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Chemistry
Chemistry
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2019-1979
IITJEE
(JEE Main & Advanced)
Chemistry
Ranjeet Shahi
© Author
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ISBN : 978-93-13196-96-9
Amines Nomenclature, classification, structure basic Chemistry involved in the preparation of the
character and identification of primary, secondary and following
tertiary amines and their basic character. — Inorganic compounds Mohr's salt, potash alum.
Diazonium Salts Importance in synthetic organic — Organic compounds Acetanilide,
chemistry. p-nitroacetan ilide, aniline yellow, iodoform.
— Chemistry involved in the titrimetric excercises -
UNIT XXV Polymers
Acids bases and the use of indicators, oxali acid vs
General introduction and classification of polymers, KMnO4, Mohr's salt vs KMnO4.
general methods of polymerization-addition and
condensation, copolymerization; Natural and — Chemical principles involved in the qualitative salt
synthetic rubber and vulcanization; some important analysis
2+ 2+ 3+ 3+ 2+ 2+ 2+ 2+
polymers with emphasis on their monomers and uses - — Cations — Pb , Cu , Al , Fe , Zn , Ni , Ca , Ba ,
polythene, nylon, polyester and bakelite. Mg2+ NH4+. Anions – CO32-, S2-, SO42-, NO2, NO3, Cl -, Br-,
I- (Insoluble salts excluded).
UNIT XXVI Biomolecules
— Chemical principles involved in the following
General introduction and importance of
experiments
biomolecules.
1. Enthalpy of solution of CuSO4
Carbohydrates Classification aldoses and ketoses;
monosaccharides (glucose and fructose), constituent 2. Enthalpy of neutralization of strong acid and
monosaccharides of oligosacchorides (sucrose, lactose, strong base.
maltose) and polysaccharides (starch, cellulose, 3. Preparation of lyophilic and lyophobic
glycogen). sols.
Proteins Elementary Idea of α-amino acids, peptide 4. Kinetic study of reaction of iodide ion with
bond, . polypeptides; proteins: primary, secondary, hydrogen peroxide at room temperature.
tertiary and quaternary structure (qualitative idea
JEE ADVANCED
PHYSICAL CHEMISTRY Chemical Kinetics Rates of chemical reactions, Order of
reactions, Rate constant, First order reactions,
General Topics Concept of atoms and molecules, Dalton's
Temperature dependence of rate constant (Arrhenius
atomic theory, Mole concept, Chemical formulae,
equation).
Balanced chemical equations, Calculations (based on
mole concept) involving common oxidation-reduction, Solid State Classification of solids, crystalline state, seven
neutralisation, and displacement reactions, Concentration crystal systems (cell parameters a, b, c), close packed
in terms of mole fraction, molarity, molality and normality. structure of solids (cubic), packing in fcc, bcc and hcp
lattices, Nearest neighbours, ionic radii, simple ionic
Gaseous and Liquid States Absolute scale of temperature,
compounds, point defects.
ideal gas equation, Deviation from ideality, van der Waals'
equation, Kinetic theory of gases, average, root mean Solutions Raoult's law, Molecular weight determination
square and most probable velocities and their relation from lowering of vapour pressure, elevation of boiling
with temperature, Law of partial pressures, Vapour point and depression of freezing point.
pressure, Diffusion of gases.
Surface Chemistry Elementary concepts of adsorption
Atomic Structure and Chemical Bonding Bohr model, (excluding adsorption isotherms), Colloids, types,
spectrum of hydrogen atom, quantum numbers, methods of preparation and general properties,
Wave-particle duality, de-Broglie hypothesis, Uncertainty Elementary ideas of emulsions, surfactants and micelles
principle, Qualitative quantum mechanical picture of (only definitions and examples).
hydrogen atom, shapes of s, p and d orbitals, Electronic
Nuclear Chemistry Radioactivity, isotopes and isobars,
configurations of elements (up to atomic number 36),
Properties of rays, Kinetics of radioactive decay (decay
Aufbau principle, Pauli's exclusion principle and Hund's
series excluded), carbon dating, Stability of nuclei with
rule, Orbital overlap and covalent bond; Hybridisation
respect to proton-neutron ratio, Brief discussion on fission
involving s, p and d orbitals only, Orbital energy diagrams
and fusion reactions.
for homonuclear diatomic species, Hydrogen bond,
Polarity in molecules, dipole moment (qualitative aspects
only), VSEPR model and shapes of molecules (linear, INORGANIC CHEMISTRY
angular, triangular, square planar, pyramidal, square Isolation/Preparation and Properties of the following Non-
pyramidal, trigonal bipyramidal, tetrahedral and metals Boron, silicon, nitrogen, phosphorus, oxygen,
octahedral). sulphur and halogens, Properties of allotropes of carbon
(only diamond and graphite), phosphorus and sulphur.
Energetics First law of thermodynamics, Internal energy,
Preparation and Properties of the following Compounds
work and heat, pressure-volume work, Enthalpy, Hess's
Oxides, peroxides, hydroxides, carbonates, bicarbonates,
law, Heat of reaction, fusion and vaporization, Second law
chlorides and sulphates of sodium, potassium,
of thermodynamics, Entropy, Free energy, Criterion of
magnesium and calcium, Boron, diborane, boric acid and
spontaneity.
borax, Aluminium, alumina, aluminium chloride and
Chemical Equilibrium Law of mass action, Equilibrium alums, Carbon, oxides and oxyacid (carbonic acid), Silicon,
constant, Le-Chatelier's principle (effect of concentration, silicones, silicates and silicon carbide, Nitrogen, oxides,
temperature and pressure), Significance of DG and DGo in oxyacids and ammonia, Phosphorus, oxides, oxyacids
chemical equilibrium, Solubility product, common ion (phosphorus acid, phosphoric acid) and phosphine,
effect, pH and buffer solutions, Acids and bases (Bronsted Oxygen, ozone and hydrogen peroxide, Sulphur,
and Lewis concepts), Hydrolysis of salts. hydrogen sulphide, oxides, sulphurous acid, sulphuric
Electrochemistry Electrochemical cells and cell reactions, acid and sodium thiosulphate, Halogens, hydrohalic acids,
Standard electrode potentials, Nernst equation and its oxides and oxyacids of chlorine, bleaching powder, Xenon
relation to DG, Electrochemical series, emf of galvanic fluorides.
cells, Faraday's laws of electrolysis, Electrolytic Transition Elements (3d series) Definition, general
conductance, specific, equivalent and molar conductivity, characteristics, oxidation states and their stabilities,
Kohlrausch's law, Concentration cells. colour (excluding the details of electronic transitions) and
calculation of spin-only magnetic moment; Coordination (boiling points, density and dipole moments), Acidity of
compounds: nomenclature of mononuclear coordination alkynes, Acid catalysed hydration of alkenes and alkynes
compounds, cis-trans and ionisation isomerisms, (excluding the stereochemistry of addition and
hybridization and geometries of mononuclear elimination), Reactions of alkenes with KMnO4 and ozone,
coordination compounds (linear, tetrahedral, square Reduction of alkenes and alkynes, Preparation of alkenes
planar and octahedral). and alkynes by elimination reactions, Electrophilic
Preparation and Properties of the following Compounds. addition reactions of alkenes with X2, HX, HOX and H2O
(X=halogen), Addition reactions of alkynes, Metal
Oxides and chlorides of tin and lead, Oxides, chlorides and
acetylides.
sulphates of Fe2+, Cu2+ and Zn2+, Potassium permanganate,
potassium dichromate, silver oxide, silver nitrate, silver Reactions of Benzene Structure and aromaticity,
thiosulphate. Electrophilic substitution reactions, halogenation,
nitration, sulphonation, Friedel-Crafts alkylation and
Ores and Minerals Commonly occurring ores and minerals
acylation Effect of o-, m- and p-directing groups in
of iron, copper, tin, lead, magnesium, aluminium, zinc and
monosubstituted benzenes.
silver.
Phenols Acidity, electrophilic substitution reactions
Extractive Metallurgy Chemical principles and reactions
(halogenation, nitration and sulphonation), Reimer-
only (industrial details excluded), Carbon reduction
Tiemann reaction, Kolbe reaction.
method (iron and tin), Self reduction method (copper and
lead), Electrolytic reduction method (magnesium and Characteristic Reactions of the following (including those
aluminium), Cyanide process (silver and gold). mentioned above) Alkyl halides, rearrangement reactions
of alkyl carbocation, Grignard reactions, nucleophilic
Principles of Qualitative Analysis Groups I to V (only Ag+,
2+ 2+ 2+ 3+ 3+ 3+ 3+ 2+ 2+ 2+ 2+ substitution reactions, Alcohols, esterification,
Hg , Cu , Pb , Bi , Fe , Cr , Al , Ca , Ba , Zn , Mn and
2+ dehydration and oxidation, reaction with sodium,
Mg ), Nitrate, halides (excluding fluoride), sulphate and
phosphorus halides, ZnCl2/concentrated HCl, conversion
sulphide.
of alcohols into aldehydes and ketones, Ethers,
Preparation by Williamson's Synthesis, Aldehydes and
ORGANIC CHEMISTRY Ketones, oxidation, reduction, oxime and hydrazone
Concepts Hybridisation of carbon, Sigma and pi-bonds, formation, aldol condensation, Perkin reaction, Cannizzaro
Shapes of simple organic molecules, Structural and reaction, haloform reaction and nucleophilic addition
geometrical isomerism, Optical isomerism of compounds reactions (Grignard addition), Carboxylic acids, formation
containing up to two asymmetric centres, (R,S and E,Z of esters, acid chlorides and amides, ester hydrolysis.
nomenclature excluded), IUPAC nomenclature of simple Amines, basicity of substituted anilines and aliphatic
organic compounds (only hydrocarbons, mono-functional amines, preparation from nitro compounds, reaction with
and bi-functional compounds), Conformations of ethane nitrous acid, azo coupling reaction of diazonium salts of
and butane (Newman projections), Resonance and aromatic amines, Sandmeyer and related reactions of
hyperconjugation, Keto-enol tautomerism, Determination diazonium salts, carbylamine reaction, Haloarenes,
of empirical and molecular formulae of simple nucleophilic aromatic substitution in haloarenes and
compounds (only combustion method), Hydrogen bonds, substituted haloarenes (excluding Benzyne mechanism
definition and their effects on physical properties of and Cine substitution).
alcohols and carboxylic acids, Inductive and resonance Carbohydrates Classification, mono and disaccharides
effects on acidity and basicity of organic acids and bases, (glucose and sucrose), Oxidation, reduction, glycoside
Polarity and inductive effects in alkyl halides, Reactive formation and hydrolysis of sucrose.
intermediates produced during homolytic and heterolytic
Amino Acids and Peptides General structure (only primary
bond cleavage, Formation, structure and stability of
structure for peptides) and physical properties.
carbocations, carbanions and free radicals.
Properties and Uses of Some Important Polymers Natural
Preparation, Properties and Reactions of Alkanes
rubber, cellulose, nylon, teflon and PVC.
Homologous series, physical properties of alkanes
(melting points, boiling points and density), Combustion Practical Organic Chemistry Detection of elements (N, S,
and halogenation of alkanes, Preparation of alkanes by halogens), Detection and identification of the following
Wurtz reaction and decarboxylation reactions. functional groups, hydroxyl (alcoholic and phenolic),
carbonyl (aldehyde and ketone), carboxyl, amino and
Preparation, Properties and Reactions of Alkenes and
nitro, Chemical methods of separation of mono-functional
Alkynes Physical properties of alkenes and alkynes
organic compounds from binary mixtures.
1
Some Basic Concepts
of Chemistry
6. The percentage composition of carbon by mole in methane is
Topic 1 Mole Concept (2019 Main, 8 April II)
(a) 75% (b) 20% (c) 25% (d) 80%
Objective Questions I (Only one correct option)
7. 8 g of NaOH is dissolved in 18 g of H 2O. Mole fraction of
1. 5 moles of AB2 weight 125 ´ 10-3 kg and 10 moles of A2 B2
NaOH in solution and molality (in mol kg- 1 ) of the solution
weight 300 ´ 10-3 kg. The molar mass of A ( M A ) and molar
respectively are (2019 Main, 12 Jan II)
mass of B ( M B ) in kg mol -1 are (2019 Main, 12 April I) (a) 0.2, 11.11 (b) 0.167, 22.20
(a) M A = 10 ´ 10-3 and M B = 5 ´ 10-3 (c) 0.2, 22.20 (d) 0.167, 11.11
(b) M A = 50 ´ 10-3 and M B = 25 ´ 10-3 8. The volume strength of 1 M H 2O2 is
-3 -3
(c) M A = 25 ´ 10 and M B = 50 ´ 10 (Molar mass of H 2O2 = 34 g mol- 1 ) (2019 Main, 12 Jan II)
(d) M A = 5 ´ 10-3 and M B = 10 ´ 10-3 (a) 16.8 (b) 22.4 (c) 11.35 (d) 5.6
2. The minimum amount of O2 ( g ) consumed per gram of 9. The amount of sugar (C12H 22O11 ) required to prepare 2 L of
reactant is for the reaction (Given atomic mass : Fe = 56, its 0.1 M aqueous solution is (2019 Main, 10 Jan II)
O =16, Mg = 24, P =31, C =12, H =1) (2019 Main, 10 April II) (a) 17.1 g (b) 68.4 g (c) 136.8 g (d) 34.2 g
(a) C3H 8 ( g ) + 5O2 ( g ) ¾® 3CO2 ( g ) + 4H 2O( l ) 10. For the following reaction, the mass of water produced from
(b) P4 ( s ) + 5O2 ( g ) ¾® P4O10 ( s ) 445 g of C57 H110 O6 is :
(c) 4Fe( s ) + 3O2 ( g ) ¾® 2Fe2O3 ( s ) 2C57 H110 O6 ( s ) + 163O2 ( g ) ® 114CO2 ( g ) + 110 H2 O ( l )
(d) 2Mg( s ) + O2 ( g ) ¾® 2MgO( s ) (2019 Main, 9 Jan II)
3. At 300 K and 1 atmospheric pressure, (a) 490 g (b) 495 g (c) 445 g (d) 890 g
10 mL of a hydrocarbon required 55 mL of O2 for complete 11. A solution of sodium sulphate contains 92 g of Na + ions per
combustion and 40 mL of CO2 is formed. The formula of the kilogram of water. The molality of Na + ions in that solution
hydrocarbon is (2019 Main, 10 April I) in mol kg-1 is (2019 Main, 9 Jan I)
(a) C4H7Cl (b) C4H 6 (c) C4H10 (d) C4H 8
(a) 16 (b) 4 (c) 132 (d) 8
4. 10 mL of 1 mM surfactant solution forms a monolayer
12. The most abundant elements by mass in the body of a healthy
covering 0.24 cm 2 on a polar substrate. If the polar head is human adult are oxygen (61.4%), carbon (22.9%), hydrogen
approximated as a cube, what is its edge length? (10.0 %), and nitrogen (2.6%). The weight which a 75 kg
(2019 Main, 9 April II)
person would gain if all 1 H atoms are replaced by 2 H atoms is
(a) 2.0 pm (b) 0.1 nm (c) 1.0 pm (d) 2.0 nm (2017 JEE Main)
5. For a reaction, (a) 15 kg (b) 37.5 kg
N 2 ( g ) + 3H 2 ( g ) ¾® 2NH 3 ( g ), identify dihydrogen (H 2 ) (c) 7.5 kg (d) 10 kg
as a limiting reagent in the following reaction mixtures. 13. 1 g of a carbonate (M 2 CO3 ) on treatment with excess HCl
(2019 Main, 9 April I)
produces 0.01186 mole of CO2 . The molar mass of M 2 CO3
(a) 56 g of N 2 + 10 g of H 2 (b) 35 g of N 2 + 8 g of H 2 in g mol -1 is (2017 JEE Main)
(c) 14 g of N 2 + 4 g of H 2 (d) 28 g of N 2 + 6 g of H 2 (a) 1186 (b) 84.3 (c) 118.6 (d) 11.86
2 Some Basic Concepts of Chemistry
14. At 300 K and 1 atm, 15 mL of a gaseous hydrocarbon 24. The normality of 0.3 M phosphorus acid (H3PO3) is
requires 375 mL air containing 20% O2 by volume for (1999, 2M)
complete combustion. After combustion, the gases occupy (a) 0.1 (b) 0.9 (c) 0.3 (d) 0.6
330 mL. Assuming that the water formed is in liquid form 25. In which mode of expression, the concentration of a solution
and the volumes were measured at the same temperature and remains independent of temperature? (1988, 1M)
pressure, the formula of the hydrocarbon is (2016 JEE Main) (a) Molarity (b) Normality (c) Formality (d) Molality
(a) C3 H8 (b) C4 H8 (c) C4 H10 (d) C3 H6 26. A molal solution is one that contains one mole of solute in
15. The molecular formula of a commercial resin used for (1986, 1M)
exchanging ions in water softening is C8 H7 SO3 Na (a) 1000 g of solvent (b) 1.0 L of solvent
(molecular weight = 206). What would be the maximum (c) 1.0 L of solution (d) 22.4 L of solution
uptake of Ca 2+ ions by the resin when expressed in mole per 27. If 0.50 mole of BaCl 2 is mixed with 0.20 mole of Na 3 PO4 ,
gram resin? (2015 JEE Main) the maximum number of moles of Ba 3 (PO4 )2 that can be
1 1 2 1 formed is (1981, 1M)
(a) (b) (c) (d)
103 206 309 412 (a) 0.70 (b) 0.50 (c) 0.20 (d) 0.10
16. 3 g of activated charcoal was added to 50 mL of acetic acid 28. 2.76 g of silver carbonate on being strongly heated yields a
solution (0.06 N) in a flask. After an hour it was filtered and residue weighing (1979, 1M)
the strength of the filtrate was found to be 0.042 N. The (a) 2.16 g (b) 2.48 g (c) 2.32 g (d) 2.64 g
amount of acetic acid adsorbed (per gram of charcoal) is 29. When the same amount of zinc is treated separately with
(2015 JEE Main) excess of sulphuric acid and excess of sodium hydroxide, the
(a) 18 mg (b) 36 mg (c) 42 mg (d) 54 mg ratio of volumes of hydrogen evolved is (1979, 1M)
17. The ratio mass of oxygen and nitrogen of a particular gaseous (a) 1 : 1 (b) 1 : 2 (c) 2 : 1 (d) 9 : 4
mixture is 1 : 4. The ratio of number of their molecule is 30. The largest number of molecules is in (1979, 1M)
(2014 Main)
(a) 1 : 4 (b) 7 : 32 (c) 1 : 8 (d) 3 : 16 (a) 36 g of water
(b) 28 g of CO
18. The molarity of a solution obtained by mixing 750 mL of
(c) 46 g of ethyl alcohol
0.5 M HCl with 250 mL of 2 M HCl will be (2013 Main)
(d) 54 g of nitrogen pentaoxide (N2 O5 )
(a) 0.875 M (b) 1.00 M (c) 1.75 M (d) 0.0975M
31. The total number of electrons in one molecule of carbon
19. Dissolving 120 g of urea (mol. wt. 60) in 1000 g of water dioxide is (1979, 1M)
gave a solution of density 1.15 g/mL. The molarity of the (a) 22 (b) 44 (c) 66 (d) 88
solution is (2011)
32. A gaseous mixture contains oxygen and nitrogen in the ratio
(a) 1.78 M (b) 2.00 M (c) 2.05 M (d) 2.22 M
of 1:4 by weight. Therefore, the ratio of their number of
20. Given that the abundances of isotopes 54 Fe, 56 Fe
and 57 Fe molecules is (1979, 1M)
are 5%, 90% and 5%, respectively, the atomic mass of Fe is (a) 1 : 4 (b) 1 : 8 (c) 7 : 32 (d) 3 : 16
(2009)
(a) 55.85 (b) 55.95 Numerical Value Based Questions
(c) 55.75 (d) 56.05 33. Galena (an ore) is partially oxidised by passing air through it
21. Mixture X = 0.02 mole of [Co(NH3 )5 SO4 ]Br and 0.02 mole at high temperature. After some time, the passage of air is
of [Co(NH3 )5 Br]SO4 was prepared in 2 L solution. stopped, but the heating is continued in a closed furnace such
1 L of mixture X + excess of AgNO3 solution ¾® Y that the content undergo self-reduction. The weight (in kg) of
Pb produced per kg of O 2 consumed is ……… .
1 L of mixture X + excess of BaCl 2 solution ¾® Z
(Atomic weights in g mol -1 : O = 16, S = 32, Pb = 207)
Number of moles of Y and Z are (2003, 1M)
(2018 Adv.)
(a) 0.01, 0.01 (b) 0.02, 0.01 34. To measure the quantity of MnCl 2 dissolved in an aqueous
(c) 0.01, 0.02 (d) 0.02, 0.02 solution, it was completely converted to KMnO4 using the
22. Which has maximum number of atoms? (2003, 1M) reaction,
(a) 24 g of C (12) (b) 56 g of Fe (56) MnCl 2 + K 2 S2 O8 + H2 O ¾® KMnO4 + H2 SO4 + HCl
(c) 27 g of Al (27) (d) 108 g of Ag (108) (equation not balanced).
23. How many moles of electron weighs 1 kg? Few drops of concentrated HCl were added to this solution
1 and gently warmed. Further, oxalic acid (225 mg) was added
(a) 6.023 ´ 1023 (b) ´ 1031 (2002, 3M)
in portions till the colour of the permanganate ion
9.108
6.023 1 disappeared. The quantity of MnCl 2 (in mg) present in the
(c) ´ 1054 (d) ´ 108 initial solution is ……… .
9.108 9.108 ´ 6.023
(Atomic weights in g mol -1 : Mn = 55, Cl = 35.5) (2018 Adv.)
Some Basic Concepts of Chemistry 3
35. In the following reaction sequence, the amount of D (in 44. In a solution of 100 mL 0.5 M acetic acid, one gram of active
gram) formed from 10 moles of acetophenone is ……. charcoal is added, which adsorbs acetic acid. It is found that the
concentration of acetic acid becomes 0.49 M. If surface area of
(Atomic weights in g mol -1 : H = 1, C = 12, N = 14,
charcoal is 3.01 ´ 102 m2 , calculate the area occupied by single
O = 16, Br = 80. The yield (%) corresponding to the acetic acid molecule on surface of charcoal. (2003)
product in each step is given in the parenthesis)
45. Find the molarity of water. Given: r = 1000 kg/m3 (2003)
O
46. A plant virus is found to consist of uniform cylindrical particles
NaOBr NH3, D Br2/KOH of 150 Å in diameter and 5000 Å long. The specific volume of
A B C
H3O+
(60%) (50%) (50%)
the virus is 0.75 cm 3 /g. If the virus is considered to be a single
particle, find its molar mass. (1999, 3M)
Br2(3 equivalent )
D 47. 8.0575 ´ 10-2 kg of Glauber’s salt is dissolved in water to
AcOH
(100%)
obtain 1 dm 3 of solution of density 1077.2 kg m -3 . Calculate
(2018 Adv.)
the molality, molarity and mole fraction of Na 2 SO4 in solution.
(1994, 3M)
Fill in the Blanks 48. A is a binary compound of a univalent metal. 1.422 g of A reacts
36. The weight of 1 ´ 1022 molecules of CuSO4 × 5H2 O is completely with 0.321 g of sulphur in an evacuated and sealed
tube to give 1.743 g of a white crystalline solid B, that forms a
…………. . (1991, 1M)
hydrated double salt, C with Al 2 (SO4 )3 . Identify A, B and C.
37. 3.0 g of a salt of molecular weight 30 is dissolved in 250 g (1994, 2M)
water. The molarity of the solution is ………. (1983, 1M)
49. Upon mixing 45.0 mL 0.25 M lead nitrate solution with
38. The total number of electrons present in 18 mL of water is 25.0 mL of a 0.10 M chromic sulphate solution, precipitation of
…………. . (1980, 1M) lead sulphate takes place. How many moles of lead sulphate are
39. The modern atomic mass unit is based on the mass of formed? Also calculate the molar concentrations of species left
…………. . (1980, 1M)
behind in the final solution. Assume that lead sulphate is
completely insoluble. (1993, 3M)
Integer Answer Type Questions 50. Calculate the molality of 1.0 L solution of 93% H2 SO4 ,
(weight/volume). The density of the solution is 1.84 g/mL.
40. The mole fraction of a solute in a solution is 0.1. At 298 K, (1990, 1M)
molarity of this solution is the same as its molality. Density
51. A solid mixture (5.0 g) consisting of lead nitrate and sodium
of this solution at 298 K is 2.0 g cm-3 . The ratio of the
nitrate was heated below 600°C until the weight of the residue
æ m ö was constant. If the loss in weight is 28.0 per cent, find the
molecular weights of the solute and solvent, çç solute ÷÷ is ...
è msolvent ø amount of lead nitrate and sodium nitrate in the mixture.
. (1990, 4M)
(2016 Adv.) 52. n-butane is produced by monobromination of ethane followed
41. A compound H2 X with molar weight of 80 g is dissolved by Wurtz’s reaction.Calculate volume of ethane at NTP
-1 required to produce 55 g n-butane, if the bromination takes
in a solvent having density of 0.4 g mL . Assuming no
change in volume upon dissolution, the molality of a 3.2 place with 90% yield and the Wurtz’s reaction with 85% yield.
(1989, 3M)
molar solution is (2014 Adv.)
53. A sugar syrup of weight 214.2 g contains 34.2 g of sugar
42. 29.2% (w/W ) HCl stock solution has density of 1.25g mL
-1 (C12 H22 O11 ). Calculate (i) molal concentration and (ii) mole
. The molecular weight of HCl is 36.5 g mol - 1 . The fraction of sugar in syrup. (1988, 2M)
volume (mL) of stock solution required to prepare a 200
mL solution 0.4 M HCl is (2012)
54. An unknown compound of carbon, hydrogen and oxygen
contains 69.77% C and 11.63% H and has a molecular weight
of 86. It does not reduces Fehling’s solution but forms a
Subjective Questions bisulphate addition compound and gives a positive iodoform
43. 20% surface sites have adsorbed N2 . On heating N2 gas test. What is the possible structure(s) of unknown compound?
(1987, 3M)
evolved from sites and were collected at 0.001 atm and 298
K in a container of volume is 2.46 cm 3 . Density of surface 55. The density of a 3 M sodium thiosulphate solution ( Na 2 S2 O3 )
sites is 6.023 ´ 1014 /cm 2 and surface area is 1000 cm 2 , find is 1.25 g per mL. Calculate (i) the percentage by weight of
sodium thiosulphate (ii) the mole fraction of sodium
out the number of surface sites occupied per molecule of
thiosulphate and (iii) the molalities of Na + and S2 O2-
3 ions.
N2 . (2005, 3M)
(1983, 5M)
4 Some Basic Concepts of Chemistry
56. (a) 1.0 L of a mixture of CO and CO2 is taken. This mixture 58. In the analysis of 0.5 g sample of feldspar, a mixture of
is passed through a tube containing red hot charcoal. The chlorides of sodium and potassium is obtained, which weighs
volume now becomes 1.6 L. The volumes are measured 0.1180 g. Subsequent treatment of the mixed chlorides with
under the same conditions. Find the composition of silver nitrate gives 0.2451 g of silver chloride. What is the
mixture by volume. percentage of sodium oxide and potassium oxide in the
(b) A compound contains 28 per cent of nitrogen and sample? (1979, 5M)
72 per cent of a metal by weight. 3 atoms of metal 59. The vapour density (hydrogen = 1) of a mixture consisting of
combine with 2 atoms of nitrogen. Find the atomic NO2 and N2 O4 is 38.3 at 26.7°C. Calculate the number of
weight of metal. (1980, 5M)
moles of NO2 in 100 g of the mixture. (1979, 5M)
57. 5.00 mL of a gas containing only carbon and hydrogen were 60. Accounts for the following. Limit your answer to two
mixed with an excess of oxygen (30 mL) and the mixture sentences, “Atomic weights of most of the elements are
exploded by means of electric spark. After explosion, the fractional”. (1979, 1M)
volume of the mixed gases remaining was 25 mL.
61. Naturally occurring boron consists of two isotopes whose
On adding a concentrated solution of KOH, the volume atomic weights are 10.01 and 11.01. The atomic weight of
further diminished to 15 mL, the residual gas being pure natural boron is 10.81. Calculate the percentage of each
oxygen. All volumes have been reduced to NTP. Calculate isotope in natural boron. (1978, 2M)
the molecular formula of the hydrocarbon gas. (1979, 3M)
9. The ratio of mass per cent of C and H of an organic 18. The number of moles of KMnO 4 that will be needed to react
compound (Cx H y O z ) is 6 : 1. If one molecule of the above completely with one mole of ferrous oxalate in acidic
compound (Cx H y O z ) contains half as much oxygen as medium is (1997)
required to burn one molecule of compound Cx H y 2 3 4
completely to CO2 and H2 O. The empirical formula of (a) (b) (c) (d) 1
5 5 5
compound Cx H y O z is (2018 Main)
(a) C3 H6 O3 (b) C2 H4 O (c) C3 H4 O2 (d) C2 H4 O3 19. The number of moles of KMnO 4 that will be needed to react
with one mole of sulphite ion in acidic solution is
10. An alkali is titrated against an acid with methyl orange as (1997)
indicator, which of the following is a correct combination? 2 3 4
(2018 Main) (a) (b) (c) (d) 1
5 5 5
Base Acid End point
20. For the redox reaction
(a) Weak Strong Colourless to pink
(b) Strong Strong Pinkish red to yellow MnO-4 + C2 O24 - + H+ ¾® Mn 2+ + CO2 + H2 O
(c) Weak Strong Yellow to pinkish red The correct coefficients of the reactants for the balanced
(d) Strong Strong Pink to colourless reaction are
11. From the following statements regarding H2 O2 choose the MnO-4 C2 O24 - H+ (1992)
solution is neutralised with Na 2 CO3 , acidified with dilute balanced equations for all the three half reaction. Find out the
acetic acid and treated with excess KI. The liberated iodine volume of 1M K 2 Cr2 O7 consumed, if the same volume of the
requires 11.3 mL of 0.05 M Na 2 S2 O3 solution for complete reducing agent is titrated in acid medium. (1989, 5M)
reduction. Find out the mole ratio of Cu 2+ to C2 O2-4 in the 46. A sample of hydrazine sulphate ( N2 H 6 SO4 ) was dissolved in
compound. Write down the balanced redox reactions 100 mL of water, 10 mL of this solution was reacted with
involved in the above titrations. (1991, 5M) excess of ferric chloride solution and warmed to complete
43. A mixture of H2 C2 O4 (oxalic acid) and NaHC2 O4 weighing the reaction. Ferrous ion formed was estimated and it,
required 20 mL of M/50 potassium permanganate solution.
2.02 g was dissolved in water and the solution made up to one
Estimate the amount of hydrazine sulphate in one litre of the
litre. Ten millilitres of the solution required 3.0 mL of 0.1 N
solution.
sodium hydroxide solution for complete neutralisation. In
another experiment, 10.0 mL of the same solution, in hot Reaction 4Fe3+ + N2 H4 ¾® N2 + 4Fe2+ + 4H+
dilute sulphuric acid medium, required 4.0 mL of 0.1 N MnO-4 + 5Fe2+ + 8H+ ¾® Mn 2+ + 5Fe3+ + 4H2 O
potassium permanganate solution for complete reaction. (1988, 3M)
Calculate the amount of H2 C2 O4 and NaHC2 O4 in the 47. 5 mL of 8 N nitric acid, 4.8 mL of 5 N hydrochloric acid and
mixture. (1990, 5M) a certain volume of 17 M sulphuric acid are mixed together
44. An organic compound X on analysis gives 24.24 per cent and made up to 2 L. 30 mL of this acid mixture exactly
carbon and 4.04 per cent hydrogen. Further, sodium extract neutralise 42.9 mL of sodium carbonate solution containing
of 1.0 g of X gives 2.90 g of silver chloride with acidified one gram of Na 2 CO3 × 10H2 O in 100 mL of water. Calculate
silver nitrate solution. The compound X may be represented the amount in gram of the sulphate ions in solution.
by two isomeric structures Y and Z. Y on treatment with (1985, 4M)
aqueous potassium hydroxide solution gives a dihydroxy 48. 2.68 ´ 10-3 moles of a solution containing an ion A n+ require
compound while Z on similar treatment gives ethanal. Find 1.61 ´ 10-3 moles of MnO-4 for the oxidation of A n+ to A O-3
out the molecular formula of X and gives the structure
in acidic medium. What is the value of n ? (1984, 2M)
of Y and Z. (1989, 5M)
49. 4.08 g of a mixture of BaO and unknown carbonate MCO3
45. An equal volume of a reducing agent is titrated separately
with 1 M KMnO4 in acid, neutral and alkaline medium. The was heated strongly. The residue weighed 3.64 g. This was
volumes of KMnO4 required are 20 mL in acid, 33.3 mL in dissolved in 100 mL of 1 N HCl. The excess acid required
neutral and 100 mL in alkaline media. Find out the oxidation 16 mL of 2.5 N NaOH solution for complete neutralisation.
state of manganese in each reduction product. Give the Identify the metal M. (1983, 4M)
Answers
Topic 1 55. (i) 37.92, (ii) 0.065, (iii) 7.73m 56. (a) 0.6, (b) 24
1. (d) 2. (c) 3. (b) 4. (a) 58. (i) 0.0179 g, (ii) 10.6 % 59. (0.437) 61. 20 %
5. (d) 6. (b) 7. (d) 8. (c) Topic 2
9. (b) 10. (b) 11. (b) 12. (c) 1. (d) 2. (b) 3. (a) 4. (a)
13. (b) 14. (*) 15. (d) 16. (d) 5. (d) 6. (*) 7. (b) 8. (c)
17. (b) 18. (a) 19. (c) 20. (b) 9. (d) 10. (c) 11. (a) 12. (d)
21. (a) 22. (a) 23. (d) 24. (d) 13. (b) 14. (c) 15. (a) 16. (d)
25. (d) 26. (a) 27. (d) 28. (a) 17. (a) 18. (b) 19. (a) 20. (a)
29. (a) 30. (a) 31. (a) 32. (c) 21. (b) 22. (c) 23. (b) 24. (a, b, d)
33. (6.47kg) 34. (126 mg) 35. (495 g) 36. (4.14 g) 25. (2992) 26. (b) 27. 7/3 28. (5)
37. (0.4) 38. (6.023´10 24 ) 39. C-12 isotope 40. 29. (2) 30. (3) 31. (1008 g) 33. (8.096 mL)
(9)
34. (0.062 M) 35. (1.334 V) 39. (85%) 41. (1.04 ´ 10 4 )
41. (8) 42. (8 mL) 43. (2) 44. (5 ´ 10 -19 m 2 )
42. (1:2) 45. (16.67 mL) 46. (6.5gL -1) 47. (6.5376 g)
45. (55.56 mol L-1) 46. (70.91 ´ 10 6g) 47.(4.3 ´ 10 -3) 50. (10.42)
48. (2) 49. (Ca)
51. (1.7 g) 52. (55.55 L) 53. (9.9 ´ 10 -3)
Hints & Solutions
Topic 1 Mole Concept 3. In eudiometry,
300 K
æ yö y
CxH y + ç x + ÷ O2 ¾¾¾® x CO2 + H2O
Key Idea To find the mass of A and B in the given question, è 4ø 1 atm 2
1. æ yö
mole concept is used. 1 mol ç x + ÷ mol x mol
è 4ø
given mass (w) yö
Number of moles( n) = 1 mL
æ
ç x + ÷ mL x mL
molecular mass (M ) è 4ø
æ yö
10 mL ç x + ÷ ´ 10 mL 10x mL
è 4ø
Compound Mass of A (g) Mass of B (g)
Given, (i) VCO2 = 10x = 40 mL Þ x = 4
AB2 MA 2 MB æ yö
(ii) VO2 = 10 ç x + ÷ mL = 55 mL
A 2B 2 2 MA 2 MB è 4ø
æ yö
We know that, Þ 10 ç 4 + ÷ = 55 [Q x = 4]
è 4ø
given mass (w)
Number of moles (n) = y ´ 10
molecular mass (M ) Þ 40 + = 55
4
n ´M = w …(A) 10 4
Using equation (A), it can be concluded that Þ y ´ = 15 Þ y = 15 ´ = 6
4 10
5(M A + 2M B ) = 125 ´ 10-3 kg …(i) So, the hydrocarbon (CxH y ) is C4H6.
-3
10(2M A + 2M B ) = 300 ´ 10 kg …(ii) 4. Given, volume = 10 mL
From equation (i) and (ii) Molarity = 1 mM = 10-3 M
1 (M A + 2M B ) æ 125 ö \Number of millimoles = 10 mL ´ 10-3 M = 10-2
=ç ÷
2 (2M A + 2M B ) è 300 ø
Number of moles = 10-5
On solving the equation, we obtain
Now, number of molecules
M A = 5 ´ 10-3
= Number of moles ´ Avogadro’s number
and M B = 10 ´ 10-3 = 10-5 ´ 6 ´ 1023 = 6 ´ 1018
So, the molar mass of A (M A ) is Surface area occupied by 6 ´ 1018 molecules = 0.24 cm2
5 ´ 10-3 kg mol -1 and B (M B ) is 10 ´ 10-3 kg mol -1.
\Surface area occupied by 1 molecule
2. (a) C3H8 (g ) + 5O2 (g ) ¾® 3CO2 (g ) + 4H2O(l ) 0.24
= = 0.04 ´ 10-18 cm2
44g 160g 6 ´ 1018
160 As it is given that polar head is approximated as cube. Thus,
Þ 1g of reactant = g of O2 consumed = 3.64 g
44 surface area of cube = a2, where
(b) P4 (s) + 5O2(g ) ¾® P4O10 (s) a = edge length
124g 160g \ a2 = 4 ´ 10-20 cm2
160
Þ1 g of reactant = g of O2 consumed = 129
. g a = 2 ´ 10-10 cm = 2 pm
124
(c) 4Fe(s) + 3O2(g ) ¾® 2Fe2O3 (s) 5. Key Idea The reactant which is present in the lesser amount,
244g 96g i.e. which limits the amount of product formed is called
96
Þ 1 g of reactant = g of O2 consumed = 0.43 g limiting reagent.
224
(d) 2Mg(s) + O2(g ) ¾® 2MgO(s) When 56 g of N2 + 10 g of H2 is taken as a combination then
48 g 32 g dihydrogen (H2 ) act as a limiting reagent in the reaction.
32 N2 (g ) + 3H2 (g ) ¾® 2NH3 (g ) …(I)
Þ 1 g of reactant = g of O2 consumed = 0.67 g 2 ´ 14 g 3 ´ 2g 2(14 + 3) g
48
28g 6g 34g
So, minimum amount of O2 is consumed per gram of reactant
(Fe) in reaction (c). 28g N2 requires 6g H2 gas.
6g
56g of N2 requires ´ 56 g = 12g of H2
28 g
Some Basic Concepts of Chemistry 9
12g of H2 gas is required for 56g of N2 gas but 8. Concentration of H2O2 is expressed in terms of volume strength,
only 10 g of H2 gas is present in option (a). i.e. “volume of O2 liberated by H2O2 at NTP”. Molarity is
Hence, H2 gas is the limiting reagent. connected to volume strength as:
In option (b), i.e. 35g of N2 + 8 g of H2. x
Molarity (M) = or x = Molarity ´ 11.2
As 28 g N2 requires 6g of H2. 112
.
6g where, x = volume strength
35g N2 requires ´ 35 g H2 Þ 7.5 g of H2. So, for 1 M H2O2, x = 1 ´ 112. = 112.
28 g
Among the given options, 11.35 is nearest to 11.2.
Here, H2 gas does not act as limiting reagent since 7.5 g of H2
gas is required for 35g of N2 and 8g of H2 is present in reaction Number of moles of solute (n)
9. Molarity =
mixture. Mass of H2 left unreacted = 8 - 7.5 g of H2. Volume of solution (in L)
= 0.5 g of H2. wB (g)
Also, n =
Similarly, in option (c) and (d), H2 does not act as limiting M B (gmol-1 )
reagent. w / MB
For 14 g of N2 + 4 g of H2. \ Molarity = B
V
As we know 28g of N2 reacts with 6g of H2.
Given, wB = mass of solute ( B ) in g
6
14 g of N2 reacts with ´ 14 g of H2 Þ 3g of H2. M B = Gram molar mass of B (C12H22O11 ) = 342 g mol -1
28
For 28g of N2 + 6 g of H2, i.e. 28g of N2 reacts with 6g of H2 Molarity = 01. M
(by equation I). Volume (V ) = 2 L
w / 342
Þ . = B
01 . ´ 342 ´ 2 g = 68.4 g
Þ wB = 01
6. Key Idea The percentage composition of a compound is given 2
by the formula. 10. 2 C57 H110O6 (s) + 163 O2 (g ) ¾® 110H2O(l ) + 114 CO2 (g )
% composition = [Composition of a substance in a compound /
Molecular mass of C57H110O6
Total composition total of compound] ´100
= 2 ´ (12 ´ 57 + 1 ´ 110 + 16 ´ 6) g = 1780 g
In CH4 , Molecular mass of 110 H2O = 110 (2 + 16) = 1980 g
mole of carbon = 1 1780 g of C57H110O6 produced = 1980 g of H2O.
mole of hydrogen = 4 1980
445g of C57H110O6 produced = ´ 445 g of H2O
1 1780
\ % of carbon by mole in CH4 = ´ 100 = 20%
1+ 4 = 495of H2O
Number of moles of solute
7. Mole fraction of solute 11. Molality (m) = ´ 1000
number of moles of solute + number of moles solvent Mass of solvent (in g)
= Mass of solute (in g) ´ 1000
number of moles of solute =
w Solute é Molecular weight of solute ù
êë ´ mass of solvent (in g)úû
n Solute Mw Solute
cSolute = = wNa+ ´ 1000 92 ´ 1000
n Solute + nSolvent w Solute w = = = 4 mol kg - 1
+ Solvent M Na+ ´ wH 2 O 23 ´ 1000
Mw Solute MwSolvent
Given, wSolute = wNaOH = 8 g 12. Given, abundance of elements by mass
Mw Solute = MwNaOH = 40g mol - 1 oxygen = 614. %, carbon = 22.9%, hydrogen = 10% and
nitrogen = 2.6%
w Solvent = w H2 O = 18g Total weight of person = 75 kg
Mw Solvent = 18 g mol- 1 75 ´ 10
Mass due to 1 H = = 7.5 kg
8 / 40 0.2 0.2 100
\ cSolute = c NaOH = = = = 0167
. 1
8 18 0.2 + 1
+ .
12 H atoms are replaced by 2 H atoms,
40 18 Mass due to 2 H = (7.5 ´ 2) kg
Moles of solute \ Mass gain by person = 7.5 kg
Now, molality (m) =
Mass of solvent (in kg)
13. M 2CO3 + 2HCl ¾® 2M Cl + H2O + CO2
w Solute 8 1g 0.01186
mole
Mw Solute 40
= ´ 1000 = ´ 1000 Number of moles of M 2CO3 reacted = Number of moles of CO2
wSolvent (in g ) 18
evolved
0.2 1
= ´1000 = 11.11 mol kg - 1 = 0.01186 [M = molar mass of M 2CO3]
18 M
Thus, mole fraction of NaOH in solution and molality of the 1
solution respectively are 0.167 and 11.11 mol kg - 1 . M = = 84.3 g mol - 1
0.01186
10 Some Basic Concepts of Chemistry
y y Moles of solute
14. CxH y (g ) + æç x + ö÷ O2 (g ) ¾® xCO2 (g ) + H2O(l ) 19. Molarity =
è 4ø 30 mL
2 Volume of solution (L)
75 mL
120
O 2 used = 20% of 375 = 75 mL Moles of urea = =2
60
Inert part of air = 80% of 375 = 300 mL
Weight of solution = Weight of solvent + Weight of solute
Total volume of gases = CO2 + Inert part of air
= 1000 + 120 = 1120 g
= 30 + 300 = 330 mL
1120 g 1
x 30 Þ Volume = ´ = 0.973 L
= Þx=2 1.15 g / mL 1000 mL / L
1 15
y 2.000
x+ Þ Molarity = = 2.05M
4 = 75 Þ x + y = 5 0.973
1 15 4 20. From the given relative abundance, the average weight of Fe can be
Þ x = 2, y = 12 Þ C2 H12 calculated as
54 ´ 5 + 56 ´ 90 + 57 ´ 5
15. We know the molecular weight of C8 H7 SO3Na A= = 55.95
100
= 12 ´ 8 + 1 ´ 7 + 32 + 16 ´ 3 + 23 = 206
we have to find, mole per gram of resin.
21. 1.0 L of mixture X contain 0.01 mole of each [Co(NH3 )5 SO4 ]Br
and [Co(NH3 )5 Br]SO4. Also, with AgNO3, only
\ 1g of C8 H7 SO3Na has number of mole [Co(NH3 )5 SO4 ]Br reacts to give AgBr precipitate as
weight of given resin 1
= = mol [Co(NH3 )5 SO4 ]Br + AgNO3 ® [Co(NH3 )5 SO4 ]NO3 + AgBr
Molecular, weight of resin 206 1.0 mol Excess 1.0 mol
Now, reaction looks like With BaCl 2, only [Co(NH3 )5 Br]SO4 reacts giving BaSO4
precipitate as
2C8 H7 SO3Na + Ca 2+ ¾® (C8 H7 SO3 )2 Ca + 2Na
[Co(NH3 )5 Br]SO4 + BaCl 2 ® [Co(NH3 )5 Br]Cl 2 + BaSO4
Q 2 moles of C8 H7 SO3Na combines with 1 mol Ca 2+ 1.0 mol Excess 1 mol
50. 93% H2SO4 solution weight by volume indicates that there is Mole of sugar
(ii) Mole fraction of sugar =
93 g H2SO4 in 100 mL of solution. Mole of sugar + Mole of water
0.1
If we consider 100 mL solution, weight of solution = 184 g = = 9.9 ´ 10-3
Weight of H2O in 100 mL solution = 184 – 93 = 91 g 0.1 + 10
Moles of solute 54. From the given elemental composition, empirical formula can
Þ Molality = ´ 1000
Weight of solvent (g) be derived as :
93 1000
= ´ = 10.42 Element C H O
98 91
Weight % 69.77 11.63 18.60
51. Heating below 600°C converts Pb(NO3 )2 into PbO but to Mole % 5.81 11.63 1.1625 (obtained by
NaNO3 into NaNO2 as dividing from M )
D 1
Pb(NO3 )2 ¾® PbO(s) + 2NO2 + O Simple ratio 5 10 1
2 2
MW : 330 222 Hence, empirical formula is C5H10O and empirical formula
D 1
NaNO3 ¾® NaNO2 (s) + O weight is 86.
2 2
MW : 85 69 Since, empirical formula weight and molecular weight both are
28 (86), empirical formula is the molecular formula also.
Weight loss = 5 ´ = 1.4 g
100 Also, the compound does not reduce Fehling’s solution,
Þ Weight of residue left = 5 – 1.4 = 3.6 g therefore it is not an aldehyde, but it forms bisulphite, it must be
Now, let the original mixture contain x g of Pb(NO3 )2. a ketone.
Q 330 g Pb(NO3 )2 gives 222 g PbO Also, it gives positive iodoform test, it must be a methyl ketone.
222 x O
\ x g Pb(NO3 )2 will give g PbO
330 ½½
Similarly, 85 g NaNO3 gives 69 g NaNO2 C3H7 — C — CH3
69 (5 - x ) Based on the above information, the compound may be one of
Þ (5 – x) g NaNO3 will give g NaNO2
85 the following :
222 x 69 (5 - x ) O CH3 O
Þ Residue : + = 3.6 g ½½ ½ ½½
330 85 CH3CH2CH2— C — CH3 or CH3 — CH— C — CH3
Solving for x gives, x = 3.3 g Pb(NO3 )2 2-pentanone 3-methyl -2-butanone
Þ NaNO3 =1.7 g.
55. (a) Let us consider 1.0 L solution for all the calculation.
52. Reactions involved are (i) Weight of 1 L solution = 1250 g
C2H6 + Br2 ¾® C2H5Br + HBr Weight of Na 2S2O3 = 3 ´ 158 = 474 g
2C2H5Br + 2Na ¾® C4H10 + 2NaBr 474
Þ Weight percentage of Na 2S2O3= ´ 100 = 37.92
Actual yield of C4H10 = 55 g which is 85% of theoretical yield. 1250
55 ´ 100 (ii) Weight of H2O in 1 L solution = 1250 - 474 = 776 g
Þ Theoretical yield of C4H10 = = 64.70 g
85 3
Mole fraction of Na 2S2O3 = = 0.065
Also, 2 moles (218 g) C2H5Br gives 58 g of butane. 776
3+
Þ 64.70 g of butane would be obtained from 18
2 + 3 ´2
´ 64.70 = 2.23 moles C2H5Br (iii) Molality of Na = ´ 100 = 7.73 m
58 776
Also yield of bromination reaction is only 90%, in order to have 56. (a) After passing through red-hot charcoal, following reaction
2.23 moles of C2H5Br, theoretically occurs
2.23 ´ 100 C(s) + CO2 (g ) ¾® 2CO(g )
= 2.48 moles of C2H5Br required. If the 1.0 L original mixture contain x litre of CO2, after
90
Therefore, moles of C2H6 required = 2.48 passing from tube containing red-hot charcoal, the new
volumes would be :
Þ Volume of C2H6 (NTP) required = 2.48 ´ 22.4 = 55.55 L.
2x (volume of CO obtained from CO2) + 1
34.2
53. Moles of sugar = = 0.1 – x (original CO) = 1 + x = 1.6 (given)
342
Þ x = 0.6
Moles of water in syrup = 214.2 – 34.2 = 180 g
Hence, original 1.0 L mixture has 0.4 L CO and 0.6 L of CO2 ,
Moles of solute
Therefore, (i) Molality = ´ 1000 i.e. 40% CO and 60% CO2 by volume.
Weight of Solvent (g)
(b) According to the given information, molecular formula of
0.1 the compound is M 3N2. Also, 1.0 mole of compound has 28 g
= ´ 1000 = 0.55
180 of nitrogen. If X is the molar mass of compound, then :
Some Basic Concepts of Chemistry 15
9. We can calculate the simplest whole number ratio of C and H 12. n-factor of dichromate is 6.
from the data given, as Also, n-factor of Mohr’s salt is 1 as :
Element Relative Molar Relative Simplest whole O. A
FeSO4 (NH4 )2 SO4× 6H2O ¾® Fe3+
mass mass mole number ratio Mohr’s salt
C 6 12 6 0.5
= 0.5 =1 Q 1 mole of dichromate = 6 equivalent of dichromate.
12 0.5
H 1 1 1 1 \ 6 equivalent of Mohr’s salt would be required.
=1 =2
1 0.5 Since, n-factor of Mohr’s salt is 1, 6 equivalent of it would also
be equal to 6 moles.
Alternatively this ratio can also be calculated directly in the
terms of x and y as Hence, 1 mole of dichromate will oxidise 6 moles of Mohr’s salt.
12x 6 13. The following reaction occur between S2O2- 2-
3 and Cr2O 7 :
= (given and molar mass of C = 12, H = 1)
y 1 26H+ + 3S2O23- + 4Cr2O27- ¾® 6SO24- + 8Cr 3+ + 13H2O
Now, after calculating this ratio look for condition 2 given in the
Change in oxidation number of Cr2O2-
7 per formula unit is 6 (it is
question i.e. quantity of oxygen is half of the quantity required
to burn one molecule of compound C xH y completely to CO2 and always fixed for Cr2O2-
7 ).
H2O. We can calculate number of oxygen atoms from this as Molecular weight
consider the equation. Hence, equivalent weight of K2Cr2O7 =
6
é yù y
CxH y + ê x + ú O2 ¾® xCO2 + H2O 14. It is an example of disproportionation reaction because the same
ë 4û 2 species (ClO- ) is being oxidised to ClO-3 as well as reduced to Cl - .
é yù é yù
Number of oxygen atoms required = 2 ´ ê x + ú = ê 2x + ú 15. Oxalic acid dihydrate H2C2O4 × 2H2O : mw = 126
ë 4û ë 2û
It is a dibasic acid, hence equivalent weight = 63
1é yù é yù
Now given, z = ê 2x + ú = ê x + ú 6.3 1000
2ë 2û ë 4û Þ Normality = ´ = 0.4 N
63 250
Here we consider x and y as simplest ratios for C and H so now Þ N 1V1 = N 2V2
putting the values of x and y in the above equation.
yù é 2ù Þ 0.1 ´ V1 = 0.4 ´ 10
é
z = ê x + ú = ê1 + ú = 1.5 Hence, V1 = 40 mL
ë 4û ë 4û
Thus, the simplest ratio figures for x , y and z are x = 1, y = 2 and 16. In MnO-4 , oxidation state of Mn is +7
z = 15
. In Cr(CN)63- , oxidation state of Cr is +3
Now, put these values in the formula given i.e.
In NiF62- , Ni is in + 4 oxidation state.
CxH yOz = C1H2O1.5
So, empirical formula will be [C1H2O1.5 ] ´ 2 = C2H4O3 In CrO2Cl 2, oxidation state of Cr is +6.
10. Methyl orange show Pinkish colour towards more acidic 17. In S8 , oxidation number of S is 0, elemental state.
medium and yellow orange colour towards basic or less acidic In S2F2, F is in – 1 oxidation state, hence S is in + 1 oxidation
media. Its working pH range is state.
In H2S, H is in +1 oxidation state, hence S is in – 2 oxidation
3.9 –4.5 state.
Pinkish Yellow
Red orange
18. The balanced redox reaction is :
Weak base have the pH range greater than 7. When methyl 3MnO-4 + 5FeC2O4 + 24H+ ¾® 3Mn 2+ + 5Fe3+
orange is added to this weak base solution it shows yellow + 10CO2 + 12H2O
orange colour. Q 5 moles of FeC2O4 require 3 moles of KMnO4
Now when this solution is titrated against 3
strong acid the pH move towards more acidic \ 1 mole of FeC2O4 will require mole of KMnO4.
1 5
range and reaches to end point near 3.9 where
HN NH2
yellow orange colour of methyl orange 19. The balanced chemical reaction is :
changes to Pinkish red resulting to similar In conjugation
2MnO-4 + 5SO23- + 6H+ ¾® 2Mn 2+ + 5SO24- + 3H2O
change in colour of solution as well.
Q 5 moles SO2-
3 reacts with 2 moles of KMnO 4
11. H2O2 acts as an oxidising as well as reducing agent, because 2
\ 1 mole of SO2-
3 will react with mole KMnO4.
oxidation number of oxygen in H2O2 is -1. So, it can be oxidised 5
to oxidation state 0 or reduced to oxidation state –2. 20. The balanced redox reaction is :
H2O2 decomposes on exposure to light. So, it has to be stored in 2MnO-4 + 5C2O24- + 16H + ¾® 2Mn 2+ + 10CO2 + 16H2O
plastic or wax lined glass bottles in dark for the prevention of
exposure. It also has to be kept away from dust. Hence, the coefficients of reactants in balanced reaction are 2, 5
and 16 respectively.
18 Some Basic Concepts of Chemistry
21. Volume strength of H2O2 = Normality ´ 5.6 = 1.5 ´ 5.6 = 8.4 V and 24 moles of NH3 = 24 ´17 = 408 g
Further, as given in question,
22. In Ba(H2PO2 )2, oxidation number of Ba is +2. Therefore, 24 moles of NH3 produced in reaction (i) is completly utilised
H2PO-2 : 2 ´ (+1) + x + 2 ´ (-2) = - 1 by 952g or 4 moles of NiCl 2 × 6H2O to produce 4 moles of
Þ x=+1 [Ni(NH3 )6 ] Cl 2.
So, 4 moles of [Ni(NH3 )6 ] Cl 2 = 4 ´ 232 = 928gms
23. Equivalent weight in redox system is defined as :
Hence, total mass of gypsum and nickel ammonia coordination
Molar mass compound [Ni(NH3 )6 ] Cl 2 = 2064 + 928 = 2992
E=
n-factor
26. Both assertion and reason are factually true but the reason does
Here n-factor is the net change in oxidation number per formula not exactly explain the assertion. The correct explanation is,
unit of oxidising or reducing agent. In the present case, n-factor methyl orange and phenolphthalein changes their colour at
is 2 because equivalent weight is half of molecular weight. Also, different pH.
1
n-factor MnSO4 ¾® Mn 2O3 1 (+ 2 ¾® + 3) 27. If x is the oxidation state of Cu then :
2
7
MnSO4 ¾® MnO2 2 (+ 2 ¾® + 4) 3 + 2 ´ 2 + 3x + 7 ´ (- 2) = 0 Þ x =
3
MnSO4 ¾® MnO-4 5 (+ 2 ¾® + 7)
28. Na2S4O6 is a salt of H2S4O6 which has the following structure
MnSO4 ¾® MnO24- 4 (+ 2 ¾® + 6)
O O
Therefore, MnSO4 converts to MnO2. (0) (v)
HO S S S S OH
24. PLAN This problem includes concept of redox reaction. A redox
reaction consists of oxidation half-cell reaction and reduction
half-cell reaction. Write both half-cell reactions, i.e. oxidation O O
half-cell reaction and reduction half-cell reaction.Then balance Þ Difference in oxidation number of two types of sulphur = 5
both the equations.
Now determine the correct value of stoichiometry of H2SO4. 29. Only F and Na show only one non-zero oxidation state.
Oxidation half-reaction, 2 I - ¾® I2 + 2 e - …(i) O = O- , O2- , O2+ ;
Here, I - is converted into I2. Oxidation number of I is increasing Cl = - 1 to + 7
from –1 to 0 hence, this is a type of oxidation reaction. N = - 3 to + 5
Reduction half-reaction P = - 3 to + 5
6H+ + ClO-3 + 6e- ¾® Cl - + 3H2O …(ii) Sn = + 2, + 4
l
Here, H2 O releases as a product. Hence, option (d) is Tl = + 1, + 3 (rare but does exist)
correct. Ti = + 2, + 3, + 4
Multiplying equation (i) by 3 and adding in equation (ii)
30. Average titrate value is 25.15, but the number of significant
6I- + ClO-3 + 6H+ ¾® Cl - + 3I2 + 3H2O figure cannot be greater than the same in either of them being
manipulated.
6I- + ClO-3 + 6H2SO4 ¾® Cl - + 3I2 + 3H2O + 6HSO-4
31. The balanced reaction is
l
Stoichiometric coefficient of HSO-4 is 6.
6CaO + P4O10 ¾® 2Ca 3 (PO4 )2
Hence, option (a), (b) and (d) are correct.
852
Moles of P4O10 = =3
25. Balanced equations of reactions used in the problem are as 284
follows Moles of CaO required = 3 ´ 6 = 18
(i) ( NH4)2SO 4 + Ca(OH)2 ¾® CaSO 4 × 2H2O + 2NH3 Mass of CaO required = 18 ´ 56 = 1008 g
1 mol 1 mol 2 mol
132 g 172 g (2 ´ 17) = 34 g
32. Meq of oxalate = 10 ´ 0.2 ´ 2 = 4
(ii) NiCl 2 × 6H2O + 6NH3 ¾® [Ni(NH3)6] Cl 2 + 6H2O Meq of MnO2 formed = Meq of oxalate = 4
1 mol 6 mol 1 mol
238 g 102 g 232 g Meq of KMnO4 in 20 mL = 4
Now, in Eq. (i) Þ Normality of H2O2 ´ 20 = 4
if, 1584 g of ammonium sulphate is used. Þ Normality of H2O2 = 0.20 N
1584 0.20
i.e., 1584 g (NH4 )2 SO4 = = 12 mol Þ Molarity of H2O2 = = 0.10 M
132 2
So, according to the Eq. (i) given above 12 moles of (NH4 )2 SO4 The balanced reactions are
produces 2KMnO4 + 5H2O2 + 3H2SO4 ¾® 2MnSO4 + 5O2
(a) 12 moles of gypsum + K2SO4 + 8H2O
(b) 24 moles of ammonia MnO2 + Na 2C2O4 + 2H2SO4 ¾® MnSO4 + Na 2SO4
Here, 12 moles of gypsum = 12 ´172 = 2064 g + 2CO2 + 2H2O
Some Basic Concepts of Chemistry 19
33. The balanced chemical reaction is The first step volume contraction can be calculated as :
CuCO3 + H2SO4 ¾® CuSO4 + H2O + CO2 æ x ö
0.5 ´ 1000 ç x + + y + 2 y÷ - (x + y) = 13
millimol of CuCO3 = = 4.048 è 2 ø
123.5 Þ x + 4 y = 26 …(i)
Þ Millimol of H2SO4 required = 4.048 The second volume contraction is due to absorption of CO2.
Q Millimol = Molarity ´ Volume (in mL) Hence, x + y = 14 …(ii)
4.048
Þ Volume = = 8.096 mL
0.50 Now, solving equations (i) and (ii),
34. The redox reaction involved are x = 10 mL, y = 4 mL and volume of He = 20 – 14 = 6 mL
IO-3 + 5I- + 6H+ ¾® 3I2 + 3H2O 10
Þ Vol % of CO = ´ 100 = 50%
20
I2 + 2S2O23- ¾® 2I- + S4O62- 4
Vol % of CH4 = ´ 100= 20%
0.1 20
millimol of KIO3 used = ´ 1000 = 0.467
214 Vol % of He = 30%
Þ millimol of I2 formed = 3 ´ 0.467 = 1.4
Þ millimol of Na 2S2O3 consumed = 2 ´ 1.4 = 2.8
38. The redox reaction involved is :
2.8 H2O2 + 2I- + 2H+ ¾® 2H2O + I2
Þ Molarity of Na 2S2O3 = = 0.062 M
45 If M is molarity of H2O2 solution, then
35. Meq of H2O2 = Meq of I2 = Meq of Na 2S2O3 0.508 ´ 1000
5M = (Q 1 mole H2O2 ºº 1 mole I2)
254
If N is normality of H2O2, then
Þ M = 0.4
N ´ 25 = 0.3 ´ 20
Also, n-factor of H2O2 is 2, therefore normality of H2O2 solution
Þ N = 0.24 is 0.8 N.
Þ Volume strength = N ´ 5.6 = 1.334 V Þ Volume strength = Normality ´ 5.6 = 0.8 ´ 5.6 = 4.48 V
36. Let the original sample contains x millimol of Fe3O4 and 39. The reaction is
y millimol of Fe2O3. In the first phase of reaction, KIO3 + 2KI + 6HCl ¾® 3ICl + 3KCl + 3H2O
Fe3O4 + I- ¾® 3Fe2+ + I2 (n-factor of Fe3O4 = 2) KIO3 required for 20 mL original KI solution = 3 millimol.
Fe2O3 + I- ¾® 2Fe2+ + I2 (n-factor of Fe2O3 = 2) Þ 7.5 millimol KIO3 would be required for original 50 mL KI.
Þ Meq of I2 formed = Meq (Fe3O4 + Fe2O3 ) Þ Original 50 mL KI solution contain 15 millimol of KI.
= Meq of hypo required
After AgNO3 treatment 5 millimol of KIO3 is required, i.e. 10
Þ 2x + 2 y = 11 ´ 0.5 ´ 5 = 27.5 …(i) millimol KI is remaining.
Now, total millimol of Fe2+ formed = 3x + 2 y. In the reaction
Þ 5 millimol KI reacted with 5 millimol of AgNO3.
Fe2+ + MnO-4 + H+ ¾® Fe3+ + Mn 2+
5
Þ Mass of AgNO3 = ´ 170 = 0.85 g
n-factor of Fe2+ = 1 1000
Þ Meq of MnO-4 = Meq of Fe2+ Þ Mass percentage of AgNO3 = 85%
Þ 3x + 2 y = 12.8 ´ 0.25 ´ 5 ´ 2 = 32 …(ii) 40. CO2 is evolved due to following reaction :
Solving Eqs. (i) and (ii), we get
2NaHCO3 ¾® Na 2CO3 + H2O + CO2
x = 4.5 and y = 9.25
pV
4.5 Moles of CO2 produced =
Þ Mass of Fe3O4 = ´ 232 = 1.044 g RT
1000
1.044 750 123.9 1
% mass of Fe3O4 = ´ 100 = 34.80% = ´ ´
3 760 1000 0.082 ´ 298
9.25 = 5 ´ 10-3
Mass of Fe2O3 = ´ 160 = 1.48 g
1000
Þ Moles of NaHCO3 in 2 g sample = 2 ´ 5 ´ 10-3 = 0.01
1.48
% mass of Fe2O3 = ´ 100 = 49.33% Þ millimol of NaHCO3 in 1.5 g sample
3
0.01
37. The reaction involved in the explosion process is = ´ 1.5 ´ 1000= 7.5
1 2
CO(g ) + O (g ) ¾® CO2 (g ) Let the 1.5 g sample contain x millimol Na 2CO3, then
2 x2
x mL mL x mL
2 2x + 7.5 = millimol of HCl = 15
CH4 (g ) + 2O2 (g ) ¾® CO2 (g ) + 2H2O(l ) Þ x = 3.75
y mL 2 y mL y mL
20 Some Basic Concepts of Chemistry
8. Rutherford’s alpha particle scattering experiment eventually 17. When alpha particles are sent through a thin metal foil, most
led to the conclusion that (1986, 1M) of them go straight through the foil, because (1984, 1M)
(a) mass and energy are related (a) alpha particles are much heavier than electrons
(b) electrons occupy space around the nucleus (b) alpha particles are positively charged
(c) neutrons are burried deep in the nucleus (c) most part of the atom is empty space
(d) the point of impact with matter can be precisely (d) alpha particles move with high velocity
determined
18. Many elements have non-integral atomic masses, because
9. The radius of an atomic nucleus is of the order of (1985, 1M) (a) they have isotopes (1984, 1M)
(a) 10-10 cm (b) 10-13 cm (b) their isotopes have non-integral masses
(c) 10-15 cm (d) 10-8 cm (c) their isotopes have different masses
(d) the constituents, neutrons, protons and electrons,
10. Bohr’s model can explain (1985, 1M)
combine to give fractional masses
(a) the spectrum of hydrogen atom only
(b) spectrum of an atom or ion containing one electron only Match the Columns
(c) the spectrum of hydrogen molecule
19. According to Bohr’s theory,
(d) the solar spectrum
En = Total energy K n = Kinetic energy
11. The increasing order (lowest first) for the values of e/m Vn = Potential energy rn = Radius of nth orbit
(charge/mass) for electron ( e ), proton (p), neutron (n) and Match the following : (2006, 6M)
alpha particle (a) is (1984, 1M)
(a) e, p, n, a (b) n, p, e, a Column I Column II
(c) n , p , a , e (d) n , a, p , e A. Vn / K n = ? p. 0
12. Rutherford’s scattering experiment is related to the size of B. If radius of nth orbit µ E nx , x = ? q. –1
the (1983, 1M)
(a) nucleus (b) atom (c) electron (d) neutron Angular momentum in lowest
C. r. –2
orbital
13. Rutherford’s experiment on scattering of a-particles showed
for the first time that the atom has (1981, 1M) 1
D. µ Zy, y = ? s. 1
(a) electrons (b) protons rn
(c) nucleus (d) neutrons
Fill in the Blanks
Objective Questions II 20. The light radiations with discrete quantities of energy are
(One or more than one correct option) called ................ . (1993, 1M)
14. The energy of an electron in the first Bohr orbit of H-atom is 21. The mass of a hydrogen is …… kg. (1982, 1M)
–13.6 eV. The possible energy value(s) of the excited state(s) 22. Isotopes of an element differ in the number of …… in their
for electrons in Bohr orbits of hydrogen is (are) (1988) nuclei. (1982, 1M)
(a) - 3.4 eV (b) - 4.2 eV (c) - 6.8 eV (d) + 6.8 eV
23. Elements of the same mass number but of different atomic
15. The atomic nucleus contains (1988, 1M) numbers are known as …… . (1983, 1M)
(a) protons (b) neutrons
(c) electrons (d) photons Subjective Questions
16. The sum of the number of neutrons and proton in the isotope 24. With what velocity should an a-particle travel towards the
of hydrogen is (1986, 1M) nucleus of a copper atom so as to arrive at a distance 10-13 m
(a) 6 (b) 5 (c) 4 (d) 3 from the nucleus of the copper atom ? (1997 (C), 3M)
24 Atomic Structure
2. The electrons are more likely to be found 7. If the de-Broglie wavelength of the electron in n th Bohr orbit in
a hydrogenic atom is equal to 15
. pa0 (a0 is Bohr radius), then
the value of n / Z is (2019 Main, 12 Jan II)
a Y (x) (a) 1.0 (b) 0.75 (c) 0.40 (d) 1.50
8. The de-Broglie wavelength ( l ) associated with a photoelectron
b x
–x varies with the frequency (n ) of the incident radiation as, [n 0 is
threshold frequency] (2019 Main, 11 Jan II)
c 1 1
(a) l µ 1
(b) l µ 3
(c) Paschen and Pfund (d) Balmer and Brackett I. An electron in an orbital of high angular momentum stays
away from the nucleus than an electron in the orbital of
4. The graph between | y |2 and r (radial distance) is shown lower angular momentum.
below. This represents (2019 Main, 10 April I) II. For a given value of the principal quantum number, the size
of the orbit is inversely proportional to the azimuthal
quantum number.
2 III. According to wave mechanics, the ground state angular
|Y| h
momentum is equal to .
2p
IV. The plot of y vs r for various azimuthal quantum numbers,
shows peak shifting towards higher r value.
r (a) I, III (b) II, III (c) I, II (d) I, IV
(a) 1s-orbital (b) 2 p-orbital 10. Heat treatment of muscular pain involves radiation of
(c) 3s-orbital (d) 2s-orbital wavelength of about 900 nm. Which spectral line of H-atom is
5. For any given series of spectral lines of atomic hydrogen, suitable for this purpose? [RH = 1´ 105 cm–1 ,
let Dn = n max - n min be the difference in maximum and h = 6.6 ´ 10-34 Js, c = 3 ´ 108 ms -1 ] (2019 Main, 11 Jan I)
minimum frequencies in cm -1 . The ratio (a) Paschen, 5 ®3 (b) Paschen, ¥ ® 3
D nLyman / D nBalmer is (2019 Main, 9 April I) (c) Lyman, ¥ ® 1 (d) Balmer, ¥ ® 2
(a) 27 : 5 (b) 5 : 4 (c) 9 : 4 (d) 4 : 1
6. The quantum number of four electrons are given below: 11. For emission line of atomic hydrogen from ni =8 to n f = n, the
1 æ 1 ö
I. n = 4 , l = 2, ml = - 2, ms = - plot of wave number (n ) against ç 2 ÷ will be (The Rydberg
2 èn ø
1
II. n = 3, l = 2, ml = 1, ms = + constant, RH is in wave number unit)
2 (2019 Main, 9 Jan I)
1 (a) non linear
III. n = 4 , l = 1, ml = 0, ms = +
2 (b) linear with slope -RH
1
IV. n = 3, l = 1, ml = 1, ms = - (c) linear with slope RH
2 (d) linear with intercept -RH
Atomic Structure 25
12. The radius of the second Bohr orbit for hydrogen atom is 18. The number of radial nodes in 3s and 2p respectively are
(Planck’s constant ( h ) = 6.6262 ´ 10- 34 Js; mass of (a) 2 and 0 (b) 0 and 2 (2005, 1M)
- 31 (c) 1 and 2 (d) 2 and 1
electron = 91091
. ´ 10 kg ; charge of electron
19. Which hydrogen like species will have same radius as that of
( e ) = 160210
. ´ 10- 19 C; permitivity of vacuum
Bohr orbit of hydrogen atom? (2004, 1M)
(Î0 ) = 8.854185 ´ 10- 12kg - 1 m - 3A 2 ) (2017 Main) (a) n = 2, Li 2+ (b) n = 2, Be3+
(a) 1.65 Å (b) 4.76 Å (c) 0.529 Å (d) 2.12 Å (c) n = 2, He+ (d) n = 3, Li 2+
13. P is the probability of finding the 1s electron of hydrogen 20. If the nitrogen atom had electronic configuration 1s7 , it would
atom in a spherical shell of infinitesimal thickness, dr, have energy lower than that of the normal ground state
at a distance r from the nucleus. The volume of this shell is configuration 1s2 2s2 2 p 3 , because the electrons would be
4 pr2 dr. The qualitative sketch of the dependence of P on r is closer to the nucleus, yet 1s7 is not observed, because it
(2016 Adv.)
violates
(a) Heisenberg uncertainty principle (2002, 3M)
P P (b) Hund’s rule
(c) Pauli exclusion principle
(a) (b) (d) Bohr postulate of stationary orbits
1 1
21. The quantum numbers + and - for the electron spin
2 2
0 r 0 r represent (2001, 1M)
(a) rotation of the electron in clockwise and anti-clockwise
direction respectively
(b) rotation of the electron in anti-clockwise and clockwise
P P
direction respectively
(c) magnetic moment of the electron pointing up and down
(c) (d) respectively
(d) two quantum mechanical spin states which have no classical
analogue
0 r 0 r 22. The wavelength associated with a golf ball weighing 200 g and
moving at a speed of 5 m/h is of the order (2001, 1M)
14. Which of the following is the energy of a possible excited
(a) 10-10 m (b) 10-20 m
state of hydrogen? (2015 Main)
(a) + 13.6 eV (b) – 6.8 eV (c) 10-30 m (d) 10-40 m
(c) –3.4 eV (d) + 6.8 eV 23. The number of nodal planes in a px orbital is (2001, 1M)
15. The correct set of four quantum numbers for the valence (a) one (b) two
electrons of rubidium atom ( Z = 37 ) is (2013 Main) (c) three (d) zero
1 1
(a) 5, 0, 0, + (b) 5, 1, 0, + 24. The electronic configuration of an element is
2 2
1 1 1s2 , 2s2 2 p 6 , 3s2 3 p 6 3d 5 , 4 s1 . This represents its (2000, 1M)
(c) 5, 1, ,1, + (d) 5, 0, 1, + (a) excited state (b) ground state
2 2
(c) cationic form (d) anionic form
16. Energy of an electron is given by
æ Z2 ö 25. The electrons, identified by quantum numbers n and l,
E = - 2.178 ´ 10-18 J ç 2 ÷ (i) n = 4, l = 1, (ii) n = 4, l = 0, (iii) n = 3, l = 2, (iv) n = 3, l = 1
çn ÷
è ø (2013 Main) can be placed in order of increasing energy, from the lowest to
Wavelength of light required to excite an electron in an highest, as (1999, 2M)
hydrogen atom from level n = 1 to n = 2 will be (a) (iv) < (ii) < (iii) < (i) (b) (ii) < (iv) < (i) < (iii)
(h = 6.62 ´ 10-34 Js and c = 3.0 ´ 108 ms -1 ) (c) (i) < (iii) < (ii) < (iv) (d) (iii) < (i) < (iv) < (ii)
(a) 1.214 ´ 10-7 m (b) 2.816 ´ 10-7 m 26. The energy of an electron in the first Bohr orbit of H-atom is
–13.6 eV. The possible energy value(s) of the excited state(s)
(c) 6.500 ´ 10-7 m (d) 8.500 ´ 10-7 m
for electrons in Bohr orbits of hydrogen is (are) (1998, 2M)
17. The kinetic energy of an electron in the second Bohr orbit (a) –3.4 eV (b) – 4.2 eV (c) – 6.8 eV (d) + 6.8 eV
of a hydrogen atom is [a0 is Bohr radius] (2012)
27. For a d-electron, the orbital angular momentum is (1997, 1M)
h2 h2 h2 h2 æ hö æ hö æ hö æ hö
(a) (b) (c) (d) (a) 6 ç ÷ (b) 2 ç ÷ (c) ç ÷ (d) 2 ç ÷
4p2 ma02 16p2 ma02 32p2 ma02 64p2 ma02 è 2p ø è 2p ø è 2p ø è 2p ø
26 Atomic Structure
28. The first use of quantum theory to explain the structure of 38. The ratio of the energy of a photon of 200 Å wavelength
atom was made by (1997, 1M) radiation to that of 4000 Å radiation is (1986, 1M)
(a) Heisenberg (b) Bohr 1
(a) (b) 4
(c) Planck (d) Einstein 4
29. Which of the following has the maximum number of unpaired 1
(c) (d) 2.
electrons ? (1996, 1M) 2
(a) Mg2+ (b) Ti 3+ (c) V3+ (d) Fe2+ 39. Which one of the following sets of quantum numbers
30. The orbital angular momentum of an electron in 2s-orbital is represents an impossible arrangement? (1986, 1M)
(1996, 1M) n l m s
1 h 1
(a) + × (b) zero (a) 3 2 –2
2 2p 2
h h 1
(c) (d) 2 × (b) 4 0 0
2p 2p 2
31. Which of the following relates to photons both as wave 1
(c) 3 2 –3
motion and as a stream of particles ? (1992, 1M) 2
(a) Interference (b) E = mc2 1
(d) 5 3 0 -
(c) Diffraction (d) E = hn 2
32. Which of the following does not characterise X-rays ? 40. Electromagnetic radiation with maximum wavelength is
(a) The radiation can ionise gases (1992, 1M) (a) ultraviolet (b) radio wave (1985, 1M)
(b) It causes ZnS to fluoresce (c) X-ray (d) infrared
(c) Deflected by electric and magnetic fields 41. Which electronic level would allow the hydrogen atom to
(d) Have wavelengths shorter than ultraviolet rays absorb a photon but not to emit a photon? (1984, 1M)
33. The correct set of quantum numbers for the unpaired electron (a) 3s (b) 2p
of chlorine atom is (1989, 1M) (c) 2s (d) 1s
n l m n l m 42. Correct set of four quantum numbers for the valence
(a) 2 1 0 (b) 2 1 1 (outermost) electron of rubidium ( Z = 37 ) is (1984, 1M)
(c) 3 1 1 (d) 3 0 0 1 1
(a) 5, 0, 0, + (b) 5, 1, 0 , +
34. The correct ground state electronic configuration of 2 2
1 1
chromium atom is (1989, 1M) (c) 5, 1, 1, + (d) 6, 0, 0, +
(a) [ Ar ] 3d 5 4 s1 (b) [ Ar ] 3d 4 4 s2 2 2
(c) [ Ar ] 3d 6 4 s0 (d) [ Ar ] 4 d 5 4 s1 43. The principal quantum number of an atom is related to the
(a) size of the orbital (1983, 1M)
35. The outermost electronic configuration of the most (b) spin angular momentum
electronegative element is (1988, 90, 1M) (c) orientation of the orbital in space
(a) ns2 np3 (b) ns2 np4 (d) orbital angular momentum
(c) ns2 np5 (d) ns2 np6 44. Any p-orbital can accommodate upto (1983, 1M)
36. The orbital diagram in which the Aufbau principle is violated (a) four electrons
(1988, 1M) (b) six electrons
(c) two electrons with parallel spins
(a)
(d) two electrons with opposite spins
(b)
Objective Questions II
(One or more than one correct option)
(c)
45. The ground state electronic configuration of nitrogen atom
(d) can be represented by (1999, 3M)
(a)
37. The wavelength of a spectral line for an electronic transition is
inversely related to (1988, 1M) (b)
(a) the number of electrons undergoing the transition
(b) the nuclear charge of the atom (c)
(c) the difference in the energy of the energy levels involved in
the transition (d)
(d) the velocity of the electron undergoing the transition
Atomic Structure 27
46. Which of the following statement (s) is (are) correct ? Passage Based Questions
(1998, 2M)
(a) The electronic configuration of Cr is [Ar] 3d 4 s (atomic 5 1 The hydrogen-like species Li2+ is in a spherically symmetric
number of Cr = 24) state S 1 with one radial node. Upon absorbing light the ion
undergoes transition to a state S 2 . The state S 2 has one radial
(b) The magnetic quantum number may have a negative value
node and its energy is equal to the ground state energy of the
(c) In silver atom, 23 electrons have a spin of one type and 24 of
hydrogen atom.
the opposite type. (atomic number of Ag = 47)
(d) The oxidation state of nitrogen in HN3 is – 3 49. The state S 1 is (2010)
76 (a) 1s (b) 2s (c) 2p (d) 3s
47. An isotone of 32 Ge is (1984, 1M)
77 77 50. Energy of the state S 1 in units of the hydrogen atom ground
(a) 32 Ge (b) 33 As
77 78
state energy is (2010)
(c) 34 Se (d) 34 Se (a) 0.75 (b) 1.50 (c) 2.25 (d) 4.50
51. The orbital angular momentum quantum number of the state
Assertion and Reason S 2 is (2010)
Read the following questions and answer as per the direction (a) 0 (b) 1 (c) 2 (d) 3
given below :
(a) Both Statement I and Statement II are correct; Statement Match the Columns
II is the correct explanation of Statement I Answer Q. 52, Q. 53 and Q. 54 by appropriately matching
(b) Both Statement I and Statement II are correct; Statement the information given in the three columns of the
II is not the correct explanation of Statement I following table.
(c) Statement I is correct; Statement II is incorrect The wave function, y n , l , ml is a mathematical function
(d) Statement I is incorrect; Statement II is correct whose value depends upon spherical polar coordinates
48. Statement I The first ionisation energy of Be is greater than ( r, q , f ) of the electron and characterised by the quantum
that of B. number n , l and ml . Here r is distance from nucleus, q is
colatitude and f is azimuth. In the mathematical functions
Statement II 2p-orbital is lower in energy than 2s. (2000)
given in the Table, Z is atomic number and a0 is Bohr radius.
(2017 Adv.)
3 æ Zr ö yn, I, ml (r)
æ Z ö 2 - çç a ÷÷
(I) 1s-orbital (i) yn, l , ml µ çç ÷÷ e è 0 ø (P)
è a0 ø
0
r/a0
1
(II) 2s-orbital (ii) One radial node (Q) Probability density at nucleus µ
a03
5 æ Zr ö
æ Z ö 2 - çç a ÷÷
(III) 2 pz-orbital (iii) yn, l ml µ çç ÷÷ re è 0 ø cosq (R) Probability density is maximum at nucleus
è a0 ø
55. Match the entries in Column I with the correctly related 68. In an atom, the total number of electrons having quantum
quantum number(s) in Column II. (2008, 6M) numbers (2014 Adv.)
1
Column I Column II n = 4, | ml | = 1 and ms = - is
2
A. Orbital angular momentum p. Principal 69. The atomic masses of He and Ne are 4 and 20 amu,
of the electron in a quantum respectively. The value of the de-Broglie wavelength of He
hydrogen-like atomic orbital. number gas at -73°C is ‘M’ times that of the de-Broglie wavelength
B. A hydrogen-like one-electron q. Azimuthal of Ne at 727°C. M is (2013 Adv.)
wave function obeying quantum 70. The work function (f) of some metals is listed below. The
Pauli’s principle. number number of metals which will show photoelectric effect when
light of 300 nm wavelength falls on the metal is (2011)
C. Shape, size and orientation r. Magnetic
of hydrogen-like atomic quantum Metal Li Na K Mg Cu Ag Fe Pt W
orbitals. number F (eV) 2.4 2.3 2.2 3.7 4.8 4.3 4.7 6.3 4.75
D. Probability density of s. Electron spin 71. The maximum number of electrons that can have principal
electron at the nucleus in quantum quantum number, n = 3 and spin quantum number,
hydrogen-like atom. number ms = -1 / 2 , is (2011)
60. The 2 px, 2 p y and 2 p z orbitals of atom have identical shapes where, a0 is Bohr’s radius. Let the radial node in 2s be at r0.
Then, find r in terms of a0.
but differ in their ........... . (1993, 1M)
(b) A base ball having mass 100 g moves with velocity
61. When there are two electrons in the same orbital, they have 100 m/s. Find out the value of wavelength of base ball.
…… spins. (1983, 1M) (2004, 2M)
74. The wavelength corresponding to maximum energy for
True/False hydrogen is 91.2 nm. Find the corresponding wavelength for
62. In a given electric field, b-particles are deflected more than He+ ion. (2003, 2M)
a-particles in spite of a-particles having larger charge. 75. Calculate the energy required to excite 1 L of hydrogen gas
(1993, 1M) at 1 atm and 298 K to the first excited state of atomic
63. The electron density in the XY-plane in 3d x 2 - y 2 orbital is hydrogen. The energy for the dissociation of H—H bond is
zero. (1986, 1M) 436 kJ mol -1 . (2000)
64. The energy of the electron in the 3d-orbital is less than that in 76. An electron beam can undergo diffraction by crystals.
the 4s-orbital in the hydrogen atom. (1983, 1M) Through what potential should a beam of electrons be
65. Gamma rays are electromagnetic radiations of wavelengths accelerated so that its wavelength becomes equal to 1.54 Å.
(1997 (C), 2M)
of 10-6 to 10-5 cm. (1983, 1M)
77. Consider the hydrogen atom to be proton embedded in a
66. The outer electronic configuration of the ground state
cavity of radius a0 (Bohr’s radius) whose charge is
chromium atom is 3d 4 4 s2 . (1982, 1M)
neutralised by the addition of an electron to the cavity in
vacuum, infinitely slowly. Estimate the average total energy
Integer Answer Type Questions of an electron in its ground state in a hydrogen atom as the
67. Not considering the electronic spin, the degeneracy of the work done in the above neutralisation process. Also, if the
second excited state ( n = 3 ) of H-atom is 9, while the magnitude of the average kinetic energy is half the
degeneracy of the second excited state of H- is (2015 Adv.) magnitude of the average potential energy, find the average
potential energy. (1996, 2M)
Atomic Structure 29
78. Calculate the wave number for the shortest wavelength 84. What is the maximum number of electrons that may be
transition in the Balmer series of atomic hydrogen.(1996, 1M) present in all the atomic orbitals with principal quantum
number 3 and azimuthal quantum number 2 ? (1985, 2M)
79. Iodine molecule dissociates into atoms after absorbing light
to 4500Å. If one quantum of radiation is absorbed by each 85. Give reason why the ground state outermost electronic
molecule, calculate the kinetic energy of iodine atoms. configuration of silicon is (1985, 2M)
(Bond energy of I2 = 240 kJ mol –1 ) 3s 3p 3s 3p
(1995, 2M)
and not
80. Find out the number of waves made by a Bohr’s electron in
one complete revolution in its 3rd orbit. (1994, 3M) 86. The electron energy in hydrogen atom is given by
81. What transition in the hydrogen spectrum would have the 21.7 ´ 10-12
En = - erg. Calculate the energy required to
same wavelength as the Balmer transition n = 4 to n = 2 of n2
He+ spectrum? (1993, 3M) remove an electron completely from the n = 2 orbit. What is
82. Estimate the difference in energy between 1st and 2nd the longest wavelength (in cm) of light that can be used to
Bohr’s orbit for a hydrogen atom. At what minimum atomic cause this transition? (1984, 3M)
number, a transition from n = 2 to n = 1 energy level would 87. Calculate the wavelength in Angstroms of the photon that is
result in the emission of X-rays with l = 3.0 ´ 10–8 m ? emitted when an electron in the Bohr’s orbit, n = 2 returns to
Which hydrogen atom-like species does this atomic number the orbit, n = 1in the hydrogen atom. The ionisation potential
correspond to? (1993, 5M) of the ground state hydrogen atom is 2.17 ´ 10-11 erg per
83. According to Bohr’s theory, the electronic energy of atom. (1982, 4M)
hydrogen atom in the nth Bohr’s orbit is given by : 88. The energy of the electron in the second and third Bohr’s
-21.7 ´ 10 -19 orbits of the hydrogen atom is - 5.42 ´ 10-12 erg and
En = J
n2 - 2.41 ´ 10-12 erg respectively. Calculate the wavelength of
Calculate the longest wavelength of electron from the third the emitted light when the electron drops from the third to the
Bohr’s orbit of the He+ ion. (1990, 3M) second orbit. (1981, 3M)
Answers
Topic 1 33. (c) 34. (a) 35. (c) 36. (b)
1. (d) 2. (a) 3. (b) 4. (c) 37. (c) 38. (d) 39. (c) 40. (b)
5. (d) 6. (c) 7. (d) 8. (b) 41. (d) 42. (a) 43. (a) 44. (d)
9. (b) 10. (b) 11. (d) 12. (a) 45. (a,d) 46. (a,b,c) 47. (b,d) 48. (c)
13. (c) 14. (a) 15. (a,b) 16. (d) 49. (b) 50. (c) 51. (b) 52. (c)
17. (a,c) 18. (a,c) 19. A ® r; B ® q; C ® p, D ® s 53. (a) 54. (d)
20. (photons) 21. (1 . 66 ´ 10 –27 kg) 22. (neutrons) 55. A ® q; B ® p, q, r, s C ® p, q, r D ® p, q, r
6
23. (isobars) 24. 6.3 ´ 10 56. Cr = [Ar] 3d 5 , 4s 1 57. 1 : 16
1
´ 9 ´ 10-31 kg ´ (6 ´ 105 ms -1 )2
2
6.626 ´ 10-34 J s ´ 3 ´ 108 ms -1
= -f
4000 ´ 10-10 m
r \ . ´ 10-21 kgm 2s -2 - 4.96 ´ 10-19 J
f = 162
The graph initially increases and then decreases. It reaches a = 3.36 ´ 10-19 J [1 kg m2s -2 = 1J]
maximum at a distance very close to the nucleus and then . eV
= 21
decreases. The maximum in the curve corresponds to the
distance at which the probability of finding the electron in 4. The ground state energy of H-atom is + 13.6 eV.
maximum. For second excited state, n = 2 + 1 = 3
2. The expression of kinetic energy of photo electrons, Z2
\ E3 (He+ ) = - 13.6 ´ 2 eV [Q for He+ , Z = 2]
1 n
KE = mv 2 = E - E0
2 22
= - 13.6 ´ 2 eV = - 6.04 eV
When, KE > > E0, the equation becomes, 3
1
KE = mv 2 = E 5. For photoelectric effect,
2
(i) KE = E - E0
1 2 hc p2 hc
Þ mv = Þ =
2 l 2m2 l
1 1
Þ l = hc ´ 2m2 ´ 2 Þ l µ 2
p p |Y|2 For 1s-orbital
number of radial node = 1–0–1=0
hc
E= = energy of incident light.
l
E0 = threshold energy or work functions, r
1 2 1 (mv )2 1 p2 where,
mv = ´ = ´ 2 KE = Kinetic energy of ejected electrons.
2 2 m2 2 m
E = Energy of incident light = hn
Q p = momentum = mv
E0 = Threshold energy = hn0
As per the given condition, n = Frequency of incident light
2
l 2 æ p1 ö n0 = Threshold frequency
=ç ÷
l 1 çè p2 ÷ø
Atomic Structure 31
So, option (c) is also correct. 17. Alpha particles passes mostly undeflected when sent through
(iv) KE = hn - hn 0 thin metal foil mainly, because
(i) it is much heavier than electrons.
(ii) most part of atom is empty space.
KE 18. Many elements have several isotopes. For such elements,
0 n0 n atomic mass is average of the atomic masses of different
isotopes, which is usually non-integral.
1 æ Ze2 ö
19. A. Vn = - ç
ç r ÷
÷
4 pe0 è ø
Slope = + h, intercept = - hn 0. So, option (d) is not correct.
6. Plan As you can see in options, energy term is mentioned hence, we 1 æ Ze2 ö
Kn = ç ÷
have to find out relation between h / l and energy. For this, we 8pe0 ç r ÷
è ø
shall use de-Broglie wavelength and kinetic energy term in eV.
h Vn
de-Broglie wavelength for an electron (l ) = Þ = - 2 ¾ (r )
p Kn
h Ze2
Þ p= …(i) B. En = - µ r -1
l 8pe0r
Kinetic energy of an electron = eV Þ x = - 1 ¾ (q )
p2 h
As we know that, KE = C. Angular momentum = l (l + 1) = 0 in 1s-orbital
2m 2p ¾ ( p).
p2 a0n2 1
\ eV = or p = 2 meV …(ii) D. rn = Þ µ Z ¾ (s)
2m Z rn
h
From equations (i) and (ii), we get = 2 meV 20. Photons have quantised energy.
l
7. Rutherford used a-particle (He 2+
nuclei) in his experiment. 10-3
21. Mass of one H-atom = kg = 1.66 ´ 10-27 kg
6.023 ´ 1023
32 Atomic Structure
r
1 2s
1 25 50 75 100
Atomic number |Y|2 For 3s-orbital
number of radial node = 3–0–1=2
2. The electrons are more likely to be found in the region a and c. At
b, wave function becomes zero and is called radial nodal surface
or simply node. r
a
Y (x)
b +x ®
¬ –x |Y|2 For 2p-orbital
number of radial node = 2–1–1=0
c
r
The graph between wavefunction (y ) and distance (r) from the
nucleus helps in determining the shape of orbital. Thus, the given graph between | y |2 and r represents 2s-orbital.
Atomic Structure 33
5. For any given series of spectral lines of atomic hydrogen. Thus, Eq. (i) becomes
Let Dn = nmax - nmin be the difference in maximum and n2
2pa0 = nl ...(ii)
minimum frequencies in cm-1. Z
For Lyman series, n2
\ 2pa0 = n (1.5 pa0) [Given, l = 1 .5 pa0]
Dn = nmax - nmin Z
General formula: n 15 . pa0 1.5
= = = 0.75
é 1 1ù Z 2pa0 2
n = 109677 ê 2 - 2 ú
êë ni nf úû 8. de-Broglie wavelength (l) for electron is given by
For Lyman n1 = 1, n2 = 2, 3, K h
l= ...(i)
æ1 1 ö æ1 ö 2 m K.E
nmax = 109,677ç - ÷ = 109,677 ç - 0÷
è1 ¥ ø è1 ø Also, according to photoelectric effect
= 109,677 KE = hn - hn 0
æ1 1 ö On substituting the value of KE in Eq (i), we get
nmin = 109,677ç - 2 ÷ h
è 1 (2) ø l=
2m ´ (hn - hn 0 )
DnLyman = nmax - nmin
é 109,677 ´ 3 ù 109,677 1
= 109,677 - = \ lµ
êë 4 úû 4 (n - n 0 )1/ 2
For Balmer series, nh
9. (I) Angular momentum, mvr =
æ 1 1ö 109677 2p
nmax = 109,677ç 2 - ÷ Þ
è (2) ¥ ø 4 Þ mvr µ n
µ distance from the nucleus
æ 1 1 ö 109677 ´ 5
nmin = 109,677ç 2 - 2 ÷ Þ (II) This statement is incorrect as size of an orbit
è (2) (3) ø 36
µ Azimuthal quantum number (l )
Dn = nmax - nmin (Q n = constant)
109,677 é 109,677 ù æ 1ö
DnBalmer = - ´ 5 = 109,677 ç ÷ (III) This statement is incorrect as at ground state,
4 êë 36 úû è 9ø n = 1, l = 0
D nLyman 109,677 / 4 Þ Orbital angular momentum (wave mechanics)
=
D nBalmer 109,677 / 9 h
= l (l + 1) =0 [Q l = 0 ]
D nLyman 9 2p
= (IV) The given plot is
D nBalmer 4
D nLyman
\The ratio of is 9 : 4. l=0 (n=1)
D nBalmer l=1 (n=2)
6. Smaller the value of (n + l ), smaller the energy. If two or more l=2 (n=3)
sub-orbits have same values of (n + l ), sub-orbits with lower y
values of n has lower energy. The (n + l ) values of the given l=3 (n=4)
options are as follows :
I. n = 4, l = 2 ; n + l = 6
II. n = 3, l = 2; n + l = 5
r
III. n = 4 , l = 1, n + l = 5
IV. n = 3, l = 1, n + l = 4 1 é æ 1 1ö ù
10. DE = hc ´ = hc ´ ê RH çç 2 - 2 ÷÷ ´ Z 2 ú
Among II and III, n = 3 has lower value of energy. Thus, the l ë è n1 n2 ø û
correct order of their increasing energies will be
1 1 hc
IV < II < III < I Þ 2- 2= [for H, atom Z = 1]
n1 n2 RH ´ l ´ Z 2 ´ hc
Circumference 2pr
7. Number of waves = Þ n= 1 1 1
Wavelength l = = ´
RH ´ l (1 ´ 10 7 m-1 ) (900 ´ 10-9 m)
\ 2pr = nl ...(i)
1 1 1
Also, we know that radius (r) of an atom is given by Þ 2
- 2=
n1 n2 9
a n2
r= 0 1 1 1 1 é\ n1 = 3,ù
Z So, in option (b) - = -0=
32 ¥ 2 9 9 ëê n2 = ¥ ûú
34 Atomic Structure
(a) It is for 2s-orbital. 23. Nodal plane is an imaginary plane on which probability of
(b) It is radial wave function for 1s. finding an electron is minimum. Every p-orbital has one nodal
plane :
(c) Correct
(d) Probability cannot be zero at a certain distance from nucleus.
13.6 px
14. \ En = - eV where, n = 1, 2, 3 ...
n2
-13.6 YZ-plane, a nodal plane
In excited states, E2 = = -3.4 eV
4
Atomic Structure 35
24. 1s2 2 s2 2 p6 3s2 3 p6 3d 5 4 s1 is ground state electronic configuration 36. Option (b) is wrong representation according to aufbau
of Cr. principle. A high energy atomic orbital (2p) cannot be filled
unless the low energy orbital (2s) is completely occupied.
25. (i) n = 4 , l = 1 Þ 4 p-orbital
(ii) n = 4 , l = 0 Þ 4s-orbital æ 1 1 ö hc
37. Transition energy (DE ) = kZ 2 çç 2
- 2 ÷÷ =
(iii) n = 3, l = 2 Þ 3d-orbital è n1 n2 ø l
(iv) n = 3, l = 1 Þ 3d-orbital 1
i.e. DE µ
According to Aufbau principle, energies of above mentioned l
orbitals are in the order of hc
(iv) 3p < (ii) 4s < (iii) 3d < (i) 4 p 38. E=
l
26. The energy of an electron in a Bohr atom is expressed as E l
Þ 1 = 2 =2
kZ 2 where, k = Constant, E2 l 1
En = - Z = Atomic number,
n2 39. n l m s
n = Orbit number
= - 13.6 eV for H (n = 1) 1
3 2 -3
- 13.6 2
when n = 2 , E2 = eV = - 3.40 eV This is the wrong set of quantum number because | m | cannot be
22
greater than l.
(n can have only integral value 1, 2, 3,…… ¥)
40. The wavelength order is
h
27. The orbital angular momentum (L) = l (l + 1) X-ray < ultraviolet < infrared < radio wave
2p
h 41. When electron jumps to lower orbit photons are emitted while
= 6 (l = 2 for d - orbital ) photons are absorbed when electron jumps to higher orbit.
2p
1s-orbital is the lower most, electron in this orbital can absorb
28. Bohr first made use of quantum theory to explain the structure of photons but cannot emit.
atom and proposed that energy of electron in an atom is
quantised. 42. The valence shell configuration of Rubidium (Rb) is
1 1
[ Kr ] 5s1 n = 5, l = 0, m = 0, s = + or -
29. Mg2+ = 1s2 2s2 2 p6 no unpaired electron 2 2
Ti 3+ = 1s2 2 s2 2 p6 3s2 3 p6 3d 1 one unpaired electron 43. The principal quantum number ‘n’ represents orbit number
3+ 2 2 6 2 6 2 hence, determine the size of orbitals.
V = 1s 2 s 2 p 3s 3 p 3d two unpaired electrons
44. According to Pauli exclusion principle, an atomic orbital can
Fe2+ = 1s2 2 s2 2 p6 3s2 3 p6 3d6 four unpaired electrons
accommodate at the most, two electrons, with opposite spins.
30. Expression for orbital angular momentum (L) is 45. Both (a) and (d) are correct. The three electrons in the
h 2p-orbitals must have same spin, no matter up spin or down spin.
L = l (l + 1) = 0 for 2s-electrons
2p 46. (a) Cr = [Ar] 3d 5 4 s1 , an exception to aufbau principle.
Q For s-orbital, l = 0. (b) For a given value of l, m can have any value from
31. Diffraction is property of wave, E = mc2 determine energy of (-l to + l), so can have negative value.
particle and E = hn determine energy of photon. Interference (c) Ag is in copper group with d 10s1 configuration,
phenomena is exhibited by both matter and waves. i.e. 46 electrons are spin paired.
32. X-rays is electrically neutral, not deflected in electric or 47. Isotones have same number of neutrons.
magnetic fields. 76 77
and 34Se78 have same number (44) of neutrons,
32 Ge , 33As
33. Cl (17) = 1s2 2 s2 2 p6 3s2 3 p5 hence they are isotones.
48. Assertion is correct Be(1s2 , 2s2 ) has stable electronic
configuration, removing an electron require more energy than
The last, unpaired electron has, n = 3, l = 1( p) and m can have the same for B(2 p1 ). Reason is incorrect
any of the three value (- 1, 0, + 1). (Aufbau principle).
34. Cr (24) = 1s2 2 s2 2 p6 3s2 3 p6 3d 5 4 s1 49. S 1 is spherically symmetrical state, i.e. it correspond to a
1442 443
Ar s-orbital. Also, it has one radial node.
The above configuration is exception to Aufbau’s principle. Number of radial nodes = n - l - l
35. Fluorine, a halogen, is the most electronegative atom, has the Þ n - 0 -1=1
electronic configuration 2s2 2 p5 (valence shell). Þ n = 2 i.e. S 1 = 2s-orbital.
36 Atomic Structure
50. Ground state energy of electron in H-atom (EH ) 67. In an one electron (hydrogenic) system, all orbitals of a shell
2 remains degenerate, hence in second excited state, the
kZ
EH = = k (Z = 1, n = 1) degeneracy of H-atom is nine
n2 3s 3p 3d
For S 1 state of Li 2+ , H(1s1) Second excited
Ground state state of H-atom
k (3)2 9 All are degenerate
E= = k = 2.25 k
22 4 degeneracy = 9
51. In S 2 state, E (Li 2+ ) = K (given) In case of many electrons system, different orbitals of a shell are
non-degenerate. Hence,
qk
K = 2p
n2 1s 1s 2s 1s 2s 2p
–
Þ n=3 H
Second excited
Since, S 2 has one radial node. Ground state First excited state
state only three p-orbitals
3 - l -1 = 1 (2px, 2py, 2pz) are
l =1 degenerate.
52. In the wave function (y ) expression for 1s-orbital of He+ , there 68. PLAN This problem is based on concept of quantum number. Follow
should be no angular part. Hence (iii) can’t be true for y 1s of the following steps to solve this problem.
He+ . Write all possible orbitals having combination of same principal,
azimuthal, magnetic and spin quantum number.
53. Correct : 2s orbital has one radial node. Then count the all possible electrons having given set of
No of radial node = n - l - 1 = 2 - 0 - 1 = 1 quantum numbers.
Also, when radial part of wave function (y ) is plotted against For n = 4, the total number of possible orbitals are
‘‘r’’, wave function changes its sign at node. 4s 4p 4d 4f
54. i is the correct expression of wave function for 1s-orbital of 0 –1 0 +1 –2 –1 0 +1 +2 –3 –2 –1 0 +1 +2 +3
hydrogenic system.
According to question | m l | = 1 , i.e. there are two possible
55. A. Orbital angular momentum values of m l , i.e. +1 and –1 and one orbital can contain
h 1
(L) = l (l + 1) maximum two electrons one having s = + and other having
2p 2
i.e. L depends on azimuthal quantum number only. s = - 1/ 2 .
B. To describe a one electron wave function, three quantum So, total number of orbitals having {| m l | = 1} = 6
numbers n, l and m are needed. Further to abide by Pauli Total number of electrons having
exclusion principle, spin quantum number(s) is also needed. 1
{| m l | = 1 and ms = - } = 6
C. For shape, size and orientation, only n, l and m are needed. 2
D. Probability density (y 2 ) can be determined if n, l and m are 69. PLAN KE = 1 mv 2 = 3 RT
known. 2 2
\ m2v 2 = 2mKE \ mv = 2mKE
56. Cr = [Ar] 3d 5 4 s1
h h h
l (wavelength) = = µ
57. 1 : 16 mv 2mKE 2m(T )
58. Heisenberg proposed uncertainty principle and de-Broglie where, T = Temperature in Kelvin
proposed wave nature of electron. h
l(He at -73° C = 200 K) =
59. orbital 2 ´ 4 ´ 200
60. 2 px ,2 py and 2pz have different orientation in space. l (Ne at 727°C = 1000 K) =
h
61. Two electrons in same orbital must have opposite spin. 2 ´ 20 ´ 1000
62. Very large mass of alpha particles than beta particles is l (He) 2 ´ 20 ´ 1000
\ =M = =5
responsible for less deflection in former case. l (Ne) 2 ´ 4 ´ 200
63. 3dx2 - y2 orbital lies in XY-plane. Thus, M =5
64. Aufbau principle. 70. Energy of photon
65. This is the wavelength of infrared radiation. hc hc 6.625 ´ 10–34 ´ 3 ´ 108
= J= eV = = 4 . 14 eV
66. Cr = 3d 5 4 s1. l el 300 ´ 10–9 ´ 1.602 ´ 10–19
Atomic Structure 37
For photoelectric effect to occur, energy of incident photons Number of H-atoms produced after dissociation
must be greater than work function of metal. Hence, only Li, Na, = 2 ´ 0.0409 ´ 6.023 ´ 1023 = 4.93 ´ 1022
K and Mg have work functions less than 4.14 V.
æ 1ö
71. When n = 3, l = 0, 1, 2 i.e. there are 3s, 3p and 3d-orbitals. If all Transition energy/atom = 2.18 ´ 10-18 ç1 - ÷ J
è 4ø
these orbitals are completely occupied as
3
= ´ 2.18 ´ 10-18 J
4
1 Þ Total transition energy
Total 18 electrons, 9 electrons with s = + and 9 with
2 3
1 = ´ 2.18 ´ 10-18 ´ 4.93 ´ 1022 J
s=– . 4
2
= 80.60 ´ 103 J = 80.60 kJ
Alternatively In any nth orbit, there can be a maximum of 2n2
electrons. Hence, when n = 3, number of maximum electrons = Therefore, total energy required
1 = dissociation energy + transition energy
18. Out of these 18 electrons, 9 can have spin –
1 2
= (17.84 + 80.60) kJ = 98.44 kJ
and remaining nine with spin + .
2
nh 76. If accelerated by potential difference of V volt, then
72. (a) mvr = 1
2p mv 2 = eV
-34 2
nh 6.625 ´ 10
Þ v= = p2
2pmr 2 ´ 3.14 ´ 9.1 ´ 10-31 ´ 0.529 ´ 10-10 Þ = eV , here p = momentum (mv )
2m
= 2.18 ´ 106 ms - 1
h h
Using de-Broglie equation, l = =
h 6.625 ´ 10-34 p 2meV
(b) l = = = 0.33 ´ 10-9 m
mv 9.1 ´ 10-31 ´ 2.18 ´ 106
6.625 ´ 10-34
Þ 1.54 ´ 10-10 =
(c) Orbital angular momentum (2 ´ 9.1 ´ 10-31 ´ 1.6 ´ 10-19 V )1/ 2
h æ hö
(L) = l (l + 1) = 2ç ÷ Solving for V gives : V = 63.56 V.
2p è 2p ø
77. The work done in the given neutralisation process is
[Q For p-orbital, l = 1 ]
¥ e2
73. (a) At radial node, y 2 must vanishes, i.e. W =-ò F dr and F =
a0 4pe0r2
2 2 r0
é 1 ù æ r0 ö - a 0 e2
¥ 2
y 22s = 0 = ê ú çç 2 - a ÷÷ e Þ W =
é 1ù
=-
e
= Total energy (E )
ë 4 2p û è 0ø 4 pe0 êë r úû
a0 4 pe0r
r0
Þ 2- = 0 Þ r0 = 2a0 Now, if ‘V’ is magnitude of potential energy, then according to
a0 given information, kinetic energy (Ek ) is V / 2. Therefore,
h 6.625 ´ 10-34 V
(b) l= = = 6.625 ´ 10-35 m E = -V + (PE is always negative)
mv 100 ´ 10-3 ´ 100 2
V
= 6.625 ´ 10-25 Å (negligibly small) =-
2
74. The general Rydberg’s equation is - e2
Þ V = - 2E =
1 æ 1 1ö 2pe0r
n= = R (Z )2 ç 2 - 2÷
çn ÷
l è 1 n2ø
78. The Rydberg’s equation for H-atom is
1
Þ µ Z2 1 æ 1 1ö
l = n (wave number) = RH çç 2 - 2 ÷÷
l n
è 1 n2ø
l (He+ ) Z (H)2 1
Þ = =
l (H) Z (He+ )2 4 For Balmer series, n1 = 2 and n2 = 3, 4 , 5, ..., ¥
l (H) 91.2 For shortest l, n2 has to be maximum, i.e. infinity. Then
Þ l (He+ ) = = nm = 22.8 nm
4 4 æ1 1ö R 1.09 ´ 107
n = RH ç - ÷ = H = = 2.725 ´ 106 m -1
pV 1 ´1 è 4 ¥ ø 4 4
75. Moles of H2 = = = 0.0409
RT 0.082 ´ 298
Þ Bond energy = 0.0409 ´ 436 = 17.84 kJ
38 Atomic Structure
79. After breaking of the bond of I2 molecule, the remaining energy For longest wavelength transition from 3rd orbit, electron must
would be distributed uniformly to iodine atoms as their kinetic jump to 4th orbit and the transition energy can be determined as
energy, i.e. æ1 1 ö
DE = + 4 ´ 21.7 ´ 10-19 ç - ÷ J = 4.22 ´ 10-19 J
E (energy of photon) = Bond energy + 2 ´ kinetic energy è 9 16 ø
6.625 ´ 10-34 ´ 3 ´ 108 240 ´ 103 hc
Þ = + 2 ´ Ek Also, Q DE =
4500 ´ 10 -10
6.023 ´ 1023 l
hc 6.625 ´ 10-34 ´ 3 ´ 108
Þ Ek = 2.16 ´ 1020 J/atom \ l= = m
DE 4.22 ´ 10-19
80. The Bohr de-Broglie relationship is
= 471 ´ 10-9 m = 471 nm
2pr = nl = circumference of Bohr’s orbit.
i.e. number of complete waves formed in one complete 84. Ten, the given value of n and l correspond to 3d-orbital which
revolution of electron in any Bohr orbit is equal to orbit number, has five fold degeneracy level.
hence three. 85. The 2nd configuration is against Hund’s rule of maximum
81. The expression for transition wavelength is given by Rydberg’s multiplicity which states that the singly occupied degenerate
equation : atomic orbitals must have electrons of like spins.
