R

From diazomethane HI(cold)
ROH + CH2N2 ROCH3 2HI, 373 K
2RI + H2O
–N2 (Excess)
From alkenes PX5
(i) Hg(OAc)2, ROH ROR 
2RX + POX3
C C (ii) NaBH4, OH – C C
H2O/dil. H2SO4
under pressure, 
O conc. H2SO4
C C + R COOH 
or mCPBA,
CH2Cl2 CH3COCl, 
Anhyd. ZnCl2
‰ Physical Properties (CH3CO)2O, 
Anhyd. ZnCl2
€ Physical state and odour : Dimethyl ether
and ethyl methyl ether are exceptionally Cl Cl
Cl2, dark
gases at room temperature while all CH3 CH O CH CH3
other ethers are colourless liquids with Cl2, h
characteristic ethereal smell. C2H5OC2H5 Al2O3
€ Solubility : Ethers are soluble in water to a 360°C
certain extent due to hydrogen bonding. CO, BF3
− Solubility decreases with increase in 150°C
500 atm
molecular mass.
− Ethers are fairly soluble in all organic SELF CHECK
solvents such as alcohol, chloroform,
benzene, etc. 5. In the reaction OCH3
€ Boiling points : Ethers have lower boiling the products are
points than isomeric alcohols due to their
(a) Br OCH3 and H2
inability to form hydrogen bonds and get
− But lower ethers have slightly higher (b) Br and CH3Br
boiling points than n-alkanes of
comparable molecular masses due to
(c) Br and CH3OH
dipole-dipole interactions.
− Higher ethers (containing carbon
atom more than four) have slightly (d) OH and CH3Br
lower boiling points than n-alkanes (IIT-JEE 2010)

chemistry today | January ‘15 39

KEY POINT € Diethyl ether provides an inert medium for
various organic reactions such as Wurtz
• Reaction of ether with excess of HX :
− When one of the alkyl group is a 3° group, reaction or preparation of Grignard and
the halide formed is a 3° halide. other organometallic reagents.
− In case of anisole, the halide formed will aLdeHydes and KetOnes
be methyl iodide.
− The order of reactivity with halogen acids ‰ These are the compounds with carbon-oxygen
follows : HI > HBr > HCl double bond ( C O) called carbonyl group
• Ethers form peroxides in presence of sunlight having general formula CnH2nO.
or ultraviolet light. ‰ Aldehydes contain carbonyl group attached to
C2H5OC2H5 + O (C2H5)2O → O either two H-atoms or one H-atom and one
Light C-atom of an alkyl/aryl group.
CH3CH2 O CH2CH3 + O2
Diethyl ether ‰ In ketones, the carbonyl group is attached to
two C-atoms of an alkyl/aryl group.
Peroxide of diethyl ether ‰ The common names of most aldehydes are
(1-Ethoxy ethyl hydroperoxide) derived from the common names of the
corresponding carboxylic acids by replacing
• Ethers form stable oxonium salts.
the ending –‘ic’ of acid with aldehyde.
273 K € The common names of ketones are derived
: :

C2H5OC2H5 + HCl (C2H5)2O+Cl–

by naming two alkyl or aryl groups bonded

Diethyl ether Diethyl oxonium chloride
to the carbonyl group.
(Bronsted—Lowry base
or Lewis base) € The IUPAC names of open chain aliphatic
• Ethers can form coordination complexes aldehydes and ketones are derived from
with Lewis acids like BF3, AlCl3, RMgX, etc. the names of the corresponding alkanes
known as etherates. by replacing the ending –‘e’ with –‘al’ and
C2H5OC2H5 + BF3 (C2H5)2O  BF3 –‘one’ respectively.
: :

Lewis acid Boron trifluoride CH3

Grignard R O(C2H5)2 Common name : Isobutyraldehyde
reagent Mg
IUPAC name : 2-Methylpropanal
(C2H5)2O X
€ Electrophilic substitution reactions : Common name : Methyl n-propyl ketone
The alkoxy group ( OR) is ortho, para IUPAC name : Pentan-2-one
directing and activates the aromatic ring ‰ Structure
towards electrophilic substitution in the
same way as phenol.  120°

‰ Uses : Ethers are used 120° C  O
: :

Nucleophilic (Lewis base)

€ as solvents in laboratory and industry.  120°

Diethyl ether acts as a solvent for oils, fats, Electrophilic (Lewis acid)
waxes, plastics and lacquers. Carbonyl group

40 chemistry today | January ‘15

‰ Preparation
Oxidation of alcohols From alkynes
K2Cr2O7 + H2SO4 dil .H2SO4
RCH2OH + [O]
HgSO4, 333 K RCHO
H2O + RCHO C C or
K2Cr2O7 + H2SO4 B2H6, THF RCOR
R2CHOH + [O] H2O2/OH –
Oxidation of 1,2-glycols
H2 O + R C R
Oppenauer oxidation OH OH
R R [O]
Catalytic dehydrogenation of alcohols C C RCOR + RCOR
R R
573 K
Etard reaction
573 K
(i) CrO2Cl2/CS2
Reductive ozonolysis of alkenes
CHCl3 (ii) H3O+
or CCl4
196 K
O O Oxo process
Zn, H2O [Co(CO)4]2
2RCHO + ZnO RCH CH2 + CO + H2 100°C, pressure
Rosenmund reduction and RCH2CH2CHO
Pd-BaSO4, S Ketones
RCOCl + H2 RCHO + HCl Wacker process
boiling xylene CuCl2
H2C CH2 + PdCl2 + H2O Air or O2
Reduction of nitriles
(i) AlH(i-Bu)2 CH3CHO + Pd + 2HCl
(ii) H2O
From alkyl halides
(i) RMgX/dry ether
(ii) H3O+
(i) SnCl2 + HCl + (CH3)2S + HX
(ii) Ether R2CO
(iii) H2O + NH4Cl
+ (CH3)2S + HX
(Stephen reduction)
From esters From lithium and cadmium salts
(i) DIBAL-H, 195 K dry
RCOOR RCHO 2RMgX + CdCl2 R2Cd + 2Mg(X)Cl
(ii) H2O ether

Gatterman—Koch reaction R2Cd + RCOCl RCOR + RCdCl

– +
CO, HCl R COO Li + CH3Li R C CH3
Anhyd. AlCl3, CuCl
Friedel—Crafts acylation
Anhyd. AlCl3

chemistry today | January ‘15 41

SELF CHECK due to the presence of two electron
donating alkyl groups making them
6. Ozonolysis of an organic compound gives more polar.
formaldehyde as one of the products. This
‰ Chemical Properties
confirms the presence of
(a) two ethylenic double bonds € Polarity of carbonyl ( C O) group :
(b) a vinyl group Aldehydes and ketones undergo
(c) an isopropyl group nucleophilic addition reactions in contrast
(d) an acetylenic triple bond. to alkenes which undergo electrophilic
(AIEEE 2011) addition reactions.
‰ Physical Properties C O C O–
€ Physical state and odour : Lower € Acidity of a-hydrogen atoms : The
members of aldehydes and ketones acidity of a-hydrogen atoms of carbonyl
(upto C10) are colourless volatile liquids
compounds is due to the strong electron
except formaldehyde which is gas at
withdrawing effect of the carbonyl group
ordinary temperature.
and resonance stabilisation of the conjugate
− Higher members of aldehydes and
ketones are solids with fruity odour. –
− Lower aldehydes have unpleasant O O O
odour but ketones possess pleasant C C C C– C C
H :B
€ Solubility : Lower members of aldehydes
and ketones (upto C4) are soluble in water € Nucleophilic addition reactions :
due to H-bonding between polar carbonyl –
Nu Nu Nu
group and water. +  slow fast
− However, solubility decreases with C O –
increase in molecular weight.
Planar Tetrahedral Addition
− Aromatic aldehydes and ketones are intermediate product
much less soluble than corresponding
− Reactivity order :
aliphatic aldehydes and ketones due to
Aldehydes > Ketones
larger benzene ring.
− However all carbonyl compounds are (steric and electronic reasons)
fairly soluble in organic solvents. HCHO > RCHO > PhCHO > RCOR
€ Boiling points : Slightly lower than > RCOPh > PhCOPh
corresponding alcohol due to lack of HCN CN
hydrogen bonding. C
− Their boiling points are slightly higher Cyanohydrin
than those of corresponding non- C
polar hydrocarbons or weakly polar OH
ethers. This is due to intermolecular (i) RMgX R
dipole-dipole interaction among polar (ii) H3O+ OH
aldehydes or ketones. ROH OR ROH OR
+  +  +  dry HCl OH dry HCl OR
C O C O C O Hemiacetal Acetal
− Among isomeric aldehydes and CH2OH O CH2
ketones, boiling points of ketones are PTS, 
slightly higher than those of aldehydes Ketal

42 chemistry today | January ‘15

7. The major product in the following reaction is O CH3
O (JEE Advanced 2014)
1. CH3MgBr, dry ether, 0°C
Cl € Nucleophilic addition - elimination
CH3 2. aq. acid
reactions :
(i) NH3
(a) H3C C NH + H2O
(ii)  Imine
(i) NH2 Z
OH C N Z + H2 O
(ii) 
Imine derivatives
(b) H2C CH3 Z = Alkyl, Aryl, OH, NH2, NHC6H5,
(c) NH NO2 , NHCONH2
€ Oxidation and reduction reactions :
Oxidation Reduction
RCOOH H2/Ni or
Pt or Pd

2[Ag(NH3)2]+OH–, OH – R
RCOO– + 2Ag LiAlH4 or NaBH4
Silver mirror test Tollens' reagent CHOH
(only aldehydes) R

R [(CH3)2CHO]3Al
2Cu2+, 5OH– C O + (CH3)2CHOH
RCOO– + Cu2O Fehling’s solution R
red ppt. R = H or Meerwein—Ponndorf Verley reduction
(only ketones)
Fehling's solution test
alkyl or
(only aliphatic aldehydes)
aryl group Zn-Hg/HCl
RCOOR Clemmensen reduction
or H2SO5
Baeyer—Villiger oxidation
HI/Red P, 423 K R
CuO or Cu(OH)2 CH2
RCOO– + Cu2O R
red ppt.
Benedict's solution test NH2 – NH2/KOH
(only aliphatic aldehydes) Wolff—Kishner reduction

€ Haloform reaction : SELF CHECK

Given by methyl ketones (even acetaldehyde).
2NaOH + I2 NaI + NaOI + H2O 8. Among the following the one that gives
positive iodoform test upon reaction with
I2 and NaOH is
CHI3↓ + 2NaOH
Iodoform (a) CH3CH2CH(OH)CH2CH3
(yellow ppt.) (b) C6H5CH2CH2OH
• Haloform test is also given by alcohols (c) H3C
containing CH3CHOH group linked to OH
C or H-atom e.g., ethanol, propan-2-ol, (d) PhCHOHCH3
butan-2-ol. (AIEEE 2006)

chemistry today | January ‘15 43

€ Reactions involving a-hydrogen atom : KEY POINT
− Aldol condensation :
• Ketoximes on treatment with acid catalyst
O such as conc. H2SO4, PCl5, H3PO4, SOCl2
 dil. NaOH
2R CH2 C H or C6H5SO2Cl, etc., undergo Beckmann
OH R O rearrangement to form a substituted amide.
R CH2 CH CH C H • This rearrangement is intramolecular
Aldol and involves 1,2-shift. It is always the anti
 –H2O R group that migrates in the Beckmann
R O rearrangement.
Unsaturated aldehyde CH3CH2CH NOH H C NHCH2CH3
Propionaldoxime N-Ethyl formamide
− Intramolecular aldol condensation : It
takes place in diketones and gives rise • The nucleophilic addition-elimination reactions
to cyclic products. with ammonia derivatives (NH2 Z) are
− Crossed aldol condensation : Aldol carried out in weakly acidic medium
condensation is carried out between (pH = 3–4).
two different aldehydes and/or • Aldehydes and ketones react with primary
ketones. amines to form azomethines (imines) known
− If both of them contain a-hydrogen as Schiff ’s base.
atoms, it gives a mixture of four H+
products. Aldehyde Alkylamine

Aldimine (A Schiff ’s base)
CH3CHO • Aldehydes and ketones that have at least one
CH3CH2CHO a-hydrogen reacts with secondary amines
CH3—CH CH—CHO to form enamines (a, b-unsaturated tertiary
Self aldol




H3C C O + HN
1. NaOH CH3 R (–H2O)
2.  R

CH3—CH C—CHO CH3 2° Amine
H2 C C N
Cross aldol


CH3CH2—CH CH—CHO Enamine
• Wittig reaction :
€ Reactions involving no a-hydrogen atom : Heat
− Cannizzaro reaction : R CH O + (C6H5)3P CH2
conc. KOH Aldehyde (Wittig reagent)
(C6H5)3P O + R CH CH2
Formaldehyde CH3OH + HCOOK Triphenyl phosphine oxide Alkene
Methanol Potassium
− Crossed Cannizzaro reaction :
O O 9. The number of aldol reaction(s) that occurs in
OH– the given transformation is
C6H5—C—H + H—C—H 
conc. aq. NaOH
Benzyl alcohol Sod. formate HO OH
− Intramolecular Cannizzaro reaction : (a) 1 (b) 2
It is given by dialdehydes having no (c) 3 (d) 4
a-hydrogen atoms. (IIT- JEE 2012)