1 æ 1 1ö 86. The required transition is n1 = 2 to n2 = ¥ and corresponding
= RH Z 2 çç 2 - 2 ÷÷
l è n1 n2 ø transition energy is
Equating the transition wavelengths of H-atom and He ion, + æ 1 1ö
DE = 21.7 ´ 10-12 çç 2 - 2 ÷÷ erg
æ 1 1ö n
è 1 n2ø
æ4 4ö
21.7
RH çç 2 - 2 ÷÷ = RH ç 2 - 2 ÷
n n è 2 4 ø = ´ 10-12 erg = 5.425 ´ 10-12 erg
è 1 2ø 4
The longest wavelength that can cause above transition can be
Equating termwise on left to right of the above equation gives
determined as :
n1 = 1 and n2 = 2
hc 6.625 ´ 10-34 ´ 3 ´ 108
82. For H-atom, the energy of a stationary orbit is determined as l= =
DE 5.425 ´ 10-12 ´ 10-7
k
En = - where, k = constant (2.18 ´ 10-18 J)
n2 = 3.66 ´ 10-7 m = 3.66 ´ 10-5 cm
æ 1ö 3
Þ DE (n = 2 to n = 1) = k ç1 - ÷ = k 87. Ionisation potential of H-like species
è 4 ø 4
-18
= E1 = 2.17 ´ 10-11 erg
= 1.635 ´ 10 J
æ 1ö
For a H-like species, energy of stationary orbit is determined as Þ DE = 2.17 ´ 10-11 ç1 - 2 ÷ ´ 10-7 J
kZ 2 è 2 ø
En = - 2
n hc
= 1.6275 ´ 10-18 J Þ l =
where, Z = atomic number DE
æ 1 1ö 6.625 ´ 10-34 ´ 3 ´ 108
Þ DE = kZ 2 çç 2 - 2 ÷÷ = m
è n1 n2 ø 1.6275 ´ 10-18
1 DE k 2 æ 1 1 ö 3 = 122 ´ 10-9 m = 1220 Å
Þ = = Z ç - ÷ = RH Z 2 ´
l hc hc è1 4 ø 4
88. Transition energy = [ - 2.41 - (- 5.42)] ´ 10-12 erg
4 4
Þ Z2 = = = 4.05
3RH l 3 ´ 1.097 ´ 107 ´ 3 ´ 10-8 = 3.01 ´ 10-12 erg
(a) P > S (b) Si < Al (a) 1.36, 1.40 and 1.71 (b) 1.36, 1.71 and 1.40
(c) Te > Se (d) Ga < Ge (c) 1.71, 1.40 and 1.36 (d) 1.71, 1.36 and 1.40
40 Periodic Classification and Periodic Properties
7. Which one of the following alkaline earth metal sulphates 19. The first ionisation potential of Na, Mg, Al and Si are in the
has its hydration enthalpy greater than its lattice enthalpy? order (1988, 1M)
(a) CaSO4 (b) BeSO4 (2015 Main) (a) Na < Mg >Al < Si (b) Na > Mg > Al >Si
(c) BaSO4 (d) SrSO4 (c) Na < Mg <Al >Si (d) Na > Mg > Al <Si
8. Which among the following is the most reactive? 20. The electronegativity of the following elements increases in
(a) Cl 2 (b) Br2 (2015 Main) the order (1987, 1M)
(c) I2 (d) ICl (a) C, N, Si, P (b) N, Si, C, P
9. Which one has the highest boiling point? (c) Si, P, C, N (d) P, Si, N, C
(a) He (b) Ne (c) Kr (d) Xe 21. Atomic radii of fluorine and neon in Angstrom units are
10. The first ionisation potential of Na is 5.1 eV. The value of respectively given by (1987, 1M)
electron gain enthalpy of Na + will be (2013 Main) (a) 0.72, 1.60 (b) 1.60, 1.60
(a) - 2.55 eV (b) - 5.1 eV (c) 0.72, 0.72 (d) None of these
(c) - 10.2 eV (d) + 2.55 eV 22. The first ionisation potential in electron volts of nitrogen and
11. Which of the following represents the correct order of oxygen atoms are respectively given by (1987, 1M)
increasing first ionisation enthalpy for Ca, Ba, S, Se and Ar? (a) 14.6, 13.6 (b) 13.6, 14.6
(2013 Main) (c) 13.6, 13.6 (d) 14.6, 14.6
(a) Ca < S < Ba < Se < Ar (b) S < Se < Ca < Ba < Ar 23. The hydration energy of Mg 2+ is larger than that of
(c) Ba < Ca < Se < S < Ar (d) Ca < Ba < S < Se < Ar (1984, 1M)
12. Identify the least stable ion amongst the following. (a) Al 3+ (b) Na + (c) Be2+ (d) Mg3+
(a) Li + (b) Be- (2002, 3M) 24. The element with the highest first ionisation potential is
(c) B- (d) C - (1982, 1M)
(a) boron (b) carbon
13. The set representing the correct order of first ionisation
(c) nitrogen (d) oxygen
potential is (2001, 1M)
25. The correct order of second ionisation potential of carbon,
(a) K > Na > Li (b) Be > Mg > Ca nitrogen, oxygen and fluorine is (1981, 1M)
(c) B > C > N (d) Ge > Si > C (a) C > N > O > F (b) O > N > F > C
(c) O > F > N > C (d) F > O > N > C
14. The correct order of radii is (2000, 1M)
(a) N < Be < B (b) F - < O2- < N3- Objective Questions II
(c) Na < Li < K (d) Fe3+ < Fe 2+ < Fe4+ (One or more than one correct option)
15. The incorrect statement among the following. (1997(C), 1M) 26. The option(s) with only amphoteric oxides is(are)(2017 Adv.)
(a) The first ionisation potential of Al is less than the first (a) NO, B2O3 , PbO, SnO2 (b) Cr2O3 , CrO, SnO, PbO
ionisation potential of Mg (c) Cr2O3 , BeO, SnO, SnO2 (d) ZnO, Al 2O3 , PbO, PbO2
(b) The second ionisation potential of Mg is greater than the
27. Ionic radii of (1999, 3M)
second ionisation potential of Na
(a) Ti 4+ < Mn 7 + (b) 35
Cl - < 37
Cl -
(c) The first ionisation potential of Na is less than the first
ionisation potential of Mg (c) K + > Cl - (d) P 3+ > P 5+
(d) The third ionisation potential of Mg is greater than third
28. The first ionisation potential of nitrogen and oxygen atoms
ionisation potential of Na
are related as follows. (1989, 1M)
16. Which of the following has the maximum number of (a) The ionisation potential of oxygen is less than the ionisation
unpaired electrons ? (1996, 1M) potential of nitrogen
(a) Mg2+ (b) Ti 3+ (b) The ionisation potential of nitrogen is greater than the
(c) V 3+ (d) Fe2+ ionisation potential of oxygen
(c) The two ionisation potential values are comparable
17. Amongst the following elements (whose electronic (d) The difference between the two ionisation potential is too large
configurations are given below), the one having the highest
ionisation energy is (1990, 1M) 29. Sodium sulphate is soluble in water whereas barium sulphate
2
(a) [Ne] 3s 3 p 1 2
(b) [Ne] 3s 3 p 3 is sparingly soluble because (1989, 1M)
2 2 10 2 3
(a) the hydration energy of sodium sulphate is more than its lattice
(c) [Ne] 3s 3 p (d) [Ar] 3d 4s 4 p energy
18. Which one of the following is the smallest in size? (b) the lattice energy of barium sulphate is more than its hydration
(1989, 1M) energy
(a) N3- (b) O2- (c) the lattice energy has no role to play in solubility
(c) F - (d) Na + (d) the hydration energy of sodium sulphate is less than its lattice
energy
Periodic Classification and Periodic Properties 41
Assertion and Reason 37. On Mulliken scale, the average of ionisation potential and
electron affinity is known as ................ (1985, 1M)
Read the following questions and answer as per the
direction given below : 38. The energy released when an electron is added to a neutral
(a) Statement I is true; Statement II is true; Statement II is gaseous atom is called …… . (1982, 1M)
the correct explanation of Statement I.
(b) Statement I is true; Statement II is true; Statement II is True/False
not the correct explanation of Statement I. 39. The basic nature of the hydroxides of group 13 (III B)
(c) Statement I is true; Statement II is false. decreases progressively down the group. (1993, 1M)
(d) Statement I is false; Statement II is true.
40. The decreasing order of electron affinity of F, Cl, Br is
30. Statement I Nitrogen and oxygen are the main F > Cl > Br. (1993, 1M)
components in the atmosphere but these do not react to
41. In group IA of alkali metals, the ionisation potential decreases
form oxides of nitrogen.
down the group. Therefore, lithium is a poor reducing agent.
Statement II The reaction between nitrogen and oxygen
(1987, 1M)
requires high temperature. (2015 Main)
31. Statement I Pb 4+ compounds are stronger oxidising 42. The softness of group IA metals increases down the group with
4+ increasing atomic number. (1986, 1M)
agents than Sn compounds.
Statement II The higher oxidation states for the group 14
elements are more stable for the heavier members of the
Subjective Questions
group due to ‘inert pair effect’. (2008, 3M) 43. Arrange the following ions in order of their increasing radii
32. Statement I Band gap in germanium is small. Li + , Mg 2+ , K + , Al 3+. (1997, 1M)
Statement II The energy spread of each germanium 44. Compare qualitatively the first and second ionisation
atomic energy level is infinitesimally small. (2007, 3M) potentials of copper and zinc. Explain the observation.
33. Statement I The first ionisation energy of Be is greater (1996, 2M
than that of B. 45. Arrange the following as stated :
Statement II 2p-orbital is lower in energy than 2s. “Increasing order of ionic size’’ N3– ,Na + , F- , O2 - , Mg 2+
(2000, (S), 1M)
(1991, 1M)
34. Statement I F-atom has a less negative electron affinity 46. Explain the following :
than Cl-atom.
Statement II Additional electrons are repelled more “The first ionisation energy of carbon atom is greater than that
effectively by 3 p-electrons in Cl-atom than by 2 p-electrons of boron atom whereas, the reverse is true for the second
in F-atom. (1998, 2M)
ionisation energy.’’ (1989, 2M)
Answers
Topic 1 21. (a) 22. (a) 23. (b) 24. (c)
1. (b) 2. (c) 3. (d) 4. (b,c,d) 25. (c) 26. (a,b) 27. (d) 28. (a,b,c)
29. (a,b) 30. (a) 31. (c) 32. (c)
Topic 2
33. (c) 34. (c)
1. (b) 2. (d) 3. (d) 4. (a)
35. (inert pair effect)
5. (a) 6. (c) 7. (b) 8. (d)
36. (higher effective nuclear charge)
9. (d) 10. (b) 11. (c) 12. (b)
37. (electronegativity) 38. (electron affinity)
13. (b) 14. (b) 15. (b) 16. (d)
17. (b) 18. (d) 19. (a) 20. (c) 39. F 40. F 41. F 42. T
Hints & Solutions
Topic 1 History and Periodic Classification First ionisation enthalpy (I.E.) of K is lowest among the given
1. Atomic number (119) = 1 1 9 options. Here, the energy required to remove an electron from 4 s1
un un en is least as only one electron is present in the outermost shell. I.E.
So, symbol of the element = uue (I) is comparatively high for Mg and Sr and two electrons
Name of the element = ununennium (fully-filled) are placed in s-orbital. Second ionisation enthalpy of
K is highest among the given options.
It is expected to be s-block element an alkali metal and the first
element in eighth period. It is the lightest element that has not Now, removal of an electron occur from p6 (fully-filled). So, high
yet been synthesised. energy is required to remove the electron. From the above
discussion, it can be concluded that (I.E 2 - I.E 1 ) value is
2. The element with Z = 120 will be an alkaline earth metal. maximum for K (potassium).
Recently, oganesson (Og) with atomic number 118 is named
by IUPAC is a noble gas and placed just two place before 120. 3. The electronegativity values of given elements on the Pauling scale
So, the general electronic configuration is represented as can be shown as follows:
[noble gas]ns2 and element with Z = 120 exist as an alkaline
Period No. Group 13 Group 14 Group 15 Group 16
earth metal.
3 Al (1.5) Si (1.8) P (2.1) S (2.5)
3. (a) Correct statement According to Moseley’s law, the 4 Ga (1.6) Ge (1.8) Se (2.4)
properties of elements are the periodic function of their 5 Te (2.01)
atomic numbers.
(b) Correct statement The whole s-block, d-block, f -block On moving from left to right across a period, i.e. from Ga to Se,
and heavier p-block elements are metal. the effective nuclear charge increases and size decreases.
(c) Correct statement Trend is not regular, Be has higher As a result, the value of electronegativity increases due to
first ionisation energy than B, nitrogen has higher first increase in the attraction between the outer electrons and the
ionisation energy than oxygen. nucleus. Whereas on moving down the group, (i.e. from Se to Te),
the atomic size increases.
(d) Inccorrect statement d-subshells are not filled
monotonically, regularity break at chromium and copper. As a result, the force of attraction between the outer electron and
the nucleus decreases. Hence, the electronegativity decreases.
4. (a) Incorrect Electrons are not filled in sub-energy levels
s, p, d and f in the same sequence.
(b) Correct Number of valence shell electrons usually 4. Element Period Group No.
No.
determine the stable valency state of an element. C 2nd 14
(c) Correct Physical and chemical properties of elements Al 3rd 13 Along the period atomic radius
are periodic function of atomic number which is the basis of S 3rd 16 decreases, so, radii : Al > S.
modern, long form of periodic table. Cs 6th 1
(d) Correct Relative ionicity of the bond between any two With the addition of a new shell, period number as well as atomic
elements is function of electronegativity difference of the radius increases. It is because of the successive addition of one
bonded atoms which in turn has periodic trend in long form extra shell of electrons. So, the order of the atomic radii of the
of periodic table. given elements will be: C < S < Al < Cs
Topic 2 Periodic Properties 5. The summary of variation of periodic properties is given in table
below:
1. The group number, number of valence electrons and valency of
an element with atomic number 15 are 15, 5 and 3 respectively. S.No. Periodic property Variation
Modern periodic table is based on the atomic number. Number Along a period Along a group
of valence electrons present in an atom decides the group
1. Atomic radius Decreases Increases
number. Electronic configuration of element having atomic
2. Electron gain Increases Decreases
number 15 = 1s2 2s2 2 p6 3s2 3 p3
enthalpy
Valence electrons
3. Electronegativity Increases Decreases
As five electrons are present in valence shell, its group number
is 15. Valency of element having atomic number 15 is +3 Thus, electronegativity decreases and atomic radius increases
(8 - 5 = 3). down a group in the periodic table.
2. The electronic configuration of given elements are as follows : 6. Number of electrons in N3- , = 7 + 3 = 10
K(19) = 1s2 2s2 2 p6 3s2 3 p6 4 s1 Number of electrons in O2- = 8 + 2 = 10
Mg(12) = 1s2 2s2 2 p6 3s2 Number of electrons in F- = 9 + 1 = 10
Sr(38) = 1s2 2s2 2 p6 3s2 3 p6 4 s2 3d 10 4 p6 5s2 Since, all the three species have each 10 electrons, hence they are
isoelectronic species.
Sc(21) = 1s2 2s2 2 p6 3s2 3 p6 4 s2 3d 1
Periodic Classification and Periodic Properties 43
It is considered that, in case of isoelectronic species as the 15. (a) Correct statement In a period, element of 2nd group has
negative charge increases, ionic radii increases and therefore the higher first ionisation potential than element of group 13.
value of ionic radii are (b) Incorrect statement Mg+ require less energy for further
N3- = 1.71 (highest among the three) ionisation than Na + because of noble gas configuration of Na + .
O2- = 1.40 F- = 136. (lowest among the three) (c) Correct statement Ionisation energy increases from left
Time Saving Technique There is no need to mug up the radius to right in a period.
values for different ions. This particular question can be solved
through following time saving. 16. Mg2+ = 1s2 2 s2 2 p6 = no unpaired electron
Trick The charges on the ions indicate the size as Ti 3+ = 1s2 2 s2 2 p6 3s2 3 p6 3d 1 = one unpaired electron
N3- > O2- > F- . Thus, you have to look for the option in which V3+ = 1s2 2 s2 2 p6 3s2 3 p6 3d 2 = two unpaired electrons
the above trend is followed. Option(c) is the only one in which
Fe2+ = 1s2 2 s2 2 p6 3s2 3 p6 3d6 = four unpaired electrons
this trend is followed. Hence, it is the correct answer.
7. As we move down the group, size of metal increases. Be has 17. [Ne] 3s2 3 p3 has highest ionisation energy, periodic trend.
lower size while SO2-
4 has bigger size, that’s why BeSO4 breaks 18. Among isoelectronic species, the relation in size is
easily and lattice energy becomes smaller but due to lower size cation < neutral < anion
of Be, water molecules are gathered around and hence hydration +
Hence, Na has smallest size.
energy increases. 19. Ionisation energy increases from left to right in a period.
On the other hand, rest of the metals, i.e Ca, Ba, Sr have bigger However, exception occur between group 2 and group 13
size and that’s why lattice energy is greater than hydration energy. elements on account of stability of electronic configuration of
Time Saving Technique In the question of finding hydration valence shell.
energy only check the size of atom. Smaller sized atom has more IE
hydration energy. Thus, in this question Be is placed upper most Group 2 = > Group 13 =
in the group has lesser size and not comparable with the size of
sulphates. Hence, BeSO4 is the right response. ns2 ns2 np1
8. Cl 2, Br2 and I2 are homonuclear diatomic molecule in which Þ The desired order is Na < Mg > Al < Si
electronegativity of the combining atoms is same, so they are 20. Electronegativity increases from left to right in a period and
more stable and less reactive, whereas, I and Cl have different decreases from top to bottom in a group. Variation is more rapid
electronegativities and bond between them are polarised and in group than in a period, hence the desired order is
reactive. Therefore, interhalogen compounds are more reactive. Electronegativity : Si < P < C < N
Time Saving Technique In this type of question of halogen, 21. Atomic radius of noble gases are greater than halogens of same
only go through the polarity of the molecules. As we know, period, hence (a) is the correct answer.
diatomic molecule does not have polarity but molecules with 22. First ionisation energy of oxygen is less than that of nitrogen on
dissimilar sizes have polarity resulting in more reactivity. the ground of stability of valence shell configuration, hence (a)
9. As we move down the group of noble gases, molecular mass is the correct answer.
increases by which dipole produced for a moment and hence 23. Hydration energy depends on charge of ion and ionic radius.
London forces increases from He to Xe. Higher the charge, greater the hydration energy. On the other
Therefore, more amount of energy is required to break these hand, smaller the size, greater the hydration energy. Charge is
forces, thus boiling point also increases from He and Xe. considered first for comparison. Hence, Mg2+ has higher
10. Na ¾® Na + + e- First IE hydration energy than Na + .
Na + + e- ¾® Na 24. Nitrogen has highest ionisation potential due to exceptional
+ stability of its valence shell configuration mentioned in question 21.
Electron gain enthalpy of Na is reverse of (IE)
Because reaction is reverse so DH (eq) = - 5.1 eV 25. For second ionisation potential, electron will have to be
removed from valence shell of the following ions:
11. Ionisation energy increases along a period from left to right and
decreases down a group. The position of given elements in the C+ (5e-) = 1s2 2s2
periodic table is as 2p
N+ (6e-) = 1s2 2s2
Group No. 2 16 18
2p
Ca S Ar
Ba Se O+ (7e-) = 1s2 2s2
2p
Thus, the order of increasing DH IE1 is Ba < Ca < Se < S < Ar
F+ (8e-) = 1s2 2s2
12. Be- is the least stable ion, Be (1s2 2s2 ) has stable electronic 2p
configuration, addition of electron decreases stability. In general, ionisation energy increases from left to right in a
13. In a group, ionisation energy decreases down the group period. However, exception occur between adjacent atoms in a
Be > Mg > Ca period, greater amount energy is required for removal of
electron from completely half-filled or completely filled orbital
14. Among isoelectronic species, greater the negative charge, than the same for adjacent atom with either less than completely
greater the ionic size, hence F- < O2- < N3- . half-filled or less than completely filled orbital. Therefore,
44 Periodic Classification and Periodic Properties
ionisation potential of O+ is greater than that of F+ . Also ionisation F atom has slightly lower affinity for the electron than chlorine.
potential of N+ is greater than C+ but less than both O+ and F+ It is due to the reason that additional electrons are repelled more
(periodic trend). Hence, overall order is 2nd IP : O > F > N > C. effectively by 2p-electrons in F than by 3p-electrons in Cl-atom.
26. (c) is incorrect because NO is neutral oxide. 35. Inert pair effect-favours lower oxidation state.
(d) is incorrect because CrO is basic oxide. 36. Higher effective nuclear charge due to greater p/e ratio.
27. (a) Ti 4+ > Mn 7+ is the correct order of size due to lower positive IP + EA
37. Electronegativity = (Mulliken formula)
2
charge on Ti 4+ .
(b) 37 Cl - = 37 Cl - : Isotopes with same charge have same size 38. Electron affinity–definition.
because isotopes differ in compositions of nuclei which do 39. Basic nature of hydroxides increases down a group.
not affect the atomic/ionic radius. 40. Cl has maximum electron affinity, hence the correct order is
(c) K+ < Cl - is the correct order. Among isoelectronic species, Cl > F > Br
anion has greater size than cation. 41. Ionisation potential decreases down the group but this is not the
(d) P3+ > P5+ is the correct order. For the same elements, lower only criteria of reducing power.
the positive charge, larger the ions. 42. In a group, size increases from top to bottom.
28. (a) and (b) are infact the same statements and both are correct. N 43. Li + < Al 3+ < Mg2+ < K+ . Size decreases from left to right in a
has slightly greater ionisation energy than oxygen which is period and it increases from top to bottom in a group. Variation
against periodic trend. This exception is due to completely is more pronounced in group than in period.
half-filled (2 p3 ) orbital in nitrogen that makes ionisation 44. Zn = 3d 10 4 s2 , Cu = 3d 10 4 s1
slightly difficult than oxygen. The first ionisation energy is greater for Zn but reverse is true for
(c) Also correct : Although N has greater first ionisation 2nd ionisation energy.
potential than oxygen, two values of ionisation potentials are
comparable since they are adjacent in a period, i.e. electrons 45. Ionic size Mg2+ < Na + < F- < O2- < N3-
are removed from same orbit during ionisation. Already explained in question 1 (i).
(d) Incorrect – opposite to (c). of the bonded atoms which in
turn has periodic trend in long form of periodic table. 46. The first ionisation energy of carbon is greater than the same of
boron as predicted from periodic trend. However, for 2nd
29. (a) Correct For greater solubility, hydration energy must be
greater than lattice energy. B+ = 1s2 ; more stable than C+ =1s2 2s2
(b) Correct Greater lattice energy discourage dissolution of a salt. 2p1
2s2
(c) Incorrect When a salt dissolve, energy is required to break
the lattice, which comes from hydration process. ionisation trend is reversed due to stability of completely filled
(d) Incorrect Explained in (A). 2s-orbital of B+ :
30. Statement I and II are true and Statement II is the correct 47. Size Ca 2+ < Ar < Cl - < S2- . Explained in (i), question 6.
explanation of statement I.
48. (i) Mg2+ , O2- , Na + and F - are all isoelectronic, has
31. Statement I is true. Stronger oxidising agent is one which itself
can easily be reduced. Pb4+ is unstable, due to inert pair effect, 10 electrons each. Among isoelectronic species, the order of
can easily be reduced to stable Pb2+ , hence a stronger oxidising size is cation < neutral < anion.
Also, between cations, higher the charge, smaller the size
agent than Sn 4+ .
and between anions, greater the negative charge, larger the
Statement II is false. Due to inert pair effect, the higher size. Therefore, the decreasing order of ionic radii :
oxidation states of group 14 elements becomes less stable for
O2- > F- > Na + > Mg2+
heavier member.
(ii) First ionisation energy increases from left to right in a period.
32. Both statements I and II are true and Statement II is the correct
explanation of statement I. However, exception occur between group 2 and 13 and group 15
and 16 where trend is reversed on the grounds of stability of
33. Statement I is true Be has higher first ionisation energy than B completely filled and completely half-filled orbitals. Therefore,
which is against periodic trend.
Ionisation energy (1st) : Na < Al < Mg < Si
Statement II is false 2s-orbital is lower in energy than 2p,
(iii) If the atoms are from same period, bond length is inversely
Aufbau’s principle.
proportional to bond order. In a group, bond length is related
34. Statement I is true; Statement II is false. directly to atomic radius. Therefore,
bond length N2 < O2 < F2 < Cl 2
(b) ICl 5 is square pyramidal and ICl -4 is square planar 7. The group having isoelectronic species is (2017 Main)
2- - + 2+ - - +
(a) O , F , Na , Mg (b) O , F , Na, Mg
(c) Both are isostructural
2- - 2+
(d) ICl 5 is trigonal bipyramidal and ICl -4 is tetrahedral (c) O , F , Na, Mg (d) O- , F- , Na + , Mg 2 +
3. The ion that has sp 3 d 2 hybridisation for the central atom, is 8. The correct statement for the molecule, CsI3 is (2014 Main)
(2019 Main, 8 April II) (a) it is a covalent molecule
(a) [ICl 2 ]- (b) [BrF2 ]- (b) it contains Cs + and I-3 ions
(c) it contains Cs 3+ and I- ions
(c) [ICl 4 ]- (d) [IF6 ]-
(d) it contains Cs + , I- and lattice I2 molecule
Chemical Bonding 47
9. The species having pyramidal shape is (2010) (a) sp, sp 3 and sp 2 respectively
(a) SO3 (b) BrF3 (c) SiO2-
3 (d) OSF2 (b) sp, sp 2 and sp 3 respectively
(c) sp 2 , sp and sp 3 respectively
10. Assuming that Hund’s rule is violated, the bond order and
(d) sp 2 , sp 3 and sp respectively
magnetic nature of the diatomic molecule B 2 is (2010)
(a) 1 and diamagnetic (b) 0 and diamagnetic 22. In the compound CH2 == CH ¾ CH2 ¾ CH2 ¾ C ºº CH, the
(c) 1 and paramagnetic (d) 0 and paramagnetic C2 ¾ C3 bonds is of (1999, 2M)
(a) sp - sp 2 (b) sp 3 - sp 3
11. The species having bond order different from that in CO is (c) sp - sp 3 (d) sp 2 - sp 3
(a) NO- (b) NO+ (2007, 3M)
23. The geometry of H2 S and its dipole moment are (1999, 2M)
(c) CN- (d) N2
(a) angular and non-zero (b) angular and zero
12. Among the following, the paramagnetic compound is (c) linear and non-zero (d) linear and zero
(2007, 3M)
(a) Na 2 O2 (b) O3 (c) N2 O (d) KO2 24. The geometry and the type of hybrid orbital present about the
central atom in BF3 is (1998, 2M)
13. Which of the following contains maximum number of lone (a) linear, sp (b) trigonal planar, sp 2
pairs on the central atom? (2005, 1M)
(c) tetrahedral, sp 3 (d) pyramidal, sp 3
(a) ClO -3 (b) XeF 4 (c) SF 4 (d) I -3
25. Which one of the following compounds has
14. Number of lone pair(s) in XeOF4 is/are (2004, 1M) sp 2 - hybridisation? (1997, 1M)
(a) 0 (b) 1 (c) 2 (d) 3 (a) CO2 (b) SO2
15. Which of the following are isoelectronic and isostructural ? (c) N2 O (d) CO
NO–3 , CO2– –
3 , ClO3 , SO3 (2003, 1M)
26. Among KO2 , AlO-2 , BaO2 and NO+2 , unpaired electron is
(a) NO–3 , CO2-
3 (b) SO3 , NO–3
present in (1997 C, 1M)
(c) ClO–3 , CO2– (d) CO2–
3 , SO3
3 (a) NO+2 and BaO2 (b) KO2 and AlO-2
16. Among the following, the molecule with the highest dipole (c) Only KO2 (d) Only BaO2
moment is (2003, 1M) -
27. The cyanide ion CN and N2 are isoelectronic, but in contrast
(a) CH 3 Cl (b) CH 2 Cl 2
to CN- , N2 is chemically inert because of (1997 C, 1M)
(c) CHCl 3 (d) CCl 4
(a) low bond energy
17. Which of the following molecular species has unpaired (b) absence of bond polarity
electron (s)? (2002, 3M) (c) unsymmetrical electron distribution
(a) N2 (b) F2 (c) O–2 (d) O2–
2 (d) presence of more number of electron in bonding orbitals
18. Specify the coordination geometry around and hybridisation 28. Among the following species, identify the isostructural pairs.
of N and B atoms in a 1 : 1 complex of BF3 and NH3 . NF3 , NO-3 , BF3 , H3 O+ , N3 H (1996, 1M)
(a) N : tetrahedral, sp 3 ; B: tetrahedral, sp 3 (2002, 3M)
(b) N : pyramidal, sp 3 ; B: pyramidal, sp 3 (a) [NF3 ,NO-3 ] and [BF3 ,H3 O+ ]
(c) N: pyramidal, sp 3 ; B: planar, sp 2 (b) [NF3 , N3 H] and [NO-3 ,BF3 ]
(d) N: pyramidal, sp 3 ; B: tetrahedral, sp 3 (c) [ NF3 , H3 O+ ] and [NO–3 , BF3 ]
19. The correct order of hybridisation of the central atom in the (d) [NF3 , H3 O+ ] and [N3 H, BF3 ]
2-
following species NH3 , [PtCl 4 ] , PCl 5 and BCl 3 is
29. Which one of the following molecules is planar? (1996, 1M)
(a) dsp 2 , dsp 3 , sp 2 and sp 3 (2001, 1M)
(a) NF3 (b) NCl 3 (c) PH3 (d) BF3
(b) sp 3 , dsp 2 , sp 3 d and sp 2
(c) dsp 2 , sp 2 , sp 3 and dsp 3 30. The maximum possible number of hydrogen bonds a water
(d) dsp 2 , sp 3 , sp 2 and dsp 3 molecule can form is (1992, 1M)
20. The common features among the species CN – , CO (a) 2 (b) 4 (c) 3 (d) 1
and NO+ are (2001, 1M)
31. The type of hybrid orbitals used by the chlorine atom in
(a) bond order three and isoelectronic ClO-2 is (1992, 1M)
(b) bond order three and weak field ligands (a) sp 3 (b) sp 2
(c) bond order two and acceptors (c) sp (d) None of these
(d) isoelectronic and weak field ligands
32. The molecule which has pyramidal shape is (1989, 1M)
21. The hybridisation of atomic orbitals of nitrogen in (a) PCl 3 (b) SO3
NO+2 , NO-3 and NH+4 are (2000, 1M) (c) CO2– (d) NO–3
3
48 Chemical Bonding
Fill in the Blanks atom does not have contribution from the d-orbital(s) is
[atomic number of S = 16 , Cl = 17 , I = 53 and Xe = 54]
51. Among N2 O, SO2 , I+3 and I–3 , the linear species are …… and (2015 adv.)
…… (1997 C, 1M) 68. A list of species having the formula XZ4 is given below
52. When N2 goes to N+2 , the N ¾ N bond distance … , and when (2014 Adv.)
O2 goes to O+2 the O ¾ O bond distance …… XeF4 , SF4 , SiF4 , BF4- , BrF4- , [Cu(NH3 )4 ] 2+ , [FeCl 4 ] 2- ,
(1996, 1M)
[CoCl 4 ] 2- and [PtCl 4 ] 2-
53. The two types of bonds present in B2 H6 are covalent and
Defining shape on the basis of the location of X and Z atoms,
…… (1994, 1M)
the total number of species having a square planar shape is
54. The kind of delocalisation involving sigma bond orbitals is
69. The total number of lone-pair of electrons in melamine is
called................. (1994, 1M)
(2013 Adv.)
55. The valence atomic orbitals on C in silver acetylide is 70. Based on VSEPR theory, the number of 90° F—Br—F
.............hybridised. (1990, 1M) angles in BrF5 is (2010)
56. The shape of CH3 + is …… . (1990, 1M)
Subjective Questions
57. …… hybrid orbitals of nitrogen atom are involved in the
formation of ammonium ion. (1982, 1M) 71. Predict whether the following molecules are isostructural or
not. Justify your answer.
58. Pair of molecules which forms strongest intermolecular (i) NMe3 (ii) N(SiMe3 )3 (2005, 2M)
hydrogen bonds is ……… . (SiH4 and SiF4 , acetone and
CHCl 3 , formic acid and acetic acid) (1981, 1M) 72. On the basis of ground state electronic configuration, arrange
the following molecules in increasing O—O bond length
59. The angle between two covalent bonds is maximum in …… . order. KO2 , O2 , O2 [AsF6 ] (2004, 2M)
(CH4 , H2 O, CO2 ) (1981, 1M)
73. Draw the shape of XeF4 and OSF4 according to VSEPR
True/False theory. Show the lone pair of electrons on the central atom.
(2004, Main, 2M)
60. The dipole moment of CH3 F is greater than that of CH3 Cl.
(1993, 1M) 74. Using VSEPR theory, draw the shape of PCl 5 and BrF5 .
61. H2 O molecule is linear. (2003, 2M)
(1993, 1M)
62. The presence of polar bonds in a polyatomic molecule 75. Draw the molecular structures of XeF 2 , XeF 4 and XeO2 F2 ,
indicating the location of lone pair(s) of electrons. (2000, 3M)
suggests that the molecule has non-zero dipole moment.
(1990, 1M) 76. Interpret the non-linear shape of H2 S molecule and
3 non-planar shape of PCl 3 using valence shell electron pair
63. sp hybrid orbitals have equal s and p character.
repulsion (VSEPR) theory. (Atomic number : H = 1, P = 15,
(1987, 1M)
S = 16, Cl = 17) (1998, 4M)
64. In benzene, carbon uses all the three p-orbitals for
77. Using the VSEPR theory, identify the type of hybridisation
hybridisation. (1987, 1M)
and draw the structure of OF2 . What are the oxidation states
65. SnCl 2 is a non-linear molecule. 1 of O and F ? (1997, 3M)
(1985, M)
2 78. Write the Lewis dot structural formula for each of
the following. Give also, the formula of a neutral molecule,
Integer Type Questions
which has the same geometry and the same arrangement of
66. The sum of the number of lone pairs of electrons on each the bonding electrons as in each of the following. An
central atom in the following species is example is given below in the case of H3 O+ and NH3 .
[TeBr6 ]2 - , [BrF2 ]+ , SNF3 and [XeF3 ]- +
é H ù é H ù
(Atomic numbers : N = 7, F = 9, S = 16, Br = 35, ê ···· ú ê ···· ú
Te = 52, Xe = 54) (2017 Adv.) êH · O · Hú êH · N · Hú
ê ·· ú ê ·· ú
67. Among the triatomic molecules/ions BeCl 2 , N-3 , N2 O, NO+2 , êë úû êë úû
O3 , SCl 2 , ICl -2 , I-3 and XeF2 , the total number of linear Lewis dot. structure Neutral .molecule (1983, 4M)
molecules(s)/ion(s) where the hybridisation of the central (i) O2- (ii) CO2- (iii) CN -
(iv) NCS-
2 3
50 Chemical Bonding
Read the following questions and answer as per the direction given
C. MnO-4 + NO-2 3.
Dimeric bridged
below: + H+ ¾® tetrahedral metal ion
(a) Statement I is correct; Statement II is correct; Statement II is D. NO-3 + H2 SO4 4.
the correct explanation of Statement I. 2+ Disproportionation
+ Fe ¾®
(b) Statement I is correct; Statement II is correct; Statement II is
not the correct explanation of Statement I.
(c) Statement I is correct; Statement II is incorrect. Codes
(d) Statement I is incorrect; Statement II is correct. A B C D A B C D
(a) 2 1, 4 3 4 (b) 1, 4 3 1, 2 1
23. Statement I The electronic structure of O 3 is
(c) 2 3 1 4 (d) 3 4 2, 3 1
+
O
·
··
·
-
·
Integer Questions
·O ·O· .
·· ·· 25. Among H2 ,He+2 , Li 2 , Be2 , B2 , C2 , N2 , O-2 and F2 , the
O number of diamagnetic species is
··
·
O ·· structure is not allowed (Atomic numbers : H = 1, He = 2, Li = 3, Be = 4, B = 5, C = 6,
Statement II ·O
·· ·· N = 7, O = 8, F = 9) (2017 Adv.)
because octet around O cannot be expanded.
(1998, 2M) Subjective Questions
Match the Columns 26. Write the MO electron distribution of O2 . Specify its bond
24. Match the reactions in Column I with nature of the order and magnetic property. (2000, 3M)
reactions/type of the products in Column II. (2007, 6M) 27. Arrange the following as stated.
Column I Column II “Increasing strength of hydrogen bonding ( X ¾ H ¾ X ).”
A. O-2 ¾® O2 + O22 - 1. Redox reaction O, S, F, Cl, N (1991, 1M)
B. 2. One of the products has 28. What effect should the following resonance of vinyl chloride
CrO24 - + H+ ¾® have on its dipole moment? (1987, 1M)
trigonal planar structure
CH2 ==CH ¾ Cl ¬¾® CH–2 +
¾ C HCl
Answers
Topic 1
1. (d) 2. (c) 3. (b) 4. (a) 49. (c) A ® 2; B ® 3; C ®1; D ®4
5. (a) 6. (b) 7. (b) 8. (b) 50. (b) A ® p, q, r, t; B ® q, r, s, t; C ® p, q, r, t; D ® p, r, s, t
9. (a) 10. (a) 11. (c) 12. (c) 51. N 2O, I -3 52. increases, decreases
13. (b, d) 14. (1) 15. (c) 16. (2) 53. three centre bond-two electrons
17. F 18. T 23. (80.2%) 54. hyperconjugation
55. sp 56. Triangular planar 57. sp 3
Topic 2
1. (d) 2. (b) 3. (c) 4. (d) 58. HCOOH and CH3COOH 59. CO2 60. F
5. (d) 6. (c) 7. (a) 8. (d) 61. F 62. F 63. F 64. F
9. (d) 10. (a) 11. (a) 12. (d) 65. T 66. (6) 68. (4) 69. (6)
13. (d) 14. (b) 15. (a) 16. (a)
Topic 3
17. (c) 18. (a) 19. (b) 20. (a)
1. (b) 2. (c) 3. (a) 4. (a)
21. (b) 22. (d) 23. (a) 24. (b)
5. (a) 6. (c) 7. (d) 8. (d)
25. (b) 26. (c) 27. (b) 28. (c)
9. (b) 10. (c) 11. (b) 12. (c)
29. (d) 30. (b) 31. (a) 32. (a)
13. (b) 14. (a) 15. (d) 16. (b)
33. (a) 34. (a) 35. (a) 36. (c)
17. (a) 18. (c) 19. (d) 20. (a, c)
37. (c) 38. (c) 39. (d) 40. (b)
21. (a, b, d) 22. (a,b) 23. (a)
41. (b) 42. (a) 43. (a) 44. (c)
24. (b) A ® 1, 4; B ® 3; C ®1, 2; D ®1 25. (6)
45. (b, c) 46. (a, c) 47. (b, c, d) 48. (a, b)
Hints & Solutions
Topic 1 Preliminary Concepts of Electrovalent and F =
2q2r – 4 q2a
(In case of dipole-dipole interaction)
and Covalent Bonding 4 p Î0 r3
1. Key Idea Isoelectronic species contains same number of From the above, it is clear that the ion-dipole interaction is the
electrons. better answer as compared to dipole-dipole interaction, i.e.
hydrogen bonding.
The species with its atomic number and number of electrons are
as follows :
H H
Species (ions) At. no. ( Z ) No. of electrons
4. C—–C
N3- 7 7 + 3 = 10
O2- 8 8 + 2 = 10 H H
-
F 9 9 + 1 = 10
Pi bond is formed by the p-orbitals whose lobes have minima in
Na + 11 11 - 1 = 10
+
the plane of molecule, hence molecular plane is the nodal plane
Li 3 3 -1 = 2 of pi-bond.
2+
Mg 12 12 - 2 = 10
5. H-bond is the strongest intermolecular force.
Thus, option (d) contains isoelectronic set of ions. All are different with 1, 0 and 2 lone pairs of electrons at central
2. KCl is the only ionic compound. The structure of PH3, O2, B2H6 atom.
and H2SO4 are given below 6. p-dichlorobenzene is non-polar.
3. Ion-ion interaction is dependent on the square of distance, i.e. 7. The carbide (C2-
2 ) ion has the following bonding pattern:
1 – –
ion-ion interaction µ : C ºº C : one sigma and two pi bonds.
r2
1 8. BF3 has triangular planar arrangement. F
Similarly, ion-dipole interaction µ
r3 Three identical vectors acting in outward F—B 120°
1 1 direction at equal angles in a plane cancel each
London force µ and dipole-dipole interaction µ F
r6 r3 other giving zero resultant, hence non-polar. sp2
Superficially it seems as both ion-dipole interaction and 9. Strongly electropositive, univalent X will form
hydrogen bonding vary with the inverse cube of distance an 1 : 1 ionic compound with strongly electronegative, univalent
between the molecules but when we look at the exact Y.
expressions of field (force) created in two situations,
it comes as X + Y ¾® X +Y -
| E | or | F | =
2| P |
(In case of ion-dipole interaction)
10. H2 is a covalent, diatomic molecule with a sigma covalent bond
4 p Î r3 between two hydrogen atoms.
Chemical Bonding 53
11. N2 has triple bond and each covalent bond is associated with one 3d 4s 4p
pair of electrons, therefore, six electrons are involved in forming
sp3
bonds in N2.
Cl– Cl– Cl– Cl– hybridisation
12. In KCN, the bonding between potassium ion and cyanide ion is 4 unpaired
electrons
ionic while carbon and nitrogen are covalently bonded in cyanide
ion as: (vii) (NH4)2NiCl 4 has Ni as central metal atom with +2 oxidation
Covalent bonds state. The electronic configuration of Ni 2+ in the complex is
+ –
[K] [ C ººN] 3d 4s 4p
24. In hydrogen peroxide (H2O2 ), oxygen is in –1 oxidation state, The hybridisation of given species are as follows :
can be oxidised to O2 (zero oxidation state) or can be reduced to l
For [ ICl2 ]- and [ BrF2 ]-
H2O (–2 oxidation state of oxygen).
1
H = (7 + 2 - 0 + 1) = 5 (sp3d )
Hence, H2O2 can act as both oxidising agent and reducing agent. 2
With strong oxidising agent like KMnO4, H2O2 acts as a
reducing agent while with strong reducing agent like H2C2O4 , it
l
For [ ICl4 ]- ,
acts as an oxidising agent. 1
H = (7 + 4 - 0 + 1) = 6 (sp3d 2 )
2
25. (i) Melting points Ionic compounds have higher melting
points than covalent compounds. l
For [ IF6 ]- ,
(ii) Boiling points Ionic compounds have higher boiling points 1
than covalent compounds. H = (7 + 6 - 0 + 1) = 7 (sp3d 3 )
2
(iii) Solubility Ionic compounds have greater solubility in water
than a covalent compound. 4. The radius of isoelectronic species is inversely proportional to
their nuclear charge or atomic number (Z). Thus, greater the
(iv) Conductivity in aqueous solution Ionic compounds have value of Z, lesser the radii of isoelectronic species.
greater electrical conductivity in aqueous solution while
covalent compounds are usually non-conducting. 5.
Species Valence MOs Bond Order Paramagnetic/
æ N b - N a ö Diamagnetic
Topic 2 VBT, Hybridisation and çç
è 2
÷÷
ø Nature
VSEPR Theory NO(15e- ) 6-1 Paramagnetic
[ 8 e- ] p 2 px2 = p 2 py2s 2 pz2 = 2.5
1. Among the given statements, correct statements are I and III 2
only. Valence bond theory (VBT) cannot explain the colour –e- p * 2 p1x =p * 2 py0s * 2 pz 0
- 6-0
exhibited by transition metal complexes. This theory cannot [ 8e ] p 2 px2 = p 2 py2s 2 pz2 =3 Diamagnetic
distinguish ligands as weak and strong field ones. NO+ (14e- ) 2
·· p * 2 px0 = p * 2 py0s * 2 pz0
2. For ICl5
N 2 (14 e- ) [ 8 e- ]p 2 px2 = p 2 py2s2 pz2 6-0
=3
Diamagnetic
1 –e- 2
H = (7 + 5 - 0 + 0) = 6 (sp3d 2 )
2 N +2 (13 e- ) p * 2 px0 = p * 2 py0 , s 2 pz0 5-0
= 2.5
Paramagnetic
2
Cl [ 8 e- ]p 2 px2 = p 2 py2s 2 pz 1
Cl Cl sp 3 d 2 hybridised
Geometry : Octahedral
p * 2 px0 = p * 2 py0s * 2 pz0
I Shape / Structure : Square pyramidal
O2 (16 e- ) [ 8 e- ] s 2 pz2p 2 px2 = p 2 py2 6-2 Paramagnetic
Cl Cl =2
2
p * 2 p1x = p * 2 p1y s * 2 pz0
For &&ICl-4 –e-
O+2 (15 e- ) [ 8 e- ] s 2 pz2p 2 px2 = p 2 py2
1
H = (7 + 4 - 0 + 1) = 6 (sp3d 2 ) 6-1
2 p * 2 p1x = p * 2 py0s * 2 pz0 = 2.5 Paramagnetic
+2e- 2
-
Cl Cl sp 3 d 2 hybridised [ 8e ] s 2 pz2p 2 px2 = p 2 py2
s O22- (18 e- )
Geometry : Octahedral
I Shape/Structure : Square planar p * 2 px2 = p * 2 py2s * 2 pz0 6 - 4 = 1 Diamagnetic
Cl Cl 2
So, only in the conversion of NO ® NO+, the bond order has
So, ICl5 and ICl-4 are isolobal but not isostructural.
increased (2.5 ® 3) and paramagnetic character has changed to
3. diamagnetic.
Key Idea The hybridisation for a central atom in a species
can be calculated using formula 6. The structure of I-3 ion is
1 –
H = (V + M - C + A )
2 I
where, H = No. of hybridised orbitals used by central atoms.
V = No. of valence electrons of the central atom.
M = No. of mono-valent atoms (bonded). I
C = No. of cationic (positive) charge.
A = No. of anionic (negative) charge. I
7. Isoelectronic species are those which contains same number of SF4 : F one lone pair at S.
electrons. F
S
Species Atomic number Number of electrons F
F
O2 - 8 10
·· ·· -
F- 9 10 I3- : I¾ I ·
· ¬¾ ·
· I ·· three lone pairs at central iodine.
·· ··
+
Na 11 10 O
2+ F ½½ F
Mg 12 10
14. Xe At central atom (Xe), there is one lone pair.
O- 8 9 F
· ·
F
Na 11 11
15. NO-3 and CO2-
3 both have 32 electrons, central atom
+
Mg 12 11 sp2 hybridised, triangular planar.
\Option (a) is correct which contains isoelectronic species 16. CH3Cl has the highest dipole moment.
O2 - , F - , Na + , Mg 2 + . 17. O-2 has odd number(17) of electrons, therefore it must contain at
8. I -3 -
is an ion made up of I 2 and I which has linear shape. least one unpaired electron.
+ é F H ù
While Cs is an alkali metal cation.
ê ½ ½ ú
9. 18. ê F ¾ B- ¬¾ N+ ¾ Hú Both ‘B’ and ‘N’ sp3 tetrahedral.
S ê ½ ½ ú
F—S==O ê ú
F H
—
F O ë û
F F
S is sp3 hybridised Pyramidal 19. NH3 = sp3 , [ PtCl 4 ]2- = dsp2 , PCl 5 = sp3d , BCl 3 = sp2
SO3 is planar (S is sp2 hybridised), BrF3 is T-shaped and SiO2-
3 is
20. All three have 14 electrons (iso electronic) with bond order of
planar (Si is sp2 hybridised). three.
O H
10. For molecules lighter than O2, the increasing order of energies
+ +
of molecular orbitals is –
N H
O==N==O, O—N==O,
é* 21.
* * é p2 p y ù * êp 2 p y ..... sp sp2 H sp3 H
s1s s 1s s 2s s 2sê ú s 2 p x s 2 p x
ë p2 p z û ê*
êëp 2 p z 1 2 3 4 5 6
22. CH2 == CH ¾ CH2 ¾ CH2 ¾ C ºº CH
where, p2 p y and p2 p z are degenerate molecular orbitals,
Hybridisation at C2 = sp2 and at C3 = sp3.
first singly occupied and then pairing starts if Hund’s rule is
obeyed. If Hund’s rule is violated in B2 , electronic 23. H2S has sp3 hybridised sulphur, therefore, angular in shape with
arrangement would be non-zero dipole moment.
ép2 p 2y
s1 s2 s
*
1s2 s2s2 s
*
2s2 ê ... H
ë p2 p z
S
No unpaired electron-diamagnetic.
H
bonding electrons - antibonding electrons
Bond order = (Non-linear, polar molecule)
2
6-4 F
= =1
2 24. F—B
11. The bond order of CO = 3. NO+ , CN- and N2 are isoelectronic F
with CO, have the same bond order as CO. NO- (16e- ) has bond sp2
order of 2. (Trigonal planar)
12. O-2 in KO2 has 17 electrons, species with odd electrons are 25. Sulphur in SO2 is sp2-hybridised.
always paramagnetic.
S
··
13. ClO-3 -
: O ¾ Cl == O one lone pair at Cl. O O
½½ Electron pair = 2 (s-bonds) + 1 (lone pair) = 3
O Hybridisation = sp 2
XeF4 : F Xe two lone pairs at Xe. Carbon in CO2 is sp-hybridised, N in N2 O is sp-hybridised,
carbon in CO is sp-hybridised.
F F
F
56 Chemical Bonding
· ·
26. Molecular orbital electronic configuration are 31. -
O ¾ Cl == O
· ·
*
* 2 *
p2 p 2y p 2 p 2y * electron pairs at Cl = 2 (s-bonds) + 2 (lone-pairs) = 4
KO2 (O-2 ) : s1s2 s 1s s2s2 s 2s2 s 2 px2 s 2 px0
p 2 p 2z * Hybridisation at Cl = sp 3
p 2 p1z
*
32. PCl 3 has sp3-hybridised phosphorus, with one lone pair.
Has one unpaired electron in p 2 p orbital. Therefore, molecule has pyramidal shape like ammonia.
AlO-2 has both oxygen in O2- state, therefore, no unpaired
33. O-2 has odd number of electrons, hence it is paramagnetic.
electron is present.
BaO2 (O2-2 )
Cl
* Cl Cl 109°
* 2 *
p 2 p 2y p 2 p 2y *
s1s2 s 1s s2s2 s 2s2 s2 px2 s 2 px0 C==C 120° C Cl
34.
p 2 p 2z *
p 2 p 2z Cl Cl Cl Cl
Has no unpaired electron. sp2-hybridised
+ sp3-hybridised
NO+2 has [O== N==O] bonding, hence no unpaired electron.
35. CO2 is linear because carbon is sp-hybridised.
27. N2 is a neutral, non-polar, inert molecule while CN - is a highly
polar, highly active ion. 36. In CH+3 , there are only three electron pairs around carbon
atom giving sp2-hybridisation state.
F
NF3 : N F BF3 : F—B +
H
28.
F H—C
F
F Triangular planar H
Pyramidal (B-sp2) sp2-hybridised
(N-sp3)
– 37. Dipole vectors in trans-1, 2-dichloroethylene are at 180° and
O O
+
directed in opposite direction, cancelling each other.
– +
NO3 : O==N H 3O : H
H H Cl
O H
Pyramidal C==C dipole moment = 0
Triangular planar
(O-sp3) H
(N-sp2) Cl
42. CO has a total of 14 electrons and CN- also has 14 electrons. On the basis of above two concepts, correct matching can be done
- - - - - as shown below:
C (6e ) + N (7e ) + e ¾® CN (14 e )
43. CO2 is a linear molecule because of sp-hybridisation around
carbon atom. A. d-d s bonding
44. For non-polar MX 3, it must have triangular planar
arrangement, i.e. there should be sp2-hybridisation around M.
CH3
½ H3C H B. p-d p bonding
45. H3C ¾ C ¾ CH3 C == C
½ H CH2CH3
CH3 Polar
Symmetric, non-polar
C. p-d p antibonding
CH3 CH3
CH3H2C CH2CH3 ½ ½
C == C H3C ¾ C ¾ C ¾ CH3
H H ½ ½
CH3 CH3
Polar Symmetric, non-polar D. d-d s antibonding
- +
46. CN and NO are isoelectronic, have the same bond order
of 3.
+ \ A ® 2, B ® 3, C ® 1, D ® 4
-
47. S== C == S O== N == O O ¾ C ºº N Hence, (c) is the correct option.
Linear Linear Linear
p 2 p1y
··
Sn
··
S
50. (A) B2 : s1s2 s
*
1s2 s2 s2 s
*
2s2 paramagnetic.
Cl Cl O O p 2 pz1
Bent Bent 6-4
Bond order = =1
48. CO2 , HgCl 2 , C2H2 are all linear. 2
Bond is formed by mixing of s and p orbitals.
49. PLAN This problem includes basic concept of bonding. It
B2 undergoes both oxidation and reduction as
can be solved by using the concept of molecular orbital
theory. Heat
B2 + O2 ¾¾® B2 O3 (Oxidation)
+ ve phase B2 + H2 ¾¾® B2 H6 (Reduction)
* *
p2 p 2y
(B) N2 : s1s2 s 1s2 s2 s2 s 2 s2 s2 px2 diamagnetic.
– ve phase 10 - 4 p 2 p 2z
Bond order = =3>2
Any orbital has two phase +ve and –ve. In the following 2
diagram, +ve phase is shown by darkening the lobes and –ve N2 undergoes both oxidation and reduction as
by without darkening the lobes. D
N2 + O2 ¾¾¾® NO
Catalyst
N2 + 3H2 ¾¾¾® NH3
In N2 , bonds are formed by mixing of s and p orbitals.
Bonding MO Antibonding MO p 2 p2y p
*
2 p2y
(C) O2- : s1s2 s
*
1s2 s2 s2 s
*
2 s2 s2 px2 *
s 2 px0
When two same phase overlap with each other, it forms p 2 pz2 p
*
2 pz1
bonding molecular orbital otherwise antibonding. -
Paramagnetic with bond order = 1.5. O2 undergoes both oxidation
s-bond and reduction and bond involves mixing of s and p-orbitals.
p 2 p2y p
*
2 p1y
(D) O2 : s1s2 s
*
1s2 s2 s2 s
*
2 s2 s2 px2 *
s 2 px0
p-bond p 2 pz2 p
*
2 pz1
Paramagnetic with bond order = 2.
O2 undergoes reduction and the bond involves mixing of s
and p-orbitals.
51. N2O and I-3 are linear species.
58 Chemical Bonding
52. Bond order in N2 is 3 while same in N+2 is 2.5, hence bond 68. PLAN This problem includes concept of hybridisation using VBT,
distance increases as N2 goes to N+2 . VSEPR theory, etc.,
Bond order in O2 is 2 while same in O+2 is 2.5, hence bond XeF4 , BrF4- ,[Cu(NH3 )4 ]2+ , [PtCl 4 ]2- are square planar as shown
distance decreases as O2 goes to O+2 . below:
53. Three centred-2 electrons.
s
54. Hyperconjugation involves delocalisation of s-electrons. F F F F
55. sp-hybridised. Xe Br
F F F F
56. Triangular planar. Carbon in CH+3
is sp hybridised. 2
3
57. sp -hybrid orbital holding the lone pair is involved in formation
of ammonium ion. 2+ 2–
H3N NH3 Cl Cl
O O
Cu Pt
½½ ½½
58. H ¾ C ¾ OH and CH3 ¾ C ¾ OH . Both are capable of forming H3N NH3 Cl Cl
H-bonds. SF4 (See-saw) as shown below:
59. CO2, it is 180°.
F
60. Dipole moment (m ) = q.d F
S
Since electronegativity of F and Cl are very close, it is the F
internuclear distance (d) that decides dipole moment here. F
Hence, C ¾ Cl bond has greater dipole moment the C-F bond.
SiF4 , BF4- , [FeCl 4 ]2- , [CoCl 4 ]2- are tetrahedral as shown below:
61. H2O is V-shaped molecule.
s
O F F
H H
V-shaped Si B
62. False F F F F
F F
63. In sp3-hybrid orbital, there is 25 % s-character and 75 %
2– 2–
p-character. Cl Cl
64. Carbon in benzene is sp2-hybridised, i.e. uses only two of its
p-orbitals in hybridisation. Fe Co
65. Sn in SnCl 2 has sp2-hybridisation. Cl Cl Cl Cl
Cl Cl
66. S.N. Species No. of s-bonds No. of L.P at
with central atom central atom Hence, correct integer is 4.
2-
(i) In [ TeBr6 ] 6 1 69. PLAN Melamine is a heterocyclic compound.
(ii) In [ BrF2 ]+ 2 2
H2N N NH2
(iii) In SNF3 4 0
(iv) In [ XeF3 ]- 3 3 N N
··
– NH2
67. Cl ¾ Be ¾ Cl N ºº N ¾® N ··
··
sp Each nitrogen atom has one pair of lone pair. Thus, in all six
sp
lone pairs.
·· +
Nºº N ® O ·· O == N == O 70. F
·· F F
sp sp
Br
All the above mentioned molecules/ions have sp-hybridised
central atom and no one pair at central atom, hence linear also.
F F
Others are :
O S Lone pair would push the Br—F bond pairs in upward direction
[Cl ¾ I ¾ Cl] and all Br—F bond angles will contract.
O O Cl Cl
sp2-bent sp3-V-shaped sp3d-linear 71. No, (i) NMe3 is pyramidal while (ii) N(SiMe3 )3 is planar. In the
–
[I ¾ I ¾ I] F ¾ Xe ¾ F latter case, pp - dp back bonding between N and Si makes N
sp2-hybridised.
sp3d-linear sp3d-linear
– 72. Bond order : O2- = 1.5, O2 = 2, O+2 = 2.5
[Although ICl 2 , I–3 and XeF2 all also are linear but in them
Bond length : O+2 < O2 < O-2
d-orbital contribute in hybridisation.]
Chemical Bonding 59
F F Half-filled
anti-bonding
Cl P Br p*-MOs
F F So, in the formation of O-2 from O2, the 17th electron goes to the
Cl Cl * *
p 2px or p 2py molecular orbital (anti-bonding) which is
Trigonal bipyramidal Square pyramidal
(P is sp3d-hybridised) (Br is sp3d 2 -hybridised) half-filled in O2.
75. 2. HF has highest boiling point among hydrogen halides because
F F it has strongest hydrogen bonding. Here, the hydrogen bond
F F O exists between hydrogen of one molecule and fluorine atom of
another molecule as shown below.
Xe Xe Xe d+ d- d+ d- d+ d-
…H¾ F…H¾ F…H¾ F
F F In this molecule, hydrogen bond behaves like a bridge between
O
F F two atoms that holds one atom by covalent bond and the other
Linear Square planar See-saw shaped by hydrogen bond.
3
76. In H2S, S is sp -hybridised with two lone pairs of electrons on it 3. Key Idea Magnetic nature can be detected by molecular
3 orbital theory. Presence of unpaired electrons means
giving V-shaped (water like) shape. In PCl 3 , P is sp -hybridised
paramagnetic and absence of unpaired electrons means
with one lone pair of electrons on it. Therefore, PCl 3 is pyramidal diamagnetic in nature.
in shape.
+2
Among the given options, CO is a diamagnetic molecule. It can
´´ ·· ´´ O be proved by molecular orbital (MO) theory. The electronic
´ ´ -1
77. ´ F ´· O ·´F ´ F F -1 configuration of given diatomic molecules are given below.
´´ ·· ´´ V-shaped l
CO (Number of electrons = 14)
Electron pair = P = 2 + 2 = 4 Electronic configuration = s1s2 , s* 1s2 , s2s2 , s* 2s2,
Hybridisation = sp3 s2 pz2 , p 2 px2 » p 2 p2y
4. C2 will be stabilised after forming anion. The electronic configuration of carbon is 1s2 2s2 2 p2. There are twelve electrons in C2. After
forming anion (i.e. C–2 ), the electronic configuration is
l
C-2 : (s1s) 2 (s*1s) 2 (s2 s) 2 (s * 2 s) 2 (p 2 px2 = p 2 p 2y ) (s2 pz1 ) or KK (s2 s) 2 (s* 2 s) 2 (p 2 px2 = p 2 p 2y ). s2 pz1
1 1
Bond order = (N b - N a ) = (9 - 4 ) = 2.5
2 2
For other options such as F2- , O-2 , NO- , the electronic configurations are as follows :
F2- : (s1s)2 (s* 1s)2 (s2s)2 (s* 2s)2 (s2 pz )2 (p 2 px2 = p 2 py2 ) (p* 2 px2 = p* 2 p2y )(s* 2 pz1 )
Bond order = 1 / 2(N b - N a ) = 1 / 2(10 - 9) = 0.5
l
O-2 : (s1s)2. (s* 1s)2 (s2s)2 (s* 2s)2 (s2 pz )2(p 2 px2 = p 2 p2y ) (p* 2 px2 = p* 2 p1y )
1 1
Bond order = (N b - N a ) = (10 - 7) = 15 .
2 2
l
NO : (s1s) (s 1s) (s 2s) (s * 2s) (s2 pz )2 (p 2 px2 = p 2 p2y ) (p* 2 px1 = p* 2 p1y )
- 2 * 2 2 2
1 1
Bond order = (N b - N a ) = (10 - 6) = 2
2 2
The value of bond order of C-2 is highest among the given options. Bond order between two atoms in a molecule may be taken as an
approximate measure of the bond length.
The bond length decreases as bond order increases. As a result, stability of a molecule increases.
5. Species MO energy order Bond order (BO) n, number of unpaired e- Magnetic character
C22- (14e- ) [ 8 e ]p =p 2s
6-0 0 Diamagnetic
2p x2 2p y 2p z2 =3
2
O2 (16e- ) [ 8 e ]s p =p p* = p* 6-2
=2 2 Paramagnetic
2p z2 2p x2 2p y2 2p1x 2p1y
2
O22- (18e- ) [ 8 e ]s p =p p* *
=p 6-4 0 Diamagnetic
2p z2 2p x2 2p y2 2p x2 2p y2 =1
2
N22- (16e- ) * * 1 6-2 2 Paramagnetic
[ 8 e ]p =p s p =p 2p y =2
2p x2 2p y2 2p z2 2p1x 2
1
Bond length µ . So order of bond length C22- < O2 = N22- < O22-
BO (Bond order) (BO = 3) (BO = 2) (BO = 1)
16. When E = B in BCl 3 , bond angle is 120°. When E = P, As or Bi It is also a diamagnetic species because of the absence of
unpaired electrons.
in ECl 3 , hybridisation at E will be sp3. Also, if central atoms are
O2 (8 + 8 = 16)
from same group, bond angle decreases down the group
provided all other things are similar. Hence, the order of bond or S2 = s1s2 , s* 1s2 , s2s2 , s* 2s2 ,
angles is BCl 3 > PCl 3 > AsCl 3 > BiCl 3 2 * 2 p1 » *p 2 p1
s 2 p , p2 p 2 » p2 p 2 p
z x y x y
1
17. Bond length µ Due to the presence of two unpaired electrons, O2 and S2 both
Bond order are paramagnetic molecules.
1 4
Bond order : CO2 = 2, CO = 3 , CO23- = 1 + = 23. Statement I is correct, given structure is one of the resonance
3 3 structure of ozone.
Therefore, order of bond length is CO23- < CO2 < CO + +
O ¬¾® O
18. H2O2 H
O O- -O O
O—O Statement II is also correct because oxygen cannot expand its
polar bond
H octet. It is also the explanation for the given structure of ozone.
Non-polar bond
24. (A) In the reaction : O-2 ¾® O2 + O22-
19. HCl does not form hydrogen bond. For formation of hydrogen 1
Oxygen on reactant side is in - oxidation state. In
bond, atleast one hydrogen atom must be bonded to one of the 2
product side, one of the oxygen is in zero oxidation state,
three most electronegative atom O , N and F.
i.e. oxidised while the other oxygen is in –1 oxidation
20. state, i.e. reduced. Hence, in the above reaction, oxygen
Species Electrons MOEC N B N A BO Magnetic
( O-1 / 2 ) is simultaneously oxidised and reduced
character disproportionated.
C2- 14 s1s2 , s * 1s2 , 10 4 3 Diamagnetic (B) In acidic medium, CrO2- 2-
4 is converted into Cr2 O7 which
2
is a dimeric, bridged tetrahedral.
s 2s2 , s * 2s2 , O– O–
p 2 px2 » - p 2 p2y ,
Cr Cr
s 2 pz2 O O
O
O O
O2+
2
14 As above 10 4 3 Diamagnetic
according to (C) MnO-4 + NO-2 + H+ ¾® Mn 2+ + NO-3
O2 16 number of 10 6 2 Paramagnetic
The above is a redox reaction and a product NO-3 has
N+2 13 electrons 9 4 2.5 Paramagnetic
trigonal planar structure.
N -2 15 10 5 2.5 Paramagnetic
(D) NO-3 + H2SO4 + Fe2+ ¾® Fe+ + NO
He+2 3 2 1 0.5 Paramagnetic The above is a redox reaction.
25. H2 , Li 2 , Be2 , C2 , N2 and F2 are diamagnetic according to
Thus, (a) is correct.
molecular orbital theory.
(b) Bond order O2+ 2 > O 2 thus,
(a) Xe (b) Ar
(c) Kr (d) Ne
4. Consider the van der Waals’ constants, a and b, for the
following gases.
Gas Ar Ne Kr Xe
a/(atm dm 6 mol -2 ) 1.3 0.2 5.1 4.1
I II III b/(10-2 dm 3 mol -1 ) 3.2 1.7 1.0 5.0
Speed, v
Which gas is expected to have the highest critical
(a) vmp of H 2 ( 300 K ); vmp of N 2(300 K); vmp of O2(400 K) temperature ? (2019 Main, 9 April I)
(b) vmp of O2 ( 400 K ); vmp of N 2(300 K); vmp of H 2(300 K) (a) Kr (b) Xe
(c) vmp of N 2(300 K); vmp of O2 ( 400 K ); vmp of H 2(300 K) (c) Ar (d) Ne
(d) vmp of N 2(300 K); vmp of H 2(300 K); vmp of O2(400 K)
5. The combination of plots which does not represent
2. Consider the following table. isothermal expansion of an ideal gas is
(2019 Main, 12 Jan II)
6 -1 3 -1
Gas a/(k Pa dm mol ) b/(dm mol )
A 642.32 0.05196
B 155.21 0.04136 p p
C 431.91 0.05196
D 155.21 0.4382 O 1/Vm O Vm
(A) (B)
a and b are van der Waals’ constants. The correct statement
about the gases is (2019 Main, 10 April I)
(a) gas C will occupy lesser volume than gas A; gas B will be pVm
lesser compressible than gas D U
(b) gas C will occupy more volume than gas A; gas B will be
more compressible than gas D O O
p Vm
(c) gas C will occupy more volume than gas A; gas B will be
(C) (D)
lesser compressible than gas D
(d) gas C will occupy more volume than gas A; gas B will be (a) ( A ) and (C ) (b) ( B ) and (C )
lesser compressible than gas D (c) ( B ) and ( D ) (d) ( A ) and ( D )
64 States of Matter
6. An open vessel at 27ºC is heated until two fifth of the air 13. For one mole of a van der Waals’ gas when b = 0 and
(assumed as an ideal gas) in it has escaped from the vessel. T = 300 K, the pV vs 1/V plot is shown below. The value of
Assuming that the volume of the vessel remains constant, the the van der Waals’ constant a (atm L mol - 2 ) (2012)
temperature at which the vessel has been heated is
(2019 Main, 12 Jan II)
24.6
(a) 750 K (b) 500 K
pV (L atm mol–1)
23.1
(c) 750ºC (d) 500ºC
21.6
7. The volume of gas A is twice than that of gas B. The
compressibility factor of gas A is thrice than that of gas B at 20.1
same temperature. The pressures of the gases for equal
number of moles are (2019 Main, 12 Jan I)
(a) p A = 2 pB (b) 2 p A = 3 pB
(c) p A = 3 pB (d) 3 p A = 2 pB 0 2.0 3.0
8. A 10 mg effervescent tablet containing sodium bicarbonate 1/ V (mol L –1)
and oxalic acid releases 0.25 mL of CO2 at T = 29815
. K and (a) 1.0 (b) 4.5 (c) 1.5 (d) 3.0
p = 1 bar. If molar volume of CO2 is 25.0 L under such 14. The term that corrects for the attractive forces present in a
condition, what is the percentage of sodium bicarbonate in real gas in the van der Waals’ equation is (2009)
each tablet? (a) nb (b) n 2 a / V 2
[Molar mass of NaHCO 3 = 84 g mol -1 ] (2019 Main, 11 Jan I) (c) - ( n 2 a / V 2 ) (d) - nb
(a) 8.4 (b) 0.84 (c) 16.8 (d) 33.6
15. The given graph represent the variations of Z
9. 0.5 moles of gas A and x moles of gas B exert a pressure of 200 pV
(compressibility factor ( Z ) = ) versus p, for three real
Pa in a container of volume 10m 3 at 1000 K. Given R is the nRT
gas constant in JK -1 mol-1 , x is (2019 Main, 9 Jan I)
gases A, B and C. Identify the only incorrect statement.
(2006, 5M)
2R 4 -R 4 +R 2R C
(a) (b) (c) (d) A
4-R 2R 2R 4+R A Ideal gas
B
10. Two closed bulbs of equal volume (V) containing an ideal gas 1 C
initially at pressure pi and temperature T1 are connected
B
through a narrow tube of negligible volume as shown in the Z
figure below. The temperature of one of the bulbs is then 0 p (atm)
raised to T2 . The final pressure p f is (2016 Main)
(a) For the gas A, a = 0 and its dependence on p is linear at all
æ T1 ö æ T ö pressure
(a) 2 pi çç ÷÷ (b) 2 pi çç 2 ÷÷ (b) For the gas B, b = 0 and its dependence on p is linear at all
è T1 + T2 ø è T1 +T2 ø
pressure
æ TT ö æ TT ö (c) For the gas C, which is typical real gas for which neither a
(c) 2 pi çç 1 2 ÷÷ (d) pi çç 1 2 ÷÷
è T1 +T2 ø è T1 +T2 ø nor b = 0 . By knowing the minima and the point of
intersection, with Z = 1, a and b can be calculated
11. If Z is a compressibility factor, van der Waals’ equation at low (d) At high pressure, the slope is positive for all real gases
pressure can be written as (2014 Main)
RT a 16. If helium and methane are allowed to diffuse out of the
(a) Z = 1 + (b) Z = 1 - container under the similar conditions of temperature and
pb VRT
pressure, then the ratio of rate of diffusion of helium to
pb pb methane is (2005)
(c) Z = 1 - (d) Z = 1 +
RT RT (a) 2.0 (b) 1.0
12. For gaseous state, if most probable speed is denoted by C *, (c) 0.5 (d) 4.0
average speed by C and root square speed by C, then for a 17. For a monatomic gas kinetic energy = E. The relation with
large number of molecules, the ratios of these speeds are rms velocity is (2004, 1M)
(a) C * : C : C =1.225 : 1.128 : 1 (2013 Main) æ 2E ö
1/ 2
æ 3E ö
1/ 2
18. Positive deviation from ideal behaviour takes place because 27. Equal weights of ethane and hydrogen are mixed in an empty
of (2003, 1M) container at 25°C. The fraction of the total pressure exerted
(a) molecular interaction between atom and pV / nRT > 1 by hydrogen is (1993, 1M)
(b) molecular interaction between atom and pV / nRT < 1 (a) 1 : 2 (b) 1 : 1 (c) 1 : 16 (d) 15 : 16
(c) finite size of atoms and pV / nRT > 1 28. At constant volume, for a fixed number of moles of a gas the
(d) finite size of atoms and pV / nRT < 1 pressure of the gas increases with rise of temperature due to
19. Which of the following volume (V ) temperature (T ) plots (a) increase in average molecular speed (1992, 1M)
represents the behaviour of one mole of an ideal gas at the (b) increase rate of collisions amongst molecules
atmospheric pressure? (2002, 3M) (c) increase in molecular attraction
(a) V(L) (38.8 L, (b) V(L) (d) decrease in mean free path
373 K) (28.6 L,
(22.4 L, (20.4 L,
373 K) 29. According to kinetic theory of gases, for a diatomic molecule
273 K) 273 K) (1991, 1M)
(a) the pressure exerted by the gas is proportional to mean
T(K) T(K) velocity of the molecule
(c) V(L) (d) V(L) (b) the pressure exerted by the gas is proportional to the root
(30.6 L,
373 K) mean velocity of the molecule
(22.4 L, (22.4 L,
273 K)
(c) the root mean square velocity of the molecule is inversely
273 K) (14.2 L,
373 K) proportional to the temperature
(d) the mean translational kinetic energy of the molecule is
T(K) T(K) proportional to the absolute temperature
20. The root mean square velocity of an ideal gas at constant 30. The rate of diffusion of methane at a given temperature is
pressure varies with density (d ) as (2001, S, 1M) twice that of a gas X. The molecular weight of X is
(a) d 2 (b) d (c) d (d) 1 / d (1990, 1M)
21. The compressibility of a gas is less than unity at STP. (a) 64.0 (b) 32.0 (c) 4.0 (d) 8.0
Therefore, 31. The density of neon will be highest at (1990, 1M)
(a) Vm > 22.4 L (b) Vm < 22.4 L (2000, 1M) (a) STP (b) 0°C, 2 atm
(c) Vm = 22.4 L (d) Vm = 44.8 L (c) 273°C, 1 atm (d) 273°C, 2 atm
22. The rms velocity of hydrogen is 7 times the rms velocity of 32. The value of van der Waals’ constant a for the gases O2 , N2 ,
nitrogen. If T is the temperature of the gas (2000, 1M) NH3 and CH4 are 1.360, 1.390, 4.170 and 2.253L2 atm mol -2
(a) T (H2 ) = T (N2 ) (b) T (H2 ) > T (N2 ) respectively. The gas which can most easily be liquefied is
(c) T (H2 ) < T (N2 ) (d) T (H2 ) = 7 T (N2 ) (a) O2 (b) N2 (c) NH3 (d) CH4
23. A gas will approach ideal behaviour at (1999, 2M) 33. A bottle of dry ammonia and a bottle of dry hydrogen
(a) low temperature and low pressure chloride connected through a long tube are opened
(b) low temperature and high pressure simultaneously at both ends the white ammonium chloride
(c) high temperature and low pressure ring first formed will be (1988, 1M)
(d) high temperature and high pressure (a) at the centre of the tube
24. According to Graham’s law, at a given temperature the ratio (b) near the hydrogen chloride bottle
rA (c) near the ammonia bottle
of the rates of diffusion of gases A and B is given by (d) throughout the length of the tube
rB
(where, p and M are pressures and molecular weights of 34. In van der Waals’ equation of state for a non-ideal gas, the
gases A and B respectively) term that accounts for intermolecular forces is (1988, 1M)
(1998, 2M)
1 1 æ a ö
æp ö æ MA ö2 æM ö æ pA ö2 (a) (V - b ) (b) RT (c) ç p + 2 ÷ (d) ( RT )-1
(a) çç A ÷÷ çç ÷÷ (b) çç A ÷÷ çç ÷÷ è V ø
è pB ø è MB ø è MB ø è pB ø
1 1 35. The average velocity of an ideal gas molecule at 27°C is
æp ö æ MB ö2 æM ö æ pB ö2 0.3 m/s. The average velocity at 927°C will be (1986, 1M)
(c) çç A ÷÷ çç ÷÷ (d) çç A ÷÷ çç ÷÷
è pB ø è MA ø è MB ø è pA ø (a) 0.6 m/s (b) 0.3 m/s (c) 0.9 m/s (d) 3.0 m/s
25. The compressibility factor for an ideal gas is (1997, 1M) 36. Rate of diffusion of a gas is (1985, 1M)
(a) 1.5 (b) 1.0 (c) 2.0 (d) ¥ (a) directly proportional to its density
26. The ratio between the root mean square speed of H2 at 50 K (b) directly proportional to its molecular weight
and that of O2 at 800 K is (1996, 1M)
(c) directly proportional to the square root of its molecular weight
1 (d) inversely proportional to the square root of its
(a) 4 (b) 2 (c) 1 (d)
4 molecular weight
66 States of Matter
37. Equal weights of methane and hydrogen are mixed in an 45. A gas described by van der Waals’ equation (2008, 4M)
empty container at 25°C. The fraction of the total pressure (a) behaves similar to an ideal gas in the limit of large
exerted by hydrogen is (1984, 1M) molar volumes
1 8 1 16 (b) behaves similar to an ideal gas in the limit of large pressures
(a) (b) (c) (d)
2 9 9 17 (c) is characterised by van der Waals’ coefficients that are
38. When an ideal gas undergoes unrestrained expansion, no dependent on the identity of the gas but are
cooling occurs because the molecules (1984, 1M) independent of the temperature
(a) are above the inversion temperature (d) has the pressure that is lower than the pressure exerted
(b) exert no attractive forces on each other by the same gas behaving ideally
(c) do work equal to loss in kinetic energy 46. If a gas is expanded at constant temperature (1986, 1M)
(d) collide without loss of energy (a) the pressure decreases
39. Helium atom is two times heavier than a hydrogen molecule. (b) the kinetic energy of the molecules remains the same
At 298 K, the average kinetic energy of a helium atom is (c) the kinetic energy of the molecules decreases
(a) two times that of a hydrogen molecule (1982, 1M) (d) the number of molecules of the gas increases
(b) same as that of a hydrogen molecule
(c) four times that of a hydrogen molecule Numerical Value Based Question
(d) half that of a hydrogen molecule 47. A closed tank has two compartments A and B, both filled
40. Equal weights of methane and oxygen are mixed in an empty with oxygen (assumed to be ideal gas). The partition
container at 25°C. The fraction of the total pressure exerted separating the two compartments is fixed and is a perfect heat
by oxygen is (1981, 1M)
insulator (Fig. 1). If the old partition is replaced by a new
1 1 2 1 273 partition which can slide and conduct heat but does not allow
(a) (b) (c) (d) ´ the gas to leak across (Fig. 2), the volume (in m3 ) of the
3 2 3 3 298
compartment A after the system attains equilibrium is ____.
41. The temperature at which a real gas obeys the ideal gas laws
over a wide range of pressure is (1981, 1M)
(a) critical temperature (b) Boyle temperature 1 m3, 5 bar
3 m3, 1 bar, 300 K
400 K
(c) inversion temperature (d) reduced temperature B
A
42. The ratio of root mean square velocity to average velocity of
a gas molecule at a particular temperature is (1981, 1M) Fig. 1
(a) 1.085 : 1 (b) 1 : 1.086 (c) 2 : 1.086 (d) 1.086 : 2
A B
Objective Questions II
(One or more than one correct option)
43. One mole of a monoatomic real gas satisfies the equation Fig. 2 (2018 Adv)
p(V - b)= RT where, b is a constant. The relationship of Assertion and Reason
interatomic potential V(r) and interatomic distance r for gas
Read the following questions and answer as per the direction given
is given by (2015 Adv.)
below :
V(r) V(r) (a) Statement I is correct; Statement II is correct;
(a) 0 (b) 0
Statement II is the correct explanation of Statement I
r r (b) Statement I is correct; Statement II is correct; Statement
II is not the correct explanation of Statement I
V(r) V(r) (c) Statement I is correct; Statement II is incorrect
(d) Statement I is incorrect; Statement II is correct
(c) 0 r
(d) 0 r 48. Statement I The pressure of a fixed amount of an ideal gas is
proportional to its temperature.
44. According to kinetic theory of gases (2011) Statement II Frequency of collisions and their impact both
(a) collisions are always elastic increase in proportion to the square root of temperature.
(2000)
(b) heavier molecules transfer more momentum to the wall
of the container 49. Statement I The value of van der Waals’ constant ‘a’ is
(c) only a small number of molecules have very high velocity larger for ammonia than for nitrogen.
(d) between collisions, the molecules move in straight lines Statement II Hydrogen bonding is present in ammonia.
with constant velocities (1998)
States of Matter 67
(a) larger mean free path for X as a compared of that of Y 64. A closed vessel with rigid walls contains 1 mole of 238
92 U and
(b) larger mean free path for Y as compared to that of X 1 mole of air at 298 K. Considering complete decay of
238 206
(c) increased collision frequency of Y with the inert gas as 92 U to 82 Pb, the ratio of the final pressure to the initial
compared to that of X with the inert gas pressure of the system at 298 K is (2015 Adv.)
(d) increased collision frequency of X with the inert gas as 65. If the value of Avogadro number is 6.023 ´ 10 23
mol -1 and
compared to that of Y with the inert gas the value of Boltzmann constant is 1.380 ´ 10 JK -1 , then
-23
51. The value of d in cm (shown in the figure), as estimated from the number of significant digits in the calculated value of the
Graham’s law, is universal gas constant is (2014 Adv.)
(a) 8 (b) 12 (c) 16 (d) 20 66. To an evacuated vessel with movable piston under external
pressure of 1 atm, 0.1 mole of He and 1.0 mole of an
Match the Columns
unknown compound (vapour pressure 0.68 atm at 0°C ) are
52. Match the gases under specified conditions listed in introduced. Considering the ideal gas behaviour, the total
Column I with their properties/laws in Column II. volume (in litre) of the gases at 0°C is close to (2011)
Column I Column II
Subjective Questions
A. Hydrogen gas ( p = 200 atm, p. compressibility
T = 273 K) factor ¹ 1 67. At 400 K, the root mean square (rms) speed of a gas X
(molecular weight = 40) is equal to the most probable speed of
B. Hydrogen gas ( p ~ 0, T = 273 K) q. attractive forces gas Y at 60 K. The molecular weight of the gas Y is (2009)
are dominant
C. CO2 ( p = 1 atm, T = 273 K) r. pV = nRT 68. The average velocity of gas molecules is 400 m s - 1 , find the
rms velocity of the gas. (2003, 2M)
D. Real gas with very large molar s. p (V - nb ) = nRT 69. The density of the vapour of a substance at 1 atm pressure
volume
and 500 K is 0.36 kg m–3 . The vapour effuses through a small
(2007, 6M) hole at a rate of 1.33 times faster than oxygen under the same
Fill in the Blanks condition.
53. The absolute temperature of an ideal gas is …… to/than the (i) Determine, (a) molecular weight (b) molar volume
average kinetic energy of the gas molecules. (1997, 1M) (c) compression factor (Z) of the vapour and (d) which
54. 8 g each of oxygen and hydrogen at 27°C will have the total forces among the gas molecules are dominating, the
kinetic energy in the ratio of …… . (1989, 1M)
attractive or the repulsive?
(ii) If the vapour behaves ideally at 1000 K, determine the
55. The value of pV for 5.6 L of an ideal gas is ......... RT, at NTP.
(1987, 1M) average translational kinetic energy of a molecule.
(2002, 5M)
56. The rate of diffusion of a gas is .......... proportional to both
.......... and square root of molecular mass. (1986, 1M) 70. The compression factor (compressibility factor) for one mole
57. C p - CV for an ideal gas is …… of a van der Waals’ gas at 0° C and 100 atm pressure is found
(1984, 1M)
to be 0.5. Assuming that the volume of a gas molecule is
58. The total energy of one mole of an ideal monoatomic gas at negligible, calculate the van der Waals’ constant ‘a’.
27°C is …… cal. (1984, 1M) (2001, 5M)
68 States of Matter
71. Calculate the pressure exerted by one mole of CO2 gas at the root mean square (rms) speed and the temperature of the
273 K if the van der Waals’ constant a = 3.592 dm 6 atm gas molecules. If the ratio of the most probable speed to root
mol -2 . Assume that the volume occupied by CO2 molecules mean square speed is 0.82, calculate the most probable speed
is negligible. (2000) for these molecules at this temperature. (1993, 4M)
72. (i) One mole of nitrogen gas at 0.8 atm takes 38 s to diffuse 81. At room temperature, the following reaction proceed nearly
through a pin-hole, whereas one mole of an unknown to completion. 2NO + O2 ¾® 2NO2 ¾® N2 O4
compound of xenon with fluorine at 1.6 atm takes 57 s to The dimer, N2 O4 , solidifies at 262 K. A 250 mL flask and a
diffuse through the same hole. Calculate the molecular 100 mL flask are separated by a stopcock. At 300 K, the
formula of the compound. nitric oxide in the larger flask exerts a pressure of 1.053 atm
and the smaller one contains oxygen at 0.789 atm.
(ii) The pressure exerted by 12 g of an ideal gas at
temperature t °C in a vessel of volume V litre is one atm. The gases are mixed by opening the stopcock and after the
When the temperature is increased by 10°C at the same end of the reaction the flasks are cooled to 220 K. Neglecting
volume, the pressure increases by 10%. Calculate the the vapour pressure of the dimer, find out the pressure and
temperature t and volume V. composition of the gas remaining at 220 K. (Assume the
(Molecular weight of the gas = 120) (1999, 5M) gases to behave ideally). (1992, 4M)
73. Using van der Waals’ equation, calculate the constant a 82. At 27° C, hydrogen is leaked through a tiny hole into a vessel
when two moles of a gas confined in a four litre flask exert a for 20 min. Another unknown gas at the same temperature
pressure of 11.0 atm at a temperature of 300 K. The value of and pressure as that of hydrogen is leaked through same hole
b is 0.05 L mol –1 . (1998, 4M) for 20 min. After the effusion of the gases the mixture exerts
74. An evacuated glass vessel weighs 50.0 g when empty 148.0 g a pressure of 6 atm. The hydrogen content of the mixture is
0.7 mole. If the volume of the container is 3 L. What is the
when filled with a liquid of density 0.98 g mL–1 and 50.5 g
molecular weight of the unknown gas? (1992, 3M)
when filled with an ideal gas at 760 mm Hg at 300 K.
Determine the molar mass of the gas. (1998, 3M) 83. Calculate the volume occupied by 5.0 g of acetylene gas at
50° C and 740 mm pressure. (1991, 2M)
75. A mixture of ideal gases is cooled up to liquid helium
temperature (4.22 K) to form an ideal solution. Is this 84. The average velocity at T1 K and the most probable at T2 K of
statement true or false ? Justify your answer in not more than CO2 gas is 9.0 ´ 104 cm s –1 . Calculate the value of T1 and T2
two lines. (1996, 1M)
(1990, 4M)
76. The composition of the equilibrium mixture (Cl 2 s 2Cl)
85. A spherical balloon of 21 cm diameter is to be filled up with
which is attained at 1200° C, is determined by measuring the hydrogen at NTP from a cylinder containing the gas at
rate of effusion through a pin-hole. It is observed that at 20 atm at 27° C. If the cylinder can hold 2.82 L of water,
1.80 mm Hg pressure, the mixture effuses 1.16 times as fast calculate the number of balloons that can be filled up.
as krypton effuses under the same conditions. Calculate the (1987, 5M)
fraction of chlorine molecules dissociated into atoms (atomic 86. Calculate the root mean square velocity of ozone kept in a closed
weight of Kr = 84) (1995, 4M)
vessel at 20° C and 82 cm mercury pressure. (1985, 2M)
77. A mixture of ethane (C2 H6 ) and ethene (C2 H4 ) occupies 40 L
87. Give reasons for the following in one or two sentences.
at 1.00 atm and at 400 K. The mixture reacts completely with
(i) Equal volumes of gases contain equal number of moles.
130 g of O2 to produce CO2 and H2 O. Assuming ideal gas
(1984, 1M)
behaviour, calculate the mole fractions of C2 H4 and C2 H6 in (ii) A bottle of liquor ammonia should be cooled before
the mixture. (1995, 4M)
opening the stopper. (1983, 1M)
78. An LPG (liquefied petroleum gas) cylinder weighs 14.8 kg
88. Oxygen is present in one litre flask at a pressure of 7.6 ´ 10-10
when empty. When full it weighs 29.0 kg and shows a
mm Hg. Calculate the number of oxygen molecules in the
pressure of 2.5 atm. In the course of use at 27° C, the weight of
flask at 0°C. (1983, 2M)
the full cylinder reduces to 23.2 kg. Find out the volume of the
gas in cubic metres used up at the normal usage conditions, 89. When 2 g of a gas A is introduced into an evacuated flask
and the final pressure inside the cylinder. Assume LPG to the kept at 25°C, the pressure is found to be one atmosphere. If
n-butane with normal boiling point of 0° C. (1994, 3M) 3 g of another gas B is then added to the same flask, the total
89. A 4 : 1 molar mixture of He and CH4 is contained in a vessel pressure becomes 1.5 atm. Assuming ideal gas behaviour,
calculate the ratio of the molecular weights M A : M B .
at 20 bar pressure. Due to a hole in the vessel, the gas
(1983, 2M)
mixture leaks out. What is the composition of the mixture
effusing out initially? (1994, 2M)
90. At room temperature, ammonia gas at 1 atm pressure and
hydrogen chloride gas at p atm pressure are allowed to effuse
80. A gas bulb of 1 L capacity contains 2.0 ´ 1021 molecules of through identical pin holes from opposite ends of a glass tube
nitrogen exerting a pressure of 7.57 ´ 103 Nm–2 . Calculate of one metre length and of uniform cross-section.
States of Matter 69
Ammonium chloride is first formed at a distance of 60 cm 93. A hydrocarbon contains 10.5 g of carbon per gram of
from the end through which HCl gas is sent in. What is the hydrogen. 1 L of the vapour of the hydrocarbon at 127°C and
value of p ? (1982, 4M) 1 atm pressure weighs 2.8 g. Find the molecular formula of
91. Calculate the average kinetic energy, in joule per molecule in the hydrocarbon. (1980, 3M)
8.0 g of methane at 27°C. (1982, 2M) 94. 3.7 g of a gas at 25°C occupied the same volume as 0.184 g of
hydrogen at 17°C and at the same pressure. What is the
92. The pressure in a bulb dropped from 2000 to 1500 mm of
molecular weight of the gas ? (1979, 2M)
mercury in 47 min when the contained oxygen leaked
through a small hole. The bulb was then evacuated. A 95. 4.215 g of a metallic carbonate was heated in a hard glass
mixture of oxygen and another gas of molecular weight 79 in tube, the CO2 evolved was found to measure 1336 mL at
the molar ratio of 1 : 1 at a total pressure of 4000 mm of 27°C and 700 mm of Hg pressure. What is the equivalent
mercury was introduced. Find the molar ratio of the two weight of the metal ? (1979, 3M)
gases remaining in the bulb after a period of 74 min. 96. Calculate the density of NH3 at 30°C and 5 atm pressure.
(1981, 3M) (1978, 2M)
Surface tension
Surface tension
I II III
(c) 0.6 cm 3 (d) 0.06 cm 3
Answers
Topic 1
1. (c) 2. (b) 3. (a) 4. (a)
5. (c) 6. (b) 7. (b) 8. (a) 53. less 54. 1 : 16 55. 0.25
9. (b) 10. (b) 11. (b) 12. (c) 56. inversely, time 57. R 58. 900
13. (c) 14. (b) 15. (b) 16. (a) 59. F 60. F 61. F 62. F
17. (a) 18. (a) 19. (c) 20. (d) 63. (4) 64. (9) 65. (4) 66. (7 L)
21. (b) 22. (c) 23. (c) 24. (c) 67. (4) 68. 435 ms -1 70. (1025) 71. (0.99 atm)
25. (b) 26. (c) 27. (d) 28. (a) 73. (6.46) 74. (123 g mol -1) 76. (0.14)
29. (d) 30. (a) 31. (b) 32. (c) 78. (2.46 m 3) 79. (8:1) 80. (407 ms -1) 81. (0.221 atm)
82. (1020 g mol -1) 83. (5.23 L) 85. (10)
33. (b) 34. (c) 35. (a) 36. (d)
86. (390.2 ms -1) 88. (2.7 ´ 1010 g mol -1)
37. (b) 38. (b) 39. (b) 40. (a)
89. (1 : 3) 90. (2.20 atm) 91. (6.2 ´ 10 -21 J/molecule)
41. (b) 42. (a) 43. (c) 44. (a)
94. (41.32g) 95. (12.15) 96. (3.42 gL -1)
45. (a,c) 46. (a,b) 47. (2.22) 48. (d)
49. (a) 50. (d) 51. (c) Topic 2
52. A ® p,s; B ® r; C® p, q; D ® r 1. (d) 2. (c) 3. (d) 4. (c)
Hints & Solutions
Topic 1 Gaseous State pV - pb = RT Þ pV = RT + pb
1. pV pb
Key Idea From kinetic gas equation, =1+
RT RT
2RT pV
Most probable velocity (vmp ) = As, Z=
M RT
where, R = gas constant, T = temperature, pb
so, Z =1+ Þ y = c + mx
M = molecular mass RT
The plot of z vs p is found to be
2RT T
vmp = , i.e. vmp µ
M M b
slope =
Gas M T ( K) T/M RT
Z
H2 2 300 300 / 2 = 150 …III (Highest)
N2 28 300 300 / 28 = 10.71 …I (Lowest)
So, The gas with high value of b will be steepest as slope is directly
I. corresponds to vmp of N2 (300 K) proportional to b. b is the van der Waals’ constant and is equal to
four times the actual volume of the gas molecules. Xe gas
II. corresponds to vmp of O2 (400 K)
possess the largest atomic volume among the given noble gases
III. corresponds to vmp of H2 (300 K) (Ne, Kr, Ar). Hence, it gives the steepest increase in the plot of Z
(compression factor) vsp.
2. For 1 mole of a real gas, the van der Waals’ equation is
æ a ö 4. Critical temperature is the temperature of a gas above which it
ç p + 2 ÷ (V - b) = RT cannot be liquefied what ever high the pressure may be. The
è V ø
kinetic energy of gas molecules above this temperature is
The constant ‘a’ measures the intermolecular force of attraction sufficient enough to overcome the attractive forces. It is
of gas molecules and the constant ‘b’ measures the volume represented as Tc.
correction by gas molecules after a perfectly inelastic binary 8a
collision of gas molecules. Tc =
27Rb
For gas A and gas C given value of ‘b’ is 8 ´ 13
.
0.05196 dm3 mol -1. Here, For Ar, Tc = = 0.0144
27 ´ 8.314 ´ 3.2
a µ intermolecular force of attraction
8 ´ 0.2
µ compressibility µ real nature For Ne, Tc = = 0.0041
27 ´ 8.314 ´ 17
.
1
µ 8 ´ 51
.
volume occupied For Kr, Tc = = 018
.
27 ´ 8.314 ´ 1.0
Value of a/(kPa dm6 mol -1) for gas A (642.32) > gas C (431.91) 8 ´ 4.1
So, gas C will occupy more volume than gas A. Similarly, for a For Xe, Tc = = 0.02
27 ´ 8.314 ´ 5.0
given value of a say 155.21 kPa dm6 mol -1 for gas B and gas D
The value of Tc is highest for Kr (Krypton).
1
µ intermolecular force of attraction 5. In isothermal expansion, pVm = K (constant)
b
µ compressibility µ real nature This relation is plotted in graph ‘C’
1 K
µ Likewise, p=
volume accupied Vm
b/(dm 3 mol -1) for gas B (0.04136) < Gas D (0.4382) This relation is plotted in graph “A”.
So, gas B will be more compressible than gas D. Thus, graph B and D are incorrect.
For them the correct graphs are:
3. Noble gases such as Ne, Ar, Xe and Kr found to deviate from
ideal gas behaviour.
Xe gas will exhibit steepest increase in plot of Z vs p.
p for graph B and U for graph D
Equation of state is given as:
RT
p= Þ p(V - b) = RT
(V - b) Vm Vm
States of Matter 71
a 14T (H2 )
Þ pV = RT - …(i) Þ 7=
V T (N2 )
1 Þ T (N2 ) = 2T (H2 ) i.e. T (H2 ) < T (N2 )
Eq. (i) is a straight equation between pV and whose slope is ‘
V
- a’. Equating with slope of the straight line given in the graph.
23. At high temperature and low pressure, the gas volume is
infinitely large and both intermolecular force as well as
20.1 - 21.6
-a= = - 1.5 molecular volume can be ignored. Under this condition
3- 2 postulates of kinetic theory applies appropriately and gas
Þ a = 1.5 approaches ideal behaviour.
14. In the van der Waals’ equation 24. Rate of effusion µ pi ; pi = Partial pressure of ith component
æ 2
n aö 1
çp+ ÷ (V - nb) = nRT µ
ç V 2 ÷ø M
è
V
n2a 25. Compressibility factor (Z ) = =1
The additional factor in pressure, i.e. corrects for Videal
V2
intermolecular force while b corrects for molecular volume. Q For ideal gas V = Videal
3RT
15. Option (b) is incorrect statement because at high pressure slope 26. Expression of rms is, urms =
M
of the line will change from negative to positive.
3R ´ 50
r(He) 16
16. = =2 :1 urms (H2 at 50 K) 2
r(CH4 ) 4 Þ =
urms (O2 at 800 K) 3R ´ 800
3 32
17. Kinetic energy (E ) = kT
2 50 32
3kT = ´ =1
RMS speed (u) = 2 800
m
27. Let x g of each gas is mixed.
2E x
Þ u= Mole of ethane =
m 30
x
18. Positive deviation corresponds to Z > 1 Mole of hydrogen =
2
pV pV x
Q Z= , for positive deviation, > 1.
nRT nRT 2 15
Mole fraction of hydrogen = =
19. Option (b) and (d) are ruled out on the basis that at the initial x x 16
+
point of 273 K, 1 atm, for 1.0 mole volume must be 22.4 L, and 2 30
it should increase with rise in temperature. Partial pressure of H2
Þ = Mole fraction of hydrogen
Option (a) is ruled out on the basis that initial and final points are Total pressure
not connected by the ideal gas equation V µ T , i.e. V /T do not = 15 : 16
have the same value at the two points.
In option (c), at the initial point, the volume is 22.4 L as required 8RT
28. Average speed =
by ideal gas equation and (V /T ) have the same value at both pM
initial and final points. i.e. at constant volume, for a fixed mass, increasing temperature
3RT increases average speeds and molecules collide more frequently
20. Root mean square velocity (urms ) = to the wall of container leading to increase in gas pressure.
M
Also, p × M = dRT 29. The mean translational kinetic energy (Î) of an ideal gas is
3
Substituting for RT / M in urms expression gives, Î= k BT ; T = Absolute temperature, i.e. Î µ T
2
3p 1
urms = Þ urms µ rCH 4 MX
d d 30. =2= Þ M X = 64
rX 16
V
21. Compressibility factor (Z ) = < 1 (given) w
Vid 31. The ideal gas equation, pV = nRT = RT
M
Þ V < 22.4 L æ wö
Q Vid (1 mol ) = 22.4 L at STP Þ pM = ç ÷ RT = dRT (d = density)
èV ø
3RT pM
22. Root mean square speed urms = Þ d=
M RT
urms (H2 ) T (H2 ) 28 i.e. density will be greater at low temperature and high
Þ = 7= ´
urms (N2 ) 2 T (N2 ) pressure.
States of Matter 73
Option (b) is wrong statement because in the limit of large 51. PLAN This problem can be solved by using the concept of Graham’s law
pressure Z > 1. of diffusion according to which rate of diffusion of non-reactive
gases under similar conditions of temperature and pressure are
Option (c) is correct statement. For a van der Waals’ gas,
inversely proportional to square root of their density.
van der Waals’ constants a and b are characteristic of a gas, 1
independent of temperature. Rate of diffusion µ
molar weight of gas
Option (d) is wrong statement because Z can be either less or
Let distance covered by X is d, then distance covered by Y is
greater than unity, hence real pressure can be less or greater than
24 – d.
ideal pressure.
If rX and rY are the rate of diffusion of gases X and Y,
46. Pressure is inversely proportional to volume at constant rX d 40
temperature, hence (a) is correct. = = =2
rY 24 - d 10
Average kinetic energy of a gas is directly proportional to
absolute temperature, hence (b) is correct. [Q Rate of diffusion µ distance travelled]
Expansion at constant temperature cannot change the number of d = 48 - 2d
molecules, hence (d) is incorrect. Þ 3d = 48 Þ d = 16 cm
Hence, (c) is the correct choice.
47. Given p1 = 5 bar, V1 = 1 m 3, T1 = 400 K
So, n1 =
5
(from pV = nRT ) 52. A. At p = 200 atm, very high pressure, Z > 1. Also, at such a
400 R æ n2a ö
high pressure, the pressure correction factor çç 2 ÷÷ can be
3 èV ø
Similarly, p2 = 1 bar, V2 = 3 m 3, T2 = 300 K, n2 =
300 R ignored in comparison to p.
Let at equilibrium the new volume of A will be (1+ x ) B. At P ~ 0, gas will behave like an ideal gas, pV = nRT .
So, the new volume of B will be (3- x ) C. CO2 (p = 1 atm, T = 273 K), Z < 1.
Now, from the ideal gas equation. D. At very large molar volume, real gas behaves like an
p1V1 pV ideal gas.
= 2 2
n1RT1 n2RT2 3
53. Less; E = RT
and at equilibrium (due to conduction of heat) 2
p1 p2 3
= 54. 1 : 16, KE = nRT . At same temperature, KE (total) µ n.
T1 T2 2
1
V1 V2 55. 0.25 RT because at NTP, 5.6 L = mole.
So, = or V1n2 = V2n1 4
n1 n2
56. Inversely, time.
After putting the values
3 5 (3 - x ) 5 57. For an ideal gas, Cp - CV = R
(1+ x ) ´ = (3 - x ) ´ or (1+ x ) =
300 R 400 R 4 3 3
58. At 27°C, E = RT = ´ 2 ´ 300 = 900 cal
11 2 2
or 4 (1+ x ) = 15 - 5x or 4 + 4 x = 15 - 5x or x =
9
59. An ideal gas cannot be liquefied because there exist no
11 20 intermolecular attraction between the molecules of ideal gas.
Hence, new volume of A i.e., (1+ x ) will comes as 1 + = or
9 9
2.22. 60. a is the measure of intermolecular force.
48. Assertion is incorrect because besides amount, pressure also 61. In a close container, gas exert uniform pressure everywhere in
depends on volume. However, reason is correct because both the container.
frequency of collisions and impact are directly proportional to 3
62. KE = RT where, T is absolute temperature (in Kelvin).
root mean square speed which is proportional to square root of 2
absolute temperature
63. (DC) Diffusion coefficient µ l (mean free path) µU mean
49. a is the measure of intermolecular force of attraction. Greater the
intermolecular force of attraction (H-bond in the present case) Thus (DC) µ l Umean
higher the value of a. RT T
But, l= Þ lµ
2 N0 sp p
50. X is a lighter gas than Y, hence X has greater molecular speed.
Due to greater molecular speed of X, it will have smaller mean 8RT
free path and greater collision frequency with the incrt gas and U mean =
pM
molecules. As a result X will take more time to travel a given
distance along a straight line. Hence X and Y will meet at a U mean µ T
distance smaller than one calculated from Graham’s law. (T )3/ 2
\ DC µ
Hence, (d) is the correct choice. p
States of Matter 75
3/ 2 3/ 2 pV 1 ´ 50
(DC)2 æp ö æ T2 ö æ p ö æ 4T1 ö (c) Z = = = 1.22
(x ) = çç 1 ÷÷ çç ÷÷ = çç 1 ÷÷ çç ÷÷ RT 0.082 ´ 500
(DC)1 è p2 ø è T1 ø è 2 p1 ø è T1 ø
(d) Q Z > 1, repulsive force is dominating.
æ 1ö
= ç ÷ (8) = 4
è 2ø 3 3
(ii) Ek = k BT = ´ 1.38 ´ 10-23 ´ 1000 J = 2.07 ´ 10-20 J
238 206 4 0 2 2
64. 92 U ¾® 82Pb + 8 2He (g ) + 6- 1b
n(gas)[Initial] = 1 (air) 70. In case of negligible molecular volume, b = 0. For 1 mole of gas
n(gas)[Final] = 8 (He) + 1(air) = 9 æ a ö
ç p + 2 ÷ V = RT
Þ At constant temperature and volume; è V ø
p µ n. a
Þ pV + = RT
pf nf 9 V
So, = = =9 pV a
pi ni 1 é pV ù
Þ + =1 Q = Zú
RT VRT ëê RT û
65. PLAN This problem can be solved by using the concept involved in
a ap
calculation of significant figure. Þ Z+ =1 Þ Z+ =1
Universal gas constant, R = kN A æ ZRT ö ZR 2T 2
çç ÷÷ RT
where, k = Boltzmann constant è p ø
and N A = Avogadro’s number ZR 2T 2 (1 - Z ) 0.5 (0.082 ´ 273)2 (1- 0.5)
Þ a= =
p 100
\ R = 1.380 ´ 10-23 ´ 6.023 ´ 1023 J/Kmol
= 8.31174 =~ 8.312 a = 1.25 atm L2 mol -2
Since, k and N A both have four significant figures, so the value 71. In case of negligible molecular volume, b = 0 and
of R is also rounded off upto 4 significant figures.
van der Waals’ equation reduces to
[When number is rounded off, the number of significant figure is
reduced, the last digit is increased by 1 if following digits ³ 5
æ n2a ö
ç p+ ÷ V = nRT
and is left as such if following digits is £ 4.] ç V 2 ÷ø
è
Hence, correct integer is (4). RT a
Þ p= - 2 (n =1 mole)
66. Since, the external pressure is 1.0 atm, the gas pressure is also V V
1.0 atm as piston is movable. Out of this 1.0 atm partial pressure 0.082 ´ 273 3.592
= - = 0.99 atm
due to unknown compound is 0.68 atm. 22.4 (22.4)2
Therefore, partial pressure of He
72. (i) For the same amount of gas being effused
= 1.00 – 0.68 = 0.32 atm.
n(He)RT 0.1 ´ 0.082 ´ 273 r1 t2 p1 M2
Þ Volume = = =7L = =
p(He) 0.32 r2 t1 p2 M1
Þ Volume of container = Volume of He. 57 0.8 M2
Þ =
38 1.6 28
67. Given, urms = umps
Þ M 2 = 252 g mol -1
3RT 2RT
Þ = Also, one molecule of unknown xenon-fluoride contain only
M (X ) M (Y )
one Xe atom [M (Xe) = 131], formula of the unknown gas
3R ´ 400 2R ´ 60 can be considered to be XeFn.
Þ =
40 M (Y ) Þ 131 + 19n = 252; n = 6.3, hence the unknown gas is XeF6.
Þ M (Y ) = 4 (ii) For a fixed amount and volume, p µ T
uav 8RT 3RT 8 1 T
68. = : = Þ = where, T = Kelvin temperature
urms pM M 3p 1.1 T + 10
V 2 é nRT ù (4 )2 é 2 ´ 0.082 ´ 300 ù Also, pressure of gas outside the cylinder is 1.0 atm.