44 chemistry today | January ‘15

10. Trichloroacetaldehyde was subjected to Uses
Cannizzaro’s reaction by using NaOH. The ‰ Formaldehyde : It is used in the
mixture of the products contains sodium
€ preparation of hexamethylene tetramine
trichloroacetate ion and another compound.
(urotropine) which is used as an antiseptic
The other compound is
and germicide.
(a) 2,2,2-trichloroethanol
(b) trichloromethanol € manufacture of synthetic dyes such as para-
(c) 2,2,2-trichloropropanol rosaniline, indigo, etc.
(d) chloroform. ‰ Acetaldehyde : It is used
(AIEEE 2011) € as an antiseptic inhalant in nose troubles.
€ Electrophilic substitution reactions : € in the preparation of paraldehyde (hypnotic)
Aromatic aldehydes and ketones undergo and metaldehyde (solid fuel).
electrophilic substitution at the ring
‰ Acetone : It is used
in which the carbonyl group acts as a
€ as a solvent for cellulose acetate, cellulose
deactivating and meta directing group.
nitrate, celluloid, lacquers, resins, etc.
‰ Distinction between aldehydes and ketones
€ in the preparation of chloroform, iodoform,
Tests with Aldehydes Ketones sulphonal and chloretone.
Schiff ’s
Pink colour No colour carbOxyLic acids
Fehling’s Red No ‰ Compounds having COOH group having
solution precipitate precipitate general formula CnH2nO2.
Tollens’ Black No black ‰ The common names end with the suffix
reagent precipitate of ppt. or silver –‘ic acid’ and have been derived from Latin
silver or silver mirror or Greek names of their natural sources.
mirror € In the IUPAC system, aliphatic carboxylic
2,4-Dinitro- Orange- Orange- acids are named by replacing the ending
phenyl- yellow or red yellow or red –‘e’ in the name of the corresponding
hydrazine well defined well defined alkane with –‘oic acid’.
crystals with crystals with CH3CH2CH2COOH
melting points melting Common name : Butyric acid
characteristic points IUPAC name : Butanoic acid
of individual characteristic ‰ Structure : The carboxylic carbon is less
aldehydes of individual electrophilic than carbonyl carbon because of
ketones the possible resonance structure.
Sodium Give brown No reaction
O: O–: O:–
: :

: : : :

hydroxide resinous mass +

C C C +
: :

does not give

this test)
Alkaline A deep Red colour
sodium red colour which
nitroprusside (formaldehyde changes to
does not orange
respond to
this test)

chemistry today | January ‘15 45

‰ Preparation € Solubility : Simple aliphatic carboxylic
Oxidation, alk. KMnO4, H3 O+ acids having upto four carbon atoms are
or CrO3-H2SO4 miscible in water due to the formation of
Primary alcohol
K2Cr2O7 + dil. H2SO4
hydrogen bonds with water.
− The solubility decreases with
K2Cr2O7 + dil. H2SO4
increasing number of carbon atoms.
or Fehling's solution
or Tollens' reagent Higher carboxylic acids are practically
Note: Primary alcohol and aldehyde give insoluble in water due to the
acids containing the same number of increased hydrophobic interaction of
C-atoms as alcohol or aldehyde. hydrocarbon part.
Mineral acid − Benzoic acid, the simplest aromatic
Hydrolysis HCl, H2SO4, etc. carboxylic acid is nearly insoluble in
Alkyl Alkali HCl cold water.
cyanide NaOH
RCOONa − Carboxylic acids are also soluble in less
or KOH
CO2 (dry ice)
polar organic solvents like benzene,
RMgX ether, alcohol, chloroform, etc.
dry ether
Grignard reagent
RCOOH € Boiling points : Carboxylic acids are higher
RCONH2  boiling liquids than aldehydes, ketones and
Alkyl amide even alcohols of comparable molecular
H2 O
masses due to more extensive association
or, (i) OH –/H2O
Acyl halide of their molecules through intermolecular
(ii) H3O+
hydrogen bonding. The H-bonds are not
(RCO)2O broken completely even in the vapour
Acid anhydride phase.
H3O+, 
RCOOR ‰ Chemical Properties
NaOH, H3O+
Ester € Acidic nature : Carboxylic acids are
RCH CHR KMnO4/OH– weaker acids than mineral acids, but they
, H3O+
are stronger acids than alcohols and many
RC CR simple phenols.
R C + H2O H3O+ +
3[O] OH
O O– O –
Alkyl benzene R C R C R C
€ Effect of substituents on acidic strength :
Fe catalyst, H2O
− Presence of electron withdrawing
groups, increases the acidic strength.
‰ Physical Properties − More the number of electron
€ Physical state : The lower fatty acids upto withdrawing groups, more will be the
C9 are colourless liquids. The higher ones acidic strength.
are colourless waxy solids. − More is the distance between
€ Odour : The first three members have a the carboxyl group and electron
sharp pungent odour. The middle ones, withdrawing group, less will be the
C4 to C9, have an odour of rancid butter. acidic strength.
The higher members do not possess any − Presence of electron releasing groups,
smell. decreases the acidic strength.

46 chemistry today | January ‘15

SELF CHECK € Ring substitution in aromatic acids :
—COOH group is deactivating and meta
11. Among the following compounds, the most directing.
acidic is
(a) p-nitrophenol COOH
(b) p-hydroxybenzoic acid Br2
(c) o-hydroxybenzoic acid COOH FeBr3, 
(d) p-toluic acid. COOH
(IIT-JEE 2011)
Conc. HNO3
‰ Chemical Reactions Conc. H2SO4, 
€ Reactions involving —OH group : NO2


P2O5, 
– H2O 12. Sodium phenoxide when heated with CO2
ROH/H+ under pressure at 125 °C yields a product which
– H2O
on acetylation produces C.
PCl3 or PCl5
RCOCl ONa 125 °C H+
or SOCl2 in pyridine
Acid chloride + CO2 5 atm B Ac2O C
NH3, 
– H2O
RCONH2 The major product C would be

€ Reactions involving proton of —OH OCOCH3 OCOCH3

group : COOH
(a) (b)
RCOONa + CO2 + H2O (c) (d)
RCOONa + CO2 + H2O
€ Reaction involving C O group : (JEE Main 2014)
O 13. A liquid was mixed with ethanol and a drop of
(i) LiAlH4/ether or B2H6/ether
R C OH RCH2OH concentrated H2SO4 was added. A compound
(ii) H3O+ (Reduction)
with a fruity smell was formed. The liquid was
€ Reaction involving —COOH group : (a) CH3OH (b) HCHO
(c) CH3COCH3 (d) CH3COOH
NaOH and CaO (AIEEE 2009)
R C OH  (Decarboxylation)
RH + Na2CO3
‰ Distinction Test between Phenol and
Carboxylic Acid
€ Reaction involving —R group :
O Test Phenol Carboxylic acid
(i) X2/Red P
RCH2 C OH R CH COOH NaHCO3 No reaction Brisk effervescence
(ii) H2O
X test of CO2 gas
-Halocarboxylic acid
(Hell-Volhard Zelinsky reaction) FeCl3 test Violet colour Buff coloured ppt.

chemistry today | January ‘15 47

Uses ‰ In common system, an aliphatic amine is
‰ Formic Acid : It is used named by prefixing alkyl group to amine, i.e.,
€ as a coagulating agent for latex in rubber alkylamine as one word.
industry. € In IUPAC system, amines are named as
€ for dehydration of halides in leather industry. alkanamines, derived by replacement of ‘e’
‰ Acetic Acid : It is used of alkane by the word ‘amine’.
€ as vinegar and for manufacturing pickles.
€ for making various dyestuffs, perfumes and
medicines. NH2

Organic cOmpOunds cOntaining Common name : Isopropylamine

nitrOgen IUPAC name : Propan-2-amine
l Preparations, Properties, Reactions and Uses ‰ Structure
l Amines, Aniline and Diazonium Salts

tips tO remember N
H3 C H
amines H
‰ The derivatives of ammonia formed by the
replacement of one or more hydrogen atoms € The angle C — N — R, (where R is C or H)
by the corresponding number of alkyl or aryl is less than 109.5° due to the presence of
groups are known as amines. lone pair on N-atom.
‰ Preparation
Reduction of nitro compounds Ammonolysis of alcohols
Sn/HCl or Fe/HCl Al2O3
or H2/Pd or LiAlH4/ether or ThO2, 

Hofmann's ammonolysis method Schmidt reaction

RX 373 K

Mendius reduction
H2/Ni or LiAlH4/ether
Reductive amination of aldehydes or
RCN ketones
or Na(Hg)/C2H5OH

Reduction of amides
NH3, H2/Ni or NaBH3CN R
150°C, 300 atm R
or Na/C2H5OH
Reduction of oximes
Gabriel phthalimide synthesis LiAlH4/ether
CO or Na/C2H5OH
(i) KOH(alc.)
(ii) RX,  Decarboxylation of -amino acids
CO –
(iii) H+ or OH /H2O,  Ba(OH)2

Hofmann’s bromamide degradation
KOH, 
Curtius reaction Hydrolysis of isocyanates
(i) NaN3/C2H5OH,  H2 O
(ii) H3O+ or NaOH,  HCl

48 chemistry today | January ‘15

KEY POINT − The intermolecular association is more
in primary amines than in secondary
• The amines of the type R1R2R3N exist in
amines due to presence of two
the form of racemic mixture that cannot be
hydrogen atoms. Therefore, the order
resolved into enantiomers because of rapid of boiling points of isomeric amines is
inversion of an enantiomer to its mirror image. 1° > 2° > 3°.
This inversion is called amine inversion,
‰ Chemical Properties
nitrogen inversion or flipping. During this,
the state of hybridisation of N changes from € Basic nature : Due to the presence of lone
sp3 to sp2. pair of electrons on nitrogen atom, amines
are basic in nature.
− Basic character of amines can be
SELF CHECK compared on the basis of inductive
14. An organic compound A upon reacting with effect of alkyl groups, steric effect and
NH3 gives B. On heating, B gives C. C in presence resonance involvement of lone pair of
of KOH reacts with Br2 to give CH3CH2NH2. electrons.
A is − Among aliphatic amines +I effect
(a) CH3CH2COOH of alkyl groups pushes the electrons
(b) CH3COOH towards nitrogen atom and so increases
(c) CH3CH2CH2COOH the basic character.
(d) CH3—CH—COOH − In gas phase, the order of basic
character is : 3 ° > 2° > 1° > NH3
CH3 − In aqueous solution, the order of basic
(JEE Main 2013) character is : 2 ° > 1° > 3° > NH3 (for
‰ Physical Properties methylamines) and 2° > 3° > 1° > NH3
€ Physical state and odour : Lower aliphatic (if alkyl group is bigger than methyl
amines are gases with smell like ammonia. group).
− Lower aromatic amines are liquids This is due to the reason that when
with characteristic unpleasant odour alkyl group is small, there is no steric
but higher ones are solids which are hindrance to H-bonding hence stability
odourless. due to H-bonding predominates.
However when alkyl group is bigger,
€ Solubility : Amines are soluble in water
there will be some steric hindrance
as they can form hydrogen bonds with to H-bonding and stability due to
water. +I effect predominates.
− As the size of alkyl group increases,
solubility decreases. SELF CHECK
− Higher amines are insoluble in water 15. Amongst the following the most basic
but soluble in organic solvents. compound is
− Aromatic amines are insoluble in water. (a) benzylamine (b) aniline
They are soluble in organic solvents (c) acetanilide (d) p-nitroaniline
such as benzene, ether, alcohol. (AIEEE 2005)
€ Boiling points : Amines show higher KEY POINT
boiling points than hydrocarbons of
comparable molecular masses due to • Aliphatic amines are stronger bases than
intermolecular hydrogen bonds. ammonia due to the +I effect of alkyl groups
− Tertiary amines have the lowest boiling present in amines.
points as they do not have hydrogen • Aromatic amines are weaker bases than
atoms linked to the nitrogen atom. ammonia due to –I effect of aryl group.

chemistry today | January ‘15 49

‰ Chemical Reactions
NaOH + – HCl CHCl3/alc. KOH
RNH2 RNH3Cl RNC (Carbylamine reaction)
–KCl, –H2O

(RNR3 ) X – RX RX RX HNO2
RNR2 RNHR ROH + N2 + H2O
Quaternary –HX –HX
salt RCHO

RN CHR (Schiff's base)
–HCl (i) CS2(alc.)
(ii) HgCl2, 
(Hofmann's mustard oil reaction)
RNH2 RCl + N2 + H2O

(RCO)2O C6H5SO2Cl
RNHSO2C6H5 (Hinsberg's test)
(Soluble in NaOH)
H2 + 2[RNH]– Na+
X2 X2 (RNH)2CO
Oxidation H2O/H+

SELF CHECK € Hofmann test : It involves the treatment

of the mixture with diethyl oxalate
16. A compound with molecular mass 180 is
(Hofmann’s reagent).
acylated with CH3COCl to get a compound
− Primary amine forms a solid dialkyl
with molecular mass 390. The number of amino
groups present per molecule of the former
− Secondary amine forms a liquid
compound is
dialkyl oxamic ester.
(a) 6 (b) 2
− Tertiary amine does not react.
(c) 5 (d) 4
€ Carbylamine test : It involves the heating
(JEE Main 2013)
of the mixture with chloroform in presence
‰ Distinction between 1°, 2° and 3° amines of alcoholic potassium hydroxide to form
€ Hinsberg’s test : It involves the treatment isocyanides (or carbylamines) which
of the mixture with benzene sulphonyl possess foul smell.
chloride (C6H5SO2Cl) called Hinsberg’s − Only aliphatic and aromatic primary
reagent. The solution is then made alkaline amines give this test.
with aqueous alkali. € Azo dye test : It involves the treatment
− Primary amine forms N-alkylbenzene of aniline with nitrous acid at 0-5°C and
sulphonamide which is soluble in alkaline solution of b-naphthol.
alkali. − Only primary aromatic amines will
− Secondary amine forms N, N-dialkyl give orange coloured azo dyes.
benzene sulphonamide which is € Hofmann mustard oil reaction : Both
insoluble in alkali. aromatic and aliphatic primary amines give
− Tertiary amine does not react. this test.