Þ a= 2 ê
- pú = 2 ê
- 11ú
n ë V - nb û (2) ë 4 - 2 (0.05) û Þ pV = nRT
= 6.46 atm L2 mol -2 nRT (14.2 - 8.4 ) ´ 103 0.082 ´ 30
Þ V = = ´ L
p 58 1
74. Mass of liquid = 148 - 50 = 98 g
= 2460 L = 2.46 m 3
98
Þ Volume of liquid = = 100 mL = volume of flask
0.98 rHe nHe M CH 4 4 16
79. = = =8
mass of gas = 50.5 - 50 = 0.50 g rCH4 n CH4 M He 1 4
æ wö Initial ratio of rates of effusion gives the initial composition of
Now applying ideal gas equation : pV = ç ÷ RT
èMø mixture effusing out. Therefore, n (He) : n (CH4 ) = 8 : 1
wRT 0.5 ´ 0.082 ´ 300
Þ M = = = 123 g mol -1 2 ´1021
pV 1 ´ 0.1 80. Number of moles = = 0.33 ´ 10-2
6 ´ 1023
75. False, ideal gas cannot be liquefied as there is no intermolecular p = 7.57 ´ 103 Nm -2
attraction between the molecules of ideal gas. Hence, there is no
point of forming ideal solution by cooling ideal gas mixture. Now, pV = nRT
pV 7.57 ´ 103 ´ 10-3
76. If ‘a’ is the degree of dissociation, then at equilibrium Þ T = = = 276 K
Cl 2 r 2Cl nR 0.33 ´ 10-2 ´ 8.314
Moles 1-a 2a Total = 1 + a 3RT 3 ´ 8.314 ´ 276
Þ urms = = m s-1 = 496 ms-1
From diffusion information
M 28 ´ 10-3
r(mix) 84 umps
= 1.16 = Also, = 0.82
r(Kr) M (mix) urms
Þ umps = 0.82 ´ urms = 0.82 ´ 496 ms-1 = 407 ms-1
Þ M (mix) = 62.4
71 81. First we calculate partial pressure of NO and O2 in the combined
Þ M (mix) = = 62.4
1+ a system when no reaction taken place.
Þ a = 0.14 pV = constant Þ p1V1 = p2V2
1.053 ´ 250
pV 1 ´ 40 Þ p2 (NO) = = 0.752 atm
77. The total moles of gaseous mixture = = 350
RT 0.082 ´ 400
0.789 ´ 100
= 1.22 p2 (O2 ) = = 0.225 atm
350
Let the mixture contain x mole of ethane. Therefore,
7 Now the reaction stoichiometry can be worked out using partial
C2H6 + O2 ¾® 2CO2 + 3H2O pressure because in a mixture.
x 2 pi µ ni
C2H4 + 3O2 ¾® 2CO2 + 2H2O 2NO + O2 ¾® 2NO2 ¾® N2O4
1.22- x Initial 0.752 atm 0.225 atm 0 0
7 x Final 0.302 0 0 0.225 atm
Total moles of O2 required = x + 3 (1.22 - x ) = + 3.66
2 2
130 x Now, on cooling to 220 K, N2O4 will solidify and only
Þ = + 3.66 unreacted NO will be remaining in the flask.
32 2
Q p µT
Þ x = 0.805 mole ethane and 0.415 mole ethene.
p1 T1
0.805 \ =
Þ Mole fraction of ethane = = 0.66 p2 T2
1.22
0.302 300
Mole fraction of ethene = 1 - 0.66 = 0.34 Þ =
p2 220
78. Weight of butane gas in filled cylinder = 29 - 14.8 kg
Þ p2 (NO) = 0.221 atm
= 14.2 kg
Þ During the course of use, weight of cylinder reduces to 23.2 kg pV 6´3
82. Total moles of gas in final mixture = = = 0.731
RT 0.082 ´ 300
Þ Weight of butane gas remaining now
= 23.2 - 14.8 = 8.4 kg Q Mole of H2 in the mixture = 0.70
Also, during use, V (cylinder) and T remains same. \ Mole of unknown gas ( X ) = 0.031
p1 n1
Therefore, = Because both gases have been diffused for same time
p2 n2
r (H2 ) 0.70 M
æn ö æ 8.4 ö é n w ù = =
Þ p2 = çç 2 ÷÷ p1 = ç ÷ ´ 2.5 ê Here, 2 = 2 ú r ( X ) 0.031 2
n
è 1ø è 14.2 ø ë n1 w1 û
Þ M = 1020 g mol -1
= 1.48 atm
States of Matter 77
nRT pV
83. V = 88. Number of moles (n) =
p RT
5 N (Number of molecules)
For acetylene gas, 5 g = mol and n=
26 N A (Avogadro number)
740 æ pV ö
p = 740 mm = atm Þ N = nNA = ç ÷ NA
760 è RT ø
æ 7.6 ´ 10-10 1 ö
T = 50° C = 323 K = çç ´ ÷ ´ 6.023 ´ 1023
760 0.082 ´ 273 ÷
Substituting in ideal gas equation è ø
10
5 0.082 ´ 323 = 2.7 ´ 10 molecules
V = ´ ´ 76 = 5.23 L
26 74 89. From the given information, it can be easily deduced that in the
8RT1 final mixture,
84. uav (average velocity ) = partial pressure of A = 1.0 atm
pM
partial pressure of B = 0.5 atm
9 ´ 104 8 ´ 8.314 T1
Þ ms-1 = pV V
100 3.14 ´ 44 ´ 10-3 Also nA = A =
RT RT
Þ T1 = 1682.5 K p V 0.5 V
nB = B =
Also, for the same gas RT RT
uav 8RT1 2RT2 8T1 1 4T1 nB 1 wB M A 3 æ M A ö
= : = ´ = Þ = = ´ = ´ç ÷
umps pM M p 2T2 pT2 nA 2 M B wA 2 çè M B ÷ø
4T1 Þ M A :M B = 1 : 3
Þ 1=
pT2 p
90. Rate of effusion (r) µ
4T1 4 ´ 1682.5 M
Þ T2 = = = 2142 K
p 3.14 r (NH3 ) 1 36.5 40 1 36.5
Þ = ´ Þ =
Hence, T1 = 1682.5 K, T2 = 2142 K r (HCl ) 17 p 60 p 17
3
4 3 4 æ 21ö 3 36.5
85. Volume of balloon = pr = ´ 3.14 ´ ç ÷ cm 3 Þ p= = 2.20 atm
3 3 è 2ø 2 17
= 4847 cm 3 » 4.85 L 3
91. KE = k BT : k B = Boltzmann’s constant
Now, when volume of H2 (g ) in cylinder is converted into NTP 2
volume, then 3
= ´ 1.38 ´ 10-23 ´ 300 J = 6.21 ´ 10-21 J/molecule
p1V1 p2V2 2
= dp kp
T1 T2 92. Rate of effusion is expressed as - =
dt M
20 ´ 2.82 1 ´ V2
Þ = , V2 = NTP volume k = constant, p = instantaneous pressure
300 273 dp k dt
Þ V2 = 51.324 L Þ - =
p M
Also, the cylinder will not empty completely, it will hold 2.82 L æp ö kt
Integration of above equation gives ln çç 0 ÷÷ =
of H2 (g ) when equilibrium with balloon will be established. p M
è ø
Hence, available volume of H2 (g ) for filling into balloon is
æ 2000 ö k 47
51.324 - 2.82 = 48.504 L Using first information : ln ç ÷=
è 1500 ø 32
48.504
Þ Number of balloons that can be filled = = 10 32 æ4ö
4.85 Þ k= ln ç ÷ …(i)
47 è 3ø
3RT 3 ´ 8.314 ´ 293
86. urms = = = 390.2 ms-1 Now in mixture, initially gases are taken in equal mole ratio,
M 48 ´ 10-3 hence they have same initial partial pressure of 2000 mm of Hg
each.
87. (i) NH3 (l ) is highly volatile, a closed bottle of NH3 (l ) contains
large number of molecules in vapour phase maintaining high After 74 min :
pressure inside the bottle. When the bottle is opened, there is æ 2000 ö 74 k
chances of bumping of stopper. To avoid bumping, bottle For O2 ln ç ÷=
ç pO ÷ 32
should be cooled that lowers the pressure inside. è 2 ø
(ii) According to Avogadro’s hypothesis, “Under identical Substituting k from Eq. (i) gives
conditions of pressure and temperature, equal volume of
æ 2000 ö
ideal gases contain equal number of molecules.” ln ç ÷ = 74 ´ 32 ln æç 4 ö÷
ç pO ÷ 32 47 è 3ø
è 2 ø
78 States of Matter
M = = = 91.84 » 92
pV 1´ 1
CH3OH (I)
Q Molar mass (M ) is same as empirical formula weight. -
CH3(CH2)11OSO3 Na + (III)
Molecular formula = Empirical formula = C7 H8
1
94. For same p and V , n µ Concentration
T
n (gas) T (H2 ) 2. Let us consider, 1.0 L of liquid water is converted into steam .
Þ =
n (H2 ) T (gas) Volume of H2O (l) = 1 L, mass = 1000 g
0.184 1000
n(H2 ) = = 0.092 Þ Volume of 1000 g steam = cm 3
2 0.0006
290 1000
Þ n(gas) = ´ 0.092 = 0.0895 Q Volume of molecules in cm 3 steam = 1000 cm 3
298 0.0006
Q 0.0895 mole of gas weigh 3.7 g \ Volume of molecules in
1000
3.7 1000 cm 3 steam = ´ 0.0006 ´ 1000 = 0.60 cm 3
\ 1 mole of gas will weigh = 41.32 g 1000
0.0895
3. Critical temperature is directly proportional to intermolecular
95. Moles of CO2 can be calculated using ideal gas equation as : force of attraction. H2O is a polar molecule, has greater
pV æ 700 ö æ 1336 ö 1 intermolecular force of attraction than O2, hence higher critical
n= =ç ÷ç ÷´ = 0.05 temperature.
RT è 760 ø è 1000 ø 0.082 ´ 300
Also, the decomposition reaction is : 4. At liquid-vapour equilibrium at boiling point, molecules in two
phase posses the same kinetic energy.
MCO3 ¾® MO + CO2
0.05 mol 0.05 mol
(a) 1, 24.62 dm 3 atm mol -1 , 606.0 dm 6 atm 2 mol -2 16. N2 + 3H2 r 2NH3
(b) 1, 24.62 dm 3 atm mol -1 , 1.65 ´ 10-3 dm -6 atm -2 mol 2 Which is correct statement if N2 is added at equilibrium
condition? (2006, 3M)
(c) 24.62 dm 3 atm mol -1 , 606.0 dm 6 atm -2 mol 2 ,
(a) The equilibrium will shift to forward direction because
1.65 ´ 10-3 dm-6 atm -2 mol 2
according to IInd law of thermodynamics, the entropy
(d) 1, 4.1 ´ 10-2 dm -3 atm -1 mol, 606 dm 6 atm 2 mol -2
must increases in the direction of spontaneous reaction
10 Consider the following reversible chemical reactions, (b) The condition for equilibrium is G(N2) + 3G(H2)
K1
A2 ( g ) + B2 ( g ) -2 AB (g ) …(i) = 2G(NH3) where, G is Gibbs free energy per mole of the
K2 gaseous species measured at that partial pressure. The
6 AB ( g ) - 3 A ( g ) + 3B ( g )
2 2 …(ii) condition of equilibrium is unaffected by the use of
The relation between K 1 and K 2 is (2019 Main, 9 Jan II)
catalyst, which increases the rate of both the forward and
backward reactions to the same extent
(a) K 2 = K 13 (b) K 1 K 2 = 3
(c) The catalyst will increase the rate of forward reaction by
1
(c) K 2 = K 1- 3 (d) K 1 K 2 = a and that of backward reaction by b
3
(d) Catalyst will not alter the rate of either of the reaction
17. Ag + + NH3 s
11. An aqueous solution contains 0.10 M H2S and 0.20 M HCl. If
[Ag(NH3 )]+ ; K 1 = 3. 5 ´ 10-3
the equilibrium constants for the formation of HS- from H2S
[Ag (NH3 )]+ + NH3 s [Ag (NH3 )2 ]+ ; K 2 = 1.7 ´10-3
. ´ 10-7 and that of S2- from HS- ions is 12
is 10 . ´ 10-13 then
the concentration of S2- ions in aqueous solution is : then the formation constant of [Ag(NH3 )2 ]+ is (2006, 3M)
(2018 Main)
(a) 6.08 ´ 10-6 (b) 6.08 ´ 106
(a) 5 ´ 10-8 (b) 3 ´ 10-20
-21 (c) 6.08 ´ 10-9 (d) None of these
(c) 6 ´ 10 (d) 5 ´ 10-19
18. Consider the following equilibrium in a closed container
12. The equilibrium constant at 298 K for a reaction,
A + B q C + D is 100. If the initial concentrations of all N2 O4 ( g ) r 2NO2 ( g )
the four species were 1 M each, then equilibrium At a fixed temperature, the volume of the reaction container
concentration of D (in mol L-1 ) will be (2016 Main) is halved. For this change, which of the following statements
(a) 0.818 (b) 1.818 hold true regarding the equilibrium constant ( K p ) and
(c) 1.182 (d) 0.182 degree of dissociation ( a ) ? (2002, 3M)
13. The standard Gibbs energy change at 300 K for the reaction, (a) Neither K p nor a changes
2A a B + C is 2494. 2 J. At a given time, the composition
1 1 (b) Both K p and a change
of the reaction mixture is [A]= , [ B ] = 2 and [C ] = . The
2 2 (c) K p changes but a does not change
reaction proceeds in the (d) K p does not change but a changes
(R = 8.314JK / mol, e = 2.718) (2015, Main)
(a) forward direction because Q > K c 19. At constant temperature, the equilibrium constant ( K p ) for
(b) reverse direction because Q > K c the decomposition reaction, N2 O4 r 2NO2 , is expressed
(c) forward direction because Q < K c 4 x2 p
by K p = , where, p = pressure, x = extent of
(d) reverse direction because Q < K c (1 - x2 )
[A]/(mol L–1)
[P]/(mol L–1)
-2 -2
(0.082 ´ 500) (8.314 ´ 773) T2
5 5
1.44 ´ 10-5 1.44 ´ 10–5
(c) (d) T2
(0.082 ´ 773)2 (0.082 ´ 773)-2 T1
22. For the chemical reaction, Time Time
3 X ( g ) + Y ( g ) r X 3Y ( g ) If T2 > T1 , the correct statement(s) is are
the amount of X 3Y at equilibrium is affected by (1999, 2M) (Assume DH s and DS s are independent of temperature and
(a) temperature and pressure ratio of ln K at T1 to ln K at T2 is greater than T2 / T1 . Here
(b) temperature only H , S , G and K are enthalpy, entropy, Gibbs energy and
(c) pressure only equilibrium constant, respectively.) (2018 Adv.)
(d) temperature, pressure and catalyst (a) DH s < 0, DS s < 0 (b) DGs < 0, DH s > 0
23. For the reaction , (c) DGs < 0, DS s < 0 (d) DGs < 0, DS s > 0
CO( g ) + H2 O( g ) r CO2 ( g ) + H2 ( g ) , *29. The % yield of ammonia as a function of time in the reaction,
N2( g )+ 3H2( g ) w 2 NH3( g ); DH < 0
at a given temperature, the equilibrium amount of CO2 ( g )
(2015 adv.)
can be increased by (1998)
(a) adding a suitable catalyst at ( p, T1 ) is given below.
(b) adding an inert gas
(c) decreasing the volume of the container
% yield
T1
(d) increasing the amount of CO( g )
24. One mole of N2 O4 ( g ) at 300 K is kept in a closed container
under one atmosphere. It is heated to 600 K when 20% by
Time
mass of N2 O4 ( g ) decomposes to NO2 (g). The resultant
pressure is (1996, 1M) If this reaction is conducted at ( p , T1 ), with T2 > T1 the %
(a) 1.2 atm (b) 2.4 atm (c) 2.0 atm (d) 1.0 atm yield by of ammonia as a function of time is represented by
25. An example of a reversible reaction is (1985, 1M)
(a) Pb(NO3 )2 ( aq ) + 2NaI ( aq ) = PbI2 ( s ) + 2NaNO3 ( aq ) T2 T1
% yield
% yield
T1 T2
(b) AgNO3 ( aq ) + HCl ( aq ) = AgCl ( s ) + HNO3 ( aq ) (a) (b)
(c) 2Na ( s ) + 2H2 O ( l ) = 2NaOH ( aq ) + H2 ( g )
(d) KNO3 ( aq ) + NaCl ( aq ) = KCl ( aq ) + NaNO3 ( aq ) Time Time
% yield
32. For the reaction, PCl 5 ( g ) r PCl 3 ( g ) + Cl 2 ( g ) the 42. When a liquid and its vapour are at equilibrium and the pressure
forward reaction at constant temperature is favoured by is suddenly decreased, cooling occurs. (1984, 1M)
(1991, 1M)
(a) introducing an inert gas at constant volume Subjective Questions
(b) introducing chlorine gas at constant volume 43. (a) In the following equilibrium N2O4 (g ) r 2NO2 (g )
(c) introducing an inert gas at constant pressure when 5 moles of each are taken, the temperature is kept at 298
(d) increasing the volume of the container K the total pressure was found to be 20 bar. Given that
(e) introducing PCl 5 at constant volume
DG °f (N2 O4 ) = 100 kJ, DG °f (NO2 ) = 50 kJ
33. The equilibrium SO2 Cl 2 ( g ) r SO2 ( g ) + Cl 2 ( g ) is (i) Find DG of the reaction.
attained at 25° C in a closed container and an inert gas, (ii) The direction of the reaction in which the equilibrium shifts.
helium is introduced. Which of the following statements (b) A graph is plotted for a real gas which follows van der Waals’
are correct? (1989, 1M) equation with pVm taken on Y-axis and p on X-axis. Find the
(a) Concentration of SO2 ,Cl 2 and SO2 Cl 2 change intercept of the line where Vm is molar volume. (2004, 4M)
(b) More chlorine is formed 44. When 3.06 g of solid NH4 SH is introduced into a two litre
(c) Concentration of SO2 is reduced evacuated flask at 27° C, 30% of the solid decomposes into
(d) None of the above gaseous ammonia and hydrogen sulphide.
34. When NaNO3 is heated in a closed vessel, oxygen is liberated (i) Calculate K c and K p for the reaction at 27°C.
and NaNO2 is left behind. At equilibrium, (1986, 1M) (ii) What would happen to the equilibrium when more solid
(a) addition of NaNO2 favours reverse reaction NH4SH is introduced into the flask? (1999, 7M)
(b) addition of NaNO3 favours forward reaction 45. (a) The degree of dissociation is 0.4 at 400 K and 1.0 atm for the
(c) increasing temperature favours forward reaction gaseous reaction PCl 5 r PCl 3 + Cl 2. Assuming ideal
(d) increasing pressure favours reverse reaction behaviour of all the gases, calculate the density of equilibrium
mixture at 400 K and 1.0 atm (relative atomic mass of P = 31.0
35 For the gas phase reaction,
C2 H4 + H2 r C2 H6
and Cl = 35.5).
(b) Given, [Ag(NH3 )+2 ] r Ag+ + 2NH3 ,
( DH = -32.7 kcal)
carried out in a vessel, the equilibrium concentration of
K c = 6.2 ´ 10-8 and K sp of AgCl
C2 H4 can be increased by (1984, 1M)
= 1.8 ´ 10-10 at 298 K.
(a) increasing the temperature
If ammonia is added to a water solution containing excess of
(b) decreasing the pressure AgCl(s) only. Calculate the concentration of the complex in
(c) removing some H2 1.0 M aqueous ammonia. (1998, 3M+5M)
(d) adding some C2 H6
46. The progress of reaction,
A r nB
Fill in the Blanks
with time, is represented in fig. use given below.
36. For a gaseous reaction 2B ¾® A, the equilibrium
constant K p is …… to/than K c .
(Concentration/mol L 1 )
(1997 C, 1M)
True/False 1 3 5 7
Time/h
39. The rate of an exothermic reaction increases with Determine :
increasing temperature. (1993, 1M) (i) the value of n
40. Catalyst makes a reaction more exothermic. (1987, 1M) (ii) the equilibrium constant, K and
(iii) the initial rate of conversion of A. (1994, 3M)
41. If equilibrium constant for the reaction,
A2 + B2 r 2 AB, is K, then for the backward reaction 47. 0.15 mole of CO taken in a 2.5 L flask is maintained at 750 K
AB r
1 1 1 along with a catalyst so that the following reaction can take place:
2
A2 + B2 , the equilibrium constant is .
2 K CO ( g ) + 2H2 ( g ) r CH3 OH( g )
(1984, 1M) Hydrogen is introduced until the total pressure of the system is
8.5 atm at equilibrium and 0.08 mole of methanol is formed.
Chemical and Ionic Equilibrium 83
Calculate (i) K p and K c and (ii) the final pressure if the 54. One mole of nitrogen is mixed with three moles of hydrogen
same amount of CO and H2 as before are used, but with no in a four litre container. If 0.25 per cent of nitrogen is
catalyst so that the reaction does not take place. (1993, 5M) converted to ammonia by the following reaction
N2 ( g ) + 3H2 ( g ) r 2NH3 ( g ), then
48. For the reaction, CO( g ) + 2H2 ( g ) r CH3 OH( g )
calculate the equilibrium constant, K c in concentration units.
hydrogen gas is introduced into a five litre flask at 327° C, What will be the value of K c for the following equilibrium?
N2 ( g ) + H2 ( g ) r NH3 ( g )
containing 0.2 mole of CO( g ) and a catalyst, until the 1 3
pressure is 4.92 atm. At this point 0.1 mole of CH3 OH( g ) is (1981, 4M)
2 2
formed. Calculate the equilibrium constant, K p and K c .
(1990, 5M) Passage Based Questions
49. The equilibrium constant K p of the reaction, Thermal decomposition of gaseous X 2 to gaseous X at 298 K takes
2SO2 ( g ) + O2 ( g ) r 2SO3 ( g )
place according to the following equation:
X 2 (g ) s 2X (g )
is 900 atm at 800 K. A mixture containing SO3 and O2 having
initial pressure of 1 and 2 atm respectively is heated at The standard reaction Gibbs energy, Dr G°, of this reaction is
constant volume to equilibrate. Calculate the partial pressure positive. At the start of the reaction, there is one mole of X 2 and no
of each gas at 800 K. X . As the reaction proceeds, the number of moles of X formed is
(1989, 3M)
given by b. Thus, bequilibrium is the number of moles of X formed at
50. N2 O4 is 25% dissociated at 37° C and one atmosphere equilibrium. The reaction is carried out at a constant total pressure
pressure. Calculate (i) K p and (ii) the percentage dissociation of 2 bar. Consider the gases to behave ideally.
at 0.1 atm and 37° C. (1988, 4M) (Given, R = 0.083 L bar K -1 mol -1 )
51. At a certain temperature, equilibrium constant ( K c ) is 16 for 55. The equilibrium constant K p for this reaction at 298 K, in
the reaction; terms of bequilibrium is
SO2 ( g ) + NO2 ( g ) r SO3 ( g ) + NO( g )
(2016 Adv.)
3. The pH of a 0.02 M NH4 Cl solution will be [Given 12. How many litres of water must be added to 1 L of an aqueous
K b (NH4 OH) = 10 -5
and log 2 = 0.301] solution of HCl with a pH of 1 to create an aqueous solution
(2019 Main, 10 April II)
with pH of 2? (2013 Main)
(a) 4.65 (b) 2.65 (c) 5.35 (d) 4.35
(a) 0.1 L (b) 0.9 L (c) 2.0 L (d) 9.0 L
4. Consider the following statements. 13. Solubility product constant ( K sp ) of salts of types MX , MX 2
I. The pH of a mixture containing 400 mL of 0.1 M H2SO4
and 400 mL of 0.1 M NaOH will be approximately 1.3. and M 3 X at temperature ‘T ’ are 4.0 ´ 10-8 , 3.2 ´ 10-14 and
II. Ionic product of water is temperature dependent. 2.7 ´ 10-15 , respectively. Solubilities (mol dm- 3 ) of the salts
III. A monobasic acid with K a = 10-5 has a pH = 5. The degree at temperature ‘T ’ are in the order (2008, 3M)
of dissociation of this acid is 50%. (a) MX > MX 2 > M 3 X (b) M 3 X > MX 2 > MX
IV. The Le-Chatelier’s principle is not applicable to (c) MX 2 > M 3 X > MX (d) MX > M 3 X > MX 2
common-ion effect.
2
The correct statements are (2019 Main, 10 April I) 14. 2.5 mL of M weak monoacidic base (K b = 1 ´ 10- 12 at
(a) I, II and IV (b) II and III 5
2
(c) I and II (d) I, II and III 25°C) is titrated with M HCl in water at 25°C. The
15
5. If solubility product of Zr3 (PO4 )4 is denoted by K sp and its concentration of H+ at equivalence point is
molar solubility is denoted by S , then which of the following (K w = 1 ´ 10- 14 at 25°C) (2008, 3M)
relation between S and K sp is correct? (2019 Main, 8 April I)
1/ 6 1/ 7
(a) 3.7 ´ 10- 13 M (b) 3.2 ´ 10- 7 M
æ K sp ö æ K sp ö
(a) S = çç ÷ (b) S = çç ÷ (c) 3.2 ´ 10- 2 M (d) 2.7 ´ 10- 2 M
÷ ÷
è 144 ø è 6912 ø
1/ 9 1/ 7
15. CH3 NH2 (0.1 mole, K b = 5 ´ 10- 4 ) is added to 0.08 mole of
æ K sp ö æ K sp ö HCl and the solution is diluted to one litre, resulting
(c) S = çç ÷
÷ (d) S = çç ÷
÷
è 929 ø è 216 ø hydrogen ion concentration is (2005, 1M)
6. If K sp of Ag 2 CO3 is 8 ´ 10- 12 , the molar solubility of (a) 1.6 ´ 10- 11 (b) 8 ´ 10- 11
(c) 5 ´ 10- 5 (d) 8 ´ 10- 2
Ag 2 CO3 in 0.1 M AgNO3 is (2019 Main, 12 Jan II)
(a) 8 ´ 10- 12 M (b) 8 ´ 10- 13 M 16. HX is a weak acid ( K a = 10-5 ). It forms a salt NaX (0.1M) on
(c) 8 ´ 10- 10 M (d) 8 ´ 10- 11 M reacting with caustic soda. The degree of hydrolysis
of NaX is (2004, 1M)
7. 20 mL of 0.1 M H2 SO4 solution is added to 30 mL of 0.2 M
(a) 0.01% (b) 0.0001%
NH4 OH solution. The pH of the resultant mixture is [pK b of (c) 0.1% (d) 0.5%
NH4 OH = 4.7] (2019 Main, 9 Jan I)
17. A solution which is 10-3 M each in Mn 2+ , Fe2+ , Zn 2+ and
(a) 9.3 (b) 5.0 (c) 9.0 (d) 5.2 Hg 2+ is treated with 10-16 M sulphide ion. If K sp of
8. An aqueous solution contains an unknown concentration of MnS, FeS, ZnS and HgS are 10-15 , 10-23 , 10-20 and 10-54
Ba 2 + . When 50 mL of a 1 M solution of Na 2SO 4 is added, respectively, which one will precipitate first? (2003, 1M)
BaSO4 just begins to precipitate. The final volume is (a) FeS (b) MgS (c) HgS (d) ZnS
500 mL. The solubility product of BaSO4 is 1 ´ 10-10 . What 18. Identify the correct order of solubility of Na 2 S, CuS and ZnS
is the original concentration of Ba 2+ ? (2018 Main) in aqueous medium. (2002)
(a) 5 ´ 10-9 M (b) 2 ´ 10-9 M (a) CuS > ZnS > Na 2 S (b) ZnS > Na 2 S > CuS
. ´ 10-9 M
(c) 11 . ´ 10-10 M
(d) 10 (c) Na 2 S > CuS > ZnS (d) Na 2 S > ZnS > CuS
9. Which of the following are Lewis acids? (2018 Main) 19. For a sparingly soluble salt A p Bq , the relationship of its
(a) PH3 and BCl 3 (b) AlCl 3 and SiCl 4 solubility product ( Ls ) with its solubility (S) is (2001, 1M)
(c) PH3 and SiCl 4 (d) BCl 3 and AlCl 3 (a) Ls = S p+q p
× p ×q q
(b) Ls = S p+q q
× p ×q p
10. Which of the following salts is the most basic in aqueous (c) Ls = S pq p
× p ×q q
(d) Ls = S pq
× ( p. q )( p + q)
solution? (2018 Main)
(a) Al(CN)3 (b) CH3 COOK 20. The pH of 0.1 M solution of the following salts increases in
(c) FeCl 3 (d) Pb(CH3 COO)2 the order (1999, 2M)
11. pK a of a weak acid (HA) and pK b of a weak base (BOH) are (a) NaCl < NH4 Cl < NaCN < HCl
3.2 and 3.4, respectively. The pH of their salt (AB) solution is (b) HCl < NH4 Cl < NaCl < NaCN
(2017 Main) (c) NaCN < NH4 Cl < NaCl < HCl
(a) 7.2 (b) 6.9 (c) 7.0 (d) 1.0 (d) HCl < NaCl < NaCN < NH4 Cl
Chemical and Ionic Equilibrium 85
21. Which of the following solutions will have pH close to 1.0 ? 30. A certain buffer solution contains equal concentration of X -
(1992, 1M) and HX. The K b for X - is 10-10 . The pH of the buffer is
(a) 100 mL of (M/10) HCl + 100 mL of (M/10) NaOH (1984, 1M)
(b) 55 mL of (M/10) HCl + 45 mL of (M/10) NaOH (a) 4 (b) 7
(c) 10 (d) 14
(c) 10 mL of (M/10) HCl + 90 mL of (M/10) NaOH
(d) 75 mL of (M/5) HCl + 25 mL of (M/5) NaOH 31. The precipitate of CaF2 , ( K sp = 1.7 ´ 10-10 ) is obtained, when
22. Amongst the following hydroxides, the one which has the equal volumes of which of the following are mixed?
(1982, 1M)
lowest value of K sp at ordinary temperature (about 25° C) is
-4 2+ -4 -
(1990, 1M) (a) 10 M Ca + 10 MF
(a) Mg(OH)2 (b) Ca(OH)2 (c) Ba(OH)2 (d) Be(OH)2 (b) 10-2 M Ca 2 + + 10-3 M F-
23. Which of the following is the strongest acid? (1989, 1M) (c) 10-5 M Ca 2 + + 10-3 M F-
(a) ClO3 (OH) (b) ClO2 (OH) (d) 10-3 M Ca 2 + + 10-5 M F-
(c) SO(OH)2 (d) SO2 (OH) 2 32. An acidic buffer solution can be prepared by mixing the
solution of (1981, 1M)
24. When equal volumes of the following solutions are mixed,
-10 (a) acetate and acetic acid
precipitation of AgCl ( K sp = 1.8 ´ 10 ) will occur only
(b) ammonium chloride and ammonium hydroxide
with (1988, 1M) (c) sulphuric acid and sodium sulphate
(a) 10-4 M (Ag + ) and 10-4 M (Cl - ) (d) sodium chloride and sodium hydroxide
(b) 10-5 M (Ag + ) and 10-5 M (Cl - ) 33. Of the given anions, the strongest base is (1981, 1M)
(c) 10 -6 +
M (Ag ) and 10 -6
M (Cl )- (a) ClO- (b) ClO-2
(d) 10 -10 +
M (Ag ) and 10 -10
M (Cl - ) (c) ClO-3 (d) ClO-4
25. The pK a of acetyl salicylic acid (aspirin) is 3.5. The pH of 34. At 90°C, pure water has [H3 O+ ] as 10-6 mol L-1 . What is the
gastric juice in human stomach is about 2-3 and the pH in the value of K w at 90°C ? (1981, 1M)
small intestine is about 8. Aspirin will be (1988, 1M) (a) 10-6 (b) 10-12 -14
(c) 10 -8
(d) 10
(a) unionised in the small intestine and in the stomach 35. The pH of 10-8 M solution of HCl in water is (1981, 1M)
(b) completely ionised in the small intestine and in the (a) 8 (b) -8
stomach (c) between 7 and 8 (d) between 6 and 7
(c) ionised in the stomach and almost unionised in the small
intestine Objective Questions II
(d) ionised in the small intestine and almost unionised in (One or more than one correct option)
the stomach
36. The K sp of Ag 2 CrO4 is 1.1´ 10-12 at 298 K. The solubility
26. The compound that is not a Lewis acid is (1985, 1M)
(in mol/L) of Ag 2 CrO4 in a 0.1 M AgNO3 solution is
(a) BF3 (b) AlCl 3 (c) BeCl 2 (d) SnCl 4
(a) 1.1 ´ 10-11 (b) 1.1 ´ 10-10
27. The conjugate acid of NH–2 is (1985, 1M) (c) 1.1 ´ 10 -12
(d) 1.1 ´ 10-9 (2013 Adv.)
(a) NH3 (b) NH2 OH (c) NH+4 (d) N2 H4
37. Aqueous solutions of HNO3 KOH, CH3 COOH and
28. The best indicator for detection of end point in titration of a CH3 COONa of identical concentrations are provided. The
weak acid and a strong base is (1985, 1M) pair(s) of solutions which form a buffer upon mixing is(are)
(a) methyl orange (3 to 4) (a) HNO3 and CH3 COOH (2010)
(b) methyl red (5 to 6) (b) KOH and CH3 COONa
(c) bromothymol blue (6 to 7.5) (c) HNO3 and CH3 COONa
(d) phenolphthalein (8 to 9.6) (d) CH3 COOH and CH3 COONa
29. A certain weak acid has a dissociation constant of 1.0 ´ 10-4 . 38. A buffer solution can be prepared from a mixture of
The equilibrium constant for its reaction with a strong base is (a) sodium acetate and acetic acid in water (1999, 3M)
(1984, 1M) (b) sodium acetate and HCl in water
(a) 1.0 ´ 10-4 (b) 1.0 ´ 10-10 (c) ammonia and ammonium chloride in water
(c) 1.0 ´ 1010 (d) 1.0 ´ 1014 (d) ammonia and sodium hydroxide in water
86 Chemical and Ionic Equilibrium
39. Which of the following statement(s) is (are) correct? Fill in the Blanks
(a) The pH of 1.0 ´ 10-8 M solution of HCl is 8 (1998, 2M) 42. In the reaction, I- + I2 ¾® I-3 , the Lewis acid is .............
(b) The conjugate base of H2 PO-4 is HPO2-
4 (1997, 1M)
(c) Autoprotolysis constant of water increases with 43. Silver chloride is sparingly soluble in water because its
temperature lattice energy is greater than .............. energy. (1987, 1M)
(d) When a solution of a weak monoprotic acid is titrated
against a strong base, at half-neutralisation point 44. An element which can exist as a positive ion in acidic
æ 1ö solution and also as a negative ion in basic solution is said to
pH = ç ÷ pK a be................... (1984, 1M)
è 2ø
45. The conjugate base of HSO–4 in aqueous solution is ……
Numerical Value Based Question (1982, 1M)
ionisation constant of HB ( K a ) = 1 ´ 10 -8
(2018 Adv.)
47. Solubility of sodium hydroxide increases with increase in
temperature. (1985, 1/2M)
Matrix Match Type 48. Aluminium chloride ( AlCl 3 ) is a Lewis acid because it can
41. Dilution processes of different aqueous solutions, with donate electrons. (1982, 1M)
(ii) If 6 g of NaOH is added to the above solution, determine the 64. An aqueous solution of a metal bromide MBr2 (0.05 M) is
final pH (assuming there is no change in volume on mixing,
saturated with H2 S. What is the minimum pH at which MS
K a of acetic acid is 1.75 ´ 10-5 mol/L. (1984, 1M) will precipitate? K sp for MS = 6.0 ´ 10-21 , concentration of
55. The average concentration of SO2 in the atmosphere over a saturated H2 S = 0.1 M, K 1 = 10-7 and K 2 = 1.3 ´ 10-13 , for
city on a certain day is 10 ppm, when the average H2 S. (1993, 3M)
temperature is 298 K. Given that the solubility of SO2 in
65. The pH of blood stream is maintained by a proper balance of
water at 298 K is 1.3653 mol/L and pK a of H2 SO3 is 1.92,
H2 CO3 and NaHCO3 concentrations. What volume of 5 M
estimate the pH of rain on that day. (2000, 5M) NaHCO3 solution should be mixed with a 10 mL sample of
56. The solubility of Pb(OH)2 in water is 6.7 ´ 10-6 M. Calculate blood which is 2 M in H2 CO3 , in order to maintain a pH of
7.4? (K a for H2 CO3 in blood is 7.8 ´ 10-7 ) (1993, 2M)
the solubility of Pb(OH)2 in a buffer solution of pH = 8.
(1999, 4M) 66. The solubility product ( K sp ) of Ca(OH)2 at 25° C is
57. (a) Find the solubility product of a saturated solution of 4.42 ´ 10-5 . A 500 mL of saturated solution of Ca(OH)2 is
Ag2CrO4 in water at 298 K if the emf of the cell
mixed with equal volume of 0.4 M NaOH. How much
Ag|Ag+ (saturated. Ag2CrO4 solution.) || Ag+ (0.1 M) | Ag is
0.164 V at 298 K. Ca(OH)2 in milligrams is precipitated? (1992, 4M)
(1998, 6M)
(b) What will be the resultant pH when 200 mL of an aqueous 67. A 40 mL solution of a weak base, BOH is titrated with 0.1N
solution of HCl (pH = 2.0) is mixed with 300 mL of an HCl solution. The pH of the solution is found to be 10.04 and
aqueous solution of NaOH (pH = 12.0) ? (1998, 6M) 9.14 after the addition of 5.0 mL and 20.0 mL of the acid
58. A sample of AgCl was treated with 5.00 mL of 1.5 M respectively. Find out the dissociation constant of the base.
Na 2 CO3 solution to give Ag 2 CO3 . The remaining solution (1991, 6M)
contained 0.0026 g of Cl – ions per litre. Calculate the 68. The solubility product of Ag 2 C2 O4 at 25° C is
solubility product of AgCl. [K sp (Ag 2 CO3 ) = 8.2 ´ 10-12 ] -11 3 -3
1.29 ´ 10 mol L . A solution of K 2 C2 O4 containing
(1997, 5M) 0.1520 mole in 500 mL water is shaken at 25° C with excess
of Ag 2 CO3 till the following equilibrium is reached
59. An acid type indicator, HIn differs in colour from its
conjugate base (In - ). The human eye is sensitive to colour Ag 2 CO3 + K 2 C2 O4 r Ag 2 C2 O4 + K 2 CO3
differences only when the ratio [ In – ] / [ HIn ] is greater than At equilibrium, the solution contains 0.0358 mole of
10 or smaller than 0.1. What should be the minimum change K 2 CO3 . Assuming the degree of dissociation of K 2 C2 O4 and
in the pH of the solution to observe a complete colour K 2 CO3 to be equal, calculate the solubility product of
change? ( K a = 1.0 ´ 10-5 ) Ag 2 CO3 . (1991, 4M)
(1997, 2M)
60. The ionisation constant of NH+4 in water is 5.6 ´ 10-10 at 69. What is the pH of a 1.0 M solution of acetic acid? To what
volume must one litre of this solution be diluted so that the
25° C. The rate constant for the reaction of NH+4 -
and OH to pH of the resulting solution will be twice the original value?
form NH3 and H2 O at 25° C is 3.4 ´ 1010 L/mol/s. Calculate Given, K a = 1.8 ´ 10-5 (1990, 4M)
the rate constant per proton transfer from water to NH3 .
70. Freshly precipitated aluminium and magnesium hydroxides
(1996, 3M)
are stirred vigorously in a buffer solution containing
61. What is the pH of a 0.50 M aqueous NaCN solution? 0.25 mol/L of NH4 Cl and 0.05 M of ammonium hydroxide.
(pK b of CN- = 4.70). (1996, 2M) Calculate the concentration of aluminium and magnesium
ions in solution.
62. Calculate the pH of an aqueous solution of 1.0 M ammonium
formate assuming complete dissociation. K b [NH4 OH] = 1.8 ´ 10-5
(pK a of formic acid = 3.8 and pK b of ammonia = 4.8) K sp [Mg(OH)2 ] = 8.9 ´ 10-12
(1995, 2M)
K sp [Al(OH)3 ] = 6 ´ 10-32
63. For the reaction, [Ag(CN)2 ]– r Ag + + 2CN-
(1989, 3M)
72. What is the pH of the solution when 0.20 mole of HCl is 76. The dissociation constant of a weak acid HA is 4.9 ´ 10-8 .
added to one litre of a solution containing After making the necessary approximations, calculate
(i) 1 M each of acetic acid and acetate ion, (i) pH
(ii) 0.1 M each of acetic acid and acetate ion? (ii) OH- concentration in a decimolar solution of the acid.
Assume the total volume is one litre. (Water has a pH of 7). (1983, 2M)
K a for acetic acid = 1.8 ´ 10-5. (1987, 5M) 77. Give reason for the statement that “the pH of an aqueous
-3 solution of sodium acetate is more than seven”.
73. The solubility of Mg(OH)2 in pure water is 9.57 ´ 10 g / L. (1982, 1M)
Calculate its solubility (in g/L) in 0.02 M Mg(NO3 )2 78. 20 mL of 0.2 M sodium hydroxide is added to 50 mL of
solution. (1986, 5M) 0.2 M acetic acid solution to give 70 mL of the solution.
74. The concentration of hydrogen ions in a 0.20 M solution of What is the pH of this solution?
formic acid is 6.4 ´ 10-3 mol/L. To this solution, sodium Calculate the additional volume of 0.2 M NaOH required to
formate is added so as to adjust the concentration of sodium make the pH of the solution 4.74.
formate to one mole per litre. (Ionisation constant of CH3 COOH = 1.8 ´ 10-5 ). (1982, 3M)
What will be the pH of this solution? The dissociation
79. How many moles of sodium propionate should be added to
constant of formic acid is 2.4 ´ 10-4 and the degree of
1 L of an aqueous solution containing 0.020 mole of
dissociation of sodium formate is 0.75. (1985, 3M) propionic acid to obtain a buffer solution of pH 4.75? What
75. A solution contains a mixture of Ag + (0.10 M) and will be pH if 0.010 moles of HCl are dissolved in the above
Hg 2+ (0.10 M) which are to be separated by selective buffer solution? Compare the last pH value with the pH of
precipitation. Calculate the maximum concentration of 0.010 M HCl solution. Dissociation constant of propionic
iodide ion at which one of them gets precipitated almost acid, K a at 25°C is 1.34 ´ 10-5 . (1981, 4M)
completely. What percentage of that metal ion is
precipitated? (1984, 4M)
K sp : AgI = 8.5 ´ 10-17 , HgI2 = 2.5 ´ 10-26
Answers
Topic 1 9. (d) 10. (b) 11. (b) 12. (d)
1. (d) 2. (a) 3. (d) 4. (a) 13. (d) 14. (d) 15. (b) 16. (a)
5. (d) 6. (d) 7. (b) 8. (b) 17. (c) 18. (d) 19. (a) 20. (b)
9. (b) 10. (c) 11. (b) 12. (b) 21. (d) 22. (d) 23. (a) 24. (a)
13. (b) 14. (b) 15. (a) 16. (b) 25. (d) 26. (c) 27. (a) 28. (d)
29. (c) 30. (a) 31. (b) 32. (a)
17. (a) 18. (d) 19. (d) 20. (d)
33. (a) 34. (b) 35. (d) 36. (b)
21. (d) 22. (a) 23. (d) 24. (b) 37. (c, d) 38. (a, b, c) 39. (b, c) 40. (4.47)
25. (d) 26. (a) 27. (d) 28. (a,c) 41. (d) 42. I2 43. hydration
29. (b) 30. (a) 31. (b, c, d) 32. (c, d, e) 44. amphoteric 45. SO 2-
4 46. F 47. F
33. (d) 34. (c, d) 35. (a, b, c, d) 36. smaller 48. F 49. (3) 50. (1.6 ´ 10 -7) 52. (8)
37. no change 38. K p = Kc ( RT ) Dn 39. T 53. (9) 55. (4.86) 56. (1.2 ´ 10 -3 M)
40. F 41. F 42. T 46. (1.2) 58. (2 ´ 10 -8) 61. (11.5) 62. (6.50) 64. (1)
52. (1.86) 53. (0.33) 55. (b) 56. (c) 65. (80) 67. (1.8 ´ 10 -5) 68. (9.67 ´ 10 -11) 69.
(27.78 ´ 10 3)
Topic 2 71. (0.177) 72. (8.7 ´ 10 -4 gL -1) 74. (4.20)
1. (d) 2. (c) 3. (c) 4. (d)
75. (99.83) 77. (>7)
5. (b) 6. (c) 7. (a) 8. (c)
Hints & Solutions
Topic 1 Chemical Equilibrium
1. The incorrect match is DG ° < 0, K < 1. (c) For the equilibrium,
For an ideal gas DG ° = - RT ln K . Dng = 2 - (2 + 1) = - 1, i.e. (-ve)
DG ° So, increase in pressure will shift the equilibrium in the
\ ln K = - and K = e- DG ° / RT forward direction.
RT
The above equation is helpful in predicting the spontaneity of Thus, statement (c) is correct.
the reaction. e.g. (d) The reaction takes place in the presence of a catalyst which is
V2O5 (s) in contact process or NO(g ) in chamber process.
(i) If DG ° < 0, – DG °/ RT = + ve and e- DG ° / RT > 1 and hence,
Thus, statement (d) is incorrect.
K > 1. It means that the reaction occur spontaneously in the
forward direction or products predominate over reactants. 4. S + O2 - SO2 , K 1
(ii) If DG ° > 0; - DG °/ RT = - ve and 1
e- DG °/ RT
< 1 and hence, K < 1. It means that the reaction is
\ SO2 - S + O2 , K 1 ¢ =
K1
non-spontaneous in forward direction (i.e. product side) but 1
or, 2SO2 - 2S + 2O2, K 1 ¢¢ = (K 1 ¢ )2 = … (i)
spontaneous in reverse direction (i.e. reactants predominate K 12
over products or the reaction occurs rarely).
(iii) When K = 1, then DG ° = 0. This situation generally occur
Þ 2S + 3O2
Now, [(i) + (ii)] gives
- 2SO3 , K 2 … (ii)
at equilibrium.
2.
2SO2 + O2 -
The value of equilibrium constant,
2SO3 , K 3
B q
moles at t = 0
At t = t eq 01
. (1 - 0. 03) 30% of 30% of 0.1
12. A + C + D
01. = 0. 03 = 0. 03 Initially at t = 0 1 1 1 1
Active mass 0. 03 0. 03 At equilibrium 1-x 1-x 1+x 1+x
= 0. 01 = 0. 01
(mol L -1) 3 3 [C ][ D ] (1 + x)(1 + x) (1 + x)2
K eq = = =
[ NH3 ][ H2S ] 0.01 ´ 0.01 [ A ][ B ] (1 - x)(1 - x) (1 - x)2
KC = = = 10-4 (mol L -1 2
)
[ NH4HS(s) ] 1 æ1 + xö
2
1+ x
Dng or 100 = çç ÷÷ or 10 =
Þ K p = KC (RT ) è1- xø 1- x
[ H+ ][ A - ] 41. It is
1
.
Ka =
[ HA ] K
(Rate)HA = k [ H+ ]HA 42. Evaporation is an endothermic process.
(Rate) HX = k [ H+ ]HX 43. (a) N2O4 (g ) r 2NO2 (g )
DG ° = 2 DG f° (NO2 ) - DG f° (N2O4 ) = 0
(Rate) HX = 100(Rate)HA
+ Also DG ° = - RT ln K = 0 , K = 1
\ Also in strong acid, [ H ] = [ HX ] = 1 M
Let the reaction shifts in forward direction.
(Rate) HX
= 100 =
[ H + ] HX
=
1 N2O4 (g ) r 2NO2 (g ) Total
(Rate) HA [ H + ] HA [ H+ ]HA 5-x 5 + 2x 10 + x
5-x 5 + 2x
1 pi : ´ 20 ´ 20
\ [ H + ] HA = 10 + x 10 + x
100
HA r H+ + A -
(5 + 2x )2 10 + x
Þ K = ´ ´ 20 = 1
(10 + x )2 5-x
1 0 0
(1 - x ) x x Þ 81x 2 + 405x + 450 = 0
x = 0.01 x = - 1.66 and – 3.33
[ H+ ][ A - ] 0.01 ´ 0.01 Both values of x indicates that reaction actually proceeds in
\ Ka = = = 1.01 ´ 10-4 backward direction.
[ HA ] 0.99
æ a ö
31. Cl - , CN - and SCN - forms precipitate with Cu (I), remove (b) ç p + ÷ (Vm - b) = RT
è Vm2 ø
Cu (I) ion from equilibrium and reaction shifts in backward
direction according to Le-Chatelier's principle. æ ap2 ö æ pV ö
çp+ ÷ çç - b÷÷ = RT
ç ( pV )2 ÷ø
32. If inert gas is introduced at constant pressure, volume of è è p ø
container will have to be increased and this will favour the
Þ [( pV 2 ) p + ap2 ][( pV ) - b ] = p ( pV )2 RT
forward reaction. Also adding PCl 5 (g ) at constant volume will
favour forward reaction because PCl 5 (g ) is a reactant. Þ p × [ pV 2 + ap ] ( pV - bp) = p ( pV 2 ) RT
33. SO2Cl 2 (g ) r SO2 (g ) + Cl 2 (g ), But p = 0
Intercept = RT Þ ( pV )3 = ( pV )2 RT
Adding inert gas at constant volume will not affect partial
pressure of reactant or products, hence will not affect 44. (i) Mole of solid NH4HS taken initially = 3.06 = 0.06
equilibrium amount of either reactant or products. 51
34. NaNO3 (s) r NaNO2 (s) + O2 (g ) , DH > 0
1 At equilibrium NH4HS (s) r NH3 (g ) + H2S (g )
2 0.018 0.018
NaNO3 and NaNO2 are in solid state, changing their amount has 2
æ 0.018 ö -5
no effect on equilibrium. Increasing temperature will favour Kc = ç ÷ = 8.1 ´ 10
forward reaction due to endothermic nature of reaction. Also, è 2 ø
increasing pressure will favour backward reaction in which 0.018 ´ 0.082 ´ 300
p (NH3 ) = = 0.22 atm
some O2 (g ) will combine with NaNO2 (s) forming NaNO3. 2
35. C2H4 + H2 r C2H6, DH = - 32.7 kcal K p = (0.22)2 = 4.84 ´ 10- 2
The above reaction is exothermic, increasing temperature will (ii) Addition of solid NH4HS will have no effect on equilibrium.
45. (a) PCl 5 (g ) r PCl 3 (g ) + Cl 2 (g ) Total moles
favour backward reaction, will increase the amount of C2H4.
Decreasing pressure will favour reaction in direction containing
more molecules (reactant side in the present case). Therefore, 1- a a a 1+ a
decreasing pressure will increase amount of C2H4. 208.5
Removing H2 , which is a reactant, will favour reaction in Average molar mass = = 148.9
1.4
backward direction, more C2H4 will be formed.
Adding C2H6 will favour backward reaction and some of the pM 1 ´ 148.9
r (density) = = = 4.54 g/L
C2H6 will be dehydrogenated to C2H4. RT 0.082 ´ 400
K
36. Smaller : K p = c (b) AgCl (s) + 2NH3 (aq) r [ Ag(NH3 )+2 ] + Cl -
RT -x 1 - 2x x x
37. changing pressure has no effect on equilibrium constant. K sp æ x ö
2
K = = 2.9 ´ 10- 3 = çç ÷÷
38. K p = K c (RT )Dn, where, Dn = Sn (products) - Sn (reactants) Kc è 1 - 2x ø
39. Rate of any reaction increases on rising temperature. x = 0.049 M
0.07 4a 2 4 (0.25)2
(i) Partial pressures : CO = ´ 8.5 Kp = 2
p= = 0.26 atm
0.34 1- a 1 - (0.25)2
0.18 When p = 0.10 atm
H2 = ´ 8.5
0.34 4 a 2 (0.1)
0.26 = Þ a = 0.62
0.08 1 - a2
CH3OH = ´ 8.5
51. SO2 (g ) + NO2 (g ) r SO3 (g ) + NO (g )
0.34
2
0.08 æ 0.34 ö x
Kp = ´ ç ÷ = 0.056 1- x 1- x x
(0.07) (0.18)2 è 8.5 ø
Qc = 1 < K c , i.e. reaction proceed in forward direction to attain
0.08
(ii) Concentrations : [CH3OH] = = 0.032 M equilibrium.
2.5 2
0.18 æ x ö
[H2 ] = = 0.072 M 16 = çç ÷÷ Þ x = 0.80
2.5 è 1- x ø
0.07 [NO] = 0.80 M, [NO2 ] = 0.20 M
[CO] = = 0.028 M
2.5
0.032 52. A2 (g ) + B2 (g ) r 2 AB (g ) Dn = 0
Kc = = 213.33
(0.028) (0.072)2 [ AB ]2 (n )2 (2x )2
K = = AB =
CO (g ) + 2H2 (g ) r CH3OH (g )
[ A2 ][ B2 ] nA2 × nB 2 (1 - x ) (2 - x )
48.
4 x2
Mole : 0.2 – 0.10 x - 0.20 0.10 Þ Total moles = x Þ 50 = 2
Þ 23x 2 - 75x + 50 = 0
4.92 ´ 5 x - 3x + 2
Þ x= = 0.5
0.082 ´ 600 752 - 4 ´ 23 ´ 50
75 ±
Þ x= = 0.93, 2.32
Þ moles of H2 at equilibrium = x - 0.2 = 0.3 46
0.1 0.3 2.32 is not acceptable because x cannot be greater than 1.
Partial pressures : CO = p, H2 = p,
0.5 0.5
Mole of AB = 2x = 2 ´ 0.93 = 1.86
0.1
CH3OH = p pV 2.05 ´ 100
0.5 53. Total moles of gases at equilibrium = = = 5.0
p RT 0.082 ´ 500
5 25 25 Out of this 5 moles, 1.0 mole is for N2 (g ) and remaining 4 moles
Kp = 2
= 2= = 0.11 atm - 2
æ pö æ 3 ö 9p 9 (4.92)2 for PCl 5 and its dissociation products.
ç ÷ ç p÷
è 5ø è 5 ø PCl 5 r PCl 3 + Cl 2
3-x x x
0.1 0.3
Concentrations : [CO] = M , [H2] = M, 3+ x = 4 Þ x =1
5 5
0.1 (0.1/ 5) 1
[CH3OH] = M Þ Kc = = 277.77 M -2. Degree of dissociation = = 0.33
5 (0.1/ 5) (0.3 / 5)2 3
r
2SO2 (g ) + O2 (g ) r SO3 (g )
54. N2 + 3H2 2NH3
49.
Initial : 1.0 3.0 0
Initial pi : 0 2 1 Equilibrium 1 – 0.25 3 – 0.75 0.05
Equilibrium pi : 2p 2+ p 1- 2p = 0.75 = 2.25
(1 - 2 p)2 0.75 2.25 0.50
Kp = 900 = [Ignoring p in comparison to 2] [N2 ] = , [H2 ] = , [NH3 ] =
(2 + p) (2 p)2 4 4 4
94 Chemical and Ionic Equilibrium
and OH- ions will also increase. As a result, the value of ionic
Q K sp is very small, we neglect S ¢ against S in Eq. (i)
product, [H+ ] ´ [ OH- ] will be increased. e.g.
\ . )2 S ¢
K sp = (01
Temperature K w (mol/L2) or 8 ´ 10- 12 = 0.01 S ¢
-14
5ºC 0186
. ´ 10 or S ¢ = 8 ´10- 12 ´ 102 = 8 ´ 10- 10 M
25ºC 1008
. ´ 10-14 Thus, molar solubility of Ag2CO3 in 0.1 M
45ºC 4.074 ´ 10 -14 AgNO3 is 8 ´ 10- 10 M.
Hence, the option (b) is correct. 7. The reaction takes place when H2SO4 is added to NH4OH is as
follows :
In statement (III), for a weak monobasic acid HA
H2SO4 + 2NH4OH ¾® (NH4 )2 SO4 + 2H2O
HA - HÅ + A s
Strong acid Weak base Salt of strong acid
(1 - a) C M aC M aC M
+ weak base
Þ pH of the solution is 5, i.e. Millimoles at t = 0 20 ´ 0.1 = 2 30 ´ 0.2 = 6 0
[H+ ] = 10-5 M = aC Millimoles at t = t 0 2 2
So, the resulting solution is a basic buffer
aC ´ aC 10-5 ´ a
Þ Ka = = [NH4OH + (NH4 )2 SO4 ].
(1 - a )C 1- a
According to the Henderson’s equation,
10-5 ´ a [(NH4 )2SO4 ]
Þ 10-5 = pOH = pK b + log
1- a [NH4OH]
Þ a = 0.5 2
Þ a % = 50 = 4.7 + log = 4.7
2
Hence, the option (c) is correct. Þ pH = 14 - pOH = 14 - 4.7 = 9.3
96 Chemical and Ionic Equilibrium
8. Its given that the final volume is 500 mL and this final volume SiCl 4 - Although this compound does not have incomplete octet
was arrived when 50 mL of 1 M Na 2SO4 was added to unknown but it shows the tendency to accept lone pair of electrons in its
Ba 2+ solution. vacant d-orbital. This tendency of SiCl 4 is visible in following
reaction.
So, we can interpret the volume of unknown Ba 2+ solution as
450 mL i.e. Cl Cl
450mL + 50mL ¾® 500mL H
Ba 2+ Na 2SO 4 BaSO 4 Si + H2O Si O
solution solution solution
Cl Cl Cl Cl H
From this we can calculate the concentration of SO2- Cl Cl
4 ion in the
solution via Lone pair acceptance
M 1V1 = M 2V2 in d-orbital
1 ´ 50 = M 2 ´ 500 Cl
(as 1M Na 2SO4 is taken into consideration) Si OH + HCl
1 Cl
M2 = . M
= 01 Cl
10
Now for just precipitation, Thus, option (b) and (d) both appear as correct but most suitable
answer is (d) as the condition of a proper Lewis acid is more well
Ionic product = Solubility product (K sp )
defined in BCl 3 and AlCl 3.
i.e. [Ba 2+ ][SO24- ] = K sp of BaSO4
10. Among the given salts
Given K sp of BaSO4 = 1 ´ 10-10 FeCl 3 is acidic in nature i.e., have acidic solution as it is the salt
So, [Ba 2+ ][0.1] = 1 ´ 10-10 of weak base and strong acid.
Al(CN) 3 and Pb(CH 3COO) 2 are the salts of weak acid and
or [Ba 2+ ] = 1 ´ 10-9 M weak base.
Remember This is the concentration of Ba 2+ ions in final CH 3COOK is the salt of strong base and weak acid.
solution. Hence, for calculating the [Ba 2+ ] in original solution Hence, the solution of CH3COOK will be most basic because of
we have to use the following reaction.
M 1V1 = M 2V2 CH3COOK + H2O - CH3COOH + KOH
(Strong base)
as M 1 ´ 450 = 10-9 ´ 500 (Weak acid)
so, M 1 = 1.1 ´ 10-9 M 11. For a salt of weak acid and weak base,
1 1
9. Key Idea Lewis acids are defined as, pH = 7 + pKa - pKb
2 2
‘‘Electron deficient compounds which have the ability to
accept atleast one lone pair.’’ Given, pK a (HA ) = 3.2, pK a ( BOH) = 3.4
The compound given are 1 1
\ pH = 7 + (3.2) - (3.4)
PH 3-Octet complete although P has vacant 3d-orbital but does 2 2
not have the tendency to accept lone pair in it. Hence, it cannot
= 7 + 1.6 - 1.7 = 6. 9
be considered as Lewis acid.
BCl 3-Incomplete octet with following orbital picture. 12. pH = 1 \ [ H+ ] = 10-1 = 0.1 M
1s 2s 2p Vacant pH = 2 \ [ H+ ] = 10-2 = 0.01 M
p- orbital
B- For dilution of HCl, M 1V1 = M 2V2
0.1 ´ 1 = 0.01 ´ V2
Used in bond V2 = 10 L
formation with
Cl having one electron Volume of water to be added = 10 - 1 = 9 L
each from B and Cl
13. MX : K sp = S 2 = 4 ´ 10- 8
Hence, vacant p-orbital of B can accept one lone pair thus it can
be considered as Lewis acid. Þ S = 2 ´ 10- 4
AlCl 3-Similar condition is visible in AlCl3 as well i.e. MX 2 : K sp = 4 S 3 = 3.2 ´ 10- 14 Þ S = 2 ´ 10- 5
Al ( Valence orbital only) =
M3X : K sp = 27S 4 = 2.7 ´ 10- 15 Þ S = 10- 4
Vacant p-orbital
3s 3p 3d vacant Order of solubility is MX > M 3 X > MX 2
2
14. mmol of base = 2.5 ´ = 1
Used in bond 5
formation with Cl
mmol of acid required to reach the end point = 1
Hence this compound can also be considered as Lewis acid.
Chemical and Ionic Equilibrium 97
K w 10- 14 Kh 10- 9 28. When a weak acid (HX) is titrated against a strong base
16. K h ( X - ) = = - 5 = 10- 9 Þ a = = = 10- 4
Ka 10 C 0.10 NaOH, basic salt (NaX) is present at the end point which
% hydrolysis = 100 a = 0.01 makes end point slightly basic with pH around 8. Hence,
phenolphthalein, that changes its colour in this pH range,
17. Minimum S2- concentration would be required for precipitation would be the best choice of indicator to detect the end point.
of least soluble HgS.
For HgS, S2- required for precipitation is 29. The reaction of HA with strong base is
K sp 10-54 HA + OH- r H2O + A -
[S2- ] = = = 10-51 M
[Hg2+ ] 10-3 [ A- ] [H+ ] K a 10- 4
K = ´ = = = 1010
18. Alkali metal salts are usually more soluble than the salts of [HA ][OH- ] [H+ ] K w 10- 14
transition metals. Also, CuS is less soluble than ZnS because of Kw
3d 9 configuration of Cu 2+ . Therefore, solubility order is 30. K a (HX ) = = 10- 4
Kb
Na 2S > ZnS > CuS
[X -]
19. Ap Bq r pA + qB pH = pK a + log
[HX ]
pS qS
Þ pK a = 4 [Q [ X - ] = [HX ]]
K sp = ( pS ) (qS )q = S (p + q) × pp × qq
p
33. The order of acidic strength of conjugate acids is K a = 1´10-8 Þ Ksp = 2 ´10-10
HOCl < HClO2 < HClO3 < HClO4 after putting the values in above formula
Reverse is the order of basic strength of their conjugate base, i.e. æ 10-3 ö
Solubility = 2 ´ 10-10 çç -8 + 1÷÷ » 2 ´10-5 = 4.47 ´ 10-3M
ClO- is the strongest base.
è 10 ø
34. K w = [H3O+ ][OH- ] = 10- 6 ´ 10- 6 = 10- 12 Hence, the value of y= 4.47
35. No matter, what is the concentration of HCl, its pH will always 41. For P, i.e. (10 mL of 0.1 M NaOH + 20 mL of 0.1 M acetic
be less than 7 at 25°C. In the present case, the solution is very acid) is diluted to 60 mL
dilute, pH will be between 6 and 7. The correct match is 1, i.e. the value of [H+] does not change on
36. PLAN In presence of common ion (in this case Ag + ion) solubility of dilution due to the formation of following buffer.
sparingly soluble salt is decreased. - +
NaOH + CH 3COOH - CH COO Na
3 + H 2O
Let solubility of Ag2CrO4 in presence of 0.1 M
Initial millimol 1 2
AgNO 3 = x
Ag2CrO4 a 2 Ag+ + CrO24-
Final millimol 1 1
Final volume – 30 mL (20 + 10) in which millimoles of
2x x
CH3COOH and CH3COO -Na + are counted.
AgNO3 a Ag+ + NO-3
0.1 0.1 For Q, i.e. (20 mL of 0.1 M NaOH + 20 mL of 0.1 M
+
Total [ Ag ] = (2x + 0.1) M » 0.1 M CH3COOH) is diluted to 80 mL
as x <<< 0.1 M The correct match is 5, i.e. the value of [H+] changes to
[CrO 2-
4 ]= xM 2 times of its initial value on dilution.
Thus, [Ag+ ]2 [CrO24- ] = K sp As per the condition given in Q the resultant solution before
dilution contain 2 millimoles of CH3COO -Na+ in 40 mL
(0.1)2 (x ) = 1.1 ´ 10-12
solution. Hence, it is the salt of weak acid and strong base. So,
Q x = 1.1 ´ 10-10 M KW K a
[H + ]initial =
37. In HNO3 and CH3COONa combination, if HNO3 is present in C
limiting amount, it will be neutralised completely, leaving C
After dilution to 80 mL, the new ‘C ’ becomes , So,
behind some excess of CH3COONa. 2
+ K wK a +
CH3COONa + HNO3 ¾® CH3COOH + NaNO3 [H ]new = or [H ] initial ´ 2
C /2
Buffer combination For R, i.e. (20 mL of 0.1 M HCl + 20 mL of 0.1 M NH 3) is
38. CH3COOH + CH3COONa = Buffer solution diluted to 80 mL
1
CH3COONa + HCl ¾® CH3COOH + NaCl The correct match is 4, i.e. the value of[H+] changes to times
2
If HCl is taken in limited quantity, final solution will have both of its initial value of dilution.
CH3COOH and CH3COONa needed for buffer solution.
As per the condition given in R the resultant solution before
Ammonia and ammonium chloride forms basic buffer. dilution contains 2 millimoles of NH4Cl in 40 mL of solution.
Hence, a salt of strong acid and weak base is formed.
39. pH of 10- 8 M solution will be between 6 and 7 but never 8. The
For this,
conjugate base of an acid is formed by removing a proton (H+ )
Kw ´ C
from acid. Therefore, HPO2- -
4 is a conjugate base of H 2PO 4 . [H+]initial =
Kb
H2O r H+ + OH- DH > 0 Now on dilution upto 80 mL new conc. becomes C /2.
Increasing temperature will increase equilibrium constant of the C
Kw ´
above endothermic reaction. + 2
So, [H ]new =
At the mid-point of titration pH = pK a Kb
1
40. Key Idea Solubility of salt of weak acid (AB) in presence or [H+]new = [H + ]initial ´
+
of H ions from buffer solution can be calculated with the 2
help of following formula. For S , i.e. 10 mL saturated solution of Ni(OH)2 in
é[H+ ] ù equilibrium with excess solid Ni(OH)2 is diluted to 20 mL
Solubility = K sp ê + 1ú and solid Ni(OH)2 is still present after dilution.
ë ka û
The correct match is 1.
Given, pH = 3, so [H+ ] = 10-3 Ni(OH)2 (s) - Ni 2+
+ 2OH-
Chemical and Ionic Equilibrium 99
as per the condition given it is a sparingly soluble salt. Hence, on 53. At the end-point, [ A - ] = 0.05
dilution the concentration of OH- ions remains constant in
saturated solution. K b ( A - ) = K w / K a = 2 ´ 10- 9
So for this solution,
[OH- ] = K bC = 2 ´ 10- 9 ´ 0.05 = 10- 5
[H+]new =[H+]initial
pOH = 5 and pH = 9
42. I2 : I- ¾® I2 = I-3
54. (i) CH3COOH r CH3COO -
+ H+
43. Hydration energy facilitate solubility. C (1 - a ) Ca Ca
44. Amphoteric If no HCl is present,
0.2
45. SO2–
4 Conjugate base is formed by removing a proton from acid. [HCl] = = 0.10 M
2
46. P2O5 is strongest acid and MgO is strongest base. [CH3COOH] = 0.10 M
The major contributor of H+ in solution is HCl.
47. NaOH + H2O ¾® NaOH (aq); DH < 0
C a (0.1)
Ka = = 1.75 ´ 10- 5
48. Lewis acid accept lone pair of electron. C (1- a )
^m a = 1.75 ´ 10- 4
49. Degree of ionisation (a) =
^¥ 6
X (ii) mmol of NaOH added = ´ 1000 = 150
Let ^ m (HY ) = x Þ ^ m (HX ) = 40
10
mmol of HCl = 500 ´ 0.2 = 100
^ m (HX ) 1 a (HX )
Þ = = [Q ^ ¥ (HX ) = ^ ¥ (HY )] mmol of CH3COOH = 500 ´ 0.2 = 100
^ m ( XY ) 10 a (HY )
After neutralisation, mmol of CH3COOH = 50
Also : K a(HX ) = (0.01) [ a( HX )]2 ...(i) mmol of CH3COONa = 50
2
K a (HY ) = (010
. ) [ a( HY )] pH = pK a = 4.75
. [10 a (HX )]2 = 10 [ a (HX )]2
= 010 ... (ii) 55. Partial pressure of SO2 in air = 10- 5 atm
K a (HX ) 0.01 1 [SO2 ]aq = 1.3653 ´ 10- 5 mol L- 1
Þ = =
K a (HY ) 10 1000
Q pK a = 1.92 and concentration of H2SO3 is very low, it is
Þ log K a (HX ) - log K a (HY ) = - 3 almost completely ionised as
Þ - log K a (HX ) - [ - log K a (HY )] = 3 H2SO3 r H+ + HSO-3
Þ pK a (HX ) - pK a (HY ) = 3 [H+ ] = 1.3653 ´ 10- 5 M
50. It is a case of simultaneous solubility of salts with a common ion. pH = – log (1.3653 ´ 10- 5 ) = 4.86
Here, solubility product of CuCl is much greater than that of
AgCl, it can be assumed that Cl– in solution comes mainly from 56. In water, K sp = 4 S 3 = 4 (6.7 ´ 10- 6 )3
CuCl.
= 1.2 ´ 10- 15
[ Cl – ] = K sp (CuCl) = 10–3 M
In buffer of pH = 8, pOH = 6, [OH- ] = 10-6
–10 + –
Now, for AgCl, K sp = 1.6 × 10 = [Ag ] [Cl ]
K sp = S [OH- ] 2
+ –3
= [Ag ] × 10
1.2 ´ 10- 15
Þ [Ag+] = 1.6 × 10–7 S = = 1.2 ´ 10- 3 M
10- 12
51. Basic salts solution will have pH > 7, will change colour of
[Ag+ ] anode
litmus paper red to blue 57. (a) E = 0.164 = – 0.059 log
0.10
KCN, K2CO3 and LiCN are the only basic salts among these.
+ -4
[Ag ] anode = 1.66 ´ 10 M
52. The hydrolysis reaction is
A - + H2O r AH + OH- [CrO24- ] =
[Ag+ ]
= 8.3 ´ 10- 5 M
2
Kw
Kh = = 10- 10 K sp = [Ag+ ]2 [CrO24- ]
Ka
[OH- ] = K hC = 10- 6 = (1.66 ´ 10- 4 )2 (8.3 ´ 10- 5 )
-
[In ] S = 0.022 M
59. pH = pK In + log 10 = pK In + 1 When = 10
[HIn]
mmol of Ca(OH)2 in 500 mL saturated solution = 11
[In - ]
= pK In + log (0.1) = pK In -1 When = 0.1 mmol of NaOH in 500 mL 0.40 M solution = 200
[HIn]
Total mmol of OH- = 200 + 2 ´ 11 = 222
pH range is pK In -1 to pK In + 1.
K sp 1 pH = 4.15
solubility of Mg(OH)2 = ´
[Mg2+ ] 2 Kw 10- 14
[OH- ] = =
[H+ ] 7 ´ 10- 5
= 1.5 ´ 10- 5 mol L- 1
= 1.5 ´ 10- 5 ´ 58 g L- 1 = 1.43 ´ 10- 10 M
= 8.7 ´ 10- 4 g L- 1 77. Sodium acetate (CH3COONa) is a basic salt (salt of strong base
74. HCOOH r H+ + HCOO-
and weak acid) therefore, its aqueous solution has pH > 7.
78. mmol of NaOH = 20 ´ 0.2 = 4
HCOONa r Na + + HCOO-
1 - 0.75 0.75 mmol of acetic acid = 50 ´ 0.2 = 10
After neutralisation, buffer solution is formed which contain 6
In the above buffer solution, the significant source of formate
ion (HCOO- ) is HCOONa. Hence, mmol CH3COOH and 4 mmol CH3COONa.
[CH3COONa]
K a = 2.4 ´ 10- 4 pH = pK a + log
[CH3COOH]
[H+ ] (0.75) 4
= = - log (1.8 ´ 10- 5 ) + log = 4.56
[HCOOH] 6
2.4 ´ 10- 4 ´ 0.20 Now, let x mmol of NaOH is further added so that pH of the
[H+ ] = = 6.4 ´ 10- 5 resulting buffer solution is 4.74.
0.75
pH = – log (6.4 ´ 10-5 ) = 4.20 Now, the buffer solution contains (4 + x ) mmol CH3COONa
and (6 - x ) mmol of CH3COOH.
76. K sp (AgI) = 8.5 ´ 10- 17 = [Ag+ ][I- ] 4+x
4.74 = - log (1.8 ´ 10- 5 ) + log
6-x
[I- ] required to start precipitation of AgI
8.5 ´ 10- 17 4+x
= = 8.5 ´ 10- 16 M Þ =1
0.10 6-x
K sp (HgI2 ) = 2.5 ´ 10- 26 = [Hg2+ ][I- ]2 Þ x = 1.0 mmol = 0.2 ´ V
-
[I ] required to start precipitation of HgI2 Þ V = 5.0 mmol NaOH.
11. The reaction, MgO( s ) + C( s ) ® Mg( s ) + CO( g ), 18 The entropy change associated with the conversion of 1 kg
for which Dr H º = + 491.1 kJ mol- 1 and of ice at 273 K to water vapours at 383 K is
-1 -1
Dr S º = 198.0 JK mol , is not feasible at 298 K. (Specific heat of water liquid and water vapour are 4.2 kJ
K -1kg-1 and 2.0 kJK -1 kg-1; heat of liquid fusion and
Temperature above which reaction will be feasible is
(a) 2040.5 K (b) 1890.0 K vapourisation of water are 334 kJ kg-1 and 2491 kJkg-1
(c) 2380.5 K (d) 2480.3 K respectively). (log 273 = 2.436, log 373 = 2.572,
12. The standard reaction Gibbs energy for a chemical reaction log 383 = 2.583 ) (2019 Main, 9 Jan II)
-1 -1
at an absolute temperature T is given by, Dr G º = A - BT (a) 9.26 kJ kg K (b) 8.49 kJ kg-1K -1
Where A and B are non-zero constants. (c) 7.90 kJ kg-1K -1 (d) 2.64 kJ kg-1K -1
Which of the following is true about this reaction?
19 Consider the reversible isothermal expansion of an ideal gas
(2019 Main, 11 Jan II)
in a closed system at two different temperatures T1 and T2
(a) Endothermic if, A < 0 and B > 0
(T1 < T2 ). The correct graphical depiction of the dependence
(b) Exothermic if, B < 0
of work done (W) on the final volume (V) is
(c) Exothermic if, A > 0 and B < 0 (2019 Main, 9 Jan I)
(d) Endothermic if, A > 0 T2 T2
|W| |W|
13. For the chemical reaction, X - Y , the standard reaction T1
T1
Gibbs energy depends on temperature T (in K) as
3 (a) (b)
DrG ° (in kJ mol–1 ) = 120 - T
8
The major component of the reaction mixture at T is O ln V O ln V
(2019 Main, 11 Jan I)
(a) Y if T = 280 K (b) X if T = 350 K |W| T2 |W| T2
(c) X if T = 315 K (d) Y if T = 300 K
T1 T1
14. Two blocks of the same metal having same mass and at
temperature T1 and T2 respectively, are brought in contact (c) (d)
with each other and allowed to attain thermal equilibrium at
constant pressure. The change in entropy, DS , for this O ln V O ln V
process is (2019 Main, 11 Jan I)
é 1/ 2 ù
(T + T2 ) éT1 + T2 ù 20. The combustion of benzene ( l ) gives CO2 ( g ) and H2 O( l ).
(a) 2 C p lnê 1 2
ú (b) C p lnê ú
êë T T
1 2 úû ë 4T1T2 û Given that heat of combustion of benzene at constant volume
is -3263.9 kJ mol -1 at 25° C; heat of combustion (in kJ
é (T + T2 )2 ù éT + T2 ù
(c) C p lnê 1 ú (d) 2 C p lnê 1 ú mol -1 ) of benzene at constant pressure will be
êë 4T1T2 úû ë 2T1T2 û (R = 8.314 JK -1 mol -1 ) (2018 Main)
15. The process with negative entropy change is (a) 4152.6 (b) -452.46
(2019 Main, 10 Jan II) (c) 3260 (d) -3267.6
(a) synthesis of ammonia from N 2 and H 2
21. DU is equal to (2017 Main)
(b) dissociation of CaSO4(s) to CaO(s) and SO3 ( g )
(a) isochoric work (b) isobaric work
(c) dissolution of iodine in water
(c) adiabatic work (d) isothermal work
(d) sublimation of dry ice
22. The standard state Gibbs free energies of formation of
16. An ideal gas undergoes isothermal compression from 5 m 3
3 -2 C(graphite) and C(diamond) at T = 298 K are
to 1 m against a constant external pressure of 4 Nm . Heat
released in this process is used to increase the temperature D f G °[C(graphite)] = 0 kJ mol -1
of 1 mole of Al. If molar heat capacity of Al is 24 J mol-1 K -1 ,
D f G °[C(diamond)] = 2.9 kJ mol -1
the temperature of Al increases by (2019 Main, 10 Jan II)
3 2 The standard state means that the pressure should be 1 bar,
(a) K (b) 1 K (c) 2 K (d) K
2 3 and substance should be pure at a given temperature. The
conversion of graphite [C(graphite)] to diamond
17 A process has DH = 200 J mol -1 and DS = 40 JK -1 mol -1 .
[C(diamond)] reduces its volume by 2 ´ 10-6 m 3 mol -1 . If
Out of the values given below, choose the minimum
C(graphite) is converted to C(diamond) isothermally at
temperature above which the process will be spontaneous
(2019 Main, 10 Jan I) T = 298K, the pressure at which C(graphite) is in
(a) 20 K (b) 4 K (c) 5 K (d) 12 K equilibrium with C(diamond), is (2017 Adv.)
Thermodynamics and Thermochemistry 105
23. One mole of an ideal gas at 300 K in thermal contact with (a) + 100 eu (b) +60 eu
surroundings expands isothermally from 1.0 L to 2.0 L (c) –100 eu (d) –60 eu
against a constant pressure of 3.0 atm. 30. A monoatomic ideal gas undergoes a process in which the
In this process, the change in entropy of surroundings ratio of p to V at any instant is constant and equals to 1. What
( DS surr ) in JK -1 is (1 L atm = 101.3 J) (2016 Adv.) is the molar heat capacity of the gas ? (2006, 3M)
(a) 5.763 (b) 1.013 (c) - 1.013 (d) - 5.763 4R 3R 5R
(a) (b) (c) (d) 0
2 2 2
24. The following reaction is performed at 298K
2NO( g ) + O2 ( g ) r 2NO2 ( g )
31. One mole of monoatomic ideal gas expands adiabatically at
initial temperature T against a constant external pressure of
The standard free energy of formation of NO(g) is
1 atm from 1 L to 2 L. Find out the final temperature
86.6 kJ/mol at 298 K. What is the standard free energy of
(R = 0.0821 L atm K - 1 mol - 1 ) (2005, 1M)
formation of NO2 ( g ) at 298 K? ( K p = 1.6 ´ 1012 ) (2015 Main) T
(a) T (b)
(a) R( 298 ) ln (1. 6 ´ 1012 ) – 86600 ( 2 )5 / 3 - 1
(b) 86600 + R( 298 ) ln (1. 6 ´ 1012 ) 2 2
(c) T - (d) T +
ln (1. 6 ´ 1012 ) 3 ´ 0.082 3 ´ 0.082
(c) 86600 –
R ( 298 ) 32. 2 moles of an ideal gas expanded isothermally and
12 reversibly from 1 L to 10 L at 300 K. What is the enthalpy
(d) 0. 5 [ 2 ´ 86600 – R ( 298 ) ln (1. 6 ´ 10 )]
change? (2004, 1M)
25. For the process, H2 O ( l ) ¾® H2 O ( g )
(a) 4.98 kJ (b) 11.47 kJ (c) –11.47 kJ (d) 0 kJ
at T = 100° C and 1 atmosphere pressure, the correct choice is
33. Spontaneous adsorption of a gas on solid surface is an
(a) DS system > 0 and DS surrounding > 0 (2014 Adv.)
exothermic process because (2004, 1M)
(b) DS system > 0 and DS surrounding < 0 (a) DH increases for system (b) DS increases for gas
(c) DS system < 0 and DS surrounding > 0 (c) DS decreases for gas (d) DG increases for gas
(d) DS system < 0 and DS surrounding < 0
34. One mole of a non-ideal gas undergoes a change of state
26. A piston filled with 0.04 mole of an ideal gas expands (2.0 atm, 3.0 L, 95 K) ¾® (4.0 atm, 5.0 L, 245 K) with a
reversibly from 50.0 mL to 375 mL at a constant temperature change in internal energy, DE = 30.0 L-atm. The change in
of 37.0°C. As it does so, it absorbs 208 J of heat. The values enthalpy ( DH ) of the process in L-atm is (2002, 3M)
of q and W for the process will be (a) 40.0 (b) 42.0
(R = 8.314 J / mol K, ln 7.5 = 2.01) (2013 Main)
(c) 44.0
(a) q = + 208 J, W = - 208 J
(d) not defined, because pressure is not constant
(b) q = - 208 J, W = - 208 J
(c) q = - 208 J, W = + 208 J 35. Which of the following statements is false? (2001, 1M)
(d) q = + 208 J, W = + 208 J (a) Work is a state function
27. For the process H2 O( l ) (1 bar, 373 K) ® H2 O( g ) (b) Temperature is a state function
(c) Change in the state is completely defined when the
(1 bar, 373 K), the correct set of thermodynamic
initial and final states are specified
parameters is (2007, 3M)
(a) DG = 0, DS = + ve (b) DG = 0, DS = - ve (d) Work appears at the boundary of the system
(c) DG = + ve, DS = 0 (d) DG = - ve, DS = + ve 36. In thermodynamics, a process is called reversible when
28. The value of log 10 K for a reaction A r B is
(2001, 1M)
(a) surroundings and system change into each other
-1
(Given : Dr H °298 K = - 54.07 kJ mol , (b) there is no boundary between system and surroundings
Dr S °298 K = 10 JK -1 mol -1 and R = 8.314 JK-1 mol-1 ; (c) the surroundings are always in equilibrium with the system
2. 303 ´ 8. 314 ´ 298 = 5705) (2007, 3M)
(d) the system changes into the surroundings spontaneously
(a) 5 (b) 10 (c) 95 (d) 100 37. For an endothermic reaction, where DH represents the
29. The direct conversion of A to B is difficult, hence it is carried enthalpy of the reaction in kJ/mol, the minimum value for
out by the following shown path the energy of activation will be (1992, 1M)
C ¾¾¾® D (a) less than DH (b) zero
¯ (c) more than DH (d) equal to DH
A B
106 Thermodynamics and Thermochemistry
38. The difference between heats of reaction at constant pressure (c) With increase in temperature, the value of K for
and constant volume for the reaction endothermic reaction increases because the entropy change
2C6 H6 ( l ) + 15O2 ¾® 12CO2 ( g ) + 6H2 O( l ) of the system is negative
(d) With increase in temperature, the value of K for exothermic
at 25° C in kJ is (1991, 1M) reaction decreases because the entropy change of the system
(a) - 7.43 (b) + 3.72 is positive
(c) - 3.72 (d) + 7.43 42. An ideal gas in thermally insulated vessel at internal
pressure = p1 , volume =V1 and absolute temperature = T1
Objective Questions II expands irreversibly against zero external pressure, as
(One or more than one correct option) shown in the diagram. The final internal pressure,
volume and absolute temperature of the gas are p2 , V2
39. A reversible cyclic process for an ideal gas is shown below.
and T2 , respectively. For this expansion
Here, p , V and T are pressure, volume and temperature,
respectively. The thermodynamic parameters q , w , H and U
pext=0
are heat, work, enthalpy and internal energy, respectively.
(2018 Adv.) pext=0 Irreversible
p1,V1,T1 p2,V2,T2
Thermal insulation
B(p2, V2, T1) (2014 Adv.)
(a) q = 0 (b) T2 = T1
Temperature (T) (c) p2V2 = p1V1 (d) p2V2g = p1V1g
The correct options is (are) 43. Benzene and naphthalene form an ideal solution at room
(a) q AC = DU BC and w AB = p2 (V2 - V1 ) temperature. For this process, the true statement(s) is (are)
(2013 Adv.)
(b) wBC = p2 (V2 - V1 ) and qBC = DH AC (a) DG is positive (b) DS system is positive
(c) DHCA < DUCA and q AC = DU BC (c) DS surroundings = 0 (d) DH = 0
(d) qBC = DH AC and DHCA > DUCA
44. The reversible expansion ob an ideal gas under adiabatic
40. An ideal gas is expanded form ( p1 , V1 , T1 ) to ( p2 , V2 , T2 ) under and isothermal conditions is shown in the figure. Which of
different conditions. The correct statement(s) among the the following statement(s) is (are) correct? (2012)
following is (are) (2017 Adv.)
(a) The work done by the gas is less when it is expanded reversibly (p1,V1,T1)
from V1 to V2 under adiabatic conditions as compared to that Iso
when expanded reversibly form V1 to V2 under isothermal the
p rma
l
Ad
conditions. ia
ba (p2,V2,T2)
(b) The change in internal energy of the gas is (i) zero, if it is tic
(p3,V3,T3)
expanded reversibly with T1 = T2, and (ii) positive, if it is
expanded reversibly under adiabatic conditions with T1 ¹ T2 V
X
constant K in terms of change in entropy is described by
(2017 Adv.)
(a) With increase in temperature, the value of K for endothermic Z
reaction increases because unfavourable change in entropy of the
surroundings decreases
(b) With increase in temperature, the value of K for exothermic V(litre)
reaction decreases because favourable change in entropy of the [Take DS as change in entropy and W as work done].
surrounding decreases
Which of the following choice(s) is (are) correct? (2012)
Thermodynamics and Thermochemistry 107
60. C p - CV for an ideal gas is ................. (b) a reversible isochoric change of state from (1.0 atm,
(1984, 1M)
40.0 L) to (0.5 atm, 40.0 L)
61. The total energy of one mole of an ideal monatomic gas at (c) a reversible isothermal compression from (0.5 atm,
27° C is ..............cal. (1984, 1M) 40.0 L) to (1.0 atm, 20.0 L)
(i) Sketch with labels each of the processes on the same
True/False p-V diagram.
62. First law of thermodynamics is not adequate in predicting (ii) Calculate the total work (W) and the total heat change
the direction of a process. (1982, 1M) (Q) involved in the above processes.
63. Heat capacity of a diatomic gas is higher than that of a (iii) What will be the values of DU, DH and DS for the
monoatomic gas. (1985, 1/2 M) overall process? (2002, 5M)
Integer Answer Type Questions 69. When 1-pentyne (A) is treated with 4 N alcoholic KOH at
175° C, it is converted slowly into an equilibrium mixture of
64. One mole of an ideal gas is taken from a to b along two paths
denoted by the solid and the dashed lines as shown in the 1.3% 1-pentyne (A), 95.2% 2-pentyne (B) and 3.5% of
graph below. If the work done along the solid line path is Ws 1, 2-pentadiene (C). The equilibrium was maintained at
and that along the dotted line path is Wd , then the integer 175° C. Calculate DG° for the following equilibria.
B r
closest to the ratio Wd / Ws is (2010)
A, DG°1 = ?
B r C,
4.5
4.0 a DG°2 = ?
3.5 From the calculated value of DG°1 and DG°2 indicate the
3.0
p 2.5 order of stability of (A), (B) and (C). Write a reasonable
(atm) reaction mechanism showing all intermediates leading to
2.0
1.5 (A), (B) and (C). (2001, 10M)
1.0
1
0.5 b 70. Show that the reaction, CO( g ) + O2 ( g ) ¾® CO2 ( g ) at
0.0 2
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 300 K, is spontaneous and exothermic, when the standard
V (L)
entropy change is -0.094 kJ mol -1 K -1 . The standard
Subjective Questions Gibbs’ free energies of formation for CO2 and CO are
–394.4 and –137.2 kJ mol -1 , respectively. (2000, 3M)
65. For the reaction, 2CO + O2 ® 2CO2 ; DH = - 560 kJ. Two
moles of CO and one mole of O2 are taken in a container of 71. A sample of argon gas at 1 atm pressure and 27° C expands
volume 1 L. They completely form two moles of CO2 , the reversibly and adiabatically from 1.25 dm3 to 2.50 dm3 .
gases deviate appreciably from ideal behaviour. If the Calculate the enthalpy change in this process CV m for argon
pressure in the vessel changes from 70 to 40 atm, find the is 12.49 JK -1 mol -1 . (2000, 4M)
magnitude (absolute value) of DU at 500 K. (1 L-atm = 0.1 kJ) 72. A gas mixture of 3.67 L of ethylene and methane on
(2006, 3M)
complete combustion at 25° C produces 6.11 L of CO2 . Find
66. 100 mL of a liquid contained in an isolated container at a out the amount of heat evolved on burning 1 L of the gas
pressure of 1 bar. The pressure is steeply increased to mixture. The heat of combustion of ethylene and methane
100 bar. The volume of the liquid is decreased by 1 mL at are - 1423 and - 891 kJ mol -1 at 25°C. (1991, 5M)
this constant pressure. Find the DH and DU . (2004, 2M)
3R 3R 73. An athlete is given 100 g of glucose (C6 H12 O6 ) of energy
67. CV value of He is always but CV value of H2 is at low
2 2 equivalent to 1560 kJ. He utilizes 50 per cent of this gained
5R energy in the event. In order to avoid storage of energy in the
temperature and at moderate temperature and more than
2 body, calculate the weight of water he would need to
5R perspire. The enthalpy of evaporation of water is 44 kJ/mol.
at higher temperature. Explain in two or three lines.
2 (1989, 2M)
(2003, 2M)
68. Two moles of a perfect gas undergo the following 74. Following statement is true only under some specific
processes : conditions. Write the conditions for that in not more than
two sentences
(a) a reversible isobaric expansion from (1.0 atm, 20.0 L)
“The heat energy q, absorbed by a gas is DH.’’ (1984, 1M)
to (1.0 atm, 40.0 L)
Topic 2 Thermochemistry
Objective Questions I (Only one correct option) 6. The standard enthalpies of formation of CO2 ( g ), H2 O( l ) and
1. Enthalpy of sublimation of iodine is glucose(s) at 25°C are - 400 kJ/mol, - 300 kJ/mol and
24 cal g -1 at 200°C. If specific heat of I2( s) and I2 (vap.) are - 1300 kJ/mol, respectively. The standard enthalpy of
combustion per gram of glucose at 25°C is (2013 Adv.)
0.055 and 0.031 cal g -1 K -1 respectively, then enthalpy of
(a) + 2900 kJ (b) - 2900 kJ
sublimation of iodine at 250°C in cal g -1 is
(c) - 16. 11 kJ (d) + 16.11 kJ
(2019 Main, 12 April I)
(a) 2.85 (b) 5.7 (c) 22.8 (d) 11.4 7. Using the data provided, calculate the multiple bond energy
(kJ mol -1 ) of a Cºº C bond C2 H2 . That energy is (take the
2. Given :
bond energy of a C ¾ H bond as 350 kJ mol -1 ) (2012)
(i) C(graphite) + O2 ( g ) ® CO2 ( g ); Dr H È = x kJ mol- 1
2C( s ) + H2 ( g ) ¾® C2 H2 ( g ) ; DH = 225 kJ mol -1
1
(ii) C(graphite) + O2 ( g ) ¾® CO2 ( g ); 2C( s ) ¾® 2C( g ) ; DH = 1410 kJ mol -1
2
H2 ( g ) ¾® 2H( g ) ; DH = 330 kJ mol -1
Dr H È = y kJ mol- 1
(a) 1165 (b) 837 (c) 865 (d) 815
1
(iii) CO ( g ) + O2 ( g ) ¾® CO2 ( g ); Dr H È = z kJ mol- 1 8. The species which by definition has zero standard molar
2
enthalpy of formation at 298 K is (2010)
Based on the above thermochemical equations, find out
(a) Br2 ( g ) (b) Cl 2 ( g )
which one of the following algebraic relationships is correct?
(2019 Main, 12 Jan II) (c) H2 O( g ) (d) CH4 ( g )
(a) y = 2 z - x (b) x = y - z 9. The bond energy (in kcal mol -1 ) of C— C single bond is
(c) z = x + y (d) x = y + z approximately (2010)
3. Given, C (graphite) + O2 ( g ) ¾® CO2 ( g ); (a) 1 (b) 10
(c) 100 (d) 1000
Dr H ° = - 393.5 kJ mol - 1
1 10. DH vap = 30 kJ/mol and DS vap = 75 Jmol –1 K –1 . Find the
H2 ( g ) + O2 ( g ) ¾® H2O( l);
2 temperature of vapour, at one atmosphere (2004, 1M)
Dr H ° = - 285.8 kJ mol - 1 (a) 400 K (b) 350 K (c) 298 K (d) 250 K
CO2 ( g ) + 2 H2O( l) ¾® CH 4( g )+2O2 ( g ); 11. Which of the following reactions defines DH f° ?
Dr H ° = + 890.3 kJ mol - 1 (2003, 1M)
(a) C(diamond) + O2 ( g ) ¾® CO2 ( g )
Based on the above thermochemical equations, the value of
1 1
Dr H ° at 298 K for the reaction, (2017 Main) (b) H2 ( g ) + F2 ( g ) ¾® HF( g )
C (graphite) + 2 H2 ( g ) ¾® CH 4( g ) will be 2 2
(c) N2 ( g ) + 3H2 ( g ) ¾® 2NH3 ( g )
(a) + 78 .8 kJ mol - 1 (b) + 144.0 kJ mol - 1 1
(d) CO ( g ) + O2 ( g ) ¾® CO2 ( g )
(c) - 74 .8 kJ mol - 1 (d) - 144.0 kJ mol - 1 2
4. The heats of combustion of carbon and carbon monoxide are 12. The DH f° for CO2 ( g ),CO( g ) and H2 O ( g ) are
-1
- 393.5 and - 283.5 kJ mol , respectively. The heat of - 393.5, - 110.5 and -241.8 kJ mol -1 respectively. The
formation (in kJ) of carbon monoxide per mole is
standard enthalpy change (in kJ mol -1 ) for the reaction
(2016 Main)
(a) 676.5 (b) -676.5 CO2 ( g ) + H2 ( g ) ¾® CO( g ) + H2 O( g ) is (2000, 1M)
(c) -110.5 (d) 110.5 (a) 524.1 (b) + 41.2
5. For the complete combustion of ethanol, (c) -262.5 (d) -41.2
C2 H 5 OH( l ) + 3O2 ( g ) ¾® 2CO2 ( g ) + 3H2 O( l ), the
amount of heat produced as measured in bomb Objective Question II
calorimeter, is 1364.47 kJ mol -1 at 25°C. Assuming (One or more than one correct option)
ideality the enthalpy of combustion, DC H, for the reaction 13. The following is/are endothermic reaction(s) (1999, 3M)
will be (R = 8.314 J K–1 mol –1 ) (2014 Main) (a) Combustion of methane
(a) - 1366. 95 kJ mol -1 (b) - 1361. 95 kJ mol -1 (b) Decomposition of water
(c) - 1460. 50 kJ mol -1 (d) - 1350. 50 kJ mol -1 (c) Dehydrogenation of ethane to ethylene
(d) Conversion of graphite to diamond
110 Thermodynamics and Thermochemistry
14. The thermal dissociation of equilibrium of CaCO3 ( s ) is Use these data to estimate the magnitude of the resonance
studied under different conditions. (2013 Adv.) energy of benzene. (1996, 2M)
CaCO3 ( s ) r CaO( s ) + CO2 ( g ) 21. The polymerisation of ethylene to linear polyethylene is
For this equilibrium, the correct statement(s) is/are represented by the reaction,
(a) DH is dependent on T n [CH2 == CH2 ] ¾® ¾[ CH2 — CH2¾
]n
(b) K is independent of the initial amount of CaCO3
(c) K is dependent on the pressure of CO2 at a given T where, n has large integral value. Given that the average
(d) DH is independent of the catalyst, if any enthalpies of bond dissociation for C == C and C ¾ C at
298 K are +590 and +311 kJ/mol respectively, calculate the
Subjective Questions enthalpy of polymerization per mole of ethylene at 298 K.
(1994, 2M)
15. In a constant volume calorimeter, 3.5 g of a gas with
molecular weight 28 was burnt in excess oxygen at 298.0 K. 22. In order to get maximum calorific output, a burner should
The temperature of the calorimeter was found to increases have an optimum fuel to oxygen ratio which corresponds
from 298.0 K to 298.45 K due to the combustion process. to 3 times as much oxygen as is required theoretically
for complete combustion of the fuel. A burner which has been
Given that the heat capacity of the calorimeter is 2.5 kJ K - 1 ,
adjusted for methane as fuel (with x litre/hour of CH4 and
the numerical value for the enthalpy of combustion of the
6x litre/hour of O2 ) is to be readjusted for butane, C4 H10 .
gas in kJ mol - 1 is (2009)
In order to get the same calorific output, what should be the
16. Diborane is a potential rocket fuel which undergoes rate of supply of butane and oxygen? Assume that losses due
combustion according to the reaction to incomplete combustion etc., are the same for both fuels
B2 H6 ( g ) + 3O2 ( g ) ¾® B2 O3 ( s ) + 3H2 O ( g ) and that the gases behave ideally. Heats of combustions:
From the following data, calculate the enthalpy change for CH4 = - 809 kJ/mol, C4 H10 = - 2878 kJ/mol (1993, 3M)
the combustion of diborane. (2000, 2M) 23. Determine the enthalpy of the reaction,
3 C3 H8 ( g ) + H2 ( g ) ® C2 H6 ( g ) + CH4 ( g ), at 25°C, using the
2B ( s ) + O2 ( g ) ¾® B2 O3 ( s ) ; DH = - 1273 kJ mol -1
2 given heat of combustion values under standard conditions.
1 Compound : H2 ( g ) CH4 ( g ) C2 H6 ( g ) C(graphite)
H2 ( g ) + O2 ( g ) ¾® H2 O ( l ) ; DH = - 286 kJ mol –1
2 DH ° (kJ/mol): -285.8 - 890.0 -1560.0 -393.0
H2 O ( l ) ¾® H2 O ( g ) ; DH = 44 kJ mol -1 The standard heat of formation of C3 H8 ( g ) is -103 kJ/mol.
(1992, 3M)
2B ( s ) + 3H2 ( g ) ¾® B2 H6 ( g ) ; DH = 36 kJ mol -1
24. Using the data (all values are in kilocalories per mol at 25° C)
17. Estimate the average S–F bond energy in SF6 . The values of given below, calculate the bond energy of C ¾ C and C ¾ H
standard enthalpy of formation of SF6 (g), S( g ) and F( g ) bonds.
are : – 1100, 275 and 80 kJ mol –1 respectively. (1999, 3M) C( s ) ¾® C( g ); DH = 172
18. From the following data, calculate the enthalpy change for H2 ( g ) ¾® 2H ( g ); DH = 104
1
the combustion of cyclopropane at 298 K. The enthalpy of H2 ( g ) + O2 ( g ) ¾® H2 O( l ); DH = - 68.0
formation of CO2 ( g ), H2 O ( l ) and propane (g) are –393.5, 2
-285.8 and 20.42 kJ mol -1 respectively. The enthalpy of C( s ) + O2 ( g ) ¾® CO2 ( g ); DH = - 94.0
isomerisation of cyclopropane to propene is -33.0 kJ mol -1 . Heat of combustion of C2 H6 = -372.0
(1998, 5M) Heat of combustion of C3 H8 = -530.0 (1990, 5M)
19. Compute the heat of formation of liquid methyl alcohol in 25. The standard enthalpy of combustion at 25° C of hydrogen,
kJ mol -1 , using the following data. Heat of vaporisation of cyclohexene (C6 H10 ) and cyclohexane (C6 H12 ) are - 241,
liquid methyl alcohol = 38 kJ/mol. Heat of formation of - 3800 and - 3920 kJ/mol respectively. Calculate the heat of
gaseous atoms from the elements in their standard states : hydrogenation of cyclohexene. (1989, 2M)
H = 218 kJ/mol, C = 715 kJ/mol, O = 249 kJ/mol. 26. An intimate mixture of ferric oxide, Fe2 O3 , and aluminium,
Average bond energies: (1997, 5M) Al, is used in solid fuel rockets. Calculate the fuel value per
C— H = 415 kJ/mol, C— O = 356 kJ/mol, gram and fuel value per cc of the mixture. Heats of
O— H = 463 kJ/mol formation and densities are as follows:
20. The standard molar enthalpies of formation of H f (Al 2 O3 ) = - 399 kcal/mol
cyclohexane (l) and benzene (l) at 25° C are -156 and H f (Fe2 O3 ) = - 199 kcal/mol
+ 49 kJ mol -1 respectively. The standard enthalpy of Density of Fe2 O3 = 5.2 g/cc, Density of Al = 2.7 g/cc
hydrogenation of cyclohexene (l) at 25° C is -119 kJ mol -1 . (1989, 2M)
Thermodynamics and Thermochemistry 111
Answers
Topic 1 Thermodynamics 56. extensive 57. zero 58. exothermic reaction
1. (c) 2. (a) 3. (b) 4. (a) 59. isolated 60. R 61. 900 62. T
5. (d) 6. (c) 7. (b) 8. (a) 63. T 64. (2) 65. (-563 kJ) 69. (12.3 kJ)
9. (a) 10. (a) 11. (d) 12. (d) 70. (-285.4 kJ)71. (- 116.4 J) 72. (49.82 kJ) 73. (318.96 g)
13. (c) 14. (c) 15. (a) 16. (d)
Topic 2 Thermochemistry
17. (c) 18. (a) 19. (c) 20. (d)
1. (c) 2. (d) 3. (c) 4. (c)
21. (c) 22. (c) 23. (c) 24. (d)
5. (a) 6. (c) 7. (d) 8. (b)
25. (b) 26. (a) 27. (a) 28. (b)
9. (c) 10. (a) 11. (b) 12. (b)
29. (b) 30. (a) 31. (c) 32. (d)
13. (b,c,d) 14. (a, b, c, d) 15. (9 kJ) 16. (-2035 kJ)
33. (c) 34. (c) 35. (a) 36. (c)
17. (309.16 kJ) 18. (-2091.32 kJ) 19. (-116.4 kJ)
37. (c) 38. (a) 39. (b,c) 40. (a, c, d)
20. (-152 kJ/mol) 21. (-32 kJ/mol)
41. (a, b) 42. (a,b,c) 43. (b,c,d) 44. (a,c,d) 22. (5.46 xL/h) 23. (-55 kJ)
45. (a,c) 46. (c,d) 47. (a,c,d) 48. (b, d) 25. (-121 kJ/mol) 27. (-372 kcal/mol)
49. (b) 50. (d) 51. (b) 52. (b) 28. (-22 kcal/mol) 29. (-41.7 kcal)
53. (c) 54. A ® r, t; B ® p, q, s; C ® p, q, s; D ® p,q, s, t 30. (54.2 kcal) 31. (-41.4 kcal)
55. A ® p, r, s; B ® r, s; C ® t; D ® p, q, t 32. (121.31 kcal) 33. (1 kJ/mol) 34. (4.7)
Hints & Solutions
Topic 1 Thermodynamics 5. q (heat) and W (work) represents path functions. These variables
1. Key Idea Work done during isothermal expansion of an are path dependent and their values depends upon the path
ideal gas is given by the equation. followed by the system in attaining that state. They are inexact
differentials whose integration gives a total quantity depending
W = - pext (V2 - V1 )
upon the path.
According to the given conditions, the expansion is against Option (a), i.e. q + W and option (d), i.e. H–TS are state
constant external pressure. So, the work done is given by functions. The value of state functions is independent to the way
following formula; in which the state is attained. All the state functions are exact
differentials and cyclic integration involving a state functions is
W = - pext (V2 - V1 )
zero.
= - 1bar (10L - 1L) = - 9 L bar (Q 1L bar =100J)
6. Given,
= -9 ´ 100 J = -0.9 kJ n = 5 mol, T2 = 200 K, T1 = 100 K
2. CV = 28 JK -1mol-1
Key Idea The relation between DH and DU is
DH = DU + DngRT DU = nCV DT
where, Dng = Snp - SnR = nCV (T2 - T1 )
= number of moles of gaseous products - number of = 5 mol ´ 28 JK -1mol-1 ´ (200 - 100) K
moles of gaseous reactants. = 14 ,000 J = 14 kJ
The general combustion reaction of a hydrocarbon is as follows : DpV = nRDT
æ yö y = nR (T2 - T1 )
CxH y + ç x + ÷ O2 ¾® xCO2 + H2O = 5 mol ´ 8 JK -1mol-1 ´ (200 - 100) K
è 4ø 2
For heptane, x = 7, y = 16 = 4000 J = 4 kJ
Þ C7H16 (l ) + 11O2(g ) ¾® 7CO2(g ) + 8H2O(l ) 7. From the 1st law of thermodynamics,
\ Dng = 7 - 11 = - 4 DU = q + W
Now, from the principle of thermochemistry, where, DU = change in internal energy
DH = DU + DngRT q = heat
Þ DH - DU = DngRT = - 4RT W = work done
The above equation can be represented for the given processes
3. A process will be spontaneous when its free energy (Gibb’s
involving ideal gas as follows:
energy) change will be negative, i.e. DG < 0.
(a) Cyclic process For cyclic process, DU = 0
Spontaneity of a process is decided by the value of DG, which
can be predicted from the Gibb’s equation, DG = DH - TDS for \ q = -W
positive/negative signs of DH and DS at any/higher/lower Thus, option (a) is correct.
temperature as: (b) Adiabatic process For adiabatic process,
q=0
DH DS Comment on DG Comment on the \ DU = W
temperature process Thus, option (b) is incorrect.
(T)
(c) Isochoric process For isochoric process, DV = 0.
<0 >0 at any temp. <0 spontaneous Thus, W =0 (QW = pDV ).
>0 <0 at any temp. >0 non-spontaneous \ DV = q
<0 <0 at lower temp. <0 spontaneous Thus, option (c) is correct.
>0 >0 at higher temp. <0 spontaneous (d) Isothermal process For isothermal process, DU = 0
\ q = -W
4. In the given system, during the compression of a spring the Thus, option (d) is correct.
workdone is 10 kJ and 2 kJ of heat is escaped to the
surroundings. So, q = - 2 kJ and W = 10 kJ 8. According to Kirchoff’s relation,
T2
According to the first law of thermodynamics,
DH = n ò C p dT …(i)
DU = q + W = - 2 kJ + 10 kJ
T1
DU = 8 kJ
where, DH = Change in enthalpy.
The change in internal energy, DU (in kJ) is 8 kJ. C p = Heat capacity at constant pressure.
Thermodynamics and Thermochemistry 113
20. Key idea Calculate the heat of combustion with the help of 24. For the given reaction,
following formula 2NO(g ) + O2 (g ) s 2NO2 (g )
DH p = DU + DngRT °
Given, DG (NO) = 86.6 kJ/mol
f
where, DH p = Heat of combustion at constant pressure
DU = Heat at constant volume (It is also called DE) DG °f (NO2 ) = ?
Dng = Change in number of moles (In gaseous state).
K p = 1.6 ´ 1012
R = Gas constant; T = Temperature.
Now, we have,
From the equation, DG ° = 2DG ° - [ 2DG °f (NO) + DG °f (O ) ]
f f (NO )
15 2 2
C6H6( l ) + O2( g ) ¾® 6CO2( g ) + 3H2O( l )
2 = - RT lnK p = 2DG °f (NO ) - [ 2 ´ 86,600 + 0 ]
2
Change in the number of gaseous moles i.e. 1
15 3 DG ° f (NO ) = [ 2 ´ 86600 - R ´ 298 ln (1.6 ´ 1012 )]
Dng = 6 - = - or -15. 2 2
2 2
DG °f (NO = 0.5 [ 2 ´ 86,600 - R ´ (298)ln (1.6 ´ 1012 )]
Now we have Dng and other values given in the question are 2)
DU = - 3263.9 kJ/mol 25. PLAN This problem is based on assumption that total entropy change
T = 25° C = 273 + 25 = 298 K of universe is zero.
R = 8.314 JK-1mol -1 At 100°C and 1 atmosphere pressure,
So, DH p = (-3263.9) + (-15
. ) ´ 8.314 ´ 10 -3
´ 298 H2O (l ) r H2O(g ) is at equilibrium.
-1
For equilibrium, DS total = 0
= - 3267.6 kJ mol and DS system + DS surrounding = 0
21. According to first law of thermodynamics, As we know during conversion of liquid to gas entropy of
DU = q + W = q - pDV system increases, in a similar manner entropy of surrounding
decreases.