52 chemistry today | January ‘15

chemistry today | January ‘15 53
−Aliphatic primary amines on heating € Its boiling point is 183°C.
with CS2 and HgCl2 give characteristic − High boiling point of aniline is due to
smell like mustard oil. intermolecular H-bonding.
− Aromatic primary amines on heating − p-Substituted anilines, being the most
with ethanolic CS2 and solid KOH symmetric, have the highest melting
give N,N′-diphenylthiourea which on points.
treatment with conc. HCl gives phenyl € It is slightly heavier than water.
isothiocyanate. € It has a characteristic odour which is not
€ Nitrous acid test : Aromatic primary pleasant.
amines react with nitrous acid at 0-5°C and € It is slightly soluble in water but readily
give benzenediazonium salts. soluble in organic solvents.
− Aliphatic primary amines react with € It is steam volatile.
cold nitrous acid at 0-5°C and give € It is toxic in nature.
alcohols with the evolution of nitrogen
‰ Chemical Properties
− Both secondary aliphatic and aromatic € Basic nature : Aromatic amines like
aniline are less basic than aliphatic amines
amines with nitrous acid give yellow oily
because of the involvement of lone pair of
compounds called N-nitrosamines. electrons in resonance with the aromatic
− Tertiary aliphatic amines with nitrous ring which now becomes less available for
acid give water soluble nitrite salts donation.
while aromatic tertiary amines udergo − Also sp2-hybridised carbon of the
electrophilic substitution to form green aromatic ring is more electron
coloured p-nitroso-N, N-dialkylamine. withdrawing than sp3-hybridised
carbon of aliphatic amines and
‰ Uses : Lower aliphatic amines are used exerts a stronger withdrawing effect
€ as solvents in laboratory and industry. resulting in less tendency to donate
€ in petroleum refining. lone pair.
− In substituted aromatic amines,
€ in the manufacture of detergents.
electron withdrawing groups decrease
aniLine the basic character and electron
releasing group increase the basic
‰ It is an aromatic amino compound in which character.
the nitrogen atom of amino group is directly
attached to aromatic ring.
• Due to a combination of steric and electronic
‰ Structure
factors, o-substituted anilines are weaker
bases than anilines regardless of the

H N H nature of the substituent whether electron

donating or electron withdrawing. This is
called ortho-effect.

‰ Physical Properties ‰ Chemical Reactions

€ Fresh aniline is a colourless oily liquid. On € Aniline undergoes electrophilic substitution
standing the colour becomes dark brown reactions. NH2 group is ortho and para
due to action of air and light. directing group.

54 chemistry today | January ‘15


OC dine
H 3C ri
(i) C ) O/py


or (
C H 3C

2 S O di
, C
Br 2

+ H pyr

(Major) D


‰ Uses : Aromatic amines are used salts due to dispersal of positive charge over
€ in the manufacture of dyes and drugs. the benzene ring.
€ as antioxidants. ‰ Physical Properties
diaZOnium saLts € These are generally colourless, crystalline
solids, which are soluble in water.
‰ General Formula : ArN2+X –, where Ar stands
€ They are unstable and explode in dry state.
for the aryl ( C6H5) group and X – is Cl–, Br–,
NO3–, HSO4–, BF4–. ‰ Chemical Properties
‰ Preparation € Reactions involving displacement of
diazo group :
C6H5NH2 + NaNO2 + 2HCl
C6H5N2+ Cl– + NaCl + 2H2O
Aniline ArI 
Benzenediazonium HBF4
ArN2+ BF4– (Balz-Schiemann)
Mechanism :

First step : H2O
> 278 K
Ar C6H5 (Gomberg
NaOH, 
(Diphenyl) reaction)
Cu2O, 
Second step : –
H ArN2+ X H3PO2/H2O
+ + Cu+
C6H5 NH2 + N O C6 H 5 N N O
H 
CuCl/HCl ArCl
or or
H CuBr/HBr ArBr Sandmeyer’s
+ +H + or reaction
C6 H 5 N N OH2 ArCN
–H + +
–H2O + Cu/HCl ArCl
C6 H 5 N N or or
Cu/HBr Gattermann
€ Stability : Arenediazonium salts are more or
Cu/KCN or reaction
stable (for short time) than alkanediazonium ArCN

chemistry today | January ‘15 55

€ Reactions involving retention of diazo ‰ Uses
group : € Diazonium salts have many synthetic
ArN NC6H4OH applications for preparing those
pH = 9-10, 0-5°C
Coupling reaction substituted aromatic compounds which
C6H5 NH2/H+
ArN NC6H4NH2 cannot be prepared by direct substitution
pH = 4-5, 0-5°C
in benzene.
ArN NC6H4N(CH3)2 € They are also used for the preparation of
HO azo dyes and indicators like methyl
ArN2+ X
– orange.
-Naphthol, NaOH
ansWer Keys (seLF cHecK)
1. (c) 2. (c) 3. (d) 4. (c) 5. (d)
SnCl2 Azo dye
6. (b) 7. (d) 8. (d) 9. (c) 10. (a)

HCl Arylhydrazine
Zn Zn 11. (c) 12. (b) 13. (d) 14. (a) 15. (a)
HCl HCl 16. (c)

1. The major product formed in reaction of OH −

4. CH3CHO + 3HCHO → (CH2OH)3CCHO
3-methylbutan-2-ol with conc. HCl is I
OH −
(a) 2-chloro-2-methylbutane II
→ (CH2OH)4C + (CH2OH)3CCOO–
(b) 2-chloro-3-methylbutane Reactions at stages I and II are respectively
(c) 2-methylbut-2-ene (a) Cannizzaro, aldol
(d) 2-methylbut-1-ene. (b) aldol, aldol
2. An organic compound of molecular formula (c) Cannizzaro, Cannizzaro
C4H10O does not react with sodium. With (d) aldol, Cannizzaro.
excess of HI, it gives only one type of alkyl
5. End products of the following sequence of
halide. The compound is
reactions are
(a) ethoxyethane (b) 2-methoxypropane
O (i) I + NaOH
(c) 1-methoxypropane (d) 1-butanol. 2
(ii) H +, (iii) 
3. Which one of the following phenols is the C CH3
strongest acid?
OH OH (a) yellow ppt. of CHI3,
(a) (b)
(b) yellow ppt. of CHI3,
(c) (d) O
(c) yellow ppt. of CHI3,
CH3 NO2 (d) none of these.
56 chemistry today | January ‘15
6. An ester (A) with molecular formula, C9H10O2 OH
was treated with excess of CH3MgBr and the (a) (b)
compound, so formed, was treated with H2SO4 HO OH CH3 HO CH3
to give an olefin (B). Ozonolysis of (B) gave a
ketone with molecular formula, C9H10O which (c) (d)
gives iodoform test. The structure of (A) is
(a) H3C OCOCH2 C6H5 11. In the following reaction,
(b) C2H5COOC6H5 +
(c) C6H5COOC2H5  
(d) p-H3CO C6H4 COCH3 H CH3
(a) a-bond is cleaved due to nucleophilic
7. An amine forms salt with BF3 as, attack by I– ion since, (CH3)2CHOH is a
Amine + BF3 → [Amine → BF3]. weak base (a good leaving group)
If the alkyl group in amine is CH3 , the order (b) b-bond is cleaved due to nucleophilic attack
of basicity towards BF3 is by I– ion since, CH3CH2CH2OH is a weak
(a) CH3NH2 > (CH3)2NH > (CH3)3N base (a good leaving group)
(b) (CH3)3N > (CH3)2NH > CH3NH2 (c) a-bond is cleaved due to electrophilic
(c) (CH3)2NH > CH3NH2 > (CH3)3N attack of I– ion.
(d) (CH3)2NH > (CH3)3N > CH3NH2 (d) b-bond is cleaved due to electrophilic attack
of I– ion.
8. Consider the following ions : O
+ 12. The product obtained when is
I. Me2N N N OH
oxidised with HIO4 is
II. O2N N N (a) (b)

III. CH3O N N (c) (d)

13. Butanenitrile may be prepared by heating
IV. CH3 N N (a) propyl alcohol with alc. KCN
(b) butyl alcohol with alc. KCN
The reactivity of these ions towards azo coupling (c) butyl chloride with alc. KCN
reactions under similar conditions is (d) propyl chloride with alc. KCN.
(a) I < IV < II < III (b) I < III < IV < II
(i) CCl4, KOH,  /200°C
(c) III < I < II < IV (d) III < I < IV < II 14. OH A B
(ii) H+/H2O CH3COCl
9. Phenol with carbon tetrachloride in presence of Pyridine, 
aqueous potassium hydroxide at 340 K followed CH3OH
by hydrolysis gives HCl (gas), 
A, B, C and D respectively are
(a) acetylsalicylic acid (b) salicylaldehyde
(a) salicylic acid, salol, aspirin and oil of winter
(c) salicylic acid (d) methyl salicylate. green
10. Which one of the following will be the major (b) salicylic acid, aspirin, salol and oil of winter
product when is heated with green
(c) salicylic acid, oil of winter green, salol and
H2SO4 in the presence of HgSO4? (d) none of the above.

chemistry today | January ‘15 57

15. 59 g of an amide obtained from a carboxylic OH
acid, RCOOH, upon heating with alkali 20. The reaction, H3C CH CH2Br
liberated 17 g NH3. The acid is O
(a) formic acid (b) acetic acid
(c) propionic acid (d) benzoic acid.
can be described as
16. The rate of esterification of acetic acid with (a) acid-base reaction followed by an
methyl alcohol (I), ethyl alcohol (II), isopropyl intramolecular SN1 reaction
alcohol (III) and tert. butyl alcohol (IV) follows (b) acid-base reaction followed by an
the order intramolecular Williamson ether synthesis
(a) I > II > III > IV (b) IV > III > II > I (c) E 2 reaction followed by an addition
(c) II > I > IV > III (d) III > IV > I > II reaction to a double bond
17. Identify the final product. (d) SN2 reaction following an intermolecular
(i) Heat Williamson ether synthesis.
(ii) NaBH4 21. Which of the following is the strongest acid?
(a) 4-Nitrobenzoic acid
(a) (b) (b) 4-Methylbenzoic acid
O HO CH2 (c) 4-Methoxybenzoic acid
(d) 4-Ethylbenzoic acid
(c) (d) 22. Which of the following on oxidation with
N alkaline KMnO4 followed by acidification with
NH2 dilute HCl does not give benzoic acid?
18. The red coloured compound formed during the (a) Toluene (b) Ethylbenzene
Victor Meyer’s test for ethyl alcohol is (c) Isopropylbenzene (d) tert-Butylbenzene
(a) CH3 C NO–Na+ 23. Which of the following will not be soluble in
sodium bicarbonate?
– + (a) 2, 4, 6-Trinitrophenol
(b) CH3 CH NO2 Na (b) Benzoic acid
NO2 (c) o-Nitrophenol
(c) CH3 CH NO2 (d) Benzenesulphonic acid
NO 24. An organic compound ‘A’ has the molecular
(d) (CH3)2C NO formula C3H6O. It undergoes iodoform
test. When staturated with HCl it gives ‘B’
NO2 of molecular formula C9H14O. ‘A’ and ‘B’
19. The order of reactivity of the following alcohols respectively are
towards conc. HCl is (a) propanal and mesityl oxide
CH3 CH3 (b) propanol and mesityl oxide
F (c) propanone and 2, 6-dimethyl-2,5-heptadien
I II -4-one
H3C CH3 (d) propanone and mesityl oxide
OH 25. Aniline is reacted with bromine water and the
III IV resulting product is treated with an aqueous
(a) I > II > III > IV (b) IV > II > III > I solution of sodium nitrite in presence of dilute
(c) IV > III > II > I (d) IV > III > I > II hydrochloric acid. The compound so formed

58 chemistry today | January ‘15

is converted into a tetrafluoroborate which is O O
subsequently heated dry. The final product is COCH3 COCH2OH
(a) p-bromoaniline (a) CH2I (b) CH3
(b) p-bromofluorobenzene
(c) 1, 3, 5-tribromobenzene O O
(d) 2, 4, 6-tribromofluorobenzene.
(c) CH2 (d)
26. A compound ‘A’ has a molecular formula
C7H7NO. On treatment with Br2 and KOH, sOLutiOns
‘A’ gives an amine ‘B’ which gives carbylamine
1. (a)
test. ‘B’ upon diazotisation and coupling with
phenol gives an azo dye. ‘A’ can be 2. (a) : Since the compound (C4H10O) does not
(a) C6H5CH NOH react with sodium, oxygen must be in the
(b) C6H5CONH2 form of ether (R OR). Further, since a single
alkyl halide is formed, the two alkyl groups
(c) C6H5CH2NO
must be same, hence, ether is ethoxyethane
(d) o, m- or p-C6H4(NH2)CHO
27. When aniline reacts with oil of bitter almonds 3. (a) : o- and p-nitrophenols are stronger acids
(C6H5CHO) condensation takes place and than m-nitrophenol. As a result, phenols (a)
benzal derivative is formed. This is known as and (c) are stronger acids than (b) and (d).
(a) iodide of Millon’s base In (c), the NO2 group is flanked by two
(b) Hinsberg’s reagent CH3 groups which push the NO2 group out
(c) acetanilide of the plane of the benzene ring. As a result of
(d) Schiff ’s base. this steric hindrance, the electron withdrawing
28. Which of the following diols would cleave into resonance effect of the nitro group will be
two fragments with HIO4? reduced and hence, the acidic character of the
(a) 1, 3-Hexanediol (b) 2, 4-Hexanediol phenol will decrease. Therefore, phenol (a) is
(c) 1, 6-Hexanediol (d) 3, 4-Hexanediol the strongest acid.
4. (d) :
29. In the reaction, CH2OH
O O OH –
Step 1 – CH3CHO + 3HCHO Aldol HOH2C C CHO
R C Cl R C + + Cl
O O -C without H
Step 2 + Cannizzaro OH –
R C+ + :NH3 R C NH2 + H reaction
step (2) is CH2OH CH2OH
(a) neutralisation HOH2C C COO– + HOH2C C CH2OH
(b) electrophilic attack at the carbonyl carbon
(c) nucleophilic attack of lone pair of N at the CH2OH CH2OH
carbonyl carbon leading to substitution O O
(i) I2 + NaOH 
(d) nucleophilic addition reaction. 5. (c) : 
(ii) H + 
30. Predict the product of the following reaction. C CH3 (-keto acid) C OH
(i) NaOI
(ii) H2O/H+, 

chemistry today | January ‘15 59

6. (a) 7. (c) 19. (c) : The reactivity of alcohols towards
8. (b) : Less stable the diazonium salt, more conc. HCl depends on the stability of
reactive it is. Since the stability decreases in carbocation being formed. When –OH group
the order : I > III > IV > II, therefore, reactivity released as OH– ion, carbocation is formed.
increases in the reverse order, i.e., I < III < IV < II. CH3 CH3
9. (c) +
F F +
10. (d) : 40% H2SO4 I II
1% HgSO4,  O
HO CH2 CH3 CH3 +
+ + Ph
11. (b) : CH3CH2CH2 O CH(CH3)2 III IV
 