In isochoric process (DV = 0), DU = q
\ DS system > 0 and DS surrounding < 0
In isobaric process (Dp = 0), DU = q
In adiabatic process (q = 0), DU = W 26. The process is isothermal expansion, hence
In isothermal process (DT = 0) and DU = 0 q= -W
\ DU is equal to adiabatic work. DE = 0
22. G = H - TS = U + pV - TS V2
W = – 2.303 nRT log
V1
Þ dG = dU + pdV + Vdp - TdS - SdT = Vdp - SdT
335
[Q dU + pdV = dq = TdS ] = - 2.303 ´ 0.04 ´ 8.314 ´ 310 ´ log
50
Þ dG = Vdp if isothermal process (dT = 0)
Þ DG = VDp = - 208 J
Now taking initial state as standard state q = + 208 J
Ggr - Ggr ° = Vgr Dp …(i) W = - 208 J (expansion work)
G d - G d ° = Vd Dp …(ii) 27. At transition point (373 K, 1.0 bar), liquid remains in
Now (ii)-(i) gives, equilibrium with vapour phase, therefore DG = 0. As
(Vd - Vgr )Dp = Gd - Ggr ° - G°
+ (Ggr vaporisation occur, degree of randomness increases, hence
d
DS > 0.
At equilibrium, Gd = Ggr
28. DG ° = DH ° - TDS ° = – 54.07 ´ 10 3 J – 298 × 10 J
Þ (Vgr - Vd )Dp = Gd ° - Ggr ° = 2.9 ´ 103 J
= – 57.05 × 103 J
2.9 ´ 103 29 29000
Þ Dp = Pa = ´ 108 Pa = bar Also, DG ° = - 2.303 RT log K
2 ´ 10-6 2 2 - DG °
Þ log K =
29000 29000 2.303 RT
p = p0 + =1+ = 14501bar
2 2 57.05 ´ 103
= = 10
23. By first law, DE = Q + W 5705
For isothermal expansion, DE = 0
29. Entropy is a state function hence,
\ Q = -W
- Qirrev = W irrev = pDV = 3(2 - 1) = 3 L atm DS A ® B = DS A ® C + DSC ® D + DS D ® B
Q (- 3 ´ 101.3) J 303.9 = 50 eu + 30 eu + (– 20 eu)
Also, DS surr = irrev = =- = - 1.013 JK-1
T 300 K 300 = 60 eu
116 Thermodynamics and Thermochemistry
DH > 0
E B
C
Reaction coordinates
V1 V2
Minimum value of activation energy must be greater than DH .
AB is isothermal and AC is adiabatic path. Work
38. DH = DE + DngRT Þ DH - DE = DngRT = - 3RT done is area under the curve. Hence, less work is
= - 3 ´ 8.314 ´ 298 = - 7433 J = – 7.43 kJ obtained in adiabatic process than in isothermal
39. In the given curve AC represents isochoric process as volume (c) It is incorrect. In adiabatic expansion cooling is observed,
at both the points is same i.e., V1 hence DU = nCvDT < 0.
Similarly, AB represents isothermal process (as both the points (d) q = 0 (adiabatic), W = 0 (Free expansion)
are at T1 temperature) and BC represents isobaric process as Hence, DU = 0, DT = 0 (Isothermal)
both the points are at p2 pressure. - DH
Now (i) for option (a) 41. DS surr =
Tsurr
qAC = DU BC = nCV (T2 - T1 )
where, n= number of moles For endothermic reaction, if Tsurr increases, DSsurr will increase.
For exothermic reaction, if Tsurr increases, DSsurr will decrease.
Cv = specific heat capacity at constant volume
Thermodynamics and Thermochemistry 117
42. PLAN This problem includes concept of isothermal adiabatic Therefore, W X ® Y ® Z = W X ® Y. Also, work is the area under the
irreversible expansion.
curve on p-V diagram.
Process is adiabatic because of the use of thermal insolution
therefore, q = 0 X Y X Y
Q pext = 0
WX ® Y
w = pext × DV = 0 ´ DV = 0 = WX®Y®Z
Internal energy can be written as WX®Y
p Z p Z
DU = q + W = 0
The change in internal energy of an ideal gas depends only on
temperature and change in internal energy (DU ) = 0 therefore,
V V
DT = 0 hence, process is isothermal and
T2 = T1 As shown above W X ® Y + WY ® Z = W X ® Y = W X ® Y® Z but not
equal to W X ® Z.
and p2V2 = p1V1
46. Resistance and heat capacity are mass dependent properties,
(d) p2V2g = p1V1g is incorrect, it is valid for adiabatic
hence they are extensive.
reversible process.
47. Internal energy, molar enthalpy are state function. Also,
Hence, only (a), (b) and (c) are correct choices. reversible expansion work is a state function because between
43. PLAN When an ideal solution is formed process is spontaneous thus given initial and final states, there can be only one reversible path.
According to Raoult’s law, for an ideal solution 48. Intensive properties are those property which do not depends
DH = 0, DVmin = 0 on amount of sample. Both temperature and refractive index
From the relation are intensive properties while enthalpy and volumes are
D G = D H - TD S extensive properties as they depends on amount of sample.
Since, DH = 0 49. Statement I is true, it is statement of first law of thermodynamics.
\ DG = - ve
Statement II is true, it is statement of second law of
i.e. less than zero. and DS surroundings = 0 thermodynamics. However, Statement II is not the correct
Therefore, DS sys = + ve explanation of statement I.
i.e. more than zero.
50. Statement I is false. At equilibrium
44. (a) Since, change of state ( p1 , V1 , T1 ) to ( p2 , V2 , T2 ) is isothermal DG = 0, G ¹ 0.
therefore, T1 = T2.
Statement II is true, spontaneous direction of reaction is towards
(b) Since, change of state ( p1 , V1 , T1 ) to ( p3 , V3 , T3 ) is an adiabatic
lower Gibbs free energy.
expansion it brings about cooling of gas, therefore, T3 < T1.
(c) Work done is the area under the curve of p-V diagram. As 51. Statement I is true.
obvious from the given diagram, magnitude of area under the dq = dE + pext dV = 0
isothermal curve is greater than the same under adiabatic DT = 0
curve, hence Wisothermal > Wadiabatic \ dE = 0 ; pext = 0
(d) DU = nCv DT \ pext dV = 0
In isothermal process, DU = 0 as DT = 0
Statement II is true. According to kinetic theory of gases,
In adiabatic process, DU = nC v (T3 - T1 ) < 0 as T3 < T1 .
volume occupied by molecules of ideal gas is zero.
Þ DU isothermal > DU adiabatic
However, Statement II is not the correct explanation of Statement I.
NOTE Here only magnitudes of work is being considered
otherwise both works have negative sign. 52. L ® M At constant V — isochoric,
45. (a) Entropy is a state function, change in entropy in a cyclic N®K
process is zero. 1
53. PLAN By Boyle’s law at constant temperature, p µ
Therefore, DS X + DS Y + DS Z =0 V
®Y ®Z ®X
Þ - DS Z ® X = DS X ® Y + DSY ® Z By Charles’ law at constant pressure, V µ T
= DS X ® Z Process taking place at
Constant temperature — isothermal
Analysis of options (b) and (c)
Constant pressure — isobaric
Work is a non-stable function, it does depends on the path Constant volume — isochoric
followed. WY ® Z = 0 as DV = 0.
Constant heat — adiabatic
118 Thermodynamics and Thermochemistry
Total work done = W1 + W2 + W3 72. Let the mixture contain x litre of CH4 and 3.67 - x litre of
= - 20 L atm + 0 + 20 ln 2 ethylene.
= – 6.14 atm CH4 + O2 ¾® CO2
From first law : q = DE + (- W ) = - W x x
(Q DE = 0 for cyclic process) C2H4 + O2 ¾® 2CO2
3.67 - x 2 (3.67 - x)
Þ q = 6.14 L atm = 622.53 J
(iii) All the states function, DU , DH and DS are zero for cyclic Given : x + 2 (3.67 - x ) = 6.11 L
process. Þ x = 1.23 L
B r A
Volume of ethylene = 2.44 L
69. At equilibrium :
pV 1 ´1
95.2% 1.3% Total moles of gases in l litre = = = 0.04
RT 0.082 ´ 298
13
Þ K1 = Also, CH4 and ethylene are in 1 : 2 volume (or mole) ratio, moles
952
0.04 2 ´ 0.04
B r C of CH4 =
3
and moles of ethylene =
3
95.2% 3.5% 0.04
35 Þ Heat evolved due to methane = ´ 891 = 11.88 kJ
Þ K2 = 3
952 2 ´ 0.04
Heat evolved due to ethylene = ´ 1423 = 37.94 kJ
Þ DG1° = - RT ln K 1 3
13 Þ Total heat evolved on combustion of 1.0L gaseous mixture
= – 8.314 ´ 448 ´ 2.303 log = 16 kJ at 25°C is 11.88 + 37.94 = 49.82 kJ
952
1560
DG2° = - RT ln K 2 73. Moles of H2O needs to perspire = = 17.72
2 ´ 44
35
= – 8.314 ´ 448 ´ 2.303 log
952 Weight of water needs to perspire = 17.72 ´ 18 = 318.96 g
= 12.3 kJ 74. At constant pressure, q = DH .
70. D rG ° = D f G ° (products) – D f G ° (reactants)
= – 394.4 – (– 137.2) = – 257.2 kJ < 0
Topic 2 Thermochemistry
The above negative value of DG indicates that the process is Key Idea When q is the amount of heat involved
1.
spontaneous.
in a system then at constant pressure
Also, DG ° = DH ° - TDS ° q = qp and C p DT = DH
Þ D H ° = D G ° + TD S °
Given reaction :
= – 257.2 + 300 (– 0.094)
I2 (s) ¾® I2 (g )
= – 285.4 kJ < 0
Specific heat of I2 (s) = 0.055 cal g -1 K -1.
71. Given : CV = 12.49 Þ C p = 20.8 Specific heat of I2 (vap) = 0.031 cal g –1K –1.
Cp
Þ = g = 1.66 Enthalpy (H 1 ) of sublimation of iodine = 24 cal g –1
CV
If q is the amount of heat involved in a system then at constant
In case of reversible adiabatic expansion : pressure q = qp and
TV g- 1= constant DH = C p DT
g-1 0.66 H 2 - H 1 = C p (T2 - T1 )
T2 æ V1 ö æV ö
Þ =ç ÷ = çç 1 ÷÷ H 2 = H 1 + DC p (T2 - T1 )
T1 çè V2 ÷ø è V2 ø
H 2 = 24 + (0.031 - 0.055) (250 - 200)
0.66
æV ö . = 22. 8 cal/g
H 2 = 24 + (-0.024 ) (50) = 24 - 12
Þ T2 = T1 çç 1 ÷÷
è V2 ø Thus, the enthalpy of sublimation of iodine at 250°C is
0.66
22.8 cal/g.
æ 1ö
= 300 ç ÷ = 189.86 K 2. Second equation given in this question is wrong. Hence, No
è 2ø
answer in correct.
Þ DH = nCp DT
If corrected second equation is given,
1 ´ 1.25 1
= ´ 20.8 ´ (189.86 - 300) J i.e. C(graphite) + O2 (g ) ¾® CO (g )
0.082 ´ 300 2
= – 116.4 J
120 Thermodynamics and Thermochemistry
and if we take the above reaction in consideration then x = y + z D cH ° (glucose) = 6[ D f H ° (CO2 ) + D f H °(H2O )]
will be the answer as:
1 - [ D f H ° (C6H12O6 ) + 6D f H ° (O 2 )]
(ii) C(graphite) + O2 (g ) ¾® CO(g ), D r H ° = y kJ/mol
2 = 6[ -400 - 300 ] - [ -1300 + 6 ´ 0 ]
1 = - 2900 kJ mol -1
(iii) CO(g ) + O2 (g ) ¾® CO2 (g ), D r H ° = z kJ/mol
2 Molar mass of C 6H12O6 = 180 g mol -1
Summing up both the equation you will get equation (i):
Thus, standard heat of combustion of glucose per gram
C(graphite) + O2 (g ) ¾® CO2 (g ), D r H °= x kJ/mol
-2900
Hence, x, y and z are related as: = = - 16.11 kJ g-1
180
x =y+ z
To solve such problem, students are advised to keep much
3. Based on given D rH ° importance in unit conversion. As here, value of R
° = - 393.5 kJ mol - 1
D f H ° = H CO …(i) (8.314 J K-1 mol -1) in JK-1 mol -1 must be converted into kJ by
2
dividing the unit by 1000.
D f H ° = H °H 2 O = - 285.8 kJ mol - 1 …(ii)
7. For calculation of C ºº C bond energy, we must first calculate
D f H ° = H °O 2 = 0.00 (elements) …(iii) dissociation energy of C2H2 as
Required thermal reaction is for D f H ° of CH4 C2H2 (g ) ¾® 2C(g ) + 2H(g ) …(i)
Thus, from III Using the given bond energies and enthalpies :
890.3 = [ D f H ° (CH4 ) + 2 D f H ° (O2 )] C2H2 (g ) ¾® 2C (g ) + 2H (g ) ; DH = - 225 kJ …(ii)
2C( s) ¾® 2C(g ); DH = 1410 kJ …(iii)
- [ D f H ° (CO2 ) + 2 D f H ° (H2O)] H2 (g ) ¾® 2H(g ) ; DH = 330 kJ …(iv)
= D f H ° (CH4 ) + 0] - [ - 393.5 - 2 ´ 285.5] Adding Eqs. (ii), (iii) and (iv) gives Eq. (i).
Þ C2H2 (g ) ¾® 2C(g ) + 2H(g ) ; DH = 1515 kJ
\ D f H ° (CH4 ) = - 74.8 kJ / mol
Þ 1515 kJ = 2 ´ (C ¾ H) BE + (C ºº C) BE
4. C(s)+ O2 (g ) ¾® CO2 (g ) ; DH = - 393.5 kJ mol -1 …(i) = 2 ´ 350 + (C ºº C) BE
1 (C ºº C) BE = 1515 - 700 = 815 kJ / mol
CO+ O2 ¾® CO2( g ); DH = - 283.5 kJ mol -1 …(ii) Þ
2
On subtracting Eq. (ii) from Eq. (i), we get
8. Elements in its standard state have zero enthalpy of formation.
Cl 2 is gas at room temperature, therefore DH °f of Cl 2 (g ) is zero.
1
C (s) + O2 (g ) ¾® CO(g );
2 9. C—C bond energy is approximately 100 kcal.
DH = (- 393.5 + 283.5)kJ mol -1 DH vap 30,000
10. T = = = 400 K
= - 110 kJ mol-1(approx.) DS vap 75
5. C2H5OH ( l ) + 3O2 (g ) ¾® 2CO2 (g ) + 3H2O(l ) 1 1
11. H2 (g ) + F2 (g ) ¾® HF(g )
DU = - 1364.47 kJ/mol 2 2
DH = DU + DngRT Here DH ° = Standard molar enthalpy of formation of HF(g).
Dng = - 1 12. CO2 (g ) + H2 (g ) ¾® CO(g ) + H2O(g )
- 1 ´ 8.314 ´ 298
DH = - 1364.47 + DH = SD f H ° (products) - SD f H ° (reactants)
1000
= – 110.5 – 241.8 – (– 393.5) = + 41.20 kJ
[Here, value of R in unit of J must be converted into kJ]
= - 1364.47 - 2. 4776 = - 1366.9476 kJ/mol 1
13. H2O ¾® H2 + O2, DH > 0
or = - 1366.95 kJ/mol 2
It is reverse of combustion of H2 (g ), hence endothermic.
6. PLAN D c H ° (Standard heat of combustion) is the standard enthalpy C2H6 ¾® C2H4 + H2; DH > 0
change when one mole of the substance is completely oxidised.
Here, more stable (saturated) hydrocarbon is being transformed
Also standard heat of formation (D f H ° ) can be taken as the
to less stable (unsaturated) hydrocarbon, hence endothermic.
standard of that substance.
C(gr) ¾® C(d) , DH > 0
H °CO 2 = D f H ° (CO2 ) = - 400 kJ mol -1
More stable allotrope is being converted to less stable allotrope.
H H° 2 O = D f H ° (H2O ) = - 300 kJ mol -1
14. PLAN Heat of reaction is dependent on temperature (Kirchhoff’s
°
Hglucose = D f H ° (glucose) = - 1300 kJ mol -1 equation) in heterogeneous system, equilibrium constant is
independent on the molar concentration of solid species.
H O° 2 = D f H ° (O2 ) = 0.00 Heat of reaction is not affected by catalyst. It lowers activation
energy.
CaCO3 (s) r CaO(s) + CO2 (g )
C6H12O6 (s) + 6 O2 (g ) ¾® 6 CO2 (g ) + 6H2O(l )
Thermodynamics and Thermochemistry 121
DH °f (H2O)(g ) = DH °f (H2O)(l ) + 44 = – 242 kJ 21. Per mole of ethylene polymerized, one C == C bond is broken
and two C—C bonds are formed.
Þ DH r° = – 1273 – 3 ´ 242 – 36 DH ° (Polym.) = 590 - 2 ´ 311
= – 2035 kJ = – 32 kJ/mol
17. SF6 (g ) ¾® S (g ) + 6F (g ) 22. At same temperature and pressure, equal volumes contain equal
DH = S DH °f (products) - S DH °f (reactants) moles of gases.
Let 1.0 L of CH4 contain ‘n’ mol
= 275 + 6 ´ 80 + 1100 = 1855 kJ
1855 Þ x L of CH4 contain nx mol
Þ Average S—F bond energy = = 309.16 kJ/mol
6 Þ Heat evolved in combustion by x L CH4 = 809 nx kJ
æ1 ö
18. Given : Cyclopropane ¾®Propene (C3H6 ); DH = - 33 kJ Now, 2878 kJ energy is evolved from 1 mole ç L ÷ C4H10.
èn ø
9
Propene (C3H6 ) + O2 ¾® 3CO2 (g ) + 3H2O (l ); 809 nx
2 Þ 809 nx kJ energy will be evolved from L of C4H10
DH = – 3 (393.5 + 285.8) – 20.42 = – 2058.32 kJ 2878 n
Adding : = 0.28 x L of C4H10
9 Also, the combustion reaction of butane is
Cyclopropane + O2 (g ) ¾® 3CO2 (g ) + 3H2 (g ) ;
2 13
C4 H10 + O2 ¾® 4CO2 + 5H2O
DH = H 1 + H 2 2
= -33 + (-2058.32)kJ 13
DH = - 2091.32 kJ Þ Rate of supply of oxygen = ´ 0.28 x ´ 3
2
19. Given : CH3OH (g ) ¾® CH3OH (l ); DH = - 38 kJ = 5.46 x L/h
C (g ) + 4H (g ) + O (g ) ¾® CH3OH (g ); 23. First we need to determine heat of combustion of C3H8 .
DH = - (3 ´ 415 + 356 + 463)
Q H = H 1 + H 2 = - 2064 kJ 3C(gr) + 4 H2 (g ) ¾® C3H8 (g ) DH °f = - 103 kJ
C(g ) ¾® C(g ); DH = 715 kJ Þ °
– 103 kJ = – 3 ´ 393 – 4 ´ 285.80 – D H comb (C3H8 )
122 Thermodynamics and Thermochemistry
° 1 1
Þ D H comb (C3H8 ) = – 2219.20 kJ 28. H2 (g ) + Cl 2 (g ) ¾® HCl (g ); DH °f
2 2
Þ DH r° = S D H comb
° °
(reactants) - S D H comb (products)
DH °f = S BE (reactants) - S BE (products)
= – 2219.20 – 285.80 + 1560 + 890
1
= – 55 kJ = (104 + 58) - 103 = – 22 kcal/mol
2
24. Let x kcal be the C—C bond energy and y kcal be the C—H bond
energy per mole. 29. C2H2 + H2 ¾® C2H4
Þ 2C(gr) + 3H2 (g ) ¾® C2H6 (g ) ; DH ° = S D H comb
° °
(reactants) - S D H comb (products)
DH ° = – 2 ´ 94 – 3 ´ 68 + 372 = – 310.6 – 68.3 – (– 337.2)
= – 20 kcal = – 41.7 kcal
Þ – 20 kcal = 2 ´ 172 + 3 ´ 104 - BE (C2H6 )
30. The standard state formation reaction of C2H2 (g ) is :
Þ BE (C2H6 ) = 676 kcal
2C(g ) + H2 (g ) ¾® C2H2 (g ); DH °f
Similarly, 3C(gr) + 4 H2 (g ) ¾® C3H8 (g ) ;
DH r° = S D H comb
° °
(reactants) - S D H comb (products)
DH ° = – 3´ 94 – 4 ´ 68 + 530
= – 24 kcal = – 2 ´ 94.05 – 68.32 – (– 310.62)
Þ – 24 kcal = 3 ´ 172 + 4 ´ 104 - BE (C3H8 ) = 54.2 kcal = DH f° (C2H2 )
Þ BE (C3H8 ) = 956 kcal 31. DH r° = S D f H ° (products) - S D f H ° (reactants)
Also, BE (C2H6 ) = 676 kcal = x + 6 y …(i) = – 94.1 + 4 (– 22.1) – (– 25.5 – 2 ´ 57.8)
BE (C3H8 ) = 956 kcal = 2x + 8 y …(ii) = – 41.4 kcal
Solving Eqs. (i) and (ii) gives 32. DH ° = S BE (reactants) - S BE (products)
y = 99 kcal (C—H) BE 1 1
Þ - 10.06 =
(104.18) + (118.32) - BE (O ¾ H)
x =82 kcal (C—C) BE 2 2
BE (O—H) = 121.31 kcal
25. + H2 33. Let C JK-1 be the heat capacity of calorimeter.
Mass of solution = 200 mL ´ 1 g mL-1 = 200 g
°
DH = S D H comb °
(reactants) - S D H comb (products) Heat evolved in Expt.1
= 57 ´ 1000 ´ 0. 1(mol ) = 5700 J
= – 3800 – 241 – (– 3920)
Þ 5700 J = (200 ´ 4.2 + C ) ´ 5.7
= – 121 kJ/mol
Þ 1000 = 200 ´ 4.2 + C …(i)
26. Fe2O3 (s) + 2Al (s) ¾® Al 2O3 (s) + 2Fe(s) Let x kJ/mol is heat evolved in neutralisation of acetic acid.
Þ x ´ 1000 ´ 010 . = (200 ´ 4.2 + C ) ´ 5.6
DH r° = DH °f (products) - DH °f (reactants)
x ´ 100
Þ = 200 ´ 4.2 + C …(ii)
= – 399 – (– 199) 5.6
= – 200 kcal From (i) and (ii) : x = 56 kJ/mol
Mass of reactants = 56 ´ 2 + 16 ´ 3 + 27 ´ 2 = 214 g Þ Enthalpy of ionisation of acetic acid
= - 56 - (- 57) = 1 kJ/mol
200
Þ Fuel value/gram = = 0.93 kcal/g
214 34. CH3COOH + NaOH ® CH3COONa + H2O
160 54 200 mmol 100 mol 0 0
Volume of reactants = cc + cc = 50.77 cc 100 mmol 0 100 mmol
5.2 2.7
A buffer is now formed.
200
Þ Fuel value/cc = = 3.94 kcal/cc [H+ ] [ CH3 COO- ]
50.77 Ka = = [ H+ ]
[CH3 COOH]
27. DH = S DH °f (products) - S DH °f (reactants) [Q [ CH3 COOH] = [ CH3 COO- ]]
= – 2 ´ 94.1 – 3 ´ 68.3 – (– 21.1) Þ pH = pK a = - log ( 2 ´ 10-5 ) = 5 - log 2 = 4.7
= – 372 kcal/mol
Objective Questions I (Only one correct option) 6. The radius of the largest sphere which fits properly at the
1. The ratio of number of atoms present in a simple cubic, body centre of the edge of a body centred cubic unit cell is
centered cubic and face centered cubic structure are, (Edge length is represented by ‘a’) (2019 Main, 11 Jan II)
respectively. (2019 Main, 12 April II) (a) 0.134 a (b) 0.027 a (c) 0.047 a (d) 0.067 a
(a) 8 : 1 : 6 (b) 1 : 2 : 4 7. A solid having density of 9 ´ 103 kgm -3 forms face centred
(c) 4 : 2 : 1 (d) 4 : 2 : 3 cubic crystals of edge length 200 2 pm. What is the molar
2. An element has a face-centred cubic (fcc) structure with a cell mass of the solid?
edge of a. The distance between the centres of two nearest [Avogadro constant = 6 ´ 1023 mol-1 , p = 3]
tetrahedral voids in the lattice is (2019 Main, 12 April I) (2019 Main, 11 Jan I)
a 3 (a) 0.03050 kg mol-1 (b) 0.4320 kg mol-1
(a) 2a (b) a (c) (d) a
2 2 (c) 0.0432 kg mol-1 (d) 0.0216 kg mol-1
3. Consider the bcc unit cells of the solids 1 and 2 with the 8. A compound of formula A2B3 has the hcp lattice. Which
position of atoms as shown below. The radius of atom B is atom forms the hcp lattice and what fraction of tetrahedral
twice that of atom A. The unit cell edge length is 50% more is voids is occupied by the other atoms ? (2019 Main, 10 Jan II)
solid 2 than in 1. What is the approximate packing efficiency 2
(a) hcp lattice- A, tetrahedral voids-B
in solid 2? (2019 Main, 8 April II) 3
1
A A A A (b) hcp lattice-A, tetrahedral voids-B
3
A 1
A A A (c) hcp lattice-B, tetrahedral voids-A
B 3
A 2
A A A (d) hcp lattice-B, tetrahedral voids-A
A 3
A A A A 9. Which primitive unit cell has unequal edge lengths
Solid 1 Solid 2 ( a ¹ b ¹ c ) and all axial angles different from 90°?
(2019 Main, 10 Jan I)
(a) 65% (b) 90% (a) Hexagonal (b) Monoclinic
(c) 75% (d) 45% (c) Tetragonal (d) Triclinic
4. The statement that is incorrect about the interstitial 10. At 100°C, copper (Cu) has FCC unit cell structure with cell
compounds is (2019 Main, 8 April II)
edge length of x Å. What is the approximate density of Cu (in g
(a) they are very hard
cm -3 ) at this temperature?
(b) they have metallic conductivity
[Atomic mass of Cu = 63.55 u] (2019 Main, 9 Jan II)
(c) they have high melting points
211 205
(d) they are chemically reactive (a) 3 (b) 3
x x
5. Element ‘B ’ forms ccp structure and ‘A ’ occupies half of the 105 422
octahedral voids, while oxygen atoms occupy all the (c) 3 (d) 3
x x
tetrahedral voids. The structure of bimetallic oxide is
(2019 Main, 8 April I) 11. The one that is extensively used as a piezoelectric material
(a) A2BO4 (b) AB2O4 is (2019 Main, 9 Jan I)
(c) A2B2O (d) A4B2 O (a) quartz (b) tridymite
(c) amorphous silica (d) mica
124 Solid State
12. Which type of ‘defect’ has the presence of cations in the 20. The packing efficiency of the two-dimensional square unit
interstitial sites? (2018 Main) cell shown below is (2010)
(a) Schottky defect (b) Vacancy defect
(c) Frenkel defect (d) Metal deficiency defect
13. A metal crystallises in a face centred cubic structure. If the
edge length of its unit cell is ‘a’, the closest approach between
two atoms in metallic crystal will be (2017 Main) l
(a) 2 a (b) 2 2 a (a) 39.27% (b) 68.02% (c) 74.05% (d) 78.54%
a 21. Which of the following fcc structure contains cations in
(c) 2 a (d)
2 alternate tetrahedral voids? (2005, 1M)
14. Sodium metal crystallises in a body centred cubic lattice with (a) NaCl (b) ZnS (c) Na 2 O (d) CaF2
a unit cell edge of 4.29Å. The radius of sodium atom is 22. A substance Ax B y crystallises in a face centred cubic (fcc)
approximately (2015 Main) lattice in which atoms A occupy each corner of the cube and
(a) 1.86Å (b) 3.22Å atoms B occupy the centres of each face of the cube. Identify
(c) 5.72Å (d) 0.93Å the correct composition of the substance Ax B y (2002, 1M)
15. CsCl crystallises in body centred cubic lattice. If ‘a’ its edge (a) AB3
length, then which of the following expressions is correct? (b) A4 B3
(2014 Main) (c) A3 B
3a
(a) r + rCl - = 3a (b) r + rCl - = (d) composition cannot be specified
Cs + Cs + 2
23. In a solid AB having the NaCl structure, A atoms occupy the
3 corners of the cubic unit cell. If all the face centred atoms
(c) r + rCl - = a (d) r + rCl - = 3a
Cs + 2 Cs +
along one of the axes are removed, then the resultant
16. The arrangement of X - ions around A + ion in solid AX is stoichiometry of the solid is (2001, S, 1M)
given in the figure (not drawn to scale). If the radius of X - is (a) AB2 (b) A2 B (c) A4 B3 (d) A3 B4
250 pm, the radius of A + is (2013 Adv.) 24. The coordination number of a metal crystallising in a
–
hexagonal close-packed structure is (1999, 2M)
X (a) 12 (b) 4 (c) 8 (d) 6
A+
Objective Questions II
(One or more than one correct option)
(a) 104 pm (b) 125 pm 25. The correct statement(s) for cubic close packed (ccp) three
(c) 183 pm (d) 57 pm dimensional structure is (are) (2016 Adv.)
17. Experimentally it was found that a metal oxide has formula (a) The number of the nearest neighbours of an atom present
M 0.98O. Metal M, present as M 2+ and M 3 + in its oxide. in the topmost layer is 12
Fraction of the metal which exists as M 3+ would be (b) The packing efficiency of atom is 74%
(a) 7.01% (b) 4.08% (2013 Main) (c) The number of octahedral and tetrahedral voids per atom
(c) 6.05% (d) 5.08% are 1 and 2, respectively
18. Which of the following exists as covalent crystals in the solid (d) The unit cell edge length is 2 2 times the radius of the atom
state? (2013 Main) 26. If the unit cell of a mineral has cubic close packed (ccp) array
(a) Iodine (b) Silicon of oxygen atoms with m fraction of octahedral holes
(c) Sulphur (d) Phosphorus occupied by aluminium ions and n fraction of tetrahedral
holes occupied by magnesium ions, m and n respectively, are
19. A compound M p X q has cubic close packing (ccp) (2015 Adv.)
arrangement of X . Its unit cell structure is shown below. The 1 1 1 1 1 1 1
(a) , (b) 1 , (c) , (d) ,
empirical formula of the compound, is (2012) 2 8 4 2 2 4 8
27. The correct statement(s) regarding defects in solids is/are
(a) Frenkel defect is usually favoured by a very small
M
difference in the sizes of cation and anion (1999)
X
(b) Frenkel defect is a dislocation defect
(c) Trapping of an electron in the lattice leads to the formation
of F-centre
(a) MX (b) MX 2 (c) M 2 X (d) M 5 X 14 (d) Schottky defects have no effect on the physical properties
of solids
Solid State 125
28. Which of the following statement(s) is/are correct? 31. The number of atoms in one of this hcp unit cell is
(a) The coordination number of each type of ion in CsCl crystal (2008, 3 ´ 4M = 12M)
is 8 (1998, 2M) (a) 4 (b) 6 (c) 12 (d) 17
(b) A metal that crystallises in bcc structure has a coordination 32. The volume of this hcp unit cell is
number of 12 64 r3
(a) 24 2 r3 (b) 16 2 r3 (c) 12 2 r3 (d)
(c) A unit cell of an ionic crystal shares some of its ions with 3 3
other unit cells 33. The empty space in this hcp unit cell is
(d) The length of the unit cell in NaCl is 552 pm. (a) 74 % (b) 47.6 % (c) 32 % (d) 26 %
(rNa + = 95 pm; rCl - =181 pm)
Match the Columns
Numerical Value 34. Match the crystal system / unit cells mentioned in Column I
29. Consider an ionic solid MX with NaCl structure. Construct a with their characteristic features mentioned in Column II.
new structure (Z) whose unit cell is constructed from the unit (2007, 6M)
cell of MX following the sequential instruction given below. Column I Column II
Neglect the charge balance. (2018 Adv.) A. Simple cubic and face p. have these cell
(a) Remove all the anions (X ) except the central one centred cubic parameters a = b = c
(b) Replace all the face centered cations (M ) by anions (X ) and a = b = g = 90°
(c) Remove all the corner cations (M ) B. Cubic and q. are two crystal
(d) Replace the central anion (X ) with cation (M ) rhombohedral systems
æ Number of anions ö C. Cubic and tetragonal r. have only two
The value of ç ÷ in Z is ___
è Number of cations ø crystallographic
angles of 90°
Assertion and Reason D. Hexagonal and s. belong to same crystal
monoclinic system
Read the following questions and answer as per the direction
given below :
(a) Statement I is correct Statement II is correct Statement II is
Integer Answer Type Questions
the correct explanation of Statement I 35. A crystalline solid of a pure substance has a face-centred
(b) Statement I is correct Statement II is correct Statement II is cubic structure with a cell edge of 400 pm. If the density of
not the correct explanation of Statement I the substance in the crystal is 8 g cm -3 , then the number of
(c) Statement I is correct Statement II is incorrect atoms present in 256 g of the crystal is N ´ 1024 . The value of
(d) Statement I is incorrect Statement II is correct N is (2017 Adv.)
30. Statement I In any ionic soid (MX ) with Schottky defects, 36. The number of hexagonal faces that are present in a truncated
the number of positive and negative ions are same. octahedron is (2011)
Statement II Equal numbers of cation and anion vacancies 37. Silver (atomic weight = 108 g mol -1 ) has a density of
are present. 10.5 g cm-3 . The number of silver atoms on a surface of area
(2001, 1M)
10-12 m2 can be expressed in scientific notation as y ´ 10 x.
The value of x is (2010)
Passage Based Questions
Subjective Questions
Passage
38. The edge length of unit cell of a metal having molecular
In hexagonal systems of crystals, a frequently encountered
weight 75 g/mol is 5 Å which crystallises in cubic lattice. If
arrangement of atoms is described as a hexagonal prism. Here, the
the density is 2 g/cc then find the radius of metal atom.
top and bottom of the cell are regular hexagons and three atoms are
(N A = 6 ´ 1023 ). Give the answer in pm. (2006, 3M)
sandwiched in between them. A space-filling model of this
structure, called hexagonal close-packed (hcp), is constituted of a 39. An element crystallises in fcc lattice having edge length
sphere on a flat surface surrounded in the same plane by six 400 pm. Calculate the maximum diameter of atom which can
identical spheres as closely as possible. Three spheres are then be placed in interstitial site without distorting the structure.
placed over the first layer so that they touch each other and (2005, 2M)
represent the second layer. Each one of these three spheres touches 40. The crystal AB (rock salt structure) has molecular weight
three spheres of the bottom layer. 6.023 y u. Where, y is an arbitrary number in u. If the
Finally, the second layer is covered with a third layer that is minimum distance betweeen cation and anion is y1 / 3 nm and
identical to the bottom layer in relative position. Assume radius of the observed density is 20 kg / m3 . Find the (i) density in
every sphere to be ‘r ’. kg / m3 and (ii) type of defect. (2004, 2M)
126 Solid State
41. (i) Marbles of diameter 10 mm are to be put in a square area 43. A metal crystallises into two cubic phases, face centred cubic
of side 40 mm so that their centres are within this area. (fcc) and body centred cubic (bcc), whose unit cell lengths
(ii) Find the maximum number of marbles per unit area and are 3.5 and 3.0 Å, respectively. Calculate the ratio of
deduce an expression for calculating it. (2003, 4M)
densities of fcc and bcc. (1999, 3M)
44. Chromium metal crystallises with a body centred cubic
42. The figures given below show the location of atoms in three
lattice. The length of the unit edge is found to be 287 pm.
crystallographic planes in a fcc lattice. Draw the unit cell for Calculate the atomic radius . What would be the density of
the corresponding structures and identify these planes in chromium in g/cm 3 ? (1997, 3M)
your diagram. (2000)
45. A metallic element crystallises into a lattice containing a
sequence of layers of ABABAB…… Any packing of layers
leaves out voids in the lattice. What percentage of this lattice
is empty space? (1996, 3M)
46. Sodium crystallises in a bcc cubic lattice with the cell edge,
a = 4.29 Å. What is the radius of sodium atom? (1994, 2M)
Answers
1. (b) 2. (c) 3. (b) 4. (d) 5. (b) 6. (d) 7. (a) 8. (c) 9. (d)
10. (d) 11. (a) 12. (c) 13. (d) 14. (a) 15. (c) 16. (a) 17. (b) 18. (b)
19. (b) 20. (d) 21. (b) 22. (a) 23. (d) 24. (a) 25. (b,c,d) 26. (a) 27. (b,c)
28. (a,c,d) 29. (3) 30. (a) 31. (b) 32. (a) 33. (d) 34. A ® p, s; B ® q; C ® q; D ® q, r
35. (2) 36. (8) 37. (7) 38. (217 pm) 39. (117 pm) 43. (1.26) 44. (7.3 g/cm 3)
45. (0.74) 46. (1.86 Å)
a2 = 2 3 rA a 3 2a - 3a
r= - a=
4 3 4 2 4 4
prA ´ zA + prB3 ´ zB
3 3 a(2 - 3 )
Packing efficiency = r=
a23 4
1 r = 0.067a
[As the atoms A are present at the edges only zA = ´ 8 = 1,
8 7. Density of a crystal
atom B is present only at the body centre zB = 1 ]
M ´Z d ´ N A ´ a3
æ4 3 ö æ4 3 ö d= 3
ÞM =
ç prA ´ 1÷ + ç prB ´ 1÷ NA ´a Z
3 ø è3
\ PE 2 = è ø
Given, d = 9 ´ 103 kg m -3
a23
M = Molar mass of the solid
4 3 4 4 3
prA + p (2rA )3 prA ´ 9 Z = 4 (for fcc crystal)
p
= 3 3
3
= 3 = N A = Avogadro’s constant = 6 ´ 1023 mol -1
(2 3 rA ) 8 ´ 3 3 rA3 2 3
a = Edge length of the unit cell
= 90.72% » 90% = 200 2 pm = 200 2 ´ 10-12 m
4. Interstitial compounds are formed when a neutral atom with a On substituting all the given values, we get
small radius occupies in an interstitial hole (tetrahedral or
(9 ´ 103 ) kg m -3 ´ (6 ´ 1023 ) mol -1 ´ (200 2 ´ 10-12 )3 m 3
octahedral voids) in a transition metal’s hcp or ccp lattices =
(host lattice). Examples of small atoms (guest atom) are H, B, C 4
and N. = 0.0305 kg mol -1
Interstitial compounds are non-stoichiometric (Birtholide) in
composition. They are very hard with very high melting points.
8. Total effective number of atoms in hcp unit lattice = Number of
octahedral voids in hcp = 6
The electrical conductivity of interstitial compounds are
comparable to that of the pure metal. These are chemically \Number of tetrahedral voids (TV) in hcp
unreactive in nature. = 2 ´ Number of atoms in hcp lattice
5. The number of element ‘B ’ in the crystal structure = 4 N = 2 ´ 6 = 12
As, formula of the lattice is A2 B3 .
Number of tetrahedral voids = 2N
Suppose, A B
Number of octahedral voids = N
æ1 ö
N 4 ç ´ TV ÷ (hcp)
\Number of ‘A’ in the crystal = = =2 è3 ø
2 2
1
Number of oxygen (O) atoms = 2N = 2 ´ 4 = 8 Þ ´ 12 6
3
\The structure of bimetallic oxide = A2 B4 O8 = AB2 O4
2
Þ 1
6. For body centred cubic bcc structure, 3
3 Þ 2 3
radius (R ) = a ...(i)
4 1
So, A = tetrahedral voids, B = hcp lattice
Where, a = edge length 3
According to question, the structure of cubic unit cell can be 9. Triclinic primitive unit cell has dimensions as, a ¹ b ¹ c and
shown as follows:
a ¹ b ¹ g ¹ 90° .
R 2r R
Among the seven basic or primitive crystalline systems, the
triclinic system is most unsymmetrical. In other cases, edge
length and axial angles are given as follows :
Hexagonal : a = b ¹ c and a = b = 90°, g = 120°
Monoclinic : a ¹ b ¹ c and a = g = 90°, b ¹ 90°
Tetragonal : a ¹ b ¹ c and a = b = g = 90°
c a = 2 = = = 0.785
r L 8r2 4
F C
b Þ % packing efficiency = 78.5%.
a
E a D 21. In ZnS, S2- (sulphide ions) are present at fcc positions giving
four sulphide ions per unit cell. To comply with 1 : 1
Body centred cubic unit cell stoichiometry, four Zn 2+ ions must be present in four alternate
tetrahedral voids out of eight tetrahedral voids present.
FD = b = a2 + a2 = 2 a
In NaCl, Na + ions are present in octahedral voids while in Na 2O,
In DAFD, Na + ions are present in all its tetrahedral voids giving the desired
c2 = a2 + b2 = a2 + ( 2 a)2 = a2 + 2 a2 2 : 1 stoichiometry. In CaF2 , Ca 2+ ions occupies fcc positions
c2 = 3 a2 Þ c = 3 a and all the tetrahedral voids are occupied by fluoride ions.
As D AFD is an equilateral triangle. 1
22. In cubic system, a corner contribute th part of atom to one unit
8
\ 3a = 4r [QC = 3r + r + r]
1
cell and a face centre contribute part of atom to one unit cell.
3a 2
Þ r=
4 Therefore,
3 3 1
Hence, rCs + + rCl- = 2 r = 2 ´ a= a Number of A per unit cell = ´ 8 = 1
4 2 8
Solid State 129
1 æ4 ö
Number of B per unit cell = ´6= 3 4 ç pr3 ÷
2 Volume of 4 spheres è 3 ø ´ 100
= =
Þ Formula = AB3 Volume of unit cell [ 2( 2r)]3
23. In NaCl, Na + occupies body centre and edge centres while Cl - ~ 74%
= 74.05% -
occupies corners and face centres, giving four Na + and four Cl - 26. Oxide ions are at ccp positions, hence 4O2– ions. Also, there
per unit cell. In the present case A represent Cl - and B represents are four octahedral voids and eight tetrahedral voids. Since ‘m’
Na + . Two face centres lies on one axis. fraction of octahedral voids contain Al 3+ and ‘n’ fraction of
1
Þ Number of A removed = 2 ´ = 1 tetrahedral voids contain Mg2+ ions, to maintain
2
Number of B is removed because it is not present on face centres. etectroneutrality 2(2Al 3+ = + 6charge) and
Þ A remaining = 4 - 1 = 3, B remaining = 4, (Mg2+ = + 2charge), will make unit cell neutral
Formula = A3 B4 2 1 1
Hence: m = = , n=
4 2 8
24. Three consecutive layers of atoms in hexagonal close packed
lattice is shown below: 27. (a) Wrong statement. A small difference in sizes of cation and
anion favour Schottky defect while Frenkel defect is
A favoured by large difference in sizes of cation and anion.
(b) Correct statement. In Frenkel defect the smaller atom or ion
gets dislocated from its normal lattice positions and occupies
the interstitial space.
(c) Correct Statement In F-centre defect, some anions leave
X B
the lattice and the vacant sites hold the electrons trapped in it
maintaining the overall electroneutrality of solid.
(d) Wrong statement : In Schottky defect, some of the atoms or
ions remaining absent from their normal lattice points
A
without distorting the original unit cell dimension. This
lowers the density of solid.
Atom X is in contact of 12 like atoms, 6 from layer B and 3 from 28. (a) The unit cell of CsCl has bcc arrangement of ions in which
top and bottom layers A each. each ion has eight oppositely charged ions around it in the
25. (a) Nearest neighbour in the topmost layer of ccp structure is 9 nearest neighbours as shown below :
thus, incorrect.
(b) Packing efficiency is 74% thus, correct.
(c) Tetrahedral voids = 2 Cs+
Octahedral voids = 1 per atom thus, correct. Cl–
4
(d) Edge length, a = r = 2 2r
2 Unit cell of CsCl
A
thus, correct (b) In bcc, coordination number of atom is 8.
Explanation Edge length = a (c) In an unit cell, a corner is shared in eight unit cells and a face
a centre is shared between two adjacent unit cells.
Radius = r
(d) In NaCl unit cell; 2(rNa+ + rCl - ) = a
AC 2 = AB 2 + BC 2
a C Þ a = 2 (95 + 181) = 552 pm
(4 r)2 = a2 + a2 = 2a2 B
Hence, a, c, d are correct.
4 r = 2a 29. The unit cell of initial structure of ionic solid MX looks like
2 a Cl– (at face centre)
Þ r= a= Þ a=2 2 r
4 2 2
Cl– (at corner)
In ccp structure, number of spheres is 4.
æ4 ö Na+ (at face)
Hence, volume of 4 spheres = 4 ç pr3 ÷
è 3 ø
Total volume of unit cell = a3 = (2 2r)3 Na+ (at corner edge)
% of packing efficiency
In NaCl type of solids cations (Na + ) occupy the octahedral
voids while anions (Cl - ) occupy the face centre positions.
130 Solid State
31. B
Q
C M
P
R S N
Truncated octahedron
A hcp unit cell
Contribution of atoms from corner = 1/ 6 Truncated octahedron unfolded in two-dimension
Contribution from face centre = 1 / 2 37. Ag crystallises in fcc unit cell with 4 atoms per unit cell.
1 1
Þ Total number of atoms per unit cell = 12 ´ + 2 ´ + 3 = 6 4 ´ 108
6 2 r= = 10.5 g cm -3.
6.023 ´ 1023 ´ a3
32. In close packed arrangement, side of the base = 2r
Þ a3 (Volume of unit cell) = 6.83 ´ 10-23 cm 3
Þ RS = r
Also MNR is equilateral triangle, Ð PRS = 30° Þ a = 4 ´ 10-8 cm = 4 ´ 10-10 m
RS 3
In triangle PRS , cos 30° = = Þ Surface area of unit cell = a2 = 1.6 ´ 10-19 m 2
PR 2
2 2 Þ Number of unit cells on 10-12 m 2 surface
Þ PR = RS = r
3 3 10-12
= = 6.25 ´ 106
2 1.6 ´ 10-19
In right angle triangle PQR : PQ = QR 2 - PR 2 = 2 r
3
Q There are two atoms (effectively) on one face of unit cell
2
Þ Height of hexagon = 2PQ = 4 r Number of atoms on 10-12 m 2 surface = 2 ´ number of unit cell
3
3 2 = 1.25 ´ 107 . [Q y ´10x ]
Þ Volume = Area of base ´ height = 6 (2r)2 ´ 4 r
4 3 Þ x = 7 Þ y = 125
.
Solid State 131
38. From the given information, the number of atoms per unit cell centres within the square = 5 (shown in diagram)
and therefore, type of unit cell can be known as Maximum number of marbles per unit area = 5 ´ 5 = 25
NM (ii) If x mm is the side of square and d is diameter of marble then
r=
NA a3 maximum number of marbles on square area with centres
within square area can be known by the following general
r N A a3 2 ´ 6 ´ 1023 ´ (5 ´ 10-8 cm )3
Þ N = = = 2 ( bcc) formula :
M 75 2
æx ö
Þ In bcc, 4 r = 3a N = ç + 1÷
èd ø
3 3
Þ r= a= ´ 5 ´ 10-10 m
4 4
= 2.17 ´ 10-10 m = 217 pm
39. In a cubic crystal system, there are two types of voids known as 42.
octahedral and tetrahedral voids. If r1 is the radius of void and r2
is the radius of atom creating these voids then
æ r1 ö ær ö N
çç ÷÷ = 0.414 and çç 1 ÷÷ = 0.225 43. Density µ
r a3
è 2 ø octa è r2 ø tetra 3 3
d1 N 1 æ a2 ö 4 3 ö
The above radius ratio values indicate that octahedral void has Þ = çç ÷÷ = æç ÷ = 1.26
larger radius, hence for maximum diameter of atom to be present d2 N 2 è a1 ø 2 è 3.5 ø
in interstitial space :
44. In bcc unit cell, 4 r = 3a
r1 = 0.414 r2
3a 3
Also in fcc, 4 r2 = 2a Þ r (Cr) = = ´ 287 pm = 124.3 pm
4 4
Þ Diameter required (2r1 ) = (2r2 ) ´ 0.414 NM
a Density of solid =
= ´ 0.414 N A × a3
2
400 ´ 0.414 N = Number of atoms per unit cell, M = Molar mass
= = 117 pm 3
2 a = Volume of cubic unit cell, N A = Avogadro’s number
3
40. (i) In rock salt like crystal AB, there are four AB units per unit 2 ´ 52 g æ 1 ö
cell. Therefore, density (d ) is = ´ çç ÷ = 7.3 g / cm 3
6.023 ´ 10 23 -8 ÷
4 ´ 6.023 y è 2.87 ´ 10 cm ø
d=
6.023 ´ 1023 ´ 8 y ´ 10-27 45. The given arrangement : ABABAB...... represents hexagonal
close-packed unit cell in which there are six atoms per unit cell.
[Q a = 2 y1/ 3 nm = 2 y1/ 3 ´ 10-9 m ]
Also, volume of unit cell = 24 2r3.
= 5 ´ 103 g/m 3 = 5 kg/m 3
Volume occupied by atoms
(ii) Since, observed density is greater than expected, theoretical Þ Packing fraction =
Volume of unit cell
density, there must be some excess metal occupying 4 1
interstitial spaces. This type of defect is known as metal = 6 ´ pr3 ´ = 0.74
3 24 2 r3
excess defect.
Þ Percent empty space = 100 (1 - 0.74) = 26%
41. (i) Side of square = 40 mm 10 mm 46. In bcc arrangement of atoms : 4 r = 3a, atoms on body
Diameter of marble = 10 mm diagonal remain in contact
Number of marble spheres along 3a 3 ´ 4.29
Þ r= = = 1.86 Å
an edge of square with their 4 4
40 mm
Partial pressure
Partial pressure
1. The mole fraction of a solvent in aqueous solution of a solute z
-1 (a) (b)
is 0.8. The molality (in mol kg ) of the aqueous solution is z y
(2019 Main, 12 April I) y x
(a) 13.88 ´ 10-2 (b) 13.88 ´ 10-1 x w w
-3
(c) 13.88 (d) 13.88 ´ 10 (0, 0) Mole fraction (0, 0) Mole fraction
of water of water
2. What would be the molality of 20% (mass/mass) aqueous
z
solution of KI? (Molar mass of KI = 166 g mol -1 ) z y
Partial pressure
Partial pressure
(2019 Main, 9 April I)
y xw
(a) 1.48 (b) 1.51 (c) (d)
(c) 1.35 (d) 1.08
x
3. Liquid M and liquid N form an ideal solution. The vapour w
pressures of pure liquids M and N are 450 and 700 mmHg,
(0, 0) Mole fraction (0, 0) Mole fraction
respectively, at the same temperature. Then correct statement of water of water
is (2019 Main, 9 April I)
x M = mole fraction of M in solution; 5. The vapour pressures of pure liquids A and B are 400 and 600
x N = mole fraction of N in solution; mmHg, respectively at 298 K. On mixing the two liquids, the
y M = mole fraction of M in vapour phase; sum of their initial volumes is equal to the volume of the final
y N = mole fraction of N in vapour phase mixture. The mole fraction of liquid B is 0.5 in the mixture.
The vapour pressure of the final solution, the mole fractions
x y
(a) M > M of components A and B in vapour phase, respectively are
xN yN (2019 Main, 8 April I)
xM y (a) 450 mmHg, 0.4, 0.6 (b) 500 mmHg, 0.5, 0.5
(b) = M
xN yN (c) 450 mmHg, 0.5,0.5 (d) 500 mmHg, 0.4,0.6
x y 6. Liquids A and B form an ideal solution in the entire
(c) M < M
xN yN composition range. At 350 K, the vapour pressures of pure A
(d) ( x M - y M ) < ( x N - y N ) and pure B are 7 ´ 103 Pa and 12 ´ 103 Pa, respectively. The
composition of the vapour in equilibrium with a solution
4. For the solution of the gases w , x, y and z in water at 298 K,
containing 40 mole percent of A at this temperature is
the Henry’s law constants ( K H ) are 0.5, 2, 35 and 40 K bar, (2019 Main, 10 Jan I)
respectively. The correct plot for the given data is
(a) x A = 0.76; xB = 0.24 (b) x A = 0.28; xB = 0.72
(2019 Main, 8 April II)
(c) x A = 0.4; xB = 0.6 (d) x A = 0.37; xB = 0.63
Solution and Colligative Properties 133
7. Which one of the following statements regarding Henry’s solution. The correct statement(s) applicable to this system is
law is not correct? (2019 Main, 8 Jan I) (are) (2017 Adv.)
(a) Different gases have different K H (Henry’s law
constant) values at the same temperature
Z
(b) Higher the value of K H at a given pressure, higher is the
solubility of the gas in the liquids pL
(c) The value of K H increases with increase of temperature
and K H is function of the nature of the gas
(d) The partial pressure of the gas in vapour phase is
1 XM 0
proportional to the mole fraction of the gas in the solution
8. 18 g of glucose (C6 H12 O6 ) is added to 178.2 g water. The (a) The point Z represents vapour pressure of pure liquid M
vapour pressure of water (in torr) for this aqueous solution is and Raoult’s law is obeyed from xL = 0 to xL = 1
(2016 Main) (b) Attractive intermolecular interactions between L - L in
(a) 76.0 (b) 752.4 (c) 759.0 (d) 7.6 pure liquid L and M - M in pure liquid M are stronger
than those between L - M when mixed in solution
9. The vapour pressure of acetone at 20°C is 185 torr.
When 1.2 g of a non-volatile substance was dissolved in (c) The point Z represents vapour pressure of pure liquid M
100 g of acetone at 20°C, its vapour pressure was 183 Torr. and Raoult’s law is obeyed when xL ® 0
The molar mass of the substance is (2015, 1M) (d) The point Z represents vapour pressure of pure liquid L
(a) 32 (b) 64 (a) 128 (b) 488 and Raoult’s law is obeyed when xL ® 1
10. The Henry’s law constant for the solubility of N2 gas in 15. Mixture(s) showing positive deviation from Raoult’s law at
water at 298 K is 1.0 ´ 105 atm. The mole fraction of N2 in air 35°C is (are) (2016 Adv.)
is 0.8. The number of moles of N2 from air dissolved in (a) carbon tetrachloride + methanol
10 moles of water of 298 K and 5 atm pressure is (2009) (b) carbon disulphide + acetone
(a) 4.0 ´ 10-4
(b) 4.0 ´ 10-5 (c) benzene + toluene
(d) phenol + aniline
(c) 5.0 ´ 10- 4 (d) 4.0 ´ 10- 6
11. A molal solution is one that contains one mole of a solute in Numerical Value Based Question
(1986, 1M) 16. Liquids A and B form ideal solution over the entire range of
(a) 1000 g of the solvent (b) 1 L of the solvent composition. At temperature T, equimolar binary solution of
(c) 1 L of the solution (d) 22.4 L of the solution liquids A and B has vapour pressure 45 torr. At the same
temperature, a new solution of A and B having mole fractions
12. For a dilute solution, Raoult’s law states that (1985, 1M)
x A and xB , respectively, has vapour pressure of 22.5 torr. The
(a) the lowering of vapour pressure is equal to the mole value of x A / xB in the new solution is ____.
fraction of solute (Given that the vapour pressure of pure liquid A is 20 Torr at
(b) the relative lowering of vapour pressure is equal to the temperature T) (2018 Adv. Paper-1)
mole fraction of solute
(c) the relative lowering of vapour pressure is proportional True/False
to the amount of solute in solution 17. Following statement is true only under some specific
(d) the vapour pressure of the solution is equal to the mole conditions. Write the condition for it.
fraction of solvent “Two volatile and miscible liquids can be separated by
13. An azeotropic solution of two liquids has boiling point lower fractional distillation into pure components.” (1994)
than either of them when it (1981, 1M)
(a) shows negative deviation from Raoult’s law
Subjective Questions
(b) shows no deviation from Raoult’s law 18. The vapour pressure of two miscible liquids A and B are 300
(c) shows positive deviation from Raoult’s law and 500 mm of Hg respectively. In a flask 10 moles of A is
mixed with 12 moles of B. However, as soon as B is added, A
(d) is saturated
starts polymerising into a completely insoluble solid. The
polymerisation follows first-order kinetics. After 100 min,
Objective Questions II 0.525 mole of a solute is dissolved which arrests the
(One or more than one correct option) polymerisation completely. The final vapour pressure of the
14. For a solution formed by mixing liquids L and M , the vapour solution is 400 mm of Hg. Estimate the rate constant of the
pressure of L plotted against the mole fraction of M in polymerisation reaction. Assume negligible volume change
solution is shown in the following figure. Here xL and x M on mixing and polymerisation and ideal behaviour for the
final solution. (2001, 4M)
represent mole fractions of L and M , respectively, in the
134 Solution and Colligative Properties
19. The molar volume of liquid benzene (density = 0.877 g/mL) same temperature by the mixing 60 g of ethanol with 40 g of
increases by a factor of 2750 as it vaporises at 20° C and that methanol. Calculate the total vapour pressure of the solution
of liquid toluene (density = 0.867 g mL-1 ) increases by a and the mole fraction of methanol in the vapour. (1986, 4M)
factor of 7720 at 20° C. A solution of benzene and toluene at 25. An organic compound (Cx H2 y O y ) was burnt with twice the
20° C has a vapour pressure of 45.0 torr. Find the mole amount of oxygen needed for complete combustion to CO2
fraction of benzene in the vapour above the solution. and H2 O. The hot gases when cooled to 0°C and 1 atm
(1996, 3M) pressure, measured 2.24 L. The water collected during
20. What weight of the non-volatile solute urea cooling weight 0.9 g. The vapour pressure of pure water at
(NH2 — CO —NH2 ) needs to be dissolved in 100 g of water, 20°C is 17.5 mm Hg and is lowered by 0.104 mm when 50 g
in order to decrease the vapour pressure of water by 25%? of the organic compound are dissolved in 1000 g of water.
What will be the molality of the solution? (1993, 3M) Give the molecular formula of the organic compound.
(1983, 5M)
21. The degree of dissociation of Ca(NO3 )2 in a dilute aqueous
solution, containing 7.0 g of the salt per 100 g of water at
26. Two liquids A and B form ideal solution. At 300 K, the
vapour pressure of a solution containing 1 mole of A and
100° C is 70%. If the vapour-pressure of water at 100° C is
3 moles of B is 550 mm of Hg. At the same temperature, if
760mm, calculate the vapour pressure of the solution.
one more mole of B is added to this solution, the vapour
(1991, 4M)
pressure of the solution increases by 10 mm of Hg.
22. The vapour pressure of pure benzene at a certain temperature Determine the vapour pressure of A and B in their pure
is 640 mm Hg. A non-volatile, non-electrolyte solid states. (1982, 4M)
weighing 2.175 g is added to 39.0 g of benzene. The vapour
pressure of the solution is 600 mm Hg. What is the molecular 27. The vapour pressure of pure benzene is 639.70 mm of Hg and
the vapour pressure of solution of a solute in benzene at the
weight of the solid substance? (1990, 3M)
same temperature is 631.9 mm of Hg. Calculate the molality
23. The vapour pressure of a dilute aqueous solution of glucose of the solution. (1981, 3M)
(C6 H12 O6 ) is 750 mm of mercury at 373 K.
Calculate (i) molality and (ii) mole fraction of the solute. 28. What is the molarity and molality of a 13% solution
(1989, 3M)
(by weight) of sulphuric acid with a density of 1.02 g/mL ?
To what volume should 100 mL of this solution be diluted in
24. The vapour pressure of ethanol and methanol are 44.5 and order to prepare a 1.5 N solution ? (1978, 2M)
88.7 mm Hg respectively. An ideal solution is formed at the
pressure of pure water at this temperature is 35 mm Hg, (a) 4 ´ 10-2 (b) 16 ´ 10-4
lowering of vapour pressure will be (c) 4 ´ 10-4 (d) 6 ´ 10-2
(Molar mass of urea = 60 g mol -1 ) (2019 Main, 10 April I)
Solution and Colligative Properties 135
6. Molecules of benzoic acid (C6H5COOH) dimerise in plots of vapour pressure (V.P.) versus temperature (T ).
benzene. ‘w’ g of the acid dissolved in 30 g of benzene [Molecular weight of ethanol is 46 g mol -1 ] (2017 Adv.)
shows a depression in freezing point equal to 2 K. If the Among the following, the option representing change in the
percentage association of the acid to form dimer in the freezing point is
solution is 80, then w is
(Given that K f = 5 K kg mol- 1 , molar mass of benzoic Water Water
V.P./bar
V.P./bar
-1 (a) 1 (b) 1
acid = 122 g mol ) (2019 Main, 12 Jan II) Ice Ice
Water+Ethanol Water+Ethanol
(a) 1.8 g (b) 1.0 g (c) 2.4 g (d) 1.5 g
7. Freezing point of a 4% aqueous solution of X is equal to 270 273 T/K 271 273 T/K
freezing point of 12% aqueous solution of Y . If molecular
weight of X is A, then molecular weight of Y is
(2019 Main, 12 Jan I) Ice Water Ice Water
V.P./bar
V.P./bar
(c) 1 (d) 1
(a) 4A (b) 2A (c) 3A (d) A
8. K 2HgI4 is 40% ionised in aqueous solution. The value of its Water+Ethanol Water+Ethanol
van’t Hoff factor (i) is (2019 Main, 11 Jan II) 270 273 T/K 271 273 T/K
(a) 1.6 (b) 1.8 (c) 2.2 (d) 2.0 15. Consider separate solution of 0.500 M C2 H5 OH (aq),
9. The freezing point of a diluted milk sample is found to be 0.100 M Mg 3 (PO4 )2 (aq), 0.250 M KBr (aq) and 0.125 M
-0.2° C, while it should have been -0.5°C for pure milk. Na 3 PO4 (aq) at 25°C. Which statement is true about these
How much water has been added to pure milk to make the solution, assuming all salts to be strong electrolytes?
diluted sample? (2019 Main, 11 Jan I) (a) They all have the same osmotic pressure (2014 Main)
(a) 2 cups of water to 3 cups of pure milk (b) 0.100 M Mg 3 (PO4 )2 (aq) has the highest osmotic
(b) 1 cup of water to 3 cups of pure milk pressure
(c) 3 cups of water to 2 cups of pure milk (c) 0.125 M Na 3 PO4 (aq) has the highest osmotic pressure
(d) 1 cup of water to 2 cups of pure milk (d) 0.500 M C2 H5 OH (aq) has the highest osmotic pressure
10. Elevation in the boiling point for 1 molal solution of 16. For a dilute solution containing 2.5 g of a non-volatile
glucose is 2 K . The depression in the freezing point for 2 non-electrolyte solute in 100 g of water, the elevation in
molal solution of glucose in the same solvent is 2 K. The boiling point at 1 atm pressure is 2°C. Assuming concentration
relation between K b and K f is (2019 Main, 10 Jan II) of solute is much lower than the concentration of solvent, the
(a) K b = 15
. Kf (b) K b = 0.5 K f vapour pressure (mm of Hg) of the solution is (take K b = 0.76
(c) K b = K f (d) K b = 2K f K kg mol -1 ). (2012)
11. A solution contain 62 g of ethylene glycol in 250 g of water (a) 724 (b) 740
is cooled upto –10º C. If K f for water is 1.86 K kg mol -1 , (c) 736 (d) 718
then amount of water (in g) separated as ice is 17. The freezing point (in°C) of solution containing 0.1 g of
(2019 Main, 9 Jan II) K 3 [Fe(CN)6 ] (mol. wt. 329) in 100 g of water
(a) 32 (b) 48 (c) 64 (d) 16 ( K f = 1.86 K kg mol -1 ) is (2011)
12. For 1 molal aqueous solution of the following compounds, -2 -2
(a) - 2.3 ´ 10 (b) -5.7 ´ 10
which one will show the highest freezing point?(2018 Main) (c) -5.7 ´ 10-3 (d) -1.2 ´ 10-2
(a) [Co(H2 O)6 ]Cl 3 (b) [Co(H2 O)5 Cl]Cl 2 × H2 O
(c) [Co(H2 O)4 Cl 2 ]Cl × 2H2 O (d) [Co(H2 O)3 Cl 3 ] × 3H2 O 18. When 20 g of naphthoic acid (C11 H8 O2 ) is dissolved in 50 g of
benzene (K f = 1.72 K kg mol - 1 ), a freezing point depression
13. The freezing point of benzene decreases by 0.45°C when
0.2 g of acetic acid is added to 20 g of benzene. If acetic of 2 K is observed. The van’t Hoff factor ( i ) is (2007, 3M)
acid associates to form a dimer in benzene, percentage (a) 0.5 (b) 1
association of acetic acid in benzene will be (c) 2 (d) 3
. K kg mol - 1)
(K f for benzene = 512 (2017 Main) 19. The elevation in boiling point, when 13.44 g of freshly
(a) 64.6 % (b) 80.4 % (c) 74.6 % (d) 94.6 % prepared CuCl 2 are added to one kilogram of water, is. [Some
14. Pure water freezes at 273 K and 1 bar. The addition of 34.5 useful data, K b = 0.52 K kg mol - 1 , molecular weight of
g of ethanol to 500 g of water changes the freezing point of CuCl 2 =134.4 g]. (2005, 1M)
the solution. Use the freezing point depression constant of (a) 0.05 (b) 0.1
water as 2 K kg mol -1 . The figures shown below represent (c) 0.16 (d) 0.21
136 Solution and Colligative Properties
Pressure (mmHg)
21. During depression of freezing point in a solution the 1. Solvent X
following are in equilibrium (2003) 2. Solution of NaCl in solvent X
3. Solvent Y
(a) liquid solvent, solid solvent 4. Solution of NaCl in solvent Y
(b) liquid solvent, solid solute
(c) liquid solute, solid solute
(d) liquid solute, solid solvent
22. The molecular weight of benzoic acid in benzene as
360
362
367
368
determined by depression in freezing point method
Temperature (K)
corresponds to
(a) ionisation of benzoic acid (1996, 1M) On addition of equal number of moles of a non-volatile solute
(b) dimerisation of benzoic acid S in equal amount (in kg) of these solvents, the elevation of
(c) trimerisation of benzoic acid boiling point of solvent X is three times that of solvent Y.
(d) solvation of benzoic acid Solute S is known to undergo dimerisation in these solvents.
23. The freezing point of equimolal aqueous solutions will be If the degree of dimerisation is 0.7 in solvent Y , the degree of
highest for (1990, 1M) dimerisation in solvent X is ____. (2018 Adv.)
(a) C6 H5 NH3 Cl (aniline hydrochloride)
(b) Ca(NO3 )2 Subjective Questions
(c) La(NO3 )3 28. 75.2 g of C6 H 5 OH (phenol) is dissolved in a solvent of
(d) C6 H12 O6 (glucose)
K f = 14. If the depression in freezing point is 7 K, then find
24. Which of the following 0.1 M aqueous solution will have
the percentage of phenol that dimerises. (2006, 2M)
the lowest freezing point? (1989, 1M)
(a) Potassium sulphate (b) Sodium chloride 29. 1.22 g C6 H5 COOH is added into two solvents and data of DTb
(c) Urea (d) Glucose and K b are given as :
25. When mercuric iodide is added to the aqueous solution of (i) In 100 g CH3COCH3 DTb = 0.17, K b = 1.7 K kg/mol
potassium iodide (1987, 2M) (ii) In 100 g benzene, DTb = 0.13 and K b = 2.6 K kg/mol
(a) freezing point is raised Find out the molecular weight of C6 H5 COOH in both the
(b) freezing point is lowered cases and interpret the result. (2004, 2M)
(c) freezing point does not change 30. Consider the three solvents of identical molar masses. Match
(d) boiling point does not change their boiling point with their K b values
Objective Questions II Solvents Boiling point Kb values
(One or more than one correct option) X 100°C 0.92
26. In the depression of freezing point experiment, it is found Y 27°C 0.63
that the (1999, 3M) Z 283°C 0.53
(a) vapour pressure of the solution is less than that of pure (2003)
solvent 3 –3
31. To 500 cm of water, 3.0 ´ 10 kg of acetic acid is added. If
(b) vapour pressure of the solution is more than that of
23% of acetic acid is dissociated, what will be the depression
pure solvent
in freezing point? K f and density of water are
(c) only solute molecules solidify at the freezing point
1.86 K kg –1 mol –1 and 0.997 g cm-3 , respectively.
(d) only solvent molecules solidify at the freezing point
(2000, 3M)
Numerical Value Based Question 32. Nitrobenzene is formed as the major product along with a
27. The plot given below shows p -T curves (where p is the minor product in the reaction of benzene with a hot mixture of
pressure and T is the temperature) for two solvents X and Y nitric acid and sulphuric acid. The minor product consists of
and isomolal solution of NaCl in these solvents. NaCl carbon : 42.86%, hydrogen : 2.40%, nitrogen : 16.67% and
completely dissociates in both the solvents. oxygen : 38.07%,
(i) Calculate the empirical formula of the minor product.
(ii) When 5.5 g of the minor product is dissolved in 45 g of
benzene, the boiling point of the solution is 1.84°C higher
Solution and Colligative Properties 137
than that of pure benzene. Calculate the molar mass of the Standard boiling point of ethanol = 351.5 K
minor product then determine its molecular and structural Vapour pressure of pure water = 32.8 mm Hg
formula. (Molal boiling point elevation constant of benzene Vapour pressure of pure ethanol = 40 mm Hg
is 2.53 K kg mol - 1 ). (1999) Molecular weight of water = 18 g mol -1
33. A solution of a non-volatile solute in water freezes at Molecular weight of ethanol = 46 g mol -1
- 0.30° C. The vapour pressure of pure water at 298 K is
In answering the following questions, consider the solutions
23.51 mm Hg and K f for water is 1.86 K kg mol -1 . Calculate
to be ideal dilute solutions and solutes to be non-volatile and
the vapour pressure of this solution at 298 K. (1998, 4M)
non-dissociative. (2008, 3 ´ 4M = 12M)
34. Addition of 0.643 g of a compound to 50 mL of benzene
35. The freezing point of the solution M is
(density : 0.879 g/mL) lowers the freezing point from 5.51° C
(a) 268.7 K (b) 268.5 K (c) 234.2 K (d) 150.9 K
to 5.03° C. If K f for benzene is 5.12, calculate the molecular
weight of the compound. (1992, 2M) 36. The vapour pressure of the solution M is
(a) 39.3 mm Hg (b) 36.0 mm Hg
Passage Based Questions (c) 29.5 mm Hg (d) 28.8 mm Hg
Passage 1 37. Water is added to the solution M such that the mole fraction
of water in the solution becomes 0.9. The boiling point of this
Properties such as boiling point, freezing point and vapour pressure
solution is
of a pure solvent change when solute molecules are added to get
(a) 380.4 K (b) 376.2 K (c) 375.5 K (d) 354.7 K
homogeneous solution. These are called colligative properties.
Applications of colligative properties are very useful in day-to-day
life.
Fill in the Blank
One of its examples is the use of ethylene glycol and water mixture 38. Given that DT f is the depression in freezing point of the
as anti-freezing liquid in the radiator of automobiles. solvent in a solution of a non-volatile solute of molality, m,
A solution M is prepared by mixing ethanol and water. The mole the quantity lim ( DT f / m ) is equal to ...... (1994, 1M)
m ®0
fraction of ethanol in the mixture is 0.9.
Given, freezing point depression constant of water Integer Answer Type Question
( K water
f ) = 1.86 K kg mol -1 39. If the freezing point of a 0.01 molal aqueous solution of a
Freezing point depression constant of ethanol cobalt (III) chloride-ammonia complex (which behaves as a
( K ethanol ) = 2.0 K kg mol -1 strong electrolyte) is - 0.0558°C, the number of chloride(s)
f
in the coordination sphere of the complex is
Boiling point elevation constant of water . K kg mol -1 ]
[ K f of water = 186 (2015 Adv.)
( K bwater ) = 0.52 K kg mol -1
40. MX 2 dissociates into M 2+ and X - ions in an aqueous
Boiling point elevation constant of ethanol
solution, with a degree of dissociation ( a ) of 0.5. The ratio of
( K bethanol ) = 1.2 K kg mol -1
the observed depression of freezing point of the aqueous
Standard freezing point of water = 273 K solution to the value of the depression of freezing point in the
Standard freezing point of ethanol = 155.7 K absence of ionic dissociation is (2014 Adv.)
Answers
Topic 1 Topic 2
1. (c) 2. (b) 3. (a) 4. (a) 1. (c) 2. (c) 3. (c) 4. (b)
5. (d) 6. (b) 7. (b) 8. (b) 5. (d) 6. (c) 7. (c) 8. (b)
9. (b) 10. (a) 11. (b) 12. (b) 9. (c) 10. (d) 11. (c) 12. (d)
13. (c) 14. (b, d) 15. (a, b) 16. (19) 13. (d) 14. (b) 15. (a) 16. (a)
17. T 19. (0.72) 20. (18.5) 21. (746.32 mm) 17. (a) 18. (a) 19. (c) 20. (a)
22. (65.25) 23. (0.75) 24. (0.657) 27. (0.158) 21. (a) 22. (b) 23. (d) 24. (a)
25. (a) 26. (a, d) 27. (0.05) 28. (75%)
28. (180.40 mL)
30. (0.23°C) 33. (23.44 mm) 34. (156 g/mol) 35. (d)
36. (a) 37. (b) 38. (K f ) 40. (2)
Hints & Solutions
Topic 1 Solution and Vapour Pressure pgas = partial pressure of the gas above its solution with a liquid
(solvent) say water.
of Liquid Solutions
cgas = mole fraction of the gas (solute) in the solution.
c H 2 O = mole fraction of water (solvent).
1. Mass of solute (w2 ) ´ 1000
Key Idea Molality ( m) =
Molar mass of solute (M 2 ) ´
mass of solvent (w1 )
w2 1000 pgas pgas
m= ´ KH
M2 w1 KH
1000
and also, m = n2 ´
n1 ´ M1
cH2O=0 cH2O=0
X solvent = 0.8 (Given) It means that nsolvent (n1 ) = 0.8 and
cgas=1 cgas=0
nsolute (n2 ) = 0.2
1000 1000
Using formula m = n2 ´ = 0.2 ´ = 13.88 mol kg -1
n1 ´ M 1 0.8 ´ 18 [ i.e. pgas = K H ] Higher the value of K H, higher
will be the partial pressure of the gas ( pgas ), at a given
2. Key Idea Molality is defined as number of moles of solute temperature. The plot of pgas vs c H2O gives a (-ve) slope.
per kg of solvent. pgas = K H - K H ´ c H2O
w2 1000 Comparing the above equation with the equation of straight line
m = ´
Mw2 w1 y = mx + c
w2 = mass of solute, Mw2 = molecular mass of solute Slope = - K H , intercept = K H
w1 = mass of solvent. So, (i) Higher the value of K H, more (-ve) will be the slope and
it is for z (K H = 40 K bar )
The molality of 20% (mass/mass) aqueous solution of KI (ii) Higher the value of K H, higher with the value of intercept,
can be calculated by following formula. i.e. partial pressure and it is also for z.
w ´ 1000
m= 2 5. (d) According to Dalton’s law of partial pressure
Mw2 ´ w1
ptotal = pA + pB
20% aqueous solution of KI means that 20 gm of KI is present in
= pA° c A + pB° c B …(i)
80 gm solvent.
20 1000 Given, pAº = 400 mm Hg, pBº = 600 mm Hg
m= ´ = 1. 506 » 1. 51mol/kg
166 80 c B = 0.5, c A + c B = 1
\ c A = 0.5
3. Key Idea For a solution of volatile liquids the partial vapour
pressure of each component of the solution is directly On substituting the given values in Eq. (i). We get,
proportional to its mole fraction present in solution. This is ptotal = 400 ´ 0.5 + 600 ´ 0.5 = 500 mm Hg
known as Raoult’s law. Mole fraction of A in vapour phase,
Liquid M and N form an ideal solution. Vapour pressures of p pAº c A 0.5 ´ 400
YA = A = = = 0.4
pure liquids M and N are 450 and 700 mm Hg respectively. ptotal ptotal 500
\ pºN > pºM Mole of B in vapour phase,
So, by using Raoult’s law YA + YB = 1
yN > xN …(i) YB = 1 - 0. 4 = 0.6
and xM > yM …(ii)
6. For ideal solution,
Multiplying (i) and (ii) we get
p = x ¢A p°A + x ¢B p°B
yN xM > yM xN
xM yM Q x ¢A = 0.4, x ¢B = 0.6
\ > p°A = 7 ´ 103 Pa, p°B = 12 ´ 103 Pa
xN yN
Thus, correct relation is (a). On substituting the given values in Eq. (i),
we get
4. According to Henry’s law (at constant temperature) p = 0.4 ´ 7 ´ 103 + 0.6 ´ 12 ´ 103
pgas = K H ´ cgas (solute) = K H ´ [1 - c H 2 O (solvent) ]
= 10 ´ 103 Pa = 1 ´ 104 Pa
pgas = K H - K H c H 2 O
Solution and Colligative Properties 139
Number of moles of solute (n) For the glucose solution (van’t Hoff factor, i = 1),
Now, molality =
Mass of solvent (in kg) DTb1m = DT f2m = 2K
Weight
n= So, Kb ´ 1 ´ 1 = K f ´ 2 ´ 1 Þ K b = 2K f
Molecular mass
wX wY 11. Considering the expression of the depression in freezing point of
= a solution,
M X ´ (wsolvent )1 MY ´ (wsolvent )2
DT f = K f ´ m ´ i
Given, wX = 4 and w(solvent )1 =96 wB ´ 1000
wY = 12 and w(solvent )2 = 88 T f° - Tf = K f ´ ´i …(i)
M B ´ wA (in g )
MX = A
4 ´ 1000 12 ´ 1000 Here, T f° = 0°C, T f = - 10°C
\ =
M X ´ 96 MY ´ 88 wB = mass of ethylene glycol = 62 g
12 ´ 1000 ´ M X ´ 96 M B = molar mass of ethylene glycol
Thus, MY = æ ö
4 ´ 1000 ´ 88 ç CH2 — CH2 ÷
ç ÷
96 ´ 12 ç ½ ½ ÷
= ´ A = 3.27A » 3A ç ÷
4 ´ 88 ç OH OH ÷
è ø
-1
8. The ionisation of K2HgI4 in aqueous solution is as follows: = 62 g mol
Greater the value of i, greater the lowering in freezing point, Actual molar mass of phenol = 94 g/mol
lower will be the freezing temperature, if molarity in all cases are Calculated molar mass
Now, van’t Hoff factor, i =
same. Therefore, K2SO4 solution has the lowest freezing point. Observed molar mass
94
25. Addition of HgI2 to KI solution establishes the following \ i= = 0.625
150.4
equilibrium :
HgI2 + 2KI r K2[HgI4 ]
Dimerisation of phenol can be shown as :
2C6H5OH r (C6 H5OH)2
The above equilibrium decreases the number of ions (4 ions on Initial 1 0
left side of reactions becomes three ions on right side), hence a
At equilibrium 1–a
2
rises the freezing point.
a
Total number of moles at equilibrium, i = 1 - a +
26. In depression of freezing point experiment, vapour pressure of 2
solution is less than that of pure solvent as well as only solvent a
molecules solidify at freezing point. i =1-
2
27. From the graph we can note a
But i = 0.625, thus, 0.625 = 1 -
DTb for solution X i.e., 2
DTb (X) = 362 - 360 = 2 a
= 1 - 0.625
Likewise, DTb for solution Y i.e., DTb (Y) = 368 - 367 = 1 2
Now by using the formula a = 0.75
DTb = i ´ molality of solution× K b Thus, the percentage of phenol that dimerises is 75%.
For solution X 29. (i) DTb = K b × m2
2 = i ´ mNaCl ´ K b (X) …(i) 1.22 1000
Þ 0.17 = 1.7 ´ ´ Þ M = 122
Similarly for solution y M 100
1= i ´ mNaCl ´ K b (Y) ……(ii) 1.22 1000
(ii) 0.13 = 2.6 ´ ´ Þ M = 244
from Eq. (i) and (ii) above M 100
K b (X) 2 The above molar masses suggests thapt benzoic acid is
= or 2 or K b (X) = 2K b (Y)
K b (Y) 1 monomeric in acetone while dimeric in benzene.
For solute S 30. Higher the value of K b of a solvent suggest that there is larger
polarity of solvent molecules, which in turn implies higher
2 S ¾® S 2 (given due to dimerisation)
boiling point due to dipole-dipole interaction.
Initial a 0
a Therefore, the correct order of K b values of the three given
Final (1 - a)
2 solvents is
æ aö Solvents Boiling point Kb
So, here i = ç1- ÷
è 2ø
X 100°C 0.63
æ a ö
DTb [ X ](s) = ç1 - 1 ÷ K b (X) Y 27°C 0.53
è 2 ø Z 283°C 0.92
æ a2ö
DTb [Y] (s) = ç1- ÷ K b (Y) 31. Mass of water = 500 ´ 0.997 g = 498.5 g
è 2 ø
Given, DTb (X)(s) = 3DTb (Y)(s) Also CH3COOH r CH3COO- + H+
æ a1 ö æ a ö 1- a a a
ç1- ÷ K b (X) = 3 ´ ç1- 2 ÷ ´ K b (Y)
è 2 ø è 2 ø Þ i = 1 + a = 1.23
æ a ö æ a ö 3 1000
or 2 ç1- 1 ÷ = 3 ç1- 2 ÷ [Q K b (X) = 2K b (Y) ] Þ - DT f = iK f × m = 1.23 ´ 1.86 ´ ´ = 0.23°C
è 2 ø è 2 ø 60 498.5
æ a ö æ 0.7 ö 32. (i) Empirical formula determination
or 2 ç1- 1 ÷ = 3 ç1- ÷ (as given, a 2 = 0.7)
è 2 ø è 2 ø Elements C H N O
or 4 - 2a 1 = 6 - 2.1 or 2a 1 = 01 . Weight % 42.86 2.40 16.67 38.07
so, a 1 = 0.05 Moles 3.57 2.40 1.19 2.38
1000 ´ K f ´ W B Simplest ratio 3 2 1 2
28. Molar mass of solute (M B ) =
W A ´ DT f
Þ Empirical formula = C3H2NO2
1000 ´ 14 ´ 75.2 5.5 1000
Þ MB = (ii) DTb = 1.84 = 2.53 ´ ´
1000 ´ 7 M 45
M B = 150.4 g per mol Þ M = 168
146 Solution and Colligative Properties
Q Empirical formula weight (84) is half of molar mass, 36. Vapour pressure = p (H2O) + p(ethanol )
molecular formula is C6H4N2O4 a dinitrobenzene :
= 32.8 ´ 0.1 + 40 ´ 0.9
NO2 = 3.28 + 36
= 39.28 mm
37. Now ethanol is solute.
NO2 0.1
(C6H4N2O4)
Molality of solute = ´ 1000 = 6.17
0.9 ´ 18
33. - DT f = K f × m2 Þ DTb = 6.17 ´ 0.52 = 3.20
Þ Tb = 373 + 3.2
0.3
Þ m2 = = 0.1613 = 376.2 K
1.86
n 1000 æ DT f ö
Also, m2 = 2 ´ = 0.1613 38. lim çç ÷÷ = K f (Cryoscopic constant)
n1 M1 m ®0è m ø
n2 0.1613 ´ 18 39. 1+ DT f = iK f m
Þ = = 2.9 ´ 10-3
n1 1000
DT f = 0 – (–0 .0558° C)
n2 n + n1 = 0.0558° C
Þ + 1= 2 = 2.9 ´ 10-3 + 1
n1 n1 0.0558
Þ i (vant Hoff’s factor) = =3
n1 1 186
. ´ 0.01
Þ = c1 = = 0.997
n1 + n2 1 + 2.9 ´ 10-3 This indicates that complex upon ionisation produces three
ions as:
Þ p = p0c 1 = 23.51 ´ 0.997 = 23.44 mm
[Co(NH3 )5 Cl]Cl 2 ® [Co(NH3 )5 Cl]2+ (aq) + 2Cl - (aq)
34. - DT f = 5.51 - 5.03 = 0.48 Thus, only one Cl is inside the coordination sphere.
Þ - DT f = 0.48 = K f × m
40. MX 2 ¾® M 2+ + 2 X -
0.643 1000
Þ 0.48 = 5.12 ´ ´ van’t Hoff factor for any salt can be calculated by using equation
M 50 ´ 0.879
i = 1 + a (n - 1)
Þ M = 156 g/mol
where, n = number of constituent ions
35. In the given solution ‘M’, H2O is solute. \ i (MX 2 ) = 1 + a (3 - 1) = 1 + 2a
0.1 (DT f )observed
Therefore, molality of H2O = ´ 1000 = 2.4 = i = 1 + 2a
0.9 ´ 46 (DT f )theoretical
Þ - DT f = K ethanol
f ´ 2.4 = 2 ´ 2.4 = 4.8
\ i = 1 + 2 ´ 0.5 Þ i=2
Þ T f = 155.7 – 4.8 = 150.9 K
1. Given, Ca 2+ + 2e- ¾
¾® Ca (s); E °= - 2.87 V
Co 3 + + e- ¾® Co 2 + ; E ° = + 181
. V Mg2+ + 2e- ¾
¾® Mg(s); E °= - 2.36 V
Pb 4 + + 2e- ¾® Pb 2 + ; E ° = + 167
. V Ni2+ + 2e- ¾
¾® Ni(s); E °= - 0.25 V
Ce4 + + e- ¾® Ce3 + ; E ° = + 161
. V The reducing power of the metals increases in the order
3+ - (2019 Main, 10 Jan I)
Bi + 3e ¾® Bi; E ° = + 0.20 V
(a) Zn < Mg < Ni < Ca (b) Ni < Zn < Mg < Ca
Oxidising power of the species will increase in the order (c) Ca < Zn < Mg < Ni (d) Ca < Mg < Zn < Ni
(2019 Main, 12 April I)
4+ 4+ 3+ 3+
6. The anodic half-cell of lead-acid battery is recharged using
(a) Ce < Pb < Bi < Co electricity of 0.05 Faraday. The amount of PbSO4
(b) Bi 3 + < Ce4 + < Pb 4 + < Co 3 + electrolysed in g during the process is (Molar mass of
(c) Co 3 + < Ce4 + < Bi 3 + < Pb 4 + PbSO4 = 303g mol -1 ) (2019 Main, 9 Jan I)
(d) Co 3 + < Pb 4 + < Ce4 + < Bi 3 + (a) 11.4 (b) 7.6 (c) 15.2 (d) 22.8
2. A solution of Ni(NO3 )2 is electrolysed between platinum 7. How long (approximate) should water be electrolysed by
electrodes using 0.1 Faraday electricity. How many mole of passing through 100 amperes current so that the oxygen
Ni will be deposited at the cathode? (2019 Main, 9 April II) released can completely burn 27.66 g of diborane?
(Atomic weight of B = 10.8 m) (2018 Main)
(a) 0.20 (b) 0.10 (c) 0.15 (d) 0.05
(a) 6.4 hours (b) 0.8 hours (c) 3.2 hours (d) 1.6 hours
3. Calculate the standard cell potential (in V) of the cell in
which following reaction takes place °
8. Given, ECl -
° 3+
= 1.36 V, ECr = - 0.74 V
2 /Cl /Cr
Fe2+ ( aq ) + Ag+ ( aq ) ¾® Fe3 + ( aq ) + Ag( s ) ° 2 - 3 + = 1.33 V, E ° -
ECr = 1.51 V
O /Cr
2 7 MnO / Mn 2 + 4
Given that,
Among the following, the strongest reducing agent is
E °Ag + / Ag = x V (2017 Main)
E °Fe 2+ / Fe = y V (a) Cr (b) Mn 2+
10. Two Faraday of electricity is passed through a solution of 17. The standard reduction potential values of three metallic
CuSO4 . The mass of copper deposited at the cathode is cations, X, Y, Z are 0.52, - 3.03 and - 1.18 V respectively.
(at. mass of Cu = 63.5 u) (2015 Main) The order of reducing power of the corresponding metals is
(a) 0 g (b) 63.5 g (c) 2 g (d) 127 g (a) Y > Z > X (b) X > Y > Z (1998, 2M)
(i) What is the cell reaction? 44. In a fuel cell hydrogen and oxygen react to produces
(ii) What is the cell emf ? How does it depend on the electricity. In the process hydrogen gas is oxidised at the
concentration of KOH? anode and oxygen at the cathode. If 67.2 L of H2 at STP react
(iii) What is the maximum amount of electrical energy that can in 15 min, what is the average current produced? If the entire
be obtained from one mole of Ni 2O3? (1994, 4M) current is used for electro deposition of copper from copper
37. The standard reduction-potential for the half-cell (II) solution, how many grams of copper will be deposited?
NO-3 ( aq ) + 2H+ + e- ¾® NO2 ( g ) + H2 O is 0.78 V Anode reaction : H2 + 2OH- ¾® 2H2 O + 2e-
+
(i) Calculate the reduction-potential in 8M H . Cathode reaction : O2 + 2H2 O + 2e- ¾® 4OH- (1988, 4M)
(ii) What will be the reduction-potential of the half-cell in a
neutral solution? Assume all the other species to be at unit 45. A cell contains two hydrogen electrodes. The negative
concentration. (1993, 2M) electrode is in contact with a solution of 10-6 M hydrogen
38. Chromium metal can be plated out from an acidic solution ions. The emf of the cell is 0.118 V at 25° C . Calculate the
containing Cr O3 according to the following equation. concentration of hydrogen ions at the positive electrode.
(1988, 2M)
Cr O3 ( aq ) + 6H+ ( aq ) + 6e- ¾® Cr ( s ) + 3H2 O
46. A 100 watt, 110 V incandecent lamp is connected in series
Calculate (i) How many grams of chromium will be plated with an electrolyte cell containing cadmium sulphate
out by 24,000 C and (ii) How long will it take to plate out solution. What weight of cadmium will be deposited by the
1.5 g of chromium by using 12.5 A current? (1993, 2M) current flowing for 10 h? (1987, 5M)
39. An aqueous solution of NaCl on electrolysis gives 47. During the discharge of a lead storage battery, the density of
H2 ( g ), Cl 2 ( g ) and NaOH according to the reaction. sulphuric acid fell from 1.294 to 1.139 g/mL. Sulphuric acid
2Cl – ( aq ) + 2H2 O r 2OH- ( aq ) + H2 ( g ) + Cl 2 ( g ) of density 1.294 g/mL is 39% H2 SO4 by weight and that of
A direct current of 25 A with a current efficiency of 62% is density 1.139 g/mL is 20% H2 SO4 by weight. The battery
passed through 20 L of NaCl solution (20% by weight). holds 3.5 L of the acid and the volume remained practically
Write down the reactions taking place at the anode and constant during the discharge.
cathode. How long will it take to produce 1kg of Cl 2 ? What Calculate the number of ampere-hours for which the battery
will be the molarity of the solution with respect to hydroxide must have been used. The charging and discharging reactions
ion? (Assume no loss due to evaporation) (1992, 3M) are
40. For the galvanic cell, Pb + SO24 - = PbSO4 + 2e- (charging)
Ag | AgCl( s ) , KCl (0.2 M) || KBr (0.001 M), AgBr (s) | Ag PbO2 + 4H+ + SO2- -
4 + 2e
Calculate the emf generated and assign correct polarity to = PbSO4 + 2H2 O (discharging) (1986, 5M)
each electrode for a spontaneous process after taking into
account the cell reaction at 25° C. 48. How long a current of 3 A has to be passed through a
[ K sp (AgCl) = 2.8 ´ 10-10 , K sp (AgBr) = 3.3 ´ 10-13] (1992, 4M) solution of silver nitrate to coat a metal surface of 80 cm2
with a 0.005 mm thick layer?
41. A current of 1.70 A is passed through 300.0 mL of 0.160M
solution of a ZnSO4 for 230 s with a current efficiency of Density of silver is 10.5 g/cm3 . (1985, 3M)
90%. Find out the molarity of Zn 2+ after the deposition Zn. 49. In an electrolysis experiment current was passed for 5 h
Assume the volume of the solution to remain constant during through two cells connected in series. The first cell contains a
the electrolysis. (1991, 4M) solution of gold and the second contains copper sulphate
42. Calculate the quantity of electricity that would be required to solution. 9.85 g of gold was deposited in the first cell. If the
reduce 12.3 g of nitrobenzene to aniline, if the current oxidation number of gold is +3, find the amount of copper
efficiency for the process is 50%. If the potential drop across deposited on the cathode of the second cell. Also calculate
the cell is 3.0 V, how much energy will be consumed? the magnitude of the current in ampere.
(1990, 3M) (Atomic weight of Au = 197 and atomic weight of
43. An acidic solution of Cu 2+ salt containing 0.4 g of Cu 2+ is Cu = 63.5) (1983, 3M)
electrolysed until all the copper is deposited. The electrolysis
50. A current of 3.7 A is passed for 6 h between nickel electrodes
is continued for seven more minutes with the volume of
in 0.5 L of a 2.0 M solution of Ni(NO3 )2 . What will be the
solution kept at 100 mL and the current at 1.2 A. Calculate
molarity of solution at the end of electrolysis? (1978, 2M)
the volume of gases evolved at NTP during the entire
electrolysis. (1989, 5M)
Topic 2 Conductivity of Electrolytic Solutions and their
Measurement and Nernst Equation
Objective Questions I (Only one correct option) 6. Given the equilibrium constant ( K C ) of the reaction :
1. The decreasing order of electrical conductivity of the Cu( s ) + 2Ag+ ( aq ) ¾® Cu2 + ( aq ) + 2Ag( s )
following aqueous solution is
0.1 M formic acid (A), is 10 ´ 1015 , calculate the Ecell
° of this reaction at 298 K.
0.1 M acetic acid (B), é RT ù
0.1 M benzoic acid (C). (2019 Main, 12 April II) êë2.303 F at 298 K = 0.059 V úû
(2019 Main, 11 Jan II)
(a) A > C > B (b) C > B > A (a) 0.4736 V (b) 0.04736 mV
(c) A > B > C (d) C > A > B (c) 0.4736 mV (d) 0.04736 V
2. Which one of the following graphs between molar
7. For the cell, Zn( s)|Zn2+ ( aq )||M x+ ( aq )|M ( s), different
conductivity (Lm ) versus C is correct?
half cells and their standard electrode potentials are given
(2019 Main, 10 April II)
below.
Na
KC M x+ (aq)/M(s)
l Au(s) Ag(s) Fe 2+ (aq) Fe(s)
(a) L m (b) L m
Na
E ° M x + / M /V
KC
KC
Cl
Cl
12. Given below are the half-cell reactions (2014 Main) Column I Column II
Mn 2 + + 2e- ¾® Mn ; E° = - 1.18 eV P. (C2 H5 )3 N + CH3 COOH 1. Conductivity decreases
2 (Mn 3+ + e- ¾® Mn 2+ ) ; E° = + 1.51 eV and then increases
X Y
The E ° for 3Mn 2 + ® Mn + 2Mn 3+ will be
Q. KI(0.1 M) + AgNO3 (0.01 M) 2. Conductivity decreases
(a) - 2. 69 V; the reaction will not occur
X Y and then does not
(b) - 2. 69 V; the reaction will occur
change much
(c) - 0. 33 V; the reaction will not occur
(d) - 0. 33 V; the reaction will occur R. CH3 COOH + KOH 3. Conductivity increases
13. The equivalent conductance of NaCl at concentration C and X Y and then does not
at infinite dilution are lC and l¥ , respectively. The correct change much
relationship between lC and l¥ is given as (where, the S. NaOH + HI 4. Conductivity does not
constant B is positive) (2014 Main) change much and then
X Y
(a) lC = l¥ + ( B ) C (b) lC = l¥ - ( B ) C increases
(c) lC = l¥ - ( B ) C (d) lC = l¥ + ( B ) C
Codes
14. Resistance of 0.2 M solution of an electrolyte is 50 W . The P Q R S P Q R S
specific conductance of the solution of 0.5 M solution of same (a) 3 4 2 1 (b) 4 3 2 1
electrolyte is 1.4 S m-1 and resistance of same solution of the (c) 2 3 4 1 (d) 1 4 3 2
same electrolyte is 280 W . The molar conductivity of 0.5 M 17. Consider the following cell reaction,
solution of the electrolyte in Sm 2mol-1 is (2014 Main) 2Fe( s ) + O2 ( g ) + 4H+ ( aq ) ¾® 2Fe2+ ( aq ) + 2H2 O ( l ),
-4 -3
(a) 5 ´ 10 (b) 5 ´ 10 E ° = 1.67 V
3 2
(c) 5 ´ 10 (d) 5 ´ 10
At [Fe2+ ] = 10-3 M, P(O 2 ) = 0.1 atm and pH = 3, the cell
15. The standard reduction potential data at 25°C is given below. potential at 25° C is (2011)
E° (Fe3 + / Fe2 + ) = + 0.77 V; E° (Fe2 / Fe) = -0.44 V; (a) 1.47 V (b) 1.77 V
E° (Cu 2 + / Cu) = + 0.34 V; E° (Cu + / Cu) = + 0.52 V; (c) 1.87 V (d) 1.57 V
E ° ( O2 ( g ) + 4H+ + 4 e- ) ¾® 2H2 O) = + 1.23 V; 18. AgNO3 (aqueous) was added to an aqueous KCl solution
- gradually and the conductivity of the solution was measured.
E ° ( O2 ( g ) + 2H2 O + 4 e ) ¾® 4OH) = + 0.40 V
The plot of conductance (L) versus the volume of AgNO3 is
E° (Cr 3 + / Cr) = -0.74 V; E° (Cr 2 + / Cr) = +0.91 V
× ×
×
××
×
given below the lists. (2013 Adv.) ×
Volume Volume Volume Volume
(P) (Q) (R) (S)
Column I Column II (2011)
P. E° (Fe 3+
/ Fe) 1. - 0.18 V (a) (P) (b) (Q) (c) (R) (d) (S)
45. The standard reduction potential of the Ag + /Ag electrode at 50. Give reasons in one or two sentences.
-17 “Anhydrous HCl is a bad conductor of electricity but
298 K is 0.799 V. Given that for AgI, K sp = 8.7 ´ 10 ,
aqueous HCl is a good conductor.” (1985, 1M)
evaluate the potential of the Ag + / Ag electrode in a saturated
solution of AgI. Also calculate the standard reduction 51. Consider the cell,
potential of the I- / AgI/Ag electrode. (1994, 3M) Zn | Zn 2 + ( aq ) (1.0 M ) || Cu 2 + ( aq ) (1.0 M ) | Cu
46. Zinc granules are added in excess to a 500 mL of 1.0 M The standard reduction potentials are 0.350 V for
nickel nitrate solution at 25° C until the equilibrium is Cu 2 + ( aq ) + 2e- ¾® Cu
reached. If the standard reduction potential of Zn 2+ / Zn and and -0.763 V for Zn 2 + ( aq ) + 2e- ¾® Zn
Ni 2+ / Ni are – 0.75 V and – 0.24 V respectively. Find out the
(i) Write down the cell reaction.
concentration of Ni 2+ in solution at equilibrium. (1991, 2M) (ii) Calculate the emf of the cell.
47. The standard reduction potential of Cu 2+ / Cu and Ag + / Ag (iii) Is the cell reaction spontaneous or not? (1982, 2M)
electrodes are 0.337 and 0.799 V respectively. Construct a
galvanic cell using these electrodes so that its standard emf is Integer Type Questions
positive. For what concentration of Ag + will the emf of the 52. The conductance of a 0.0015 M aqueous solution of a weak
cell, at 25° C, be zero if the concentration of Cu 2+
is 0.01 M? monobasic acid was determined by using a conductivity cell
(1990, 3M) consisting of platinised Pt electrodes. The distance between
the electrodes is 120 cm with an area of cross section of 1 cm
48. The standard reduction potential at 25° C of the reaction, 2
. The conductance of this solution was found to be 5 ´ 10-7
2H2 O + 2e- r H2 + 2OH- , is -0.8277 V. Calculate the
S. The pH of the solution is 4. The value of limiting molar
equilibrium constant for the reaction,
conductivity ( L°m ) of this weak monobasic acid in aqueous
2H2 O r H3 O+ + OH- at 25° C. (1989, 3M)
solution is Z ´ 102 S cm -1 mol -1 . The value of Z is
49. The emf of a cell corresponding to the reaction. (2017 Adv.)
Zn( s ) + 2H+ ( aq ) ¾® Zn 2+ (0.1M) + H2 , ( g ,1atm) 53. All the energy released from the reaction
is 0.28 V at 25° C. X ® Y , Dr G ° = - 193 kJmol -1 is used for oxidising M + as
Write the half-cell reactions and calculate the pH of the M + ® M 3 + + 2e- , E ° = - 0.25 V.
solution at the hydrogen electrode. Under standard conditions, the number of moles of M +
E° ( Zn 2+ / Zn ) = -0.76 V E ° + =0
H /H2
oxidised when one mole of X is converted to Y is
(1986, 4M)
[F = 96500 C mol - ] (2015 Adv.)
Answers
Topic 1 Topic 2
1. (b) 2. (d) 3. (a) 4. (c) 1. (a) 2. (c) 3. (b) 4. (c)
5. (b) 6. (b) 7. (c) 8. (a) 5. (d) 6. (a) 7. (a) 8. (b)
9. (d) 10. (b) 11. (d) 12. (b) 9. (b) 10. (c) 11. (c) 12. (a)
13. (c) 14. (a) 15. (c) 16. (a) 13. (c) 14. (a) 15. (d) 16. (a)
17. (a) 18. (b) 19. (d) 20. (c) 17. (d) 18. (d) 19. (b) 20. (b)
21. (d) 22. (c) 23. (c) 24. (a) 21. (b) 22. (b) 23. (c) 24. (–14.16)
25. (a, b) 26. (a,b,d) 27. (10) 25. (b) 26. (d) 27. (b) 28. (c)
28. (–11.62 JK mol -1) 29. (b) 30. (d) 29. (c) 30. (d) 31. (a) 32. (b)
31. (d) 33. (8 ´ 10 -5
M) 34. (0001 V) 35. (300 cm ) 2
33. (c) 34. (d) 35. (55) 37. (1010)
36. (-245.11 kJ) 39. (1.4085 M) 40. (-0.037 V) 41. (0.154 M) 38. (0.05 M) 40. (2.45 ´ 10 -12
) 41. (5.89 ´ 10 7)
12
42. (347.40 kJ) 44. (190.50 g) 45. (10 -4
M) 46. (19.1 g) 42. (6.88 ´ 10 ) 43. (- 0.222 V) 44. (0.7926 V) 46. (1.7 ´ 1017)
47. (265 Ah) 48. (125 s) 49. (0.80 A) 50. (1.172 M) 47. (1.57 ´ 10 -9) 48. (1.04 ´ 10 -14 ) 49. (8.6)
52. (6 ´ 10 2 S cm -1 mol -1) 53. (4 mol)
Hints & Solutions
Topic 1 Electrochemical Cells 5. Reducing power of an element
Key Idea Negative E ° means that redox couple is weaker 1
1. µ
oxidising agent than H+ /H2 couple. Positive E° means that Standard reduction potential
redox couple is a stronger oxidising agent than H+ / H2 Here, E °
M2 + / M
values of the given metals are as,
couple Metals Ni Zn Mg Ca
3+ - 2+
Given, Co + e ¾¾® Co ; E ° = + 1.81 V E°( V ) - 0.25 - 0.76 - 2.36 - 2.87
Pb4+ + 2e- ¾¾® Pb2+ ; E ° = + 1.67 V ¾¾¾¾¾¾¾¾¾¾¾¾¾¾®
Reducing power
4+ - 3+ Thus, the correct order of increasing reducing power of the
Ce + e ¾¾® Ce ; E ° = + 1.61 V
given metal is,
Bi3+ + 3e- ¾¾® Bi; E ° = + 0.20 V
Ni < Zn < Mg < Ca.
Oxidising power of the species increases in the
order of Bi3 + < Ce4+ < Pb4+ < Co3+ . 6. Key Idea This question is based upon Faraday’s first law
Higher the emf value, stronger the oxidising power. The which states that “Mass of any substance deposited or
maximum value of emf is possessed by Co3+ . Hence, it has liberated at any electrode is directly proportional to the
maximum oxidising power. Whereas Bi3+ possess the lowest quantity of electricity passed.”
emf value. Hence, it has minimum oxidising power. During charging:
2. A solution of Ni(NO3 )2 is electrolysed between platinum Pb + SO24 - ¾® PbSO4 + 2e-
electrodes using 0.1 Faraday electricity. It means that 0.1 Þ 1 F º 1 g-equiv. of PbSO4
equivalent of Ni2+ will be discharged. 1 303
= mol of PbSO 4 Þ g PbSO4
Electrolysis of Ni(NO3 )2 gives 2 2
Ni2+ + 2e- ¾® Ni (Atomic mass of Ni = 58.7) 303
\ 0.05 F º ´ 0.05 g of PbSO4
Number of equivalents = Number of moles ´ number of electrons. 2
. = Number of moles ´ 2
01 = 7.575 g of PbSO4
01
. 7. Given that, i = 100 amp. also, 27.66 g of diborane (B2 H6 )
\Number of moles of Ni = = 0.05
2
Molecular mass of B2 H6 = 10.8 ´ 2 + 6 = 27.6
3. Fe2+ (aq) + Ag + (aq) ¾® Fe3 + (aq) + Ag(s) Given mass 27.66
Number of moles of B2 H6 in 27.66 g = = »1
º
\ Ecell = Eº - Eº = xV - E º … (i) Molar mass 27.6
Ag + /Ag Fe3+ / Fe2 + Fe3+ / Fe2 +
Now consider the equation
Now, for two half-cells B2H6 + 3O2 ¾® B2O3 + 3H2O
(i) Fe2+ + 2e- ¾® Fe; EFe
º
2+
/ Fe
= E1º = yV DG2º = - 2FE1º From the equation we can interpret that 3 moles of oxygen is
required to burn 1 mole (i.e. 27.6 g) B2 H6 completely.
(ii) Fe3 + + 3e- ¾® Fe ; EFe
º
3+ = E2º = zV DG2º = - 3FE2º
/ Fe Also consider the electrolysis reaction of water i.e.
So, Fe3 + + e– ¾® Fe2+ ; E º = E3º = ? H2O s 2H+ + O--
Fe3+ / Fe2 +
; DG3º = - 1 ´ FE3º +2e -
2H+ ¾¾® 2H ¾® H2
Cathode
Again, DG3º = DG2º - DG1º 2 such
-- Anode
O ¾¾® O ¾¾® O2
Þ - FE3º = - 3FE2º - (- 2FE1º ) -
-2e atoms
Þ - E3º = 2E1º - 3E2º Þ E3º = 3E2º - 2E1º From the above equation it can be easily interpreted that in
Þ E º 3+ 2 + = (3z - 2 y) V electrolysis of water for the production of 1 mole of oxygen
Fe / Fe from 1 mole of H2O at anode 4 moles electrons are required.
So, from equation (i) Likewise for the production of 3 moles of O2 12(3 ´ 4 ) moles of
º
Ecell = xV - (3z - 2 y) V = (x - 3z + 2 y) V electrons will be needed.
So, the total amount of charge required to produce 3 moles of
4. Higher the standard reduction potential (E ºMn+ / M ), better is
oxygen will be 12 ´ F or 12 ´ 96500
oxidising agent. Among the given, E °S2O 28- / SO 24- is highest, hence We know Q = it
S2O2- So, 12 ´ 96500 = 100 ´ t in seconds
8 is the strongest oxidising agent.
12 ´ 96500
The decreasing order of oxidising agent among the given option or = tin hours = 3.2 hours
is as follows: 100 ´ 3600
S2O28- > Au 3+ > O2 > Br2
Electrochemistry 157
8. The substances which have lower reduction potentials are 15. One of the requirement for electrolyte used in salt-bridge is, both
° 3 + / Cr = - 0.74 V) is
stronger reducing agents. Therefore, Cr (ECr cation and anion must have comparable size so that they migrate
towards electrodes of opposite polarity at comparable speeds.
the strongest reducing agent among all the other given options.
16. Higher the value of reduction potential, stronger the oxidising
9. Oxidation at anode agent.
H2 (g ) ¾® 2H+ (aq)+ 2e-; ESHE
° = 0.00 V
Q E° : Z > Y > X
Reduction at cathode Þ Y will oxidise X but not Z.
M 4+ (aq)+ 2e- ¾® M 2+ (aq); EM° 4+ / M 2+ = 0.151 V
17. Lower the value of E°, stronger the reducing agent.
Net: M 4+ (aq) + H2 (g ) ¾® M 2+ (aq) + 2H+ (aq); Reducing power:
[ M 2+ ] [ H+ ] 2 [ M 2+ ] Y (E ° = - 3.03 V) > Z (E ° = - 1.18 V) > X (E ° = 0.52 V).
K= ° = 0.151 V ) =
(Ecell
4+
[ M ] pH 2 [ M 4+ ] 18. Fe2+ + 2e- ¾® Fe ; E° = - 0.41V
0.059 2+ -
° -
Ecell = Ecell log K Zn ¾® Zn + 2e ; E°= + 0.76V
2 2+ 2+
0.059 [ M 2+ ] Þ Fe + Zn ¾® Zn + Fe ; E° = + 0.35V
0.092 = 0151. - log 4+
2 [M ] 19. In a lead storage battery, sulphuric acid is consumed as :
0.059 x Pb + PbO2 + 2H2SO4 ¾® 2PbSO4 + 2H2O
0.059 = log10
2
\ x
log10 = 2 20. In a galvanic cell, oxidation occur in the left hand electrode
chamber and reduction in right hand electrode chamber. In the
\ x=2
following cell.
10. Given, Q = 2F
Pt | H2 (g ) | HCl (l )||AgCl (s) | Ag(s)
Atomic mass of Cu = 63.5u
The cell reactions are :
Valency of the metal Z = 2 1
H (g ) ¾® H+ + e- At anode
We have, CuSO4 ¾® Cu 2+ + SO24- 2 2
- -
AgCl(s) + e ¾® Ag + Cl At cathode
Cu 2+ + 2 e- ¾® Cu
1mol 2mol 1mol =63.5g 1
2F Net : H2 (g ) + AgCl (s) ¾® H+ + Ag(s) + Cl -
2
Alternatively.
E 2 ´ 63.5 21. One gram equivalent of an electrolyte required 1.0 mole of
W = ZQ = × 2F = 2E = = 63.5
F 2 electronic charge for discharging.
11. Higher the standard reduction potential, better is oxidising 22. In aqueous solution, only those ions who are less electropositive
°
agent. Among the given EMnO -
/ Mn 2+
is highest, hence MnO -4 is than hydrogen (E° > 0) would be deposited.
4
the strongest oxidising agent. Therefore, in the present case, only Ag, Hg and Cu would be
deposited on passing electricity through aqueous solution of
12. 0.01 mol of H2 = 0.02 g equivalent
these ions, Mg will not be deposited.
Þ Coulombs required = 0.02 ´ 96500 = 1930 C
Also, higher the value of E°, easier will be their reduction,
Þ Q = It = 1930 C
1930 therefore, the sequence in which ions will be deposited on
Þ t= = 19.3 ´ 104 s increasing voltage across the electrodes is :
10 ´ 10- 3
Ag, Hg, Cu.
13. In electrolytic cell electrolysis occur at the cost of electricity :
23. Faraday’s law of electrolysis is related to equivalent weight of
At cathode : M n+ + ne ¾® M
electrolytes as “the number of Faraday’s passed is equal to the
(electron gone in solution) number of gram equivalent of electrolytes discharged.”
At anode : X n- ¾® X + ne-
24. Lower the value of E°, stronger the reducing agent.
(electron supplied to anode)
Therefore, electron is moving from cathode to anode via internal 25. PLAN This problem is based on characteristics of salt-bridge.
circuit. Functions of salt-bridge are
14. MnO-4 cannot be used for oxidation of Fe2+ in HCl medium (i) It connects the two half-cells and completes the cell circuit.
because the following reaction is spontaneous : (ii) It keeps the solutions of two half-cells and complete the cell
circuit but does not participate chemically in the cell
MnO-4 + Cl - ¾® Mn 2+ + Cl 2; E° = 1.51 - 1.40 = 0.11 V reaction.
In all other cases, the redox process between oxidising agent and (iii) It maintains the diffusion of ions from one electrode to
medium (HCl or H2SO4) are non-spontaneous, would not another electrode.
interfere oxidation of Fe2+ . (iv) A cell reaction may also occur in the absence of salt-bridge.
Sometimes, both the electrodes dip in the same electrolyte
158 Electrochemistry
solution and in such cases we do not require a salt-bridge.” Now by using the Nernst equation
So, option (c) is incorrect. RT [Product]
Ecell = E°cell - ln
(v) This prevent mixing of two electrolytic solutions hence, nF [Reactant]
option (d) is incorrect choice. After putting the values
Hence, correct choices are (a), (b). RT [ A n+ ]2
0 = Ecell
° - ln
26. Metals with E° value less than 0.96 V will be able to reduce NO-3 2nF [ B 2n+ ]
in aqueous solution.Therefore, metals V (E° = - 1.19 V), RT [ 2 ]2 RT
or E° = ln = ln 4 …(i)
Fe (E° = – 0.04 V), Hg (E° = 0.86 V) will all reduce NO-3 but Au 2 nF [1] 2nF
(E° = 1.40 V) cannot reduce NO-3 in aqueous solution. Further from the formula,
27. (10) Equation of cell reaction according to the cell notation DG ° = - nFE ° Þ DG ° = - 2nFE °
given, is Now putting the value of E° from eq. (i)
Reduction RT
DG ° = - 2nF ´ ln 4 …(ii)
2nF
Mg(s) + Cu2+(aq) Mg2+(aq) + Cu(s) DG ° = - RT ln 4
Finally, using the formula
Oxidation D G ° = D H ° - TD S °
° = 2.70 V, T = 300 K
Given, Ecell DG ° = 2DG ° - TDS ° (as DH ° = 2DG °, given)
D G ° = TD S °
with [Mg 2+ (aq)]=1 M and [Cu 2+ (aq)]=1 M
DG ° - RT ln 4
or DS ° = =
and n= 2 T T
Further, Ecell = 2 . 67 V (from eq. (ii), DG ° = - RT ln 4)
with [Cu 2+(aq) ]=1M = - R ln 4 = - 8.3 ´ 2 ´ 0.7
and [Mg 2+ (aq)]= xM (as all values given)
. J/K-mol
= - 1162
F
and = 11500 KV -1 500
R 29. Moles of NaCl electrolysed = 4 ´ = 2.0
1000
where F = Faraday constant, R = gas constant
From the formula, Þ moles of Cl 2 produced = 1.0
2+
RT [Mg (aq)] 2Cl - ¾® Cl 2 + 2e-
° -
Ecell = Ecell ln 2+
nF [Cu (aq)] Hg
30. At cathode Na + + e- ¾¾® Na(Hg)
After putting the given values Amalgam
RT x Two moles of Na formed during electrolysis would produce two
2.67 = 2.70 - ln
2F 1 moles of Na(Hg) amalgam.
R ´ 300 Þ mass of amalgam = 2 ´ (23 + 200) = 446 g
or 2.67 = 2.70 - ´ ln x
2F 31. Two Faraday of electric charge would be required for
- R ´ 300 electrolysis of 2.0 moles of NaCl.
-0.03 = ´ ln x
2F
Þ total coulombs = 2 ´ 96500 = 193000 C
0.03 ´ 2 F
or ln x = ´ ° . Also, left
300 R 32. Since, activities of all the ions are unity, Ecell = Ecell
0.03 ´ 2 ´ 11500 hand electrode is at lower reduction potential, it act as anode and
= = 2.30
300 E ° = E ° (Ce4+ , Ce3+ ) - E ° (Fe3+ , Fe2+ ) = 0.84
So, ln x = 2.30
i.e. electrons will flow from left to right hand electrode and
or x =10 (as given ln (10) = 2.30)
current from right hand electrode [Pt (2)] to left hand electrode
28. Given, [Pt(1)].
A (s)| A n+ (aq, 2 M ) || B 2n+ (aq, 1 M ) | B (s) [Fe3+ ][Ce3+ ]
Also, E = E ° - 0.0592 log
So, reactions at respective electrode will be [Fe2+ ][Ce4+ ]
Anode A (s)¾® A n+ + ne- ´ 2 As electrolysis proceeds, E will decrease and therefore, current.
Cathode B 2n+ + 2 ne- ¾® B (s) 2 ´ 10- 3 ´ 16 ´ 60
33. The number of Faraday’s passed =
Overall reaction 96500
2 A (s) + B 2n+ (aq) ¾® 2 A n+ (aq) + B (s) = 1.99 ´ 10- 5
Further, Þ number of gram equivalent of Cu 2+ deposited
DH ° = 2DG ° and Ecell = 0 is also given = 1.99 ´ 10- 5
Electrochemistry 159
1.99 1.5 9
Þ number of moles of Cu 2+ deposited = ´10- 5 » 10- 5 (ii) Number of gram equivalent of Cr = ´6=
2 52 52
Absorbance is directly proportional to [Cu 2+ ]. Therefore, Þ Coulombs required for 1.5 g Cr =
9
´ 96500 = It
if ‘C’ be the initial molarity, 0.5 C will be the final molarity. 52
Þ 0.5 C ´ 0.25 = 10- 5 Þ C = 8 ´ 10- 5 M 9 ´ 96500
Þ t= s = 22.27 min
9.65 ´ 60 ´ 60 52 ´ 12.5
34. The number of Faraday’s passed = = 0.36 F
96500 39. At anode 2Cl - ¾® Cl 2 + 2e-
After electrolysis : [Ag+ ] = 1.36 M At cathode 2H2O + 2e- ¾® H2 + 2OH-
0.36 1000
[Cu 2+ ] = 1 – = 0.82 M 1 kg Cl 2 = equivalent of Cl 2 = 28.17 equivalent
2 35.5
E1 (before electrolysis) = E ° Þ Theoretical electricity requirement = 28.17 F
0.0592 [Ag+ ]2 Q Efficiency is only 62%
E2 (after electrolysis) = E ° - log \ Electricity requirement (experimental)
2 [Cu 2+ ]
28.17 ´ 100
0.0592 (1.36)2 = F = 45.44 F
Þ E1 - E2 = log = 0.01 V (decreased) 62
2 0.82
Þ 45.44 ´ 96500 = 25 t (in second)
35. Coulombs passed = 8.46 ´ 8 ´ 60 ´ 60 = 243648 C Þ t = 48.72 h
Number of Faraday’s passed =
243648
= 2.52 Also, gram equivalent of HO- produced = 28.17
96500 28.17
63.5 Þ Molarity of HO- = = 1.4085 M
Weight of Cu plated = 2.52 ´ g = 80.01 g 20
2
2.8 ´ 10- 10
80.01 40. [Ag+ ] in left hand electrode chamber =
Volume of Cu plated = = 7.62 cm 3 0.2
10.5 = 1.4 ´ 10- 9 M
7.62
Þ Area plated out = = 3000 cm 2 3.3 ´ 10- 13
0.00254 [Ag+ ] in right hand electrode chamber =
0.001
36. Given, FeO (s)/Fe (s) E° = – 0.87 V = 3.3 ´ 10- 10 M
and Ni 2O3 /NiO (s) E° = + 0.40 V
[Ag+ ] anode
Electrode at lower reduction potential act as anode and that at emf = 0 – 0.0592 log
[Ag+ ] cathode
higher reduction potential act as cathode.
(i) Electrodes reaction : 1.4 ´ 10- 9
= – 0.0592 log = – 0.037 V
Fe(s) + 2OH- ¾® FeO (s) + H2O (l ) 3.3 ´ 10- 10
E° = + 0.87 V Therefore, the cell as written is non-spontaneous and its reverse
Ni 2O3 (s) + H2O (l ) + 2e- ¾® 2NiO (s) + 2OH- E° = 0.40 V will be spontaneous with emf = 0.037 V.
Net : Fe (s) + Ni 2O3 (s) ¾® 2NiO (s) + FeO (s) 1.7 ´ 230
41. Faraday’s passed = = 4.052 ´ 10- 3 F
E° = 1.27 V 96500
(ii) Emf is independent of concentration of KOH. Faradays used for reduction of Zn 2+ = 4.052 ´ 10- 3 ´ 0.9
(iii) Maximum amount of energy that can be obtained = DG ° = 3.65 ´ 10- 3
Þ DG ° = - nE ° F = – 2 ´ 1.27 ´ 96500 J = – 245.11 kJ
Þ Meq. of Zn 2+ reduced = 3.65
i.e. 245.11 kJ is the maximum amount of obtainable energy.
Initial meq. of Zn 2+ = 300 ´ 0.16 ´ 2 = 96
1
37. (i) E = 0.78 – 0.0592 log 2 = 0.887 V Þ Meq. of Zn 2+ remaining = 96 - 3.65 = 92.35
8
1 92.35 1
(ii) E = 0.78 – 0.0592 log = – 0.0488 V Þ Molarity of Zn 2+ = ´ = 0.154 M
(10- 7 )2 2 300
Zn Fe 0.32
2. [Zn + Fe 2+ ® Zn2+ + Fe] - 0.44 - (- 0.76) = + 0.32 V for 2e- + . V
= + 016
2
Zn Au
216
.
3. [ 3Zn + 2Au 3+ ® 3Zn 2+ + 2Au] 1.40 - (-0.76) = + 2.4 V for 6e- + = + 0.36 V
6
Zn Fe
153
.
4. [ 3Zn + 2Fe3+ ® Zn 2+ + 2Fe2+ ] . V for 2e-
0.77 - (-0.76) = + 153 + = + 0.765 V
2
E ° = - 1.18 V
Þ Ec° = 0.92 - 0.72 = 0.20 V 2
Mn 2+ ¾ ¾ ¾ ¾ ¾® Mn
Note 10 -6 molal HCl is a very dilute solution. \ For Mn 2+ disproportionation,
So, 10 -6 m ~
- 10 -6 M E° = - 1. 51 V - 1.18 V = - 2. 69 V < 0
9. The relationship between standard electrode potential (E° ) and Thus, all reaction will not occur.
equilibrium constant (K ) of the cell reaction, 13. According to Debye Huckel Onsager equation,
Zn(s)+ Cu 2+(aq) c Zn 2+(aq)+ Cu(s) lC = l ¥ - B C
can be expressed as,
where, lC = limiting equivalent conductivity at concentration C
RT
E° = ln K Þ K = enFE °/ RT l ¥ = limiting equivalent conductivity at infinite dilution
nF
C = concentration
Given, n = 2, F = 96000 C mol -1
14. In order to solve the problem, calculate the value of cell constant
E° = 2 V, R = 8 JK -1mol -1
of the first solution and then use this value of cell constant to
T = 300 K calculate the value of k of second solution. Afterwards, finally
2 ´ 96000 ´ 2
calculate molar conductivity using value of k and m.
8 ´ 300
\ K =e = e160 For first solution,
10. The redox reaction is : Zn(s) + Cu 2+ ¾® Zn 2+ + Cu k = 1.4 Sm -1, R = 50 W, M = 0.2
2.303 RT 1 l
The Nernst equation is E = E ° - log10 Specific conductance (k ) = ´
2F R A
1 l
2.303RT 1.4 Sm -1 = ´
= 11
. - 50 A
2F
l
Þ = 50 ´ 1.4 m -1
A
Electrochemistry 163
Conductance
n2 = 2 E2° = - 0.44 V
Q Fe3+ + 3e- ¾® Fe n3 = 3 E3° = ?
n E ° + n2E °2 0.77 + 2(-0.44) -0.11
E °3 = 1 1 = = = -0.04 V
n3 3 3
Volume of acid added
Thus, P — (3)
II. Strong Weak Conductance increases
Net reaction
(CH 3COOH) (KOH) slightly as NH+4 (salt) is
4 H2O r 4 H+ + 4 OH-
hydrolysed forming HCl.
is obtained from n E° After neutral point, it acid
2H2O ¾® O 2 + 4 H+ + 4 e- n1 = 4 -1.23 V increases rapidly due to
2H2O + O 2 + 4 e- ¾® 4OH- n2 = 4 + 0.40 V addition of strong
+ -
4H2O ¾® 4H + 4 e n3 = 4 ? Conductance
n1E °1 + n2E °2
E °3 = = E °1 + E °2
n3
= - 1.23 + 0.40 = -0.83 V
Thus, Q — (4)
(R) Cu 2+ + Cu ¾® 2Cu + Volume of acid added
For thus E° of Cu 2+ ¾® Cu +
is also required. n E° III. Weak Strong Conductivity decreases
Cu 2+ + 2e- ¾® Cu 2 0.34 V (CH 3COOH) (KOH) due to neutralisation of
conducting strong base
Cu ¾® Cu + + e- 1 - 0.52 V
and then remains constant
2+ - +
Cu + e ¾® Cu E°3 ? due to addition of weak
n E ° + n2E2 ° 2 ´ 0.34 + 1 ´ (-0.52) acid.
E3 ° = 1 1 = = 0.16 V
n3 1
Conductance
Also, n E°
Cu ¾® Cu + + e- n1 = 1, - 0.52 V
Cu 2+ + e- ¾® Cu + n2 = 1 0.10 V
2+ +
Cu + Cu ¾® 2Cu
Weak acid added
E° = - 0.52 + 0.16 = - 0.36 V to strong base
Thus, (R) — (1)
164 Electrochemistry
Ecell = 0 -
2.303 RT
log
0.05
>0 = 24 ´ 10-7 + 24 ´ 10-7 + 7 ´ 10-7
F 1
= 55 ´ 10-7 S m -1
Hence, | Ecell | = Ecell = 0.70 V and DG < 0 for spontaneity of
reaction. = 55 (in terms of 10- 7 S m -1 )
0.0538
28. Ecell = E ° - log 0.0025 = 0.139 V » 140 mV 36. (a) DG ° = S DG °f (products) - S DG °f (reactants)
1
= – 109 – (– 129 + 77) kJ = – 57 kJ
° >0
29. For spontaneous redox reaction : Ecell
Cell : Ag | AgCl, Cl - || Ag+ | Ag
For 2I- + Cl 2 ¾® 2Cl - + I2
E° = 1.36 – 0.54 = 0.82 V > 0 For K sp ; reaction is AgCl (s) r Ag+ + Cl -
i.e. Cl 2 will spontaneously oxidise I- . DG ° = + 57 kJ
° < 0, they are non-spontaneous.
In other cases Ecell Þ DG ° = - RT ln K sp
DG ° 57 ´ 1000
30. For the reaction : Þ log K sp = - =- = - 10
2.3 RT 2.3 ´ 8.314 ´ 298
3+ 2+ +
E° of Ag+ + Cl - r AgCl
(i) 4Fe + 2H2O ¾® 4Fe + 4H + O2; E° = - 0.46 V
Now,
(ii) 4Mn 3+ + 2H2O ® 4Mn 2+ + 4H+ + O2;E° = + 0.27 V
DG ° 57000
As evidenced above, reaction (i) is non-spontaneous, therefore, E° = - = = 0.59 V
Fe3+ is stable in acid solution. However, reaction (ii) is nF 96500
spontaneous Mn 3+ oxidises H2O to O2 and itself reduced to (b) The cell reaction is :
Mn 2+ in acidic medium. Zn + 2Ag+ r Zn 2+ + 2Ag; E ° = 1.56 V
31. Sodium fusion extract from aniline produces NaCN which 0.059 [Zn 2+ ]
2+ 4- Þ 0 = E° - log
reacts with Fe to form [Fe(CN)6 ] . The complex ion then 2 [Ag+ ] 2
reacts with Fe3+ to give blue precipitate of prussian blue. [Zn 2+ ] 2E ° 2 ´ 1.56
Fe3+ + [Fe(CN)6 ]4- r Fe4[Fe(CN)6 ]3 Þ log =
[Ag+ ] 2 0.059
=
0.059
= 52.88
Prussian blue
32. E° for 2Ag+ + C6H12O6 + H2O r 2Ag(s)
6.539 ´ 10- 2
Moles of Zn added = = 10- 3
65.39
+ C6H12O7 + 2H+ is 0.75 V
0.0592 2E ° Þ Moles of Ag formed = 2 ´ 10- 3.
Also E ° = log K Þ log K = = 25.33
2 0.0592 37. Given,
Þ ln K = 2.303 log K = 58.35
In 2+ + e- ¾® In + E° = – 0.40 …(i)
+
33. On increasing concentration of NH3 , the concentration of H ion
Þ DG ° = 0.40 F
decreases, therefore,
In 3+ + 2e- ¾® In + E° = – 0.42 …(ii)
° - 0.0592 log [ H+ ]2 = 0 - 0.0592 ´ 2 log 10- 11
Ered = Ered
2 2 Þ DG ° = 0.84 F
= 0.65 V Subtracting (i) from (ii)
i.e. Ered increases by 0.65 V. In 3+ + e ¾® In 2+ ; DG ° = 0.44 F = – E ° F
34. NH3 has no effect on the E° of glucose/gluconic acid electrode. Þ E° = - 0.44 V
Now, for : Cu 2+ + In 2+ ¾® Cu + + In 3+
35. The solubility of AgBr in 10- 7 M AgNO3 solution is determined as
AgBr r
E ° = E ° (Cu 2+ / Cu + ) - E ° (In 3+ / In 2+ )
Ag+ + Br -
S + 10- 7 S = 0.15 – (– 0.44) = 0.59 V
AgNO3 ¾® Ag +
+ NO-3 Also E° = 0.0590 log K
S + 10- 7 10-7 E°
Þ log K = = 10 Þ K = 1010
K sp = 14 ´ 10-14 = S (S + 10-7 ) 0.059
166 Electrochemistry
38. (a) pH = – log [H+ ] In saturated Ag2CrO4 solution present in anode chamber :
+ Ag2CrO4 (s) r 2Ag+ + CrO24-
In pure water, [H ] depends on value of K w which is
1.7 ´ 10- 4 M 1.7 ´ 10- 4 M
K w = [H+ ][OH- ] 2
Q K w is a function of temperature, [H+ ] will change K sp = [Ag+ ]2 [CrO24- ]
with temperature. æ 1.7 ö
(b) Let the emf of first cell be X volt. = (1.7 ´10- 4 )2 ç ´ 10- 4 ÷
è 2 ø
Þ emf of 2nd cell = (X + 0.03) volt = 2.45 ´ 10- 12
[Cu 2+ ] in 2nd cell = 0.50 M
[Cu 2+ ] in 1st cell = ?
41. For 2 Fe3+ + 3I- r 2Fe2+ + I-3
E ° = E ° (Fe3+ / Fe2+ ) - E ° (I-3 / I- )
2.303 RT [Zn 2+ ]
E1 = E1° - log = 0.77 – 0.54 = 0.23 V
2F [Cu 2+ ] 0.0592
Q E° = log K (n = 2)
2.303 RT [Zn 2+ ] 2
E2 = E1° - log 2E ° 2 ´ 0.23
2F [Cu 2+ ]2 log K = = = 7.77
0.0592 0.0592
2.303 RT é [Cu 2+ ]2 ù Þ K = 5.89 ´ 10 7
Þ E2 - E1 = ê log ú
2F [Cu 2+ ]1 û
Fe2+ + Ce4+ r Fe3+ + Ce3+
ë
42.
0.50
Þ 0.03 = 0.03 log E° = E° (Ce4+ / Ce3+ ) – E° (Fe3+ / Fe2+ )
[Cu 2+ ]1
= 1.44 – 0.68 = 0.76 V
0.50 Q
Þ = 10 Þ [Cu 2+ ]1 = 0.05 M E° = 0.0592 log K
[Cu 2+ ]1 E° 0.76
Þ log K = = = 12.83
1 0.0592 0.0592
39. At anode H2 ¾® H+ + e- ; E° = 0 Þ K = 6.88 ´ 1012
2
- -
At cathode AgCl (s) + e ¾® Ag + Cl ; E° = ? 43. pH = 14
1
(i) Cell reaction : H2 + AgCl (s) ¾® Ag + H+ + Cl - Þ pOH = 0
2
Þ [OH- ] = 1.0 M
(ii) DG ° = - nE ° F = DH ° - T DS °
At 15°C : – 0.23 ´ 96500 = DH ° - 288 DS ° …(i) K sp = 10- 19 = [Cu 2+ ][OH- ]2
At 35°C : – 0.21 ´ 96500 = DH ° - 308 DS ° …(ii) 10- 19
Þ 96500 (0.23 - 0.21) = - 20 DS ° Þ [Cu 2+ ] = = 10- 19
[OH- ]2
96500 ´ 0.02
Þ DS ° = - = - 96.5 J For reaction : Cu 2+ + 2e- ¾® Cu; E° = 0.34 V
20
Substituting value of DS ° in (i) 0.0592 1
E = E° - log
DH ° = 288 ´ (- 96.5) - 0.23 ´ 96500 = – 49.987 kJ 2 [Cu 2+ ]
(iii) At 25°C 0.0592
= 0.34 – log 1019 = – 0.222 V
- E ° ´ 96500 = - 49987 - 298 (- 96.5) 2
Þ E° = 0.22 V
44. For reaction,
AgCl (s) + e ¾® Ag + Cl - ; E° = 0.22 V 2Hg + 2Fe3+ r Hg2+
-
Þ 2+
2 + 2Fe
+ -
Ag ¾® Ag + e ; E° = – 0.80 V Initial : 10 - 3 M 0 0
Adding : AgCl (s) ¾® Ag + Cl ; + -
E° = – 0.58 V Equilibrium : 5 ´ 10 - 5 4.75 ´ 10 - 4 9.5 ´ 10 - 4
2N2 O5 ( g ) ¾® 4NO2 ( g ) + O2 ( g ) 20
The initial concentration of N2 O5 is 3.00 mol L-1 and it is
Enthalpy 15
2.75 mol L -1 after 30 minutes. The rate of formation of NO2 (kJ mol–1)10
D
is (2019 Main, 12 April II)
-3 -1 -1 -2 -1 -1 5
(a) 4167
. ´ 10 mol L min (b) 1667
. ´ 10 mol L min A+B
-3 -1 -1 -3 -1
C
(c) 8.333 ´ 10 mol L min (d) 2.083 ´ 10 mol L min -1
Reaction
coordinate
2. In the following reaction; xA ® yB
é d[ A ]ù é d[B ]ù (a) D is kinetically stable product.
log 10 ê- ú = log 10 ê ú + 0.3010 (b) Formation of A and B from C has highest enthalpy of activation.
ë dt û ë dt û
(c) C is the thermodynamically stable product.
A and B respectively can be (2019 Main, 12 April I)
(d) Activation enthalpy to form C is 5 kJ mol -1 less than that to
(a) n-butane and iso-butane (b) C2H2 and C6 H6
form D.
(c) C2H4 and C4 H8 (d) N2O4 and NO2
6. The given plots represent the variation of the concentration
3. For the reaction of H 2 with I2 , the rate constant is
of a reaction R with time for two different reactions (i) and
2.5 ´ 10- 4 dm3 mol- 1 s- 1 at 327ºC and 10. dm 3 mol- 1 s- 1 (ii). The respective orders of the reactions are
at 527ºC. The activation energy for the reaction, in (2019 Main, 9 April I)
kJ mol- 1 is (R = 8.314 JK - 1 mol- 1 ) (2019 Main, 10 April II) (i) (ii)
(a) 59 (b) 72 (c) 150 (d) 166
In [R] [R]
4. A bacterial infection in an internal wound grows as
N ¢ ( t ) = N0 exp ( t ), where the time t is in hours. A dose of
antibiotic, taken orally, needs 1 hour to reach the wound. time time
Once it reaches there, the bacterial population goes down as
dN N (a) 1, 1 (b) 0, 2
= - 5N 2 . What will be the plot of 0 vs t after 1 hour ? (c) 0, 1 (d) 1, 0
dt N
(2019 Main, 10 April I) k1 k2
7. For a reaction scheme, A ¾® B ¾® C , if the rate of
formation of B is set to be zero then the concentration of B is
N0 N given by (2019 Main, 8 April II)
(a) (b) 0
N N æk ö
(a) k1k2[ A ] (b) çç 1 ÷÷[ A ]
t(h) t(h) è k2 ø
(c) (k1 - k2 )[ A ] (d) (k1 + k2 )[ A ]
N0 N0 8. For the reaction, 2 A + B ® C , the values of initial rate at
(c) (d)
N N different reactant concentrations are given in the table below.
The rate law for the reaction is (2019 Main, 8 April I)
t(h) t(h)
Chemical Kinetics 169
[A](mol L-1 ) [B](mol L-1 ) Initial rate Choose the correct option.
(mol L-1s-1 ) (a) Both I and II are wrong
(b) Both I and II are correct
0.05 0.05 0.045
(c) I is wrong but II is right
0.10 0.05 0.090 (d) I is right but II is wrong
0.20 0.10 0.72
15 For the reaction, 2A + B ¾® products
(a) rate = k [A ][B ]2 (b) rate = k [A ]2[B ]2
When concentration of both (A and B) becomes double, then
(c) rate = k [A ][B ] (d) rate = k [A ]2[B ]
rate of reaction increases from 0.3 mol L -1 s -1 to
9. For a reaction, consider the plot of ln k versus 1/ T given in 2.4 mol L -1 s -1 .
the figure. If the rate constant of this reaction at 400 K is When concentration of only A is doubled, the rate of reaction
10- 5 s - 1 , then the rate constant at 500 K is increases from 0.3 mol L -1 s -1 to 0.6 mol L -1 s -1 .
(2019 Main, 12 Jan II) Which of the following is true? (2019 Main, 9 Jan II)
(a) The whole reaction is of 4th order
(b) The order of reaction w.r.t. B is one
Slope = –4606 (c) The order of reaction w.r.t. B is 2
ln k
(d) The order of reaction w.r.t. A is 2
16 The following results were obtained during kinetic studies of
1/ T the reaction; (2019 Main, 9 Jan I)
(a) 4 ´ 10 -4 -1
s (b) 10 -6 -1
s 2A + B ¾® Products
-4 -1
(c) 10 s (d) 2 ´ 10- 4 s- 1 Initial rate of
[A] [B]
Experiment reaction
10 Decomposition of X exhibits a rate constant of 0.05 mg/year. (in mol L-1 ) (in mol L-1)
(in mol L-1 min -1)
How many years are required for the decomposition of 5 mg
I. 0.10 0.20 6.93 ´ 10-3
of X into 2.5 mg? (2019 Main, 12 Jan I)
(a) 20 (b) 25 (c) 40 (d) 50 II. 0.10 0.25 6.93 ´ 10-3
11. The reaction, 2 X ® B is a zeroth order reaction. If the initial III. 0.20 0.30 1386
. ´ 10-2
concentration of X is 0.2 M, the half-life is 6 h. When the
The time (in minutes) required to consume half of A is
initial concentration of X is 0.5 M, the time required to reach
(a) 5 (b) 10
its final concentration of 0.2 M will be (2019 Main, 11 Jan II) (c) 100 (d) 1
(a) 7.2 h (b) 18.0 h (c) 12.0 h (d) 9.0 h
17. Which of the following lines correctly show the temperature
12. If a reaction follows the Arrhenius equation, the plot lnk vs dependence of equilibrium constant, K , for an exothermic
1/(RT) gives straight line with a gradient (- y) unit. reaction? (2018 Main)
The energy required to activate the reactant is In K A
(2019 Main, 11 Jan I)
B 1
y
(a) unit (b) - y unit (c) yR unit (d) y unit (0, 0) T(K)
R
××
××
13. For an elementary chemical reaction, ××
××
C
××
k1 ××
D
A2 = 2A , the expression for d[dtA ] is
k -1 (a) A and B (b) B and C
(2019 Main, 10 Shift II) (c) C and D (d) A and D
(a) 2k1[ A2 ] - k-1[ A ]2 (b) k1[ A2 ] - k-1 [ A ]2 18. At 518°C, the rate of decomposition of a sample of gaseous
(c) 2k1[ A2 ] - 2k-1 [ A ]2 (d) k1[ A2 ] + k-1[ A ]2 acetaldehyde, initially at a pressure of 363 Torr, was 1.00
14. Consider the given plots for a reaction obeying Arrhenius Torr s -1 when 5% had reacted and 0.5 Torr s -1 when 33%
equation (0°C < T < 300°C) : ( k and E a are rate constant and had reacted. The order of the reaction is : (2018 Main)
activation energy, respectively) (2019 Main, 10 Jan I)
(a) 2 (b) 3
(c) 1 (d) 0
19. Two reactions R1 and R2 have identical pre- exponential
k k
factors. Activation energy of R1 exceeds that of R2 by 10 kJ
mol- 1 . If k1 and k2 are rate constants for reactions R1 and R2 ,
æk ö
respectively at 300 K, then ln çç 2 ÷÷ is equal to
Ea T(°C)
( R = 8.314 J mol - 1K - 1 ) è k1 ø (2017 Main)
I II
(a) 8 (b) 12 (c) 6 (d) 4
170 Chemical Kinetics
20. Decomposition of H2 O2 follows a first order reaction. In 50 26. Plots showing the variation of the rate constant ( k ) with
min, the concentration of H2 O2 decreases from 0.5 to 0.125 M temperature (T ) are given below. The plot that follows
in one such decomposition. When the concentration of H2 O2 Arrhenius equation is (2010)
reaches 0.05 M, the rate of formation of O2 will be (2016 Main)
(a) 6.93 ´ 10-4 mol min -1 (b) 2.66 L min -1 at STP
k k
(c) 1.34 ´ 10-2 mol min -1 (d) 6.93 ´ 10-2 mol min -1 (a) (b)
21. Higher order (>3) reactions are rare due to (2015 Main)
(a) low probability of simultaneous collision of all the reacting
T T
species
(b) increase in entropy and activation energy as more molecules are
involved k k
(c) (d)
(c) shifting of equilibrium towards reactants due to elastic collisions
(d) loss of active species on collision
22. For the elementary reaction, M ¾® N , the rate of T T
disappearance of M increases by a factor of 8 upon doubling the
concentration of M . The order of the reaction with respect to M 27. For a first order reaction, A ® P, the temperature (T )
is (2014 Adv.) dependent rate constant ( k ) was found to follow the
(a) 4 (b) 3 equation :
(c) 2 (d) 1 2000
log k = + 6.0
23. For the non-stoichiometric reaction, 2 A + B ® C + D, the T
following kinetic data were obtained in three separate the pre-exponential factor A and the activation energy Ea ,
experiments, all at 298 K. (2014 Main) respectively, are (2009)
Initial Initial Initial rate of (a) 1.0 ´ 106 s- 1 and 9.2 kJ mol - 1
concentration concentration formation of C (b) 6.0 s- 1 and 16.6 kJ mol - 1
[A] [B] (mol L -1s -1)
(c) 1.0 ´ 106 s- 1 and 16.6 kJ mol - 1
(i) 0.1 M 0.1 M 1. 2 ´ 10-3
(d) 1.0 ´ 106 s- 1 and 38.3 kJ mol - 1
(ii) 0.1 M 0.2 M 1. 2 ´ 10-3
28. Under the same reaction conditions, initial concentration
(iii) 0.2 M 0.1 M 2. 4 ´ 10-3
of 1.386 mol dm -3 of a substance becomes half in 40 s and
The rate law for the formation of C is 20 s through first order and zero order kinetics
dC dC æk ö
(a) = k[ A ][ B ] (b) = k[ A ] 2[ B ] respectively. Ratio çç 1 ÷÷ of the rate constants for first
dt dt
dC dC è k0 ø
(c) = k[ A ][ B ] 2 (d) = k[ A ] order ( k1 ) and zero order ( k0 ) of the reaction is
dt dt
(2008, 3M)
24. In the reaction, P + Q ¾® R + S , the time taken for 75% (a) 0.5 mol -1 dm 3 (b) 1.0 mol dm -3
reaction of P is twice the time taken for 50% reaction of P. The (c) 1.5 mol dm -3 (d) 2.0 mol -1 dm 3
concentration of Q varies with reaction time as shown in the
figure. The overall order of the reaction is (2013 Adv.) 29. Consider a reaction, aG + bH ® products. When
concentration of both the reactants G and H is doubled, the
rate increases by eight times. However, when
[Q]0
concentration of G is doubled keeping the concentration of
H fixed, the rate is doubled. The overall order of the
[Q]
reaction is (2007, 3M)
Time (a) 0 (b) 1
(a) 2 (b) 3 (c) 0 (d) 1 (c) 2 (d) 3
25. The rate of a reaction doubles when its temperature changes 30. Which one of the following statement(s) is incorrect about
from 300 K to 310 K. Activation energy of such a reaction will order of reaction? (2005, 1M)
(a) Order of reaction is determined experimentally
be ( R = 8.314 JK -1 mol -1 and log 2 = 0.301)
(b) Order of reaction is equal to sum of the power of
(a) 53.6 kJ mol -1 (b) 48.6 kJ mol -1 (2013 Main)
concentration terms in differential rate law
(c) 58.5 kJ mol -1 (d) 60.5 kJ mol -1
(c) It is not affected with stoichiometric coefficient of the
reactants
(d) Order cannot be fractional
Chemical Kinetics 171
31. (A) follows first order reaction, ( A ) ® product. 39. The rate constant of a reaction depends on (1981, 1M)
Concentration of A, changes from 0.1 M to 0.025 M in (a) temperature
40 min. Find the rate of reaction of A when concentration of (b) initial concentration of the reactants
A is 0.01 M. (c) time of reaction
(2004, 1M)
(d) extent of reaction
(a) 3.47 ´ 10–4 M min –1 (b) 3.47 ´ 10-5 M min –1
(c) 1.73 ´ 10-4 M min –1 (d) 1.73 ´ 10-5 M min –1 Objective Questions II
32. In a first order reaction the concentration of reactant (One or more than one correct option)
decreases from 800 mol/dm3 to 50 mol/dm3 in 2 ´ 104 s. The 40. For a first order reaction A( g ) ¾® 2B( g )+ C ( g ) at
rate constant of reaction in s -1 is (2003, 1M) constant volume and 300 K, the total pressure at the
(a) 2 ´ 104 (b) 3.45 ´ 10-5 beginning ( t = 0 ) and at time t are p0 and pt , respectively.
(c) 1.386 ´ 10-4 (d) 2 ´ 10-4 Initially, only A is present with concentration [ A ]0 , and t1 / 3
33. Consider the chemical reaction, is the time required for the partial pressure of A to reach 1/3 rd
N2 ( g ) + 3H2 ( g ) ¾® 2NH3 ( g ) of its initial value. The correct option(s) is (are) (Assume that
all these gases behave as ideal gases) (2018 Adv.)
The rate of this reaction can be expressed in terms of time
derivatives of concentration of N2 ( g ), H2 ( g ) or NH3 ( g ).
In(3p0–pt)
Identify the correct relationship amongst the rate expressions
t1/3
(a) (b)
d [N2 ] 1 d [H2 ] 1 d[NH3 ]
(a) Rate = - =- =
dt 3 dt 2 dt (2002, 3M)
d [N2 ] d [H2 ] d [NH3 ]
(b) Rate = - = -3 =2 Time [A]0
dt dt dt
Rate constant
d [N2 ] 1 d [H2 ] 1 d [NH3 ] In(p0–pt)
(c) Rate = = =
dt 3 dt 2 dt (c) (d)
d [N2 ] d [H2 ] d [NH3 ]
(d) Rate = - =- =
dt dt dt
34. If I is the intensity of absorbed light and C is the Time [A]0
concentration of AB for the photochemical process.
AB + hn ® AB* , the rate of formation of AB* is directly 41. In a bimolecular reaction, the steric factor P was
proportional to (2001, 1M)
experimentally determined to be 4.5. the correct option(s)
among the following is(are) (2017 Adv.)
(a) C (b) I
(a) The activation energy of the reaction is unaffected by the value
(c) I 2 (d) C × I
of the steric factor
35. The rate constant for the reaction, 2N2 O5 ¾® 4NO2 + O2 (b) Experimentally determined value of frequency factor is higher
than that predicted by Arrhenius equation
is 3.0 ´ 10-5 s -1 . If the rate is 2.40 ´ 10-5 mol L - 1 s - 1 , then
(c) The value of frequency factor predicted by Arrhenius equation
the concentration of N2 O5 (in mol L - 1 ) is (2000, 1M) is higher than that determined experimentally
(a) 1.4 (b) 1.2 (d) Since P = 4.5, the reaction will not proceed unless an effective
(c) 0.04 (d) 0.8 catalyst is used
36. The half-life period of a radioactive element is 140 days. 42. According to the Arrhenius equation, (2016 Adv.)
After 650 days, one gram of the element will reduce to (a) a high activation energy usually implies a fast reaction
(1986) (b) rate constant increases with increase in temperature. This is
1 1 1 1
(a) g (b) g (c) g (d) g due to a greater number of collisions whose energy exceeds
2 4 8 16 the activation energy
37. A catalyst is a substance which (1983, 1M) (c) higher the magnitude of activation energy, stronger is the
(a) increases the equilibrium concentration of the product temperature dependence of the rate constant
(b) changes the equilibrium constant of the reaction (d) the pre-exponential factor is a measure of the rate at which
(c) shortens the time to reach equilibrium collisions occur, irrespective of their energy
(d) supplies energy to the reaction 43. For the first order reaction,
38. The specific rate constant of a first order reaction depends on 2N2 O5 ( g ) ¾® 4NO2 ( g ) + O2 ( g ) (2011)
the (1983, 1M) (a) the concentration of the reactant decreases exponentially with time
(a) concentration of the reactant (b) the half-life of the reaction decreases with increasing temperature
(b) concentration of the product (c) the half-life of the reaction depends on the initial concentration
(c) time of the reactant
(d) temperature (d) the reaction proceeds of 99.6% completion in eight half-life
duration
172 Chemical Kinetics
44. The following statement (s) is are correct (1999, 3M) The comparison of the b- activity of the dead matter with that of the
1 carbon still in circulation enables measurement of the period of the
(a) A plot of log K p vs is linear
T isolation of the material from the living cycle. The method
(b) A plot of log [X] vs time is linear for a first order reaction, however, ceases to be accurate over periods longer than 30,000 yr.
x®p The proportion of 14 C to 12 C in living matter is 1 : 1012.
1
(c) A plot of log p vs is linear at constant volume (2006, 3 ´ 4M = 12M)
T
1 48. Which of the following option is correct?
(d) A plot of p vs is linear at constant temperature
V (a) In living organisms, circulation of 14 C from atmosphere is high
so the carbon content is constant in organism
45. For the first order reaction, (1998, 2M)
(b) Carbon dating can be used to find out the age of earth crust and
(a) the degree of dissociation is equal to (1 - e- kt ) rocks
(b) a plot of reciprocal concentration of the reactant vs time gives a (c) Radioactive absorption due to cosmic radiation is equal to the
straight line rate of radioactive decay, hence the carbons content remains
(c) the time taken for the completion of 75% reaction is thrice the constant in living organisms
1 (d) Carbon dating cannot be used to determine concentration of
of the reaction 14
2 C in dead beings
(d) the pre-exponential factor in the Arrhenius equation has the
49. What should be the age of fossil for meaningful
dimension of time, T -1
determination of its age?
46. A catalyst (1984, 1M) (a) 6 yr
(a) increases the average kinetic energy of reacting molecules (b) 6000 yr
(b) decreases the activation energy (c) 60,000 yr
(c) alters the reaction mechanism (d) It can be used to calculate any age
(d) increases the frequency of collisions of reacting species 50. A nuclear explosion has taken place leading to increase in
concentration of C14 in nearby areas. C14 concentration is C1
Numerical Value in nearby areas and C 2 in areas far away. If the age of the
fossil is determined to be T1 and T2 at the places respectively
47. Consider the following reversible reaction,
then
A( g )+ B( g ) - AB( g )
(a) the age of fossil will increase at the place where explosion has
The activation energy of the backward reaction exceeds that 1 C
taken place and T1 - T2 = ln 1
of the forward reaction by 2RT (in J mol -1 ). If the l C2
pre-exponential factor of the forward reaction is 4 times that (b) the age of fossil will decrease at the place where explosion has
of the reverse reaction, the absolute value of DGs (in J 1 C
taken place and T1 - T2 = ln 1
mol -1 ) for the reaction at 300 K is ……… . l C2
(Given ; ln( 2 ) = 0.7 RT = 2500 J mol -1 at 300 K and G is the (c) the age of fossil will be determined to be the same
T C
Gibbs energy) (2018 Adv.) (d) 1 = 1
T2 C 2
Passage Based Questions
Fill in the Blanks
Passage 51. In Arrhenius equation, k = A exp (- E a / RT )
. A may be termed
Carbon-14 is used to determine the age of organic material. The
as the rate constant at ......... (1997, 1M)
procedure is based on the formation of 14 C by neutron capture in the
upper atmosphere. 52. For the reaction : N2 ( g ) + 3H2 ( g ) ¾® 2NH3 ( g )
14 1 14 1 Under certain conditions of temperature and partial pressure
7 N + 0n ¾® 6 C + 1p
14 14 of the reactants, the rate of formation of NH3 is 0.001 kg/h-1.
C is absorbed by living organisms during photosynthesis. The C
content is constant in living organism once the plant or animal dies, The rate of conversion of H2 under the same condition is ....
the uptake of carbon dioxide by it ceases and the level of 14 C in the kg /h -1 . (1994, 1M)
dead being, falls due to the decay which C-14 underoges 53. The hydrolysis of ethyl acetate in ........... medium is a ..........
14 14
6 C ¾® 7 N + b- order reaction. (1986, 1M)
14
The half-life period of C is 5770 yr. 54. The rate of chemical change is directly proportional to
The decay constant ( l ) can be calculated by using the following ............. (1985, 1M)
0.693
formula l = .
t1 / 2
Chemical Kinetics 173
Integer Answer Type Questions 64. (i) The rate constant of a reaction is 1.5 ´ 107 s-1 at 50° C and
56. An organic compound undergoes first order decomposition. 4.5 ´ 107 s-1 at 100° C. Evaluate the Arrhenius parameters
The time taken for its decomposition to 1/8 and 1/10 of its A and Ea . (1998, 5M)
initial concentration are t1 / 8 and t1 / 10 respectively. What is the 1
(ii) For the reaction, N2O5 (g ) ¾® 2NO2 (g ) + O2 (g ),
[t ] 2
value of 1 / 8 ´ 10 ? (log 10 2 = 0.3)
[ t1 / 10 ] calculate the mole fraction N2O5 (g ) decomposed at a
(2012)
constant volume and temperature, if the initial pressure is
57. The concentration of R in the reaction R ¾® P was 600 mm Hg and the pressure at any time is 960 mm Hg.
measured as a function of time and the following data is Assume ideal gas behaviour.
obtained :
65. The rate constant for the first order decomposition of a
[ R ] (molar) 1.0 0.75 0.40 0.10
certain reaction is described by the equation
t (min) 0.0 0.05 0.12 0.18
1.25 ´ 104 K
The order of the reaction is (2010) log k (s -1 ) = 14.34 -
T
Subjective Questions (i) What is the energy of activation for the reaction?
58. 2 X ( g ) ¾® 3Y ( g ) + 2 Z ( g ) (ii) At what temperature will its half-life period be 256 min?
(1997, 5M)
Time 0 100 200
66. One of the hazards of nuclear explosion is the generation of
(in min)
Sr 90 and its subsequent incorporation in bones. This
Partial pressure of 800 400 200 nucleide has a half-life of 28.1 yr. Suppose one microgram
X (in mm of Hg)
was absorbed by a new-born child, how much Sr 90 will
Assuming ideal gas condition. Calculate remain in his bones after 20 yr. (1995, 2M)
(a) order of reaction
67. At 380° C, the half-life period for the first order
(b) rate constant
(c) time taken for 75% completion of reaction decomposition of H2 O2 is 360 min. The energy of activation
(d) total pressure when px = 700 mm (2005, 4M) of the reaction is 200 kJ mol -1 . Calculate the time required
59. For the given reaction, A + B ¾® Products for 75% decomposition at 450° C. (1995, 4M)
Following data are given 68. From the following data for the reaction between A and B
Initial conc. Initial conc. Initial rate [A], (mol/L) [B], (mol/L) Initial rate (mol L–1s–1) at
(m/L) (m/L) [mL–1s –1 ]
300 K 320 K
[ A ]0 [ B ]0 -4 -5 -4
2. 5 ´ 10 3. 0 ´ 10 5. 0 ´ 10 2.0 ´ 10-3
0.1 0.1 0.05
0.2 0.1 0.1 5.0 ´ 10-4 6.0 ´ 10-5 4.0 ´ 10-3 —
0.1 0.2 0.05
1. 0 ´ 10-3 6. 0 ´ 10-5 1. 6 ´ 10-2 —
(a) Write the rate equation.
(b) Calculate the rate constant. (2004, 2M) Calculate
64
60. Cu (half-life = 12.8 h) decays by b emission (38%), b+ (i) the order of the reaction with respect to A and with
emission (19%) and electron capture (43%). Write the decay respect to B.
products and calculate partial half-lives for each of the decay (ii) the rate constant at 300 K.
processes. (2002) (iii) the pre-exponential factor. (1994, 5M)
61. The rate of first order reaction is 0.04 mol L–1s –1 at 10 min and
69. The gas phase decomposition of dimethyl ether follows first
0.03 mol L–1s –1 at 20 min after initiation. Find the half-life of the order kinetics
reaction. (2001, 5M)
CH3 — O— CH3 ( g ) ¾® CH4 ( g ) + H2 ( g ) + CO ( g )
62. A hydrogenation reaction is carried out at 500 K .If the same The reaction is carried out in a constant volume container at
reaction is carried out in the presence of a catalyst at the same 500° C and has a half-life of 14.5 min. Initially only
rate, the temperature required is 400 K. Calculate the dimethyl ether is present at a pressure of 0.40 atm. What is
activation energy of the reaction if the catalyst lowers the the total pressure of the system after 12 min? Assume ideal
activation barrier by 20 kJ mol -1 . (2000, 3M) gas behaviour. (1993, 4M)
174 Chemical Kinetics
99
70. A first order reaction, A ® B, requires activation energy of period of 42 Mo , which is a beta emitter, is 66.6 h. Find
-1 99
70 kJ mol . When a 20% solution of A was kept at 25° C for the minimum amount of 42 Mo required to carry out the
20 min, 25% decomposition took place. What will be the experiment in 6.909 h. (1989, 5M)
percentage decomposition in the same time in a 30% solution -6
maintained at 40°C ? Assume that activation energy remains 76. A first order gas reaction has k = 1.5 ´ 10 per second at
constant in this range of temperature. (1993, 4M)
200° C. If the reaction is allowed to run for 10 h, what
percentage of the initial concentration would have change in
71. Two reactions (i) A ® products (ii) B ® products, follow the product? What is the half-life of this reaction?
first order kinetics.The rate of the reaction (i) is doubled (1987, 5M)
when the temperature is raised from 300 K to 310 K. 77. While studying the decomposition of gaseous N2 O5 , it is
The half-life for this reaction at 310 K is 30 min. At the same observed that a plot of logarithm of its partial pressure versus
temperature B decomposes twice as fast as A. If the energy of time is linear. What kinetic parameters can be obtained from
activation for the reaction (ii) is half that of reaction (i), this observation? (1985, 2M)
calculate the rate constant of the reaction (ii) at 300 K.
(1992, 3M)
78. Radioactive decay is a first order process. Radioactive
3 1
carbon in wood sample decays with a half-life of 5770 yr.
72. The nucleidic ratio, 1H to 1H in a sample of water is What is the rate constant (in yr - 1 ) for the decay? What
8.0 ´ 10- 18 : 1. Tritium undergoes decay with a half-life fraction would remain after 11540 yr? (1984, 3M)
period of 12.3 yr. How many tritium atoms would 10.0 g of 79. A first order reaction is 20% complete in 10 min. Calculate
such a sample contain 40 yr after the original sample is (i) the specific rate constant of the reaction, and
collected. (1992, 4M) (ii) the time taken for the reaction to go to 75% completion.
73. The decomposition of N2 O5 according to the equation, (1983, 2M)
2N2 O5 ( g ) ¾® 4NO2 ( g ) + O2 ( g ) 80. Rate of reaction, A + B ® products is given below as a
is a first order reaction. After 30 min from the start of the function of different initial concentrations of A and B
decomposition in a closed vessel, the total pressure
[A] mol/L [B] (mol/L) Initial rate
developed is found to be 284.5 mm of Hg. On complete
(mol L–1 min –1 )
decomposition, the total pressure is 584.5 mm of Hg.
Calculate the rate constant of the reaction. (1991, 6M)
0.01 0.01 0.005
0.02 0.01 0.010
74. In Arrhenius equation for a certain reaction, the value of A and
13 -1 –1 0.01 0.02 0.005
Ea (activation energy) are 4 ´ 10 s and 98.6 kJ mol
respectively. If the reaction is of first order, at what Determine the order of the reaction with respect to A and B.
temperature will its half-life period be 10 min? (1990, 3M)
What is the half-life of A in the reaction ? (1982, 4M)
Answers
1. (b) 2. (c) 3. (d) 4. (a) 48. (c) 49. (b) 50. (a) 51. T = ¥
5. (d) 6. (d) 7. (b) 8. (a) 52. 0.0015 53. acidic first or basic, second
9. (c) 10. (d) 11. (b) 12. (d) 54. concentration of reactant(s) at that instant
13. (c) 14. (b) 15. (c) 16. (b) 55. T 56. (9) 57. (0)
17. (a) 18. (a) 19. (d) 20. (a) 58. (960 mm Hg) 61. (25 min) 62. (100 kJ mol -1)
21. (a) 22. (b) 23. (d) 24. (d) 63. (3.26 ´ 10 -3
mol L -1 -1
min ) 66. (6.1 ´ 10 -7 g)
25. (a) 26. (a) 27. (d) 28. (a)
67. (20.74 min) 69. (0.75 atm) 70. (67 %)
29. (d) 30. (d) 31. (a) 32. (c)
71. (3.26 ´ 10 -2 min -1
) 72. (5.6 ´ 10 5)
33. (a) 34. (d) 35. (d) 36. (d)
73. (5.2 ´ 10 -3 min -1
) 74. (311.34 K)
37. (c) 38. (d) 39. (a) 40. (a,d) -16
75. (3.56 ´ 10 g) 78. (0.25)
41. (a,c) 42. (b,c,d) 43. (a,b,d) 44. (a,b,d)
80. (1.386 min)
45. (a,d) 46. (b,c) 47. (+8500J/ mol)
Hints & Solutions
1. For the reaction, H2 + I2 ¾® 2HI
Key Idea The rate of a chemical reaction means the speed Given k 1 = 2.5 ´ 10-4 dm3mol-1s -1
with which the reaction takes place.
For R ¾® P T1 = (273 + 327) K = 600 K
Rate of disappearance of R k 2 = 1 dm 3mol -1 s -1 at T2 = (273 + 527) K = 800 K
Decrease in conc.of R D[ R]
= =- k2 Ea æ T2 - T1 ö
Time taken Dt Now, log = ç ÷
k 1 2.303R çè T1T2 ÷ø
Rate of appearance of P
Increase in conc. of P D[ P] 1 Ea æ 800 - 600 ö
= =+ Þ log = çç ÷÷
Time taken Dt 2.5 ´ 10-4 2.303 ´ 8.314 ´ 10-3 è 600 ´ 800 ø
Given, [N2O5 ]initial = 3.00 mol L- 1 (10 ´ 103 ) E 200
Þ log = a ´
2.5 0.019 48 ´ 104
After 30 min, [N2O5 ] = 2 .75 mol L- 1
Þ log 4 + 3 log10 -~ E ´ 0.022
a
2N2O5 (g ) ¾® 4NO2 (g ) + O2 (g )
2 ´ log 2 + 3
t= 0 3.0 M Þ Ea =
t = 30 2.75 M
0.022
3.6 ~
From the equation, it can be concluded that = – 163.6kJ mol -1
0.022
1 - D[N2O5 ] 1 D[NO2 ]
´ = ´ 4. The expression for bacterial growth is
2 Dt 4 Dt
-1 N = N 0et
- D[N2O5 ] - (2.75 - 3.00) mol L 0.25
= = Þ N0
Dt 30 30 = e- t
N
D[NO2 ] D (N2O5 ) D[NO2 ] 0.25
and =-2 Þ =- 2 ´ From 0 to 1 hour N ¢ (t ) = N 0et
Dt Dt Dt 30
= - 1667
. ´ 10- 2 mol L- 1 min - 1 dN
From 1 hour onwards, = -5N 2
dt
2. In the given reaction; x A ¾¾® y B On differentiating the above equation from N ¢ to N we get.
é - d[ A ]ù é d[ B ]ù N t
log10 = log10 + 0.3010 -2
êë dt úû êë dt úû òN dN = -5ò dt [Q At 1 hour, N ¢= eN 0]
eN0 1
Value of log 2 = 0.3010
é 1 1 ù
Substituting 0.3010 by log2
ê N - eN ú = 5(t - 1)
é d[ A ]ù é d[ B ]ù ë 0û
log10 - = log10 + log 2 Multiply both sides by N 0, we get
êë dt úû êë dt úû
N0 1 N 1
Using logarithm rules, - = 5N 0 (t - 1) or, 0 = 5N 0 (t - 1) +
N e N e
é - d[ A ]ù é d[ B ]ù 1 é d [ A ]ù é d[ B ]ù N0 é1 ù
= 2´ Þ- = …(i) = 5N 0t + - 5N 0
ëê dt ûú ëê dt ûú 2 ëê dt ûú êë dt ûú N ëê e ûú
Using the rate equation (i) to determine the reaction involved is On comparing the above equation with equation of straight line,
2A ¾¾® B y = mx + c
Option that fits correct in the above reaction is (c). 1
We get m = 5N 0, c = - 5N 0
2C2H4 ¾¾® C4H8 . e
N0
\ Plot of vs t is shown aside.
3. N
Key Idea The Arrhenius equation for rate constants at two
different temperatures is
k Ea é T2 - T1 ù
log 2 = [where, T2 > T1]
k 1 2.303R êë T1T2 úû
N0
where, k 1 and k 2 are rate constants at temperatures T1 and T2, —
N
respectively.
R = Gas constant, Ea = Activation energy t(h)
176 Chemical Kinetics
t
Chemical Kinetics 177
Þ In the given problem, Taking log on both sides of the Eq. (i), the equation
T1 = 400K, T2 = 500 K E
becomes ln k = ln A - a
k 1 = 10- 5 s - 1, k 2 = ? RT
E
- a (Slope) = - 4606
R
On substituting all the given values in Eq. (ii), we get ln/k
k æ 1 1 ö
ln -2 5 = 4606 ç - ÷
10 è 400 500 ø
k 1/RT
ln -2 5 = 2.303
10 On comparing with equation of straight line
k2 1
= 10 Þ k 2 = 10- 4 s - 1 ( y = mx + c), the nature of the plot of lnk vs will be:
10- 5 RT
Therefore, rate constant for the reaction at (i) Intercept = C = ln A
500 K is 10- 4s - 1. (ii) Slope/gradient = m = - Ea = - y Þ Ea = y
So, the energy required to activate the reactant, (activation
10. Given, rate constant (k) = 0.05 mg/year energy of the reaction, Ea is = y )
Thus, from the unit of k, it is clear that the reaction is zero order. k1
Now, we know that 13. The elementary reaction, A2 c 2A
k -1
a
half-life (t1/ 2 ) for zero order reaction = o follows opposing or reversible kinetics,
2k
where, ao = initial concentration, (i) Rate of the reaction,
k = rate constant r = rforward - rbackward
5 mg = k 1[ A2 ] - k - 1[ A ]2 … (i)
t1/ 2 = = 50 years
2 ´ 0.05 mg / year (ii) Again, rate of the reaction can be expressed as,
Thus, 50 years are required for the decomposition of 5 mg of X d [ A2 ] 1 d[ A ]
r=- =+
into 2.5 mg. dt 2 dt
So, the rate of appearance of A, i.e.
11. For zero order reaction,
d[ A ]
[ A0 ] - [ At ] = kt ...(i) = 2r = 2k 1[ A2 ] - 2 k - 1 [ A ]2 [from Eq. (i)]
where, [ A0 ] = initial concentration dt
[ At ] = final concentration at time ‘t’ 14. The Arrhenius equation is,
k = rate constant k = A. e- E a / RT
[A ]
Also, for zero order reaction, t1/ 2 = 0 where, k = rate constant,
2k A = Arrhenius constant, Ea = activation energy,
Given, t1/ 2 = 6 h and [ A0 ] = 0.2 M and T = temperature in K
0.2
\ 6= From the equation, it is clear that k decreases exponentially with
2k Ea . So, the plot-I is correct.
0.2 1 In the plot-II, k is plotted with temperature (in °C but not in K).
or, k= =
2 ´ 6 60 So, at 0°C, k ¹ 0 and k will increase exponentially with
Now, from Eq. (i) temperature upto 300°C. Therefore, the plot-II is also correct.
[ A0 ] - [ At ] = kt 15. For the reaction, 2A + B ¾® products.
Given, [ A0 ] = 0.5 M, [ At ] = 0.2 M Let, the rate expression is
1 é 1ù r µ [ A ]a [ B ]b
\ 0.5 - 0.2 = ´t Qk =
60 êë 60 úû a b
r2 æ 2 A ö æ 2 B ö
1 Expt 1 =ç ÷ ç ÷
0.3 = ´t r1 è A ø è B ø
60
2.4
t = 0.3 ´ 60 = 18 h Þ = 2a ´ 2b Þ 23 = 2a + `b
0.3
12. The temperature dependence of rate of a chemical reaction is Þ 3=a+ b … (i)
expressed by Arrhenius equation as, k = Ae- E a / RT …(i) a b
r2 æ 2 A ö æ B ö
where, A = Arrhenius factor or frequency factor or Expt 2 =ç ÷ ç ÷
pre-exponential factor r1 è A ø è B ø
R = Gas constant, Ea = Activation energy 0.6
Þ = 2a ´ 1 Þ 21 = 2a Þ a = 1 …(ii)
0.3
178 Chemical Kinetics
1 [ A ]0 1 800 4 ln 2 - 1 2 p0
Þ k= ln = ln = s or kt = ln
t [ A ] 2 ´ 104 50 2 ´ 104 ( 3 p0 - pt )
= 1.386 ´ 10- 4 s- 1 or kt = ln 2 p0 - ln ( 3 p0 - pt )
33. For any general reaction, or ln ( 3 p0 - pt ) = - kt + ln 2 p0
aA + bB ¾® cC + dD It indicates graph between ln (3p0 - pt ) vs ‘t’ will be a straight
1 d [A] 1 d[ B ] line with negative slope , so option (a) is correct
Rate = - =-
a dt b dt 1 p0 1
1 d [C ] 1 d [ D ] t1/3 = ln = ln 3
= = k p0 / 3 k
c dt d dt
Þ For N2 + 3H2 ¾® 2NH3 It indicates t1/ 3 is independent of initial concentration so, option
d [ N2 ] 1 d [ H2 ] 1 d [ NH3 ] (b) is incorrect.
Rate = - =- = Likewise, rate constant also does not show its dependence over
dt 3 dt 2 dt
initial concentration. Thus, graph between rate constant and
34. Rate will be directly proportional to both concentration and [ A ]0 will be a straight line parallel to X-axis.
intensity, i.e. rate of formation of AB * µ C × I .
41. If steric factor is considered, the corrected Arrhenius equation
35. The unit of rate constant (t - 1) indicating that the decomposition will be
reaction following first order kinetics. -Ea
log
[ X ]0
=
kt
Þ log [ X ] = log [ X 0 ] -
kt
,
48. Living plants maintain an equilibrium between the absorption of
[ X ] 2.3 2.3 C14 (produced due to cosmic radiation) and the rate of decay of
C14 present inside the plant. This gives a constant amount of C14
i.e. log [ X ] vs ‘t’ will give a straight line.
per gram of carbon in a living plant.
Also at constant temperature, pV = constant
49. Fossil whose age is closest to half-life of C-14 (5770 yr) will
1
Þ Plot of p vs will give a straight line. yield the most accurate age by C-14 dating.
V N
50. lT = ln 0
45. For a first order reaction : N
1 where N 0 = Number of C14 in the living matter and
kt = ln where, a = degree of dissociation. N = Number of C14 in fossil. Due to nuclear explosion,
1- a
amount of C14 in the near by area increases. This will increase
Þ 1 - a = e- kt Þ a = 1 - e- kt N 0 because living plants are still taking C-14 from atmosphere,
1 ekt during photosynthesis, but N will not change because fossil will
Also = , i.e. plot of reciprocal of concentration of not be doing photosynthesis.
[ A ] [ A ]0
Þ T (age) determined in the area where nuclear explosion has
reactant vs time will be exponential. occurred will be greater than the same determined in normal
1 100 2 ln 2 area.
Time for 75% = ln = = 2 (t1/ 2 )
k 100 - 75 k C C 1 C
Also, lT1 = ln 1 Þ lT2 = ln 2 Þ T1 - T2 = = ln 1
The Arrhenius equation is : C C l C2
Ea C = Concentration of C-14 in fossil.
ln k = ln A -
RT
The dimensions of k and A must be same. For first order 51. k = A e- Ea / RT : At T = ¥ , k = A
reaction, dimensions of k is t - 1. 1 d [ H2 ] 1 d [ NH3 ]
52. - =
46. A catalyst lowers the activation energy by enabling the reaction 3 dt 2 dt
to continue through an alternative path, i.e. catalyst changes the - d [ H2 ] 3 d [ NH3 ] 3
Þ = = ´ 0.001 = 0.0015 kg h - 1 .
reaction mechanism. However, catalyst does not affect either dt 2 dt 2
average kinetic energies of reactants or the collision frequency.
53. acidic, first or basic, second.
47. For the reaction, 54. Rate is directly proportional to concentration of reactants.
A (g ) + B (g ) - AB(g )
Given Ea b = Ea f + 2RT or Ea b - Ea f = 2RT 55. R µ [Reactant]
Further On doubling the concentration of reactant, rate would be double.
Af [ A ]0
A f = 4 Ab or =4 56. For a first order process kt = ln
Ab [A]
Now, rate constant for forward reaction, where, [ A ]0 = initial concentration.
- E a f / RT [ A ] = concentration of reactant remaining at time “t”.
k f = Af e
[ A ]0
Likewise, rate constant for backward reaction, Þ kt1/ 8 = ln = ln 8 …(i)
[ A ]0 / 8
- E ab / RT
k b = Ab e [ A ]0
and kt1/ 10 = ln = ln 10 …(ii)
At equilibrium, [ A ]0 /10
Rate of forward reaction = Rate of backward reaction t1/ 8 ln 8
Therefore, = = log 8 = 3 log 2 = 3 ´ 0.3 = 0.9
kf t1/ 10 ln 10
i.e., k f = k b or = k eq
kb t1/ 8
Þ ´ 10 = 0.9 ´ 10 = 9
- E a f / RT t1/ 10
Af e Af - (E a f - E ab ) / RT
so k eq = - E ab / RT
= e
Ab e Ab 57. Rate of reaction is constant with time.
After putting the given values 58. (a) Partial pressure becomes half of initial in every 100 min,
Af therefore, order = 1.
k eq = 4 e2 (as Ea b - Ea f = 2RT and = 4) 800
Ab (b) k ´ 100 = ln = ln 2 Þ k = 6.93 ´ 10-3 min - 1
400
182 Chemical Kinetics
(c) For 75% reaction; time required = 2 ´ half-life = 200 min 62. k 500 = A e- E1 / RT1
(d) 2 X (g ) ¾® 3Y (g ) + 2 Z (g ) k 400 = A e- E 2 / RT2
3
800 - x x x
2 Q k 500 = k 400
3 E1 E E2 T2 400 4
Total pressure = 800 + x Þ = 2 Þ = = =
2 RT1 RT2 E1 T1 500 5
Also 800 - x = 700 Þ x = 100 Also E1 = E2 + 20000 J
3 E1 - 20,000 4
Þ Total pressure = 800 + ´ 100 = 950 mm Hg Þ = Þ E1 = 100,000 J = 100 kJ mol -1
2 E1 5
a
(Rate)1 0.05 1 æ 1 ö [ A ]0
59. = = = ç ÷ Þ a = 1; order w.r.t A. 63. kt = ln
(Rate)2 0.10 2 è 2 ø [A]
Order w.r.t B = 0 1
Þ 4.5 ´ 10- 3 ´ 60 = ln Þ [ A ] = 0.76 M
(a) Rate = k [ A ] [A]
Rate 0.05 Þ Rate = k [ A ] = 4.5 ´ 10- 3 ´ 0.76
(b) k = = = 0.5 s- 1
[ A ] 0.10 = 3.42 ´ 10-3 mol L-1 min -1
64 38% 0 64 k 2 Ea æ T2 - T1 ö
60. 29 Cu ¾® - 1b + 30Zn 64. (i) ln = ç ÷
k1
k1 R çè T1T2 ÷ø
64 19% 0 64
29 Cu ¾® + 1b + 28 Ni æ 4.5 ´ 107 ö Ea æ 50 ö
k2 Þ ln çç ÷= çç ÷÷
7÷
64 0 43% 64
è 1.5 ´ 10 ø 8.314 è 323 ´ 373 ø
29 Cu + - 1e ¾® 28 Ni
k3 Þ Ea = 22 kJ
64 Ea
Above are the parallel reactions occurring from Cu . Also ln k = ln A -
k 1 38 T k 1 38 T3 RT
= = 2 = 2 and = = 7 22 ´ 1000
k 2 19 T1 k 3 43 T1 At 50°C : ln A = ln (1.5 ´ 10 ) - = 8.33
8.314 ´ 323
T1 , T2 and T3 are the corresponding partial half-lives.
Þ A = 4.15 ´ 103 s- 1
Also k = k1 + k2 + k3
1
ln 2 ln 2 ln 2 ln 3 (ii) N2O5 (g ) ¾® 2NO2 (g ) + O2 (g )
Þ = + + 2
T T1 T2 T3
600 - p 2p p/ 2
1 1 1 1 1 1 43
Þ = + + = + + 3
T T1 T2 T3 T1 2T1 38T1 Total pressure = 960 = 600 + p Þ p = 240 mm
2
1 æ 1 43 ö Þ Partial pressure of N2O5 (g ) remaining = 600 – 240
= ç1 + + ÷
T1 è 2 38 ø = 360 mm
1 æ 38 + 19 + 43 ö 100 360
= ç ÷= Þ Mole fraction = = 0.375
T1 è 38 ø 38T1 960
100T 100 65. (i) The Arrhenius equation is
Þ T1 = = ´ 12.8 = 33.68 h Ea
38 38 log k = log A -
2.303 RT
T2 = 2T1 = 67.36 h
38T1 38 ´ 33.68 Comparing with the given equation :
T3 = = = 29.76 h Ea
43 43 1.25 ´ 104 = Þ Ea = 239.33 kJ mol -1
2.303 R
61. R = k [A] (ii) When half-life = 256 min,
Þ R1 = k [ A ]1 and R2 = k [ A ]2 ln 2 0.693 - 1
k= = s = 4.5 ´ 10- 5 s- 1
R1 4 [ A ]1 t1/ 2 256 ´ 60
Þ = =
R2 3 [ A ]2 1.25 ´ 104
Þ = 14.34 – log 4.5 ´ 10- 5 = 16.68
[ A ]1 4 T
Also k (t2 - t1 ) = ln = ln
[ A ]2 3 1.25 ´ 104
Þ T = = 669 K
ln 2 4 16.68
Þ ´ 10 = ln
t1/ 2 3 w
66. k t = ln 0
10 log 3 3 w
Þ t1/ 2 = = = 25 min
log 4 - log 3 0.6 - 0.48 ln 2 10- 6 g
Þ ´ 20 = ln Þ w = 6.1 ´ 10- 7 g
28.1 w
Chemical Kinetics 183
5 100
Þ 584.5 = p0 Þ p0 = 233.8 mm Þ = 1.055
2 100 - x
Let the pressure of N2O5 decreases by ‘p’ amount after 30 min. Þ x = 5.25% reactant is converted into product.
Therefore, ln 2 0.693
Half-life = = = 462000 s = 128.33 h
2N2O5 ¾® 4NO2 + O2 k 1.5 ´ 10- 6
p
At 30 min : p0 - p 2p
2 [ A ]0
77. For a first order process : ln = kt Þ ln [ A ] = ln [ A ]0 - kt
3 [A]
Total pressure = p0 + p = 284.5
2 If the reactant is in gaseous state
2 [ A ]0
Þ p = (284.5 - 233.8) = 33.8 and kt1/ 10 - ln = ln 10 …(ii)
3 [ A ]0 / 10
p0
Now, kt = ln t ln 8
p0 - p Therefore, 1/ 8 = = log 8 = 3 log 2 = 3 ´ 0.3 = 0.9
t1/ 10 ln 10
1 233.8
Þ k= ln min - 1 = 5.2 ´ 10- 3 min - 1 t1/ 8
30 233.8 - 33.8 Þ ´ 10 = 0.9 ´ 10 = 9
t1/ 10
74. Arrhenius equation is : ln p = ln p0 - kt …(i)
Ea where p is the partial pressure of reactant remaining unreacted at
log k = log A -
2.303 RT instant ‘t’ and p0 is its initial partial pressure.
ln 2 0.693 Also, from equation (i), ln p vs t would give a straight line.
when t1/ 2 = 10 min, k = = = 1.115 ´ 10- 3 s- 1
t1/ 2 10 ´ 60 Therefore, decomposition of N2O5 following first order kinetics.
Ea ln 2 0.693 - 1
Þ = log A - log k 78. k = = yr = 1.2 ´ 10- 4 yr - 1
2.303 RT t1/ 2 5770
A 4 ´ 1013 1 ln 2 1
= log = log = 16.54 Also kt = ln = ´ 11540 = ln 4 Þ f = = 0.25
f 5770 4
k 1.115 ´10- 3
Ea 98.6 ´ 1000 79. For a first order reaction,
Þ T = =
2.303 R ´ 16.54 2.303 ´ 16.54 ´ 8.314 [ A ]0
kt = ln
= 311.34 K [A]
75. The minimum rate of decay required after 6.909 h is where [ A ]0 = Initial concentration of reactant
346 particles min . -1 [ A ] = Concentration of reactant remaining
unreacted at time t.
Þ Rate = kN
1 [ A ]0 1 100 1 5
Rate 346 ´ 66.6 ´ 60 (i) Þ k = ln = ln = ln
Þ N = = = 1.995 ´ 106 atoms t [ A ] 10 100 - 20 10 4
k 0.693
N ln 2 N 2.303 (log 5 - 2 log 2)
Þ kt = ln 0 Þ ´ 6.909 = ln 0 = 0.0715 = min = 0.023 min –1
-1
N 66.6 N 10
N0 1 100 2 ln 2 2 ´ 0.693
Þ = 1.074 (ii) t = ln = = = 60 min
N k 25 k 0.023
Þ N 0 = 1.074 ´ N = 1.074 ´ 1.995 ´ 106 80. Looking at the rate data of experiment number 1 and 2 indicates
6
= 2.14 ´ 10 atoms of Mo that rate is doubled on doubling concentration of A while
concentration of B is constant. Therefore, order with respect to A
2.14 ´ 106 is 1. Similarly, comparing data of experiment number 1 and 3,
Þ Mass of Mo required = ´ 99 = 3.56 ´ 10- 16 g
6.023 ´ 1023 doubling concentration of B, while concentration of A is
constant, has no effect on rate.
76. k = 1.5 ´ 10- 6 s- 1 Therefore, order with respect to B is zero.
100 Þ Rate = k [ A ]
kt = ln
100 - x 0.005 0.693
Þ k= = 0.5 min - 1 =
100 0.010 t1/ 2
Þ ln = 1.5 ´ 10- 6 s- 1 ´ 10 ´ 60 ´ 60 s = 0.0054
100 - x 0.693
Þ t1/ 2 = = 1.386 min
0.5
235
Fill in the Blanks 21. The number of neutrons emitted when 92 U undergoes
142 90
15. (a) 235 1 137 97 controlled nuclear fission to 54 Xe and 38 Sr is (2010)
92 U + 0n ¾® 52 A + 40 B + ......
82 0
(b) 34 Se ¾® 2 - 1e + ...... (2005, 1M ´ 2 = 2M) Subjective Questions
16. A radioactive nucleus decays by emitting one alpha and two beta 22. The total number of a and b particles emitted in the nuclear
particles, the daughter nucleus is.... of the parent. (1989, 1M) reaction 238 214
is ..... .
92 U ¾® 82Pb (2009)
14
17. The number of neutrons in the parent nucleus which gives N -7a
234
on beta emission is ........... (1985, 1M) 23. 92 X ¾¾® Y. Find out atomic number, mass number of Y
-6b
18. Elements of the same mass number but different atomic number and identify it. (2004)
are known as ……… (1983, 1M)
24. 238
is radioactive and it emits a and b particles to form
92 U
19. An element Z M A undergoes an a-emission followed by two 82 Pb
206
. Calculate the number of a and b particles emitted in this
successive b -emissions. The element formed is …… conversion.
(1982, 1M) 238 238 206
An ore of 92 U is found to contain 92 U and 82 Pb in the
238
Integer Answer Type Questions weight ratio of 1 : 0.1. The half-life period of 92 U is 4.5 ´ 109
yr. Calculate the age of the ore. (2000)
20. The periodic table consists of 18 groups. An isotope of copper, 14
25. Write a balanced equation for the reaction of N with
on bombardment with protons, undergoes a nuclear reaction
a-particle.
yielding element X as shown below. To which group, element 234
26. 90 Th disintegrates to give 82 Pb206 as the final product. How
X belongs in the periodic table? (2012)
many alpha and beta particles are emitted during this process?
63
29 Cu + 11 H ¾® 610 n + 42a + 211 H + X (1986, 2M)
Answers
A-4
1. (a) 2. (c) 3. (a) 4. (b) 16. isotope 17. eight 18. isobars 19. ZM
5. (b) 6. (c) 7. (a) 8. (b) 20. (8) 21. 3 22. (8) 206
23. 84 PO
9. (b, d) 10. (a, b) 11. (a, c, d) 12. (a, d)
24. (7.12 ´ 10 8yr) 26. (13)
13. (a) 14. (b) 15. 2 0n1, 36 Kr
82
Plot of the number of neutrons against the number of protons in 16. Isotope : Z X A ¾® 2He4 + 2 -1e0 + ZY A - 4
stable nuclei (shown by dots). 17. 8 : 6 C14 ¾® 7 N14 + 0
-1e
9 b 8 d
10. PLAN 4 Be + aX ¾® 4 Be + c Y
18. Isobars have same mass number but different atomic number.
A-4
Atomic number same 19. ZM : Z M A ¾® 2He4 + 2 -1e0 + ZM A - 4
4 + a=4 + c
20. Balancing the given nuclear reaction in terms of atomic number
9+ b=8+ d (charge) and mass number:
0 a=0 63
+ 1 H1 ¾® 60 n1 + 2 He4 (a ) + 21 H1 + 26 X 52
If X = 0g 29 Cu
b=0
The atomic number 26 corresponds to transition metal Fe which
c=0
Y = 10 n belongs to 8th group of modern periodic table.
d =1 235 142 90
21. 92 U ¾® 54Xe + 38 Sr + 30 n1
a =1
If X = 11 p 22. 238 214
+ 6 2He4 + 2 0
b =1 92 U ¾® 82Pb -1e
c =1 Þ Number of (a + b ) = 6 + 2 = 8
Y = 12 D 234
d =2 23. 92 X ¾® 7 2He4 + 6 -1e0 + 84Y
206
9 206
4 Be + 00 g ¾® 84 Be + 10n Y is 84 Po .
9 1 8 2 238 206
4 Be + 1p ¾® 4 Be + 1D 24. 92 U ¾® 82Pb + 8 2He4 + 6-1 e0
11. In the following nuclear reactions, there occur decrease in Present : N 0 - N N
atomic number (Z ) w (U) 1
A
Given, = = 10
ZX ¾® 2He4 + Z - 2Y
A- 4
, a - emission w (Pb) 0.1
A 0 A N (U) 10 206 N 0 - N
ZX ¾® +1e + Z-1Y , positron emission Þ = ´ =
A 0 A N (Pb) 238 1 N
ZX + -1e ¾® Z - 1Y , electron capture
N 238 N0 238 2298
In beta emission, increase in atomic number is observed. Þ = Þ =1+ =
A 0 A
N 0 - N 2060 N0 - N 2060 2060
ZX ¾® -1e + Z + 1Y , b -emission
Now, applying first order rate law
12. If sum of mass number of product nuclides is less than the sum æ ln 2 ö æ N0 ö (t ) æ N0 ö
çç ÷÷ t = ln çç ÷÷ Þ t = 1/ 2 log çç ÷÷
of parent nuclides, then neutron emission will occur. In both (a) t N - N log 2
è 1/ 2 ø è 0 ø èN0 - N ø
and (d), sum of mass number of product nuclides is one unit less
than the sum of parent nuclides, neutron emission will balance 4.5 ´ 109 2298
= log = 7.12 ´ 108 yr
the mass number. 0.3 2060
14
13. After atomic number 20, proton-proton repulsion increases 25. 7N + 2He4 ¾® 9F
18
immensely, more neutrons are required to shield this 26. 234 206
+ 7 2He4 + 6 -1e0
90 Th ¾® 82Pb
11. Among the colloids cheese (C), milk (M) and smoke (S), the 2. The diameter of the dispersed particle is not much
correct combination of the dispersed phase and dispersion smaller than the wavelength of the light used.
medium, respectively is (2019 Main, 11 Jan II) 3. The refractive indices of the dispersed phase and
(a) C : liquid in solid; M : liquid in liquid; S : solid in gas dispersion medium are almost similar in magnitude.
(b) C : solid in liquid; M : liquid in liquid; S : gas in solid 4. The refractive indices of the dispersed phase and
(c) C : liquid in solid; M : liquid in solid; S : solid in gas dispersion medium differ greatly in magnitude.
(d) C : solid in liquid; M : solid in liquid; S : solid in gas (a) 1 and 4 (b) 2 and 4 (c) 1 and 3 (d) 2 and 3
12. An example of solid sol is (2019 Main, 11 Jan I) 19. For a linear plot of log ( x / m ) versus log p in a Freundlich
(a) gem stones (b) hair cream
adsorption isotherm, which of the following statements is
(c) butter (d) paint
correct? (k and n are constants) (2016 Main)
13. Haemoglobin and gold sol are examples of (a) 1/n appears as the intercept
(2019 Main, 10 Jan II)
(a) negatively and positively charged sols, respectively (b) Only 1/n appears as the slope
(b) negatively charged sols æ1ö
(c) log ç ÷ appears as the intercept
(c) positively charged sols ènø
(d) positively and negatively charged sols, respectively (d) Both k and 1/n appear in the slope term
14. Which of the following is not an example of heterogeneous 20. Methylene blue, from its aqueous solution, is adsorbed on
catalytic reaction? (2019 Main, 10 Jan I) activated charcoal at 25°C. For this process, the correct
(a) Haber’s process statement is (2013 Adv.)
(b) Combustion of coal (a) the adsorption requires activation at 25°C
(c) Hydrogenation of vegetable oils (b) the adsorption is accompanied by a decreases in enthalpy
(d) Ostwald’s process (c) the adsorption increases with increase of temperature
(d) the adsorption is irreversible
15. The correct match between item-I and Item-II is
(2019 Main, 9 Jan II) 21. The coagulating power of electrolytes having ions Na + , Al 3+
A. Benzaldehyde P. Dynamic phase and Ba 2+ for arsenic sulphide sol increases in the order
(2013 Main)
B. Alumina Q. Adsorbent
(a) Al 3+ < Ba 2+ < Na + (b) Na + < Ba 2+ < Al 3+
C. Acetonitrile R. Adsorbate
(c) Ba 2+ < Na 2+ < Al 3+ (d) Al 3+ < Na + < Ba 2+
(a) (A) ® (R) ; (B) ® (Q); (C) ® (P)
(b) (A) ® (P); (B) ® (R); (C) ® (Q) 22. Among the electrolytes Na 2 SO4 , CaCl 2 , Al 2 (SO4 )3 and
(c) (A) ® (Q); (B) ® (P); (C) ® (R) NH4 Cl, the most effective coagulating agent for Sb 2 S3 sol is
(d) (A) ® (Q); (B) ® (R); (C) ® (P) (2009, 1M)
(a) Na 2SO4 (b) CaCl 2
16. Which of the salt-solution is most effective for coagulation
(c) Al 2 (SO4 )3 (d) NH4Cl
of arsenious sulphide? (2019 Main, 9 Jan II)
(a) BaCl 2 (b) AlCl 3 23. Among the following, the surfactant that will form micelles
(c) Na 3PO4 (d) NaCl in aqueous solution at the lowest molar concentration at
ambient conditions, is (2008, 3M)
17. Adsorption of a gas follows Freundlich adsorption isotherm. (a) CH3 (CH2 )15 N+ (CH3 )3 Br - (b) CH3 (CH2 )11 OSO-3 Na +
In the given plot,x is the mass of the gas adsorbed on mass m
x (c) CH3 (CH2 )6 COO- Na + (d) CH3 (CH2 )11 N+ (CH3 )3 Br -
of the adsorbent at pressure p × is proportional to
m 24. Lyophilic sols are (2005, 1M)
(2019 Main, 9 Jan I) (a) irreversible sols
(b) prepared from inorganic compounds
(c) coagulated by adding electrolytes
2 unit (d) self-stabilising
x
log m
4 unit 25. Spontaneous adsorption of a gas on solid surface is an
exothermic process, because (2004, 1M)
(a) DH increases for system (b) DS increases for gas
log p (c) DS decreases for gas (d) DG increases for gas
26. Rate of physisorption increases with (2003, 1M)
(a) p2 (b) p1/ 4 (c) p1/ 2 (d) p
(a) decrease in temperature (b) increase in temperature
18. The Tyndall effect is observed only when following (c) decrease in pressure (d) decrease in surface area
conditions are satisfied (2017 Main) 27. When the temperature is increased, surface tension of water
1. The diameter of the dispersed particles is much smaller (2002, 1M)
than the wavelength of the light used. (a) increases (b) decreases
(c) remains constant (d) shows irregular behaviour
190 Surface Chemistry
Amount of gas
absorbed
200 K
absorbed
Answers
1. (c) 2. (b) 3. (d) 4. (b) 21. (b) 22. (c) 23. (a) 24. (d)
5. (c) 6. (c) 7. (d) 8. (a) 25. (c) 26. (a) 27. (b) 28. (a, c)
9. (d) 10. (d) 11. (a) 12. (a) 29. (b, c, d) 30. (a, c) 31. (a, d) 32. (a, b, d)
13. (d) 14. (b) 15. (a) 16. (b) 33. (b)
17. (c) 18. (b) 19. (b) 20. (b)
Hints & Solutions
1. Statement (c) is incorrect about colloids. Colligative Adsorption isobar (Pressure, p = constant)
properties such as relative lowering of vapour pressure,
elevation in boiling point, depression in freezing point and
osmotic pressure of a colloidal solution is of low order than
x
the true solution at the same concentration. —
m
2. Peptisation is a process of converting precipitate into
colloidal solution. This process involves the shaking of
precipitate with the dispersion medium in the presence of T
small amount of electrolyte. The electrolyte added is called
peptising agent. So, the rate of physical adsorption of the gas, increases with p
(when, T is constant) and decreases with T (when p is constant).
During peptisation, the precipitate adsorbs one of the ions of
the electrolyte on its surface. This causes the development of 5. Correct match is
positive or negative charge on precipitates, which ultimately (A) ® (iii); (B) ® (i); (C) ® (ii); (D) ® (iv)
breakup into smaller particles of the size of a colloid. (i) TiCl4 + AlCl3 (Ziegler- Natta catalyst) is used to prepare
3. The explanation of the given statements are as follows : polyethylene from ethene.
(a) Colloidal medicines are more effective because they Zieglar-Natta
catalyst
(dispersed phase) have larger surface area. n CH2 CH2 CH2 CH2 n
Thus, option (a) is incorrect. Ethene Polyethylene
(b) Brownian motion of dispersed phase particles in colloidal (ii) V2O5 (Vanadium pentoxide) is used as catalyst to prepare
solution is faster if the viscosity of the solution is very H2SO4 from contact process. Reaction involved is
low. Thus, option (b) is incorrect. V 2O 5
2SO2 ( g ) + O2 ( g ) ¾¾® 2SO3 ( g )
(c) Addition of alum(K 2SO4 × Al2(SO4 )3 × 24H2O), an
It is the key step in the manufacture of H2SO4.
electrolyte to water makes it fit for drinking purposes
because alum coagulates mud particles from water. (iii) Fe (Iron) is used as catalyst in Haber’s process for the
Thus, option (c) is incorrect. manufacture of ammonia.
Fe( s )
(d) Precipitation of lyophobic solution particles by N2 (g ) + 3H2 (g ) ¾¾® 2NH3 (g )
electrophoresis is called cottrell precipitation.
(iv) Pd (Palladium) is used to prepare ethanal. Reaction involved is
Thus, option (d) is correct.
PdCl 2/CuCl 2
4. For physisorption or physical adsorption, H 2C == CH 2 + O2 ¾¾¾¾® CH 3CHO
H 2O
Adsorption isotherm (Temperature, T = constant) is shown
This reaction is also known as Wacker’s process.
below:
6. In CuSO4 × 5H2O, one molecule of water is indirectly connected to
Cu. In this molecule, four water molecules form coordinate bond
x x with Cu 2+ ion while one water molecule is associated with H-bond
— Moderate pressure zone, — µ p1/n
m m with SO2-
4 .
Structure of CuSO4 × 5H2 O
p
H H
where, x = amount of adsorbate, m = amount of adsorbent,
d– d+
x O O H H O– O
= degree of adsorption H
m Cu2+ O S
H d– d+
1 1 O O H H O– O
= order of the reaction, where, 0 < < 1 and so,
n n
1< n < ¥ H H
1
x [Cu(H 2O)4 ] SO4 × H 2O
Here, = Kp 2,
m 7. The aerosol is a kind of colloid in which solid is dispersed in gas.
x
1 e.g. smoke, dust.
i.e. µ p2
m
192 Surface Chemistry
15. The chemical nature of hydrogen peroxide is 25. Hydrogen peroxide in its reaction with KIO4 and NH2 OH
(2019 Main, 10 Jan I)
respectively, is acting as a (2014 Adv.)
(a) oxidising and reducing agent in both acidic and basic medium (a) reducing agent, oxidising agent
(b) oxidising and reducing agent in acidic medium, but not in (b) reducing agent, reducing agent
basic medium (c) oxidising agent, oxidising agent
(c) reducing agent in basic medium, but not in acidic medium (d) oxidising agent, reducing agent
(d) oxidising agent in acidic medium, but not in basic medium 26. In which of the following reactions H2 O2 acts as a reducing
16. The metal that forms nitride by reacting directly with N 2 of agent? (2014 Main)
+ -
air, is (2019 Main, 9 Jan II) I. H2O2 + 2H + 2e ¾® 2H2O
(a) Rb (b) K (c) Cs (d) Li II. H2O2 - 2e- ¾® O2 + 2H+
17. What is reason of temporary hardness of water? III. H2O2 + 2e- ¾® 2OH-
(2019 Main, 9 Jan II)
(a) Na 2SO 4 (b) CaCl 2 (c) NaCl (d) Ca(HCO 3) 2 IV. H2O2 + 2OH- - 2e- ¾® O2 + 2H2O
(a) I and II (b) III and IV (c) I and III (d) II and IV
18. The isotopes of hydrogen are (2019 Main, 9 Jan I)
(a) deuterium and tritium only 27. A sodium salt of an unknown anion when treated with MgCl 2
(b) protium and deuterium only gives white precipitate only on boiling. The anion is
(c) protium, deuterium and tritium (2004, 1M)
(d) tritium and protium only (a) SO2- (b) HCO-3 (c) CO2- (d) NO-3
4 3
19. Hydrogen peroxide oxidises [Fe(CN)6 ]4- to [Fe(CN)6 ]3- in 28. A dilute aqueous solution of Na 2 SO4 is electrolysed using
acidic medium but reduces [Fe(CN)6 ]3- to [Fe(CN)6 ]4- in platinum electrodes. The products at the anode and cathode
alkaline medium. The other products formed are, are respectively (1996, 1M)
respectively. (2018 Main) (a) O2 , H2 (b) S2O2–
8 , Na (c) O2 , Na (d) S2O2–
8 , H2
(a) (H2O + O2 ) and H2O (b) (H2O + O2 ) and (H2O + OH- ) 29. Hydrolysis of one mole of peroxodisulphuric acid produces
(c) H2O and (H2O + O2 ) (d) H2O and (H2O + OH- ) (a) two moles of sulphuric acid (1996, 1M)
(b) two moles of peroxomono sulphuric acid
20. Both lithium and magnesium display several similar
(c) one mole of sulphuric acid and one mole of peroxomono
properties due to the diagonal relationship; however, the one
sulphuric acid
which is incorrect is (2017 Main)
(d) one mole of sulphuric acid, one mole of peroxomono sulphuric
(a) Both form basic carbonates
acid and one mole of hydrogen peroxide
(b) Both form soluble bicarbonates
(c) Both form nitrides 30. The species that do not contain peroxide ions, is (1992, 1M)
(d) nitrates of both Li and Mg yield NO2 and O2 on heating (a) PbO2 (b) H2O2 (c) SrO2 (d) BaO2
21. The hottest region of Bunsen flame shown in the figure given 31. The metallic lustre exhibited by sodium metal is explained
below is (2016 Main) by (1987, 1M)
Region 4 (a) diffusion of sodium ions
Region 3 (b) oscillation of loose electron
Region 2 (c) excitation of free protons
Region 1 (d) existence of body centred cubic lattice
32. A solution of sodium sulphate in water is electrolysed using
inert electrodes. The products at cathode and anode are
(a) region 2 (b) region 3 (c) region 4 (d) region 1 respectively (1987, 1M)
22. Which one of the following statements about water is false? (a) H2 , O2 (b) O2 , H2 (c) O2 , Na (d) O2 , SO2
(2016 Main) 33. Nitrogen dioxide cannot be obtained by heating (1985, 1M)
(a) Water can act both as an acid and as a base (a) KNO3 (b) Pb(NO3 )2 (c) Cu(NO3 )2 (d)AgNO3
(b) There is extensive intramolecular hydrogen bonding in the
34. The oxide that gives H2 O2 on treatment with a dilute acid is
condensed phase
(a) PbO2 (b) Na 2O2 (1985, 1M)
(c) Ice formed by heavy water sinks in normal water
(c) MnO2 (d) TiO2
(d) Water is oxidised to oxygen during photosynthesis
35. Molecular formula of Glauber’s salt is (1985, 1M)
23. The main oxides formed on combustion of Li, Na and K in (a) MgSO4 × 7H2O (b) CuSO4 × 5H2O
excess of air respectively are (2016 Main)
(c) FeSO4 × 7H2O (d) Na 2SO4 × 10H2O
(a) LiO2, Na 2O2 and K 2O (b) Li 2O2, Na 2O2 and KO2
(c) Li 2O, Na 2O2 and KO2 (d) Li 2O , Na 2O and KO2 36. Heavy water is (1983, 1M)
(a) H2O18
24. Which of the following atoms has the highest first ionisation (b) water obtained by repeated distillation
energy? (2016 Main) (c) D2O
(a) Na (b) K (c) Sc (d) Rb (d) water at 4°C
196 s-Block Elements
37. A solution of sodium metal in liquid ammonia is strongly 46. Statement I LiCl is predominantly a covalent compound.
reducing due to the presence of (1981, 1M) Statement II Electronegativity difference between Li and
(a) sodium atoms (b) sodium hydride Cl is too small. (1998, 2M)
(c) sodium amide (d) solvated electrons
47. Statement I The alkali metals can form ionic hydrides
38. The temporary hardness of water is due to calcium which contain the hydride ion, H- .
bicarbonate can be removed by adding (1979, 1M)
Statement II The alkali metals have low electronegativity,
(a) CaCO3 (b) Ca(OH)2 (c) CaCl 2 (d) HCl
their hydrides conduct electricity when fused and liberate
hydrogen gas at the anode. (1994, 2M)
Objective Questions II
(One or more than one correct option) Fill in the Blanks
39. The pair(s) of reagents that yield paramagnetic species is/are 48. Hydrogen gas is liberated by the action of aluminium with
(a) Na and excess of NH3 (b) K and excess of O2 concentrated solution of ……… . (1987, 1M)
(c) Cu and dilute HNO3 (d) O2 and 2-ethylanthraquinol
49. Sodium dissolved in liquid ammonia conducts electricity
40. The compound(s) formed upon combustion of sodium metal because of …… (1985, 1M)
in excess air is (are) (2007, 2M)
50. The adsorption of hydrogen by palladium is commonly
(a) Na 2O2 (b) Na 2O (c) NaO2 (d) NaOH
known as …… (1983, 1M)
41. Sodium nitrate decomposes above » 800°C to give
51. Iodine reacts with hot NaOH solution. The products are NaI
(a) N2 (b) O2 (1998, 2M)
and …… (1980, 1M)
(c) NO2 (d) Na 2 O
42. Highly pure dilute solution of sodium in liquid ammonia True/False
(a) shows blue colour (1998, 2M)
52. Sodium when burnt in excess of oxygen gives sodium oxide.
(b) exhibits electrical conductivity
(1987, 1M)
(c) produces sodium amide
(d) produces hydrogen gas Subjective Questions
43. When zeolite, which is hydrated sodium aluminium silicate, 53. A white solid is either Na 2 O or Na 2 O2 . A piece of red litmus
is treated with hard water, the sodium ions are exchanged paper turns white when it is dipped into a freshly made
with (1990, 1M) aqueous solution of the white solid.
(a) H+ ions (b) SO2–
4 ions (c) Mg2+ ions (d) OH- ions (i) Identify the substance and explain with balanced
44. Sodium sulphate is soluble in water, whereas barium equation.
sulphate is sparingly soluble because (1989, 1M) (ii) Explain what would happen to the red litmus if the
(a) the hydration energy of sodium sulphate is more than its white solid were the other compound. (1999, 4M)
lattice energy 54. Hydrogen peroxide acts both as an oxidising and as a
(b) the lattice energy of barium sulphate is more than its reducing agent in alkaline solution towards certain first row
hydration energy transition metal ions. Illustrate both these properties of H2 O2
(c) the lattice energy has no role to play in solubility using chemical equations. (1998, 4M)
(d) the hydration energy of sodium sulphate is less than its
55. Element A burns in nitrogen to give an ionic compound B.
lattice energy
Compound B reacts with water to give C and D. A solution of
Assertion and Reason C becomes ‘milky’ on bubbling carbon dioxide gas. Identify
A, B, C and D. (1997, 3M)
Read the following questions and answer as per the direction given
below : 56. Complete and balance the following chemical reaction.
(a) Statement I is correct; Statement II is correct; Statement Anhydrous potassium nitrate is heated with excess of
II is the correct explanation of Statement I metallic potassium
(b) Statement I is correct; Statement II is correct; Statement KNO3 ( s ) + K ( s ) ¾® K + K (1992, 1M)
II is not the correct explanation of Statement I 57. Give reasons in one or two sentences for the following:
(c) Statement I is correct; Statement II is incorrect
(d) Statement I is incorrect; Statement II is correct “H2 O2 is a better oxidising agent than H2 O.” (1986, 1M)
45. Statement I Alkali metals dissolve in liquid ammonia to give 58. Sodium carbonate is prepared by Solvay process but the
blue solution. same process is not extended to the manufacture of
Statement II Alkali metals in liquid ammonia give solvated potassium carbonate, explain. (1981, 1M)
species of the type [ M ( NH 3 )n ]+ (M = alkali metals). 59. Water is a liquid, while H2 S is a gas at ordinary temperature.
(2007, 3M) Explain . (1978, 1M)
s-Block Elements 197
(a) (i) - (D); (ii) - (A); (iii) - (B); (iv) - (C) Subjective Questions
(b) (i) - (B); (ii) - (C); (iii) - (A); (iv) - (D)
(c) (i) - (C); (ii) - (B); (iii) - (D); (iv) - (A) 21. Identify (X) in the following synthetic scheme and write their
(d) (i) - (C); (ii) - (D); (iii) - (B); (iv) - (A) structures.
9. The amphoteric hydroxide is (2019 Main, 11 Jan I) *
Ba CO3 + H2 SO4 ¾® X (gas) (C* denotes C14 ) (2001, 1M)
(a) Be(OH)2 (b) Ca(OH)2 (c) Sr(OH)2 (d) Mg(OH)2
10. The metal used for making X-ray tube window is 22. Give reasons for the following in one or two sentences only :
(2019 Main, 10 Jan I) “BeCl 2 can be easily hydrolysed.” (1999, 2M)
(a) Na (b) Be (c) Mg (d) Ca
198 s-Block Elements
23. The crystalline salts of alkaline earth metals contain more alkaline solution. The solution on exposure to air produces a
water of crystallisation than the corresponding alkali metal thin solid layer of B on the surface. Identify the compounds A
salts. Why? (1997, 2M) and B. (1996, 3M)
24. Calcium burns in nitrogen to produce a white powder which 25. Arrange the following in increasing order of basic strength :
dissolves in sufficient water to produce a gas A and an MgO, SrO, K 2 O, NiO, Cs2 O (1991, 1M)
Answers
Topic 1 41. (a, b, d) 42. (a, b) 43. (a, d) 44. (a, b)
1. (a) 2. (c) 3. (c) 4. (a) 45. (b) 46. (c) 47. (a) 48. NaOH
5. (d) 6. (d) 7. (b) 8. (c) 49. solvated electrons 50. occlusion 51. NaIO 3
9. (a) 10. (c) 11. (a) 12. (c) 52. F
13. (d) 14. (d) 15. (a) 16. (d)
17. (d) 18. (c) 19. (c) 20. (a)
Topic 2
1. (d) 2. (b) 3. (b) 4. (d)
21. (a) 22. (b) 23. (c) 24. (c)
5. (c) 6. (a) 7. (d) 8. (d)
25. (a) 26. (d) 27. (b) 28. (a)
9. (a) 10. (b) 11. (c) 12. (b)
29. (c) 30. (a) 31. (b) 32. (a)
13. (b) 14. (d) 15. (a) 16. (b, c, d)
33. (a) 34. (b) 35. (d) 36. (c)
17. (a) 18. (b) 19. dry HCl 20. F
37. (d) 38. (b) 39. (a, b, c) 40. (a, b)
Li+ possesses the maximum degree of hydration due to its small 11. (I) H2 is a 100% pollution free fuel. So, statement (I) is correct.
size. As a consequence of hydration enthalpy, their mobility (II) Molecular weight of H2(2u).
also get affected. Cs+ has highest and Li + has lowest mobility in 1
aqueous solution. = ´ molecular weight of butane,
29
7. All the statements are correct. K+ being metallic unipositive C 4H10 (LPG) [58u].
ions work as enzyme activators. These also participate in many So, compressed H2 weighs ~30 times more than a petrol tank
reactions of glycolysis and Kreb’s cycle to produce ATP from and statement (II) is correct.
glucose. (III) NaNi 5, Ti - TiH2 etc. are used for storage of H2 in small
Being unipositive these are also equally responsible for nerve quantities. Thus, statement (III) is correct.
signal transmission along with Na + . (Na + ion-pump theory) (IV) On combustion values of energy released per gram of liquid
8. Metal (A) is rubidium (Rb). In excess of air, it forms RbO2( X ). dihydrogen (H2 ) : 142 kJ g -1, and for LPG : 50 kJ g -1. So,
X is a superoxide that have O-2 ion. It is due to the stabilisation staement (IV) is incorrect.
r s
of large anion by large cations through lattice energy effects. 12. Na H is an example of ionic or saline hydride. These hydrides
RbO2 (X ) gets easily hydrolysed by water to form the are formed when hydrogen combines with metals having less
hydroxide, H2O2 and O2. electronegativity and more electropositive character with
The reaction involved are as follows: respect to hydrogen.
Rb + O2 ¾® RbO2 (superoxide) Except Be and Mg, all s-block metals form saline hydrides.
(X)
Hydrides of p-block elements are covalent in nature, viz,
2RbO2 + 2H2O ¾® 2RbOH + H2O2 + O2 electron deficient hydrides (by group-13 elements),
(X) electron-precise hydrides (by group-14 elements), and
electron-rich hydrides (by group 15-17 elements). Hydrides of
9. Hardness of water sample can be calculated in terms of ppm
d , f -block metals are called interstitial or metallic hydrides.
concentration of CaCO3.
13. Sodium metal on dissolution in liquid ammonia gives a deep
Given, molarity = 10-3M blue solution due to the formation of ammoniated electrons. The
i.e. 1000 mL of solution contains 10-3 mole of CaCO3. reaction is represented as follows:
\Hardness of water = ppm of CaCO3 Na (s) + (x + y) NH3 (l ) ¾® [Na(NH)x ]+ + [ e(NH 3 ) y ]
10-3 ´ 1000 [Ammoniated Na + [Ammoniated
= ´ 106 or expanded Na] electrons]
1000
Ammoniated (solvated) electrons show electronic transition in
= 100 ppm
visible region and the solution becomes deep blue coloured.
10. GaH3, AlH3 and B2H6 are the hydrides of group-13 (ns2np1 ), This deep blue solution also shows the following properties due
whereas SiH4 is an hydride of group 14. to the presence of ammoniated electrons.
(i) It is strongly reducing in nature.
H H (ii) It is paramagnetic.
sp2 sp2 (iii) It is a good conductor of electricity.
Ga Al
H H H H
14. Hydrogen has three isotopes:
6e – around 6e – around
Ga 3+ <8e – (octet) Al 3+ <8e – (octet) 1 2 3
1H 1H 1 H
(GaH3) (AlH3)
3c–2e – bridge bond Protium (P) Deuterium (D) Tritium (T)
H 3
H sp H p 1 1 1
B B
H H n 0 1 2
H
B is sp3, but cannot satisfy octet due n 0 1 2
to the attachment of two 3c-2e –
bridge bonds (B–H–B) p
n
So, B2H6, AlH3 and GaH3 are electron deficient hydrides. Only tritium (T) is radioactive, because of its very high value,
p
But, SiH4 is an electron precise hydride of group-14 (ns2np2 ),
æn ö
i.e. these hydrides can have the required number of electrons to çç = 2÷÷ .
write their conventional Lewis structures. èp ø
H 15. H2O2 can act as both oxidising and reducing agents in both
8e– around Si (Octet gets satisfied)
Si acidic and basic medium.
H H2 O2 as oxidising agent
H H
l
In acidic medium: H2 O2 + 2H+ + 2e- ¾® 2H2 O
200 s-Block Elements
16. Among the group-1 metals, only Li is able to form its nitride, 24. Order of first ionisation energy is Sc > Na > K > Rb.
Li 3N. [All alkaline earth metals of group-2 form their nitride, Due to poor shielding effect, removal of one electron from 4s
M 3N2] orbital is difficult as compared to 3s-orbital.
6Li + N 2 ¾® 2Li 3N (Ruby red solid)
(Air) 25. PLAN This problem can be solved by using concept of oxidant and
reductant.
I II
[ 3M + N 2 ¾® M 3N 2 ] Oxidant Oxidant increases the oxidation number of the
Å Å species with which it is reacted.
Li is the smallest metal ion of group-1. Smaller size of Li and
larger size of nitride ion, N 3- , enable Li Å to polarise the Reductant Reductant decreases the oxidation number of the
spherical electron cloud of N 3- and it gives higher stability to species with which it is reacted.
Li 3N. H2O2 reacts with KIO4 in the following manner:
17. Temporary hardness of water is due to presence of soluble +7 +5
Ca(HCO3 )2 or Mg(HCO3 )2. KIO4 + H2O2 ¾® KIO3 + H2O + O2
Permanent hardness of water is due to the presence of CaCl 2 or On reaction of KIO4 with H2O2, oxidation state of I varies from
CaSO4 or MgCl 2 or MgSO4. +7 to +5, i.e. decreases. Thus, KIO4 gets reduced hence, H2O2 is
Temporary hardness of water is also called carbonate hardness a reducing agent here.
which can be easily removed by boiling or by treatment with With NH2OH, it given following reaction:
Ca(OH)2 (Clark’s method). -1 +3
N H2OH + H2O2 ¾® N 2 O3 + H2O
18. There are three known isotopes of hydrogen, each possessing an
atomic number 1 and atomic masses 1, 2 and 3 respectively. In the above reaction, oxidation state of N varies from –1 to +3.
These are named as protium (1 H), deuterium Here, oxidation number increases, hence H2O2 is acting as an
(2 H or D) and tritium (3 H or T) oxidising agent here.
The most common isotope is the ordinary hydrogen usually Hence, (a) is the correct choice.
called protium. It consists of one proton in the nucleus and an 26. Release of electron is known as reduction. So, H2O2 acts as
electron revolving around it. reducing agent when it releases electrons.
The second isotope of hydrogen is called heavy hydrogen or Here, in reaction (II) and (IV), H2O2 releases two electron,
deuterium. It consists of one proton and one neutron in the
hence reaction (II) and (IV) is known as reduction.
nucleus and an electron revolving around it. The third isotope of
hydrogen is called tritium. It consists of one proton and two In reaction (I) and (III), two electrons are being added, so (I)
neutrons in the nucleus and an electron revolving around it. and (III) represents oxidation.
19. Both reactions in their complete format are written below 27. Mg(HCO3 )2 on boiling decomposes to give white precipitate of
(i) In acidic medium, MgCO3 as:
-1 -2
2+ 4- + 3+ 3- Heat
[Fe (CN)6 ] + H2 O2 + 2H ¾® [Fe (CN)6 ] + 2H2 O Mg(HCO3 )2 (aq) ¾¾® MgCO3 ¯ + H2O + CO2
(ii) In alkaline medium,
-1 28. Electrolysis of aqueous Na 2SO4 gives H2 (g ) at cathode and
[Fe3+ (CN)6 ]3- + H2 O2 + 2OH- ¾®
O2 (g ) at anode.