H Thus, the order of stability of these carbocations
CH3CH2CH2OH +(CH3)2CH is IV > III > II > I. Hence, the order of reactivity
Weak base (more stable will also be same.
O 20. (b)
12. (b) :
CHO 21. (a) : 4-Nitrobenzoic acid is the strongest acid
OH as –NO2 group shows –I and –M effects at
13. (d) : CH3CH2CH2Cl + alc. KCN ortho and para positions and it is a stronger
CH3CH2CH2CN + KCl electron withdrawing group.
14. (a)
22. (d) 23. (c)
15. (b) : RCONH2 + NaOH → RCOONa + NH3
59 g (1 mole) 17 g (1 mole) 24. (c) : (CH3)2C O + H3CCOCH3 + O C(CH3)2
Thus, wt. of 1 mole of RCONH2 = 59 g A, Propanone (C3H6O), gives iodoform test (3 molecules)
In other words, R + 12 + 16 + 14 + 2 = 59 HCl
→ (CH3)2C CHCOCH C(CH3)2
\ R = 59 – 44 = 15 g 2,6-Dimethyl-2,5-heptadien-4-one
Molecular mass of R is 15 which corresponds
to CH3 group, hence RCOOH should be 25. (d)
16. (a) : The reactivity of alcohols towards 26. (b) : C6H5CONH2  C6H5NH2
(A) (B)
esterification increases as :
3° < 2° < 1° < CH3OH C6H5N C 
 NaBH4
17. (d) : –H2O
Aniline gives azo dye test.
O NH2 N ZnCl2
27. (d) : C6H5NH2 + OHCC6H5 
This class of compounds is called Schiff ’s base
18. (a) : H
P + I2 AgNO2 or anils.
28. (d) : CH3 CH2 CH CH CH2 CH3
CH3 C NO–Na+
Only vicinal diols are cleaved by HIO4.
Sod. salt of nitrolic acid 29. (c) 30. (d)
(Red colouration) nn

60 chemistry today | January ‘15

BOARD 2015

Series-8 Amines and Biomolecules

Time : 3 hrs. Marks : 70

(i) All questions are compulsory.
(ii) Question numbers 1 to 5 are very short-answer questions and carry 1 mark each.
(iii) Question numbers 6 to 10 are short-answer questions and carry 2 marks each.
(iv) Question numbers 11 to 22 are also short-answer questions and carry 3 marks each.
(v) Question number 23 is value based question and carries 4 marks.
(vi) Question numbers 24 to 26 are long-answer questions and carry 5 marks each.
(vii) Use Log Tables, if necessary. Use of calculator is not allowed.

1. Give IUPAC name of sulphanilic acid. (i) C2H5NH2, C6H5NH2, NH3, C6H5CH2NH2
2. Give an example of reducing and non-reducing and (C2H5)2NH
(ii) Aniline, p-nitroaniline, p-toluidine.
sugar each.
8. Write the reaction
3. Name the products formed when a nucleotide
(i) which indicates the presence of five –OH
from DNA containing thymine is hydrolysed.
groups in glucose molecule.
4. Trimethylamine and n-propylamine have the (ii) which indicates the presence of a primary
same molecular weight but the former boils at alcoholic group in glucose.
lower temperature than the latter. Give reason. 9. Nitration of aniline gives m-nitroaniline in good
5. Complete the following reaction : yield although —NH2 group is o,p-directing.
NH2 Explain.
(i) NaNO2/H2SO4 10. Write short notes on
273–278 K (i) Carbylamine reaction
(ii) HBF4
(ii) Hofmann bromamide reaction.
6. Distinguish between : OR
(i) Globular protein and fibrous protein
What happens when
(ii) a-Glucose and b-glucose.
(i) Nitroethane is treated with LiAlH4?
7. Arrange the following in increasing order of (ii) Benzenediazonium chloride reacts with
their basic strength : phenol in basic medium?

chemistry today | January ‘15 61

11. What is the basic structural difference between OR
starch and cellulose? Mention the type of linkage responsible for the
12. (i) Name the diseases caused due to the formation of the following :
deficiency of (i) Primary structure of protein.
(a) vitamin K and (ii) Cross linkage of polypeptide chains.
(b) vitamin A. (iii) a-helix formation.
(iv) b-sheet structure.
(ii) Why cannot vitamin C be stored in our
20. Account for the following observations :
(i) Sulphanilic acid is insoluble in water but is
13. Account for the following : soluble both in aqueous bases and aqueous
(i) Ammonolysis of alkyl halide does not give mineral acids.
a corresponding amine in pure state. (ii) Tertiary amines do not undergo acylation
(ii) AgCl dissolves in aqueous methylamine reaction.
solution. (iii) Aniline readily reacts with bromine to give
14. Give reasons for the following :
(i) Aniline does not undergo Friedel–Crafts 21. Give the structures of A, B and C in the following
reaction. reactions :
(ii) Diazonium salts of aromatic amines + –
(i) C6H5N2Cl A B
are more stable than those of aliphatic NH3

Fe/HCl NaNO2 + HCl
(iii) Gabriel phthalimide synthesis is preferred (ii) C6H5NO2 A 273 K
for synthesising primary amines. H2O/H +

15. (i) Hormones are chemical messengers.
NH3 NaOH/Br2
Explain. (iii) CH3COOH A B

(ii) State the main function of insulin and NaNO2/HCl
22. Define the following and give one example of
16. Complete the following reactions :
(i) C6H5N2+Cl– + H3PO2 + H2O →
(i) Isoelectric point
(ii) C6H5N2+Cl– + C2H5OH →
(ii) Mutarotation
(iii) C6H5NH2 + Br2(aq) →
(iii) Enzymes
17. How are the following reactions carried out? 23. Rohan, had been complaining about stomach
Write the equations and conditions. ache every now and then. His teacher called
(i) Acetic acid to ethylamine the parents and asked them to stop giving him
(ii) Bromocyclohexane to cyclohexanamine. junk food and include fibre and vitamin rich
(iii) Aniline to benzonitrile. food like sprouts, fruits, whole wheat bread and
18. What is the difference between a nucleoside green leafy vegetables in his diet plan.
and a nucleotide? (i) What values are expressed by the teacher?
(ii) Give two examples of water soluble
19. Write short notes on vitamins.
(i) Glycosidic linkage (iii) What is the importance of fibre rich food?
(ii) Peptide linkage. (iv) Why do children need a protein rich diet?

62 chemistry today | January ‘15

24. (i) An optically active compound having 26. (i) An organic compound (A) having
molecular formula, C6H12O6 is found in molecular formula C2H5O2N on reduction
two isomeric forms (A) and (B) in nature. gives a compound (B) with molecular
When (A) and (B) are dissolved in water formula C2H7N. (B) on treatment with
they show the following equilibrium : HNO2 gives (C) which gives positive
(A) Equilibrium mixture (B) iodoform test. Identify A.
[a]D +111° +52.2° +19.2°
(a) What are such isomers called? (ii) Write the structures of the reagents/
(b) Can they be called enantiomers? organic compounds A to F in the following
Justify your answer. sequence of reactions :
(c) What is invert sugar? HNO3(conc.) Sn/HCl CHCl3/KOH
A H2SO4(conc.)
B C Heat
(ii) Give reasons for the following :
(a) Glucose and fructose give the same H2/Pt F
(b) Amino acids are amphoteric in nature. CH3
(i) Answer the following questions briefly : OR
(a) What are the two good sources of (i) An organic compound (A) with molecular
vitamin A? formula C4H11N, capable of being resolved
(b) What are reducing sugars? into optical isomers gives a base soluble
(c) Why is vitamin C essential to us? Give product with benzenesulphonyl chloride.
its important sources. What is the structure and IUPAC name of
(ii) Define the following terms in relation to (A)? What happens when this compound
proteins : (A) is treated with acetyl chloride?
(a) Primary structure (b) Denaturation. (ii) Which amine in each of the following pairs
25. (i) Give one chemical test to distinguish is a stronger base? Give reason.
between the following pairs of compounds : (a) CH3 CH CH3 and
(a) Methylamine and dimethylamine
(b) Secondary and tertiary amines NH2
(ii) Write the chemical reaction stating the
reaction conditions required for each of
the following conversions : (b) CH3CH2CH2NH2 and
(a) Methyl bromide to ethylamine CH3NHCH2CH3
(b) Aniline to phenol SolutionS
(c) p-Toluidine to 2-bromo-4-methylaniline
OR 1. 4-Aminobenzenesulphonic acid
(i) Write the chemical reaction stating the 2. Reducing sugar – glucose
reaction conditions required for each of Non-reducing sugar – starch
the following conversions : 3. The products of hydrolysis would be
(a) Aniline to chlorobenzene thymine, b-D-2-deoxyribose and phosphoric
(b) Acetaldehyde to ethylamine acid.
(ii) Give one chemical test to distinguish
between the following pairs of compounds : 4. n-Propylamine has two H-atoms on N-atom and
(a) Ethylamine and aniline hence undergoes intermolecular H-bonding
(b) Aniline and benzylamine whereas trimethylamine being 3° amine does
(c) Aniline and N-methylaniline not undergo H-bonding.

chemistry today | January ‘15 63

N2 Cl
– 9. Although –NH2 is o, p-directing group but
in case of nitration, aniline is protonated to
5. become anilinium ion which is meta directing.
273–278 K
Hence, m-nitroaniline is obtained in good
Aniline Benzenediazonium
chloride + –
N2 BF4
10. (i) Carbylamine reaction : Aliphatic and
aromatic primary amines on heating
with chloroform and ethanolic
Benzenediazonium potassium hydroxide form isocyanides
or carbylamines which are foul smelling
6. (i) Globular proteins are spherical in shape substances.
and are usually soluble in water whereas R NH2 + CHCl3 + 3KOH(alc.)
fibrous proteins have linear thread-like R NC + 3KCl + 3H2O
structure and are insoluble in water. (foul smell)
(ii) a-Glucose and b-glucose differ in (ii) Hofmann bromamide reaction : Primary
configuration of –OH group on the amines when heated with Br2 and aqueous
or ethanolic solution of NaOH lose a
anomeric carbon (C1). In a-glucose, the
carbon atom and are converted to the
–OH group at C1 is towards right while in
corresponding amines.
b-glucose, the –OH group at C1 is towards CH3CONH2 + Br2 + 4NaOH 
left. Acetamide
2H2O + Na2CO3 + 2NaBr + CH3NH2
7. (i) C6H5NH2 < NH3 < C6H5CH2NH2 Methylamine
< C2H5NH2 < (C2H5)2NH OR
(ii) O2N NH2 < NH2 (i) C2H5NO2 dry ether C2H5 NH2 + 2H2O
Nitroethane Ethylamine
+ –
< H3 C NH2 N NCl OH
OH – (pH = 9–10)
CHO (ii) +
273–278 K
8. (i) (CHOH)4 + 5(CH3CO)2O Benzenediazonium Phenol
Acetic anhydride
Glucose N N OH + HCl
CHO p-Hydroxyazobenzene
(Orange dye)
O 11. The basic structural difference between starch
and cellulose is of linkage between the glucose
CH2O C CH3 units. In starch, there is a-D-glycosidic linkage.
Glucose pentaacetate Both the components of starch-amylose and
(ii) amylopectin are polymers of a-D-glucose.
CHO conc. COOH conc. COOH Amylose is water soluble component which
HNO3 HNO3 constitutes about 15–20% of starch. Chemically
amylose is a long unbranched chain with
CH2OH COOH CH2OH 200–1000 a-D-(+)-glucose units held by C1–C4
Saccharic acid
Glucose Gluconic acid glycosidic linkage.