[Fe2+ (CN)6 ]4- + O2 + 2H2O
29. Peroxodisulphuric acid (H2S2O8 ) on complete hydrolysis gives
Hence, H2O (for reaction (i)) and O2 + H2O
(for reaction (ii)) are produced as by product. two moles of H2SO4 and one mole of H2O2 as
O O
20. Mg can form basic carbonate while Li cannot. ½½ ½½
5 Mg2 + + 6 CO2–
3 + 7H 2O ¾® 4MgCO 3 × Mg(OH)2 HO ¾ S -¾¾ O ¾ O ¾¾- S ¾ OH ® 2H2SO4 + H2O2
×5H2O + 2 HCO-3 ½½ HO ¾ H H ¾ OH ½½
O O
21. Region 1 (Pre-heating zone)
Region 2 (Primary combustion zone, hottest zone) On partial hydrolysis, it gives one mole of H2SO4 and one mole
Region 3 (Internal zone) of peroxomonosulphuric acid as
Region 4 (Secondary reaction zone)
s-Block Elements 201
54. KMnO4 + H2O2 ¾® MnO2 + KOH + O2 4. Names of magnesium alloys are given by two letters followed by
OA RA two numbers. The common alloying elements are A (Aluminium),
FeSO4 + H2O2 ¾® Fe3+ + H2O Z (zinc), T (tin), M (manganese) etc. Numbers indicate
RA OA respective nominal compositions of main alloying elements, e.g.
55. 3M + N2 ¾® M 3 N2 ‘AZ 91’ implies the composition of the alloy as : Al = 9%, Zn =
A B 1% and Mg = 100 – (9 + 1) = 90%
M 3N2 + 6H2O ¾® 3M (OH)2 + 2NH3 Among the alloys given, Mg – Al (Magnalium ; Mg = 5%, Al
B C D =95%) is being light, tough and strong, hence it is used in
aircrafts.
M (OH)2 + CO2 ¾® MCO3
C Milkyness 5. The structures of beryllium chloride in the solid state and vapour
phase, respectively are dimeric and chain. In vapour phase at
M can be either Ca or Ba but essentially not Mg because
above 900°C, BeCl2 is monomeric having a linear structure Cl
Mg(OH)2 is very sparingly soluble in water.
¾Be¾Cl. The bonding in BeCl2 is covalent and Be atom
56. 2KNO3 (s) + 10K(s) ¾® 6K2O (s) + N2 (g ) accommodates 2 + 2 = 4 electrons in the two sp-hybrid orbitals.
57. In H2O2 , the peroxide ion (O2-
2 ) is unstable, has tendency to pass
Below 900°C, beryllium chloride in vapour phase exists as a
into stable oxide state (O2- ). Hence, H2O2 is a good oxidising mixture of monomer BeCl2 and dimer Be2Cl4.
agent while H2O is stable. 6. Magnesium powder burns in air to give MgO and Mg 3N2. MgO
58. In Solvay process, NaHCO3 is extracted from the solution by does not combine with excess oxygen to give any superoxide.
fractional crystallisation, which is then heated to convert it into Mg reacts with nitrogen to form magnesium nitride (Mg 3N2 ).
Na 2CO3 × KHCO3 , being more soluble than NaHCO3 , cannot be
extracted by fractional crystallisation. Hence, Solvay process Mg + O2 ¾® MgO
fails in production of K2CO3. 3Mg + N2 ¾® Mg3N2
59. Water forms stronger intermolecular H-bonds, therefore it is 7. Key Idea According to Fajan’s rule, degree of covalency
liquid at room temperature while H2S cannot form such strong (ionic potential), f µ-polarisation power of the
intermolecular bonds, gas at room temperature.
cation µ charge on the cation
1
Topic 2 Group II Elements µ
size of the cation
.
1. In comparison to boron, beryllium has lesser nuclear charge and
greater first ionisation enthalpy. Alkaline earth metals contains bipositive (H2+ ) ions in their
compounds.
Electronic configuration of Be(4 ) = 1s2 , 2s2.
So, here
It possess completely filled s-orbitals. Hence, high amount of
(i) Charge on cation, i.e. + 2 is constant.
energy is required to pull the electron from the gaseous atom.
Beryllium (4) lies left to the boron (5) and on moving from left (ii) Halide present (X - ) is also constant.
to right an electron is added due to which nuclear charge So, the covalent character depends on the size of alkaline earth
increases from Be to B. metal. As we move down the group, size of metal ion increases.
2. The correct sequence of thermal stability of carbonates is Be2+ < Mg2+ < Ca 2+ < Sr 2+ < Ba 2+
MgCO3 < CaCO3 < SrCO3 < BaCO3 So, Be2+ readily forms covalent compounds like BeX 2, because
On moving down the group, i.e. from Mg to Ba, atomic radius of very high positive charge density over its small size, so that it
generally increases. It is due to the addition of shell. As a result, readily polarises anionic spherical electron cloud.
the atomic size increases. CO2- 3 is a large anion. Hence, more 8. (i) Washing soda (Na 2CO3 × 10H2O) is manufactured in Solvay
stabilised by Ba 2+ (large cation) and less stabilised by Mg2+ . process. In this method, CO2 gas is passed through a
Therefore, BaCO3 has highest thermal stability followed by conc. solution of NaCl saturated with NH3. It gives ammonium
SrCO3, CaCO3 and MgCO3. carbonate followed by ammonium hydrogen carbonate.
3. Baking soda (NaHCO3 ) is not a hydrated solid. Thus, ( X ) is not The obtained NH4HCO3 is treated with solution of NaCl which
result in the formation of NaHCO3. The crystal obtained are
baking soda. Thus, option (a) and (c) are incorrect. Dead burnt
heated to obtain Na 2CO3.
plaster (CaSO4 ) is obtained from gypsum via the formation of
plaster of Paris. NaCl + NH3 + CO 2 + H2O ¾® NaHCO3 + NH4Cl
380-393 K 1 > 393K D Crystallisation
CaSO4 ×2H2O ¾¾¾® CaSO4 × H2O ¾¾¾® CaSO4 2NaHCO3 ¾¾¾¾®Na 2CO3 ¾¾¾¾¾® Na 2CO3 × 10H2O
Gypsum -1/ 2 H 2 O 2 1
- H 2 O Dead burnt plaster - H2O, CO2
Plaster of Paris 2
(anhydrous) (ii) Mg(HCO3 )2 and Ca(HCO3 )2 cause temporary hardness to
Therefore, the reaction takes place as follows : water that can be easily removed by boiling.
< 373K > 373K
Na 2CO3 × 10H2O ¾¾® Na 2CO3 × H2O ¾¾®
-9H 2 O
Na 2CO3 (iii) NaOH is manufactured by Castner-Kellner process.
-H 2 O
Washing soda Monohydrate Anhydrous white powder
(X ) (Y ) (soda ash) (Z ) In this reaction, Na amalgam flows out and treated with
water to give NaOH and H2 gas. During electrolysis,
s-Block Elements 203
hydrogen is evolved at cathode and chlorine is evolved at in the group has lesser size and not comparable with the size of
anode, which are the by product of this process. sulphates. Hence, BeSO 4 is the right response.
–
Electrolysis
Carbon anode 2Cl –2e Cl2 13. Thermal stability of salts with common anion depends on
2NaCl(aq) + polarising power of cation. Greater the polarising power, lower
Hg cathode 2Na +2e
be their thermal stability. Hence,
BeCO3 (IV) < MgCO3 (II) < CaCO3 (III) < K2CO3 (I)
2Na (Na/Hg)
H 2O 14. The reaction involved is
2NaOH(aq) +H2
BaO2 + H2SO4 ¾® BaSO4 + H2O2
The most electronegative atom, oxygen, in BaSO4 and H2O2 has
(iv) Portland cement constitutes, tricalcium aluminosilicate, -2 and -1 oxidation state respectively.
3CaO ×Al 2O3. SiO2, i.e. Ca 3Al 2O6 × SiO2.
9. For group-2 metal hydroxides, basicity increases down the 15. Electrolysis of molten CaCl 2 gives calcium at cathode
group, as: Ca 2+ + 2e- ¾® Ca (at cathode)
Be(OH)2 < Mg(OH)2 < Ca(OH)2 < Sr(OH)2 < Ba(OH)2 In case of electrolysis in aqueous medium, less electropositive
This is because as the size of metal atom increases, M—OH H+ is reduced at cathode rather than Ca 2+.
bond length increases or M—OH bond become weaker thus
16. Ca(OH)2 + Ca(HCO3 )2 ¾® 2CaCO3 ¯ + 2H2O
readily breaks to release OH - ions which are responsible for the (Clark’s method)
basicity of these solutions.
But Be(OH)2 shows amphoteric (basic as well as acidic) NaOCl + H2 ¾® NaOH + HOCl
character as it reacts with acid and alkali both which is shown in HO- + HCO-3 ¾® CO23- + H2O
the following reactions. Be(OH)2 as a base :
Be(OH)2 + 2HCl ¾® BeCl 2 + 2H2O Ca(HCO3 )2 + Na 2CO3 ¾® CaCO3 ¯ + 2NaHCO3
Be(OH)2 as an acid : 17. Magnesium ammonium phosphate is precipitated out.
Be(OH)2 + 2NaOH ¾® Na 2[Be(OH)4 ] MgSO4 + NH4OH + Na 2HPO4 ¾® Mg(NH4 )PO4 ¯ + Na 2SO4
10. Among the four elements given, Na, Be, Mg and Ca, Be has 18. Si is used in solar cells, because of its semi-conductor properties.
highest IE value because of its smallest size and 2s2 valence shell
configuration.
19. Anhydrous MgCl 2 is obtained by heating hydrated salt in stream
So, X-ray cannot cause ionisation from the material used, i.e. Be of dry HCl.
in the tube window, which may cause interference in the study. 20. Heating MgCl 2 × 6H2O brings about partial dehydration as
I
11. A saturated aqueous solution of M (NO3 )2 on crystallisation D
MgCl 2 × 6H2O ¾® Mg(OHCl) + HCl + 5H2O
II
will produce hydrated crystal, M (NO3 )2 × nH2O only when * * *
21. BaCO 3 + H 2SO 4 ¾® BaSO 4 + H 2O + CO 2 (C = C14)
hydration enthalpy (DH °hyd ) of M 2 + ion will be appreciably
22. Be in BeCl 2 is electron deficient, short of two lone pair of
more negative. electrons from stable octet. H2O has lone pair of electrons, reacts
Hydration of an ion depends on its size. Smaller the size of an with BeCl 2.
ion, higher will be its charge density and as a result it will remain
more solvated (hydrated) through ion dipole interaction.
23. Alkaline earth metal salts have M 2+ ions which has very high
polarising power compared to polarising power of monovalent
Size of group-2 metal ions increases on going down the group.
metal ion (M + ) of alkali metal. Due to high polarising power of
So, their ability to form hydrated crystals follows the order:
Be2 + >> Mg 2 + >> Ca 2 + >> Sr 2 + >> Ba 2 + M 2+ , it associate more water than M + .
Thus, Ba(NO3 )2 is slightly or almost insoluble in water. 24. A = NH3 , B = CaCO3.
12. As we move down the group, size of metal increases. Be has Reactions involved are :
lower size while SO2-
4 has bigger size, that’s why BeSO 4 breaks Heat
3Ca + N2 ¾¾® Ca 3N2
easily and lattice energy becomes smaller but due to lower size Ca 3N2 + 6H2O ¾® 3Ca(OH)2 + 2NH3
of Be, water molecules are gathered around and hence hydration A
energy increases. On the other hand, rest of the metals, i.e. Ca, Ca(OH)2 + CO2 ¾® CaCO3 + H2O
Ba, Sr have bigger size and that’s why lattice energy is greater (From air) B
than hydration energy. 25. Basic strength (i) decreases from left to right in period and
Time saving technique In the question of finding hydration (ii) increases from top to bottom in group. Therefore,
energy only check the size of atom. Smaller sized atom has more NiO < MgO < SrO < K2O < Cs2O Basic strength
hydration energy. Thus, in this question Be is placed upper most
14. The correct statement(s) for orthoboric acid is/are(2014 Adv.) Fill in the Blank
(a) It behaves as a weak acid in water due to self ionisation
(b) Acidity of its aqueous solution increases upon addition of
20. The two types of bonds present in B2 H6 are covalent and
ethylene glycol ……… (1994, 1M)
(c) It has a three-dimensional structure due to hydrogen bonding True/False
(d) It is a weak electrolyte in water
21. The basic nature of hydroxide of group 13 (group IIIA)
15. In the reaction, 2 X + B2 H6 ¾® [BH2 ( X )2 ] +[BH4 ] - decreases progressively down the group. (1993, 1M)
the amine(s) X is/are (2009)
22. All the Al ¾ Cl bonds in Al 2 Cl 6 are equivalent. (1989, 1M)
(a) NH3 (b) CH3NH2
(c) (CH3 )2 NH (d) (CH3 )3 N
Integer Answer Type Question
Assertion and Reason 23. Three moles of B2 H6 are completely reacted with methanol.
Read the following questions and answer as per the direction The number of moles of boron containing product formed is
given below : (2015 Adv.)
(a) Statement I is correct; Statement II is correct Statement II is the 24. The value of n in the molecular formula Ben Al2 Si 6O18 is
correct explanation of Statement I
(2010)
(b) Statement I is correct; Statement II is correct Statement II is
not the correct explanation of Statement I Subjective Questions
(c) Statement I is correct; Statement II is incorrect
25. AlF3 is insoluble in anhydrous HF but when little KF is added
(d) Statement I is incorrect; Statement II is correct to the compound it becomes soluble. On addition of BF3,
16. Statement I Boron always forms covalent bond. AlF3 is precipitated. Write the balanced chemical equations.
(2004, 2M)
Statement II The small size of B3+ favours formation of
covalent bond. (2007, 3M) 26. (i) How is boron obtained from borax? Give chemical
equations with reaction conditions.
17. Statement I In water, orthoboric acid behaves as a weak
monobasic acid. (ii) Write the structure of B2H6 and its reaction with HCl.
(2002)
Statement II In water, orthoboric acid acts as a proton
donor. (2007, 3M) 27. Compound X on reduction with LiAlH4 gives a hydride Y
18. Statement I Al(OH)3 is amphoteric in nature. containing 21.72% hydrogen alongwith other products. The
compound Y reacts with air explosively resulting in boron
Statement II Al ¾ O and O ¾ H bonds can be broken with trioxide. Identify X and Y. Give balanced reactions involved
equal ease in Al (OH)3 . (1998 , 2M) in the formation of Y and its reaction with air.
Draw the structure of Y. (2001, 5M)
Match the Column
28. Aluminium sulphide gives a foul odour when it becomes
19. Match the following. (2006, 6M)
damp. Write a balanced chemical equation for the reaction.
Column I Column II (1997, 2M)
A. Bi 3+
® (BiO) +
p. Heat 29. Anhydrous AlCl 3 is covalent. From the data given below,
predict whether it would remain covalent or become ionic in
B. [AlO2 ]- ® Al(OH)3 q. Hydrolysis aqueous solution.
C. SiO44 - ® Si 2O67 - r. Acidification (Ionisation energy for Al = 5137 kJ mol –1
D. (B4O27 - ) ® [B(OH)3 ] s. Dilution by water DH hydration for Al 3+ = – 4665 kJ mol –1
DH hydration for Cl - = - 381 kJ mol -1
(1997, 2M)
Subjective Questions X Y Z
26. Starting from SiCl 4 , prepare the following in steps not Yeast Fermentation Ethanol
exceeding the number given in parenthesis (give reactions Mica Graphite Abrasive
only). Superphosphate Crystalline cubic Insulator
(i) Silicon Carbon fibres Layer structure Fertiliser
(ii) Linear silicon containing methyl group only Rock salt Diamond structure Reinforced
(iii) Na 2SiO3 (2001, 5M) plastics
27. Draw the structure of a cyclic silicate, (Si 3 O9 )6– with proper Carborundum Bone ash Preservative
(1989, 3M)
labelling. (1998, 4M)
30. Give reasons for the following in one or two sentences :
28. Write the balanced equation for the preparation of crystalline
silicon from SiCl 4 . (1990, 1M) “Graphite is used as a solid lubricant.” (1985, 1M)
29. Each entry in column X is in some way related to the entries 31. Give reason for the following in one or two sentences :
in columns Y and Z. Match the appropriate entries. “Solid carbon dioxide is known as dry ice.” (1983, 1M)
Answers
Topic 1 Topic 2
1. (a) 2. (a) 3. (b) 4. (a) 1. (d) 2. (c) 3. (c) 4. (b)
5. (c) 6. (c) 7. (b) 8. (a) 5. (b) 6. (d) 7. (d) 8. (b)
9. (a) 10. (b) 11. (b) 12. (a, b, c) 9. (d) 10. (a) 11. (c) 12. (a)
13. (a, c, d) 14. (b, d) 15. (a, b, c) 16. (a) 13. (a) 14. (d) 15. (b, d) 16. (a)
17. (a) 18. (a) 17. (c) 18. glass 19. Buckminster
19. A ® q; B ® r; C ® p ; D ® q, r 20. ( R3SiO) 2 21. silicones 22. T 23. T
20. Three centre two electron bond or banana bond. 24. T 25. F
21. F 22. F 23. (3) 24. (3)
increases on moving from B to Tl. This is because as we move 3. The stability order of + 3 and + 1 oxidation states of group 13
down the group, the atomic size of elements goes on increasing,
elements will be:
whereas the ionisation energy decreases, due to which the
strength of metal oxide (MO) bond goes on decreasing. Thus, B3 + > Al 3 + > Ga 3 + > In 3 + >>Tl 3+
boron trioxide or boron oxide is acidic and reacts with basic (order of + 3 oxidation state)
oxides to give metal borates. Aluminium and gallium oxides are B+ <<Al + < Ga + < In + < Tl +
amphoteric while oxides of indium and thallium are basic in (order of + 1 oxidation state)
nature. The presence of two oxidation states in p-block elements is due
2. Diborane (B2H6 ) reacts independently with O2 and H2O to to the inert pair effect.
produce B2O3 and H3BO3 respectively. Diborane is a Because of the presence of poor shielding d and f -orbitals, as
colourless, highly toxic gas, having boiling point 180 K. we move from Ga to Tl, effective nuclear charge of these
Because of its inflammable nature, it catches fire spontaneously elements increases so as to hold the valence ns2 electrons
when exposed to air and burns in oxygen releasing an enormous tightly. It causes difficulty to the ionisation of ns2-electrons and
amount of energy as: it remains inert, only np1-electron ionises to give + 1 oxidation
B2H6 + 3O2 ¾¾® B2O3 + 3H2O + 1976 kJ/mol state.
208 p-Block Elements-I
4. The structure of B2H6 can be shown as : 10. In BCl 3, bond angle = 120°.
H H H In PCl 3 , AsCl 3 and BiCl 3 , central atom is sp3 hybridised.
H
H eH Since P, As and Bi are from the same group, bond angle
–2
3c–3e 2c 3
B B Þ B B sp decreases down the group. Hence, overall order of bond
H angle is :
H
H H H B > P > As > Bi
H
In B2H6, four 2-centre-2-electron (2c - 2e) bonds are present in the 11. Graphite has layered structure and conducted electricity
same plane and two 3-centre-2-electron (3c - 2e) bonds are present in moderately. Silica and diamond have 3-dimensional
another plane. network structures and non-conducting.
5. Let, us consider the electronegativity values of the given elements, 12. (a) Three centre two
Group-1 Group-2 Group-13 Group-19 H H H electron bond
CH3 CH3
Period 2 Þ Li Be B C C
(1 . 0) (1 . 5) (2 . 0) (2 . 5)
Al Al
Period 3 Þ Al CH3 C CH3
(1. 5) *
Z H H H
Be and Al show diagonal relationship which is based on their same
r
(b) BCl 3 is stronger Lewis acid than AlCl 3 due to greater
value (Z* is effective nuclear charge, r = atomic radius). So, they have
extent of pp - pp back bonding in AlCl 3.
similar electronegativity.
(c) Three centre four
6. Due to inert pair effect, group-13 elements (ns2np1 ) show + 3 and + 1 electron bond
oxidation states in their compounds. Stability order of these oxidation Cl Cl Cl
states will be as,
Al Al
l
+ 3 oxidation states Cl Cl Cl
B3+ > Al3+ > Ga 3+ > In3+ > Tl3+
(d) Three centre two
B3+ does not exist in free states. All B(III) compounds are covalent. electron bond
l
+ 1 oxidation states H H H
B+ < Al+ < Ga + < In + < Tl+ B B
H H H
B+ does not exist in ionic as well covalent compounds.
7. Due to poor shielding of d-orbital in Ga, atomic radius of Ga is smaller 13. Na 2B4O7 × 10H2O (borax) is actually made of two
than that of Al. Thus, Ga < Al < In < Tl. tetrahedral and two triangular units, and is actually written
8. Orthoboric acid is a very weak acid, direct neutralisation does not asNa 2[B4O5 (OH)4 ]× 5H2O.
complete. However, addition of cis-diol allow the reaction to go to OH
completion by forming a stable complex with [B(OH)4 ]- as: s sp3
O—B O sp2
HO OH CH2 ¾ OH
HO—B O B—OH
B + 2½ ¾® O
HO OH CH2 ¾ OH O—B
sp2 s
H2C ¾ O O ¾ CH2 sp3 OH
½ B ½ + 2H2O
H2C ¾ O O ¾ CH2 (a) Thus, correct.
(b) Boron atoms are in different planes thus, incorrect.
9. Orthoboric acid is a weak, monobasic, Lewis acid. (c) Two sp2 and two sp3-hybridised B atoms thus,
OH has deficiency of a lone-pair correct.
(Lewis acid) (d) Each boron has one ¾ OH group thus, correct.
HO—B
14. (a) It does not undergo self ionisation in water but accepts
OH an electron pair from water, so it behaves as weak
monobasic acid.
pp - pp backbonding between ‘B’ and ‘O’ decreases acid strength
greatly : H3BO3 + H2O r B(OH)-4 + H+
pp–p Hence, (a) is incorrect.
p
(b) When treated with 1, 2-dihydroxy or polyhydroxy
HO—B—OH compounds, they form chelate (ring complex) which
effectively remove [ B(OH)4 ]- species from solution
OH
and thereby produce maximum number of H3O+ or H+
ions, i.e. results in increased acidity.
p-Block Elements-I 209
(c) Boric acid crystallises in a layer structure in which planar Al(OH)3 + NaOH ¾® Na[Al(OH)4 ]
triangular BO3-
3 ` ions are bonded together through hydrogen
Acid
bonds. Therefore, both statements are correct and statement II is a
correct explanation of statement I.
One trigonal
planar B(OH) 3 unit 19. (A) Bi 3+ hydrolysis to (BiO)+ ¾ q.
H H
(B) [AlO2 ]- exist in basic medium, on acidification gives
H H Al(OH)3 ¾ r.
H H
B (C) Orthosilicate (SiO4-
4 ) on heating changes into pyrosilicate
H Si 2O6-
H H 7 ¾ p.
B B
H H H (D) Tetraborate ion [B4O2- 7 ] on treatment with dil. acid
H H H hydrolysis gradually to orthoboric acid ¾ q, r.
H
H H H 20. Three centred two electron bonds.
B B
H H
H H H H
B B B Covalent bonds
H H
H H H H H H
H H
Three centred two electron
(d) In water the pK a value of H3BO3 is 9.25. bridged B—H—B bonds
H3BO3 + H2O r B(OH)-4 + H+ ; pKa = 9.25 12. The basic nature of hydroxide of group-13 increases from top to
So, it is a weak electrolyte in water. bottom due to increase in electropositive character.
15. Diborane (B2H6 ) undergoes unsymmetric cleavage with NH3 , 22. In Al 2Cl6 , Al–Cl bonds are not equivalent :
primary and secondary amine while tertiary amine brings about Cl Cl Cl
symmetrical cleavage of B2H6 as : Al Al The bridged Al—Cl bonds
are different from terminal
H H H Cl Cl Cl Al—Cl bonds.
B B + NH3 or 1° amine
or 2° amine 23. B2H6 + 6 CH3OH ¾® 2[B(OCH3 )3 ] + 6H2
H H H
Unsymmetric
Therefore, from 3 moles of B2H6 , 6 moles of B(OCH3 )3 will be
X
cleavage 24. BenAl 2Si6O18 , 2n + 6 + 24 - 36 = 0 Þ n = 3
+ –
[BH2(X)2] [BH4]
H H H
25. 3KF + AlF3 ¾® B2H5Cl + H2
B B + 2R3N 2H3B(R3N) K3AlF6 + 3BF3 ¾® AlF3 ¯ + 3KBF4
ppt
H H H
Symmetrical 26. (i) Na 2B4O7 + HCl ¾® NaCl + H3BO3
cleavage
D
H3BO3 + HCl ¾® BCl 3 + H2O
16. Small size and high charge on B3+ makes it highly polarising.
Therefore, in most of its compounds, boron forms covalent D
BCl 3 + Al ¾® B + AlCl 3
bonds.
H H H
Hence, both statement I and statement II are correct and (ii) B2H6 : B B
statement II is a correct explanation of statement I. H H H
17. Orthoboric acid is a weak, monobasic, Lewis acid and the poor It has 4 terminal B—H bonds. There are two B—H—B, three
acidic character is due to pp - pp backbondings as: centred two electron bridged bonds.
pp–pp B2H6 + HCl ¾® B2H5Cl + H2
Backbonding decreases electron
HO—B—OH deficiency at boron, decreases LiAlH4
27. Compound X ¾¾¾® Y a hydride + other compound.
its Lewis acid strength. Hydride Y contains 21.72% hydrogen.
OH
D
Y + O2 ¾® B2O3 + H2O
18. Due to small size and high charge on Al in Al(OH)3 the fission
Therefore, Y is a hydride of boron and it is obtained by reduction
ability of Al—O and O—H bonds become comparable and of X with LiAlH4. So, X is either BCl 3 or BF3.
compound can give both H+ and HO- under appropriate
4BCl 3 + LiAlH4 ¾® B2H6 + 3AlCl 3 + 3LiCl
reaction conditions as: 1442443
X Y Other products
Al(OH)3 + 3HCl ¾® AlCl 3 + 3H2O
Base Molar mass of B2H6 = 2 ´ 11 + 6 = 28
210 p-Block Elements-I
% of H in B2H6 =
6
´ 100 = 21.5 » 21.72 In SiO4-
4 ion, each Si atom is bonded to four oxygen atoms
28 tetrahedrally.
B2H6 + 3O2 ¾® B2O3 + 3H2O + Heat
Y 3. Catenation property is an unique property of group 14 elements.
Down the group 14, catenation power decreases as:
Structure of Y (B2H6 )
C > Si > Ge » Sn
H
Å Pb does not show catenation.
3
H 1.3 9ÅH 4. Silica occurs in nature in several amorphous and crystalline
97° 1.1
B B 122° forms. Kieselguhr is the amorphous form of silica. Quartz,
tridymite and cristobalite are crystalline forms of silica.
H H
5. C60 is aromatic allotrope of carbon containing 12 pentagons and
H 20 hexagons. It is a fullerene having a shape like soccer ball and
1.77 Å called Buckminster fullerene.
(a) There are 4 terminal B—H bonds. 6. The property of self-linking of atoms of an element through
(b) There are two 3-centre-2-electron B—H—B bridged covalent bonds to form straight or branched chains and rings of
bonds. different sizes is called catenation. Down the group, catenation
(c) Terminal H—B—H planes are perpendicular to bridged tendency decreases due to decrease in element bond strength.
B—H—B bonds. Carbon (C), silicon (Si), germanium (Ge), tin (Sn), lead (Pb) are
group-14 elements.
28. Al 2S3 + 6H2O ¾® 2Al(OH)3 ¯ + 3H2S(g )
Foul odour Catenation tendency is highest in carbon while silicon has second
Foul odour on damping of Al 2S3 is due to the formation of H2S highest tendency of catenation among all elements of family due
gas as shown above. to higher bond energy. The decreasing tendency of catenation
among group 14 elements is as follows:
29. The total hydration energy of AlCl 3
C >> Si > Ge » Sn
= Hydration energy of Al 3+ + 3 ´ Hydration energy of Cl -
However, Pb does not show catenation.
= - 4665 + 3 (- 381) kJ/mol
= - 5808 kJ/mol 7. Carbon (C) has greatest ability to form stable pp-pp multiple
The above hydration energy is more than the energy required for bonds. 2p-orbitals of this element participate in the process. The
ionisation of AlCl 3 into Al 3+ and 3Cl - . stability of multiple bonds of C is attributed to their closeness
with C-nucleus. Thus, the smaller size of C plays a significant
Due to this reason, AlCl 3 becomes ionic in aqueous solution. In
aqueous solution, it is ionised completely as role in the process.
AlCl 3 + 6H2O ¾® [Al(H2O)6 ]3+ + 3Cl - 8. The compounds given are the tetrahalides
(MCl 4) of group 14 elements. For the hydrolysis, (nucleophilic
substitution) of MCl 4 the nature of the M—Cl bond should be as:
Topic 2 Groups 14 Elements
d+ d–
1. The C ¾ C bond length is maximum in diamond having value M——Cl
154 pm. Here, each carbon atom undergoes sp3 hybridisation
and linked to four other carbon atoms by using hybridised It must expand its covalency beyond 4 by the use
of its vacant d-orbital which will accommodate the
orbitals in tetrahedral fashion. It has a rigid three-dimensional lone pair of electrons of H 2O (the–nucleophile).
network of carbon atoms.
sp3d
C ¾ C bond length within the layers of graphite is 141.5 pm. In sp3
C60, C ¾ C distances between single and double bonds are 143.5 Cl3 M——Cl Cl3 M——Cl
d + d – OH2
pm and 138.3 pm respectively. d0
O
H H
2. The basic structural unit of feldspar, –HCl
Transition state
4-
zeolites, mica and asbestos is (SiO4 ) . These all are silicates.
3H2O sp3
All silicates involve two types of Si ¾ O bonds. M(OH)4 Cl3 M—(OH)
–3HCl
(i) Terminal Si¾ O bonds in which oxygen is bonded to a
silicon and not other atom. Here, M can be Si, Sn and Pb because they have vacant
(ii) Bridging Si ¾ O ¾ Si bonds in which oxygen is bonded to nd-orbital. But, carbon is a member of second period (n = 2,
two silicon atoms. l = 0, 1),
O– s it does not have d-orbital (l = 2). So, CCl 4 will not be hydrolysed
and correct option is (b).
Si O–
9. Silicones are polysiloxanes with general chemical formula,
O– O– s s [R2SiO]n, where R is an organic group such as:
¾ CH3 , ¾ C2 H5 , ¾ C6 H5 etc.
p-Block Elements-I 211
Silicones have many useful properties: 14. PbI4 is least stable, has doubtful existence. It is due to inert pair
(i) They repel water and form watertight seals. effect, the stable oxidation state of lead is + 2.
(ii) They are heat resistant because of constancy of properties
over a wide range of temperature (- 100° to 250° C). 15. Diamond has a three-dimensional network structure, a hard
substance where graphite is soft due to layered structure.
(iii) Silicones are non-toxic.
In graphite, only three valence electrons are involved in bonding
(iv) Silicones are biocompatible because these do not support and one electron remain free giving electrical conductivity. In
microbiological growth and these have high gas diamond, all the four valence electrons are covalently bonded
permeability at room temperature. hence, insulator.
(v) They are resistant to O2, O3 and UV-radiation.
Diamond is better thermal conductor than graphite. Electrical
(vi) Silicones are formulated to be electrically insulative.
conductivity is due to availability of free electrons, thermal
(vii) Silicone grease is typically used as a lubricant for brake conduction is due to transfer of thermal vibrational energy from
components in automobiles, since it is stable at high one atom to another atom. A compact and precisely aligned
temperature, is not water soluble and is a odourless viscous crystals like diamond thus facilitate better movement of heat.
liquid.
In graphite C ¾ C bond acquire some double bond character,
10. In sheet silicates, three out of four oxygen of SiO4-
4 unit are hence, higher bond order than in diamond.
shared as shown below :
16. In group 13, 14, 15 as we descend down in group, the higher
– – oxidation state becomes less tenable due to inert pair effect.
– Therefore, lead show +2 as stable oxidation state. Hence, Pb4+
act as a strong oxidising agent, itself reduced to Pb2+ very easily.
– Both statement I and statement II are correct and statement II is a
– – – – correct explanation of statement I.
17. SiCl 4 reacts with water due to vacant d-orbitals available with
Three oxygens of every Si as:
– – – – tetrahedra are
shared with others
H 2O SiCl4
– – –
–
2. The number of pentagons in C60 and trigons (triangles) in (a) H3PO4 > H3PO2 > H3PO3 > H4P2O6
white phosphorus, respectively, are (2019 Main, 10 April II) (b) H3PO4 > H4P2O6 > H3PO3 > H3PO2
(a) 20 and 3 (b) 12 and 4 (c) H3PO2 > H3PO3 > H4P2O6 > H3PO4
(c) 20 and 4 (d) 12 and 3 (d) H3PO3 > H3PO2 > H3PO4 > H4P2O6
3. The oxoacid of sulphur that does not contain bond between 10. The species in which the N-atom is in a state of
sulphur atoms is (2019 Main 10 April I) sp hybridisation is (2016 Main)
(a) H2S2O3 (b) H2S2O4 (a) NO-2 (b) NO-3
(c) H2S2O7 (d) H2S4O6 (c) NO2 (d) NO+2
4. The correct order of the oxidation states of nitrogen in NO, 11. The pair in which phosphorus atoms have a formal oxidation
NO2 , NO2 and N2 O3 is (2019 Main, 9 April I)
state of +3 is (2016 Main)
(a) NO2 < NO < N2O3 < N2O (b) N2O < NO < N2O3 < NO2 (a) pyrophosphorous and hypophosphoric acids
(c) O2 < N2O3 < NO < N2O (d) N2O < N2O3 < NO < NO2 (b) orthophosphorous and hypophosphoric acids
5. The pair that contains two P¾ H bonds in each of the (c) pyrophosphorous and pyrophosphoric acids
oxoacids is (2019 Main, 10 Jan II) (d) orthophosphorous and pyrophosphorous acids
(a) H4P2O5 and H4P2O6 (b) H3PO3 and H3PO2 12. The product formed in the reaction of SOCl 2 with white
(c) H4P2O5 and H3PO3 (d) H3PO2 and H4P2O5
phosphorus is (2014 Adv.)
6. When the first electron gain enthalpy (De g H ) of oxygen is (a) PCl 3 (b) SO2Cl 2
(c) SCl 2 (d) POCl 3
- 141 kJ/ mol, its second electron gain enthalpy is
(2019 Main, 9 Jan II) 13. Which of the following properties is not shown by NO?
(a) a positive value (a) It is paramagnetic in liquid state (2014 Main)
(b) a more negative value than the first (b) It is a neutral oxide
(c) almost the same as that of the first (c) It combines with oxygen to form nitrogen dioxide
(d) negative, but less negative than the first (d) Its bond order is 2.5
7. Good reducing nature of H3 PO2 is attributed to the presence 14. Concentrated nitric acid upon long standing, turns
of (2019 Main, 9 Jan II) yellow-brown due to the formation of (2013 Main)
(a) two P¾ H bonds (b) one P¾ H bond (a) NO (b) NO2
(c) two P¾ OH bonds (d) one P ¾ OH bond (c) N 2O (d) N 2O4
214 p-Block Elements-II
15. Which of the following is the wrong statement? (2013 Main) 27. Polyphosphates are used as water softening agents because
(a) ONCl and ONO - are not isoelectronic they (2002, 3M)
(b) O3 molecule is bent (a) form soluble complexes with anionic species
(c) Ozone is violet-black in solid state (b) precipitate anionic species
(d) Ozone is diamagnetic gas (c) form soluble complexes with cationic species
(d) precipitate cationic species
16. The reaction of white phosphorus with aqueous NaOH gives
phosphine alongwith another phosphorus containing 28. The number of S ¾ S bonds in sulphur trioxide trimer,
compound. The reaction type, the oxidation states of (S3 O9 ) is (2001, 1M)
phosphorus in phosphine and the other product respectively (a) three (b) two
are (2012) (c) one (d) zero
(a) redox reaction, - 3 and - 5 29. Ammonia can be dried by (2000, 1M)
(b) redox reaction, 3 and + 5 (a) conc. H2SO4 (b) P4O10
(c) disproportionation reaction, - 3 and + 5 (c) CaO (d) anhydrous CaCl 2
(d) disproportionation reaction, - 3 and + 3
30. Amongst H2 O, H2 S, H2 Se and H2 Te, the one with the
17. Which ordering of compounds is according to the highest boiling point is (2000, 1M)
decreasing order of the oxidation state of nitrogen? (2012)
(a) H2O because of hydrogen bonding
(a) HNO3 , NO, NH4Cl, N2 (b) HNO3 , NO, N2 , NH4Cl
(b) H2Te because of higher molecular weight
(c) HNO3 , NH4Cl, NO, N2 (d) NO, HNO3 , NH4Cl, N2
(c) H2S because of hydrogen bonding
18. Extra pure N 2 can be obtained by heating (2011) (d) H2Se because of lower molecular weight
(a) NH3 with CuO (b) NH4NO3
31. The correct order of acidic strength is (2000, 1M)
(c) (NH4 )2 Cr2O7 (d) Ba(N3 )2 (a) Cl 2O7 > SO2 > P4O10 (b) CO2 > N2O5 > SO3
19. The reaction of P4 with X leads selectively to P4 O6 . The X, is (c) Na 2O > MgO > Al 2O3 (d) K 2O > CaO > MgO
(a) dry O2 (2009) 32. The number of P ¾ O ¾ P bonds in cyclic metaphosphoric
(b) a mixture of O2 and N2 acid is (2000, 1M)
(c) moist O2 (a) zero (b) two (c) three (d) four
(d) O2 in the presence of aqueous NaOH 33. One mole of calcium phosphide on reaction with excess
water gives (1999, 2M)
20. The percentage of p-character in the orbitals forming
(a) one mole of phosphine
P—P bonds in P4 is (2007, 3M)
(b) two moles of phosphoric acid
(a) 25 (b) 33 (c) 50 (d) 75
(c) two moles of phosphine
21. Which of the following is not oxidised by O3 ? (2005, 1M) (d) one mole of phosphorus pentaoxide
(a) KI (b) FeSO4
34. Sodium thiosulphate is prepared by (1996, 1M)
(c) KMnO4 (d) K 2MnO4
(a) reducing Na 2SO4 solution with H2S
22. Which gas is evolved when PbO2 is treated with (b) boiling Na 2SO3 solution with S in alkaline medium
concentrated HNO3? (2005) (c) neutralising H2S2O3 solution with NaOH
(a) NO2 (b) O2 (d) boiling Na 2SO3 solution with S in acidic medium
(c) N2 (d) N2O
35. There is no S ¾ S bond in (1991, 1M)
23. A pale blue liquid obtained by equimolar mixture of two (a) S 2O2– (b) S 2O2– (c) S2O2– (d) S2O2–
4 5 3 7
gases at – 30°C is (2005, 1M)
(a) N2O (b) N2O3 36. Which one of the following is the strongest base? (1989, 2M)
(c) N2O4 (d) N2O5 (a) AsH3 (b) NH3 (c) PH3 (d) SbH3
24. Which of the following isomers of phosphorus is 37. Amongst the trihalides of nitrogen, which one is least basic?
thermodynamically most stable? (2005, 1M) (a) NF3 (b) NCl 3 (1987, 1M)
(a) Red (b) White (c) NBr3 (d) NI3
(c) Black (d) Yellow 38. Which of the following oxides of nitrogen is a coloured gas ?
25. Which of the following has —O—O— linkage? (2004, 3M) (a) N2O (b) NO (1987,1M)
(a) H2S2O6 (b) H2S2O8 (c) N2O4 (d) NO2
(c) H2S2O3 (d) H2S4O6
39. The bonds present in N2 O5 are (1986, 1M)
26. For H3PO3 and H3PO4, the correct choice is (2003, 1M) (a) only ionic (b) covalent and coordinate
(a) H3PO3 is dibasic and reducing (c) only covalent (d) covalent and ionic
(b) H3PO3 is dibasic and non-reducing
(c) H3PO4 is tribasic and reducing 40. A gas that cannot be collected over water is (1985, 1M)
(a) N2 (b) O2 (c) SO2 (d) PH3
(d) H3PO3 is tribasic and non-reducing
p-Block Elements-II 215
Passage Codes
P Q R S P Q R S
There are some deposits of nitrates and phosphates in earth’s
(a) 4 2 3 1 (b) 3 2 1 4
crust. Nitrates are more soluble in water. Nitrates are
(c) 1 4 2 3 (d) 3 4 2 1
difficult to reduce under the laboratory conditions but
microbes do it easily. Ammonia forms large number of
complexes with transition metal ions. Hybridisation easily Fill in the Blanks
explains the ease of sigma donation capability of NH3 and 62. The lead chamber process involves oxidation of SO2 by
PH3 . Phosphine is a flammable gas and is prepared from atomic oxygen under the influence of ………as catalyst.
white phosphorus. (2008, 3 ´ 4M = 12M) (1992, 1M)
58. Among the following, the correct statement is 63. In P4 O10 , the number of oxygen atoms bonded to each
(a) Phosphates have no biological significance in humans phosphorus atom is ……… . (1992, 1M)
(b) Between nitrates and phosphates, phosphates are less abundant
in earth’s crust 64. The basicity of phosphorus acid (H3 PO3 ) is ………
(c) Between nitrates and phosphates, nitrates are less abundant in (1990, 1M)
earth’s crust 65. ……… phosphorus is reactive because of its highly strained
(d) Oxidation of nitrates is possible in soil tetrahedral structure. (1987, 1M)
59. Among the following, the correct statement is
(a) Between NH3 and PH3 , NH3 is a better electron donor True/False
because the lone pair of electrons occupies spherical ‘s’ orbital 66. Nitric oxide, though an odd electron molecule, is
and is less directional diamagnetic in liquid state. (1991, 1M)
(b) Between NH3 and PH3 , PH3 is a better electron donor
because the lone pair of electrons occupies sp3-orbital and is
67. The H ¾ N ¾ H bond angle in NH3 is greater than the
more directional H ¾ As ¾ H bond angle in AsH3 . (1984, 1M)
(c) Between NH3 and PH3 , NH3 is a better electron donor 68. In aqueous solution, chlorine is a stronger oxidising agent
because the lone pair of electrons occupies sp3-orbital and is than fluorine. (1984, 1M)
more directional 2+
69. Dilute HCl oxidises metallic Fe to Fe . (1983, 1M)
(d) Between NH3 and PH3 , PH3 is a better electron donor
because the lone pair of electrons occupies spherical ‘s’ orbital
and is less directional
Integer Answer Type Question
70. The total number of lone pair of electrons in N2O3 is
60. White phosphorus on reaction with NaOH gives PH3 as one
(2015 Adv.)
of the products. This is a
(a) dimerisation reaction (b) disproportionation reaction 71. Among the following, the number of compounds that can
(c) condensation reaction (d) precipitation reaction react with PCl 5 to give POCl 3 is O2 , CO2 , SO2 , H2 O,
H2 SO4 , P4 O10 . (2011)
Match the Columns 72. The total number of diprotic acids among the following is
61. The unbalanced chemical reactions given in Column I show H3PO4 H2SO4 H3PO3
missing reagent or condition (?) which are provided in H2CO3 H2S2O7 H3BO3
Column II. Match Column I with Column II and select the H3PO2 H2CrO4 H2SO3 (2010)
correct answer using the codes given below the Columns.
(2013 Adv.) Subjective Questions
Column I Column II 73. Draw the structure of P4O10. (2005)
77. Give reason(s), why elemental nitrogen exists as a diatomic 84. Draw the structure of P4 O10 and identify the number of
molecule whereas elemental phosphorus is a tetra atomic single and double P ¾ O bonds. (1996, 3M)
molecule? (2000, 2M)
85. Account for the following. Write the answers in four or five
78. The Haber’s process can be represented by the following sentences only.
scheme.
(i) The experimentally determined N ¾ F bond lengths in NF3
CaCO3 is greater than the sum of the single bond covalent radii of N
and F.
CaO + CO2 (ii) Mg 3 N2 when reacted with water gives of NH3 but HCl is
H 2O NH3.H2O not obtained from MgCl 2 on reaction with water at room
temperature.
B
(iii) (SiH3 )3 N is a weaker base than (CH3 )3 N.
NaHCO3 (1995, 2M ´ 3 = 6M)
NaCl
86. Complete and balance the following reactions. (1994, 1M)
+D
Heat
C + H2O Ca 5 (PO4 )3 F + H2SO4 + H2O ¾¾®
NH3 + H2O + E K + 5CaSO4 × 2H2 O + K
A
Identify A, B, C, D and E . (1999, 5M)
87. In the following reaction, identify the compounds A and B
PCl 5 + SO2 ¾® A + B (1994, 1M)
79 (a) In the following equation
A + 2B + H2 O ¾® C + 2D 88. Complete and balance the following reaction.
(A = HNO2 , B = H2SO3 , C = NH2OH). Red phosphorus is reacted with iodine in the presence of
water.
Identify D. Draw the structures of A, B, C and D.
P + I2 + H2 O ¾® K + K (1992, 1M)
(b) In the contact process for industrial manufacture of
sulphuric acid, some amount of sulphuric acid is used as a 89. Give reasons in two or three sentences only.Sulphur dioxide
starting material. Explain briefly. What is the catalyst used is a more powerful reducing agent in the alkaline medium
in the oxidation of SO2? (1999, 10M) than in acidic medium. (1992, 2M)
80. Complete and balance the following chemical equations. 90. Draw the two resonance structures of ozone which satisfy
the octet rule. (1991, 1M)
(i) P4O10 + PCl 5 ¾®
91. Give reasons in one or two sentences.
(ii) SnCl 4 + C2H5Cl + Na ¾® (1998, 1 M ´ 2 = 2M)
Ammonium chloride is acidic in liquid ammonia solvent.
81. (a) Thionyl chloride can be synthesised by chlorinating SO2 (1991, 1M)
using PCl5. Thionyl chloride is used to prepare
anhydrous ferric chloride starting from its hexahydrated 92. Write the balanced chemical equations for the following.
salt. Alternatively, the anhydrous ferric chloride can also (i) Sodium nitrite is produced by absorbing the oxides of
be prepared from its hexahydrated salt by treating with nitrogen in aqueous solution of washing soda.
2,2-dimethoxypropane. Discuss all this using balanced (ii) Nitrogen is obtained in the reaction of aqueous ammonia
chemical equations. with potassium permanganate.
(b) Reaction of phosphoric acid with Ca3(PO4)2 yields a (iii) Elemental phosphorus reacts with concentrated HNO3 to
fertiliser “triple superphosphate” represent the same give phosphoric acid.
through balanced chemical equation. (1998, 5M)
(iv) Sulphur is precipitated in the reaction of hydrogen
82. A soluble compound of a poisonous element M, when sulphide with sodium bisulphite solution.
heated with Zn / H2 SO4 , gives a colourless and extremely (v) Carbon dioxide is passed through a suspension of
poisonous gaseous compound N, which on passing through limestone in water. (1991, 1 ´ 5 = 5M)
a heated tube gives a silvery mirror of element M. Identify
M and N. (1997, 2M) 93. Write the balanced chemical equation for the following
reactions.
83. Write balanced equations for the following.
(i) Aqueous solution of sodium nitrate is heated with zinc
(i) Phosphorus is treated with concentrated nitric acid. dust and caustic soda solution.
(ii) Oxidation of hydrogen peroxide with potassium (ii) Sodium iodate is added to a solution of sodium bisulphite
permanganate in acidic medium. (1990, 2M)
(iii) Manufacture of phosphoric acid from phosphorus. 94. Write the two resonance structures of N2 O that satisfy the
(iv) Reaction of aluminium with aqueous sodium hydroxide. octet rule. (1990, 2M)
(1997, 1M ´ 4 = 4M)
218 p-Block Elements-II
95. Draw balanced equations for 104. Write down the balanced equation for the reactions when
(i) the preparation of phosphine from CaO and white (i) calcium phosphate is heated with a mixture of sand and
phosphorus. carbon.
(ii) the preparation of ammonium sulphate from gypsum,
(ii) ammonium sulphate is heated with a mixture of nitric
ammonia and carbon dioxide. (1990, 2M)
oxide and nitrogen dioxide. (1985, 2M)
96. Explain the following (1989, 2M)
105. Draw the resonance structures of nitrous oxide.
(1985, 90, 2M)
(i) H3 PO3 is a dibasic acid.
(ii) Phosphine has lower boiling point than ammonia. 106. Show with balanced chemical reaction what happens when
following are mixed?
97. Write the balanced chemical equations for the following.
(i) Hypophosphorous acid is heated. Aqueous solution of ferric sulphate and potassium iodide.
(1984, 1M)
(ii) Sodium chlorate reacts with sulphur dioxide in dilute
sulphuric acid medium. 107. Write the matched set (of three) for each entry in Column A
98. Arrange the following as indicated. CO2 , N2 O5 , SiO2 , SO3 A B C
in the order of increasing acidic character. Asbestos Paramagnetic Air pollutant
99. Give balanced equations for the following. Lithium metal Silicates of Ca and Mg Electron donor
(i) Phosphorus reacts with nitric acid to give equimolar ratio
Nitric oxide Reducing agent
of nitric oxide and nitrogen dioxide.
(ii) Carbon dioxide is passed through a concentrated aqueous (1984, 2M)
solution of sodium chloride saturated with ammonia. 108. Complete and balance the following reactions.
(1988, 3M)
(i) HNO3 + HCl ¾® NO + Cl 2
100. Give reason for “valency of oxygen is generally two, whereas
sulphur shows valency of two, four and six.” (1988, 1M)
(ii) Ce3+ +S2O2– 2–
8 ¾® SO4 + Ce
4+
101. Explain the following in one or two sentences. (iii) Cl 2 + OH– ¾® Cl – + ClO– (1983, 3M)
(i) Magnesium oxide is used for the lining of steel making 109. Explain, “orthophosphoric acid, H3 PO4 is tribasic but
furnace.
phosphorous acid, H3 PO3 is dibasic”. (1982, 1M)
(ii) The mixture of hydrazine and hydrogen peroxide with a
copper (II) catalyst is used as a rocket fuel. 110. Give structural formula for the following.
(iii) Orthophosphorous acid is not tribasic acid. (i) Phosphorous acid, H3 PO3
(iv) The molecule of magnesium chloride is linear, whereas (ii) Pyrophosphoric acid, H4 P2 O7 (1981, 2M)
that of stannous chloride is angular. (1987, 4M)
111. Sulphur melts to a clear mobile liquid at 119°C, but on
102. Write balanced equations for the following. (1987, 2M)
further heating above 160° C, it becomes viscous, explain.
(i) Phosphorus is reacted with boiling aqueous solution of (1981, 1M)
sodium hydroxide in an inert atmosphere.
(ii) Dilute nitric acid is slowly reacted with metallic tin. 112. Explain the following in not more than two sentences .
103. Complete and balance the following reactions. (i) Conc. HNO3 turns yellow in sunlight.
(i) S + OH– ¾® S2– + S2 O2– (ii) Bleaching powder loses its bleaching properties when it
3 + ......
is kept in an open bottle for a long time. (1980, 2M)
(ii) ClO–3 + I– + H2 SO4 ¾® Cl – + HSO–4 + ...... + ......
(1986, 2M)
5. The type of hybridisation and number of lone pair(s) of 15. The set with correct order of acidic strength is (2001, 1M)
electrons of Xe in XeOF 4 , respectively, are (a) HClO < HClO2 < HClO3 < HClO4
(2019 Main, 10 Jan I) (b) HClO4 < HClO3 < HClO2 < HClO
(a) sp3d 2 and 1 (b) sp3d and 2 (c) HClO < HClO4 < HClO3 < HClO2
(c) sp3d and 1 (d) sp3d 2 and 2 (d) HClO4 < HClO2 < HClO3 < HClO
6. Which of the following reactions is an example of a redox 16. Which one of the following species is not a pseudo halide?
reaction? (2017 Main) (1997, 1M)
(a) XeF4 + O2F2 ¾® XeF6 + O2 (a) CNO– (b) RCOO- (c) OCN- (d) NNN-
(b) XeF2 + PF5 ¾® [XeF] + PF6- 17. The following acids have been arranged in the order of
decreasing acidic strength. Identify the correct order.
(c) XeF6 + H2O ¾® XeOF4 + 2HF
ClOH (I), BrOH (II), IOH (III) (1996, 1M)
(d) XeF6 + 2H2O ¾® XeO2F2 + 4HF (a) I > II > III (b) II > I > III
(c) III > II > I (d) I > III > II
7. The products obtained when chlorine gas reacts with cold and
dilute aqueous NaOH are (2017 Main) 18. KF combines with HF to form KHF2 . The compound
(a) ClO and-
ClO-3 (b) ClO-2and ClO-3 contains the species (1996, 1M)
(a) K + , F - and H+ (b) K + , F – and HF
(c) Cl - and ClO -
(d) Cl -
and ClO-2
(c) K + and [HF2 ] – (d) [KHF]+ and F –
8. Which among the following is the most reactive?
(2015 Main) 19. Bromine can be liberated from potassium bromide solution
(a) Cl 2 (b) Br2 (c) I2 (d) ICl by the action of (1987, 1M)
(a) iodine solution (b) chlorine water
9. Which one has highest boiling point? (2015 Main)
(c) sodium chloride (d) potassium iodide
(a) He (b) Ne (c) Kr (d) Xe
10. Under ambient conditions, the total number of gases released 20. Chlorine acts as a bleaching agent only in the presence of
(1983, 1M)
as products in the final step of the reaction scheme shown (a) dry air (b) moisture
below is (2014 Adv.)
(c) sunlight (d) pure oxygen
Complete
hydrolysis 21. HBr and HI reduce sulphuric acid, HCl can reduce KMnO4
XeF6 P + Other product
and HF can reduce (1981, 1M)
HO–/H2O
(a) H2SO4 (b) KMnO4
Q (c) K 2Cr2O7 (d) None of these
Slow disproportionation
in HO–/H2O Objective Questions II
Products (One or more than one correct option)
(a) 0 (b) 1 (c) 2 (d) 3
22. The correct statement(s) about the oxoacids, HClO4 and
HClO, is (are) (2017 Adv.)
11. Among the following oxoacids, the correct decreasing order (a) The central atom in both HCl O4 and HClO is sp3-hybridised
of acidic strength is (2014 Main)
(a) HOCl > HClO2 > HClO3 > HClO4 (b) HCl O4 is formed in the reaction between Cl 2 and H2O
(b) HClO4 > HOCl > HClO2 > HClO3 (c) The conjugate base of HCl O4 is weaker base than H2O
(c) HClO4 > HClO3 > HClO2 > HOCl (d) HCl O4 is more acidic than HClO because of the resonance
(d) HClO2 > HClO4 > HClO3 > HOCl stabilisation of its anion
12. The shape of XeO2 F2 molecule is 23. The colour of the X 2 molecules of group 17 elements
(2012)
(a) trigonal bipyramidal (b) square planar changes gradually from yellow to violet down the group.
(c) tetrahedral (d) see-saw This is due to (2017 Adv.)
(a) decrease in p * - s * gap down the group
13. Aqueous solution of Na 2 S2 O3 on reaction with Cl 2 gives (b) decrease in ionisation energy down the group
(2008, 3M)
(c) the physical state of X 2 at room temperature changes from
(a) Na 2S4O6 (b) NaHSO4
gas to solid down the group
(c) NaCl (d) NaOH
(d) decreases in HOMO-LUMO gap down the group
14. When I- is oxidised by KMnO4 in alkaline medium, I- 24. The compound(s) with two lone pairs of electrons on the
converts into (2004, 1M) central atom is (are) (2016 Adv.)
(a) IO-3 (b) I2 (a) BrF5 (b) ClF3
(c) IO-4 (d) IO- (c) XeF4 (d) SF4
220 p-Block Elements-II
25. The correct statement(s) regarding, 30. Argon is used in arc welding because of its
(i) HClO, (ii) HClO2 , (iii) HClO3 and (iv) HClO4 is (are) (a) low reactivity with metal
(b) ability to lower the melting point of metal
(a) the number of Cl == O bonds in (ii) and (iii) together is two
(c) flammability
(b) the number of lone pair of electrons on Cl in (ii) and (iii)
(d) high calorific value
together is three
(c) the hybridisation of Cl in (iv) is sp3 31. The structure of XeO3 is
(d) amongst (i) to (iv), the strongest acid is (i) (a) linear (b) planar
(c) pyramidal (d) T-shaped
Passage Based Questions 32. XeF4 and XeF6 are expected to be
(a) oxidising (b) reducing
Passage 1
(c) unreactive (d) strongly basic
The reactions of Cl 2 gas with cold-dilute and hot-concentrated
NaOH in water give sodium salts of two (different) oxoacids
Match the Columns
of chlorine, P and Q, respectively. The Cl 2 gas reacts with
SO2 gas in the presence of charcoal, to give a product R. R 33. All the compounds listed in Column I react with water.
reacts with white phosphorus to give a compound S. On Match the result of the respective reactions with the
hydrolysis, S gives an oxoacid of phosphorus T. (2013 Adv.) appropriate options listed in Column II. (2010)
41. Complete the following chemical equations: (ii) increasing oxidation number of iodine
(i) KI + Cl 2 ¾® (ii) KClO3 + I2 ¾® (1996, 2M) I2 , HI, HIO4 , ICl (1986, 2M)
42. Give reasons in two or three sentences only for 49. Give reason in one or two sentences.
(i) Bond dissociation energy of F2 is less than that of Cl 2 . Fluorine cannot be prepared from fluorides by chemical
reduction method. (1985, 1M)
(ii) Sulphur dioxide is a more powerful reducing agent in the
alkaline medium than in acidic medium. (1992, 2M) 50. Complete and balance the following reaction.
Cl 2 + OH– ¾® Cl – + ClO– (1983, 3M)
43. Write the balanced chemical equation for the following:
Sodium bromate reacts with fluorine in the presence of alkali. 51. Explain the following in not more than two sentences.
44. Arrange the following as indicated. HOCl, HOClO2 , Bleaching powder loses its bleaching properties when it is
HOClO3 , HOClO in increasing order of thermal stability kept in an open bottle for a long time. (1980, 2M)
(1988, 2M) 52. Give reasons for the following in one or two sentences.
45. Give balanced equation for the following: (i) Hydrogen bromide cannot be prepared by the action of
Iodate ion reacts with bisulphite ion to liberate iodine. (1988, 3M) conc. sulphuric acid on sodium bromide.
46. Mention the products formed in the following (ii) When a blue litmus paper is dipped into a solution of
hypochlorous acid, it first turns red and then later gets
“Chlorine gas is bubbled through a solution of ferrous
decolourised. (1979, 2M)
bromide.” (1986, 2M)
53. Write the balanced equations involved in the preparation of
47. Complete and balance the following reaction:
ClO–3 + I– + H2SO4 ¾® Cl – + HSO–4 + ......+ ......
(i) bleaching powder from slaked lime (1979, 10M)
(1986, 2M)
(ii) nitric oxide from nitric acid
48. Arrange the following in the order of (iii) chlorine from sodium chloride
(i) increasing bond strength HCl, HBr, HF, HI (iv) anhydrous aluminium chloride from alumina
Answers
Topic 1
1. (a) 2. (b) 3. (c) 4. (b) 61. (d) 62. NO2 63. Four 64. Two
5. (d) 6. (a) 7. (a) 8. (d) 65. white 66. T 67. T 68. F
9. (b) 10. (d) 11. (d) 12. (a) 69. T 70. (8) 71. 4 72. 6
13. (a) 14. (b) 15. (c) 16. (c)
Topic 2
17. (b) 18. (d) 19. (b) 20. (d)
1. (a) 2. (b) 3. (d) 4. (b)
21. (c) 22. (b) 23. (b) 24. (c)
5. (a) 6. (a) 7. (c) 8. (d)
25. (b) 26. (a) 27. (c) 28. (d)
9. (d) 10. (c) 11. (c) 12. (a)
29. (c) 30. (a) 31. (a) 32. (c)
13. (a) 14. (a) 15. (a) 16. (b)
33. (c) 34. (b) 35. (d) 36. (b)
17. (a) 18. (c) 19. (b) 20. (b)
37. (a) 38. (d) 39. (b) 40. (c)
21. (d) 22. (a, c, d) 23. (b, c) 24. (b, c)
41. (d) 42. (a) 43. (b,c) 44. (a,b,c)
25. (b, c) 26. (a) 27. (a) 28. (c)
45. (b, d) 46. (a, c, d) 47. (a, b, c) 48. (c)
29. (a) 30. (a) 31. (c) 32. (a)
49. (a, c, d) 50. (a, d) 51. (6) 52. (a)
33. A ® p, s B ® p, q, r, t C ® p, q, t D® p
53. (a) 54. (a) 55. (b) 56. (a)
34. KI3 35. F 36. 5
57. (b) 58. (c) 59. (c) 60. (b)
Hints & Solutions
Topic 1 Elements and Compounds of H2 S 2 O3 (thiosulphuric acid), H2 S 2 O4 (hyposulphurous or
Group 15 and 16 dithionous acid) and H2 S 4 O6 (tetrathionic acid) contains S¾S
bonds.
1. The correct statement is that (SiH3 )3 N is planar and less basic O
than (CH3 )3 N. The compounds trimethylamine (CH3 )3 N and
trisilylamine (SiH3 )3 N have similar formulae, but have totally H2S2O3 Þ HO—S—OH
different structures. In trimethylamine the arrangement of
S
electrons is as follows :
O OH
1s 2s 2p H2S2O4 Þ S——S
Electronic structure of
nitrogen atom HO O
(ground state) O O
Three unpaired electrons
form bonds with CH3 groups
tetrahedral arrangements of H2S4O6 Þ HO—S—S—S—S—OH
three bond pairs and one lone pair
The expression of second electron gain enthalpy of oxygen will be, 12. PLAN This problem is based on chemical properties of
O - (g )+ e- ¾® O 2- (g,) DegH 2 = + ve phosphorus.
DegH 2 of oxygen is positive, i.e. endothermic, because a strong White phosphorus on reaction with thionyl chloride (SOCl 2 )
electrostatic repulsion will be observed between highy negative O - produces phosphorus trichloride.
and the incoming electron (e- ). A very high amount of energy will P4 (s) + 8SOCl 2 (l ) ¾® 4PCl 3 (l ) + 4SO2 (g ) + 2S2Cl 2 (g )
be consumed (endothermic) by the system to overcome the But if amount of thionyl chloride (SOCl 2 ) is in excess then it
electrostatic repulsion. produces phosphorus pentachloride.
7. The structure of H3PO2 (hypophosphorous) acid is P4 + 10SOCl 2 (l ) ¾® 4PCl 5 + 10SO2
O 13. NO is paramagnetic in gaseous state because in gaseous state,
P it has one unpaired electron.
H
HO H Total number of electrons present = 7 + 8 = 15 e -
Due to the presence of two P ¾ H bonds, H3 PO 2 acts a strong Hence, there must be the presence of unpaired electron in
reducing agent. e.g. gaseous state while in liquid state, it dimerises due to
+1 +1 0 +5 unpaired electron.
4 Ag NO 3 + H3PO 2 + 2H2O ¾® 4 Ag ¯ + H3 PO 4 + 4 HNO 3
8. The thermal decomposition of given compounds is shown below 14. NO 2 is a brown coloured gas and imparts this colour to
concentrated HNO 3 during long standing.
D
(NH4 )2 Cr2O7 ¾® N2 + 4H2O + Cr2O3 4 HNO 3 ¾® 2H2O + 2NO 2 + 3O 2
-
D
NH4NO2 ¾® N2 + 2H2O 15. (a) ONCl = 8 + 7 + 17 = 32 e
D
ONO- = 8 + 7 + 8 + 1 = 24 e- (correct)
(NH4 )2 SO4 ¾® 2NH3 +H2SO4
O
(b)
Ba(N3 )2 ¾® Ba + 3N2
O O
Thus, only (NH4 )2 SO4 does not gives N2 on heating (It give NH3 ).
While rest of the given compounds gives N2 on their thermal Central O-atom is sp 2 -hybridised with 1 lone pair, so
decomposition. bent shape (correct).
+5 +4 +3 +1
9. H3 P O 4 > H4 P2 O6 > H3 P O 3 > H3 P O 2 (c) In solid state, ozone is violet-black. Ozone does not
exist in solid state, thus incorrect.
10. Species Hybridisation (d) O 3 has no unpaired electrons, so diamagnetic (correct).
Hence, (c) is the correct.
2
N sp 16. The reaction of white phosphorus with aqueous alkali is
–
O O
O P4 + 3NaOH + 3H2O ¾® PH3 + NaH2PO2
N In the above reaction, phosphorus is simultaneously
– sp2 +1
O O oxidised [P4 (0) ¾® NaH2 P O2 ] as well as reduced
-3
alongwith gaseous nitrogen, hence no additional step of 28. The structure of S3O9 is
separation is required. O O
Other reactions are S
Heat
NH4NO3 ¾¾® N2O + 2H2O O O
O O
Heat
2NH3 + 3CuO ¾¾® 3Cu + 3H2O + N2 S S
O O O
Heat
(NH4 )2 Cr2O7 ¾¾® Cr2O3 + 4H2O + N2 It has no S—S linkage.
19. In limited supply of oxygen, phosphorus is oxidised to its lower 29. CaO, a basic oxide, is most suitable for drying of basic ammonia.
oxide P4O6 while excess of oxygen gives P4O10. A mixture of O2 30. H2O, due to its ability to form intermolecular H-bonds.
and N2 is used for controlled oxidation of phosphorus into P4O6.
31. Corresponding acids are HClO4, H2SO3 and H3PO4. Hence, the
20. In P4, all phosphorus are sp3-hybridised and has 75%
order of acidic strength is
p-character.
Cl 2O7 > SO2 > P4O10
P
sp3 32. The structure of cyclic metaphosphate is
–
P P O O
P
O O
P O O
– P P –
21. In KMnO4, Mn is already in its highest oxidation state (+7), O
O
O
cannot be oxidised by any oxidising agent.
There is three P—O—P bonds.
22. PbO2 + HNO3 ¾® Pb(NO3 )2 + H2O + O2
33. Ca 3P2 + 6H2O ¾® 3Ca(OH)2 + 2PH3
23. Equimolar amounts of NO and NO2 at –30°C gives N2O3 (l ) -
OH
which is a blue liquid. 34. Na 2SO3 + S ¾¾® Na 2S2O3
D
-30 °C
NO(g ) + NO2 (g ) ¾¾® N2O3 (l ) 35. S2O27 - has no S—S linkage.
( Blue) O O
½½ ½½
24. Black phosphorus is thermodynamically most stable allotrope -
O— S — O— S — O-
of phosphorus. ½½ ½½
It is due to three dimensional, network structure of polymeric O O
black phosphorus. All others have atleast one S—S linkage.
25. H2S2O8 is a peroxy acid, has—O—O—linkage 36. Amongst XH3 where ‘X ’ is group-15 elements, basic strength
O O decreases from top to bottom. Hence, NH3 is strongest base.
½½ ½½ 37. The electron withdrawing inductive effect of halogen decreases
HO— S — O— O— S — OH electron density on nitrogen, lowers basic strength. Since,
½½ ½½ fluorine is most electronegative, NF3 is least basic.
O O
Peroxodisulphuric acid 38. NO2 (g ) is deep brown coloured.
26. H3PO3 is a dibasic, reducing acid. H3PO4 is tribasic, 39. In N2O5, there are s (sigma) covalent bonds, p (pi) bonds and
non-reducing acid. coordinate covalent bonds as
O O O O
½½ ½½ N N
H— P— OH HO— P— OH O
½ ½ O O
OH OH
Dibasic, reducing Tribasic, non -reducing 40. SO2 cannot be collected over water because it reacts with water
27. Polyphosphates are used as water softening agents because they forming H2SO3.
form soluble complexes with cationic species of hard water. SO2 + H2O ¾® H2SO3
Na 2[Na 4 (PO3 )6 ]+ CaSO4 ¾® Na 2[(Ca 2 (PO3 )6 ] + Na 2SO4 41. Quicklime (CaO) is used for drying NH3 gas because both are
Soluble complex
basic, do not react. On the other hand, H2SO4 and P2O5 are
acidic, reacts with ammonia forming salts. CaCl 2 forms
complex with ammonia.
p-Block Elements-II 225
42. NO is lighter than O2. (b) N2O5 has no unpaired electron and is thus, diamagnetic
thus, (b) is correct.
D2O is commonly known as heavy water.
(c)
N2 is lighter than O2, effuse at faster rate under identical O O
experimental conditions. NH3 liquefies at very low temperature.
N O N
Therefore, liquid NH3 is used as a refrigerant.
O O
43. Among the given compounds, those which generate N2 on thermal There is no N—N bond, thus, (c) is incorrect.
decomposition below 300°C are ammonium dichromate i.e., (d) N2O5 + Na ¾® NaNO3 + NO2
(NH4 )2Cr2 O7 and barium azide or nitride i.e., Ba(N3 )2 . Reactions N2O5 vapours are of brownish colour. Thus, (d) is
of their thermal decomposition are given below correct.
D
(i) (NH4 )2 Cr2O7 ¾¾¾¾® N2 + Cr2O3 + 4H2O 46. Plan Due to resonance, bond lengths between two atoms are
Below 300 °C equal. Species is said to be diamagnetic if all electrons are
It is an exothemic reaction with paired.
DH = - 429.1 ± 3 kcal/ mol. Process is endothermic if it takes place with absorption of
D heat.
(ii) Ba(N3 )2 ¾¾¾¾¾¾¾¾® Ba + 3N2
Around 160 ° and above
O 218 O
r
O
r
Ammonium nitrate (NH4NO 3) on heating below 300°C gives pm s
116.80°
®® s
O O O O
N 2O as O O
D
NH4NO3 ¾¾¾¾® N2O + 2H2O bent molecule all electrons paired thus, diamagnetic
below 300 °C
2 O 3 ¾® 3 O 2 DH ° = - 142 kJ mol -1
However, on rapid heating or explosion
Exothermic
(i.e. above 300°C) it gives off nitrogen as
Rapid heating Thus, (b) is incorrect. (a, c, d) are correct.
¾® 2N2 + O2 + 4H2O
2NH4NO3 ¾ ¾ ¾ ¾ ¾
or explosion 47. The structures of these oxides are
Magnesium nitride (Mg3N2 ) does not decompose at lower O O
temperatures being comparatively more stable. Its thermal
decomposition requires a minimum temperature of 700°C and N N ¾® O N N
proceeds as
¾®
Mg3N2 ¾700¾-¾¾
1500°C
® 3Mg + N2
(a) (b) O
44. Statement wise explanation is
O O O O
(i) Statement (a) Bi 2O5 is a metallic oxide while N2O5 is a
non-metallic oxide. N N N N
Metallic oxides being ionic are basic in nature while non O
¾
¾
®
®
metallic oxides being covalent are acidic in nature. This O O O O
confirms more basic nature of Bi 2O5 in comparison to N2O5. (c) (d)
Hence, this is a correct statement.
(ii) Statement (b) The electronegativity difference between N(3) and (a), (b), (c) have N—N bonds.
F(4) is less as compared to the electronegativity difference
between Bi (1.7) and F(4). More electronegativity difference
48. 2NH3 + OCl - ¾® H2N— NH2 + H2O + Cl -
leads to ionic compounds. Thus, NF3 must be more covalent in 49. The structure of P4 is
nature as compared to BiF3. Hence, this statement is also correct.
(iii) Statement (c) In NH3 intermolecular hydrogen bonding is P
present, which is altogether absent in PH3. Thus, PH3 boils at
lower temperature than NH3. P P
Hence, this is also a correct statement.
(iv) Statement (d) Due to smaller size of N the lone pair-lone pair
repulsion is more in N—N single bond as compared to O—P P
single bond. This results to weaker N—N single bond as
It has six P—P single bonds.
compared to P—P single bond. Hence, this statement is incorrect.
There are four lone pairs on four phosphorus. P—P—P
45. P4O10 is a dehydrating agent and converts HNO3 into N2O5 bond angles are of 60°.
2HNO3 ¾® N2O5 + H2O Heat
50. NH4NO3 ¾¾® N2O + 2H2O
P4O10 + 6H2O ¾® 4H3PO4
(a) P4 + 20HNO3 ¾® 4H3PO4 + 20NO2 + 4H2O NH2OH × HCl + NaNO2 ¾® NaCl + 2H2O + N2O
Thus, (a) is incorrect. However, NH4NO2 on heating gives N2.
226 p-Block Elements-II
O
Phosphorus has vacant 3d-orbitals, it can expand its valence
P P O shell beyond eight electrons, its both trihalides and
O pentahalides exist.
O O Passage
P
MnO 2
Conclusion 6 bridging oxo groups are present in the KClO 3 ¾¾® KCl + O 2
D W
compound.
5. H4 P2 O5 D HNO 3
P P 56. (a)
H O H
OH OH 57. (b)
Conclusion 1 bridging oxo group is present in the compound.
Passage
6. H5 P3O10 58. Due to greater solubility in water and prone to microbial
O O O attack, nitrates are less abundant in earth’s crust.
59. NH3 is stronger Lewis base than PH3. In a group of hydrides,
P P P
HO O O OH basic strength decreases down the group.
OH OH OH 60. White phosphorus undergo disproportionation in alkaline
Conclusion 2 bridging oxo groups are present in the medium.
compound. P4 + NaOH ¾® PH3 + NaH2PO2
7. H2S 2 O3 Warm (3)
S 61. (P) 2PbO2 + 2H2SO4 ¾¾¾® 2PbSO4 + O2 + 2H2O
S Cl 2 ( 4 )
HO (Q) Na 2S2O3 + H2O ¾¾® NaHSO4 + HCl
OH
O I2 (2 )
(R) N2H4 ¾¾® N2 + Hl
Conclusion This compound does not contain any bridging
oxo group.
p-Block Elements-II 227
— —
—
Oxides of N2
HO—S—OH P——OH HO—C—OH
62. NO2 : 2SO2 (g ) + O2 (g ) ¾¾¾¾® 2SO3 (g )
(NO2 ) O H OH
63. O O O O O
—
— —
— —
— —
O P O HO—S—O—S—OH HO—Cr—OH HO—S—OH
O O O
O
O Others are
O P P O
O O
—
—
P HO—B—OH P
P
O O
HO OH OH OH H H OH
O Triprotic Monobasic Monoprotic
Here four oxygen atoms are bonded to each phosphorus Lewis acid
atom. 73. O
64. H3PO3 [O == PH(OH)2 ] is a dibasic acid. P
O O
65. White phosphorus has highly strained, tetrahedral
structure, therefore highly reactive. O
O
66. In liquid state, nitric oxide (NO) dimerises into (NO)2 O P P O
and odd electrons disappear giving diamagnetic property.
2NO ¾® O == N— N== O (l ) P
Paramagnetic Diamagnetic O O
O
67. Both ‘N’ and ‘As’ in corresponding hydrides are (P4O10)
sp3-hybridised. If central atoms are from same group,
bond angle decreases from top to bottom if all other 74. Cl 2O7 < SO3 < CO2 < B2O3 < BaO
things are similar. Hence, H—N—H bond angle in NH3 +4 +4 +2 +2.5
is greater than H—As—H bond angle in AsH3. 75. A = NaH SO3 ; B = Na 2 SO3 ; C = Na 2 S2O3; D = Na 2 S4 O6
68. Halogens are all good oxidising agent and their oxidising 76. (i) Al 4C3 + 12H2O ¾® 4Al(OH)3 + 3CH4
power decreases from top to bottom (F2 to I2) in group. (ii) CaNCN + 5H2O ¾® CaCO3 + 2NH4OH
Any halogen above in group oxidises halides down in
group from their aqueous solution. Hence, Cl 2 can (iii) 4BF3 + 3H2O ¾® H3BO3 + 3HBF4
oxidise Br - to Br2, I- to I2 but cannot oxidise F- to F2 (iv) NCl 3 + 3H2O ¾® NH3 + 3HOCl
rather F2 can oxidise Cl - to Cl 2. (v) 2XeF4 + 3H2O ¾® Xe + XeO3 + F2 + 6HF
77. Nitrogen in N2 are bonded by one sigma and two pi bonds. Phosphorus
69. Fe is more electropositive than hydrogen, displaces H+
ions from acid solution as : and other elements of this period, due to larger size, are very less likely
to form pi bonds, hence P4 is formed in which there is no pi bonds.
Fe + 2HCl ¾® FeCl 2 + H2 78. In given scheme : A = Ca (OH)2
70. N2O3 has two proposed structures. B = NH4HCO3, C = Na 2CO3
·· D = NH4Cl and E = CaCl 2
O·
· ··
·· ·· ·· ·· ·· ·· 79. (a) HNO2 + 2H2SO3 + H2O ¾® NH2OH + 2H2SO4
O == N ¾ O ¾ N == O and ·· N¾ N A B C D
·· ·· ·· O
·· ·· (b) In SO3 + H2O ¾® H2SO4, sulphuric acid is obtained in misty
O
·· form and the reaction is explosive. By adding H2SO4, above
In both cases, number of lone pair of electrons are eight. reaction is prevented :
71. PCl5 produces POCl3 with the following reagents H2SO4 + SO3 ¾® H2S2O7 (oleum)
PCl 5 + SO2 ¾® POCl 3 + SOCl 2 H2S2O7 + H2O ¾® 2H2SO4
PCl 5 + H2O ¾® POCl 3 + 2HCl In the contact process, V2O5 is used as catalyst.
2PCl 5 + H2SO4 ¾® SO2Cl 2 + 2POCl 3 + 2HCl 80. (i) P4O10 + 6PCl 5 ¾® 10 POCl 3
6PCl 5 + P4O10 ¾® 10POCl 3 (ii) SnCl 4 + 2C2H5Cl + 2Na ¾® Na 2SnCl 4 + C4H10
228 p-Block Elements-II
81. (a) PCl 5 + SO2 ¾® POCl 3 + SOCl 2 SO2 + 2OH - ¾® SO24- + 2H + + 2e-
(b) Ca 3 (PO4 )2 + 4H3PO4 ¾® 3Ca(H2PO4 )2 Hence, the above reaction proceeds in forward direction on
triple superphosphate increasing concentration of HO- ion. H+ is on product side,
adding H+ retards the reaction by sending it in backward
82. The poisonous element M may be As. On the basis of given
information direction.
Zn /HCl 90. + +
AsCl 3 + 6H ¾¾® AsH3 + 3HCl O O
N
– –
D O O O O
2AsH3 ¾® 2As + 3H2
M
83. (i) P4 + 20HNO3 ¾® 4H3PO4 + 20NO2 + 4H2O 91. Ammonia, in liquid state undergo self-ionisation as :
2NH3 q NH4+ + NH2-
(ii) 3KMnO4 + 5H2O2 + 3H2SO4 ¾® K2SO4
+ 2MnSO4 + 5O2 + 8H2O
Thus, addition of NH4Cl to liquid ammonia increases
(iii) P4 + 20HNO3 ¾® 4H3PO4 + 20NO2 + 4H2O
concentration of NH4+ in solution and NH4Cl act as acid.
(iv) 2Al + 2NaOH + 2H2O ¾® 2NaAlO2 + 3H2
84. 92. (i) Na 2CO3 + NO + NO2 ¾® 2NaNO2 + CO2
O
(ii) 2KMnO4 + 2NH3 ¾® 2MnO2 + 2KOH + 2H2O + N2
O P O
(iii) P4 + 20HNO3 ¾® 4H3PO4 + 20NO2 + 4H2O
4 P==O bonds (iv) 2H2S + NaHSO3 + H+ ¾® 3S + 3H2O + Na +
O
O P O P O (v) CaCO3 + CO2 + H2O ¾® Ca(HCO3 )2
93. (i) NaNO2 + Zn + NaOH ¾® 3Na 2ZnO2 + NH3 + H2O
P (ii) 2NaIO3 + 5NaHSO3 ¾® 3NaHSO4 + 2Na 2SO4
O O
O + I2 + H2O
+ - - +
94. N ºº N— O ¬¾® N == N == O
85. (i) The size of both nitrogen and fluorine are very small as well
D
as they have very high electron density. Thus in NF3, N and 95. (i) 15CaO + 4P4 ¾® 5Ca 3P2 + 3P2O5
F repel each other stretching the N—F bond. Hence, in NF3,
[Ca 3P2 + 6H2O ¾® 3Ca(OH)2 + 2PH3 ] ´ 5
N—F bond lengths are greater than the sum of their single
bond covalent radii. 15CaO + 4P4 + 30H2O ¾® 15Ca(OH)2
(ii) Mg3N2 + 6H2O ¾® 3Mg(OH)2 + 2NH3 + 3P2O5 + 10PH3
MgCl 2 is a salt of strong acid HCl and strong base Mg(OH)2
(ii) 2NH3 + CO2 + H2O ¾® (NH4 )2 CO3
and therefore, not hydrolysed in aqueous solution.
(iii) In (SiH3 )3 N, the lone pair of nitrogen is involved in pp - dp CaSO4 + (NH4 )2 CO3 ¾® CaCO3 ¯ + (NH4 )2 SO4
bonding, less available on nitrogen for donation to a Lewis gypsum
acid, a weaker Lewis base CaSO4 + 2NH3 + CO2 + H2O ¾® CaCO3 ¯ + (NH4 )2 SO4
pp-dp
96. (i) In H3PO3, there is only two replaceable H, hence dibasic
H3Si—N——SiH3
O
½½
SiH3 H— P — OH H—of OH are acidic, dibasic.
Carbon does not have any vacant d-orbitals, no such pp -dp ½
bonding occur in trimethyl amine, lone pair of nitrogen is OH
available for donation to Lewis acid, hence a stronger Lewis (ii) NH3 molecules are associated by intermolecular
base. H—bonds.
Heat
86. Ca 5 (PO4 )3 F + 5H2SO4 + 10H2O ¾® 3H3PO4 97. (i) 2H3PO2
D
¾® PH3 + H3PO4 (Disproportionation)
+ 5CaSO4 × 2H2O + HF hypophosphorus
acid
87. PCl 5 + SO2 ¾® POCl 3 + SOCl 2 +
A B (ii) NaClO3 + SO2 ¾10¾H¾® NaCl + S + 5H2O
88. Red phosphorus reacts with iodine in the presence of water to 98. SiO2 < CO2 < N2O5 < SO3
form H3PO3 and HI as–
2P + 3I2 + 6H2O ¾® 2H3PO3 + 6HI 99. (i) 4P + 10HNO3 + H2O ¾® 5NO + 5NO2 + 4H3PO4
89. SO2 acts as reducing agent on account of following reaction : (ii) NaCl + NH4OH + CO2 ¾® NH4Cl + NaHCO3
p-Block Elements-II 229
D
104. (i) 2Ca 3 (PO4 )2 + 6SiO2 + 10C ¾® 6CaSiO3 Topic 2 Element and Compound of
+ 10CO + P4 Group 17 and 18
(white) 1. Radium (Ra) is a radioactive element. Ra belongs to group 2
(ii) (NH4 )2 SO4 + NO + NO2 ¾® 2N2 + 3H2O + H2SO4 (alkaline earth metals), it is not a noble gas.
Note In question noble gas which does not exist in the
+ - - + atmosphere is asked and answer is Ra. But Ra (radium) is an
105. N ºº N— O ¬¾® N== N ==O alkaline earth metal and not noble gas. It can be Rn (radon) and
106. Fe2 (SO4 )3 + 2KI ¾® 2FeSO4 + K2SO4 + I2 is misprint in JEE Main Paper.
In the above reaction, strong reducing agent, iodide, reducing 2. Halogens form halates and halides with hot and concentrated
ferric salt into ferrous salt. solution of NaOH as :
3 X 2 + 6NaOH ¾® 5NaX + NaXO3 + 3H2 O
107. A B C So, Cl2 will also give Cl- (as NaCl) and ClO3-
Asbestos Silicates of Ca and Mg Donar (as NaClO3 ) in the above reaction.
Lithium metal Reducing agent Electron donor Thus, option (b) is correct.
Note When halogens react with cold and dilute solution of
Nitric oxide Paramagnetic Air pollutant
NaOH, hypohalites and halides are produced as:
108. (i) 2HNO3 + 6HCl ¾® 2NO + 3Cl 2 + 4H2O X 2 + 2NaOH ¾® NaX + NaXO + H 2O
(ii) 2Ce3 + + S2O28- ¾® 2SO24- + 2Ce4 + 3. Iodine reacts with concentrated HNO 3to yield HIO 3 along
(iii) Cl 2 + 2OH - -
¾® Cl + ClO + H2O - with NO 2 and H2 O. The reaction involved in as follows :
I2 + 10HNO3 ¾® 2HIO3 + 10NO2 + 4H2O
109. Orthophosphoric acid (H3PO4 ) has three replaceable (acidic) The oxidation state of ‘I’ in HIO 3 is + 5 as calculated below :
hydrogen while orthophosphorus acid (H3PO3 ) has only two 1 + x + 3(-2) = 0
replaceable hydrogen.
x - 5 = 0, x = + 5
230 p-Block Elements-II
4. Chemical reactivity of halogens decreases down the group. Complete sequence of reaction can be shown as
XeF6+3H2O XeO3+ 3H2F2
The chemical reactivity follows the order.
–
\ F2 > Cl2 > Br2 > I2. OH
17. Among oxyacids of halogens, if there are same number of (b) Number of Lone Pair on Cl in (ii) and (iii) together is three.
oxygens bonded to central atom, higher the electronegativity of Hence, correct.
halogen, stronger the acid. Hence, (c) In (iv), Cl is sp3-hybridised. Hence, correct.
IOH < BrOH < ClOH (d) Amongst (i) to (iv), the strongest acid is (iv). Hence, wrong.
18. All others has at least one S-S linkage. Passage 1 Q. Nos. (26-27)
KF + HF ¾® K+ + HF2- Cold
2NaOH + Cl 2 ¾¾® NaCl + NaOCl + H2O
19. Among halogens, oxidising power decreases from top to bottom. P
Hence, the upper halogen oxidises lower halides from aqueous hot
6NaOH + 3Cl 2 ¾¾® 5NaCl + NaClO3 + 3H2O
solution. Chlorine will oxidise bromide into bromine. Q
20. Moist chlorine gives nascent oxygen, act as oxidising agent : NaOH
HOCl ¾¾® NaOCl
Cl 2 + H2O ¾® HCl + HOCl hypochlorous P
HOCl ¾® HCl + [O] acid
nascent oxygen NaOH
(bleaching action) HClO3 ¾¾® NaClO3
21. Fluorine, being the most electronegative, its size is very small. chloric acid Q
Therefore, it does not have a tendency to loose electrons. Hence, Cl 2 + SO2 ¾® SO2Cl 2
HF does not act as a reducing agent. R
10 SO2Cl 2 + P4 ¾® 4PCl 5 + 10 SO2
22. (a) ClO-4 is more stable than ClO .-
R S
(b) Incorrect : Cl 2 + H2O ¾® HCl + HOCl PCl 5 + 4H2O ¾® H3PO4 + 5 HCl
(c) T
O
Passage 2 Q.Nos. (28-29)
HO Cl O HO Cl
28. The involved redox reactions are :
sp3 sp3
O 2H+ + OCl - + 2I- ¾® Cl - + I2 + H2O …(i)
(d) HClO4 is stronger acid than H2 O.
I2 + 2S2O2-
3 ¾® 2I + -
S4O62- …(ii)
23. Colour of halogen arises due to transition from HOMO to LUMO
in the visible region. On moving down a group, the difference in Also the n-factor of S2O2-
3 is one as
energy between HOMO and LUMO decreases electronic 2S2O3 ¾® S4O62- + 2e-
2-
==
is Cl 2O as
H ¾ O ¾ Cl == O H ¾ O ¾ Cl == O
2 HOCl ¾® Cl 2O + H2O
==
30. Ar, being inert, provide inert atmosphere in arc welding, and (ii) Sulphur dioxide is a more powerful reducing agent in
prevent from undesired oxidation. alkaline medium because nascent hydrogen is produced in
·· the presence of moisture
31. O == Xe == O
i.e. SO2 + 2H2 O ¾® H2 SO4 + 2H
½½
O And alkaline solution neutralises the acid i.e. H2 SO4 and
3 shift the equilibrium in the forward direction producing
Xe is sp -hybridised with one lone pair. Hence, molecule of more nascent hydrogen. But in acidic medium the
XeO3 has pyramidal shape. equilibrium will suppressed resulting in a lesser amount
32. Both XeF4 and XeF6 are strong oxidising agent. of nascent hydrogen.
33. (CH3 )2 SiCl 2 + H2O ¾® (CH3 )2 Si(OH)2 + 2HCl 43. NaBrO3 + 3F2 ¾® 3F2O + NaBr
CH3 CH3 Cl 44. HOCl < HOClO < HOClO2 < HOClO3
Polymerisation
—Si—O—Si—O—Si—O 45. 2IO-3 + 5HSO-3 ¾® I2 + H2O + 3HSO-4 + 2SO24-
CH3 CH3 CH3 46. Cl 2 + FeBr2 ¾® FeCl 3 + Br2
silicone
3 47. ClO-3 + 6I- + 6H2SO4 ¾® Cl - + 6HSO-4 + 3I2 + 3H2O
3XeF4 + 6H2O ¾® XeO3 + 2Xe + 12HF + O2
2 48. (i) Bond strength is inversely related to bond length. Hence,
1 bond energy : HI < HBr < HCl < HF
Cl 2 + H2O ¾® HCl + HOCl ¾® HCl + O2
2 (ii) HI(– 1) < I2 (0) < ICl(+1) < HIO4 (+7)
VCl 5 + H2O ¾® VOCl 3 + 2HCl
49. F2 itself, is the strongest oxidising agent. Therefore, chemical
34. KI + I2 ¾® KI3
reagent cannot oxidise fluoride to fluorine.
35. Among HX, acidic strength increases from HF to HI.
50. Complete and balance the following reactions
36. Br2 is disproportionated in basic medium as Cl 2 + 2OH- ¾® Cl - + ClO- + H2O
3Br2 + 3Na 2CO3 ¾¾® 5NaBr + NaBrO3 + 3CO2
51. The bleaching action of bleaching powder is due to presence of
37. 2XeF4 + 3H2O ¾® Xe + XeO3 + F2 + 6HF available chlorine, but in contact of moisture, it releases chlorine
38. F F decreasing the amount of available chlorine. Hence, bleaching
F F O property decreases gradually as bleaching powder is kept in open
container for long time.
Xe Xe Xe 52. (i) HBr is a stronger reducing agent, reduces cencentrated
F F H2 SO4 to SO2 . Hence, HBr cannot be prepared by heating
O bromide salts with concentrated H2 SO4 .
F F
linear square planar see-saw shaped (ii) Hypochlorous acid is acidic in nature, therefore it turns
39. Halogen above in the group oxidises halide below to it from blue litmus paper into red. However, HOCl is also an
their aqueous solution, e.g. oxidising acid (bleaching), it bleaches red colour to
Cl 2 + 2I- (aq) ¾® 2Cl - + I2 finally colourless.
40 °C
40 °C
40. Ca(OH)2 + Cl 2 ¾¾® CaOCl 2 + H2O 53. (i) Ca(OH)2 + Cl 2 ¾® CaOCl 2 + H2 O
41. (i) 2KI + Cl 2 ¾¾® 2KCl + I2 (ii) 3Cu + 8HNO3 (dil) ¾® 3Cu(NO3 )2 + 4H2 O + 2NO
(ii) 2KClO3 + I2 ¾¾® 2KIO3 + Cl 2 (iii) 2NaCl + 2H2 SO4 + MnO2 ¾® Na 2 SO4 + MnSO4
42. (i) Due to small size and high electron density of fluorine + 2H2O + Cl 2
atom, there exist a significant repulsions between D
fluorine atoms in F2 , they have greater tendency to get (iv) Al 2 O3 + 3C + 3Cl 2 ¾® 2AlCl 3 + 3CO
apart. Hence, bond energy of F2 is less than that of Cl 2 .
This is against to bond-length bond-energy
relationship,.
16. Which of the following combination will produce H 2 gas? 25. The colour of light absorbed by an aqueous solution of
(2017 Adv.) CuSO4 is (2012)
(a) Fe metal and conc. HNO3 (a) orange-red (b) blue-green
(b) Cu metal and conc. HNO3 (c) yellow (d) violet
(c) Au metal and NaCN (aq) in the presence of air 26. Which of the following will not be oxidised by O3 ? (2005)
(d) Zn metal and NaOH (aq) (a) KI (b) FeSO4 (c) KMnO4 (d) K 2MnO4
17. Which of the following compounds is metallic and 27. Which of the following pair is expected to exhibit same
ferromagnetic? (2016 Main) colour in solution? (2005, 1M)
(a) CrO2 (b) VO2 (a) VOCl 2; FeCl 2 (b) CuCl 2; VOCl 2
(c) MnO2 (d) TiO2 (c) MnCl 2; FeCl 2 (d) FeCl 2; CuCl 2
18. The reaction of zinc with dilute and concentrated nitric acid, 28. When I- is oxidised by MnO-4 in alkaline medium,
respectively, produce (2016 Main) I- converts into (2004)
(a) NO2 and NO (b) NO and N2O (a) IO-3 (b) I2 (c) IO-4 (d) IO-
(c) NO2 and N2O (d) N2O and NO2
29. The pair of compounds having metals in their highest
19. The geometries of the ammonia complexes of Ni 2 + , Pt 2 + and
oxidation state is (2004, 1M)
Zn 2+ , respectively, are (2016 Main) (a) MnO2 , FeCl 3 (b) [MnO4 ]- , CrO2Cl 2
(a) octahedral, square planar and tetrahedral
(c) [Fe(CN)6 ]3- , [Co(CN)3 ] (d) [NiCl 4 ]2- , [CoCl 4 ]-
(b) square planar, octahedral and tetrahedral
(c) tetrahedral, square planar and octahedral 30. (NH4 )2 Cr2 O7 on heating gives a gas which is also given by
(d) octahedral, tetrahedral and square planar (a) heating NH4NO2 (2004, 1M)
20. Which of the following compounds is not yellow coloured? (b) heating NH4NO3
(2015 Main) (c) Mg3N2 + H2O
(a) Zn 2 [ Fe (CN)6 ] (b) K 3 [ Co (NO2 )6 ] (d) Na(comp.) + H2O2
(c) (NH4 )3 [ As (Mo3O10 )4 ] (d) BaCrO 4
31. When MnO2 is fused with KOH, a coloured compound is
21. Which series of reactions correctly represents chemical formed, the product and its colour is (2003, 1M)
relations related to iron and its compound? (2014 Main) (a) K 2MnO4, purple green (b) KMnO4, purple
Dil. H SO
2 4 2 4 2 H SO ,O Heat (c) Mn 2O3, brown (d) Mn 3O4, black
(a) Fe ¾¾¾¾¾® FeSO4 ¾¾¾¾¾® Fe2 (SO4 ) 3 ¾¾¾® Fe
2O , Heat CO, 600°C CO, 700°C 33. On heating ammonium dichromate, the gas evolved is
(d) Fe ¾¾¾¾® Fe3O4 ¾¾¾¾® FeO ¾¾¾¾¾® Fe
(a) oxygen (b) ammonia (1999, 2M)
22. Four successive members of the first row transition elements (c) nitrous oxide (d) nitrogen
listed below with atomic numbers. Which one of them is 34. In the dichromate dianion (1999, 2M)
expected to have the highest E °M 3+ / M 2+ value? (2013 Main) (a) 4 Cr—O bonds are equivalent
(b) 6 Cr—O bonds are equivalent
(a) Cr (Z = 24) (b) Mn (Z = 25)
(c) all Cr—O bonds are equivalent
(c) Fe (Z = 26) (d) Co (Z = 27)
(d) all Cr—O bonds are non-equivalent
23. Consider the following reaction, (2013 Main)
35. Which of the following compounds is expected to be
z
xMnO-4 + y C2 O24 - + zH+ ¾® xMn 2+ + 2 y CO2 + H2 O coloured? (1997, 1M)
2 (a) Ag2SO4 (b) CuF2 (c) MgF2 (d) CuCl
The values of x, y and z in the reaction are, respectively
(a) 5, 2 and 16 (b) 2, 5 and 8 36. Ammonium dichromate is used in some fireworks. The green
(c) 2, 5 and 16 (d) 5, 2 and 8 coloured powder blown in the air is (1997, 1M)
(a) CrO3 (b) Cr2O3 (c) Cr (d) CO
24. Which of the following arrangements does not represent the
correct order of the property stated against it? (2013 Main) 37. The reaction which proceed in the forward direction is
(a) V2+ < Cr 2+ < Mn 2+ < Fe2+ : paramagnetic behaviour (a) Fe2O3 + 6HCl ¾® 2FeCl 3 + 3H2O (1991, 1M)
(b) Ni 2+
< Co 2+ 2+
< Fe < Mn 2+
: ionic size (b) NH3 + H2O + NaCl ¾® NH4Cl + NaOH
3+ 3+ 3+ 3+
(c) Co < Fe < Cr < Sc : stability in aqueous solution (c) SnCl 4 + Hg2Cl 2 ¾® SnCl 2 + 2HgCl 2
(d) Sc < Ti < Cr < Mn : number of oxidation states (d) 2CuI + I2 + 4H+ ¾® 2Cu2 + + 4KI
Transition and Inner-Transition Elements 235
38. Zinc-copper couple that can be used as a reducing agent is (b) Vapours when passed into NaOH solution gives a yellow
obtained by (1984, 1M) solution of Na 2CrO4
(a) mixing of zinc dust and copper gauge (c) Chlorine gas is evolved
(b) zinc coated with copper (d) Chromyl chloride is formed
(c) copper coated with zinc
48. Which of the following alloys contains Cu and Zn?
(d) zinc and copper wires welded together
(a) Bronze (b) Brass (1993, 1M)
39. How many unpaired electrons are present in Ni 2 + ? (c) Gun metal (d) Type metal
(a) 0 (b) 2 (1981, 1M)
49. The aqueous solution of the following salts will be coloured
(c) 4 (d) 8
in case of (1990, 1M)
40. One of the constituent of German silver is (1980, 1M) (a) Zn(NO3 )2 (b) LiNO3 (c) Co(NO3 )2 (d) CrCl 3
(a) Ag (b) Cu (c) Mg (d) Al (e) potash alum
41. Which of the following dissolves in concentrated NaOH 50. Potassium manganate (K 2 MnO4 ) is formed when (1988, 2M)
solution? (1980, 1M)
(a) chlorine is passed into aqueous KMnO4 solution
(a) Fe (b) Zn (c) Cu (d) Ag
(b) manganese dioxide is fused with KOH in air
(c) formaldehyde reacts with potassium permanganate in the
Objective Questions II presence of strong alkali
(One or more than one correct option) (d) potassium permanganate reacts with conc. H2SO4
42. The correct statement(s) about Cr 2+ and Mn 3+ is/are [atomic
number of Cr = 24 and Mn = 25] (2015 Adv.) Assertion and Reason
2+
(a) Cr is a reducing agent Read the following questions and answer as per the direction
(b) Mn 3+ is an oxidising agent given below :
(a) Statement I is true; Statement II is true; Statement II is
(c) both Cr 2+ and Mn 3+ exhibit d 4 electronic configuration
the correct explanation of Statement I.
(d) when Cr 2+ is used as a reducing agent, the chromium ion
(b) Statement I is true; Statement II is true; Statement II is
attains d 5 electronic configuration
not the correct explanation of Statement I.
43. Fe3+ is reduced to Fe2+ by using (2015 Adv.) (c) Statement I is true; Statement II is false.
(a) H2O2 in presence of NaOH (d) Statement I is false; Statement II is true.
(b) Na 2O2 in water 51. Statement I Zn 2 + is diamagnetic.
(c) H2O2 in presence of H2SO4 Statement II The electrons are lost from 4s orbital to
(d) Na 2O2 in presence of H2SO4 form Zn 2 + . (1998, 2M)
44. Which of the following halides react(s) with AgNO3 ( aq ) to 52. Statement I To a solution of potassium chromate if a
give a precipitate that dissolves in Na 2 S2 O3 ( aq ) ? strong acid is added, it changes its colour from yellow to
(a) HCl (b) HF (c) HBr (d) HI orange.
45. Reduction of the metal centre in aqueous permanganate ion Statement II The colour change is due to the change in
involves (2011) oxidation state of potassium chromate. (1988, 2M)
(a) three electrons in neutral medium
(b) five electrons in neutral medium Fill in the Blanks
(c) three electrons in alkaline medium 53. The compound Y Ba 2 Cu 3 O7 which show super conductivity
(d) five electrons in acidic medium
has copper in oxidation state …… assuming that the rare earth
46. Which of the following statement (s) is/are correct? (1998) element Yttrium in its usual +3 oxidation state. (1994, 1M)
(a) The electronic configuration of Cr is [Ar] 3d 5 4s1 (Atomic 54. The outermost electronic configuration of Cr is ……
number of Cr = 24) (1994, 1M)
(b) The magnetic quantum number may have a negative value
55. Fehling’s solution A consists of an aqueous solution of
(c) In silver atom, 23 electrons have a spin of one type and 24 of
copper sulphate while Fehling’s solution B consists of an
the opposite type (Atomic number of Ag = 47)
alkaline solution of …… (1990, 1M)
(d) The oxidation state of nitrogen in HN3 is – 3
56. The salts ……… and …… are isostructural. (FeSO4 ×7H2 O,
47. Which of the following statement(s) is/are correct when a
mixture of NaCl and K 2 Cr2 O7 is gently warmed with CuSO4 × 5H2 O,MnSO4 × 4H2 O,ZnSO4 × 7H2 O (1990, 1M)
Subjective Questions 72. Show with balanced equations for the reactions when
(i) potassium permanganate interacts with manganese
Moist air Zn
63. (B ) ¬¾¾ MCl 4 ¾® (A) dioxide in the presence of potassium hydroxide.
W hite fumes ( M = Transition (purple colour) (ii) potassium ferricyanide is heated with concentrated
with pungent smell element colourless)
sulphuric acid. (1985, 2M)
Identify the metal M and hence MCl 4 . Explain the difference
73. State the conditions under which the following preparations
in colours of MCl 4 and A. (2005)
are carried out. Give necessary equations which need not be
64. Give reasons : CrO3 is an acid anhydride. (1999, 2M ) balanced.
65. A compound of vanadium has a magnetic moment of “Potassium permanganate from manganese dioxide”
(1983, 1M)
1.73 BM. Work out the electronic configuration of the
vanadium ion of the compound. (1997) 74. Complete and balance the following reactions (1983, 2M)
Answers
1. (c) 2. (d) 3. (d) 4. (b) 37. (a) 38. (b) 39. (b) 40. (b)
5. (a) 6. (d) 7. (b) 8. (c) 41. (b) 42. (a, b, c) 43. (a, b) 44. (a, c, d)
9. (b) 10. (a) 11. (c) 12. (b) 45. (a, c, d) 46. (a, b, c, d) 47. (a, b, d) 48. (b, c)
13. (a) 14. (d) 15. (d) 16. (d) 49. (c, d) 50. (b, c) 51. (b) 52. (c)
5 1
17. (a) 18. (d) 19. (a) 20. (a) 53. x = +7 / 3 54. 3d 4s 55. Rochelle salt
21. (d) 22. (d) 23. (c) 24. (a) 56. FeSO 4 × 7 H 2O and ZnSO 4 × 7H 2O 57. PbO 2
25. (a) 26. (c) 27. (b) 28. (a) 58. F 59. F 60. (6) 61. (8)
29. (b) 30. (a) 31. (a) 32. (d) 62. (7)
33. (d) 34. (b) 35. (b) 36. (b)
Hints & Solutions
1. Thermal decomposition of Mn compound (X), i.e. KMnO4 at 6. The maximum number of possible oxidation states of actinoids
513 K results in compound Y(i.e. K 2MnO4), MnO2 and a are shown by neptunium (Np) and plutonium (Pu). These
gaseous product. MnO2 reacts with NaCl and concentrated actinoids exhibit oxidation states of +3, +4, +5 and +6.
H2SO4 to give a pungent gas Z(i.e. Cl2). The reactions involved 7. The lanthanide ion that would show colour is Sm3+ . Colour of a
are as follows : compound depends on the number of electrons in 4 f -orbitals.
2KMnO4 ¾513
¾¾ K
® K2MnO4 + MnO2 + O2 (g ) Electronic configuration of given lanthanides are as follows:
D
( X) (Y )
Gd 3+ = 4 f 7
MnO2 + 4NaCl + 4 H2SO4 ¾®
Sm 3+ = 4 f 5
MnCl 2 + 4NaHSO4 + 2H2O + Cl 2 (g )
(Z ) La 3+ = 4 f 0
Pungent gas. Lu 3+ = 4 f 14
2. The pair that has similar atomic radii is Mo and W. It is due to Gd 3+ have half-filled 4 f -orbitals.
lanthanoid contraction. The factor responsible for lanthanoid
La 3+ have no electron in 4 f -orbitals.
contraction is the imperfect shielding of one electron by another
in the same set of orbitals. Shielding of 4 f is very less due to its Lu 3+ have fully-filled 4 f -orbitals.
diffused shape. As a result, nuclear charge increases. Hence, Mo Only Sm 3+ contain 4 f 5. The electrons can easily undergoes
and W have similar atomic radii.
excitation. That result in a formation of colour.
3. The 3d-transition series is
8. The correct order of atomic radii is
Sc Ti V Cr Mn Fe Co Ni Cu Zn
Atomic number 21 22 23 24 25 26 27 28 29 30
Europium (Eu) > Cerium (Ce) > Holmium (Ho) > Nitrogen (N)
Þ
The electronic configuration of Sc (Z = 21) is [Ar] 3d 1 , 4 s2. 19. [Ni(NH3 )6 ] 2+ sp3d 2 octahedral
Due to the presence of only one 3d-electron [Pt(NH3 )4 ] 2+ dsp2 square planar
(no pairing energy) and two 4s-electrons, they easily ionise to
achieve most stable +3 oxidation state. [Zn(NH3 )4 ] 2+ sp3 tetrahedral
20. Zn 2[ Fe(CN)6 ], K3[ Co(NO2 )6 ] and (NH4 )3As [ Mo3O10 ] 4 show
11. In the lanthanoid series, atomic number of fourteen 4 f -block
colour due to d-d transition while BaCrO4 is coloured due to
elements ranges from 58 (Ce) to 71 (Lu). charge transfer phenomenon.
Ytterbium, Yb(Z = 70) has electronic configuration : Further according to spectrochemical series the strong ligand
[ Xe ] 4 f 14 6s2. So, the 71nth electron of lutetium, Lu (Z = 71) possessing complex has higher energy and hence lower
should enter into 5d orbital and its (here, Lu is ‘X ’) electronic wavelength. Therefore, complexes containing NO2 , NH+4 , O2-
configuration will be : [ Xe ]4 f 14 5d 1 6s2. It happens so, because etc., ligands show yellow colour while CN- forces the complex
f -block elements have general electronic configuration, to impart white colour.
(n - 2) f 1 - 14 (n - 1)d 1- 10ns2. Therefore, option (c) is correct. Spectrochemical series
12. Lanthanoid contraction in the lanthanoid series takes place due I- < Br - < S2- < SCN- < Cl - < NO-3 < N-3 < F- < OH-
to the presence of electron(s) in the 4 f -orbitals. f -orbitals have < C2O24- » H2O < NCS- < CH3CN < py < NH3 < en
poor shielding effect. As a result, the effective nucleur charge < bipy < Phen < NO-2 < PPh 3 < CN- » CO
will be more experienced by the 5d and 6s- electrons and it will 21. PLAN Analyse each reaction given in the question and choose the
cause contraction or decrease in both atomic and ionic radii. correct answer on the basis of oxidation state and stability of
iron compounds. Use the concept of Ellingham diagram to
13. For transition metals, solve this problem.
°
DH Atomisation µ Strength of metallic bonding The correct reactions are as follows:
µ Number of unpaired electrons in the metal atom (a) Fe + dil. H2SO4 ¾® FeSO4 + H2
For the given 3d-transition metals, 1
H2SO4 + 2FeSO4 + O2 ¾® Fe2 (SO4 )3 + H2O
V Fe Cu Zn 2
3d 34 s2 3d64 s2 3d 104 s1 3d 104 s0 D
Fe2 (SO4 )3 ¾¾® Fe2O3 (s) + 3SO3
n=3 n=4 n=0 n=0 The given reaction is incorrect in question
[Q n = no. of unpaired electrons]
22. SRP value normally increases from left to right in the period of
D° H Atomisation (kJ mol -1) = 515 418 339 130 d-block elements. Some SRP value are exceptionally higher due
So, absence of unpaired d-electrons and larger size of Zn atoms, to stability of product ion. e.g.
make the crystal lattice of Zn less closely packed. E° = + 1.57 V; E°
Mn 3+ / Mn 2+
= + 1.97 V
Co3+ / Co2 +
14. Zinc oxide (ZnO) when react with Na 2O it act as acid while with Thus, EM° 3+ / M2+ is highest for Co.
CO2 it act as base. Therefore, it is an amphoteric oxide.
ZnO + Na 2 O ¾® Na 2 ZnO2 23. The half equations of the reaction are
Acid Base Salt MnO -4 ¾® Mn 2+
ZnO + CO2 ¾® ZnCO3 C2O24- ¾® CO2
Base Acid Salt
The balanced half equations are
15. The reaction takes place as follows MnO-4 + 8H+ + 5e- ¾® Mn 2+ + 4H2O
Na 2C2O4 + H2SO4 ¾® Na2 SO4 + H2O + CO + CO2
(X) (Conc.) Effervescence C2O24- ¾® 2CO2 + 2e-
Na 2C2O4 + CaCl 2 ¾® CaC2O4 + 2NaCl On equating number of electrons, we get
(X) White ppt. 2 MnO-4 + 16H+ + 10e- ¾® 2Mn 2+ + 8H2O
5CaC2O4 + 2KMnO4 + 8H2SO4 ¾® K2SO4 + 5CaSO4
Purple 5C2O24- ¾® 10CO2 + 10e-
+ 2MnSO4 + 10CO2 + 8H2O On adding both the equations, we get
Colourless
Hence, X is Na 2C2O4. 16
2MnO-4 + 5C2O-4 + 16H+ ¾® 2Mn 2+ + 2 ´ 5CO2 + H2O
16. Zn + 2NaOH ¾® Na 2ZnO2 + H2 2
Amphoteric Thus x , y and z are 2, 5 and 16 respectively.
17. Only three elements iron (Fe), cobalt (Co) and nickel (Ni) show 24. (a) V2+ = 3 unpaired electrons
ferromagnetism at room temperature. CrO2 is also a metallic and Cr 2+ = 4 unpaired electrons
ferromagnetic compound which is used to make magnetic tapes Mn 2+ = 5 unpaired electrons
for cassette recorders.
Fe2+ = 4 unpaired electrons
18. Zn + 4HNO3 ¾® Zn (NO3 )2 + 2H2O + 2NO2 Hence, the order of paramagnetic behaviour should be
(Conc.)
V2+ < Cr 2 + < Fe2 + < Mn 2 +
4Zn + 10HNO3 ¾® 4Zn (NO3 )2 + N2O + 5H2O
(Dil.) (b) Ionic size decreases from left to right in the same period.
Transition and Inner-Transition Elements 239
(c) (As per data from NCERT) 40. German silver is an alloy of copper (56%), Zn (24%) and
Co3+ / Co2+ = 1.97; Ni(20%).
Fe 3+
/Fe 2+
= 0.77; 41. Zn being amphoteric, dissolves in both acid and base :
Cr 3+ / Cr 2+ = - 0.41 Zn + 2NaOH ¾® Na 2ZnO2 + H2
Sc 3+
is highly stable (It does not show + 2). 42. In aqueous solution Cr 2+ (3d 4 ) acts as a reducing agent,
(d) The oxidation states increases as we go from group 3 to oxidising itself to Cr 3+ (3d 3 ) that gives a completely half-field
group 7 in the same period. t2g level in octahedral ligand field of H2O.
(b) Mn 3+ (3d 4 ) is an oxidising agent as it is reduced to
25. The aqueous solution of CuSO4 consist of the complex
Mn 2+ (3d 5 ) , a completely half-filled stable configuration.
[Cu(H2O)4 ]2+ ion which absorbed in orange-red region and
impart deep blue colouration to solution. (c) Both Cr 2+ and Mn 3+ have d 4 configuration.
26. KMnO4 is itself a very strong oxidising agent, O3 cannot oxidise it. (d) 3d 4 Cr 2+ (aq) ¾R.¾
¾A
® Cr 3+ (aq)+ e–
Hence (d) is wrong statement.
27. In CuCl 2, Cu 2 + has d 9 configuration, exhibit d-d transition and
show colour. Similarly in VOCl 2, V 4 + has d 1 configuration, can 43. H2O2 is alkaline medium acts as reducing agent, reduces Fe3+ to
exhibit d-d transition and show colour. Fe2+. In acidic medium the same H2O2 oxidises Fe2+ to Fe3+.
28. MnO-4 + I- + OH- ¾® MnO24- + IO-3 44. Solubilities of silver halides in water decreases from fluoride
(AgF) to iodide (AgI). Silver fluoride is readialy soluble in
29. In MnO-4 , Mn 7+ is in highest oxidation state possible for Mn. In water, hence when AgNO3 solution is added to HF solution (HF
CrO2Cl 2, Cr6+ is in highest oxidation state possible for Cr. being weak acid, its solution maintain very low concentration of
F - ) no precipitate of AgF is formed.
30. Ammonium dichromate on heating produces N2 (g). NH4NO2
also gives N2 on heating : HCl, HBr and HI being all strong acid, forms precipitates of
AgCl, AgBr and AgI when AgNO3 solution is added to their
D
(NH4 )2 Cr2O7 ¾® N2 + Cr2O3 + 4H2O aqueous solution.
D HCl(aq) + AgNO3(aq) ¾® AgCl (s) + HNO3(aq)
NH4NO2 ¾® N2 + 2H2O Curdy white
31. K2MnO4 (purple green) is formed which is the first step of HBr (aq) + AgNO3(aq) ¾® AgBr (s) + HNO3(aq)
preparation of KMnO4. Pale yellow
49. Co2+ (3d 7 ) and Cr 3+ (3d 3 ) have allowed d-d transition, Na 2S2O3 is a strong reducing agent which on reaction with I 2
therefore produces coloured aqueous solution. produces I - .
Na 2S2O3 + I2 ¾® 2I- + Na 2S4O6
D
50. 2KOH + MnO2 + O2 ¾® K2MnO4 + H2O Therefore, no reaction takes place between Na 2S2O3 and iodide
HCHO + KMnO4 + 2KOH ¾® K2MnO4 + H2O ion.
Hence, correct integer is (7).
+ HCOOH
51. Both Statement I and Statement II are independently true but 63. A = [Ti(H2O)6 ]3+ and M = Ti, B = TiO2, Ti(IV) has no
Statement II is not the correct explanation of Statement I. electron in 3d-orbital, no d-d transition is possible, therefore
Diamagnetism is due to lack of unpaired electron in MCl 4 is colourless. In A, there is one electron in 3d-orbital and
Zn 2+ (3d 10 ). its d-d transition is responsible for colour.
52. Statement I is true but Statement II is false : 64. CrO3 is anhydride of chromic acid :
K2CrO4 + H2SO4 ¾® K2Cr2O7 + K2SO4 + H2O CrO3 + H2O ¾® H2CrO4
Yellow Orange Chromic acid
In both K2CrO4 and K2Cr2O7 , chromium is in +6 oxidation state. 65. m = n (n + 2) BM where ‘n’ is number of unpaired electrons.
53. Y = +3, 2Ba = 2 ´ 2 = 4 1.73 = n (n + 2) Þ n = 1; V4+ = 3d 1
7 ‘O’ = 7 ´ (-2) = - 14
7 66. (i) 2KMnO4 + 5H2O2 + 3H2SO4 ¾® K2SO4
3 + 4 + (-14 ) + 3x = 0 Þ x=+
3 + 2MnSO4 + 5O2 + 8H2O
5 1
54. 3d 4 s (ii) 4Zn + 10HNO3 ¾® 4Zn(NO3 )2 + N2O + 5H2O
55. Rochelle salt. 67. (i) 3MnO24- + 4H+ ¾® MnO2 + 2MnO-4 + 2H2O
56. FeSO4 × 7H2O and ZnSO4 × 7H2O
(ii) 3SO2 (aq) + Cr2O27- + 2H+ ¾® 3SO24- + 2Cr 3+ + H2O
57. PbO2, a strong oxidising agent, oxidises Mn 2+ to MnO-4 .
68. (NH4 )2 S2O8 + 2H2O + MnSO4 ¾® MnO2
58. Zn 2+ (3d 10 ) has no unpaired electron–diamagnetic.
+ 2H2SO4 + (NH4 )2 SO4
59. Cu cannot reduce Fe2+
69. (i) K2Cr2O7 + 4NaCl + 6H2SO4 ¾® 2CrO2Cl 2
60. In neutral or faintly alkaline solution, MnO-4 is reduced to MnO2
+ 4NaHSO4 + 3H2O + 2KHSO4
and S2O2- 2-
3 is oxidised to SO 4 .
(ii) 2KMnO4 + 3MnSO4 + 2H2O ¾® 5MnO2
Change in ON = 4 units + K2SO4 + 2H2SO4
2– 2– +
MnO4
– + 1/2 S2 O3 SO 4 MnO2
+7 +2 +6 +4 70. (i) 2Mn 2+ + 5PbO2 + 4H+ ¾® 2MnO-4 + 2H2O + 5Pb2+
Change in ON = 3 units (ii) 6Ag+ + AsH3 + 3H2O ¾® 6Ag + H3AsO3 + 6H+
3 71. Most transition metals have partially filled d-orbitals which
Thus, 4MnO-4 + S2O23- ¾® 3SO24- + 4 MnO2 absorb in visible region and undergo d-d transition, which is
2
responsible for colour.
or 8MnO-4 + 3S2O23- ¾® 6SO24- + 8MnO2
72. (i) 2KMnO4 + 4KOH + MnO2 ¾® 3K2MnO4 + 2H2O
Thus, moles of SO2- -
4 formed by 8 moles of MnO 4 = 6
(ii) K4Fe(CN)6 + 6H2SO4 + 6H2O ¾®
61. The balanced redox reaction is 2K2SO4 + FeSO4 + 3(NH4 )2 SO4 + 6CO
MnO-4 + [Fe(H2O)2 (C2O4 )2 ]2 - + 8H+ ¾® Mn 2+ + Fe3+ 73. Potassium permanganate can be prepared from MnO2 under the
+ 4CO2 + 6H2O following conditions :
r [ H+ ] 8 Heat
MnO2 + KOH + O2 ¾® K2MnO4 + H2O
Þ –
= =8
r [ MnO 4 ] 1
K2MnO4 + Cl 2 ¾® KMnO4 + KCl
62. Acidified K2Cr2O7 , CuSO4 , H2O2, Cl 2, O3, FeCl 3 and HNO3 74. (i) 4Zn + NO-3 + 10H+ ¾® 4Zn 2+ + NH+4 + 3H2O
oxidise aq. iodide to iodine. Alkaline KMnO4 oxidise aq. iodide (ii) Cr2O27 - + 3C2H4O + 8H+ ¾® 3C2H4O2 + 2Cr 3+ + 4H2O
to IO-3 .
(c) [Pt(en)2 Cl 2 ]2+ (d) [Zn(en)Cl 2 ] 8. Consider the following reaction and statements :
[Co(NH3 ) 4Br2 ]+ + Br - ¾® [Co(NH3 )3 Br3 ] + NH3
3. The maximum possible denticities of a ligand given below
towards a common transition and inner-transition metal ion, I. Two isomers are produces if the reactant complex ion is
respectively, are (2019 Main, 9 April II) a cis-isomer.
sooc coos II. Two isomers are produced if the reactant complex ion is
a trans-isomer.
N N N
sooc
coos coos III. Only one isomer is produced if the reactant complex ion
is a trans-isomer.
(a) 8 and 8 (b) 8 and 6 (c) 6 and 6 (d) 6 and 8 IV. Only one isomer is produced if the reactant complex ion
4. The one that will show optical activity is (en = ethane-1, is a cis-isomer.
2-diamine) (2019 Main, 9 April I) The correct statements are (2018 Main)
A A (a) (I) and (II) (b) (I) and (III)
A B B B (c) (III) and (IV) (d) (II) and (IV)
(a) M (b) M
9. Which one of the following complexes shows optical
B A B B
isomerism? (2016 Main )
B A (a) cis [Co(en)2 Cl 2 ]Cl (b) trans [Co(en)2 Cl 2 ]Cl
A A (c) [Co(NH3 )4 Cl 2 ]Cl (d) [Co(NH3 )3 Cl 3 ]
A
(c) M en (d) en M en
10. The number of geometric isomers that can exist for square
B planar [Pt(Cl)(py)(NH3 )(NH2 OH)]+ is (py = pyridine).
(2015 Main)
B A (a) 2 (b) 3 (c) 4 (d) 6
5. The following ligand is 11. Which of the following complex species is not expected to
NEt2 exhibit optical isomerism? (2013 Main)
N (a) [Co(en)3 ]3+ (b) [Co(en)2 Cl 2 ]+
(c) [Co (NH3 )3Cl 3 ] (d) [Co(en)(NH3 )Cl 2 ]+
O– –
O 12. As per IUPAC nomenclature, the name of the complex
[Co (H2 O)4 (NH3 )2 ]Cl 3 is (2012)
(2019 Main, 8 April I) (a) tetraaquadiaminecobalt (III) chloride
(a) hexadentate (b) tetradentate (b) tetraaquadiamminecobalt (III) chloride
(c) bidentate (d) tridentate
242 Coordination Compounds
(c) diaminetetraaquacobalt (III) chloride (b) Statement I is true; Statement II is true; Statement II is not the
(d) diamminetetraaquacobalt (III) chloride correct explanation of Statement I.
13. Geometrical shapes of the complexes formed by the reaction (c) Statement I is true; Statement II is false.
of Ni 2+ with Cl - , CN- and H2 O, respectively, are (d) Statement I is false; Statement II is true.
(2011)
(a) octahedral, tetrahedral and square planar 20. Statement I The geometrical isomers of the complex
(b) tetrahedral, square planar and octahedral [ M (NH3 )4 Cl 2 ] are optically inactive.
(c) square planar, tetrahedral and octahedral Statement II Both geometrical isomers of the complex
(d) octahedral, square planar and octahedral [ M (NH3 )4 Cl 2 ] possess axis of symmetry. (2008, 3M)
dxz, dyz dxy 9. The compound that inhibits the growth of tumors is
(2019 Main, 8 April II)
dx2 – y2 dx2 – y2 (a) trans-[Pt(Cl)2 (NH3 )2 ] (b) cis-[Pd(Cl)2 (NH3 )2 ]
dz2 dz2 (c) cis-[Pt(Cl)2 (NH3 )2 ] (d) trans-[Pd(Cl)2 (NH3 )2 ]
(c) E (d) E 10. The correct order of the spin only magnetic moment of metal
dxy dyz, dxz
ions in the following low spin complexes, [V(CN)6 ]4- ,
dxz, dyz dxy
[Fe(CN)6 ]4- , [Ru(NH3 )6 ]3+ , and [Cr(NH3 )6 ]2+ , is
(2019 Main, 8 April I)
3. The complex ion that will lose its crystal field stabilisation
(a) Cr 2+ > Ru3+ > Fe2+ > V2+
energy upon oxidation of its metal to +3 state is
(b) V2+ > Cr 2+ > Ru3+ > Fe2+
(c) V2+ > Ru3+ > Cr 2+ > Fe2+
(d) Cr 2+ > V2+ > Ru3+ > Fe2+
(Phen =
N N 11. The magnetic moment of an octahedral homoleptic Mn(II)
complex is 5.9 BM. The suitable ligand for this complex is
Ignore pairing energy (2019 Main, 12 April I)
(a) CN- (b) ethylenediamine
(a) [Co(phen)3 ]2+ (b) [Ni(phen)3 ]2+
(c) NCS- (d) CO
(c) [Zn(phen)3 ]2+ (d) [Fe(phen)3 ]2+
12. The pair of metal ions that can given a spin-only magnetic
4. The crystal field stabilisation energy (CFSE) of moment of 3.9 BM for the complex [M (H2 O)6 ]Cl 2 , is
[Fe(H2 O)6 ]Cl 2 and K 2 [NiCl 4 ], respectively, are (2019 Main, 12 Jan I)
(2019 Main, 10 April II) (a) Co2+ and Fe2+ (b) Cr 2+ and Mn 2+
(a) - 0.4 D o and - 12
. Dt (b) - 0.4 D o and - 0.8 D t (c) V2+ and Co2+ (d) V2+ and Fe2+
(c) - 2.4 D o and - 12
. Dt (d) - 0.6 D o and - 0.8 D t
13. The metal d-orbitals that are directly facing the ligands in
5. The incorrect statement is (2019 Main, 10 April II) K 3 [Co(CN)6 ] are (2019 Main, 12 Jan I)
(a) the gemstone, ruby, has Cr 3 + ions occupying the octahedral (a) dxz , d yz and d 2 (b) d 2 2 and d 2
z x - y z
sites of beryl (c) dxy , dxz and d yz (d) dxz and d 2 2
x - y
(b) the color of [CoCl(NH3 )5 ]2 + is violet as it absorbs the yellow 14. Mn 2 (CO)10 is an organometallic compound due to the
light presence of (2019 Main, 12 Jan I)
(c) the spin only magnetic moments of Fe(H2O)6 ]2 + and (a) Mn ¾ C bond (b) Mn ¾ O bond
[Cr(H2O)6 ]2 + are nearly similar (c) C¾ O bond (d) Mn ¾ Mn
(d) the spin only magnetic moment of [Ni(NH3 )4 (H2O)2 ]2 + is 15 The number of bridging CO ligand(s) and Co ¾ Co bond(s)
in Co2 (CO )8 , respectively are (2019 Main, 11 Jan II)
2.83 BM
(a) 2 and 0 (b) 0 and 2 (c) 4 and 0 (d) 2 and 1
6. Three complexes,
16. The coordination number of Th in K 4 [Th(C2 O4 )4 (OH2 )2 ] is
[CoCl(NH3 )5 ]2+ (I), [Co(NH3 )5 H2 O]3+ (II) and
(C2O24 - = Oxalato) (2019 Main, 11 Jan II)
3+
[Co(NH3 )6 ] (III) (a) 14 (b) 10 (c) 8 (d) 6
244 Coordination Compounds
17. Match the metals (Column I) with the coordination 26. On treatment of 100 mL of 0.1 M solution of
compound(s)/enzyme(s) (Column II). (2019 Main, 11 Jan I) CoCl3 .6H2O with excess of AgNO3 ; 1.2 ´ 1022 ions
Column I Column II are precipitated. The complex is (2017 Main)
(A) Co (i) Wilkinson catalyst (a) [Co(H2O)4 Cl 2 ] Cl × 2H2O (b) [Co(H2O)3 Cl 3 ] × 3H2O
(B) Zn (ii Chlorophyll (c) [Co(H2O)6 ]Cl 3 (d) [Co(H2O)5 Cl] Cl 2 × H2O
(C) Rh (iii) Vitamin B 12 27. The pair having the same magnetic moment is
(D) Mg (iv) Carbonic anhydrase [at. no. Cr = 24, Mn = 25, Fe = 26 and Co = 27]
A B C D (a) [Cr(H2O)6 ]2+ and [Fe(H2O)6 ]2+ (2016 Main)
(a) (i) (ii) (iii) (iv) (b) [Mn(H2O)6 ]2+ and [Cr(H2O)6 ]2+
(b) (iv) (iii) (i) (ii) (c) [CoCl 4 ]2- and [Fe(H2O)6 ]2+
(c) (iii) (iv) (i) (ii)
(d) [Cr(H2O)6 ]2+ and [CoCl 4 ]2-
(d) (ii) (i) (iv) (iii)
18. The difference in the number of unpaired electrons of a metal ion 28. Among [Ni(CO)4 ], [ NiCl 4 ]2 - , [ Co(NH3 )4 Cl 2 ] Cl,
in its high-spin and low-spin octahedral complexes is two. The Na 3 [ CoF6 ], Na 2 O2 and CsO2 , the total number of
metal ion is (2019 Main, 10 Jan II) paramagnetic compounds is (2016 Adv.)
(a) Mn 2+ (b) Fe2+ (c) Ni 2+ (d) Co2+ (a) 2 (b) 3 (c) 4 (d) 5
19. A reaction of cobalt (III) chloride and ethylene diamine in a 1 : 2 29. The colour of KMnO4 is due to (2015 Main)
mole ratio generates two isomeric products A (violet coloured) (a) M ® L charge transfer transition
and B (green coloured). A can show optical activity, but B is (b) d ® d transition
optically inactive. What type of isomers does A and B represent ? (c) L ® M charge transfer transition
(2019 Main, 10 Jan II)
(d) s ® s* transition
(a) Ionisation isomers (b) Coordination isomers
(c) Geometrical isomers (d) Linkage isomers 30. The equation which is balanced and represents the
20. Wilkinson catalyst is (2019 Main, 10 Jan I) correct product(s) is (2014 Main)
(a) [(Et 3P)3 RhCl] (b) [(Et 3P)3 IrCl](Et = C2H5) (a) Li 2O + 2KCl ¾® 2LiCl + K 2O
(c) [(Ph 3P)3 RhCl] (d) [(Ph 3P)3 IrCl] (b) [CoCl(NH3 )5 ]+ + 5H+ ¾® Co2+ + 5NH+4 + Cl -
21. Homoleptic octahedral complexes of a metal ion ‘M 3 + ’ with three (c) [Mg(H2 O)6 ]2+ + (EDTA)4 - ¾¾¾¾¾®
Excess NaOH
monodentate ligands L1 , L2 and L3 absorb wavelengths in the
region of green, blue and red respectively. The increasing order of [Mg(EDTA)]2+ + 6H2 O
the ligand strength is (2019 Main, 9 Jan II) (d) CuSO4 + 4KCN ¾® K 2 [Cu(CN)4 ] + K 2SO4
(a) L1 < L2 < L3 (b) L2 < L1 < L3 31. The octahedral complex of a metal ion M 3+ with four
(c) L3 < L1 < L2 (d) L3 < L2 < L1
monodentate ligands L1 , L2 , L3 and L4 absorb
22. The complex that has highest crystal field splitting energy ( D ), is wavelengths in the region of red, green, yellow and blue,
(2019 Main, 9 Jan II) respectively. The increasing order of ligand strength of
(a) [Co(NH3 )5 Cl] Cl 2 (b) [Co(NH3 )5 (H2O)]Cl 3 the four ligands is (2014 Main)
(c) K 3[Co(CN)6 ] (d) K 2[CoCl 4 ] (a) L4 < L3 , L2 < L1 (b) L1 < L3 < L2 < L4
23. The highest value of the calculated spin only magnetic moment (c) L3 < L2 < L4 < L1 (d) L1 < L2 < L4 < L 3
(in BM) among all the transition metal complexes is 32. Consider the following complex ions, P, Q and R.
(2019 Main, 9 Jan I)
(a) 5.92 (b) 3.87 (c) 6.93 (d) 4.90 P = [ FeF6 ]3 - , Q = [ V(H 2O )6 ]2 + and R = [ Fe(H 2O )6 ]2 +
24. Two complexes [Cr(H 2O)6 ]Cl3 (A) and [Cr(NH3 )6 ]Cl3 (B) are The correct order of the complex ions, according to their
violet and yellow coloured, respectively. The incorrect statement spin-only magnetic moment values (in BM) is
(2013 Adv.)
regarding them is (2019 Main, 9 Jan I) (a) R < Q < P (b) Q < R < P
(a) D o value for (A) is less than that of (B) (c) R < P < Q (d) Q < P < R
(b) both absorb energies corresponding to their complementary colours
33. NiCl 2 {P(C2 H5 )2 (C6 H5 )}2 exhibits temperature
(c) D o values of (A) and (B) are calculated from the energies of violet
and yellow light, respectively dependent magnetic behaviour
(d) both are paramagnetic with three unpaired electrons
(paramagnetic/diamagnetic) the coordination
geometries of Ni 2+ in the paramagnetic and
25. The recommended concentration of fluoride ion in drinking water diamagnetic states respectively, are (2012)
is up to 1 ppm as fluoride ion is required to make teeth enamel (a) tetrahedral and tetrahedral
harder by converting [3Ca 3 (PO4 )2 × Ca(OH)2 ] to : (2018 Main) (b) square planar and square planar
(a) [CaF2 ] (b) [3(CaF2 ) × Ca(OH)2 ] (c) tetrahedral and square planar
(c) [3Ca 3 (PO4 )2 × CaF2 ] (d) [3{Ca 3 (PO4 )2} × CaF2 ] (d) square planar and tetrahedral
Coordination Compounds 245
34. Among the following complexes (K-P), (2011) 44. The complex ion which has no ‘d’-electrons in the central
K 3 [Fe(CN)6 ] (K), [Co(NH3 )6 ]Cl 3 (L), metal atom is (2001, 1M)
Na 3 [Co (ox)3 ] (M), [Ni(H2 O)6 ] Cl 2 (N), (a) [MnO4 ]– (b) [Co(NH3 )6 ]3+
K 2 [Pt(CN)4 ](O), [Zn(H2 O)6 ](NO3 )2 (P) (c) [Fe(CN)6 ]3– (d) [Cr(H2O)6 ]3+
the diamagnetic complexes are
(a) K, L, M, N (b) K, M, O, P 45. The geometry of Ni(CO)4 and Ni(PPh 3 )2 Cl 2 are (1999, 2M)
(c) L, M, O, P (d) L, M, N, O (a) both square planar
(b) tetrahedral and square planar, respectively
35. The complex showing a spin only magnetic moment of
(c) both tetrahedral
2.82 BM is (2010)
(d) square planar and tetrahedral, respectively
(a) Ni(CO)4 (b) [NiCl 4 ]2-
(c) Ni(PPh 3 )4 (d) [Ni(CN)4 ]2- 46. Which of the following is formed when excess of KCN is
added to aqueous solution of copper sulphate? (1996, 1M)
36. The spin only magnetic moment value (in Bohr magneton (a) Cu (CN)2
units) of Cr(CO)6 is (2009) (b) K 2[Cu(CN)4 ]
(a) 0 (b) 2.84 (c) K[Cu(CN)2 ]
(c) 4.90 (d) 5.92 (d) K 3[Cu(CN)4 ]
37. Among the following, the coloured compound is (2008, 3M) 47. Among the following ions, which one has the highest
(a) CuCl paramagnetism? (1993, 1M)
(b) K 3[Cu(CN)4 ] (a) [Cr(H2O)6 ]3+ (b) [Fe(H2O)6 ]2+
(c) CuF2 (c) [Cu(H2O)6 ]2+ (d) [Zn(H2O)6 ]2+
(d) [Cu(CH3CN)4 ]BF4
48. Amongst Ni(CO)4 , [Ni(CN)4 ]2– and NiCl 2–
4 (1991, 1M)
38. Both [Ni(CO)4 ] and [Ni(CN)4 ]2- are diamagnetic. The
hybridisations of nickel in these complexes respectively, are (a) Ni(CO)4 and NiCl 2–
4 are diamagnetic and [Ni(CN)4 ]
2–
is
(a) sp3 , sp3 (b) sp3 , dsp2 (2008, 3M) paramagnetic
2
(c) dsp , sp 3 2
(d) dsp , dsp 2 (b) [NiCl 4 ]2- and [Ni(CN)4 ]2– are diamagnetic and Ni(CO)4 is
paramagnetic
39. Among the following metal carbonyls, the C—O bond order
is lowest in (2007, 3M)
(c) Ni(CO)4 and [Ni(CN)4 ]2– are diamagnetic and [NiCl 4 ]2- is
(a) [Mn(CO)6 ]+ (b) [Fe(CO)5 ] paramagnetic
(c) [Cr(CO)6 ] (d) [V(CO)6 ] - (d) Ni(CO)4 is diamagnetic and [NiCl 4 ]2- and [Ni(CN)4 ]2– are
paramagnetic
40. If the bond length of CO bond in carbon monoxide is
1.128 Å, then what is the value of CO bond length in 49. Amongst the following, the lowest degree of paramagnetism
Fe(CO)5? (2006) per mole of the compound at 298 K will be shown by
(1988, 2M)
(a) 1.15 Å (b) 1.128 Å
(a) MnSO4 × 4H2O (b) CuSO4 × 5H2O
(c) 1.72 Å (d) 1.118 Å
(c) FeSO4 × 6H2O (d) NiSO4 × 6H2O
41. Spin only magnetic moment of the compound Hg[Co(SCN)4 ]
is (2004, 1M) Objective Question II
(a) 3 (b) 15 (One or more than one correct option)
(c) 24 (d) 8
50. The correct statement (s) regarding the binary transition
42. The compound having tetrahedral geometry is (2004, 1M) metal carbonyl compounds is (are) (Atomic numbers :
(a) [Ni(CN)4 ]2– (b) [Pd(CN)4 ]2– Fe = 26, Ni = 28) (2018 Adv.)
(c) [PdCl 4 ]2– (d) [NiCl 4 ]2– (a) Total number of valence shell electrons at metal centre in
Fe(CO)5 or Ni(CO) 4 is 16
43. Mixture X = 0.02 mole of [Co(NH3)5SO4]Br and 0.02 mole of (b) These are predominantly low spin in nature
[Co(NH3)5Br]SO4 was prepared in 2 L of solution. (c) Metal-carbon bond strengthens when the oxidation state of the
1 L of mixture X + excess AgNO3 ® Y metal is lowered
1 L of mixture X + excess BaCl2 ® Z (d) The carbonyl C—O bond weakens when the oxidation state of
Number of moles of Y and Z are (2003) the metal is increased
(a) 0.01, 0.01 (b) 0.02, 0.01
(c) 0.01, 0.02 (d) 0.02, 0.02
246 Coordination Compounds
51. The correct option(s) regarding the complex 55. The hybridisation of A and B are
[Co(en)(NH3 )3 (H2 O)]3+ (en = H2 NCH2 CH2 NH2 ) is (are) (a) dsp2 , sp3 (b) sp3 , sp3
(2018 Adv.) (c) dsp2 , dsp2 (d) sp3d 2 , d 2sp3
(a) It has two geometrical isomers
(b) It will have three geometrical isomers, if bidentate ‘en’ is
replaced by two cyanide ligands
Match the Columns
(c) It is paramagnetic 56. Match each set of hybrid orbitals from List–I with complexes
(d) It absorbs light at longer wavelength as compared to given in List-II.
[Co(en)(NH3 )4 ]3+ List–I List–II
52. Addition of excess aqueous ammonia to a pink coloured P. dsp2 1. [FeF6 ]4-
aqueous solution of MCl 2 × 6H2 O( X ) and NH4 Cl gives an Q. sp3 2. [Ti(H2O)3 Cl 3 ]
octahedral complex Y in the presence of air. In aqueous 3 2
R. sp d 3. [Cr(NH3 )6 ]3+
solution, complex Y behaves as 1 : 3 electrolyte. The reaction
of X with excess HCl at room temperature results in the S. d 2sp3 4. [FeCl 4 ]2-
formation of a blue colured complex Z. The calculated spin 5. [Ni(CO)4 ]
only magnetic moment of X and Z is 3.87 B.M., whersas it is 6. [Ni(CN)4 ]2-
zero for complex Y .
Among the following options, which statement(s) is (are) The correct option is (2018 Adv.)
(a) P ® 5; Q ® 4, 6; R ® 2, 3; S ® 1
correct? (2017 Adv.)
(b) P ® 5,6; Q ® 4; R ® 3; S ® 1,2
(a) The hybridisation of the central metal ion in Y is d 2sp3
(c) P ® 6; Q ® 4, 5; R ® 1; S ® 2, 3
(b) Addition of silver nitrate to Y given only two equivalents of (d) P ® 4,6; Q ® 5, 6; R ® 1,2; S ® 3
silver chloride
57. Match each coordination compound in Column I with an
(c) When X and Y are in equilibrium at 0°C, the colour of the
appropriate pair of characteristics from Column II and
solution is pink
select the correct answer using the codes given below the
(d) Z is a tetrahedral complex
Columns (en = H2 NCH2 CH2 NH2 ; atomic numbers : Ti = 22;
Cr = 24; Co = 27; Pt = 78) (2014 Adv.)
Assertion and Reason
Column I Column II
Read the following questions and answer as per the direction
given below : (A) [Cr(NH3 )4 Cl 2 ]Cl 1. Paramagnetic and exhibits
(a) Statement I is true; Statement II is true; Statement II is the ionisation isomerism
correct explanation of Statement I. (B) [Ti(H2O)5 Cl](NO3 )2 2. Diamagnetic and exhibits
cis-trans isomerism
(b) Statement I is true; Statement II is true; Statement II is not the
correct explanation of Statement I. (C) [Pt(en)(NH3 )Cl]NO3 3. Paramagnetic and exhibits
cis-trans isomerism
(c) Statement I is true; Statement II is false.
(d) Statement I is false; Statement II is true. (D) [Co(NH3 )4 (NO3 )2 ]NO3 4. Diamagnetic and exhibits
ionisation isomerism
53. Statement I [Fe(H2 O)5 NO]SO4 is paramagnetic.
Codes
Statement II The Fe in [Fe(H2 O)5 NO]SO4 has three A B C D A B C D
unpaired electrons. (2008, 3M) (a) 4 2 3 1 (b) 3 1 4 2
(c) 2 1 3 4 (d) 1 3 4 2
Passage Based Questions 58. Match the complexes in Column I with their properties listed
The coordination number of Ni 2 + is 4. in Column II. (2007, 6M)
NiCl 2 + KCN (excess) ¾® A (cyano complex)
Column I Column II
NiCl 2 + conc. HCl (excess) ¾® B (chloro complex)
(A) [Co(NH3 )4 (H2O)2 ]Cl 2 p. Geometrical isomers
54. Predict the magnetic nature of A and B.
(B) [Pt(NH3 )2 Cl 2 ] q. Paramagnetic
(a) Both are diamagnetic
(b) A is diamagnetic and B is paramagnetic with one unpaired (C) [Co(H2O)5 Cl]Cl r. Diamagnetic
electron (D) [Ni(H2O)6 ]Cl 2 s. Metal ion with +2
(c) A is diamagnetic and B is paramagnetic with two unpaired oxidation state
electrons
(d) Both are paramagnetic Fill in the Blanks
59. The IUPAC name of [Co(NH3 )6 ] Cl 3 is …… (1994, 1M)
Coordination Compounds 247
True/False 67. Deduce the structures of [NiCl 4 ]2– and [Ni(CN)4 ]2–
60. Both potassium ferrocyanide and potassium ferricyanide are considering the hybridisation of the metal ion. Calculate the
diamagnetic. magnetic moment (spin only) of the species. (2002, 5M)
(1989, 1M)
61. The electron density in the xy plane in 3dx 2 - orbital is 68. A metal complex having composition Cr(NH3 )4 Cl 2 Br has
2
y
zero. (1986, 1M) been isolated in two forms A and B. The form A reacts with
AgNO3 to give a white precipitate readily soluble in dilute
Integer Answer Type Questions aqueous ammonia, whereas B gives a pale yellow precipitate
soluble in concentrated ammonia.
62. For the octahedral complexes of Fe3+ in SCN-
(thiocyanato-S) and in CN- ligand environments, the Write the formula of A and B and state the hybridisation of
difference between the spin only magnetic moments in Bohr chromium in each. Calculate their magnetic moments
magnetons (when approximated to the nearest integer) is (spin-only value). (2001, 5M)
[atomic number of Fe = 26 ] (2015 Adv.) 69. Draw the structures of [Co (NH3 )6 ]3+ , [Ni(CN)4 ]2– and
63. In the complex acetylbromidodicarbonylbis [Ni(CO)4 ] . Write the hybridisation of atomic orbitals of the
(triethylphosphine) iron (II), the number of Fe¾ C bond (s) transition metal in each case. (2000, 4M)
is (2015 Adv.) 70. A, B and C are three complexes of chromium (III) with the
64. EDTA 4- is ethylenediaminetetraacetate ion. The total empirical formula H12 O6 Cl 3 Cr. All the three complexes have
number of N ¾ Co ¾ O bond angles in [Co(EDTA)] - water and chloride ion as ligands.
complex ion is (2013 Adv.) Complex A does not react with concentrated H2 SO4 , whereas
complexes B and C lose 6.75% and 13.5% of their original
Subjective Questions mass, respectively, on treatment with concentrated H2 SO4 .
Identify A, B and C. (1999, 2M)
65. NiCl 2 in the presence of dimethyl glyoxime (DMG) gives a
71. Identify the complexes which are expected to be coloured.
complex which precipitates in the presence of NH4 OH,
Explain (1994, 2M)
giving a bright red colour.
(i) [Ti(NO3 )4 ] (ii) [Cu(NCCH3 )]+ BF4
(a) Draw its structure and show H-bonding
(b) Give oxidation state of Ni and its hybridisation (iii) [Cr(NH3 )6 ] Cl3 (iv) K3 [VF6 ]
(c) Predict whether it is paramagnetic or diamagnetic (2004, 4M) 72. Give reasons in two or three sentences only for the
66. Write the IUPAC name of the compound following :
K 2 [Cr(NO)(CN)4 (NH3 )] . Spin magnetic moment of the “The species [CuCl 4 ]2– exists, while [CuI4 ]2– does not
complex m = 1.73 BM. Give the structure of anion.
(2003, 4M)
exist.” (1992, 1M)
Answers
Topic 1 17. (c) 18. (d) 19. (c) 20. (c)
1. (d) 2. (c) 3. (d) 4. (c) 21. (c) 22. (c) 23. (a) 24. (c)
5. (b) 6. (a) 7. (c) 8. (b) 25. (c) 26. (d) 27. (a) 28. (b)
9. (a) 10. (b) 11. (c) 12. (d) 29. (c) 30. (b) 31. (b) 32. (b)
13. (b) 14. (c) 15. (b) 16. (c) 33. (c) 34. (c) 35. (b) 36. (a)
17. (a) 18. (b,d) 19. (c,d) 20. (b) 37. (c) 38. (b) 39. (b) 40. (a)
21. (a) 22. paramagnetism 23. (5) 41. (b) 42. (d) 43. (a) 44. (a)
24. (6) 25. (6) 26. (3) 45. (c) 46. (d) 47. (b) 48. (c)
Topic 2 49. (b) 50. (b, c) 51. (a, b, d) 52. (a, b, d)
1. (d) 2. (a) 3. (d) 4. (b) 53. (a) 54. (c) 55. (a) 56. (c)
5. (a) 6. (b) 7. (b) 8. (a) 57. (b) 58. A ® p, q, s B ® p, r, s C ® q, s D ® q, s
9. (c) 10. (b) 11. (c) 12. (c) 59. hexaammine cobalt (III) chloride 60. F
13. (b) 14. (a) 15. (d) 16. (b) 61. F 62. (4) 63. (3) 64. (8)
Hints & Solutions
Topic 1 Nomenclature and Isomerism of
Coordination Compounds A A
B
1. Key Idea The total number of ligands to which the metal is
B
en M en
directly attached is called coordination number. M
B
The coordination numbers of Co and Al in [Co(Cl)(en)2]Cl and B
K 3[ Al(C2O4 )3 ] are 5 and 6 respectively.
In first complex, ‘en’ is a didentate ligand and ‘Cl’ is a A A
unidentate ligand. (b) (d)
B
[Co(Cl)(en)2]Cl, coordination number = 1 + 2 ´ 2 = 1 + 4 Þ 5 A B
So, the coordination number is 5.
M
For K 3 [Al(C2O4 )3 ], ‘C2O24 - ’ is a didentate ligand.
Coordination number = 3 ´ 2 = 6. B A
4. Optical activity is the ability of a chiral molecule to rotate the 7. Let the oxidation state of Cr in all cases is ‘ x’
plane of polarised light, measured by a polarimeter. A chiral (i) Oxidation state of Cr in [Cr(H2O)6 ]Cl 3
molecule does not have any plane of symmetry. If a molecule x + (0 ´ 6) + (-1 ´ 3 ) = 0
possess any plane of symmetry, then it is an achiral molecule. or x + 0 - 3 = 0 or x = + 3
Given options (a), (b) and (d) possess plane of symmetry. (ii) Oxidation state of Cr in [Cr(C6H6 )2 ]
x + (2 ´ 0) = 0 or x = 0
Coordination Compounds 249
(iii) Oxidation state of Cr in 10. [Pt(Cl)(py)(NH3 )(NH2OH)]+ is square planar complex. The
K2[Cr(CN)2 (O)2 (O2 )(NH3 )] structures are formed by fixing a group and then arranging all
1 ´ 2 + x + (-1 ´ 2 ) + (-2 ´ 2 ) + (-2 ) + 0 = 0 the groups.
or 2 + x - 2 - 4 - 2 = 0 or x - 6 = 0 Py Py
NH3 NH3
hence x = + 6
Thus, +3, 0 and +6 is the answer. Pt Pt
8. If the reactant is cis isomer than following reaction takes place.
Cl NH2OH HOH2N Cl
Br Br Br
NH3 Br NH3 Br NH3 Br
Py Cl
Br–
+
Pt
NH3 NH3 NH3 Br NH3 NH3 HOH2N NH3
NH3 NH3 Br
Cis-isomer Facial Meridonial Hence, this complex shows three geometrical isomers.
i.e. two isomers are produced. If the reactant is trans isomer than 11. Optical isomerism is exhibited by only those complexes which
following reaction takes place. lacks elements of symmetry. [Co(NH3 )3 Cl 3] shows facial as
Br Br well as meridional isomerism. But both the forms contain plane
NH3 NH3 NH3 NH3 of symmetry. Thus, this complex does not exhibit optical
Br–
isomerism.
12. First of all, the compound has complex positive part
NH3 NH3 NH3
‘‘[Co(H2O)4 (NH3 )2 ]3+ therefore, according to IUPAC
Br
conventions, positive part will be named first. Secondly, in
Br Br writing name of complex, ligands are named first in alphabetical
Trans Meridonial order, irrespective of its charge, hence “ammine” will be written
i.e. only 1 isomer is produced. Thus, statement (I) and (III) are prior to “aqua”. Therefore, name of the complex is
correct resulting to option (b) as the correct answer. [Co(H2O)4 (NH3 )2 ]Cl 3. Diamminetetraaqua cobalt (III)
chloride.
9. Cl Cl
Cl NOTE In alphabetical order, original name of ligands are
considered not the initials of prefixes. Also, special precaution
en Co en Co en should be taken in spelling name of NH3 ligand as it is ammine.
:
:
:
[Co(NH3 )4 Cl 2 ]Cl can exist in both cis and trans forms that are
given below: dsp2
Cl + NH3 +
d 8 -configuration in strong ligand field gives dsp2-hybridisation,
H 3N NH3 H3N Cl hence square planar geometry.
Co Co Ni 2+ + 4Cl – ¾¾® [NiCl 4 ]2–
:
:
:
trans-[Co(NH3)4Cl2]Cl cis-[Co(NH3)4Cl2]Cl
(optically inactive) (optically inactive) sp2
[Co(NH3 )3 Cl 3 ] exists in fac and mer-isomeric forms and both d -configuration in weak ligand field gives sp 3-hybridisation,
8
are optically inactive. hence tetrahedral geometry. Ni 2+ with H 2O forms
NH3 NH3 [Ni(H 2O)6] 2+ complex and H 2O is a weak ligand.
Cl NH3 Cl NH3 3d
:
:
:
:
Co Co
4s 4p 4d
Cl NH3 Cl Cl
:
:
:
:
:
:
Cl NH3
fac-isomer mer-isomer sp3d2
(optically inactive) (optically inactive)
Therefore, [Ni(H 2O)6] 2+ has octahedral geometry.
250 Coordination Compounds
14. HOOCH2C CH2COOH 19. Both [Pt(en)2 Cl 2 ]Cl 2 and [Pt(NH3 )2 Cl 2 ] are capable of showing
N—CH2CH2—N
HOOCH2C CH2COOH geometrical isomerism.
H2O NH3
Pt NH2
NH2 NH2
H3N Cl Cl Cl NH2 O
trans 3+
Co3+ O Co O Co3+
O NH2 O Cl
C. [Co Br2Cl 2 ]2- sp3 tetrahedral
Cl Cl O
NH2
Cl
[PtBr2Cl 2 ]2- dsp2 square planar
Cis Trans Cis
D. [Pt (NH3 )3 (NO3 )]Cl [ Pt (NH3 )3 (NO3 )Cl ] Cl
Cl
[ Pt (NH3 )3 Cl ] NO3 ] NH2
NH2 NH2 O
ionisation Co3+
Co3+
[Pt(NH3 )3 Cl]Br [ Pt (NH3 )3 Cl ] Br O NH2 O
O
[ Pt (NH3 )3 Br ] Cl
ionisation Cl
Cis Trans
Coordination Compounds 251
24. All six complex will show cis-trans isomerism 27. (i) [Co(NH3 )5 Cl]2+ (ii) Li[AlH4 ]
Cl
en + + 28. [Cr(NH3 )5 CO3 ]Cl
Cl : pentaamminecarbonatochromium (III) chloride.
Co 3+ and en Co 3+ en 29. (i) [Co(NH3 )5 ONO]Cl 2
: pentaamminenitritocobalt (III) chloride.
Cl (ii) K3[Cr(CN)6 ] : potassium hexacyanochromate (III)
en
cis Cl
trans
O
Topic 2 Bonding and Important Property
O
O 3–
Cl 3–
of Coordination Compounds
O Cl O O 1. The compound used in the treatment of lead poisoning is EDTA.
O O
Medication occurs through chelation therapy. Calcium
Cr3+ and Cr3+ disodium ethylenediamine tetraacetic acid chelates divalent
metal ion such as Pb2 + from plasma and interstitial body fluids.
Cl O O O
O O
O Cl The metal displaces Ca and is chelated, mobilised and usually
trans excreted. Less then 5% CaNa 2EDTA is absorbed in the
O O
gastrointestinal tract and it possibly increases the absorption of
+ + – Pb present in the tract. Therefore, it is not recommended for oral
OH2 OH CN
use. It is usually given intravenously.
H2 O OH H2O OH2 NC NH3
Fe3+ and Fe3+ Fe3+ and 2. Complete removal of both the axial ligands (along the z-axis)
NC NH3 from an octahedral complex leads to the following splitting
H2O OH H2 O OH2
OH2 OH CN pattern.
cis trans cis
dx2–y 2
– 2+ 2+
NH3 en Cl
dxy
NC CN NH3 Energy
Co 3+ and en Co 3+ en eg
Fe3+
NC CN Cl
en dz2
NH3 NH3 t2g
cis trans
trans
2+
2+
NH3 Cl dxzdyz
H3N
H3N NH3
Cl The single electron in the dx2 - y2 orbital is being repelled by four
Co3+ and Co3+
NH3
ligands, while the electron in the dz2 orbital is only being
H3 N OH2 H3N
repelled by two ligands. Thus, the energy of the dx2 - y2 increases
NH3 OH2
relative to that of dz2 . A more stable arrangement arises when
cis trans
both the eg electrons pair up and occupy the lower energy dz2
25. mmol of complex = 30 ×0.01 = 0.3 orbital. This leaves the dx2 - y2 orbital empty.
Also, 1 mole of complex [Cr(H2O)5Cl]Cl2 gives only two moles Thus, four ligands can now approach along + x , - x, + y and - y
of chloride ion when dissolved in solution directions without any difficulty as dx2 - y2 orbital is empty.
However, ligands approaching along + z and -z directions meet
[Cr(H2O)5 Cl]Cl 2 ¾® [Cr(H2O)5 Cl]2+ + 2Cl – very strong repulsive forces from filled dz2 orbitals. Thus, only
Þ mmol of Cl – ion produced from its 0.3 mmol = 0.6 four ligands succeed in bonding to the metal. A square planar
complex is formed, the attempt to form an octahedral complex
Hence, 0.6 mmol of Ag+ would be required for precipitation. being unsuccessful.
Þ 0.60 mmol of Ag+ = 0.1M × V(in mL) Þ V = 6 mL Key Idea Crystal field splitting occurs due to the presence
3.
PPh3 of ligands in a definite geometry. In octahedral complexes
26. Cl Cl CO
the energy of two, eg orbitals will increase by (0.6) D o and
Rh Rh that of three t2g will decrease by (0.4) D o .
H3N CO H 3N PPh3 The complex ion that will lose its crystal field stabilisation
energy upon oxidation of its metal to +3 state is [ Fe(phen)3 ]2+ .
Cl PPh3
-e-
Rh [Fe(phen)3 ]2+ ¾¾® [Fe(phen)3 ]3+
OC H 3N
252 Coordination Compounds
In [Fe(phen)3 ]2+ , electronic configuration of Fe2+ is 3d6 4 s0. (b) [Co(Cl)(NH3 )5 ]2+ is a low spin octahedral complex of Co3+ .
Phenanthrene is a strong field symmetrical bidentate ligand. The It absorbs low energy yellow light and high energy
splitting of orbital in Fe2+ is as follows: complementary violet light will be shown off. Thus,
statement (b) is correct.
eg
(c) [Fe(H2O)6 ]2+ and [Cr(H2O)6 ]2+ are the high-spin octahedral
+0.6 Do complexes of Fe2+ (3d6 , n = 4 ) and Cr 2+ (3d 5 , n = 5) ions
Fe2+ and weak field ligand, H2O respectively. So, spin-only
–0.4 Do magnetic moment = n(n + 2) of the complexes.
t2g [Fe(H2O)6 ]2+ , m 1 = 4 (4 + 2)
CFSE = 6 ´ -0.4 Do = -2.4 Do . (n = 4 ), = 24 = 4.89 BM
The splitting of orbital and arrangement of electrons in Fe3+ is as [Cr(H2O)6 ]2+ , m 2 = 5(5 + 2)
follows :
(n = 5), = 35 = 5.92 BM
eg So, m 1 » m 2.Thus, statement (c) is correct.
(d) [Ni(NH3 )4 (H2O)2 ]2+ is also a high-spin octahedral complex
+0.6 Do
Fe3+
of Ni2+ (3d 8 , n = 2)
–0.4 Do m = 2(2 + 2) = 8 = 2.83 BM
t2g Thus, statement (d) is correct.
CFSE = 5 ´ -0.4 Do = -2. 0 Do 6. Key Idea The wavelength (l ) of light absorbed by the
Fe2+ upon oxidation of its metal to +3 state lose its CFSE from complexes is inversely proportional to its D 0 CFSE
-2.4 D o to -2.0D o . (magnitude). D 0 (CFSE) µ 1 / l
4. Key Idea Crystal field stabilisation energy (CFSE) for The complexes can be written as:
octahedral complexes = (-0.4 x + 0.6 y)D o I. [CoCl(NH3 )5 ]2+ º [Co(NH3 )5 (Cl)]2+ ]
where, x = number of electrons occupying t2g orbital. II. [Co[NH3 ]5 H2O]3+ º [Co(NH3 )5 (H2O)]3+
y = number of electrons occupying eg orbital. III. [Co(NH3 )5 ]3+ º [Co(NH3 )5 (NH3 )]3+
CFSE for tetrahedral complexes So, the differentiating ligands in the octahedral complexes of
= (-0.6x + 0.4 y)D t Co (III) in I, II and III are Cl s, H2O and NH3 respectively. In the
where, x = number of electrons occupying e orbital. spectrochemical series, the order of this power for crystal field
y = number of electrons occupying t orbital. splitting is Cl - < H2O < NH3.
In [Fe(H2O)6 ]Cl2, H2O is a weak field ligand, so it is a high So, the crystal field splitting energy (magnitude) order will be
spin (outer orbital) octahedral complex of Fe2+ . DCFSE
0 (I) < DCFSE
0 (II) < DCFSE
0 (III)
eg and the order of wavelength (l ) of light absorbed by the
Fe2+(3d6) = complexes will be
t2g é 1ù
CFSE
l (I) > l (II) > l (III) êëQ Energy (D 0 ) µ l úû
\ CFSE = (-0.4 x + 0.6 y)D o
= [ -0.4 ´ 4 + 0.6 ´ 2 ]D o = - 0.4 Do 7. The degenerate orbitals of [Cr(H2O)6 ]3+ are dxz and d yz.
In K2[NiCl 4 ], Cl - is a weak field ligand, so it is a high spin Electronic configuration of Cr3 + is 3d 5 4 s1. The five d-orbitals
in an isolated gaseous atom or ion have same energy, i.e. they
tetrahedral complex of Ni2+ .
are degenerate. This degeneracy has been removed due to the
t ligand electron–metal electron repulsions in the octahedral
Ni2+(3d6)= complex to yield three orbitals of lower energy, t2g set and two
e orbitals of higher energy, eg set.
(eg)
\CFSE = (-0.6 ´ 4 + 0.4 ´ 4 )D t = - 0.8D t
dx 2–y2 dz2
5. The explanation of given statements are as follows : D0
(a) Ruby, a pink or blood-red coloured gemstone belongs to Free metal ion (t2g)
corundum (Al 2O3 , alumina) system which has trigonal dxy dxz dyz
crystalline lattice containing the repeating unit of
Al 2O3 – Cr 3+ . So, ruby does not belong to beryl lattice 8. [ Fe(H2O)6 ]2 Þ It will form 2 cationic species. i.e.
II
(Be3Al 2Si6O18 ). I. (i)As [ Fe(H2O)6 ]2+ Þ High spin octahedral complex of Fe2+ .
Thus, statement (a) is incorrect. Fe2+ : 3d6 , x = 4 (unpaired electrons)
m = 4 (4 + 2) BM = 4.9 BM
Coordination Compounds 253
III
or (ii) as [ Fe(H2O)6 ]3+ = High spin octahedral complex of Fe3+ . 11. The magnetic moment of the magnitude 5.9 BM suggest the
presence of 5 unpaired electrons in Mn(II). This can be cross
Fe3 + : 3d5 , x = 5, m = 5 (5 + 2) = 5.92 BM verified by putting the value (5) of unpaired electrons in the
[H2O is a neutral weak field ligand] formula, m = n(n + 2) BM
So, [ Fe(H2O)6 ]2+ will be the cationic specie, m = 4.9 BM. Thus, the valence electronic configuration of Mn(II) in the
[ Fe(CN)6 ] will have two anionic complexes complex is
II
II. (i) [ Fe(CN)6 ]4– Þ Low spin, octahedral complex of Fe2+ . Mn2+=
3d 4s 4p 4d
As CN- is a strong ligand it will pair up the electrons.
d2sp3
The octahedral homoleptic complex suggests
Fe2+(3d6) sp3d 2-hybridisation in the complex, i.e.
sp3d2-hybridisation
n=0, m=0 Mn2+=
III
or, (ii) [ Fe(CN)6 ]3– Þ Low spin octahedral complex of Fe3+ . 3d 4s 4p 4d
10. Key Idea In presence of strong field ligands, D 0 > p, for Therefore, Co 2+ and V 2+ contains same value of magnetic
fourth electron it is more energetically favourable to occupy moment (3.9 BM).
t2 g orbital with configuration t24geg0and form low spin complexes. 13. In K3 [Co(CN)6 ], Co have +3 oxidation state and electronic
The correct order of the spin only magnetic moment of metal ions configuration of Co3 + is [Ar ] 18 3d 6.
in the given low-spin complexes is V2+ > Cr 2+ > Ru 3+ > Fe2+ . 3d6 4s0 4p0
All the given complexes possess strong field ligands Co3+=
(CN, NH3 ). Hence, readily form low spin complexes.
As, CN - is a strong field ligands so it pairs up the de- s
Complex Oxidation Configuration Orbital No. of
state splitting unpaired 3d6
electrons \ [Co(CN)6]3–= XX XX XX XX XX XX
eg Inner orbital
d2sp3 -hybridised
complex
[V(CN)6]4– V
2+ 3
t2g eg
0
3 (6e- pairs donated
by 6 CN- ligands)
t2g
In an octahedral complex, the metal is at the centre of the
eg octahedron and the ligands are at the six corners. The lobes of the
[Cr(NH3)6]2+ Cr2+ 4
t2g eg0 2 eg orbitals (dx2 - y2 and dz2 ) point along the axes x , y and z under
t2g
the influence of an octahedral field, the d- orbitals split as follow.
eg
5 0
dx2-y2, dz 2
[Ru(NH3)6]3+ Ru3+ t2g eg 1
t2g
eg
Average dxy, dyz, dxz
d-orbitals energy of
[Fe(CN)6]4– Fe2+ 6 0
t2g eg 0 Splitting of d-orbitals
in free ion the d-orbitals
t2g in a spherical in an octahedral
crystal field crystal field
254 Coordination Compounds
As the d-orbitals, i.e. dx2 - y2 and dz2 are vacant. Hence, these Total number of bridging CO ligands = 2
and the Co ¾ Co bond = 1
both orbitals are directly facing the ligands in K3 [Co(CN)6 ].
14. Mn 2 (CO)10 is an organometallic compound due to the 16. Coordination number is defined as the total number of ligands to
presence of Mn¾ C bond. The metal-carbon bond in which the metal is directly attached.
organometallic compounds possess both s and-p character. Here, C2O24 - is a bidentate ligand,
The M¾ C s bond is formed by the donation of lone pair of
¾
O¾
electrons from the carbonyl carbon into a vacant orbital of C¾O ¾
¾
the metal. The M¾ C p-bond is formed by the donation of M (Metal)
C¾O ¾
pair of electrons from a filled d-orbital of metal into vacant O ¾
¾
antibonding p* orbital of CO. The M ¾ L bonding creates a
and H2 O is a monodentate ligand, H2O M
synergic effect which strengthens the bond between CO and
the metal. So, total number of sites offered by C2O24 - and H2O ligands
The structure of Mn 2(CO)10 is shown below : around Th(IV) = Coordination number of Th (IV)
CO CO = 4 ´ 2(by C2O24 -) + 2 ´ 1(by H2O) = 10
CO CO
CO Mn Mn CO 17. (A) Co is present in vitamin B12 (iii) having molecular formula,
CO CO CO
II
CO C63H88 CoN14O14P.
15. The structure of Co2 (CO)8 (a polynuclear metal carbonyl) can (B) Zn is present in carbonic anhydrase (iv) in which three
be written as: histidine units and the —OH group coordinate with one Zn
(II) ion.
OC C CO (C) Rh is present in Wilkinson catalyst (i) having molecular
formula [(Ph 3P)3 RhCl] .
OC——Co——–Co——CO
(D) Mg is present in chlorophyll (ii) having molecular formula
OC C CO II
C55H70O6N4 Mg (chlorophyll-b).
18. The difference in the number of unpaired electrons of different metal ions in their high spin and low spin octahedral complexes are given in
the table below :
Metal ion Number of e- in high spin complex ( n1 ) Number of e- in low spin complax ( n2 ) n2 - n1
2+
Mn 3d 4s 4p 3d 4s 4p 5 -1 = 4
4d 4d
n1=5 n2=1
2+
Fe 3d 4s 4p 3d 4s 4p 4-0 = 4
4d 4d
n1=4 n2=0
Ni 2+ 3d 4s 4p
4d
n1=2
2+
Ni does not form low spin octahedral complexes.
2+
Co 3d 4s 4p 3d 4s 4p 3 -1 = 2
4d 4d
\ n1=3 \ n1=1
Coordination Compounds 255
19. According to the situation given in question, reactions are as The highest value of n in transition metal complex is 5 in its
follows: d 5-configuration.
III III \ m = 5(5 + 2) BM = 5.916 BM
CoCl3 + 2en ¾® [Co(en)2Cl2]Cl
·· ù
CH2 — N H2ú 24. ‘A’ absorbs yellow light of less energy and emits violet light of
high energy (complementary colour) because H2O is a weak
en = ethylene-1, 2-diamine, ½ ú
field ligand. But in case of ‘B’, due to presence of strong field
CH2 — NH2 ú
·· úû ligand (NH3 ), it absorbs high energy violet light and emits low
energy complementary yellow colour.
Cl
en D(CFSE) is measured with help of wavelength of the colour
Cl absorbed by the given coordination compound, as
III c
Co Cl en Co en Cl D O = hn = h ´
l
Cl Both the complexes contain three unpaired electrons. Therefore,
en
Cl both are paramagnetic.
‘A’ Optically active ‘B’ Optically inactive
(cis-form) (trans-form) 25. Fluoride ions help in making teeth enamel harder by converting
(Violet) (Green) [3Ca 3 (PO4 )2 × Ca(OH)2 ] i.e. Hydroxy apatite to
[3Ca 3 (PO4 )2 × CaF2 ] i.e., Fluorapatite (Harder teeth enamel) via
20. Wilkinson’s catalyst is a s-bonded organometallic compound following reaction:
[(Ph 3P)3 RhCl] . It is commercially used for hydrogenation of [3Ca 3 (PO4 ) 2 × Ca(OH) 2 ] + 2F - ¾® [3Ca 3 (PO4 ) 2 × CaF2 ] + 2OH-
From
alkenes and vegetable oils (unsaturated). drinking
water
IUPAC name Chloridotris (triphenylphosphene) rhodium (I).
Number of moles of solute
21. In homoleptic complexes, the metal atom/ion is linked to only 26. Molarity (M) =
Volume of solution (in L)
one type of ligand. Assuming, ligands are neutral, the octahedral
complexes of M 3+ can be, \ Number of moles of complex
[ M (L1 )6 ]3+ ,[ M (L2 )6 ]3+ and [ M (L3 )6 ]3+ =
Molarity ´ volume (in mL)
(I) (II) (III)
1000
l Absorption Green Blue Red (wavelength) 01
. ´ 100
= = 0.01 mole
So, lLIII
3 > lL1 > lL2
I II 1000
1 Number of moles of ions precipitate
\ D°absorption : DLII2 > DLI1 > DLIII3 [Q Energy (D, CFSE) µ ]
l
. ´ 1022
12
We know, ligand strength µ D°absorption = = 0.02 moles
6.02 ´ 1023
So, the increasing order of the ligand strength will be,
L3 < L1 < L2 \Number of Cl - present in ionisation sphere
Number of moles of ions precipitated 0.02
22. All of the complex given are the octahedral complexes of Co = = =2
Number of moles of complex 0.01
(III) except K 2[CoCl 4], which is a tetrahedral complex of Co
(II) (sp3-hybridised). \2 Cl - are present outside the square brackets, i.e. in ionisation
é 4 ù sphere. Thus, the formula of complex is
We know, Dt < Do êëQ D t = 9 D o úû
[Co(H2 O) 5 Cl]Cl 2 ×H2 O.
So, the octahedral complexes (a, b, c) have higher D o values 27.
than that of tetrahedral, K2[CoCl 4 ]. Complex ion Electronic Number of unpaired
Now, for the complexes, a, b and c, configuration of electrons (n)
the magnitude of D o µ ligand strength, which is based on their metal ion
positions in the spectrochemical series.
[Cr(H2O)6 ]2+ Cr 2+ ; [Ar] 3 d 4 ;4
Cl - < H2O < NH3 < CN-
Hence, K3[Co(CN)6 ] will have the highest D value. [Fe(H2O)6 ]2+ Fe 2+ ; [Ar] 3 d6 ; 4
23. The spin only magnetic moment (m) (in BM) is given by [Mn(H2O)6 ]2+ Mn2+ ; [Ar] 3 d 5 ;5
m (in BM) = n(n + 2)
where, n = number of unpaired electrons [CoCl 4 ]2- Co 2+ ; [Ar] 3 d 7 ;3
256 Coordination Compounds
28. 1
µ
Compounds Hybridisation Unpaired Magnetic Wavelength of light absorbed
electron(s) character l L1 L2 L3 L4
Ni(CO)4 sp3 No Diamagnetic Absorbed light Red Green Yellow Blue
[NiCl 4 ]2 - sp3 two Paramagnetic Wavelength of absorbed light decreases.
[Co(NH3 )4 Cl 2 ]Cl 3 2
sp d No Diamagnetic \ Increasing order of energy of wavelengths absorbed reflect
3 2 greater extent of crystal field splitting, hence, higher field
Na 3[CoF6 ] sp d three Paramagnetic
strength of the ligand.
Na 2O2 — No Diamagnetic Energy blue (L4 ) > green (L 2 ) > yellow (L 3 ) > red (L 1 )
(O22 - ) \ L4 > L2 > L3 > L1 in field strength of ligands.
CsO2 — One Paramagnetic
32. PLAN Spin only magnetic moment have the formula n( n + 2) BM,
O-2 (superoxide where N is the number of unpaired electrons. In the presence of
ion is weak ligand (as H 2O, Cl - , F - ) there is no pairing of electrons,
paramagnetic) and electrons donated by ligands are filled in outer vacant
orbitals.
29. KMnO4 ¾® K + + MnO-4 In the presence of strong ligand (as CN- , CO, NH3 , en)
electrons are paired and electrons from ligands are filled in
\ In MnO-4 , Mn has + 7 oxidation state having no electron in available inner orbitals
d-orbitals.
number of
Unpaired
electrons
Complex
It is considered that higher the oxidation state of metal, greater is
Atomic
Magnetic
O.N.
E.C.
moment
the tendency to occur L ®M charge transfer, because ligand is
able to donate the electron into the vacant d-orbital of metal.
Since, charge transfer is laporate as well as spin allowed,
therefore, it shows colour. P : [FeF6 ]3 - 26 +3 [Ar]3d 5 5 35 BM
Time saving Technique There is no need to check all the four weak ligand
options. Just find out the oxidation state of metal ion. If Q : [V(H2O)6 ]2+ 23 +2 [Ar] 3 15 BM
oxidation state is highest and ligand present there is of electron
weak ligand
donating nature, gives LMCT, which shows more intense
colour. R :[Fe(H2O)6 ]2+ 26 +2 [Ar]3d6 4 24 BM
30. This problem is based on conceptual mixing of properties of Thus, order of spin-only magnetic moment = Q < R < P
lithium oxide and preparation, properties of coordination
33. In the given complex, NiCl 2 {P (C2H5 )2 (C6H5 )}2 nickel is in
compounds. To answer this question, keep in mind that on
adding acid, ammine complexes get destroyed. + 2 oxidation state and the ground state electronic configuration
(a) Li 2O + KCl ¾® 2LiCl + K2O of Ni 2+ ions in free gaseous state is
This is wrong equation, since a stronger base K2O cannot be 3d 8 4s0 4p0
generated by a weaker base Li 2O. Ni2+
(b) [CoCl(NH3 )5 ]+ + 5H+ ¾® Co2+ ( aq) + 5 NH+4 + Cl -
For the given four coordinated complex to be paramagnetic, it
This is correct. All ammine complexes can be destroyed by
must possess unpaired electrons in the valence shell. To satisfy
adding H Å . Hence, on adding acid to [CoCl(NH3 )5 ], it gets
this condition, four lone pairs from the four ligands occupies the
converted to Co2+ ( aq)+ NH+4 and Cl - . four sp3-hybrid orbitals as :
OH-
(c) [Mg (H2O)6 ]2+ + EDTA4- ¾¾® [ Mg( EDTA)]2+ + 6H2O Ni2+
:
:
:
:
Excess
This is wrong, since the formula of complex must be sp3
[Mg(EDTA)]2+ as EDT. Therefore, geometry of paramagnetic complex must be
(d) The 4th reaction is incorrect. It can be correctly tetrahedral. On the otherhand, for complex to be diamagnetic,
represented as there should not be any unpaired electrons in the valence shell.
2CuSO4 + 10KCN ¾® 2K3[Cu(CN)4 ] This condition can be fulfilled by pairing electrons of
+ 2K2SO4 + (CN)2 3d-orbitals against Hund’s rule as
31. Arrange the complex formed by different ligands L 1 , L 2 , L 3 and Ni2+
:
:
:
34. For a diamagnetic complex, there should not be any unpaired 42. [NiCl 4 ]2 - : Ni 2+ (3d 8 )
electron in the valence shell of central metal. Tetrahedral
sp3-hybridisation
In K3[Fe(CN)6], Fe (III) has d 5-configuration (odd electrons),
hence it is paramagnetic.
In [Co(NH3)6]Cl3, Co (III) has d 6-configuration in a strong
ligand field, hence all the electrons are paired and the complex is 3d 8 4s
diamagnetic. Under influence of weak ligand field
In Na3[Co(ox)3], Co (III) has d 6-configuration and oxalate being
In all other complexes, hybridisation at central metal is dsp2 and
a chelating ligand, very strong ligand and all the six electrons
complexes have square planar geometries.
remains paired in lower t2g level, diamagnetic.
43. In 1 L solution, there will be 0.01 mole of each [Co(NH3 )5 SO4 ]
In [Ni(H2O)6]Cl2, Ni (II) has 3d 8 -configuration and H2O is a
Br and [Co(NH3 )5 Br]SO4. Addition of excess of AgNO3 will
weak ligand, hence
give 0.01 mole of AgBr. Addition of excess of BaCl 2 will give
3d 0.01 mole of BaSO4.
44. In MnO-4 , Mn + 7 has 3d 0 configuration.
Paramagnetic
45. In Ni (CO)4, Ni is in 3d 10 state due to strong ligand field produced
:
:
:
:
:
:
3 2
sp d by CO. Hence, Ni is sp3-hybridised and complex is tetrahedral. In
NiCl 2 (PPh 3 )2 , Ni 2+ has 3d 8 -configuration. Due to weak ligand
In K2[Pt(CN)4], Pt(II) has d 8 -configuration and CN– is a strong
ligand, hence all the eight electrons are spin paired . Therefore, field, Ni is sp3-hybridised and complex is tetrahedral.
complex is diamagnetic.
46. Cu 2+ + CN- ¾® CuCN ¯
In [Zn(H2O)6](NO3)2, Zn (II) has 3d 10configuration with all the CuCN + 3CN- ¾® [Cu(CN)4 ]3 -
ten electrons spin paired, hence diamagnetic.
47. Fe in [Fe(H2O)6 ]2+ has maximum (four) unpaired electrons, has
35. Magnetic moment = 2.83 BM indicates that there is two
highest paramagnetism.
unpaired electrons.
48. In Ni (CO)4, Ni has 3d 10-configuration, diamagnetic. In
u = n(n + 2) BM = 8 BM = 2.82 BM Ni (CN)4 ]2- , Ni has 3d 8 -configuration but due to strong ligand
field, all the d-electrons are spin paired giving
In [NiCl 4 ]2- , Ni has d 8 configuration and Cl - is a weak ligand : dsp2-hybridisation, diamagnetic.
3d In [NiCl 4 ]2- , Ni has 3d 8 -configuration and there is two unpaired
Ni2+
:
:
:
:
40. In CO, bond order = 3. In metal carbonyls like Fe(CO)5, due to Fe(3d6,4s2) Ni(3d8,4s2)
dp - pp back-bonding, bond order of CO decreases slightly 3d 4s 4p 3d 4s 4p
therefore, bond length increases slightly.
41. In Hg [Co(SCN)4 ], Co2+ has 3d 7 configuration. SCN - produces [Fe(CO)5] [Ni(CO)4]
weak ligand field, no pairing of electrons in d-orbitals occurs
against Hund’s rule, hence : Rearrangement Rearrangement
2+ dsp3 sp3
Co : m = 3 (3 + 2) BM = 15 BM
3d7 Hence, this statement is incorrect.
258 Coordination Compounds
(ii) Statement (b) Carbonyl complexes are predominantly low Statement (d) According to CFT, absorption of light by
spin complexes due to strong ligand fields. Hence, this coordination complexes depends upon CFSE i.e., crystal field
statement is correct. splitting energy (D 0)as
(iii) Statement (c) For central metal lowering of oxidation state 1
D0 µ
results to increase in electron density on it. This in turn l
results to increase in extent of synergic bonding. Thus, we
Among the complexes given [Co (en) (NH3)4 ]3+ has more D 0
can say ‘‘metal carbonyl bond strengthens, when oxidation
state of metal is lowered’’. value as compared to complex [Co(en) (NH3)3(H2O) ]3+ . Thus,
Hence, it is a correct statement. [Co (en) (NH3)3(H2O) ]3+ absorbs the light at longer wavelength
(iv) Statement (d) Increase in positive charge on metal (i.e., for d-d transition.
increase in oxidation state) results to decrease in synergic Hence, this statement is also correct.
bonding strength. Note : For any complex, the value of D 0 can be calculated via the
This in turn makes C—O bond stronger instead of weaker. difference or gap between eg and t2g values.
Hence this statement is also incorrect.
Excess NH 4 OH / NH 4 Cl
51. Statement wise explanation is 52. [Co(H2O) 6 ] Cl 2 ¾¾¾¾¾¾¾® Co(NH3 ) 6 ]Cl 3
O 2 (Air) Y
Pink (X)
Statement (a) [Co(en)(NH3 )3 H2O ]3+ have following 2 2+ -
geometrical isomers. [Co(H2 O) 6 ] + 4Cl ¾® [CoCl 4 ]2 -
X (Excess) blue Z
NH3 NH3
NH3 H2O
(a) Since NH3 is moderately strong ligand, hybridisation of
cobalt in Y is d 2sp3.
en Co en Co
(b) Cobalt is sp3-hybridised in [CoCl 4 ]2- .
NH3 NH3 (c) [Co(NH 3 ) 6 ]Cl 3 + 3AgNO3 (aq) ¾® 3AgCl ¯
H2O NH3 Y
Fac Mer (d) [CoCl 4 ]2- + 6H2O q [Co(H2O)6 ] 2+ + 4Cl - ; DH < 0
[ M ( AA )b3 c] type complex Blue Pink
Hence, this is correct statement. 53. In the complex [Fe(H2O)5 NO]SO4, Fe is in +1 oxidation state
Statement (b) If bidentate ligand ‘en’ is replaced by two because NO is in +1 state. Also NO is a strong ligand, complex
cyanide ligands then [Co(NH3 )3 (H2O)(CN)2 ]+ is formed. has 3d 7 -configuration at Fe(I) as :
It is [ Ma3 b2 c ] type complex which has following 3 geometrical
isomers.
NH3 NH3
N C NH3 N C NH3
3d7 Strong ligand field
Co Co
N C NH3 H2O NH3
H2O CN
(Fac) Fac with respect to NH3 and
Mer with respect to —CN Three unpaired electrons
NH3
54. A is diamagnetic, square planar complex because of strong
N C H2O
ligand field of CN- .
Co
N C NH3 Ni(CN)42 –(Ni2+) :
NH3
(Mer) dsp2
Diamagnetic
Hence, this statement is also correct.
7 2 B is paramagnetic, tetrahedral complex because of weak ligand
Statement (c) Co metal has [ Ar ]3d 4 s configuration while in
[Co(en)(NH3 )3 (H2O )]3+ it is in +3 oxidation state. Thus, Co 3+ field of Cl - .
has [Ar]3d6 configuration. NiCl42 –(Ni2+) :
3d 4s
Co3+ = sp3
Paramagnetic
As en is a strong ligand, so pairing will occur 55. Described in 2, A has dsp2 hybridisation while B has
3d 4s
sp3-hybridisation of Ni.
56. For, P i.e. dsp2, It is seen in [Ni(CN)4 ]2 -
Due to the presence of all paired electrons it show diamagnetic
behaviour rather than paramagnetic. Ni ¾[Ar]3d 8 4 s2
Hence, this statement is incorrect. Ni2+ ¾[Ar]3d 8
Coordination Compounds 259
Thus, in [Ni(CN)4 ]2 - 3d 4s 4p 4d
Fe2+
dsp2-hybridisation
F– F– F– F– F– F–
3d 4s 4p
Ni2+ Structure : Octahedral
So, 1 is the correct match for R.
CN– CN– CN– CN–
For S i.e., d 2 sp 3
Structure : Square planar
It is seen in [Ti(H2O)3 Cl3 ] and [Cr(NH3 )6 ]3+
So correct match for P is 6.
Ti ¾[Ar]3d 2 4 s2
For Q i.e., sp3
Ti3+ ¾[Ar]3d 1
It is seen in [FeCl4 ]2 - and Ni(CO)4
3d 4s 4p
Fe - [Ar]3d6 4 s2
Ti3+
2+ 6
Fe - [Ar]3d
3d 4s 4p Here, both H2O and Cl are weak ligands
Fe2+ So, in [Ti(H2O)3 Cl3 ]
d2sp3 hybridisation
As Cl - is a weak ligand so when it approaches towards central
metal pairing of unpaired electrons does not take place. 3d 4s 4p
Ti3+
Thus, in [FeCl4 ]2 -
H2O H2O H2O Cl– Cl– Cl–
sp3 hybridisation
3d 4s 4p Structure Octahedral
Fe2+ Likewise in [Cr(NH3)6]3+
Cl– Cl– Cl– Cl– Cr ¾ [Ar]3d 5 4 s1
Structure-Tetrahedral Cr 3+ ¾ [Ar]3d 3 4 s0
Likewise in Ni(CO)4 3d 4s 4p
Ni ¾[Ar]3d 8 4 s2 Cr3+
3d 4s 4p
Ni
Here, NH 3 is also a weak field ligand so due to its approach no
pairing takes place in Cr.
As CO is a strong ligand, hence when it approaches towards Thus, In [Cr(NH3 )6 ]3+
central metal atom pairing of unpaired electron of central atom
d2sp3 hybridisation
takes place.
Thus, in Ni(CO)4
3d 4s 4p
sp3 hybridisation
Cr3+–
3d 4s 4p
NH3 NH3 NH3 NH3 NH3 NH3
Ni
CO CO CO CO So for, S-2 and 3 are the correct match.
Structure Tetrahedral 57. PLAN This problem is based on concept of VBT and magnetic
properties of coordination compound.
So, for Q-4 and 5 are correct match.
Draw VBT for each coordination compound.
For R i.e., sp3d 2
If unpaired electron is present then coordination compound will
It is seen in [FeF6]4- be paramagnetic otherwise diamagnetic.
Fe ¾ [Ar]3d6 4 s2 Coordination compounds of [MA4 B2 ] type show geometrical
Fe 2+ ¾ [Ar]3d6 isomerism. Molecular orbital electronic configuration (MOEC)
for various coordination compound can be drawn using VBT as
3d 4s 4p 4d
Fe2+
260 Coordination Compounds
×× ×× ×× ××
×× K3[Fe(CN)6] : Fe
en en NH3 Cl Potassium ferricyanide
4s2
3d 6
n=0
[Fe(CN)6]3 - :
Magnetic property = diamagnetic
Ionisation isomers are [Pt(en)2 (NH3 )Cl]NO3 d 2 sp3
and [Pt(en)2 NH3 (NO3 )]Cl Has one unpaired electron, paramagnetic
D. MOEC of [Co(NH3 )4 (NO3 )2 ]NO3 61. False : Lobes of 3dx2 - y2 orbitals lies in X Y plane on the X and
×× ×× ×× ×× ×× ×× Y coordinate axes, therefore electron density of dx2 - y2 orbital in
X Y plane is non-zero.
NH3NH3 NH3 NH3NO3NO3
n=0 62. When S is donor atom of SCN- , it produces weak ligand field
and forms high spin complex as
Magnetic property = Diamagnetic
Geometrical isomers are [ Fe(SCN)6 ]3- : Fe3+ (3d 5 ) =
4s 4p 4d
NO3 NH3
H3N NH3 NO3 NH3 3d 5(n-5) sp3d2
CO and CO Spin only magnetic moment (m s ) = 5 (5 + 2) BM = 35 BM
H3N NH3 NO3 NH3
In case of CN- ligand, carbon is the donor atom , it produces
NO3 NH3 strong ligand field and forms low spin complex as
Trans Cis [Fe(CN)6 ]3- : Fe3+ (3d 5 )
Thus, magnetic property and isomerism in given coordination 3d 4s 4p
compound can be summarised as
(P) [Cr(NH3 )4 Cl 2 ]Cl ® Paramagnetic and exhibits cis-trans d2sp3
isomerism (3) Spin only magnetic moment (m s ) = 1 (1 + 2) BM = 3 BM
(Q) [Ti(H2O)5 Cl](NO3 )2 ® Paramagnetic and exhibits
ionisation isomerism (1) Hence, difference in spin only magnetic moment
(R) [Pt(en)(NH3 )Cl]NO3 ® Diamagnetic and exhibits = 35 - 3 » 4 BM
ionisation isomerism (4) C O
63. Br
(S) [Co(NH3 )4 (NO3 )2 ]NO3 ® Diamagnetic and exhibits O
==
(II)
cis-trans isomerism (2) Et3P Fe C ¾ CH 3
\ P ® 3, Q ® 1, R ® 4, S ® 2 acetylbromidodicarbonylbis
Et3P
Hence, (b) is the correct choice. C O (triethylphosphine)iron (II)
Coordination Compounds 261
CH2
CO 1 A gives white precipitate AgCl with excess of AgNO3 which
4
O Co O
2 dissolve in excess ammonia. Therefore, A must be
3 CO [Cr(NH3 )4 Br2 ]Cl.
O O
Each N has four N ¾ Co ¾ O bonds thus total eight N ¾ Co ¾ O B gives a pale yellow precipitate with excess of AgNO3, which
bonds. dissolve in concentrated ammonia solution. Therefore,
H precipitate is AgBr and complex B is [Cr(NH3 )4 ClBr]Br.
65. H
O O In both A and B, hybridisation of chromium is d 2sp3 and
N N CH 3 magnetic moment : m = n (n + 2) BM = 0
H 3C
C C
(3d6, strong ligand, no unpaired electron)
Ni
C C 69. NH3 3+ 2–
H 3C N N CH 3 H 3N NH3 NC CN
O O Co Ni
H H
Ni-DMG complex H 3N NH3 NC CN
Oxidation state of Ni is +2 and hybridisation is dsp . 2 NH3
d 2sp3-octahedral dsp2-square planar
m = 0 (no unpaired electron) hence, diamagnetic. CO
66. The spin-only magnetic moment (m) of the complex is 1.73 BM.
It indicates that nucleus of complex, chromium ion has one Ni
CO
unpaired electron. So, the ligand NO is unit positively charged. OC CO
K2[Cr(NO) (CN)4 (NH3 )] sp3-tetrahedral
potassium amminetetracyanonitrosoniumchromate (I)
70. A has no water molecules of crystallisation.
Cr+1 : Hence, A is [Cr(H2O)6 ]Cl 3.
5 0 Both B and C loses weight with concentrated H2SO4, therefore,
3d 4s
both B and C have some water molecules of crystallisation.
Cr(I) “under influence of strong ligand field”.
Moreover, weight loss with C is just double of the same with B
indicates that number of water molecules of crystallisation of C
d 2sp3
is double of the same for B. Therefore, B has one and C has two
Octahedral water molecules of crystallisation.
NO 2– B = [Cr(H2O)5 Cl]Cl 2 × H2O, C = [Cr(H2O)4 Cl 2 ]Cl × 2H2O
NC CN 71. (i) [Ti(NO3 )4 ]: Ti 4+ (3d 0 ) No d-electron, no d-d transition
Cr possible, colourless.
(ii) [Cu(NCCH3 )]BF4 : Cu + (3d 10 ) All d-orbitals are
NC NH3 completely filled, no d-d transition possible, colourless.
CN (iii) [Cr(NH3 )6 ]Cl 3 : Cr 3+ (3d 3 ) Complex has allowed
Octahedral geometry d-d-transitions from t2g to eg level, hence coloured.
67. [NiCl 4 ] 2 - : Ni 2+ (3d 8 ), weak ligand field. (iv) K3[VF6 ]: V3+ (3d 2 ) Complex has allowed d-d-transitions
from t2g to eg level, hence coloured.
Ni2+(3d 8) :
72. I- is a strong reducing agent, reduces Cu 2+ to Cu + and
sp3 precipitate out as stable CuI.
2. The idea of froth floatation method came from a person X and 8. The Mond process is used for the (2019 Main, 8 April II)
this method is related to the process Y of ores. X and Y , (a) purification of Ni (b) extraction of Mo
respectively, are (2019 Main, 12 April I) (c) purification of Zr and Ti (d) extraction of Zn
(a) fisher woman and concentration 9. With respect to an ore, Ellingham diagram helps to predict the
(b) washer woman and concentration feasibility of its (2019 Main, 8 April I)
(c) fisher man and reduction (a) electrolysis (b) zone refining
(d) washer man and reduction (c) vapour phase refining (d) thermal reduction
3. The correct statement is (2019 Main, 10 April II) 10. The pair that does not require calcination is
(a) zone refining process is used for the refining of titanium. (2019 Main, 12 Jan II)
(b) zincite is a carbonate ore. (a) ZnO and MgO (b) ZnO and Fe2O3 × xH2O
(c) sodium cyanide cannot be used in the metallurgy of silver. (c) ZnCO3 and CaO (d) Fe2O3 and CaCO3 × MgCO3
(d) aniline is a froth stabiliser. 11. In the Hall-Heroult process, aluminium is formed at the
4. Match the refining methods Column I with metals Column II. cathode. The cathode is made out of (2019 Main, 12 Jan I)
(a) platinum (b) carbon
Column I Column II (c) pure aluminium (d) copper
(Refining Methods) (Metals)
12. The reaction that does not define calcination is
I. Liquation (A) Zr D
(a) Fe2O3 × XH2O ¾® Fe2O3 + XH2O (2019 Main, 11 Jan II)
II. Zone refining (B) Ni D
(b) ZnCO3 ¾® ZnO + CO2
III. Mond process (C) Sn D
(c) CaCO3 × MgCO3 ¾® CaO + MgO + 2CO2
IV. van Arkel method (D) Ga
D
(d) 2Cu2S + 3O2 ¾® 2Cu2O + 2SO2
(2019 Main, 10 April I)
(a) I- (C) ; II-(D); III-(B) ; IV-(A) 13. Match the ores ( Column A ) with the metals (Column B).
(b) I- (B) ; II-(C); III-(D) ; IV-(A)
(c) I- (C) ; II-(A); III-(B) ; IV-(D) Column A Column B
(d) I- (B) ; II-(D); III-(A) ; IV-(C) Ores Metals
5. The one that is not a carbonate ore is (2019 Main, 9 April II) A. Siderite P. Zinc
(a) siderite (b) calamine (c) malachite (d) bauxite B. Kaolinite Q. Copper
6. Assertion For the extraction of iron, haematite ore is used. C. Malachite R. Iron
Reason Heamatite is a carbonate ore of iron. D. Calamine S. Aluminium
(2019 Main, 9 April II)
(2019 Main, 11 Jan I)
Extraction of Metals 263
(a) A - P; B- Q; C - R; D- S (b) Al 2O3 is mixed with CaF2 which lowers the melting point of
(b) A - R; B- S; C - P; D- Q the mixture and brings conductivity
(c) A - Q; B- R; C - S; D- P (c) Al 3+ is reduced at the cathode to form Al
(d) A - R; B- S; C - Q; D- P (d) Na 3AlF6 serves as the electrolyte
14. The electrolytes usually used in the electroplating of gold 21. The metal that cannot be obtained by electrolysis of an
and silver, respectively, are (2019 Main, 10 Jan II) aqueous solution of its salts is (2014 Main)
(a) [Au(OH)4 ]- and [Ag(OH)2 ]- (a) Ag (b) Ca
(b) [Au(NH3 )2 ]+ and [Ag(CN)2 ]- (c) Cu (d) Cr
(c) [Au(CN)2 ]- and [Ag(CN)2 ]- 22. Sulphide ores are common for the metals (2013 Adv.)
(d) [Au(CN)2 ]- and [AgCl 2 ]- (a) Ag, Cu and Pb (b) Ag, Cu and Sn
(c) Ag, Mg and Pb (d) Al, Cu and Pb
15. Hall-Heroult’s process is given by (2019 Main, 10 Jan I)
Coke, 1673 K 23. In the cyanide extraction process of silver from argentite ore,
(a) ZnO + C ¾¾¾¾® Zn + CO
the oxidising and reducing agents used are (2012)
(b) Cr2O3 + 2Al ¾¾® Al 2O3 + 2Cr (a) O2 and CO respectively
(c) 2Al 2O3 + 3C ¾
¾® 4Al + 3CO2 (b) O2 and Zn dust respectively
(d) Cu2+ (aq) + H2 (g ) ¾
¾® Cu(s) + 2H+ (aq) (c) HNO3 and Zn dust respectively
(d) HNO3 and CO respectively
16. The correct statement regarding the given Ellingham
diagram is (2019 Main, 9 Jan II) 24. Oxidation states of the metal in the minerals haematite and
O magnetite, respectively, are (2011)
® 2Cu 2
+O 2 (a) II, III in haematite and III in magnetite
4Cu
(b) II, III in haematite and II in magnetite
–300 (c) II in haematite and II, III in magnetite
(d) III in haematite and II, III in magnetite
DGº (kJ/mol)
2C
+O
nO 2 ®2
–600 O2 ® 2Z CO 25. Native silver metal forms a water soluble complex with a
2Zn+ dilute aqueous solution of NaCN in the presence of
O3 (a) nitrogen (b) oxygen (2008, 3M)
3 Al 2
® 2/
l+O 2 (c) carbon dioxide (d) argon
4/3 A
–1050 26. Extraction of zinc from zinc blende is achieved by
500ºC 800ºC 2000ºC
Temperature (ºC) (a) electrolytic reduction (2007, 3M)
(b) roasting followed by reduction with carbon
(a) At 800°C, Cu can be used for the extraction of Zn from ZnO
(c) roasting followed by reduction with another metal
(b) At 1400°C, Al can be used for the extraction of Zn from ZnO
(d) roasting followed by self-reduction
(c) At 500°C, coke can be used for the extraction of Zn from ZnO
(d) Coke cannot be used for the extraction of Cu from Cu 2O 27. Which ore contains both iron and copper? (2005, 1M)
(a) Cuprite (b) Chalcocite
17. The ore that contains both iron and copper is
(2019 Main, 9 Jan I) (c) Chalcopyrite (d) Malachite
(a) malachite (b) azurite 28. The methods chiefly used for the extraction of lead and tin
(c) dolomite (d) copper pyrites
from their ores are respectively (2004, 1M)
18. Which one of the following ores is best concentrated by froth (a) self-reduction and carbon reduction
floatation method? (2016 Main) (b) self-reduction and electrolytic reduction
(a) Siderite (b) Galena (c) carbon reduction and self-reduction
(c) Malachite (d) Magnetite (d) cyanide process and carbon reduction
19. From the following statements regarding H2 O2 choose the 29. In the process of extraction of gold,
incorrect statement. (2015 Main) O2
(a) It can act only as an oxidising agent
Roasted gold ore + CN– + H2O ¾® [ X ] + HO
(b) It decomposed on exposure to light [ X ] + Zn ¾® [Y ] + Au
Identify the complexes [X] and [Y]. (2003, 1M)
(c) It has to be stored in plastic or wax lined glass bottles in dark - 2-
(d) It has to be kept away from dust (a) X = [Au(CN)2 ] , Y = [Zn(CN)4 ]
(b) X = [Au(CN)4 ] 3 – ,Y = [Zn (CN)4 ] 2–
20. In the context of the Hall-Heroult process for the extraction
of Al, which of the following statements is false? (c) X = [Au(CN)2 ] - , Y = [Zn(CN)6 ] 4-
(a) CO and CO2 are produced in this process (2015 Main) (d) X = [Au(CN)4 ] - , Y = [ Zn(CN)4 ] 2-
264 Extraction of Metals
30. Anhydrous ferric chloride is prepared by (2002) 39. Type of bonds present in CuSO4 × 5H2O are only (1983)
(a) heating hydrated ferric chloride at a high temperature (a) electrovalent and covalent
in a stream of air (b) electrovalent and coordinate covalent
(b) heating metallic iron in a stream of dry chlorine gas (c) electrovalent, covalent and coordinate covalent
(c) reaction of ferric oxide with hydrochloric acid (d) covalent and coordinate covalent
(d) reaction of metallic iron with hydrochloric acid 40. In metallurgy of iron, when limestone is added to the blast
31. Which of the following process is used in extractive furnace, the calcium ion ends up in (1982)
metallurgy of magnesium? (2002, 3M) (a) slag
(a) Fused salt electrolysis (b) gangue
(b) Self-reduction (c) metallic calcium
(c) Aqueous solution electrolysis (d) calcium carbonate
(d) Thermite reduction 41. Iron is rendered passive by treatment with concentrated
32. The chemical composition of ‘slag’ formed during the (a) H2SO4 (b) H3PO4 (1982)
smelting process in the extraction of copper is (2001, 1M)
(c) HCl (d) HNO3
(a) Cu2O + FeS (b) FeSiO3
(c) CuFeS2 (d) Cu2S + FeO Objective Questions II
(One or more than one correct option)
33. Electrolytic reduction of alumina to aluminium by
Hall-Heroult process is carried out (2000, 1M) 42. Extraction of copper from copper pyrite (CuFeS 2 ) involves
(a) in the presence of NaCl (2016 Adv.)
(b) in the presence of fluorite (a) crushing followed by concentration of the ore by
(c) in the presence of cryolite which forms a melt with lower froth-floatation
melting temperature (b) removal of iron as slag
(d) in the presence of cryolite which forms a melt with higher (c) self reduction step to produce ‘blister copper’ following
melting temperature evolution of SO2
34. The chemical process in the production of steel from (d) refining of ‘blister copper’ by carbon reduction
haematite ore involve (2000, 1M) 43. Copper is purified by electrolytic refining of blister copper.
(a) reduction The correct statement(s) about this process is/are (2015 Adv.)
(b) oxidation (a) impure Cu strip is used as cathode
(c) reduction followed by oxidation (b) acidified aqueous CuSO4 is used as electrolyte
(d) oxidation followed by reduction (c) pure Cu deposits at cathode
(d) impurities settle as anode-mud
35. In the commercial electrochemical process for aluminium
extraction, the electrolyte used is (1999, 2M) 44. Upon heating with Cu 2 S, the reagent(s) that give copper
(a) Al(OH)3 in NaOH solution metal is/are (2014 Adv.)
(b) an aqueous solution of Al 2 (SO4 )3 (a) CuFeS2 (b) CuO
(c) a molten mixture of Al 2O3 and Na 3AlF6 (c) Cu2O (d) CuSO4
(d) a molten mixture of AlO(OH) and Al(OH)3 45. The carbon-based reduction method is not used for the
36. The major role of fluorspar (CaF2 ) which is added in small extraction of (2013 Adv.)
amount in the electrolytic reduction of alumina dissolved in (a) tin from SnO2
(b) iron from Fe2O3
fused cryolite (Na 3 AlF6 ) is (1993, 1M)
(c) aluminium from Al 2O3
(a) as a catalyst
(d) magnesium from MgCO3 , CaCO3
(b) to make the fused mixture very conducting
(c) to increase the temperature of the melt 46. Extraction of metal from the ore cassiterite involves (2011)
48. Of the following, the metals that cannot be obtained by 55. Match each of the reactions given in Column I with the
electrolysis of the aqueous solution of their salts are corresponding product(s) given in Column II. (2009)
(a) Ag (b) Mg (c) Cu (1990, 1M)
(d) Al (e) Cr Column I Column II
49. In the electrolysis of alumina, cryolite is added to (1986, 1M) A. Cu + dil. HNO3 p. NO
(a) lower the melting point of alumina B. Cu + conc. q. NO2
(b) increase the electrical conductivity
HNO3
(c) minimise the anode effect
(d) remove impurities from alumina C. Zn + dil. HNO3 r. N2 O
D. Zn + conc. s. Cu(NO3 )2
Assertion and Reason HNO3
Read the following questions and answer as per the direction t. Zn(NO3 )2
given below :
(a) Statement I is correct; Statement II is correct; Statement II is 56. Match the conversions in Column I with the type(s) of
the correct explanation of Statement I. reaction(s) given in Column II. (2008, 6M)
(b) Statement I is correct; Statement II is correct; Statement II is
not the correct explanation of Statement I. Column I Column II
(c) Statement I is correct; Statement II is incorrect.
(d) Statement I is incorrect; Statement II is true.
A. PbS ¾® PbO p. Roasting
Passage Based Questions 57. Match the extraction processes listed in Column I with
Passage metals listed in Column II. (2006, 6M)
Copper is the most noble of the first row transition metals and Column I Column II
occurs in small deposits in several countries. Ores of copper include
chalcanthite (CuSO4 × 5H2 O), atacamite (Cu 2 Cl(OH)3 ), cuprite A. Self-reduction p. Lead
(Cu 2 O), copper glance (Cu 2 S) and malachite (Cu 2 (OH)2 CO3 ). B. Carbon reduction q. Silver
However, 80% of the world copper production comes from the ore
chalcopyrite (CuFeS2 ). The extraction of copper from chalcopyrite C. Complex formation and r. Copper
involves partial roasting, removal of iron and self-reduction. displacement by metal
(2010) D. Decomposition of iodide s. Boron
51. Partial roasting of chalcopyrite produces
(a) Cu 2S and FeO (b) Cu 2O and FeO 58. Each entry in Column X is in some way related to the entries in
(c) CuS and Fe2O3 (d) Cu 2O and Fe2O3 Columns Y and Z. Match the appropriate entries. (1988, 3M)
52. Iron is removed from chalcopyrite as
(a) FeO (b) FeS (c) Fe2O3 (d) FeSiO3 Column X Column Y Column Z
60. Match the following metals listed in Column I with 76. A1 and A2 are two ores of metal M . A1 on calcination gives
extraction processes listed in Column II. (1979, 2M) black precipitate, CO2 and water.
n Black solid + CO2 + H2O
Column I Column II tio
l c ina
A. Silver p. Fused salt electrolysis Ca
Roasting
Dil. H ; A2 Metal + gas
A1 Cl
B. Calcium q. Carbon reduction
KI
C. Zinc r. Carbon monoxide I2 + ppt. K 2Cr2O7
+ H2SO4
reduction
D. Iron s. Amalgamation Green colour
63. Silver chloride is sparingly soluble in water because its 80. Write the chemical reactions involved in the extraction of
lattice energy greater than ……….. energy. (1987)
silver from argentite. (2000, 2M)
True/False 84. Write a balanced equation for the reaction of argentite with
KCN and name the products in the solution. (1996)
69 Cu + disproportionate to Cu 2+ and elemental copper in
85. Give reasons for the following
solution.
(1991) “Although aluminium is above hydrogen in the
70. Silver chloride is more soluble in very concentrated sodium electrochemical series, it is stable in air and water.”
(1994, 1M)
chloride solution than in pure water. (1984, 1M)
86. Complete the following reaction :
71. Dilute HCl oxidises metallic Fe to Fe2+ . (1983, 1M) Sn + 2KOH + 4H2 O ¾® ...... + ....... (1994)
72. Silver fluoride is fairly soluble in water. (1982)
87. Give briefly the isolation of magnesium from sea water by
the Dow’s process.
Subjective Questions Give equations for the steps involved. (1993, 3M)
73. Give the coordination number of Al in the crystalline state of 88. Complete and balance the following reaction :
AlCl3. (2009, 2M)
Copper reacts with HNO3 to give NO and NO2 in the molar
74. Give the number of water molecule (s) directly bonded to the ratio of 2:1
metal centre in CuSO4 × 5H2O. (2009, 2M) Cu + HNO3 ¾® KK + NO + NO2 + KK (1992)
75. Write balanced chemical equation for developing a black and 89. Write balanced equation for the extraction of “Copper from
white photographic film. Also give reason, why the solution copper pyrites by self reduction.” (1990, 2M)
of sodium thiosulphate on acidification turns milky white 90. Give balanced equations for the extraction of “Silver from
and give balance equation of this reaction. (2005, 2M) silver glance by cyanide process.” (1988, 1M)
Extraction of Metals 267
91. Answer the following questions briefly (i) Metals can be recovered from their ores by chemical methods
(i) What is the actual reducing agent of haematite in blast furnace? (ii) High purity metals can be obtained by zone refining method.
(ii) Give the equation for the recovery of lead from galena by air (1984, 2M)
reduction. 94. Give reason for the following in one or two sentences :
(iii) Why is sodium chloride added during electrolysis of fused “Silver bromide is used in photography.” (1983)
anhydrous magnesium chloride? 95. State the conditions under which the preparation of
(iv) Zinc, not copper is used for the recovery of metallic silver from alumina from aluminium is carried out. Give the necessary
complex [Ag(CN)2 ]– , explain. equations which need not be balanced. (1983, 2M)
(v) Why is chalcocite roasted and not calcinated during recovery of 96. Write the chemical equations involved in the extraction of
copper? (1987, 5M)
lead from galena by self reduction process. (1979, 2M)
92. Write balanced chemical equation for the following
97. Write balanced equation involved in the preparation of tin
“Gold is dissolved in aqua regia.” (1987)
metal from cassiterite. (1979)
93. Each of the following statement is true, only under some
specific conditions. Write the condition for each subquestion in
not more than 2 sentences.
Answers
1. (a) 2. (b) 3. (d) 4. (a) 53. (c) 54. A ® p, q, s; B ® t; C ® q; D ® r
5. (d) 6. (d) 7. (d) 8. (a) 55. A ® p, s; B ® q, s; C ® r, t; D ® q, t
9. (d) 10. (a) 11. (b) 12. (d)
56. A ® p; B ® q; C ® r, s; D ® p, s
13. (d) 14. (c) 15. (c) 16. (b)
57. A ® p, r; B ® p; C ® q; D ® s
17. (d) 18. (b) 19. (a) 20. (d)
58. A ® q, o; B ® p, n; C ® r, m
21. (b) 22. (a) 23. (b) 24. (d)
59. A ® q; B ® r; C ® s; D ® p
25. (b) 26. (b) 27. (c) 28. (a)
60. A ® s; B ® p; C ® q; D ® q, r; E ® t
29. (a) 30. (b) 31. (a) 32. (b)
61. H 2S 62. Sintering, Smelting
33. (c) 34. (a) 35. (c) 36. (b)
37. (d) 38. (c) 39. (c) 40. (a) 63. Hydration 64. Zn 65. Sn 66. Al
67. Lime, calcium phosphate 68. K [Ag(CN) 2 ]
41. (d) 42. (a,b,c) 43. (b,c,d) 44. (b,c,d)
69. T 70. T 71. T 72. T
45. (c,d) 46. (a,d) 47. (a,c) 48. (b,d)
73. (6) 74. (4) 78. (2)
49. (a,b) 50. (b) 51. (b) 52. (d)
4. Refining of crude metals results pure metals and its impurities 9. With respect to an ore, Ellingham diagram helps to predict the
get separated out. feasibility of its thermal reduction. It is a graph representation of
I. Liquation In this method low melting metals like Gibbs energy change versus absolute temperature.
Sn, Pb, Bi and Hg can be made to flow down through a 0
sloping surface leaving behind the higher melting impurities –100 2Cu 2O
on the hearth. –200 4Cu+O 2
2FeO
–300 2Fe+ O 2
II. Zone refining The basic principle of the method is, C+O2 CO2
impurities are more soluble in the molten metal than in the –400
DGº/kJ mol–1 of O2
2C+O
2CO 2 2
solid state of the metal. This method is useful to produce –500 +O 2 O 2CO
2CO 2Zn
semiconductors and ultra-pure metals like B, Ga, In, Si and –600
2Zn
+O 2
Ge. –700
III. Mond process –800
l +O 3
–900 2/3 A 2
330-350 K 450-470 K O2
Crude nickel (s) + 4CO(g) Ni(CO)4(g)
–1000 4/3 Al+ 2Mg
O
(Impure) (Volatile compound) +O 2
–1100 2Mg
Recycled Ni(s)
4CO(g) + –1200
(Pure)
IV. van Arkel method 0°C 400°C 800°C 1200°C 1600°C 2000°C
273 K 673 K 1073 K 1473 K 1873 K 2273 K
500-600 K 1700-1800 K Temperature
M (s) + 2I2 (g) MI4(g)
(Crude (Volatile compound) Gibbs energy (DGº) versus T plots (schematic)
metal) for the formation of some oxides (Ellingham diagram)
Recycled M(s)
2I2(g) +
(Ultra-pure) Generally, the diagram consists of plots of DG ° versus T for the
formation of oxides of elements
Here, M = Zr, Hf, Ti
2xM (s) + O2 (g ) ¾¾® 2M x O(s)
Hence, the correct matching is Thermal reduction product
I® (C), II®(D), III ®(B), IV ® (A). In this reaction, amount of gas decreases thus, randomness
5. Bauxite is not a carbonate ore. Its chemical formula is Al 2O3 or decreases. Hence, DS becomes negative. Therefore, the value of
free energy increases with increase in temperature. There is a
AlOx(OH)3 - 2x , where 0 < x < I. Chemical formula of other ores
point in a curve below which DG is negative. So, M xO is stable.
given in options are as follows:
Above this point, M xO will decompose on its own.
Siderite-FeCO3
Calamine-ZnCO3 10. The hydroxide, hydrated oxides and carbonate ores, after
concentration, are subjected to calcination. In the process, the
Malachite-CuCO3 × Cu(OH)2
ore is heated below its melting point in the limited supply or
6. Only assertion is correct and reason is incorrect. Haematite is absence of air. As the result, these are converted into their
not a carbonate ore. It is an oxide ore, i.e. Fe2O3. Cast iron is oxides.
extracted chiefly from its oxide ore (haematite) by heating in the So, among the given options, the options having either
presence of coke and limestone in a blast furnace. carbonates (e.g. ZnCO3 and CaCO3 × MgCO3) or hydrated oxide
7. Cryolite ore (Na 3AlF6, sodium hexafluoroaluminate) contain (e.g. Fe2O3 × xH2O), require calcination while pair of option (a),
i.e. ZnO and MgO does not require calcination.
fluorine while other given options such as malachite
(Cu 2 (CO)3 (OH)2 ), sphalerite ((Zn,Fe)S) and bauxite (Al 2O3 ) 11. In the Hall - Heroult’s process, aluminium in formed at the
does not contain fluorine. cathode. The cathode is made out of carbon. In this method,
Al 2O3 is melted with cryolite, Na 3[AlF6 ] and electrolysed in a
8. Mond process is used in the purification of Ni. It is a vapour graphite lined steel tank, which serves as the cathode. The anode
phase refining process. is also made of graphite.
It is based on the principle that Ni is heated in the presence of The cell runs continuously and at intervals molten aluminium is
carbon monoxide to form nickel tetracarbonyl, which is a drained from the bottom of the cell and more bauxite is added.
volatile complex. This complex is then decomposed by The electrolytic reactions are as follows:
subjecting it to a higher temperature (450-470 K) to obtain pure
nickel metal. At cathode Al3+ + 3e- ¾® Al
roasting) in absence of air to give its oxide as in options (a), (b) 19. H2O2 acts as an oxidising as well as reducing agent, because
and (c). Here, volatile non-metallic oxides like H2O, CO2, are oxidation number of oxygen in H2O2 is -1. So, it can be oxidised
also produced. to oxidation state 0 or reduced to oxidation state –2.
Roasting is valid mainly for sulphide ores like option (d), where
SO2 gets liberated. In this reaction, calcination cannot be used. H2O2 decomposes on exposure to light. So, it has to be stored in
plastic or wax linked glass bottles in dark for the prevention of
13. The correct match is: A ® R; B ® S; C ® Q; D ® P. exposure. It also has to be kept away from dust.
(A) Siderite is an ore of iron with molecular formula FeCO 3 (R). 20. (a) In Hall-Heroult process for extraction Al, carbon anode is
(B) Kaolinite is an ore of aluminium with molecular formula oxidised to CO and CO2.
Al 2Si 2(OH)2O 5 (S). (b) When Al 2O3 is mixed with CaF2, it lowers the melting point
(C) Malachite is an ore of copper with molecular formula of the mixture and brings conductivity.
CuCO 3 × Cu(OH)2 (Q). (c) Al 3+ is reduced at cathode to form Al.
(D) Calamine is an ore of zinc with molecular formula (d) Here, Al 2O3 is an electrolyte, undergoing the redox process.
ZnCO 3 (P). Na 3AlF6 although is an electrolyte but serves as a solvent, not
14. Electroplating is a process of coating one metal or metal object electrolyte.
with a very thin layer of another metal typically applying a 21. Higher the position of element in the electrochemical series
direct electric current. more difficult is the reduction of its cations.
Electrolytes used in the electroplating of gold and silver are
If Ca 2+ (aq) is electrolysed, water is reduced in preference to it.
given in the table below:
Hence, it cannot be reduced electrolytically from their aqueous
Pure metal solution.
Article to block acts an
be plated anode by which
Electrolyte Ca 2+ ( aq) + H2O ¾® Ca 2+ + OH- + H2
Process (aqueous
out acts as electroplating
solution) 22. Element Ores Name
cathode will be done
Ag Ag 2 S Argentite
(a) Gold Article Au( s ) I
Na[A u(CN)2 ] Cu CuFeS2 Copper pyrites
plating
(Sodium Pb PbS Galena
auro-cyanide) Sn SnO2 Cassiterite
(b) Silver Article Ag( s ) I
Na[A g(CN)2 ] Mg MgCO3 × CaCO3 Dolomite
plating
(Sodium argento Al Al 2 O3 × xH2 O Bauxite
cyanide)
23. The reactions involved in extraction of silver by cyanide process
15. Hall-Heroult’s process is an electro-reduction process by which are
pure alumina (Al 2O3 ) is reduced to crude Al. Ag2S + CN- + O2 ¾® [Ag(CN)2 ]- + SO2 …(i)
In this process, electrolysis of a fused mixture of Al 2O3, [Ag (CN)2 ]- + Zn ¾® [Zn (CN)4 ]2- + Ag …(ii)
Na 3[AlF6 ] (cryolite) and CaF2 (fluorspar) is carried out at carbon
cathode and graphite anode. In reaction (i), sulphide is oxidised to SO2 by oxygen. In the
reaction (ii), silver ion (Ag+ ) is reduced to Ag by Zn. Therefore,
The overall reaction is represented as:
O2 is oxidising agent and Zn is reducing agent.
2Al 2O3 + 3C ¾® 4Al + 3CO2
24. Haematite is Fe2O3, in which oxidation number of iron is III.
16. From the Ellingham diagram, we can say that any oxide with Magnetite is Fe3O4 which is infact a mixed oxide (FeO × Fe2O3),
lower value of DG ° is more stable than a oxide with higher value hence iron is present in both II and III oxidation state.
of DG °. We can also predict that the oxide placed higher in the
diagram can be reduced by the element involved in the 25. A water soluble complex with silver and dilute aqueous solution
formation of its oxide placed lower at that temperature in the of NaCN is Na[Ag(CN)2 ]. In the cyanide process, the native
diagram. silver is crushed and treated with aqueous NaCN solution and
aerated.