64 chemistry today | January ‘15

chemistry today | January ‘15 65
Amylopectin is insoluble in water and (ii) Diazonium salts of aromatic amines are
constitites about 80–85% of starch. It may more stable due to the dispersal of the
contain 2000 – 3000 glucose units. It is a positive charge over the benzene ring. As
branched chain polymer of a-D-glucose a result C N bond acquires some double
units in which chain is formed by C1–C4 bond character.
glycosidic linkage whereas branching occurs + + – + – + –

N N: N N: N N: N N:
by C1–C6 glycosidic linkage. On the other
hand, cellulose is a linear polymer of + +

b-D-glucose in which C1 of one glucose

unit is connected to C4 of the other through
(iii) Gabriel phthalimide synthesis involves
b-D-glycosidic linkage.
the nucleophilic attack on alkyl halide
12. (i) (a) Deficiency of vitamin K causes and during the reaction, the alkyl group
impaired blood clotting. attaches to the attacking nitrogen atom.
(b) Deficiency of vitamin A causes Since further attack on a second molecule
xerophthalmia. of alkyl halide is not possible, so pure
(ii) Vitamin C is a water soluble vitamin. primary amines are formed in this reaction
Water soluble vitamins when supplied without any impurity of 2° and 3° amines.
regularly in the diet cannot be stored in
15. (i) Hormones are molecules that transfer
our body because they are readily excreted
information from one group of cells to
in urine.
distant tissues or organ and thus control
13. (i) During ammonolysis, 1° amines obtained the metabolism. So, they act as chemical
behave as nucleophiles and can further messengers.
react with alkyl halides to form secondary (ii) Insulin controls the level of glucose in
and tertiary amines and finally quaternary blood and adrenaline prepares animals and
ammonium salt. humans for emergency in many ways by
R X + NH3 RNH2 R2NH raising the pulse rate and blood pressure,

RX + etc.
R3N R 4N X –

+ –
(ii) AgCl dissolves in aqueous methylamine 16. (i) C6H5N2Cl + H3PO2 + H2O
solution due to formation of complex C6H6 + N2 + H3PO3 + HCl
compound. + –
AgCl + 2CH3NH2 → [Ag(CH3NH2)2]+Cl– (ii) C6H5N2Cl + C2H5OH
C6H6 + N2 + CH3CHO + HCl
14. (i) In Friedel–Crafts reaction, AlCl3 is added Benzene
as a catalyst which is a Lewis acid. It forms a NH2 NH2
salt with aniline due to which the nitrogen Br Br
of aniline acquires positive charge and (iii) + 3Br2(aq) + 3HBr
acts as a strong deactivating group, hence
aniline does not undergo Friedel–Crafts Br
17. (i) CH3COOH + NH3 CH3CONH2

NH2 Acetic acid Acetamide

+ (i) LiAlH4/ether
+ AlCl3

NH2AlCl3 CH3CH2NH2 (ii) H2O

66 chemistry today | January ‘15

H3O+ –H2O
Peptide linkage
Cyclohexanamine Biomolecule Type of linkage
NH2 N+2 Cl– CN (i) Primary structure Peptide bond (linkage)
of protein
NaNO2 + HCl Cu/KCN
(ii) (ii) Cross linkage
Hydrogen bonds
273-278 K
Aniline Benzonitrile of polypeptide
disulphide linkages,
chains van der Waals and
18. Nucleoside is formed by condensation of a electrostatic forces of
purine or pyrimidine base with pentose sugar attraction
at 1′ position. When nucleoside is linked to
(iii) a-helix formation Intramolecular
phosphoric acid at 5′ position of sugar moiety,
hydrogen bonds
a nucleotide is formed.
(iv) b-sheet structure Intermolecular
(i) Nucleoside has two units - pentose sugar
hydrogen bonds
and a nitrogenous base.
(ii) Nucleotide has three units - phosphate 20. (i) Sulphanilic acid forms Zwitter ion
group, pentose sugar and a nitrogenous therefore, it is soluble both in bases and
base. mineral acids but is insoluble in water due
to greater hydrocarbon part due to which
19. (i) Glycosidic linkage : The two monosa- it cannot form H-bonds with water.
ccharide units are joined together through (ii) Tertiary amines do not undergo acylation
an oxide linkage formed by loss of a reaction because they do not have nitrogen
molecule of H2O. Such a linkage between attached to hydrogen.
two monosaccharide units through oxygen (iii) In Aniline, —NH2 group is electron
atom is called glycosidic linkage. releasing, therefore, it increases electron
CH2OH density at o and p-positions, and forms
H O H 2, 4, 6-tribromoaniline.
H – CuCN/KCN H2O/H +
OH H 21. (i) C6H5N+2Cl C6H5CN
HO Benzenediazonium Cyanobenzene
H HO (A)
O Glycosidic linkage chloride
H HO  (–H2O) Benzoic acid (B)
CH2OH Benzamide (C)
(ii) Peptide linkage : A peptide bond is an (ii) C6H5NO2 Fe/HCl
C6H5NH2 273 K
amide linkage formed between –COOH Nitrobenzene Aniline (A)
group of one a-amino acid and –NH2 H2O/H + + –
group of the other a-amino acid by loss of Phenol (C)
a water molecule. chloride (B)

chemistry today | January ‘15 67

(iii) CH3COOH Heat
Ethanoic acid Ethanamide (A) (ii) (a) CHOH
CH3NH2 (CHOH)3 –C6H5NH2, –2H2O, –NH3
Methanol (C) Methanamine (B)
22. (i) Isoelectric point : The pH at which there is Glucose CH NNHC6H5
no net migration of the amino acid under +3C6H5NHNH2
the influence of an applied electric field is –C6H5NH2, –2H2O, – NH3
called isoelectric point. e.g., (CHOH)3
Amino acid Isoelectric point CH2 OH
Neutral pH = 5 – 6.3 Glucosazone
(CHOH)3 or Fructosazone
Acidic pH = 3 – 5.4
Basic pH = 7.6 – 10.8 CH2 OH
(ii) Mutarotation : It is the spontaneous During osazone formation, the
change in optical rotation when an reaction occurs only at C1 and C2.
optically active substance is dissolved in As glucose and fructose differ from
water, e.g., a-glucose, when dissolved in each other only in the arrangement
water, its optical rotation changes from of atoms at C1 and C2, therefore they
+111° to +52.5°. give the same osazone.
(iii) Enzymes : They are biological catalysts (b) Since amino acids have both acidic
+ –
which catalyse specific biochemical (–NH3) as well as basic (–COO) groups,
reactions, e.g., therefore, they are amphoteric in
Invertase nature.
C12H22O11 + H2O Acidic Basic
Sucrose + OH – + –
D-Glucose D-Fructose R R
-Amino acid H + OH –
23. (i) Teacher has expressed her responsibility (Zwitter ion)
and concern about the health of children.
(ii) Vitamin B complex and vitamin C.
(iii) Fibre rich food prevents constipation R
which is responsible for many other OR
problems. (i) (a) Two good sources of vitamin A are
(iv) Children require protein rich diet to build carrots and butter.
muscles for the growth. (b) All those carbohydrates which contain
free aldehyde or ketone group and
24. (i) (a) These are called anomers.
reduce Tollens’ reagent or Fehling’s
(b) They cannot be called enantiomers as solution are known as reducing sugars.
they are not the mirror images of each (c) Vitamin C is essential for us because
other. its deficiency causes scurvy (bleeding
(c) The laevorotatory mixture of D-(+)- gums) and pyorrhea (loosening
glucose and D-(–)-fructose obtained and bleeding of teeth). Its sources
by the hydrolysis of sucrose is known are citrus fruits, amla, green leafy
as invert sugar. vegetables.

68 chemistry today | January ‘15

(ii) (a) Primary structure : The specific OR
sequence in which the various + –
NH2 N2Cl
a-amino acids present in a protein
are linked to one another is called its NaNO2 + HCl CuCl/HCl
(i) (a)
primary structure. 273-278 K

(b) Denaturation : The loss of biological Aniline Benzenediazonium chloride

activity of a protein by changing Cl
the pH, temperature or by adding
some salt due to disruption of
native structure of protein is called Chlorobenzene
denaturation. (b)
25. (i) (a) Methylamine and dimethylamine

can be distinguished by carbylamine CH3 C O + NH3 –H O
test. Methylamine, a primary amine, Acetaldehyde Acetaldimine

gives offensive smell on heating with H2/Ni

chloroform and alcoholic solution of CH3CH2NH2

KOH whereas dimethylamine does Ethylamine
not react. (ii) (a) Ethylamine and aniline can be
(b) Secondary amine reacts with distinguished by azo dye test. Aniline
benzenesulphonyl chloride to form reacts with HNO2 at 273-278 K
N,N-dialkylbenzenesulphonamide followed by treatment with an
which is insoluble in KOH. Tertiary alkaline solution of 2-naphthol and
amine does not react. gives a brilliant orange or red coloured
Alc. KCN LiAlH4
(ii) (a) CH3Br  CH3CN ether
Methyl bromide CH3CH2NH2 Ethylamine does not form dye. It will
Ethylamine give brisk effervescene due to the
(b) evolution of N2 but solution remains
NH2 N2Cl

OH clear.
(b) Aniline and benzylamine can also be
+ HCl Warm
distinguished by azo dye test. Aniline
Aniline Benzenediazonium Phenol
gives azo dye test while benzylamine
chloride does not.
(c) (c) Aniline when heated with an alcoholic
solution of KOH and CHCl3 gives
(CH3CO)2O Br2 offensive smell of phenyl isocyanide
Pyridine CH3COOH while N-methylaniline being a
CH3 CH3 secondary amine does not give this
p-Toluidine test.
Br + – Br (A) (B)
H or OH
Hydrolysis CH3CH2NH2 + HNO2 CH3CH2OH
(B) (C)
2-Bromo-4-methylaniline Iodoform

chemistry today | January ‘15 69

(ii) Structures of reagents/organic compounds : H
A = Benzene,
B = Nitrobenzene, N With acetyl chloride, compound (A) forms
O amide.
C = Aniline, N CH3CH2CH NH2 + CH3 C Cl
D = Phenyl isocyanide, N C H
E = Methyl phenyl amine, NH NH2
CH3 (ii) (a) CH3 CH CH3 is more basic
CH3CO than CH3 CH COOCH3 because
F = Acetic anhydride, O
OR – COOCH3 is an electron withdrawing
group which decreases the electron
(i) As compound (A) is giving a base soluble density on nitrogen atom.
product with Hinsberg’s reagent, it means (b) Since 2° amines are more basic than
the compound is a primary amine with 1° amines, so, CH3NHCH2CH3 is
–NH2 group. As the compound is capable more basic than CH3CH2CH2NH2.
of being resolved into optical isomers, it Because in 2° amine there are two
indicates the presence of chiral carbon. electron releasing groups and in
Therefore, the structure of compound (A) 1° amine only one electron releasing
is group is present.

70 chemistry today | January ‘15

The questions given in this column have been prepared strictly on the basis of NCERT Chemistry for Class XII.
This year JEE (Main & Advanced)/AIPMT/AIIMS/other PMTs have drawn their papers heavily from NCERT books.

SECTION - I cuprous cyanide gives another compound

Only One Option Correct Type Y. When compound Y is treated with H2/Ni
compound Z is obtained. Compound Z is
This section contains 20 multiple choice questions. Each
(a) benzyl alcohol (b) benzylamine
question has four choices (a), (b), (c) and (d), out of which
(c) N-ethylaniline (d) phenol.
ONLY ONE is correct.
6. Aqueous solution of nickel sulphate on treating
1. Among the following, the compound that is
with pyridine and then adding a solution of
both paramagnetic and coloured is
sodium nitrate gives dark blue crystals of
(a) K2Cr2O7 (b) (NH4)2[TiCl6]
(a) [Ni(py)4]SO4
(c) VOSO4 (d) K3[Cu(CN)4]
(b) [Ni(py)2(NO2)2]
2. Aldol condensation between which of the
(c) [Ni(py)4](NO2)2
following compounds followed by dehydration
gives methyl vinyl ketone? (d) [Ni(py)3(NO2)]2SO4
(a) Methanal and ethanal 7. m-Chlorobenzaldehyde on reaction with
(b) Two moles of formaldehyde concentrated KOH at room temperature gives
(c) Methanal and propanone (a) potassium m-chlorobenzoate and
(d) Two moles of ethanal m-hydroxybenzaldehyde
3. tert-Butyl bromide on treatment with sodium (b) m-hydroxybenzaldehyde and
methoxide yields m-chlorobenzyl alcohol
(a) sodium tertiary butoxide (c) m-chlorobenzyl alcohol and
(b) tert-butyl methyl ether m-hydroxybenzyl alcohol
(c) tert-butyl alcohol (d) potassium m-chlorobenzoate and
(d) isobutylene. m-chlorobenzyl alcohol.
4. In a close packed structure of mixed oxides, the 8. Which of the following statements are
lattice is composed of oxide ions, one-eighth incorrect?
of tetrahedral voids are occupied by divalent (i) Resins are thermoplastics.
cations ‘A’ while one-half of octahedral voids (ii) Nylon-6 is an example of addition
are occupied by trivalent cations ‘B’. The homopolymers.
formula of the oxide is (iii) Neoprene is a synthetic rubber.
(a) A2BO4 (b) AB2O3 (iv) Buna-S is a polymer of 1, 3-butadiene and
(c) A2BO3 (d) AB2O4 acrylonitrile.
5. Aniline is treated with NaNO2/HCl at 0°C to (a) (i), (iii), (iv) (b) (ii), (iii)
give compound X which on treatment with (c) (i), (ii), (iv) (d) All are incorrect.

chemistry today | JaNUaRY ‘15 71

9. For the dilute solution, Raoult’s law states that (a) 1st (b) 2nd
(a) the lowering of vapour pressure is equal to (c) 3rd (d) 4th
the mole fraction of the solution 13. Which of the following are intermediates
(b) the relative lowering of vapour pressure is in the reaction of excess of CH3MgBr with
equal to the mole fraction of the solute C6H5COOC2H5 to make 2-phenyl-2-propanol?
(c) the relative lowering of vapour pressure
is proportional to the amount of solute in
solution A.
(d) the vapour pressure of the solution is equal
to the mole fraction of solvent.
10. In a set of reactions, acetic acid yields a product S. O
B. C6H5 C CH3

C. C6H5 C CH3
The compound S would be

C COOH (a) A and B (b) A, B and C

(a) . (c) A and C (d) B and C
14. For a first-order reaction, the time required for
COOH 99.9% of the reaction to take place is nearly
CH2 C CH3 (a) 10 times that required for half the reaction
(b) (b) 100 times that required for two-third of the
OH reaction
OH (c) 10 times that required for one-fourth of the
CH3 reaction
(c) (d) 20 times that required for half of the
CN reaction.
15. Calculate the ebullioscopic constant for water.
C CH3 The heat of vaporisation is 40.685 kJ mol–1.
(d) (a) 0.512 K kg mol–1 (b) 1.86 K kg mol–1
(c) 5.12 K kg mol–1 (d) 3.56 K kg mol–1
11. Which of the following statements about
lanthanides is incorrect? 16. Antiseptic chloroxylenol is
(a) All lanthanides are highly dense metals. (a) 4-chloro-3,5-dimethylphenol
(b) More characteristic oxidation state of (b) 3-chloro-4,5-dimethylphenol
lanthanides is +3. (c) 4-chloro-2,5-dimethylphenol
(c) Lanthanides are separated from one (d) 5-chloro-3,4-dimethylphenol.
another by ion exchange method. CH3
(d) Ionic radii of trivalent lanthanides steadily (CH3CO)2O Br2 / CH3COOH
increase with increase in atomic number. 17. A B
12. The presence or absence of hydroxy group on H+ / H2O
which carbon atom of sugar differentiates RNA NH2 X
and DNA? What is X ?

72 chemistry today | JaNUaRY‘15

CH3 CH3 In the light of the data given, which of the
Br following reaction(s) will take place?
(a) (b) (a) Pb2+ + 2Ag → 2Ag+ + Pb
Br (b) Pb2+ + H2 → 2H+ + Pb
NH2 NH2 (c) 2H+ + 2Ag → 2Ag+ + H2
(d) 2Ag+ + Pb → Pb2+ + 2Ag
COCH3 22. A positive carbylamine test is given by
(c) (d) (a) N, N-dimethylaniline
COCH3 (b) 2, 4-dimethylaniline
(c) N-methyl-o-methylaniline
(d) p-methylbenzylamine.
18. Strength of acidity is in order
OH OH 23. Potassium manganate (K2MnO4) is formed
I. II. (a) chlorine is passed into aqueous KMnO4
CH3 (b) manganese dioxide is fused with potassium
OH hydroxide in air
NO2 (c) formaldehyde reacts with potassium
permanganate in presence of a strong
NO2 (d) potassium permanganate reacts with
concentrated sulphuric acid.
(a) II > I > III > IV (b) III > IV > I > II
24. Which of the following synthesis gives
(c) I > IV > III > II (d) IV > III > I > II
19. For H3PO3 and H3PO4 the correct choice is Mg (i) HCHO
(a) 2-Bromohexane dry ether
(a) H3PO3 is dibasic and reducing (ii) H3O+
(b) H3PO3 is dibasic and non-reducing O
(c) H3PO4 is tribasic and reducing Mg (i)
(b) 2-Bromopentane dry ether
(d) H3PO3 is tribasic and non-reducing. (ii) H3O+

20. Among the electrolytes Na2SO4, CaCl2, Al2(SO4)3

(c) 3-Bromopentane
and NH4Cl, the most effective coagulating agent
for Sb2S3 sol is Mg (i) CH3COCH3
(a) Na2SO4 (b) CaCl2 (d) 1-Bromobutane dry ether
(ii) H3O+
(c) Al2(SO4)3 (d) NH4Cl
25. Adsorption is accompanied by
SECTION - II (a) decrease in enthalpy of the system
One or More Options Correct Type (b) increase in entropy of the system
This section contains 5 multiple choice questions. Each (c) decrease in free energy of the system
question has four choices (a), (b), (c) and (d), out of which (d) TDS for the process is positive.
ONE or MORE are correct. SECTION - III
21. The half-cell (electrode) reactions with their Paragraph Type
appropriate standard reduction potentials are : This section contains 2 paragraphs each describing
(i) Pb2+ + 2e– Pb (E° = –0.13 V) theory, experiment, data, etc. Six questions relate to two
(ii) Ag+ + e– Ag (E° = +0.80 V) paragraphs with three questions on each paragraph.

chemistry today | JaNUaRY ‘15 73

Each question of a paragraph has only one correct A SN2 reaction proceeds with complete
answer among the four choices (a), (b), (c) and (d). stereochemical inversion while a SN1 reaction
Paragraph for Questions 26 to 28 proceeds with racemisation.
A few elements like carbon, sulphur, gold and 29. The number of possible enantiomeric pairs that
noble gases, occur in free state while others in can be produced during monochlorination of
combined forms in the earth’s crust. The extraction 2-methylbutane is
and isolation of an element from its combined (a) 2 (b) 3
form involves various principles of chemistry. The (c) 4 (d) 1
process of metallurgy and isolation should be such 30. The reactions
that it is chemically feasible and commercially
viable. The extraction and isolation of metals from CH3Br + OH– CH3OH + Br–
ores involve the following major steps : CH3(CH2)5
– Concentration of the ore. OH –
H 3C C Br
– Isolation of the metal from its concentrated H
– Purification of the metal.
obey the mechanism predominantly
26. According to Ellingham diagram, the oxidation
(a) SN1 (b) SN2
reaction of carbon to carbon monoxide may
be used to reduce which one of the following (c) SE1 (d) SE2
oxides at the lowest temperature? 31. The organic chloro compound, which shows
(a) Al2O3 (b) Cu2O complete stereochemical inversion during a
(c) MgO (d) ZnO SN2 reaction is
27. In the cyanide extraction process of silver from (a) CH3Cl (b) (C2H5)2CHCl
argentite ore, the oxidising and reducing agents (c) (CH3)3CCl (d) (CH3)2CHCl
used are SECTION - IV
(a) O2 and CO respectively Matching List Type
(b) O2 and Zn dust respectively
This section contains 3 multiple choice questions. Each
(c) HNO3 and Zn dust respectively question has matching lists. The codes for the lists have
(d) HNO3 and CO respectively. choices (a), (b), (c) and (d), out of which ONLY ONE is
28. When the sample of copper with zinc impurity correct.
is to be purified by electrolysis, the appropriate 32. Match the List I with List II and select the correct
electrodes are answer using the code given below the lists :
Cathode Anode List I List II
(a) pure zinc pure copper Compounds pKb value
(b) impure sample pure copper P. Ammonia 1. 8.92
(c) impure zinc impure sample Q. Methanamine 2. 9.38
(d) pure copper impure sample. R. Benzenamine 3. 3.38
S. N, N-Dimethylaniline 4. 4.75
Paragraph for Questions 29 to 31
Nucleophilic substitution reactions in haloalkanes (a) 2 1 3 4
proceed by two different mechanisms : (b) 1 2 3 4
– Substitution nucleophilic bimolecular (SN2) (c) 4 1 2 3
– Substitution nucleophilic unimolecular (SN1) (d) 4 3 2 1

74 chemistry today | JaNUaRY‘15

33. Match the List I with List II and select the correct Reason : [Co(en)2Cl2]+ complex ion has an
answer using the code given below the lists : octahedral geometry.
List I List II 36. Assertion : Both SO2 and SO3 are reducing
P. 1 mole of Al3+ to Al 1. 482500 C agents.
Reason : Both SO2 and SO3 bleach the articles
Q. 1 mole of MnO4– to 2. 96500 C
Mn2+ by reduction.
R. 1 mole of H2O to O2 3. 289500 C 37. Assertion : Heat of chemisorption is always
greater than heat of physisorption.
S. 1 mole of FeO to Fe2O3 4. 193000 C Reason : Chemisorption involves stronger
P Q R S bonds than physisorption.
(a) 3 4 2 1 38. Assertion : Bakelite is a thermosetting plastic.
(b) 3 1 4 2 Reason : In thermosetting plastics, the polymeric
(c) 1 3 2 4 chains are held together by strong ionic bonds.
(d) 4 3 1 2 39. Assertion : The cell constant of a cell does not
34. Match the List I with List II and select the correct depend upon the nature of the material of the
answer using the code given below the lists : electrode.
List I List II Reason : The observed conductance of a solution
Interhalogen Shape depends upon the nature of the material of the
compounds electrodes.
P. XY 1. T-shaped 40. Assertion : In strongly acidic solutions, aniline
Q. XY3 2. Square pyramidal becomes more reactive towards electrophilic
R. XY5 3. Linear reagents.
S. XY7 4. Pentagonal Reason : The amino group being completely
bipyramidal protonated in strongly acidic solution, the lone
P Q R S pair of electrons on the nitrogen is available for
(a) 1 2 4 3 resonance.
(b) 4 3 1 2 SECTION - VI
(c) 3 1 2 4 Integer Value Correct Type
(d) 4 1 2 3
This section contains 10 questions. The answer to each
SECTION - V question is a single digit integer, ranging from 0 to 9
Assertion-Reason Type (both inclusive).
In the following questions, a statement of assertion is 41. A binary solid (A+B–) has a zinc blende
followed by a statement of reason. Mark the correct structure with B– ions constituting the lattice
choice as : and A+ ions occupying 25% tetrahedral holes.
(a) If both assertion and reason are true and reason is The formula of solids is ABx. The value of x is
the correct explanation of assertion.
42. Of the following compounds methanal,
(b) If both assertion and reason are true but reason is 2-methylpentanal, benzaldehyde, benzo-
not the correct explanation of assertion.
phenone, cyclohexanone, 1-phenylpro-
(c) If assertion is true but reason is false.
panone, phenylacetaldehyde, butan-1-ol
(d) If both assertion and reason are false. and 2, 2-dimethylbutanal, the total number
35. Assertion : The total number of isomers shown of compounds that can undergo aldol
by [Co(en)2Cl2]+ complex ion is three. condensation is

chemistry today | JaNUaRY ‘15 75

43. In the complex, [Fe(EDTA)]–, the coordination 2. (c) :
number of the metal ion is
44. Time required to complete a definite fraction of OH O
a reaction varies inversely to the concentration
of reactant, then the order of reaction is H2 C CH2 C CH3

45. When Cl2 is passed through hot and

concentrated solution of KOH, the compound
formed is KClOx. The value of x is 3. (d) : Tertiary alkyl halides would undergo
46. The total number of optically active compounds elimination to produce alkenes. Thus, tert-butyl
from the following list is bromide on heating with methoxide ion mainly
C2H5NHCH3, undergoes elimination to form isobutylene.
CH3CH2CH(CH3)N(CH3)C2H5, 4. (d) : No. of oxide ions (O2–) per unit cell = 1
+ No. of tetrahedral voids per ion in lattice = 2
[Ph(CH3 )(C 2 H5 ) NH]I− ,
No. of divalent cations (A) = 1 × 2 = 1
+ 8 4
[(C 2 H5 )(CH3 )2 N H] I− , No. of octahedral voids per ion in lattice = 1
1 1
C 6 H5 (CH3 ) (C 2 H5 ) N − O− , No. of trivalent cations (B) = 1 × =
2 2
(CH3)(C2H5)NCH(CH3)2 Hence, Formula = A1/4B1/2O = AB2O4
47. If 0.15 g of a solute dissolved in 15 g of solvent
is boiled at a temperature higher by 0.216 °C,
than that of the pure solvent, the molecular 5. (b) :
weight of the substance is 1 × 10x g. The value
of x is (Molal elevation constant for the solvent
is 2.16 °C)
48. Total number of isomers of C5H11Cl is
(optical isomers not included.)
49. van’t Hoff factor of Hg2(NO3)2 if it is 100%
ionised in aqueous solution is
50. An alloy of Pb-Ag weighing 1.08 g was 6. (c) : NiSO4 + 4py + 2NaNO2 Na2SO4
dissolved in dilute HNO3 and the volume made + [Ni( py )4 ](NO2 )2
to 100 mL. A silver electrode was dipped in the
solution and EMF of the cell set-up was 0.62 V. 7. (d) : It is an example of Cannizzaro’s reaction.
Pt(s), H2(g) |H+ (1 M) | | Ag+(aq)|Ag(s)
The percentage of Ag in the alloy is
[E°cell = 0.80 V, 2.303 RT/F = 0.06 at 25 °C]

1. (c) : K2Cr2O7 → Cr+6 : 3d0

8. (c) : Resins are thermosetting plastics. Nylon-6
(NH4)2[TiCl6] → Ti+4 : 3d0 is an example of condensation homopolymers.
VOSO4 → V+4 : 3d1 Buna-S is a polymer of 1,3-butadiene and
K3[Cu(CN)4] → Cu+ : 3d10 styrene.

76 chemistry today | JaNUaRY‘15

9. (b) log 2 0.3010
10. (a) : t1/2 = ×t = × t = 0.10 t
3 3
\ t = 10t1/2

RT02 M
15. (a) : K b =
1000∆H vapour
8.314 × (373.15)2 × 18
= × 10−3
1000 × 40.685
= 0.512 K kg mol–1

11. (d) : Ionic radii of trivalent lanthanides steadily

16. (a) : H3C CH3
decrease with increase in atomic number due
to lanthanide contraction. Chloroxylenol
12. (b) : The sugar molecule found in RNA is (4-Chloro-3,5-dimethylphenol)
D-ribose while the sugar molecule in DNA is
D-2-deoxyribose. The sugar D-2-deoxyribose
differs from ribose only in the substitution of 17. (b) :
hydrogen for an — OH group at 2-position.

13. (b) :

18. (b) : An electron withdrawing group increases

the acidic strength while an electron releasing
group decreases the acidic strength of phenol.
19. (a) : Structure of H3PO3 is P
Since it has only two —OH groups so it is dibasic
and it has one P — H bond so it is reducing.
1 100 1 100 20. (c) : Sb2S3 is a negative sol and according to
14. (a) : k = ln = ln
t 100 − 99.9 t 0. 1 Hardy- Schulze rule :
ln 2 1  ln 2  (i) Ions carrying charge opposite to that of sol
or = ln 103 ∴ k =
t1/2 t  t1/2  particles are effective in causing coagulation.
(ii) Coagulating power of an electrolyte is
log 2 1 3
or = × log 103 = directly proportional to the valency of the
t1/2 t t active ions.

chemistry today | JaNUaRY ‘15 77

\ Out of the given options, the most effective directly to the metal by heating with coke as the
coagulating agent is Al2(SO4)3 or Al3+ ion. lines of C, CO and C, CO2 lie below Cu, Cu2O
at much lower temperature (500-600 K).
21. (d) : Ag+ + e– Ag(E° = +0.80 V) – at cathode
Cu2O + C 2Cu + CO
Pb Pb + 2e– (E° = +0.13 V) – at anode

E°cell = E°cathode – E°anode 27. (b) : Silver ore is oxidised by using oxygen from
E°cell = 0.80 – 0.13 air as follows :
E°cell = 0.67 V 4Ag + 8NaCN + 2H2O + O2(air)
Any redox reaction would occur spontaneously 4Na[Ag(CN)2] + 4NaOH
if the free energy change (DG) is negative Sodium argentocyanide
DG° = –nFE°cell oxidation
Ag(0) Ag(+1)
When E°cell is positive, the cell reaction is Silver is precipitated from the solution by
spontaneous and serves as a source of electrical addition of Zn powder in a finely divided
energy. condition.
22. (b,d) : Both aliphatic and aromatic primary
amines give positive carbylamine test. Hence,
2,4-dimethylaniline and p-methylbenzylamine reduction
give this test. Ag(+1) Ag(0)
23. (b,c): 2MnO2 + 4KOH + O2 28. (d) : The impure metal is made anode while a thin
2K2MnO4 + 2H2O sheet of pure metal acts as cathode. On passing
HCHO + 2KMnO4 + 2KOH the current, the pure metal is deposited on the
2K2MnO4 + H2O + HCOOH cathode and equivalent amount of the metal gets
dissolved from the anode.
24. (b) : CH3 CH CH2 CH2 CH3 dry ether Cl2
29. (a) : CH3 CH CH2 CH3
CH3 CH CH2 CH2 CH3 *
CH3 CH CH2 CH2 CH3 * CH3
CH3 Cl

30. (b) : SN2 order for reactions are 3° < 2° < 1°

methyl halide follows SN2 mechanism. In SN2
25. (a,c) : As adsorption is spontaneous, DG for the reactions inversion in configuration occurs.
process is –ve. Adsorption is accompanied by
31. (a) : In SN2 reactions, the nucleophile attacks
decrease in randomness, therefore DS and TDS
from back side resulting in the inversion of
for the process is also negative. As DS for the
molecule. Also, as we move from 1° alkyl halide
process is –ve and the process is spontaneous,
to 3° alkyl halide, the crowding increases and
DH for the process has to be –ve (and
+I effect increases which makes the carbon
DH > TDS in magnitude) i.e., enthalpy of the
bearing halogen less positively polarised and
system decreases.
hence less readily attacked by the nucleophile.
26. (b) : In the graph of Df G° vs T for formation of
oxides, the Cu2O line is almost at the top. So, 32. (d) : Smaller the value of pKb , stronger is the
it is quite easy to reduce oxide ores of copper base. Aliphatic amines are stronger bases

78 chemistry today | JaNUaRY‘15

than ammonia due to +I effect of alkyl groups 37. (a) : As physisorption involves only van der Waals
leading to high electron density on the nitrogen forces of attraction and no chemical change,
atom. Aromatic amines are weaker bases than the process is exothermic but the enthalpy of
ammonia as the lone pair of electrons on adsorption is quite low (20-40 kJ mol–1) as
the nitrogen atom gets delocalized over the compared to (200-400 kJ mol–1) in case of
benzene ring and thus is less easily available for chemisorption.
protonation. 38. (c) : Thermosetting plastics are cross-linked
33. (b) : Charge required to reduce high polymers formed from their monomers by
Al3+ + 3e– Al condensation polymerization. In these polymers
1 mole of Al to Al ; Q = 3 × F = 3 × 96500 the chains are held together by strong covalent
= 289500 C bonds. Bakelite is also a condensation polymer
MnO4– + 8H+ + 5e– Mn2+ + 4H2O and formed by condensation polymerization of
formaldehyde and phenol.
1 mole of MnO4– to Mn2+; Q = 5 × F
= 5 × 96500 = 482500 C 39. (b)
1 40. (d) : In strongly acidic solutions, aniline
H2O O + 2 H+ + 2e − becomes less reactive towards electrophilic
2 2
1 mole of H2O to O2; Q = 2 × F The amino group being completely protonated
= 2 × 96500 = 193000 C in strongly acidic solution, the lone pair of
1 1 electrons on the nitrogen is no longer available
FeO + HO Fe O + H+ + e −
2 2 2 2 3 for resonance.
1 mole of FeO to Fe2O3 41. (2) : No. of B– ions in unit cell
Q = 1 × F = 96500 C 1 1
=8× +6× =4
34. (c) : 8 2
Molecule Total Bond Lone Shape Now A ion occupies 25% of tetrahedral holes
no. of pairs pairs 8 × 25
= =2
e–s pairs 100
around Thus, ratio of B– to A+ is 2 : 1 or formula is
X AB2.
XY 4 1 3 Linear 42. (4) : 2-Methylpentanal, cyclohexanone,
XY3 5 3 2 Bent
1-phenylpropanone and phenylacetaldehyde
T-shaped contain a-hydrogen atoms and hence undergo
aldol condensation.
XY5 6 5 1 Square
pyramidal 43. (6) : EDTA is a hexadentate ligand.
XY7 7 7 0 Pentagonal 2nd order
bipyramidal 1
44. (2) :
35. (b) : [Co(en)2Cl2]+ exists in cis-and trans-isomers
out of which only cis-isomer will show optical t
activity. 45. (3) : 6KOH + 3Cl2 5KCl + KClO3 + 3H2O
(hot and conc.)
36. (d) : SO2 is a reducing agent while SO3 is an
46. (3) : Three compounds are optically active.
oxidising agent. Only SO2 bleaches the articles
by reduction. CH3CH2 C H(CH3 )N(CH3 )C 2 H5

chemistry today | JaNUaRY ‘15 79

+ 50. (1) : H2 + 2Ag+ 2H+ + 2Ag
[Ph(CH3 )(C 2 H5 ) N H] I−
2.303 RT 1
+ Ecell = Ecell
° − log
C6H5(CH3)(C2H5)N O– nF [Ag + ]2
0.62 = 0.80 + 0.06 log [Ag+]
47. (2) : Given : Weight of solute (WB) = 0.15 g;
− 0.18
Weight of solvent (WA) = 15 g; Change in the or log[Ag + ] = = −3
boiling temperature (DTb) = 0.216 °C ; Molal
or [Ag+] = 1.0 × 10–3 M
elevation constant (Kb) = 2.16 °C
= 1.0 × 10–3 × 108 = 0.108 g L–1
K b × WB × 1000 \ Amount of Ag in 100 mL solution
MB =
∆Tb × WA = 0.0108 g
∴ % Ag = × 100 = 1%
2.16 × 0.15 × 1000 1.08
= = 100 g or 1 × 102 g nn
0.216 × 15
48. (8) : CH3 CH2 CH2 CH2 CH2 Cl M P
Cl A I Y T N L R
Cl L O N B A R I U M
Cl R O O
Winners of December 2014 Crossword
CH3 CH CH CH3 Arkaprava Mahapatra, Bankura (West Bengal)
Cl Kashish Arora, Ambala Cantt. (Haryana)
Suraj Chatterjee, Kolkata (West Bengal)
Senders of December 2014 Crossword
CH3 C CH2 Cl Muhammad Haneefa. A. (Kerala)
Devjit Acharjee, Kolkata (West Bengal): The idea is very
innovative. It is like ‘oxygen’ to all chemistry lovers. By
49. (3) : Hg2(NO3)2 Hg22+ + 2NO3– solving it, anyone can enhance his knowledge in chemistry.
Divya Acharya, Palampur (Himachal Pradesh): It was a
Total ions = 3 wonderful experience for me. I enjoyed it a lot.

80 chemistry today | JaNUaRY‘15

Mukul C. Ray, Odisha
Performance of Atmospheric Air - Know Your Air a parcel of warm air rises, it expands and uses
This is a concept of our day-to-day life. its own energy to push back the molecules of
The barometric formula is surroundings and gets cooled. Cool air can absorb
lower concentration of water vapour than warm air.
P = P0e −h/H Thus water vapours accumulate to form cloud. That
where P0 is the pressure at the sea level and H = is why a cloudy sky is seen as rising air and clear sky
which is about 8 km. Here, T is the temperature, g is as descending air.
the acceleration due to gravity and M is the average van der Waals Constants
molar mass of air, which is around 29 grams per The van der Waals equation is a semi-empirical
mole. equation because the ideal gas laws on which it is
It implies that the pressure and the density fall to based can be derived from pure theory, but ‘a’ and
about half at a height of about 6 km. ‘b’ are empirical parameters found by trial and error
24 method. One can start with any plausible estimates
for ‘a’ and ‘b’, vary them, compare the results with
18 the measured P, V and T behaviour, and select
Altitude, h/km

the values that give the best agreement with the
experimental findings.
6 2r
No other molecule
can bring its centre
0 0.5 1 to this space
Pressure, P/P0
Variation of pressure with altitude as
predicted by barometric formula
Now one important point is, moist air is less dense
The space shown above with radius 2r
than dry air. At a given temperature and pressure, is wasted for two molecules
a given volume of air contains same number of About van der Waal constant ‘b’ the logic is, in
molecules as per Avogadro’s hypothesis. But most case of ideal gas, the entire volume of the container
of the molecules of air have higher molar mass than is available for molecules to move about as the
water. By water coming in, the average molar mass molecules occupy negligible volume. But in real
of air decreases. gas, molecular volume cannot be neglected. The
The term “weather”, means local variation of subtracted volume for a single molecule is four
pressure, temperature and composition of air. times the molecular volume. For one mole of
A small region of air is termed as “parcel”. When molecules, the subtracted volume is ‘b’.

chemistry today | January ‘15 81

It is well known that, pressure correction is due to As temperature increases, these values of V come
intermolecular attraction. For some gases, values of closer and at one stage they coalesce to a single
‘a’ and ‘b’ vary as : point. The temperature at which this happens is
Value of ‘a’ (in atm L2 mol–2) called the critical temperature of gas.
SO2 > Cl2 > C2H6 > NH3 > CO2 > CH4 > O2 > For CO2 this temperature is 304 K. But the
N2 > H2 > He oscillations, the van der Waal loops, are unrealistic.
Value of ‘b’ (in L mol ) For example; an increase in pressure cannot lead to
an increase in volume (P-V diagram cannot have a
C2H6 > SO2 > Cl2 > CH4 > CO2 > N2 > NH3 >
positive slope).
O2 > H2 > He
Significance :
The order might be different in different books but
€ At the critical temperature, the gaseous state
this one is absolutely correct.
appears to transform continuously into
Note : Both ‘a’ and ‘b’ decrease with increase in
condensed state and there is no visible surface
temperature but ‘a’ decreases much more rapidly
between the two states of matter.
than ‘b’.
€ The densities of the gas and the liquid states
Critical Temperature of Gas and its Implication of the same matter are identical at this
With slight mathematical manipulation van der temperature.
Waals equation can be converted to a cubic equation € A gas cannot be condensed to liquid by
of volume. application of pressure unless the temperature
 RT  2 a ab is less than the critical temperature.
V 3 − b +  V + V − =0
 P  P P € Easily liquefiable gases have higher critical
For any given P at constant temperature, three temperature. For example, in case of ammonia
it is 132 °C and for hydrogen it is –240 °C.
values of V will be there, either all are real or one
real, two imaginary (imaginary values always € Most practical significance is, it is used to
appear in pairs). Now when plotted, the graph looks distinguish between vapour and gas as :
like the one shown below. – A vapour is the gaseous phase of a substance
below its critical temperature.
100 – A gas is the gaseous phase of a substance
T = 350 K
above its critical temperature.
304 K 325 K – The pressure and the molar volume at the
80 (Tcritical)
critical temperature are called critical
291 K pressure and critical volume respectively
for the substance.
p in air

Note : Critical temperature of water is 373 °C

40 and the vapour pressure at this temperature is
273 K
218 atm.
Collision Frequency and Mean Free Path
Vliquid Vvapour Considering ‘z’ is the average number of collisions
0 0.1 0.2 0.3 0.4 one molecule make in a unit time in unit volume
Vmol and ‘l’ as the mean free path that is the average
Isotherms of carbon dioxide according distance travelled between two collisions, it can be
to the van der Waals equation
written that

82 chemistry today | January ‘15

chemistry today | January ‘15 83
Distance between collisions per unit volume per unit time (sometimes this z is
Vav = also called as collision frequency but strictly writing
Time between collisions
the former should be written as z1 and the latter
Mean free path λ
= = as z11)
Time of flight 1/ z
σVav P 2
By applying kinetic model, z11 =
kT 2k 2T 2
σP The term P/kT is the number density. For one
where σ is the collision cross-section (it is equal to molecule, the number of collisions is given by the
πd2,where d is the distance between the centres of expression of z above. Following unitary method,
the two colliding molecules) and k is the Boltzmann for all molecules, it should be multiplied by P/kT.
constant. Thus But by the way each collision is counted twice hence
σVav P there comes a denominator 2. From this equation
z= again it can be concluded that
2σVav P € At constant temperature, z11 ∝ P2
Note : Some books write it as . The
kT € For constant pressure, z11 ∝ T −3/2
equation looks totally different. The logic is very € For variable pressure, z11 ∝ T1/2
simple. When two molecules are moving towards
2σVav P
each other in a straight axis with velocity Vav, the Note : Those books, which write z as ,
relative velocity of one is 2Vav. This means when the σVav P 2
collisions are head on the velocity becomes 2Vav. would now write z11 as
2k 2T 2
For other orientations it would have lower values. It
turns out that in an average collision, the molecules Viscosity of Gas Increases with Temperature
move at right angle to each other and the relative For liquids, the viscosity decreases with increase
speed is 2Vav . So surely this a better equation. in temperature, whereas for gases it increases with
But to learn the effect of temperature and pressure increase in temperature. The viscous resistance in
it is considered as given. fluids is due to the intermolecular cohesion and
The consequences of these equations are the molecular momentum transfer in the direction
summarised below : normal to the flow. Since in liquids the molecules
€ As l ∝ 1/P, the mean free path decreases as the are closely packed, the molecular effects are less and
pressure increases. the viscous effect is mainly due to intermolecular
€ As z ∝ P, the collision frequency increases with attraction. When temperature increases cohesion
the pressure of the gas. decreases and hence for liquids viscosity decreases
with increase in temperature.
€ As z ∝ Vav and Vav ∝ In gases the molecules are widely spread and
hence molecular cohesion forces are negligible.
Heavy molecules have lower collision frequency
Since the molecular activity increases with
than light molecules.
increase in temperature, viscosity of gas increases
Now there is a slight variation :
with increase in temperature in the low-pressure
If z is the number of collisions (not the number of range.
collisions a single molecule is making) taking place

84 chemistry today | January ‘15

chemistry today | January ‘15 85
1. A galvanic cell is composed of two hydrogen (a) k1 = k2 = k3 (b) 2k1 = k2 = 3k3
electrodes, one of which is a standard one. In k k3
which of the following solutions should the (c) 4k1 = k2 = 3k3 (d) 1 = k2 =
2 3
other electrode be immersed to get maximum 5. A yellow solid known to be a single compound is
e.m.f.? completely insoluble in hot water but dissolves
(a) 0.1 M HCl (b) 0.1 M CH3COOH in hot dilute HCl to give an orange solution.
(c) 0.1 M H3PO4 (d) 0.1 M H2SO4 When this solution is cooled, a white crystalline
2. Consider oxidation of following compounds : ppt. is formed. This white ppt. redissolves on
I. CH2 CHCH2OH A CH2 CHCHO heating the solution. The compound is
CH3C CH2 (a) Fe(OH)3 (b) PbCrO4
(c) K2CrO4 (d) Co(OH)2
CH3COOH 6. Aluminium chloride exists as dimer, Al2Cl6 in
solid state as well as in solution of non-polar
IV. CH3CH CHCH3 CH3COOH solvents such as benzene. When dissolved in
A, B, C and D are oxidising agents which are water, it gives
respectively (a) Al3+ + Cl–
A B C D (b) [Al(H2O)6]3+ + Cl–
(a) MnO2 Cu/D H2CrO4 KMnO4/D (c) [Al(OH)6]3– + HCl
(b) Cu/D MnO2 H2CrO4 KMnO4/D (d) Al2O3 + HCl
(c) MnO2 Cu/D KMnO4/D H2CrO4
(d) MnO2 H2CrO4 Cu/D KMnO4/D 7. The major product of the following reaction is
3. Which is not correctly matched? (i) H+
H3 C CH3
(1) Basic strength of oxides : Cs2O < Rb2O < O (ii) H2O
K2O < Na2O < Li2O
(2) Stability of peroxides : Na2O2 < K2O2 < (a)
Rb2O2 < Cs2O2
(3) Stability of bicarbonates : LiHCO3 <
NaHCO3 < KHCO3 < RbHCO3 < CsHCO3 CH3
(b) H3C
(4) Melting point : NaF < NaCl < NaBr < NaI
(a) 1 and 4 (b) 1 and 3
(c) 1 and 2 (d) 2 and 3
4. For the reaction 2A B + 3C; if
d[ A] 2 d[ B] d[C] CH3
− = k1 [ A] ; = k2[ A]2 ; = k3 [ A]2
dt dt dt (d) H3C
the correct relation between k1, k2, and k3 is O

86 chemistry today | January ‘15

8. If a complex formed by one Ni2+ ion and some substances X, Y, Z and A are respectively
Cl– ions and some PPh3 molecules does not (a) Mg3N2, MgO, NH3, CuSO4·5H2O
show geometrical isomerism and its solution (b) Mg(NO3)2, MgO, H2, CuSO4·5H2O
does not show electrical conductance then, (c) MgO, Mg3N2, NH3, [Cu(NH3)4]SO4
which is correct about the complex? (d) Mg(NO3)2, MgO, H2O2, CuSO4·5H2O
(a) It is square planar. 13. Which of the following is a mixed anhydride?
(b) It is tetrahedral. (a) Cl2O7 (b) Cl2O3
(c) It is diamagnetic. (c) ClO2 (d) Cl2O5
(d) None of the above is correct.
14. 20 g of a sample of Ba(OH)2 is dissolved in
9. An alkene with molecular formula C8H16 on 10 mL of 0.5 N HCl solution. The excess of HCl
oxidation with hot KMnO4 gives acetone and was titrated with 0.2 N NaOH. The volume
3-pentanone. The structure of the alkene is of NaOH used was 10 mL. The percentage of
(a) (CH3)2 C C(C2H5)2 Ba(OH)2 in the sample is
(a) 1.08 (b) 1.28
(b) (c) 1.34 (d) 1.21
15. Decreasing order of reactivity in Williamson’s
(c) (C2H5)2C CHCH2CH3 ether synthesis of the following :
(d) (CH3)2C CH(CH2)3CH3 I. Me3CCH2Br II. CH3CH2CH2Br
10. For two gases, A and B with molecular weights III. CH2 CHCH2Cl IV. CH3CH2CH2Cl
MA and MB, it is observed that at a certain (a) III > II > IV > I (b) I > II > IV > III
temperature, T, the mean velocity of A is equal (c) II > III > IV > I (d) I > III > II > IV
to the root mean square velocity of B. Thus, the 16. If 15/16 quantity of a radioactive element
mean velocity of A can be made equal to the disintegrates in two hours, its half life would
mean velocity of B, if be
(a) A is at temperature T and B at T ′, T > T ′ (a) 1 hour (b) 45 min
(b) A is lowered to a temperature T ′ < T while (c) 30 min (d) 15 min.
B is at T 17. Which among the following is a hydride?
(c) both A and B are raised to a higher (a) Rogalite (b) Nitrolim
temperature (c) Hydrolith (d) Minium
(d) both A and B are placed at lower
temperature. 18. Inorganic graphite is
(a) B3N3H6 (b) B2H6
(c) BN (d) BF3
19. The standard molar enthalpies of formation of
cyclohexane(l) and benzene(l) at 25°C are –156
In the above reaction sequence ‘C’ is
and 49 kJ mol–1 respectively. The standard
(a) (b) enthalpy of hydrogenation of cyclohexene(l)
at 25°C is –119 kJ mol–1. The magnitude of
(c) (d) none of these. resonance energy of benzene is
(a) –152 kJ (b) 152 kJ
12. In the following reactions, (c) 201 kJ (d) –201 kJ
20. Hyperconjugation is most useful for stabilizing
which of the following carbocations?
(a) Neopentyl (b) tert-Butyl
(c) Isopropyl (d) Ethyl

chemistry today | January ‘15 87

21. When the following five anions are arranged Correct processes are
in order of decreasing ionic radius, the correct (a) (I), (II), (IV) (b) (I), (II), (III)
sequence is (c) (II), (IV) (d) all of these.
(a) Se2–, I–, Br–, O2–, F–
(b) I–, Se2–, O2–, Br–, F–
(c) Se2–, I–, Br–, F–, O2– 27.
(d) I–, Se2–, Br–, O2–, F–
22. The distance between an octahedral and A is
tetrahedral voids in fcc lattice would be
3a 3a 3a (a) (b)
(a) 3 a (b) (c) (d)
2 3 4
23. In the following reaction,

(c) (d)

28. A 300 mL solution of NaCl was electrolysed for

the structure of the major product X is 6 minutes. If the pH of the final solution was
12.24, the average current used is
(a) 5 A (b) 1.32 A
(c) 1.4 A (d) 1.29 A
29. Chlorination of propane is carried out in the
(b) presence of sunlight. The % yield of major and
minor alkyl halides will be
(a) 92 %, 8 % (b) 70 %, 30 %
(c) (c) 80 %, 20 % (d) 86 %, 14 %
30. pKa values of CH3COOH, CCl3COOH,
C6H5OH and C6H5SO3H are 4.79, 0.9, 10.0 and
–2.6. The leaving tendency of their conjugate
bases increases in the order
(a) C6H5O– < CH3COO– < CCl3COO–
< C6H5SO3–
24. There is loss in weight when mixture of Li2CO3 (b) C6H5O– < C6H5SO3– < CH3COO–
and Na2CO3.10H2O is heated strongly. This < CCl3COO–
loss is due to (c) CCl3COO– < C6H5O– < C6H5SO3–
(a) Li2CO3 (b) Na2CO3.10H2O < CH3COO–
(c) both (a) and (b) (d) none of these. (d) CCl3COO– < CH3COO– < C6H5SO3–
25. While testing BO3 , there is green-edged flame < C6H5O–
on heating the salt with conc. H2SO4 and ANSWER KEY
C2H5OH. Green colour is of 1. (d) 2. (a) 3. (a) 4. (d) 5. (b)
(a) (CH3)3B (b) (C2H5O)3B 6. (b) 7. (d) 8. (b) 9. (a) 10. (b)
(c) B2O3 (d) H3BO3 11. (a) 12. (c) 13. (c) 14. (b) 15. (c)
26. Of the following reduction processes, 16. (c) 17. (c) 18. (c) 19. (a) 20. (b)
(I) Fe2O3 + C → Fe (II) ZnO + C → Zn 21. (d) 22. (d) 23. (b) 24. (c) 25. (b)
(III) Ca3(PO4)2 + C → P 26. (d) 27. (a) 28. (c) 29. (a) 30. (a)
(IV) PbO + C → Pb mm

88 chemistry today | January ‘15

chemistry today | January ‘15 89
Heat produced in one second by each student
Heat produced in one second by 60 students
soLUtioN set 17 = 200 × 60 = 12000 joules
Heat produced in 20 minutes = 12000 × 20 × 60
1. (d) 2. (c)
= 144 × 105 joules
3. (c) : According to Raoult’s law; \ Change in enthalpy of air, DH = n⋅Cp⋅DT
p° − p
= x2 ⇒ 74.66 − 74.01 = x2 7
144 × 105 = 2.45 × 104 × × 8.314 × ∆T
p° 74.66 2
\ DT = 20.2 K
If M is the molar mass of hydrocarbon, then
7. (c) 8. (a)
n2 2/M
x2 = = 9. (2) : Since (A) forms hydrochloride and
n1 + n2 (100 / 78) + (2 / M )
dissolves in water to give a neutral solution, it
74.66 − 74.01 2/M contains both a basic and an acidic functional
\ = groups. It is likely to be an amino acid as
74.66 (100 / 78) + (2 / M )
–1 the molecular formula contains one N and
⇒ M = 177.7 g mol
two O-atoms. On decarboxylation it forms an
mC : mH = 94.4 : 5.6 amine (B). Therefore, (B) is a saturated amine.
94.4 5.6 (B) reacts with NaNO2 and dilute HCl forming
Thus, atomic ratio is NC : NH = :
12 1 (E), C2H5OH. Thus, (B) is CH3CH2NH2.
= 7.87 : 5.6 = 1.4 : 1 = 7 : 5 (A) also reacts with NaNO2 and dilute HCl
Hence, empirical formula is C7H5. forming (C), a hydroxy acid which forms a
Empirical formula mass = 89 g mol –1 cyclic diester (C6H8O4) on heating.
* NaOH
Molar mass 177.7CH3CHCOOH CH3CH2NH2
No. of C7H5 units = = ≈2 CaO
(B) NaNO
Empirical formula mass 89 NH2 2
Molar mass 177.7 + dil. HCl
= ≈2
Empirical formula mass 89 NaNO2
+ dil. HCl
Hence, molecular formula = C14H10 (E)
4. (b) : (CH3)3CBr + NaOC2H5 cannot be applied CH3CHCOOH
for synthesising the ether because sod. ethoxide, OH
being a strong base, will preferentially cause (C)
elimination reaction. 
3 –H2O
(CH3)3CBr  2 5
→ (CH3)2C CH2 + HBr
In the reaction of iso-butene with ethanol, (C) CH3CH CHCH3
iso-butene will form tert-butyl cation which CO O
reacts with ethanol, a nucleophile to form (D)
ether. Thus in (A), the N of –NH2 group is attached to
H+ +
(CH3)2C CH2 → (CH3 )2 C CH3 a 2° C-atom.
(i) CH CH OH
3 2
→ (CH3 )3COCH2CH3 10. (5) : Zn2+ + 4NH3 [Zn(NH3)4]2+
+ 2+
(ii) − H [Zn(NH3 )4 ]
Kf = = 2 × 109
5. (c) 2+
[Zn ][NH3 ] 4

6. (b) : Volume of the room = 10 × 15 × 4 = 600 m3 [Zn(NH3 )4 ]2+

= 60 × 104 L = [NH3 ]4 × 2 × 109
[Zn2+ ] = 104 × 2 × 109 = 2 × 1013
Moles of air in the room at 25°C and 1 atm
pressure, 2+
[Zn ]
PV 1 × 60 × 104 = 5 × 10−14
n= = = 2.45 × 104 [Zn(NH3 )4 ]2+ nn
RT 0.0821 × 298
90 chemistry today | January ‘15
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92 chemistry today | January ‘15

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1 2 3
7. Antidote for CO poisoning. (8)
8. Crystalline SiO2 is. (6) 4
12. Another name of hydrochloric 6 7
acid. (12) 8 9 10
13. Complex nitrogenous substances,
isolated from the plants which 13
when administered into the body
produce some physiological 14

action. (9)
15 16
14. A liquid-liquid colloidal system. (8)
17 18
15. Colloidal solution of gold in water
is called. (15) 20
17. Natural wax is also known as. (9)
21 22
20. Measures the relative densities of
two liquids. (10) 23

22. A platonic hydrocarbon shaped

like a tetrahedron and has not yet
been synthesized. (12) 25

23. Impurity present in ruby is . (8)

24. Used in pyrotechnics, flares and photographic 6. Mg(ClO4)2 is used as a drying agent under the
flashbulbs. (9) name. (9)
25. Difference between the potential required for the 9. The number of five membered rings in
evolution of the gas and its standard reduction fullerene. (6)
potential. (11) 10. Disease caused by the deficiency of essential amino
DOWN acids. (11)

1. The pressure developed inside the cell due to the 11. A dye formed when C6H5CHO reacts with
dimethylaniline. (14)
inflow of water into it is called. (6)
16. Freon-12, the most widely used refrigerant is
2. An alloy used to make permanent magnets. (6)
manufactured from carbon tetrachloride by
3. Method by which lighter earthy particles are ______ reaction. (6)
freed from the heavier ore particles by washing 18. A leaving group such as H+ which departs without
with water. (10) an electron pair is called an. (11)
4. Word derived from the Greek word ‘kinesis’ which 19. A waste product from steel industry having
means movement. (8) properties similar to cement. (6)
5. A derivative of phenol present in thyme and 21. The amount of space taken up by an object. (6)
mint. (6) nn

chemistry today | January ‘15 93

94 chemistry today | January ‘15