It is happening in case of ZnO for its reduction by Al at 1400°C.
4Ag + 8NaCN + 2H2O + O2 ¾® 4Na [Ag(CN)2 ]
17. The formulae of the given ores are as follows: + 4NaOH
Malachite : CuCO3 × Cu(OH)2
26. Zinc blende contain ZnS which is first roasted partially and then
Copper pyrites : CuFeS2 subjected to reduction with carbon
Dolomite : CaMg(CO3 )2 ZnS + O2 ¾® ZnO + SO2 Roasting
Azurite : Cu 3 (CO)3 (OH)2
D
ZnO + C ¾® Zn + CO Carbon reduction
18. Sulphide ores are concentrated by froth floatation method e.g.
Galena (PbS) 27. Chalcopyrite contain both iron and copper.
270 Extraction of Metals
28. Lead is mainly extracted by self-reduction process while tin is 43. (a) is wrong statement. Impure copper is set as anode where
extracted by carbon reduction method. copper is oxidised to Cu 2+ and goes into electrolytic
29. Au + 2CN- ¾® [Au(CN)2 ]- solutions.
X
(b) CuSO4 is used as an electrolyte in purification process.
(c) Pure copper is deposited at cathode as:
2Au(CN)-2 + Zn ¾® [Zn(CN)4 ] 2-
+ 2Au
Y Cu 2+ + 2e– ¾® Cu : (At cathode)
30. Heating iron in stream of dry chlorine gas gives FeCl 3 in (d) Less active metals like Ag, Au etc settle down as anode mud.
anhydrous form. In all other cases (a and c) hydrated FeCl 3 is 1100 °C
obtained while in (d), FeCl 2 is formed. 44. (b) 4CuO ¾¾¾® 2Cu 2O + O2
31. Mg is extracted by electrolysis of molten MgCl 2. D
2Cu 2O + Cu 2S ¾® 6Cu + SO2
32. Iron present in copper pyrite is removed by forming FeSiO3 as D
(c) Cu 2S + 2Cu 2O ¾® 6Cu + SO2
slag.
720 °C 1
33. Cryolite is added to alumina in order to lower the melting point. (d) CuSO4 ¾¾¾® CuO + SO2 + O2
2
34. Haematite ore contain Fe2O3 which is reduced by CO in the blast 1100 °C
furnace as 4CuO ¾¾¾® 2Cu 2O + O2
Fe2O3 + CO ¾® Fe + CO2 D
2Cu 2O + Cu 2S ¾® 6Cu + SO2
35. Al 2O3 mixed with cryolite Na 3[AlF6 ]is fused and electrolysed in Reaction is believed to proceed as
the extraction of Al. Cu 2S r 2Cu + + S2-
36. Fluorspar (CaF2 ) improve the electrical conductivity during 2Cu 2O r 4 Cu + + 2O2-
electrolytic reduction of alumina.
S2- + 2O2- ¾® SO2 + 6e-
37. Al itself is a very strong reducing agent.
6Cu + + 6e- ¾® 6Cu ; Ecell o
= 0.52
38. In thermite welding, Al acts as a reducing agent Here, copper sulphide is reduced to copper metal. Solidified
2Al + Fe2O3 ¾® Al 2O3 + 2Fe + Heat copper has blistered appearance due to evolution of SO2 and
39. The actual representation of CuSO4 × 5H2O (blue vitriol) is thus obtained copper is known as blister copper.
[Cu(H2O)4 ]SO4 × H2O and it has covalent, ionic and coordinate
Other compounds which give Cu are
covalent bonds.
1100 °C
40. Ca 2+ end up in CaSiO3 (slag). (i) CuO as 4CuO ¾¾¾® 2Cu 2O + O2
41. Iron is rendered passive by concentrated HNO3 due to formation D
2Cu 2O + Cu 2S ¾® 6Cu + SO2
of a thick protective layer of Fe3O4.
720 °C 1
42. CuFeS2 (copper pyrite) is converted into copper into following (ii) CuSO4 as CuSO4 ¾¾® CuO + SO2 + O2
2
steps: D
4CuO ¾® 2Cu 2O + O2
Step I Crushing (grinding ) followed by concentration by
froth-floatation process. D
2Cu 2O + Cu 2S ¾® 6Cu + SO2
Step II Roasting of ore in the presence of SiO2 which removes iron
While CuFeS2 will not give Cu on heating. The heating in the
as slag (FeSiO3). presence of O2 gives Cu 2S and FeS with the evolution of SO 2.
2CuFeS2 + O2 ¾® Cu 2S + 2FeS + SO2
45. Al has greater affinity for oxygen, hence oxide is not reduced by
2FeS + 3O2 ¾® 2SO2 + 2FeO carbon. MgO and CaO (formed in the calcination from
FeO + SiO2 ¾® FeSiO3 (Slag) carbonates) are stable species and not reduced by carbon.
Step III Self-reduction in Bessemer converter
1300 °C
2Cu 2S + 3O2 ¾® 2Cu 2O + 2SO2 During Smelting SnO2 + C ¾¾¾® Sn + CO
2Cu 2O + Cu 2S ¾® 6Cu + SO2 D 4Fe + 3 CO
2Fe2O3 + 3 C ¾® 2
Copper obtained is blister copper (98% pure).
Step IV Refining of blister copper is done by electrolysis 46. The important ore of tin is cassiterite (SnO2). Tin is extracted
from cassiterite ore by carbon reduction method in a blast furnace.
Impure copper—Anode
SnO2 + 2C ¾ ¾® Sn + 2CO
Pure copper— Cathode
At anode : Cu ¾® Cu 2+ + 2e- The product often contain traces of iron which is removed by
-
blowing air through the melt to oxidise to FeO which then floats
At cathode : Cu 2+
+ 2e ¾® Cu to the surface.
Carbon-reduction method is not used. Thus, (d) is incorrect. 2Fe + O2 ¾
¾® 2FeO
Extraction of Metals 271
47. Addition of manganese to iron improve hardness of steel as well 57. Extraction Metals
as remove oxygen and sulphur. methods extracted
A. Self reduction r. Copper, (P) Lead
48. Magnesium and aluminium are both highly electropositive,
more electropositive than water cannot be obtained by B. Carbon reduction p. Lead
electrolysis of aqueous solution of their salts. C. Complex formation q. Silver :
49. Alumina (Al 2O3 ) has very high melting point and it is poor and displacement Ag 2 S + NaCN
by metal ¾® Na[Ag(CN)2 ]
conductor of electricity. Both these factors posses difficulty in
electrolysis of molten alumina. Na[Ag(CN)2 ] + Zn
Cryolite, Na 3AlF6, when mixed with alumina, lowers melting ¾® Na 2 [Zn(CN)4 ]
point as well as improve electrical conductivity, hence helps in + Ag
electrolysis of Al 2O3. D. Decomposition of s. Boron :
iodide D 3
50. Al(OH)3 is amphoteric BI 3 ¾® B + I2
2
Al(OH)3 + 3HCl ¾® AlCl 3 + 3H2O
Base
Al(OH)3 + NaOH ¾® Na[Al(OH)4 ] 58. Column X Column Y Column Z
Acid
Invar Fe, Ni Watch spring
High charge and small size of Al 3+ makes Al—O and O—H
bonds equally ionisable. Nichrome Co, Ni Heating element
55. A. 3Cu + 8HNO3 ¾® 3Cu(NO3 )2 + 2NO + 4H2O B. Calcium is extracted by electrolysis of fused CaCl 2.
Dil. C. Zinc is extracted by carbon reduction method
B. Cu + 4HNO3 ¾® Cu(NO3 )2 + 2NO2 + 2H2O ZnO + C ¾® Zn + CO
Conc. D. Iron is extracted by both carbon reduction method and CO
C. 4Zn + 10HNO3 ¾® 4Zn(NO3 )2 + N2O + 5H2O reduction methods
Dil. Fe2O3 + 3C ¾® 2Fe + 3CO
D. Zn + 4HNO3 ¾® Zn(NO3 )2 + 2NO2 + 2H2O Fe2O3 + 3CO ¾® 2Fe + 3CO2
Conc. E. Copper is extracted by self reduction methods
O2
56. A. PbS ¾® PbO + SO2, roasting Cu 2S + O2 ¾® Cu 2O + SO2
B. CaCO3 ¾® CaO + CO2 ; calcination Cu 2O + Cu 2S ¾® Cu + SO2
C. ZnS ¾® Zn, can be done by carbon reduction 61. H 2S Ag2S (black) is formed on the surface.
or self reduction
D
D. Cu 2S ¾® Cu, roasting followed by self reduction 62. ZnO + C ¾¾® Zn + CO = Smelting
sintering
272 Extraction of Metals
63. Hydration energy Energy required to break the crystal lattice 77. Anhydrous AlCl 3 is more soluble in diethyl ether as the oxygen
during dissolving process comes from hydration. If lattice atom of ether donate its lone-pair of electrons to the vacant
energy is very high and hydration energy is low, salt becomes orbital of Al in electron deficient AlCl 3. In case of hydrated
sparingly soluble.
AlCl 3, Al is not electron deficient as oxygen of water molecule
64. Zn Galvanisation involves coating of iron with zinc metal in has already donated its lone-pair of electrons to compensate
order to prevent if from rusting. electron deficiency of Al.
65. Sn Cassiterite is an ore of tin. Cl Cl
66. Al Aluminium reduces Fe2O3 to Fe. ½ ·· ½ ··
Cl — Al ¬¾ OH2 Cl — Al ¬¾ OEt 2
67. Lime, calcium phosphate In basic Bessemer process, the ·· ··
½ ½
Bessemer converter is lined with lime but in acid Bessemer Cl Cl
process, it is lined with silica. In basic Bessemer process, hydrated anhydrous
phosphorus is slagged off as calcium phosphate :
78. The reactions involved in the extraction of lead from galena
P4 + 5O2 ¾® P4O10
(PbS) by self reduction are
6CaO + P4O10 ¾® 2Ca 3 (PO4 )2
2PbS + 3O2 ¾® 2PbO + 2SO2
Thomas slag
PbS + 2PbO ¾® 3Pb + SO2
68. K [Ag(CN)2 ] : AgCl + 2KCN ¾® K[Ag(CN)2 ] + KCl PbS + 2O2 ¾® PbSO4 (side reaction)
69. True: Cu + is unstable PbSO4 + PbS ¾® 2Pb + 2SO2
H+ In litharge (PbO), the oxidation state of Pb is +2
2Cu + ¾® Cu 2+ + Cu
79. The common photographic film is coated with AgBr and during
70. True Complex (Na[AgCl 2 ]) formation increases solubility of developing of photographic film, the unreacted AgBr is
otherwise sparingly soluble AgCl. removed by Na 2S2O3 as
71. True Iron is more electropositive than hydrogen AgBr + 2Na 2S2O3 ¾® Na 3[Ag(S2O3 )2 ] + NaBr
Fe + 2HCl ¾® FeCl 2 + H2 80. 4NaCN + Ag2S ¾® 2Na[Ag(CN)2 ] + Na 2S
72. True : Solubility of silver halides decreases down in the group 2Na[Ag(CN)2 ] + Zn ¾® Na 2[Zn(CN)4 ] + 2Ag
Solubility : AgF > AgCl > AgBr > AgI 81. 2Cu + H2O + CO2 + O2 ¾® Cu(OH)2 × CuCO3
Green
(basic copper carbonate)
73. In crystalline state, AlCl 3 has rock-salt like structure with
coordination number of Al = 6. 2000 °C
82. C + O2 ¾¾¾® CO
74. Four, the complex has formula [Cu(H2O)4 ] SO4 × H2O 3CO + Fe2O3 ¾® 2Fe + 3CO2
CaCO3 ¾® CaO + CO2
75. (a) 2AgBr + C6H4 (OH)2 ¾® 2Ag + 2HBr + C6 H4O2
Hydroquinone Quinone
CaO + SiO2 ¾® CaSiO3
(developer) Slag
H2O
AgBr + 2Na 2S2O3 ¾® Na 3[Ag(S2O3 )2 ] + NaBr 83. Al + NaOH ¾¾® NaAlO2+ 32 H2
(b) Na 2S2O3 + 2H+ ¾® 2Na + + H2SO3 + S ¯
Colloidal 84. 4KCN + Ag2S ¾® 2K[Ag(CN)2 ] + K2S
sulphur
Potassium
76. A1 is basic copper carbonate (Cu(OH)2 × CuCO3 ) while A2 is dicyanoargentate (I)
Cu 2S. The confirmatory reactions are : 85. Due to formation of protective, inert layer of Al 2O3 on surface.
D 86. Sn + 2KOH + 4H2O ¾® K2[Sn(OH)6 ] + 2H2
(i) CuCO3 × Cu(OH)2 ¾® CuO + CO2 + H2O
Black
HCl 87. Sea water (contain MgCl 2) + Ca(OH)2
(ii) CuCO3 × Cu(OH)2 ¾® CuCl 2 + CO2 + H2O
KI
¾® Mg(OH)2 ¯ + CaCl 2 ( aq )
CuCl 2 ¾® Cu 2 I2 ¯ + KCl + I2
D (i) Mg(OH)2 + 2HCl ¾® MgCl 2 + 2H2O
Roasting Heat to
A2 ¾¾¾® Cu 2O + SO2 ¾¾¾® MgCl 2 ( s )
Dryness
Cu 2S + Cu 2O ¾® Cu + SO2
Fusion electrolysis
SO2 is a reducing gas that gives green colour with acidified (ii) MgCl 2 (s) ¾¾¾® Mg2+ + 2Cl - ¾¾¾® Mg
NaCl
K2Cr2O7 as (At cathode)
3SO2 + K2Cr2O7 + H2SO4 ¾® K2SO4 + Cr2 (SO4 )3
Green 88. 7Cu + 20HNO3 ¾® 7Cu(NO3 )2 + 4NO + 2NO2 + 10H2O
+ 4H2O
Extraction of Metals 273
89. 2CuFeS2 + O2 ¾® Cu 2S + 2FeS + SO2 However, if the metal is highly electropositive, e.g. Al, Mg
Copper pyrite etc., no reducing agent exist for reduction of their ions
2Cu 2S + 3O2 ¾® 2Cu 2O + 2SO2 (Al 3+ , Mg2+ ) and they are obtained by electrolytic
Roasting
2FeS + 3O2 ¾® 2FeO + 2SO2 reduction of their molten salt.
FeS + SiO2 ¾® FeSiO3 (ii) Metals like Ge is required in high purity, can be readily
Flux Slag melted and can easily crystallise out from the melt form.
2Cu 2O + Cu 2S ¾® 6Cu + SO2 Bessemerisation
94. AgBr is sensitive to visible light.
90. Ag2S + 2NaCN ¾® 2AgCN + Na 2S
hn 1
AgBr ¾¾® Ag + Br2
AgCN + NaCN ¾® Na[Ag(CN)2 ] 2
2Na[Ag(CN)2 ] + Zn ¾® Na 2[Zn(CN)4 ] + 2Ag A photographic plate coated with AgBr, when exposed to
91. (i) Carbon monoxide : light, gets blackened due to the above reaction.
93. (i) If the metal is moderately electropositive, e.g. Fe, Sn, Pb or 97. SnO2 + 2C ¾® Sn + 2CO( g ), Carbon reduction method.
Cu, they can be obtained from their ore by chemical
reduction methods.
(a) o -toluidine (b) oleic acid (c) MgCl 2 × MgSO4 (d) MgSO4
(c) m-cresol (d) benzamide 9. CuSO4 decolourises on addition of KCN, the product is
2. When metal ‘M ’ is treated with NaOH, a white gelatinous (a) [Cu(CN)4 ]2 - (2006, 3M)
precipitate ‘X ’ is obtained, which is soluble in excess of (b) Cu2 + get reduced to form [Cu(CN)4 ]3 -
NaOH. Compound ‘X ’ when heated strongly gives an oxide
(c) Cu(CN)2
which is used in chromatography as an adsorbent. The metal
(d) CuCN
‘M ’ is (2018 Main)
(a) Zn (b) Ca (c) Al (d) Fe 10. A solution when diluted with H2 O and boiled, it gives a
white precipitate. On addition of excess NH4 Cl / NH4 OH,
3. In the following reaction sequence in aqueous solution, the
the volume of precipitate decreases leaving behind a white
species X, Y and Z, respectively, are (2016 Adv.)
gelatinous precipitate. Identify the precipitate which
Ag + Ag + With time dissolves in NH4 OH / NH4 Cl. (2006, 3M)
S2 O23 - ¾® X ¾® Y ¾¾® Z (a) Zn(OH)2 (b) Al(OH)3
(Clear solution) (White ppt.) (Black ppt.)
(c) Mg(OH)2 (d) Ca(OH)2
(a) [Ag(S2O3 )2 ]3- , Ag2S2O3 , Ag2S
(b) [Ag(S2O3 )3 ]5- , Ag2SO3 , Ag2S
11. A metal nitrate reacts with KI to give a black precipitate
which on addition of excess of KI convert into orange colour
(c) [Ag(SO3 )2 ]3- , Ag2S2O3 , Ag solution. The cation of metal nitrate is (2005, 1M)
(d) [Ag(SO3 )3 ]3- , Ag2SO4 , Ag (a) Hg2+ (b) Bi 3+ (c) Sn 2+ (d) Pb2+
4. In Carius method of estimation of halogens 250 mg of an 12. (NH4 )2 Cr2 O7 on heating gives a gas which is also given by
organic compound gave 141 mg of AgBr. The percentage of (2004, 1M)
bromine in the compound is (atomic mass Ag = 108, Br = 80) (a) Heating NH4NO2 (b) Heating NH4NO3
(2015 Main) (c) Mg3N2 + H2O (d) Na(comp. ) + H2O2
(a) 24 (b) 36 (c) 48 (d) 60
13. A sodium salt of an unknown anion when treated with
5. Upon treatment with ammoniacal H 2S , the metal ion that MgCl 2 gives white precipitate only on boiling. The anion is
precipitates as a sulphide is (2013 Adv.) (2004, 1M)
(a) Fe (III) (b) Al (III) (a) SO2–
4 (b) HCO–3 (c) CO2-
3 (d) NO-3
(c) Mg (II) (d) Zn(II)
14. [ X ] + H2 SO4 ® [Y ] a colourless gas with irritating smell
6. Passing H2 S gas into a mixture of Mn 2+ , Ni 2+ , Cu 2+ and
[Y ] + K 2 Cr2 O7 + H2 SO4 ¾® green solution
Hg 2+ ions in an acidified aqueous solution precipitates
[ X ] and [Y ] are (2003, 1M)
(a) CuS and HgS (b) MnS and CuS (2011)
(a) SO23- , SO2 (b) Cl - , HCl
(c) MnS and NiS (d) NiS and HgS
(c) S2- , H2S (d) CO23- , CO2
Qualitative Analysis 275
15. A gas X is passed through water to form a saturated solution. (a) Mn 2+ shows the characteristic green colour in the flame
The aqueous solution on treatment with silver nitrate gives a test
white precipitate. The saturated aqueous solution also (b) Only Cu 2+ shows the formation of precipitate by passing
dissolves magnesium ribbon with evolution of a colourless H2 S in acidic medium
gas Y. Identify X and Y. (2002, 3M) (c) Only Mn 2+ shows the formation of precipitate by passing
(a) X = CO2, Y = Cl 2 (b) X = Cl 2 , Y = CO2 H2 S in faintly basic medium
(c) X = Cl 2 , Y = H2 (d) X = H2 , Y = Cl 2
(d) Cu 2+ / Cu has higher reduction potential than Mn 2+ / Mn
16. An aqueous solution of a substance gives a white precipitate (measured under similar conditions)
on treatment with dilute hydrochloric acid, which dissolves
25. The reagent(s) that can selectively precipitate S2 - from a
on heating. When hydrogen sulphide is passed through the
hot acidic solution, a black precipitate is obtained. The mixture of S2 - and SO24 - in aqueous solution is (are)
substance is a (2000, 1M) (2016 Adv.)
+ (a) CuCl 2 (b) BaCl 2
(a) Hg2+
2 salt (b) Cr 2+
salt (c) Ag salt (d) Pb 2+
salt
(c) Pb(OOCCH3 )2 (d) Na 2[ Fe(CN)5 NO]
17. In nitroprusside ion the iron and NO exist as Fe (II) and NO+ 26. The pair(s) of ions where both the ions are precipitated upon
rather than Fe (III) and NO. These forms can be
passing H2S gas in presence of dilute HCl, is (are)
differentiated by (1998, 2M)
(2015 Adv.)
(a) estimating the concentration of iron
(a) Ba 2+ , Zn 2+ (b) Bi 3+ , Fe3+
(b) measuring the concentration of CN
(c) measuring the solid state magnetic moment (c) Cu2+ , Pb2+ (d) Hg2+ , Bi 3+
(d) thermally decomposing the compound 27. For the given aqueous reaction which of the statement(s) is
18. An aqueous solution FeSO4 × Al 2 (SO4 )3 and chrome alum is Dilute H2 SO4
(are) true? Excess KI + K 3 [Fe(CN)6 ] ¾¾¾¾¾®
heated with excess of Na 2 O2 and filtered. The materials
obtained are (1996, 1M)
Brownish-yellow solution
(a) a colourless filtrate and a green residue ¯ ZnSO4
(b) a yellow filtrate and a green residue (White precipitate + Brownish-yellow filtrate)
(c) a yellow filtrate and a brown residue ¯ Na 2 S2 O3
(d) a green filtrate and brown residue Colourless solution (2012)
19. The brown ring complex compound is formulated as (a) The first reaction is a redox reaction
+ (b) White precipitate is Zn 3[ Fe(CN)6 ]2
[Fe(H2 O)5 (NO) ] SO4 . The oxidation state of iron is
(c) Addition of filtrate to starch solution gives blue colour
(1987, 1M)
(a) 1 (b) 2 (c) 3 (d) 0 (d) White precipitate is soluble in NaOH solution
20. Which one amongst the following pairs of ions cannot be 28. A solution of colourless salt H on boiling with excess NaOH
separated by H2 S in dilute HCl? (1986, 1M) produces a non-flammable gas. The gas evolution ceases
(a) Bi 3+ , Sn 4+ (b) Al 3+ , Hg2+ after sometime. Upon addition of Zn dust to the same
solution, the gas evolution restarts. The colourless salt(s) H
(c) Zn 2+ , Cu2+ (d) Ni 2+ , Cu2+
is (are) (2008, 4M)
21. The compound insoluble in acetic acid is (1986, 1M) (a) NH4NO3 (b) NH4NO2
(a) calcium oxide (b) calcium carbonate (c) NH4Cl (d) (NH4 )2 SO4
(c) calcium oxalate (d) calcium hydroxide
29. Which of the following statement(s) is(are) correct when a
22. The ion that cannot be precipitated by both HCl and H2 S is mixture of NaCl and K 2 Cr2 O7 is gently warmed with
(a) Pb2– (b) Cu+ (1982, 1M) conc. H2 SO4 ? (1998, 2M)
(c) Ag+ (d) Sn 2+ (a) A deep red vapour is evolved
(b) The vapour when passed into NaOH solution gives a
23. For the equilibrium, 2H 2O - H3O+ + OH - , the value yellow solution of Na 2CrO4
of DGº at 298 K is approximately (2019 Main 11 Jan II) (c) Chlorine gas is evolved
(a) - 80 kJ mol - 1 (b) 100 kJ mol - 1 (d) Chromyl chloride is formed
(c) 80 kJ mol - 1 (d) - 100 kJ mol - 1 30. Which of the following statement(s) is (are) correct with
reference to the ferrous and ferric ions ? (1998, 2M)
Objective Questions II (a) Fe3+ gives brown colour with potassium ferricyanide
(One or more than one correct option) (b) Fe2+ gives blue precipitate with potassium ferricyanide
(c) Fe3+ gives red colour with potassium thiocyanate
24. The correct option(s) to distinguish nitrate salts to Mn 2+ and
(d) Fe2+ gives brown colour with ammonium thiocyanate
Cu 2+ taken separately is (are) (2018 Adv.)
276 Qualitative Analysis
31. The reagents, NH4 Cl and aqueous NH3 will precipitate medium. However, it gave a precipitate (R) with H2 S in an
(1991, 1M) ammoniacal medium. The precipitate R gave a coloured solution
(a) Ca 2+ (b) Al 3+ (c) Bi 3+ (d) Mg2+ (S ), when treated with H2 O2 in an aqueous NaOH medium.
2+
(e) Zn 36. The precipitate P contains (2013 Adv.)
(a) Pb2+ (b) Hg2+
2 (c) Ag+ (d) Hg2+
Assertion and Reason
37. The coloured solution S contains
Read the following questions and answer as per the direction (a) Fe2 (SO4 )3 (b) CuSO4 (c) ZnSO4 (d) Na 2CrO4
given below :
(a) Statement I is correct Statement II is correct Statement II is Passage 3
a correct; explanation of Statement I When a metal rod M is dipped into an aqueous colourless
(b) Statement I is correct; Statement II is correct Statement II is concentrated solution of compound N , the solution turns light blue.
not the correct explanation of Statement I. Addition of aqueous NaCl to the blue solution gives a white
(c) Statement I is correct; Statement II is incorrect. precipitate O. Addition of aqueous NH 3 dissolves O and gives an
(d) Statement I is incorrect; Statement II is correct. intense blue solution. (2011)
32. Statement I Sulphate is estimated as BaSO4 , not as MgSO4 . 38. The metal rod M is
(a) Fe (b) Cu (c) Ni (d) Co
Statement II Ionic radius of Mg 2+ is smaller than that
39. The compound N is
of Ba 2+ . (1998, 2M) (a) AgNO3 (b) Zn(NO3 )2
33. Statement I A very dilute acidic solution of Cd 2+ and (c) Al(NO3 )3 (d) Pb(NO3 )2
Ni 2+ gives yellow precipitate of CdS on passing H2 S. 40. The final solution contains
(a) [Pb(NH3 )4 ]2+ and [CoCl 4 ]2-
Statement II Solubility product of CdS is more than that
of NiS. (1989, 2M) (b) [Al(NH3 )4 ]3+ and [Cu(NH3 )4 ]2+
(c) [Ag(NH3 )2 ]+ and [Cu(NH3 )4 ]2+
Passage Based Questions (d) [Ag(NH3 )2 ]+ and [Ni(NH3 )6 ]2+
Passage 1
Passage 4
An aqueous solution of metal ion M 1 reacts separately with
reagents Q and R in excess to give tetrahedral and square planar p-amino-N, N-dimethylaniline is added to a strongly acidic
complexes, respectively. An aqueous solution of another metal ion solution of X. The resulting solution is treated with a few drops of
M 2 always forms tetrahedral complexes with these reagents. aqueous solution of Y to yield blue colouration due to the formation
Aqueous solution of M 2 on reaction with reagent S gives white of methylene blue. Treatment of the aqueous solution of Y with the
precipitate which dissolves in excess of S. The reactions are reagent potassium hexacyanoferrate (II) leads to the formation of
summarised in the scheme given below an intense blue precipitate. The precipitate dissolves on excess
Q R addition of the reagent. Similarly, treatment of the solution of Y
Tetrahedral excess M1 excess Square planar with the solution of potassium hexacyanoferrate (III) leads to a
Q R
brown colouration due to the formation of Z.
Tetrahedral M2 excess Tetrahedral
excess 41. The compound X, is (2009, 1M)
(a) NaNO3 (b) NaCl
S, stoichiometric amount
(c) Na 2SO4 (d) Na 2S
S
White precipitate excess
Precipitate 42. The compound Y, is (2009, 1M)
dissolves (a) MgCl 2 (b) FeCl 2
34. M1 , Q and R, respectively are (c) FeCl 3 (d) ZnCl 2
(a) Zn 2+ , KCN and HCl (b) Ni 2+ , HCl and KCN 43. The compound Z, is (2009, 1M)
2+ 2+ (a) Mg2[Fe(CN)6 ] (b) Fe[Fe(CN)6 ]
(c) Cd , KCN and HCl (d) Co , HCl and KCN
(c) Fe4[Fe(CN)6 ]3 (d) K 2 Zn 3[Fe(CN)6 ]2
35. Reagent S is
(a) K 4[Fe(CN)6 ] (b) Na 2HPO4
(c) K 2CrO4 (d) KOH
Fill in the Blanks
44. The formula of the deep red liquid formed on warming
Passage 2 dichromate with KCl in concentrated sulphuric acid is...
An aqueous solution of a mixture of two inorganic salts,when (1993, 1M)
treated with dilute HCl, gave a precipitate (P) and filtrate (Q). The 45. If metal ions of group III are precipitated by NH4 Cl and
precipitate (P) was found to dissolve in hot water. The filtrate (Q) NH4 OH without prior oxidation by conc. HNO3 . …… is not
remained unchanged, when treated with H2 S in a dilute mineral acid completely precipitated. (1984, 1M)
Qualitative Analysis 277
62. A colourless inorganic salt (A) decomposes completely at solution of K 2 HgI4 . The aqueous solution of the mixture on
about 250° C to give only two products (B) and (C), leaving treatment with BaCl 2 gives a white precipitate which is
no residue. The oxide (C) is a liquid at room temperature and sparingly soluble in conc. HCl.
neutral to moist litmus paper, while the gas (B) is a neutral On heating the mixture with K 2 Cr2 O7 and conc. H2 SO4 , red
oxide. vapours A are produced. The aqueous solution of the
White phosphorus burns in excess of (B) to produce a strong mixture gives a deep blue colouration B with potassium
white dehydrating agent. Write balanced equations for the ferricyanide solution. Identify the radicals in the given
reactions involved in the above process. (1996, 3M) mixture and write the balanced equations for the formation
63. Gradual addition of KI solution of Bi(NO3 )3 solution of A and B. (1991, 4M)
initially produces a dark brown precipitate which dissolves 71. Write the balanced chemical equations for the following
in excess of KI to give a clear yellow solution. Write (i) Silver chloride is treated with aqueous sodium cyanide and
chemical equations for the above reactions. (1996, 2M) the product thus formed is allowed to react with zinc in
64. A scarlet compound A is treated with conc. HNO3 to give a alkaline medium.
(ii) Cobalt (II) solution reacts with KNO2 in acetic acid
chocolate brown precipitate B. The precipitate is filtered
medium. (1989, 2M)
and the filtrate is neutralised with NaOH. Addition of KI to
the resulting solution gives a yellow ppt C. The brown ppt B 72. Give reasons for, “The colour of mercurous chloride,
on warming with conc. HNO3 in the presence of Mn(NO3 )2 Hg 2 Cl 2 , changes from white to black when treated with
produces a pink coloured solution due to the formation of D. ammonia.” (1988, 1M)
Identify A, B, C and D. Write the reaction sequence. 73. A mixture of two salts was treated as follows :
(1995, 4M)
(i) The mixture was heated with maganese dioxide and
65. An orange solid A on heating gave a green residue B, a concentrated sulphuric acid, when yellowish green gas was
colourless gas C and water vapour. The dry gas C on passing liberated.
over heated Mg gave a white solid D. D on reaction with (ii) The mixture on heating with sodium hydroxide solution
water gave a gas E which formed dense white fumes with gave a gas which turned red litmus blue.
HCl. Identify A to E and give the reaction involved. (iii) Its solution in water gave blue precipitate with potassium
(1993, 3M) ferricyanide and red colouration with ammonium
66. The acidic aqueous solution of ferrous ion forms a brown thiocyanate.
complex in the presence of NO-3 , by the following two (iv) The mixture was boiled with potassium hydroxide and the
liberated gas was bubbled through an alkaline solution of
steps : K2HgI4 to give brown precipitate.
[Fe(H2 O)6 ]2+ + NO–3 + H+ ¾® K + [Fe(H2 O)6 ]3+ Identify the two salts. Give ionic equations for reactions
involved in the tests (i), (ii) and (iii). (1987, 5M)
[Fe(H2 O)6 ]2+
+ K ¾® ...... + H2 O
74. Write balanced equation for the following “potassium
Complete and balance the equation. (1993, 2M)
permanganate is reacted with warm solution of oxalic acid
67. A light bluish green crystalline compound responds to the in the presence of sulphuric acid.” (1987, 1M)
following tests
75. Mention the products formed in the following:
(i) Its aqueous solution gives a brown precipitate or
(i) Zinc oxide is treated with excess of sodium hydroxide
colouration with K2[HgI4 ].
solution.
(ii) Its aqueous solution gives a blue colour with K3[Fe(CN)6 ].
(ii) Iodine is added to a solution of stannous chloride.
(iii) Its solution in hydrochloric acid gives a white precipitate
(iii) Sulphur dioxide gas, water vapour and air are passed over
with BaCl 2.
heated sodium chloride. (1986, 3M)
Identify the ions present and suggest the formula of the
compound. (1992, 4M)
76. What happen when
(i) hydrogen sulphide is bubbled through an aqueous solution
68. In the following reaction, identify the compounds/reaction of sulphur dioxide.
conditions represented by the alphabets A and B.
(ii) aqueous ammonia is added dropwise to a solution of copper
Heat in B
PbS ¾¾¾® A + PbS ¾® Pb + SO2 sulphate till it is in excess.
air (1991, 1M) (iii) tin is treated with concentrated nitric acid.
69. Give reason in one or two sentences for the following (iv) CrCl 3 solution is treated with sodium hydroxide and then
“The hydroxides of aluminium and iron are insoluble in with hydrogen peroxide.
water. However, NaOH is used to separate one from other. (v) Pb3O4 is treated with nitric acid. (1985, 5M)
(1991, 2M)
77. Write down the balanced equations for the reactions, when,
70. The gas liberated, on heating a mixture of two salts with ‘a mixture of potassium chlorate, oxalic acid and sulphuric
NaOH, gives a reddish brown precipitate with an alkaline acid is heated. (1985, 1M)
Qualitative Analysis 279
78. When 16.8 g of white solid, X were heated, 4.4 g of acid gas (vi) Residue D from step (iii) is heated on charcoal in a reducing
A, that turned lime water milky was driven off together with flame. It gives a magnetic substance.
1.8 g of a gas B which condensed to a colourless liquid. Name the compound A, B, C, D and E. (1980, 4M)
The solid that remained, Y, dissolved in water to give an 80. Explain the following in not more than two sentences.
alkaline solution, which with excess barium chloride A solution of FeCl 3 in water gives a brown precipitate on
solution gave a white precipitate Z. The precipitate standing. (1980, 1M)
effervesces with acid giving of carbon dioxide. Identify A, B 81. The precipitation of second group sulphides in qualitative
and Y and write down the equation for the thermal analysis is carried out with hydrogen sulphide in the presence
decomposition of X. (1984, 4M) of hydrochloric acid but not in nitric acid. Explain. (1979, 2M)
79. Compound A is a light green crystalline solid. It gives the 82. A white amorphous powder A on heating yields a colourless,
following tests non-combustible gas B and a solid C. The later compound
(i) It dissolves in dilute sulphuric acid. No gas is produced. assumes a yellow colour on heating and changes to white on
(ii) A drop of KMnO4 is added to the above solution. The pink cooling. C dissolves in dilute hydrochloric acid and the
colour disappears. resulting solution gives a white precipitate with K 4 Fe(CN)6
solution. A dissolves in dil. HCl with the evolution of gas,
(iii) Compound A is heated strongly. Gases B and C, with
which is identical in all respect with B.
pungent smell, come out. A brown residue D is left behind.
(iv) The gas mixture (B and C) is passed into a dichromate The gas B turns lime water milky, but the milkiness
solution. The solution turns green. disappears with the continuous passage of gas. The solution
(v) The green solution from step (iv) gives a white precipitate E of A as obtained above, gives a white ppt E on addition of
with a solution of barium nitrate. NaOH solution, which dissolves on further addition of base.
Identify the compounds A, B, C, D and E. (1979, 4M)
Answers
1. (c) 2. (c) 3. (a) 4. (a) 29. (a, b, c, d) 30. (b, c) 31. (b, c) 32. (b)
5. (d) 6. (a) 7. (b) 8. (a) 33. (c) 34. (b) 35. (d) 36. (d)
9. (b) 10. (a) 11. (b) 12. (a)
37. (d) 38. (b) 39. (a) 40. (c)
13. (b) 14. (a) 15. (c) 16. (d)
17. (c) 18. (c) 19. (a) 20. (a) 41. (d) 42. (c) 43. (b) 44. CrO2Cl 2
21. (c) 22. (c) 23. (c) 24. (b,d) 45. Fe3+ 46. True 47. True 48. (6 or 7)
25. (a) 26. (c, d) 27. (a, c, d) 28. (a, b) 50. (5.92 BM)
CH3 CH3 Aluminium hydroxide on strong heating gives alumina (Al 2O3 )
which is used as an adsorbent in chromatography. This reaction
It does not react with H2O, 5% HCl and 10% NaHCO3. can be seen as :
Oleic acid (C18 H34O2 ) is soluble in 10% NaOH and 10% D
2Al(OH)3 ¾® Al 2O3 + 3H2O
NaHCO3 due to the presence of COOH group.
280 Qualitative Analysis
´
Weight of AgBr
´ 100 2HCl + Mg ¾® MgCl 2 + H2 (g )
Weight of organic bromide
16. PbCl 2 is soluble in hot water and PbS (black) is formed on
80 141 1128000
\ % of Br = ´ ´ 100 = = 24% passing H2S(g ) through acidic solution.
188 250 47000
17. Fe(II) and Fe(III) will have different values of magnetic moment
5. PLAN Ksp (ZnS) is very high and Zn 2+ is precipitated as ZnS by high due to different number of unpaired electrons in their d-orbitals.
concentration of S 2- formed when H 2S is passed in ammoniacal
solution. 18. Yellow filtrate contains CrO5 and brown residue contain Fe2O3.
H 2S a Zn + + S 2- (I)
H + OH - a H 2O (II)
+ 19. The total positive valency is +2 (because the only anion is
SO2-
4 ) . Therefore, oxidation state of Fe must be +1.
Reaction (I) is favoured in forward side if H+ is removed
immediately by OH- (NH4OH) . 20. Both Bi 3+ and Sn 4+ belongs to same analytical group II.
2+ 2-
Zn +S ¾® ZnS ¯ 21. CaC2O4 is insoluble in acetic acid. This distinguishes Ca 2+ from
White ppt
Ba 2+ ion.
Fe3+ and Al 3+ are precipitated as hydroxide.
6. In acidic medium, H2S is very feebly ionised giving very small 22. Ag+ is precipitated by HCl only while all others are precipitated
concentration of sulphide ion for precipitation. Therefore, the by passing H2S in the presence of HCl.
most insoluble salts CuS and HgS are precipitated only. 23. We know that,
7. Hg2+ + 2I- ¾® HgI2 (red) DG° = - 2.303 RT log K
Also, given equilibrium is
HgI2 + 2KI ¾® K2[HgI4 ] –
Soluble 2H2O - H3O+ + O H
Hg 2+
+ Co(SCN)2 ¾® Co[Hg(SCN)4 ] [H+ ][OH- ] = 10-14 or K = 10- 14
Blue
\ DG ° = - 2.303 ´ 8.314 JK–1mol-1 ´ 298K ´ log10-14
8. MgSO4 + NH4OH + Na 2HPO4 ¾® Mg(NH4 )PO4 ¯
White = 79881.8J mol - 1 = 79.8kJ » 80 kJ mol - 1
+ Na 2 SO4 + H2 O
24. Statement wise explanation is
9. CuSO4+ 2KCN ¾® Cu(CN)2 + K2SO4 Statement (a) Mn 2+ produces yellow-green colour in flame
CN test while Cu 2+ produces bluish-green colour in flame test.
2Cu(CN)2 ¾® 2Cu(CN) + ½ (Cyanogen) Thus, due to the presence of green colour in both the cases,
Unstable CN flame test is not the suitable method to distinguish between
CuCN + 3KCN ¾® 3K+ + [Cu(CN)4 ]3- nitrate salts ofCu 2+ and Mn 2+. Hence this statement is wrong.
Statement (b) Cu 2+ belong to group II of cationic or basic
10. Zn 2+ + 2H2O ¾® Zn(OH)2 ¯ + 2H+ radicals. It gives black ppt. of CuS if H2S is passed through it in
White the presence of acid (e.g HCl). Mn 2+ does not show this
Qualitative Analysis 281
property hence this can be considered as a suitable method to 28. NH4NO3 + NaOH ¾® NaNO3 + NH3 + H2O
distinguish between Mn 2+ and Cu 2+.
NH4NO2 + NaOH ¾® NaNO2 + NH3 + H2O
Hence, this statement is correct.
Statement (c) In faintly basic medium when H2S is passed both 29. When mixture of NaCl is heated with K2Cr2O7 in concentrated
Cu 2+ and Mn 2+ forms precipitates. Thus, it is not suitable H2SO4, red vapour of chromyl chloride (CrO2Cl 2 ) is produced.
method to distinguish between them. Vapours of chromyl chloride when passed through NaOH,
Hence, this statement is incorrect solution turns yellow due to formation of Na 2CrO4. Some
Statement (d) The standard reduction potential of Cu 2+/Cu is chlorine gas is also evolved owing to the following side
+0.34 V while that of Mn 2+/Mn is –1.18V. This can be used to reaction :
distinguish between Cu 2+ and Mn 2+. In general less 6Cl - + Cr2O72- + 14H+ ¾® 3Cl 2 (g ) + 2Cr 3+ + 7H2O
electropositive metals have higher SRP.
Hence, this statement is correct. 30. The blue precipitate of Fe2+ ion with potassium ferricyanide is
due to formation of Turnbull’s blue KFe[Fe(CN)6 ].
25. S2– + CuCl 2 ¾® CuS ¯ (black ppt.)
Fe2+ + K 3 [Fe(CN)6 ] ¾® KFe[Fe(CN)6 ] + 2K +
SO24- + CuCl 2 ¾® Soluble, Thus
(a) CuCl 2 selectively precipitates S2– . The red colour of Fe3+ ion with potassium thiocyanate is due to
formation of [Fe(SCN)3 ].
(b) S2– + BaCl 2 ¾® BaS ¯ (soluble)
Fe3+ + 3KSCN ¾® [Fe(SCN)3 ] + 3K +
SO24- + BaCl 2 ¾® BaSO4 ¯ (white ppt.) Red coloured
(b) precipitates SO2- 2-
4 and not S . 3+ 3+
31. Both Al and Bi are precipitated as their hydroxides.
(c) S2– + Pb2+ ¾® PbS ¯ (black ppt.)
32. As MgSO4 is soluble in water, so not used for estimation of SO2-
SO24- + Pb2+ ¾® PbSO4 ¯ (white ppt.)
4
ion.
S2- and SO2-
4 , both are precipitated. 33. Cation Cd 2+ belongs to group II while Ni 2+ belongs to group
2-
(d) S + Na 2 [ Fe (CN)]5 NO ¾® Na 4 [ Fe (CN)]5 NOS] III of analytical group. Group II radicals are precipitated by
Sodium nitroprusside (Purple colour) passing H2S(g ) through acidic solution of salt but radicals of
But no colour with SO2- group III are precipitated by passing H2S(g ) in NH3 /NH4Cl
4 .
buffer solution of salt due to greater solubility products of later
26. Only radicals of I and II group of qualitative analysis get salts.
precipitated with H2S in the presence of dilute HCl. 34. PLAN This problem can be solved by using concept of chemical
+
(c) Cu 2+ + H2S ¾H¾® CuS ¯ reactions of transition metal ions (,) colour and structure of
Black transition metal compounds.
+
Pb2+ + H2S ¾H¾® PbS ¯ Here, among given four option Ni 2+ and Zn 2+ has ability to form
Black tetrahedral as well as square planar complex depending upon
+
(d) Hg2+ + H2S ¾H¾® HgS ¯ types of reagent used.
Black
Ni 2+ on reaction with KCN forms square planar complex
H+
Bi 3+
+ H2S ¾ ¾® Bi 2S3 ¯ [Ni(CN)4 ]2- due to strong field strength of CN.
Brown ppt
Ba , Zn
2+ 2+
and Fe 3+
are not precipitated as sulphide. Ni 2+ + KCN ¾® [Ni(CN)4 ]2-
Square planar
+3 2+
27. K3 [Fe(CN)6 ] + KI (excess) ¾® While on reaction with HCl, Ni forms stable tetrahedral
+2 complex [Ni(Cl)4 ]2-.
K4[Fe(CN)6 ] + KI3 (redox)
Brownish yellow Zn 2+ , on the other hand, on reaction with KCN as well as HCl
solution produces tetrahedral complex because of its d 10 electronic
K4[Fe(CN)6 ] + ZnSO4 ® K2Zn 3[Fe(CN)6 ]2 configuration.
HCl
or K2 Zn[Fe(CN)6 ] [ZnCl4]2–
White ppt KCN
Zn2+ [Zn(CN)4]2–
I-3 + 2Na 2S2O3 ¾® Na 2 S4O6 + 2NaI + I2 KOH
[Zn(OH)4]2–
Brownish Clear (Turns starch excess
White ppt
yellow solution solution
filtrate blue) Complete reaction sequence can be shown as
K2Zn[Fe(CN)6 ] reacts with NaOH as
K2Zn[Fe(CN)6 ] + NaOH ¾® [Zn(OH)4 ]2 - + [Fe(CN)6 ] 4-
282 Qualitative Analysis
[NiCl4]2–
HCl(Q)
Ni2+
KCN(R)
[Ni(CN)4]2– 42. Y is FeCl 3.
excess excess
Tetrahedral (M1) Square planar 43. Compound Z is Fe[Fe(CN)6 ].
HCl(Q) KCN(R) [Zn(CN)4]2–
[ZnCl4]2– Zn2+
excess (M2)
excess 44. Heating chloride salt with K2Cr2O7 in conc. H2SO4 gives off a
Tetrahedral Tetrahedral
KOH (s)
deep vapour of chromyl chloride (CrO2Cl 2 ) .
B (H2S) produces D (s) : 61. The poisonous element M may be As. On the basis of given
information :
2H2S + SO2 ¾® 2H2O (l ) + 3S ¯
B E D Zn
AsCl 3 + 6H ¾¾® AsH3 + 3HCl
Anhydrous CuSO4 produces blue colour in water. H2 SO4 N
Solution C produces ppt first with NH3 /NaOH which dissolve in D
2AsH3 ¾¾® 2As + 3H2
excess NH3 /NaOH. Hence, A must be ZnS. M
ZnS + dil. H2SO4 ¾® ZnSO4 (aq) + H2S(g ) 250 °C
A 62. A ¾¾® B + C
C
Inorganic salt Neutral Neutral oxide
oxide (liquid)
ZnSO4 + 2NaOH ¾® Zn(OH)2 ¯ + Na 2SO4
C White Oxide C is liquid and neutral to litmus, so it is H2O. White
2- phosphorus burns in excess of B to give P4O10.
Zn(OH)2 + 2NaOH ¾® [Zn(OH)4 ] + 2Na +
Therefore, B is N2O.
D D
55. Na 2B4O7 ¾® 2NaBO2 + B2O3 NH4NO3 ( A ) ¾® N2O + 2H2O (l )
D B
CoO + B2O3 ¾® Co(BO2 )2
Blue P4 + 10N2O ¾® P4O10 + 10N2
284 Qualitative Analysis
63. On addition of KI solution to a Bi(NO3 )3 solution, firstly a dark 70. Formation of a reddish-brown precipitate with alkaline K2HgI4
brown precipitate of BiI3 is formed that dissolve in excess of KI solution indicates the presence of NH+4 ion and the gas liberated
forming a clear yellow solution of BiI-4 : is ammonia :
Bi 3+ + 3I- ¾® BiI3 ¯ ¾®
I-
BiI-4 NH+4 + OH- ¾® H2O + NH3 (g )
Dark Clear yellow NH2
brown solution Hg
C× HNO3 Filtered 2K2HgI4 + 3NaOH + NH+4 ¾® O ¯
64. A (Pb3O4 ) ¾¾® B (PbO2 ) ¾¾® Pb(NO3 )2 Hg
Scarlet Chocolate Filtrate I
Filtrate is neutralised with NaOH and on reaction with KI, gives + 4KI + 3NaI + 3OH-
yellow ppt of PbI2.
On treatment with BaCl 2, a white precipitate is formed which
Pb(NO3 )2 + 2KI ¾® PbI2 ¯ + 2KNO3 indicates the presence of SO2-
4 anion :
Yellow
PbO2 on warming with conc. HNO3 in presence of Mn(NO3 )2 SO24- + BaCl 2 ¾® BaSO4 ¯ + 2Cl -
White
produced pink solution due to formation of Pb(MnO4 )2 (I).
5PbO2 + 2Mn(NO3 )2 + 4HNO3 ¾® Pb(MnO4 )2 With K2Cr2O7 and conc. H2SO4, red vapour of CrO2Cl 2 is
evolved. This indicates presence of Cl - ion.
+ 4Pb(NO3 )2 + 2H2O
On treatment with potassium ferricyanide, formation of deep
Þ A = Pb3O4, B = PbO2 , C = PbI2 and D = Pb(MnO4 )2. blue solution indicates presence of Fe (II) ion :
D Fe2+ + Fe(CN)63- ¾® Fe4[Fe(CN)6 ]3
65. A ¾® B ¯ + C + H2O (v )
Orange solid Green Colourless Blue
74. 2KMnO4 + 3H2SO4 + 5H2C2O4 ¾® K2SO4 + 2MnSO4 (v) The sulphuric acid (formed in previous step) gives white ppt.
with Ba(NO3 )2 due to formation of BaSO4 (E) :
+ 8H2 O + 10CO2
H2SO4 + Ba(NO3 )2 ¾® BaSO4 ¯ + 2HNO3
75. (i) ZnO + 2NaOH ¾® Na 2ZnO2 + H2O White ( E )
(ii) Sn 2+ + I2 ¾® Sn 4+ + 2I- (vi) The residue D when heated on charcoal in a reducing flame
1 reduces to iron (Fe) which is a magnetic substance.
(iii) SO2 + H2O + O2 + 2NaCl ¾® Na 2SO4 + 2HCl
2 Hence, A = FeSO4, B = SO2, C = SO3, D = Fe2O3 and
76. (i) SO2 + 2H2S ¾® 3S + 2H2O E = BaSO4.
(ii) CuSO4 + 4NH3 ¾® [Cu(NH3 )4 ]SO4 80. FeCl 3 is a salt of strong acid and weak base. In water, it hydrolyses
(iii) Sn + 3HNO3 ¾® H2SnO3 + 4NO2 + H2O slowly producing brown ppt of Fe(OH)3.
Conc. Metastannic
acid FeCl 3 + 3H2O ¾® 3HCl + Fe(OH)3 ¯
(iv) H2O2 + CrCl 3 + NaOH ¾® Na 2CrO4 + NaCl + H2O Brown
Yellow
81. Nitric acid is a strong oxidising agent, oxidises H2S to S.
(v) Pb3O4 ¾® 2PbO + PbO2
2PbO + PbO2 + 4HNO3 ¾® 2Pb(NO3 )2 + 2H2O+ PbO2 ¯ 82. (i) The compound C produced by heating A is white in colour and
changes to yellow on heating, thus compound C may be ZnO.
77. 3KClO3 + 3H2SO4 ® 3KHSO4 + HClO4 + 2ClO2 + H2O C with dil. HCl and K4[Fe(CN)6 ] gives white ppt. This
(COOH)2 + C × H2SO4 ¾® CO + CO2 + H2O confirms that the compound C must be ZnO.
D
78. (X) is NaHCO3 (M = 84). The reactions involved are : A ¾® ZnO + B (gas)
‘C ’
2NaHCO3 ¾® Na 2CO3 (s) + CO2 (g ) + H2O (g )
X Y A B ZnO + 2HCl ¾® ZnCl 2 + H2O
C
168 g 106 g 44 g 18 g 2ZnCl 2 + K4[Fe(CN)6 ] ¾® 4KCl + Zn 2[Fe(CN)6 ] ¯
Þ 16.8 g 10.6 g 4.4 g 1.8 g
White ppt
CO2 + Ca(OH)2 ¾® CaCO3 ¯ + H2O
(ii) The gas B turns lime water milky and milkiness disappear with
H2O (g ) is condensed to liquid water. continuous passage of gas. Hence, the gas is CO2 and
Na 2CO3 + BaCl 2 ¾® BaCO3 + 2NaCl compound A in ZnCO3.
Y Z
CO2 + Ca(OH)2 ¾® H2O + CaCO3 ¯
BaCO3 + 2HCl ¾® BaCl 2 + H2O + CO2 B
Z
CaCO3 + CO2 + H2O ¾® Ca(HCO3 )2
79. Compound A is a light green crystalline solid, so it may be
FeSO4. D
ZnCO3 ¾® ZnO + CO2
(i) FeSO4 is a salt of strong acid and weak base, so it A C B
hydrolyses in dil. H2SO4 but no gas is evolved. (iii) The solution of A gives white ppt of ZnS D with NH4OH and
(ii) FeSO4 is a strong reducing agent, thus decolourises KMnO4 excess of H2S.
solution :
ZnCO3 + HCl ¾® CO2 + ZnCl 2
5Fe2+ + MnO4- + 8H+ ¾® 5Fe3+ + Mn 2+ + 4H2O B
Purple Colourless
(iii) FeSO4 on strong heating gives both SO2 (B) and SO3 (C ) NH4 OH
ZnCl 2 + H2S ¾¾¾® 2HCl + ZnS¯ (white)
gases alongwith a residue of Fe2O3 (D ). D
D
2FeSO4 ¾® Fe2O3 + SO2 + SO3 (iv) The solution of A also gives initially a white ppt E with NaOH,
D B C which dissolve in excess of reagent.
(iv) The gaseous mixture reduced dichromate solution to green
ZnCl 2 + 2NaOH ¾® Zn(OH)2 ¯ + 2NaCl
solution and also gives H2SO4 in solution : E (white)
Cr2O72- + 3SO2 + 2H+ ¾® 3SO24- + H2O + 2Cr 3+
Green Zn(OH)2 + 2NaOH ¾® Na 2[Zn(OH)4 ]
Soluble
H2O + SO3 ¾® H2SO4
CH3 H
H
H3C CH Br
CH3
(2019 Main, 10 Jan II)
(a) 3-bromo-3-methyl-1,2-dimethylprop-1-ene
CH3
(b) 3-bromo-1,2-dimethylbut-1-ene
CH2 (2019 Main, 12 April II) (c) 2-bromo-3-methylpent-3-ene
(a) 3-methyl-4-(3-methylprop-1-enyl)-1-heptyne (d) 4-bromo-3-methylpent-2-ene
(b) 3, 5-dimethyl-4-propylhept-6-en-1-yne
(c) 3-methyl-4-(1-methylprop-2-ynyl)-1-heptene CO2H
(d) 3, 5-dimethyl-4-propylhept-1-en-6-yne H OH
H Cl
2. The correct IUPAC name of the following compound is 6. The absolute configuration of is (2016 Main)
NO2
CH3
(a) (2S, 3R) (b) (2S, 3S)
(c) (2R, 3R) (d) (2R, 3S)
1
CH3 21. The IUPAC name of the compound
H CH2 == CH ¾ CH(CH3 )2 is (1987, 1M)
10. H
3 (a) 1,1-dimethyl-2-butene (b) 3-methyl-1-butene
2 (c) 2-vinyl propane (d) None of these
H H
22. An isomer of ethanol is (1986, 1M)
CH3 (a) methanol (b) diethyl ether
C 2 is rotated anti-clockwise 120° about C 2 -C 3 bond. The (c) acetone (d) dimethyl ether
resulting conformer is (2004, 1M) 23. The IUPAC name of the compound having the formula is
(a) partially eclipsed (b) eclipsed CH3
(c) gauche (d) staggered ½
11. Which of the following compounds exhibits, H3 C ¾ C ¾ CH==CH2
½
stereoisomerism? (2002, 3M) CH3
(a) 2-methylbutene-1 (b) 3-methylbutyne-1 (1984, 1M)
(c) 3-methylbutanoic acid (d) 2-methylbutanoic acid (a) 3, 3, 3-trimethyl-1-propene
(b) 1, 1, 1-trimethyl-2-propene
12. The number of isomers for the compound with molecular (c) 3, 3-dimethyl-1-butene
formula C2 BrClFI is (2001, 1M) (d) 2, 2-dimethyl-3-butene
(a) 3 (b) 4 (c) 5 (d) 6
24. Which of the following compounds will exhibit cis-trans
13. Which of the following compounds will exhibit geometrical (geometrical) isomerism ? (1983, 1M)
isomerism ? (2000, 1M) (a) 2-butene (b) 2-butyne
(a) 1-phenyl-2-butene (b) 3-phenyl-1-butene (c) 2-butanol (d) butanal
(c) 2-phenyl-1-butene (d) 1,1-diphenyl-1-propene
25. The compound which is not isomeric with diethyl ether is
14. The optically active tartaric acid is named as D-(+)-tartaric (a) n-propyl methyl ether (b) butane-1-ol (1981, 1M)
acid because it has a positive (1999, 2M) (c) 2-methyl propane-2-ol (d) butanone
(a) optical rotation and is derived from D-glucose
(b) pH in organic solvent Objective Questions II
(c) optical rotation and is derived from D-(+)-glyceraldehydes (One or more than one correct option)
(d) optical rotation when substituted by deuterium
26. The IUPAC name(s) of the following compound is (are)
15. How many optically active stereoisomers are possible for (2017 Adv.)
butane-2, 3-diol ? (1997, 1M)
(a) 1 (b) 2 (c) 3 (d) 4 H 3C Cl
CH3 CH3 34. Which of the following have asymmetric carbon atom?
H OH HO H (1989, 1M)
Cl Br H Cl
½ ½ ½ ½
(a) H ¾ C ¾ C ¾ H (b) H ¾ C ¾ C ¾ Cl
HO H HO H ½ ½ ½ ½
Cl Cl H H H H
P Q H Cl H H
½ ½ ½ ½
(a) M and N are non-mirror image stereoisomers (c) H ¾ C ¾ C ¾ D (d) H ¾ C ¾ C ¾ CH3
(b) M and O are identical ½ ½ ½ ½
H H Br OH
(c) M and P are enantiomers
(d) M and Q are identical 35. Keto-enol tautomerism is observed in (1988, 2M)
O O
29. The correct statement(s) about the compound (2009) ½½ ½½
H3 C(HO) HC ¾ CH == CH ¾ CH(OH)CH3 ( X ) is/are (a) C6H5 ¾ C ¾ H (b) C6H5 ¾ C ¾ CH3
H
Cl
(2008, 4M) Assertion and Reason
(a) the compound is optically active
Read the following questions and answer as per the direction
(b) the compound possesses centre of symmetry given below :
(c) the compound possesses plane of symmetry (a) Statement I is correct; Statement II is correct; Statement II is
(d) the compound possesses axis of symmetry the correct explanation of Statement I
32. Tautomerism is exhibited by (1998, 2M) (b) Statement I is correct; Statement II is correct; Statement II is
not the correct explanation of Statement I
¾
(a) ¾
¾ CH== CH ¾ OH (b) O ¾ ¾O
¾ (c) Statement I is correct; Statement II is incorrect
¾ (d) Statement I is incorrect; Statement II is correct
¾ 38. Statement I Molecules that are non-superimposable on
(c) ¾
¾O (d) ¾
¾O their mirror images are chiral.
Statement II All chiral molecules have chiral centres.
¾
¾
¾
¾
O (2007, 3M)
O
33. Which of the following compounds will show geometrical Fill in the Blanks
isomerism ? (1998, 2M)
39. Isomers which are ……… mirror images are known as
(a) 2-butene (b) propene
……… (superimposable, non-superimposable,
(c) 1-phenyl propene (d) 2-methyl-2-butene
enantiomers, diastereomers, epimers) (1988, 1M)
Organic Chemistry Basics 289
True/False 46. (a) Draw Newman’s projection for the less stable staggered
form of butane.
40. 2, 3, 4-trichloropentane has three asymmetric carbon atoms.
(1990, 1M)
(b) Relatively less stability of the staggered form is due to
(i) Torsional strain
41. m-chlorobromobenzene is an isomer of m-bromochloro
benzene. 1 (ii) van der Waals’ strain
(1985, M)
2 (iii) Combination of the above two (2004, 5M)
Integer Answer Type Questions 47. Glycerine contain one ……… hydroxy group. (2004)
42. The total number of stereoisomers that can exist for M is 48. Identify the pairs of enantiomers and diastereomers from the
(2015 Adv.) following (2000, 2M)
H3C CH3
CH3 CH3 CH3
H OH HO H HO H
HO H HO H H OH
3. The increasing order of nucleophilicity of the following 10. Which amongst the following is the strongest acid?
nucleophiles is (2019 Main, 10 April II) (2019 Main, 9 Jan I)
È (a) CHBr3 (b) CHI3
(1) CH3 COÈ2 (2) H2O (3) CH3 SO3È (4) O H
(c) CHCl 3 (d) CH(CN)3
(a) (1) < (4) < (3) < (2) (b) (2) < (3) < (1) < (4)
(c) (4) < (1) < (3) < (2) (d) (2) < (3) < (4) < (1)
11. Which of the following compounds will be suitable for
Kjeldahl’s method for nitrogen estimation? (2018 Main)
4. In chromatography, which of the following statements is
NH2
incorrect for R f ? (2019 Main, 10 April II)
(a) R f value depends on the type of chromatography (a) (b)
(b) Higher R f value means higher adsorption N
(c) R f value is dependent on the mobile phase
(d) The value of R f can not be more than one NO2 N+2Cl–
(d) DCM and H2O will make turbid/colloidal mixture (c) 3% (d) 5%
Organic Chemistry Basics 291
16. A gaseous hydrocarbon gives upon combustion 0.72 g of 24. The correct acidity order of the following is (2009)
water and 3.08 g of CO 2. The empirical formula of the OH OH COOH COOH
hydrocarbon is (2013 Main)
(a) C2H4 (b) C3H4 (c) C6H5 (d) C7 H8
17. The order of stability of the following carbocations
(c) H2C==C==C==CH2
½½
(b)
40. Which of the following, has the most acidic hydrogen?
O2N (2000)
– (a) 3-hexanone
C (b) 2, 4-hexanedione
(c) 2, 5-hexanedione
(d) 2, 3-hexanedione
OH
Organic Chemistry Basics 293
41. The most unlikely representation of resonance structures of 47. The number of sigma and pi-bonds in 1-butene 3-yne are
p-nitrophenoxide ion is (1999) (1989, 1M)
– – (a) 5 sigma and 5 pi (b) 7 sigma and 3 pi
O O O O
+
(c) 8 sigma and 2 pi (d) 6 sigma and 4 pi
N N
48. The compound which gives the most stable carbonium ion
on dehydration is (1989, 1M)
(a) (b) CH3
½
(a) CH3 ¾ CH ¾ CH2OH (b) CH3 ¾ C¾ OH
½ ½
O– O– CH3 CH3
– O –
O O O– OH
+ + ½
N N (c) CH3CH2 ¾ CH2 ¾ CH2OH (d) CH3 ¾ CH ¾ CH2CH3
49. Polarisation of electrons in acrolein may be written as
(c) (d) (1988, 1M)
d+
O O
d- ½½ d- ½½
O– O (a) H2C== CH ¾ C ¾ H (b) H2C== CH ¾ C ¾ H
d+
42. Among the following compounds, the strongest acid is d-
(1998) O O
(a) HCººCH (b) C6H6 d- d+ ½½ d+ ½½
(c) H2C== CH ¾ C ¾ H (d) H2C== CH ¾ C ¾ H
(c) C2H6 (d) CH3OH
50. The bond between carbon atom (1) and carbon atom (2) in
43. In the following compounds (1997)
compound
OH OH OH OH Nºº C ¾ CH== CH2
1 2
involves the hybridisation as (1987, 1M)
(a) sp2 and sp2 (b) sp3 and sp
(c) sp and sp2 (d) sp and sp
NO 2
CH 3 NO 2
Objective Questions II
(I) (II) (III) (IV ) (One or more than one correct option)
The order of acidity is 51. Among P, Q, R and S, the aromatic compounds(s) is/are
(a) III > IV > I > II Cl
(b) I > IV > III > II NaH
AlCl3 Q
(c) II > I > III > IV P
(d) IV > III > I > II
O
44. What is the decreasing order of strength of the bases? (NH4)2CO3 HCl
R S
OH - , NH2- , H ¾ Cºº C - and CH3 ¾ CH2- (1997) 100-115°C
O O
(a) CH3 ¾ CH2- > NH2- > H ¾ Cºº C > OH - -
(2013 Adv.)
(a) P (b) Q (c) R (d) S
(b) H ¾ Cºº C - > CH3 ¾ CH2- > NH2- > OH -
52. The hyperconjugative stabilities of tert-butyl cation and
(c) OH - > NH2- > H ¾ Cºº C - > CH3 ¾ CH2- 2-butene, respectively, are due to (2013 Adv.)
(d) NH2- > H ¾ Cºº C > OH > - -
CH3 ¾ CH2- (a) s ® p (empty) and s ® p* electron delocalisations
(b) s ® s* and s ® p electron delocalisations
45. The hybridisation of carbon atoms in C ¾ C single bond (c) s ® p (filled) and s ® p electron delocalisations
H ¾ C ºº C ¾ CH==CH2 is (1991, 1M)
(d) p (filled) ® s* and s ® p* electrons delocalisations
(a) sp3 - sp3 (b) sp2 - sp3
53. Amongst the given options, the compound(s) in which all
(c) sp - sp2 (d) sp3 - sp the atoms are in one plane in all the possible conformations
(if any), is/are (2011)
46. Amongst the following, the most basic compound is H H H
(a) benzylamine (b) aniline (1990, 1M) (a) C¾ C (b) H ¾ C ºº C¾ C
(c) acetanilide (d) p-nitroaniline H2C CH2 CH2
(c) H2C == C == O (d) H2C == C == CH2
294 Organic Chemistry Basics
54. In the Newman’s projection for 2,2-dimethylbutane 57. Phenol is less acidic than (1986)
X (a) acetic acid (b) p-methoxy phenol
H3C CH3
(c) p-nitrophenol (d) ethanol
Column I Column II
H3C O O
O
A. p.
aq NaOH
Nucleophilic substitution
18
O O
B. ½½ 18
CH2CH2CH2OH
H2SO4 q. Electrophilic substitution
O O
½½
C. CH2CH2CH2Cl CH3MgI r. Dehydration
CH3
CH2CH2CH2C(CH3)2
D. H2SO4 s. Nucleophilic addition
OH
H 3C CH3 t. Carbanion
Organic Chemistry Basics 295
61. Match the reaction in Column I with appropriate options in Column II. (2010)
Column I Column II
p. Racemic mixture
—N2Cl + —OH
A.
0°C NaOH/H2O
—N N— —OH
OH OH O q. Addition reaction
½ ½ H 2SO 4 CH3
B. H3C — C — — C — CH3 ¾¾¾® C
½ ½ H3C C—CH3
CH3 CH3 CH3
O r. Substitution reaction
1. LiAlH4
—–C
2. H3O +
CH3
C.
OH
—–HC
CH3
s. Coupling reaction
SH— —Cl Base S
D.
t. Carbocation intermediate
Answers
Topic 1 17. (d) 18. (c) 19. (c) 20. (b)
1. (d) 2. (c) 3. (b) 4. (c) 21. (c) 22. (b) 23. (d) 24. (a)
5. (d) 6. (a) 7. (b) 8. (a) 25. (b) 26. (d) 27. (a) 28. (d)
9. (c) 10. (c) 11. (d) 12. (d) 29. (c) 30. (c) 31. (a) 32. (a)
13. (a) 14. (c) 15. (b) 16. (a) 33. (a) 34. (a) 35. (c) 36. (b)
17. (a) 18. (b) 19. (b) 20. (a) 37. (b) 38. (b) 39. (d) 40. (b)
21. (b) 22. (d) 23. (c) 24. (a) 41. (b) 42. (d) 43. (d) 44. (a)
25. (d) 26. (b,c) 27. (a,c,d) 28. (a,b,c) 45. (d) 46. (a) 47. (b) 48. (b)
29. (a,d) 30. (b,c,d) 31. (a,d) 32. (a,c,d) 49. (d) 50. (c) 51. (a,b,c,d) 52. (a)
33. (a,c) 34. (c,d) 35. (b,d) 36. (d) 53. (b,c) 54. (b,d) 55. (b,c) 56. (c,d)
37. (7) 38. (c) 57. (a,c) 58. (d) 59. (a)
39. Non-superimposable, Enantiomers 40. False 60. A ® r, s, t; B ® p, s; C ® r, s; D ® q, r
41. False 42. (2) 43. (3) 44. (7) 61. A ® r, s; B ® t; C ® p, q; D ® r
62. hyperconjugation
Topic 2
63. less 64. cyclic 65. butanedioic acid
1. (c) 2. (b) 3. (c) 4. (b)
66. triangular planar 67. geminal, same
5. (b) 6. (b) 7. (a) 8. (d)
68. sp3 69. cylopropane 70. propene 71. aniline
9. (a) 10. (d) 11. (b) 12. (d)
13. (c) 14. (a) 15. (b) 16. (d) 72. tert-butyl carbonium ion, 73. (6) 74. (4)
Hints & Solutions
Topic 1 Nomenclature and Isomerism While naming the compound, the longest chain that have
1. The IUPAC name for the given compound is principal functional group ¾ COOH is choosen and numbered
3, 5-dimethyl-4-propylhept-1-en-6-yne. in such a manner that the principal functional group gets the
CH3 lowest possible number. ¾ OH act as substituent and used as
H3C 7 CH prefix in nomenclature.
5
Longest possible
4 6 chain containing 5. While naming the compound, alkene gets priority over
2 3
double and functional group ( ¾ Br ) and numbering starts from alkene side.
CH3 triple bond
1 Hence, IUPAC name: 4-bromo-3-methyl pent-2-ene
CH2 1
CH3 CH3
If both double and triple bonds are present in the compound, the
2 H
endings like-en-yne, a (numeral) dien-(numeral)-yne etc., are 3
4
used. Numbers as low as possible are given to double and triple H
bonds as a set. CH3 Br
5
2. The IUPAC name of the given compound is
6. 1
NO2
COOH
2
4 H OH
Incorrect
3
Correct
3 H Cl
way
way
4
2 CH3
1 Cl
For C-2, order of priority of substituents is
CH3 OH > CH(Cl) (CH3 ) > COOH
2- chloro-1-methy l- 4-nitrobenzene For C-3, order of priority of substituents is
Here, the given compound contains two or more functional Cl > CH(OH)COOH > CH3
groups. So, the numbering is done in such a way that the sum of
Hence, according to CIP rules,
the locants is the lowest.
O OH 3
3. COOH
1
H 2 1
OH 2S
Acetone No additional stability H Cl 3R
with the ‘enol’ form
3
H CH3
O O
O O OH
5
Acetylacetone
This enol-form is highly stable
because of intramolecular 7. CN has the highest priority.
1
H-bonding (6-membered stability)
and due to extended conjugation. 2 CN
Br
O O (–R) (2-bromo-5-hydroxybenzonitrile)
O O
O Br
1 2
Ethyl acetoacetate 1 2 NH2 H
(EAA)
CH3 C
H H 3C
In both of the compounds, C -2 of C == O group is a part of the acid Br2
C==C CCl4
C H
O O 8. CH3
½½ ½½
H3C H
Br
derivative (ester, ¾ C ¾ OEt and acid amide, ¾ C ¾ NH2). So,
CH3
C2 O does not take part in enolisation, because it is already in
H Br
resonance (–R) with the derivative group itself.
H Br
4. The IUPAC name of the given compound is CH3
3-hydroxy-4-methylpentanoic acid. (meso)
CH3 OH O
½ 4 ½½
5 ½3 2 1 9. C6H5 ¾ C ¾ Cl : Benzene carbonyl chloride
H3 C ¾ C H ¾ C H ¾ C H2 ¾ C OOH
Principal chain
298 Organic Chemistry Basics
1
CH3 H 19. Compounds with same empirical formula but different
molecular formula have same percentage composition of
H H H H elements but different molecular weight.
3 120° 3
10. 2 2 H H
Anti-clockwise 1
H H H ½ ½
H 3C
20. H— C — C — H ; Ethane has the smallest sized group (H)
CH3 CH3 ½ ½
H (gauche) H H
½* bonded to carbons, hence there will be least hindered rotation
11. CH3 — CH2 — C ¾ COOH : Has a chiral carbon, optically active. about C—C bond.
½
CH3 1 2 3 4
(2-methylbutanoic acid) 21. CH2 == CH— CH — CH3 : 3-methyl-1-butene
½
F Cl F I CH3
12. C == C + C == C Geometrical isomers
22. Ethers and alcohols (saturated, acyclic) with same number of
Br I Br Cl carbons are always isomeric.
F Br F I CH3 — O— CH3 and CH3 — CH2 — OH are functional isomers.
C == C + C == C Geometrical isomers
23. Double bond has preference over alkyl group hence :
Cl I Cl Br
CH 3
F Cl F Br
4 ½3 2 1
C == C + C == C Geometrical isomers H3 C— C ¾ CH == CH2 : 3,3-dimethyl-l-butene
I Br I Cl ½
CH3
H3C CH2 — Ph H CH2 — Ph H3 C CH3 H CH3
13. C == C C == C
24. C== C C== C
H H H3C H
cis trans H H H3 C H
cis-2- butene trans-2- butene
1-phenyl-2-butene
14. The ‘D’ term in name is derived from D-glyceraldehyde. 25. Diethyl ether (C2H5OC2H5 ) will be isomeric with all 4-carbon
15. M saturated alcohols. Butanone (CH3CH2COCH3 ) is unsaturated,
CH3 CH3 CH3 has two hydrogen less than the diethylether.
H OH HO H H OH 26. Since, there is no principal functional groups, numbering of
HO H H OH H OH disubstituted benzene is done in alphabetical order as
Cl
CH3 CH3 CH3
1
I II III
6 2
I and II are optically active while III is optically inactive
(meso form ). 5 3
16. Conformers can be interconverted through rotation about C—C 4
bond. H CH3
· ·
·O · Hence IUPAC name of this compound is 1-chloro-4-methyl
½ benzene.
17. H— C == C ¾ CH3 :
½ Also, toluene is an acceptable name in IUPAC, hence this
H compound can also be named as 4-chloro toluene.
Enol of acetone
It has 9 s (6 with H, two C—C and one C ¾ O), one p-bond and 27. PLAN This problem is based on structure and nomenclature of
two lone-pairs. organic compound.
Draw structure of each compound and write IUPAC name of the
given compound.
18.
I II Match the molecular formula of given compound with
III molecular formula of compound given in choices.
The combination of names for possible isomeric alcohols with
molecular formula C4H10O is/are
IV V
Organic Chemistry Basics 299
H
Cl H OH (c) ==O r —OH
OH H OH
CH3 CH3
O HO
P
300 Organic Chemistry Basics
==O r
38. Molecules that are non-superimposable on its mirror image are
(d) —OH
optically active and known as chiral molecule. However, for
chirality of molecule, presence of chiral centre is not essential,
O O e.g.
H3C CH3
H3C CH3 H3C H
33. (a) C == C + C == C C==C==C
H H H CH3
cis-2- butene trans-2- butene
H H
H H Ph Molecule is chiral but does not possesses any chiral carbon.
H
(c) C == C + C == C 39. Non-superimposable, Enantiomers.
Ph CH3 H CH3
cis-1-phenylpropene trans-1- phenylpropene
True / False
34. A carbon bonded to four different atoms or groups is called 40. It has only two asymmetric carbon, carbon no.3 is not
asymmetric.
asymmetric carbon :
Cl H 41. They are identical.
½ ½*
(c) CH3 — C*— D (d) BrCH2 — C— CH3 42. Although the compound has two chiral carbons (indicated by
½ ½ stars), it does not has four optically active isomers as expected.
H OH It is due to its existence in cis-form only.
CH3
35. Carbonyl compounds containing a-H show keto-enol CH3 CH3
tautomerism. H3C
O OH *
½½ ½
(b) C6H5 ¾ C ¾ CH3 r C6H5 — C == CH2
*
H3C CH3
O O O O
½½ ½½ cis-form
(d) C6H5 ¾ C ¾ CH2 ¾ C ¾ CH3 r
trans-form
(only hypothetical)
O OH
½½ ½ The above shown transformation does not exist due to restricted
C6H5 ¾ C ¾ CH== C— CH3 rotation about the bridge head carbons, hence only cis-form and
CH3 CH3 its mirror image exist.
½ Cl 2 ½ 43. PLAN This problem can be solved by using concept of conformational
36. CH3 — C — CH3 ¾¾® CH3 — C — CH 2Cl analysis of given organic compound. To solve the question
½ hn ½ draw the stable conformational structures of organic
H H CH3 compound and determine the net resultant dipole moment.
½ The conformations of the given compound are as follows
+ CH3 — C — CH3
Cl
½
Cl Br Cl
Cl CH3 Br
37. (7) As given in the question 3 stereocentres are visible, i.e. Br CH3 Cl Br
= =
Br Cl Br Cl
OH OH
CH3 CH3
H3C CH3
* *
H H H
* 1
½ ½ ½ 5
HO C H3 ¾ C*2 ¾ C*3 ¾ C*4 ¾ CH3
OH
½ ½ ½
Hence, the total number of stereoisomers = 23 = 8 Cl Cl Cl
But out of these the following one is optically inactive due to Cl CH3 Br
symmetry
Br Cl Br Cl Br Cl
OH OH
CH3 Br Br Cl Cl CH3
CH3 CH3 CH3
(Me-Me)gauche (Br-Me)gauche (Cl-Me)gauche
HO
OH
Hence, total number of optically active stereoisomers=7
Organic Chemistry Basics 301
These three have non-zero dipole moment due to 48. I and III are mirror images of one another as well as they are
non-cancellation of all dipole moment created by C—Cl and non-superimposable while II is a meso form.
C—Br bond. Þ (I + III) = Enantiomers
44. CH2CH3 CH3 CH3 I + II and II + III = Diastereomers
CH3 OH
49. O
CH3 CH3
H H CH3 H H
½ 2 1
meso 50. H3C— N — C—
3
CH2 — CH3
pair of enantiomers ½ ½ 5
Þ Total seven isomers CH3 CH2CH3
4
2. Organic compound ‘A’ contain phosphorus as it gives positive At ‘a’ and ‘e’, N-atoms are sp3 (s% = 25) hybridised, whereas at ‘
test with ammonium molybdate. Phosphorus present in organic b’, ‘c’ and ‘d’, N-atoms are sp2 (s% = 33) hybridised. So, ‘b’, ‘c’
compound ‘A’ get oxidised with Na 2O2 and form Na 3PO4. and ‘d’ are the favourable sites for protonation
2P + 5Na 2O2 ¾® 2Na 3PO4 + 2Na 2O
(H+ is a Lewis acid, i.e. electrons acceptor).
Compound Sodium phosphate
Na 3PO4 in presence of HNO3 form H3PO4 and NaNO3. 7. The correct option is :
Na 3PO4 + 3HNO3 ¾¾® H3PO4 + 3NaNO3 (A) ® (Q); (B) ® (R); (C) ® (S)
Upon cooling, a few drops of ammonium molybdate solution are (A) H2O and sugar mixture They do not react chemically. On
added. A yellow ppt. confirms the presence of phosphorus in the heating, solubility of sugar in H2O increases and on rapid
organic compound. cooling of saturated solution, sugar recrystallises (Q).
H3PO4 +12 (NH4 )2 MoO4 + 21HNO3 ¾® (B) H2O and aniline mixture Aniline is steam volatile but
(NH4 )3 PO4.12MoO3 ¯ +21NH4NO3+12H2O insoluble in H2O. So, steam distillation (R) is employed for
Yellow ppt. their separation.
3. Higher the basicity of a base, stronger will be its nucleophilic (C) H2O and toluene mixture Toluene is steam non-volatile
power.
and also insoluble in H2O. So, differential extraction method
Again we know, a weaker acid produces a stronger base
(S) can be used to separate them.
(conjugate), i.e. a stronger nucleophile.
- HÅ 8. In Dumas method, organic compound is heated with dry cupric
Acid ¾¾® Conjugate base oxide in a combustion tube in the atmosphere of CO2. Upon
H3O+ H2O heating, C and H present are oxidised to CO2 and water vapours
CH3SO3H CH3SOÈ3 while N 2 is set free. Let, the molecular formula of the organic
CH3CO2H CH3COÈ2 compound (1 mol) be C xH yN z. In Dumas method,
y y z y
H2O È
OH Cx H y N z + æç 2x + ö÷ CuO ® xCO2 + H 2 O + N 2 + æç 2x + ö÷ Cu
1 mol è 2 ø 2 2 è 2 ø
Acid Base strength
y z
strength º Nucleophilicity x mol mol mol
2 2
Thus, the correct order of nucleophilicity of given nucleophiles y z
are as follows : Now, x = 6, = 4 Þ y = 8 and = 1Þ z = 2
-
2 2
H2O(2) < CH3SO-3 (3) < CH3CO-2 (1) < O H(4) \ Molecular formula of the compound is C6H8 N2.
4. In chromatography, the expression of retention factor (R f ) is 9. Dichloromethane, DCM (CH2Cl 2 ) is heavier (density
Distance travelled by the compound from origin = 13266
. g cm-3) than water (density = 1 g cm -3 ). So, DCM and
Rf = <1
Distance travelled by the solvent from origin H2O will stay as lower and upper layer respectively in the
The value of R f signifies the relative ratio of migration of each separating funnel (SF).
component of the mixture with respect to the developing solvent 10. We know, a stronger acid produces its stable or weaker conjugate
used. R f value depends on the type of adsorption base. Here, CH(CN)3 produces the most stable conjugate base
chromatography like TLC (Thin-Layer Chromatography), (NC)3 C- . Stronger -R and -I effects of the CN - group, make
paper chromatography etc. The R f value is also the
the carbanion (conjugate base) very stable. The resonance
characteristic of a compound (sample) for a given developing
hybrid structure of [(NC)3 C]- is as follows:
solvent at a given temperature.
When the compound in the sample (usually less polar) is weakly CN
d– d+ –
adsorbed the spot will travel a shorter distance from the origin (NC) C H NC C y +H Å (NC)2C C N
3
and hence the R f value will be decreased. (–I)
C N (–R)
5. In column chromatography, separation of mixture of
compounds (adsorbate) takes place over a column of solid y
adsorbent (silica gel and Al 2O3 ) packed in a glass tube. N
When an appropriate eluant (liquid) is allowed to flow down the C
column, the compounds present in the mixture get adsorbed to N C C
different extent on the adsorbent column and thus complete C
separation takes place. N
Thus, column chromatography is based on the differential
adsorption of the substance on the solid phase. Resonance hybrid structure of [NC)3C]–
However, halogen (X = Cl, Br, I) show -I effect but + R effect
6. All sites (a, b, c, d, e) of the given molecule have lone pair on
of halogens, destabilises the carbanion, X 3C – (conjugate base of
N-atoms. Higher the ease of donation of lp of electrons of N,
more favourable will be the site for protonation. Ease of the haloform, HCX 3 ).
donation of lp of e s, i.e. Lewis basicity inversely depend on the s
percentage of s-character in hybridisation of ‘N’ which will X2C X (+R,–I )
decide the electronegativity of ‘N’. Thus, CH(CN)3 is the strongest acid among the given options.
Organic Chemistry Basics 303
11. Estimation of nitrogen through Kjeldahl’s method is not suitable ammonium sulphate and ammonium sulphate to sodium
for organic compounds containing nitrogen in ring or nitrogen in sulphate.
nitro or azo groups. It is because of the fact that nitrogen of these (b) Calculate millimoles (m moles) of N present in organic
compounds does not show conversion to Ammonium sulphate compound followed by mass of N present in organic
((NH4 )2 SO4 ) during the process. Hence, among the given compound using the concept of stoichiometry.
compounds only aniline can be used suitably for estimation of (c) At last, calculate % of N present in organic compound using
nitrogen by Kjeldahl’s method. formula
12. Aromatic compounds are stable due to resonance while Mass of N ´ 100
non-aromatics are not. According to Huckel’s rule (or 4 n + 2 % of N =
Mass of organic compound
rule), “For a planar, cyclic compound to be aromatic, its p cloud
must contain (4 n + 2)p electrons, where, n is any whole Mass of organic compound = 1.4 g
number.” Thus, Let it contain x m mole of N atom.
Organic compound ¾® NH3
and x m mole
,
O N 2NH3 + H2SO4 ¾® (NH4 )2 SO4 …(i)
(6pe– system) (4pe– + 2e– system) (6pe– system) 6 m mole
initially taken
are aromatic and stabilised by resonance.
They follow Huckel’s rule. H2SO4 + 2 NaOH ¾® Na 2SO4 + 2 H2O ...(ii)
2 m mole NaOH reacted.
is non-aromatic, hence, Hence, m moles of H2SO4 reacted in Eq. (ii) = 1
least stabilised by resonance.
Þ m moles of H2SO4 reacted from Eq. (i) = 6 - 1
O = 5 m moles
13. Glycerol with high boiling point (290°C) can be separated from Þ m moles of NH3 in Eq. (i) = 2 ´ 5 = 10 m moles
spent lye by distillation under reduced pressure. This process is Þ m moles of N atom in the organic compound
used to purify liquids having very high boiling points. By this = 10 m moles
process, liquid is made to boil at lower temperature than its Þ Mass of N = 10 ´ 10-3 ´ 14 = 0.14 g
boiling point by lowering the pressure on its surface.
14. ¾ OH group displays both kinds of effect; an electron Mass of N present in
organic compound
withdrawing acid-strengthening inductive effect from the % of N = ´100
meta-position and an electron-releasing acid weakening Mass of organic compound
resonance effect from the para-position (at this position, 0 .14
resonance effect overweighs the inductive effect). Þ % of N = ´ 100
1.4
Thus, III > IV.
o-hydroxybenzoic acid (II) is far stronger than the = 10%
corresponding meta and para isomers as the carboxylate ion is 16. 18 g H2 O contains 2g H
stabilised by intramolecular H-bonding.
2,6-dihydroxybenzoic acid (I) forms carboxylate ion which is \ 0.72 g H2O contains 0.08 g H
further stabilised by intramolecular H-bonding, Thus, correct 44 g CO2 contains 12 g C
order is \ 3.08 g CO2 contains 0.84 g C
I > II > III > IV 0.84 0.08
d- \ C:H = :
O O d+ d- d- 12 1
C H d+ O O d+
H C H = 0.07 : 0.08 = 7 : 8
O O O \ Empirical formula = C7 H8
17. The order of stability of carbocation will be
CH2+
II I
(Most stable)
15. THINKING PROCESS This problem is based on the estimation of > CH2 CH CH2 > CH3 CH2 CH2
percentage of N in organic compound using Kjeldahl’s method. Use
the concept of stoichiometry and follow the steps given below to solve Benzyl Allyl Propyl
the problem. ( resonance ( resonance (stabilised by
(a) Write the balanced chemical reaction for the conversion of N stabilised with more stabilised) +I effect)
present in organic compound to ammonia, ammonia to canonical forms)
(III) (I) (II)
304 Organic Chemistry Basics
OH OH OH OH 22. I is most stable because it has more covalent bonds and negative
charge on electronegative nitrogen. III is more stable than II and
IV due to greater number of covalent bonds. Between II and IV,
18. > > >
II is more stable since, it has negative charge on electronegative
atom and positive charge on electropositive atom. Hence,
NO2 Cl CH3 OCH3 overall stability order is
(–M, –I ) ( –I) (+I, (+M) I > III > II > IV
(hyper conjugation)
(III) (I) (II) (IV) 23. H at C 2 will migrate giving resonance stabilised carbocation.
Electron releasing group decreases while electron withdrawing H H
+
group increases acidic strength by destabilising and stabilising ½ + ½ H-
the phenoxide ion formed respectively. H3C ¾ C ¾ C ¾ C ¾ CH3 ¾® H3C ¾ C ¾ CH2CH(CH3 )2
shift
½ ½ ½ ½
SbCl 5 Å OH H CH 3 OH
19. Cl ¾ CH ¾ CH3 ¾¾® Ph ¾ CH ¾ CH3 + SbCl6-
½ Toluene (Carbocation) ¬® H3C ¾ C ¾ CH2 ¾ CH(CH3 )2
Ph (planar) ½½
+
(- ) OH
¾® Ph ¾ CH ¾ CH3
½ —OH < Cl— —OH <
Cl 24.
( d and l ) mixture
I II
+ SbCl 5
20. Allene is the name given to propdiene, H2C == C == CH2 . H3C— —COOH < —COOH
Allene
Hybridisation of an atom is determined by determining the
IV III
number of hybrid orbitals at that atom which is equal to the + I effect
number of sigma (s) bonds plus number of lone pairs at the decreases acid strength
concerned atom.
Cl has overall electron withdrawing effect, increases acid
Pi(p ) bonds are not formed by hybrid orbitals, therefore, not strength.
counted for hybridisation.
H p H
H s H –
s s
C C C s
s
25. H—C—CH—CH2 H—C==CH—CH2
H s H +
H H
26. The s-electron of C ¾ H bond is delocalised with p-orbitals of
Here, the terminal carbons have only three sigma bonds p-bond.
associated with them, therefore, hybridisation of terminal carbons
is sp3. The central carbon has only two sigma bonds associated, + 3°, has resonance
O O stability
hence hybridisation at central carbon is sp. +
I
21. A mono-substituted benzoic acid is stronger than a +
mono-substituted phenol as former being a carboxylic acid. has no resonance stability but 2°
Among the given substituted benzoic acid, ortho-hydroxy acid II
is strongest acid although —OH causes electron donation by
+
resonance effect which tends to decrease acid strength. 2°, has resonnce
O O
It is due to a very high stabilisation of conjugate base by + stability
III
intramolecular H-bond which outweigh the electron donating
resonance effect of —OH.
+ 1°, has no resonance stability
O
IV
COOH –
O Therefore, overall stability order is : I > III > II > IV
H+ +
H 27. The following structure has like charge on adjacent atoms,
OH O therefore, least stable
The overall order of acid-strength of given four acids is + O
+
ortho-hydroxybenzoic acid (pKa = 2.98) > Toluic acid N
-
pKa = 4.37) > p-hydroxybenzoic acid (pKa = 4.58) >
p-nitrophenol (pKa = 7.15) O-
Organic Chemistry Basics 305
29. A spontaneous neutralisation will occur between strong acid and 38. I is most basic due to formation of resonance stabilised
strong base as conjugate acid .
+
NH NH2
+
H3C— H3C ¾ C H
¾® H3C ¾ C
—SO3H + CH3COONa
strong base NH2 N H2
strong acid ··
NH2
– + ¬® H3C ¾ C
H3C— —SO3Na + CH3COOH
weak acid NH2
+
weak base resonance stabilised
+ -
conjugate acid
30. H2C== CH ¾ CH ¾ CH ¾ O ¾ CH3 IV is amide, least basic.
-
Lone pair of oxygen is not the part of this mode of O O
delocalisation. ½½ · · ½ +
CH3 ¾ C ¾ N H2 ¬® CH3 ¾ C == NH2
31. Carboxylic acid is stronger acid than ammonium ion, hence lone pair is part of delocalisation
+ +
—COOH(X) is most acidic. Z (NH3 ) is more acidic than Y (NH3 ) Also, among alkyl amines, 2° is more basic than 1° amine.
due to – I effect of —COOH on Z. Hence, overall acid strength Hence, overall order of basic strength is
order is 1>3>2>4
X > Z > Y
39.
32. CH3Cl has highest dipole moment. —CH2—NH2
33. H2C ==CH ¾ C ºº N
2 Lone pair is not taking part in resonance, most basic. In other
sp2 sp sp sp cases, lone pair of nitrogen is part of delocalisation which
decreases Lewis base strength.
34. In general, the order of acid strength is
¾ C ºº CH < ROH < H2O < PhOH < R ¾ COOH
40. A methylene ( ¾ CH2 ¾ ) with carbonyl on both side is highly
Therefore, during stepwise neutralisation of given acid, acidic.
—COOH will be neutralised first. O O
In the second step, the phenolic —OH, assisted by – I effect of ½½ ½½
CH3 ¾ C ¾ CH2 ¾ C ¾ CH2 ¾ CH3
¾ NO2 at meta position will be neutralised. *
HOOC has very acidic H.
OH O
–
41. O— ==N
O2N 2 moles of O
CH NaNH2 octet of nitrogen is violated.
– 42. Although alcohols are weaker acid than water, it is stronger than
OOC ammonia and terminal alkynes.
OH OH
43. Nitro group from para position exert electron withdrawing
+ 2NH3 resonance effect, increases acidity of phenol the most. This is
followed by meta nitrophenol in which nitro group exert
O2N
electron withdrawing effect on acidity. CH3— is an electron
CH donating group, decreases acid strength. Hence, the overall
order is
( 4 n + 2) = p electron delocalised.
Cl CH3
+ On C2 — C3 axis, X = CH3 , Y = CH3
– On C1 — C2 axis, X = H, Y = C2H5
+ AlCl3 + AlCl4
CH3
Aromatic ½
P 55. H3C ¾ C — CH3 m =0
– ½
CH3
+ NaH + H2 H3C H
C == C m ¹0
Aromatic
Q H C2H5
unsymmetrical
O OH
H5C2 C2H5
r C == C m ¹0
O (NH4)2CO3 HCl
O D, 100–115°C ; H H
N
Aromatic CH3 CH3
H S ½ ½
Aromatic CH3 ¾ C — C — CH3 m =0
R ½ ½
CH3 CH3
symmetrical
Organic Chemistry Basics 307
O O +
O 18 +
OH
½½ ½½ OH H
56. H ¾ C ¾ OH H 2N ¾ C ¾ NH2 C. Ph Ph
:OH
Nucleophilic addition
sp2 sp2
CH3 –H+ Ph –H2 O+
O Ph
½ ½½ HO O O
CH3 ¾ C — O ¾ H CH3 ¾ C ¾ H 18
Dehydration
½
sp 3 CH3 sp 3 H
+
D. Ph –H2O
57. Phenol is less acidic than a carboxylic acid (acetic acid). Nitro OH +
group from para position exert electron withdrawing resonance Friedel-
effect, increases acid strength. Therefore, phenol is less acidic Craft alkylation
than p-nitro phenol.
Electrophilic
On the other hand, methoxy group from para position, donate substitution
electrons by resonance effect, decreases acid strength of phenol.
Also ethanol is weaker acid than phenol due to resonance
stabilisation in phenoxide ion. 61. +
—N2 + —OH
Hence,
ethanol < p-methoxyphenol < phenol < p-nitrophenol < acetic
acid —N==N— —OH
¾¾increasing acid strength ¾¾®
58. Statement I is incorrect; Statement II is correct. Intramolecular this is an example of electrophilic substitution at para position
H-bonding in ortho-hydroxy benzoic acid lowers the boiling of phenol, giving a coupling product.
point. O H O–
59. Statement I is correct; Statement II is correct; Statement II is the
correct explanation of Statement I. Ph—C—CH3 + H—Al–—H Ph—C—CH3
O CH S
2 OH HS— —Cl Base
—S– —Cl + Cl
O H2O O
Ph Ph
Nucleophilic
carbanion substitution
–H2O O
Ph 62. Hyperconjugation.
Dehydration 63. Less, stable free radical is formed.
O– 64. Cyclic
O H
CH3MgBr
Cl Ph O O
B. Ph CH
Cl C
Ph O H3C CH3
SN 2
H3C
308 Organic Chemistry Basics
O O 77. OH OH
½½ ½½ OH NH2
65. HO ¾ C ¾ CH2 ¾ CH2 ¾ C ¾ OH
butanedioic acid Distillation
74. Aromatic alcohols and carboxylic acids forms salt with NaOH,
will dissolve in aqueous NaOH : COOH COOH
characteristic
foul smell of isocyanide
COOH OH OH COOH
78. p-methoxy benzoic acid is the weakest and p-nitrobenzoic acid
is the strongest acid among these acids. Chloro group has overall
electron withdrawing effect on ring, therefore, increases acid
strength of benzoic acid. Methyl group decreases acid strength
N of benzoic acid by + I effect. Therefore,
H3C CH3 Ka
p-methoxy benzoic acid 3.3 ´ 10- 5
+ p-methyl benzoic acid 4.2 ´ 10- 5
NH3 benzoic acid 6.4 ´ 10- 5
p-chlorobenzoic acid 10. 2 ´ 10- 5
p-nitrobenzoic acid 36.2 ´ 10- 5
75. is more acidic due to – I effect of F.
79. H ¾ C ºº C ¾ H is more acidic than CH2 == CH2.
F 80. Intramolecular H-bonding in ortho-hydroxybenzaldehyde
decreases its melting point as well as boiling point.
+ Molecules of p-hydroxybenzaldehyde is symmetrical,
OH O¾H
associated together by intermolecular H-bonds, has higher
+ boiling point and melting point.
- O¾H
76. O
H
- O
H
Intramolecular H-bonding
Organic Chemistry Basics 309
The correct order of their boiling point is 8. Benzyl chloride (C6H5CH2Cl) can be prepared from toluene
(a) I > II > III by chlorination with (1998)
(b) III > II > I (a) SO2Cl2 (b) SOCl2
(c) II > III > I (c) Cl2 (d) NaOCl
(d) III > I > II
9. (CH3)3CMgCl on reaction with D2O produces (1997)
CH3 Cl 2 , hv (a) (CH3)3CD (b) (CH3)3OD
4. ¾¾¾® N (isomeric products) C5 H11 Cl
(c) (CD3)3CD (d) (CD3)3OD
H 3C 10. When cyclohexane is poured on water, it floats because
(a) cyclohexane is in ‘boat’ form (1997, 1M)
CH3
(b) cyclohexane is in ‘chair’ form
Fractional distillation (c) cyclohexane is in ‘crown’ form
¾¾¾¾¾¾¾® M (isomeric products) (d) cyclohexane is less dense than water
What are N and M ? (2006, 5M)
11. The C ¾ H bond distance is the longest in (1989, 1M)
(a) 6, 6 (b) 6, 4
(c) 4, 4 (d) 3, 3 (a) C2H2 (b) C2H4
(c) C2H6 (d) C2H2Br2
Hydrocarbons 311
12. The compound which has one isopropyl group, is (1989, 1M) 15. The compound with highest boiling point is (1982, 1M)
(a) 2,2,3,3-tetramethyl pentane (b) 2,2-dimethyl pentane (a) 2-methyl butane (b) n -pentane
(c) 2,2,3-trimethyl pentane (d) 2-methyl pentane (c) 2, 2-dimethyl propane (d) n-hexane
13. The highest boiling point is expected for (1986, 1M) 16. Marsh gas mainly contains (1980, 1M)
(a) iso-butane (b) n-octane (a) C2H2 (b) CH4
(c) 2, 2, 3, 3-tetramethyl butane (d) n-butane (c) H2S (d) CO
14. Which of the following compounds does not dissolve in
conc. H2 SO4 even on warming ? (1983, 1M)
Integer Answer Type Question
(a) Ethylene (b) Benzene 17. The maximum number of isomers (including stereoisomers)
(c) Hexane (d) Aniline that are possible on mono-chlorination of the following
compound, is CH3 CH2 CH( CH3 ) CH2 CH2 (2011)
(a) 0 (b) 1 (c) 2 (d) 4 (a) bromine, CCl 4 (b) H2 , Lindlar catalyst
(c) dilute H2SO4 , HgSO4 (d) ammoniacal CuCl 2 solution
13. The synthesis of 3-octyne is achieved by adding a
22. In the presence of peroxide, hydrogen chloride and hydrogen
bromoalkane into a mixture of sodium amide and an alkyne.
iodide do not give anti-Markownikoff’s addition to alkenes
The bromoalkane and alkyne respectively are (2010)
because (2001, 1M)
(a) BrCH2CH2CH2CH2CH3 and CH3CH2C ºº CH
(a) both are highly ionic
(b) BrCH2CH2CH3 and CH3CH2CH2C ºº CH
(b) one is oxidising and the other is reducing
(c) BrCH2CH2CH2CH2CH3 and CH3C ºº CH (c) one of the steps is endothermic in both the cases
(d) BrCH2CH2CH2CH3 and CH3CH2C ºº CH (d) all the steps are exothermic in both the cases
14. The number of stereoisomers obtained by bromination of 23. The reaction of propene with HOCl proceeds via the addition
trans-2-butene is (2007) of (2001)
(a) 1 (b) 2 (a) H+ in the first step (b) Cl+ in the first step
(c) 3 (d) 4 (c) OH– in the first step (d) Cl+ and OH– single step
15. The reagent(s) for the following conversion, 24. Hydrogenation of the adjoining compound in the presence of
poisoned palladium catalyst gives
Br ?
H H H 3C H
Br CH3
is/are (2007, 3M)
(a) alcoholic KOH
H3C H
H (2001, 1M)
(b) alcoholic KOH followed by NaNH2 (a) an optically active compound
(c) aqueous KOH followed by NaNH2 (b) an optically inactive compound
(d) Zn/CH3OH (c) a racemic mixture
16. CH3 — CH == CH2 + NOCl ¾® P; Identify the adduct. (d) a diastereomeric mixture
(2006, 3M) 25. Propyne and propene can be distinguished by (2000)
(a) CH3 —CH—CH2 (b) CH3— CH—CH2 (a) conc. H2SO4 (b) Br2 in CCl4
½ ½ ½ ½ (c) dil. KMnO4 (d) AgNO 3 in ammonia
Cl NO NO Cl
Cl 26. Which one of the following alkenes will react fastest with H2
½
(c) CH3—CH2 ¾ CH (d) CH2 —CH2—CH2 under catalytic hydrogenation condition ? (2000, 1M)
½ ½ ½ R R R H
NO NO Cl
(a) (b)
17. Cyclohexene is best prepared from cyclohexanol by which of H H R H
the following? (2005)
R R R R
(a) conc. H3PO4 (b) conc. HCl / ZnCl2 (c) (d)
(c) conc. HCl (d) conc. HBr
R H R R
18. 2-hexyne gives trans-2-hexene on treatment with (2004, 1M)
(a) Li/NH3 (b) Pd/BaSO4
27. The product(s) obtained via oxymercuration
(c) LiAlH4 (d) Pt/H2
(HgSO4 + H2 SO4 ) of 1-butyne would be (1999, 2M)
O
19. 2-phenyl propene on acidic hydration, gives (2004, 1M) ½½
(a) 2-phenyl-2-propanol (a) CH3 ¾ CH2 ¾ C ¾ CH3
(b) 2-phenyl-1-propanol (b) CH3 ¾ CH2 ¾ CH2 ¾ CHO
(c) 3-phenyl-1-propanol (c) CH3 ¾ CH2 ¾ CHO + HCHO
(d) 1-phenyl-2-propanol (d) CH3 ¾ CH2 ¾ COOH + HCOOH
Hydrocarbons 313
28. In the compound, H , the C2-C3 bond is of the (a) (M and O) and (N and P) are two pairs of enantiomers
type (1999, 2M) (b) Bromination proceeds through trans-addition in both the
(a) sp - sp2 (b) sp3 - sp3 (c) sp - sp3 (d) sp2 - sp3 reactions
(c) O and P are identical molecules
29. The reaction of CH3 CH==CH OH with HBr (d) (M and O) and (N and P) two pairs of diastereomers
gives (1998, 2M)
Assertion and Reason
(a) CH3CHBrCH2 OH
Read the following questions and answer as per the direction
given below :
(b) CH3CHBrCH2 Br (a) Statement I is correct Statement II is correct Statement II is
a correct explanation of Statement I.
(b) Statement I is correct Statement II is correct Statement II is
(c) CH3CH2CHBr OH
not the correct explanation of Statement I.
(c) Statement I is correct Statement II is incorrect.
(d) CH3CH2CHBr Br (d) Statement I is incorrect Statement II is correct.
30. Which one of the following has the smallest heat of 38. Statement I Addition of bromine to trans-2-butene yields
hydrogenation per mole ? (1993, 1M) meso-2, 3-dibromo butane.
(a) 1-butene (b) trans-2-butene Statement II Bromine addition to an alkene is an
(c) cis-2-butene (d) 1, 3-butadiene electrophilic addition. (2001, 1M)
31. The number of structural and configurational isomers of a 39. Statement I Dimethyl sulphide is commonly used for the
bromo compound, C5 H9 Br, formed by the addition of HBr to reduction of an ozonide of an alkene to get the carbonyl
2-pentyne respectively, are (1988, 1M) compound.
(a) 1 and 2 (b) 2 and 4 (c) 4 and 2 (d) 2 and 1 Statement II It reduces the ozonide giving water soluble
32. Acidic hydrogen is present in (1985, 1M) dimethyl sulphoxide and excess of it evaporates. (2001, 1M)
(a) ethyne (b) ethene (c) benzene (d) ethane
40. Statement I 1-butene on reaction with HBr in the presence
33. Baeyer’s reagent is (1984, 1M) of a peroxide produces 1-bromobutane.
(a) alkaline permanganate solution
Statement II It involves the formation of a primary radical.
(b) acidified permanganate solution
(2000, 1M)
(c) neutral permanganate solution
(d) aqueous bromine solution 41. Statement I Addition of Br2 to 1-butene gives two optical
34. When propyne is treated with aqueous H2 SO4 in the presence isomers.
of HgSO4 , the major product is (1983, 1M) Statement II The product contains one asymmetric carbon.
(a) propanal (b) propyl hydrogen sulphate
(1998 , 1M)
(c) acetone (d) propanol
35. The compound 1, 2-butadiene has (1983, 1M) Passage Based Questions
(a) only sp-hybridised carbon atoms
(b) only sp2-hybridised carbon atoms Passage 1
(c) both sp and sp2-hybridised carbon atoms Pd-BaSO4 (i) B2H6
C8H6 C8H8
(d) sp, sp2 and sp3-hybridised carbon atoms H2 (ii) H2O2,NaOH, H2O
X
H2O
36. Which of the following will decolourise alkaline KMnO4 HgSO4,H2SO4
solution? (1980, 1M) (i) EtMgBr, H2O
C8H8 Y
(ii) H+, Heat (2015 Adv.)
(a) C3H8 (b) CH4 (c) CCl 4 (d) C2H4
42. Compound X is
Objective Questions II OH
(One or more than one correct option) (a) CH3 (b) CH3
37. The correct statement(s) for the following addition reactions
is (are) (2017 Adv.)
OH
H3C H (c) (d) CHO
H3C H
Br2/CHCl3 Br2/CHCl3
(i) M and N (i) O and P
H CH3 H CH3
314 Hydrocarbons
H3C 52. Acetylene is treated with excess sodium in liquid ammonia. The
(c) H ¾ C¾ C ºº C¾ CH3 product is reacted with excess methyl iodide. The final product is
…… . (1983, 1M)
H3C
53. …… is most acidic. (Ethane, Ethene, Ethyne) (1981, 1M)
H3C
(d) H3C¾ C¾ C ºº C¾ H True/False
H3C 54. Moist ethylene can be dried by passing it through concentrated
Passage 3 sulphuric acid. (1981)
Schemes 1 and 2 describe sequential transformation of
alkynes M and N. Consider only the major products formed in Integer Answer Type Question
each step for both schemes. 55. The total number of cyclic isomers possible for a hydrocarbon with
the molecular formula C4 H6 is (2010)
Hydrocarbons 315
Subjective Questions this information two isomeric structures can be proposed for
alkene (A). Write their structures and identify the isomer which
56. Monomer A of a polymer on ozonolysis yields two moles on catalytic hydrogenation (H2/Pd - C) gives a racemic mixture.
of HCHO and one mole of CH3 COCHO. (2001)
(a) Deduce the structure of A.
(b) Write the structure of all cis form of polymer of compound 61. What would be the major product in the following reaction?
A. (2005, 2M)
H2
57. A biologically active compound, Bombykol (C16H30O) is Lindlar’s catalyst
obtained from a natural source. The structure of the
CH3
(2000, 1M)
compound is determine by the following reactions.
62. Complete the following reactions with appropriate reagents :
(a) On hydrogenation, Bombykol gives a
compound A, C16H34O, which reacts with
acetic anhydride to give an ester. (a) ==
(b) Bombykol also reacts with acetic anhydride to
give another ester, which on oxidative
D D OH CH3
ozonolysis (O3/H2O2) gives a mixture of
(b) CH3 C==C
butanoic acid, oxalic acid and 10-acetoxy H3C D—C—C—H
decanoic acid. H3C CH3
H3C D
Determine the number of double bonds in CH3 CH3 (1999)
Bombykol. Write the structures of compound
A and Bombykol. How many geometrical 63. Complete the following reactions with appropriate structures of
isomers are possible for Bombykol? products/reagents :
58. Identify X, Y and Z in the following synthetic scheme and Br (i) NaNH (3 equivalent)
C6H5CH == CH2 ¾®
2
[ A ] ¾¾¾¾¾¾¾¾¾®
2
[B]
write their structures. (ii) CH3I (1998, 2M)
(i) NaNH 64. Write the intermediate steps for each of the following reactions :
CH3 CH2 ¾ C ºº C ¾ H ¾¾¾¾®
2
(ii) CH3CH2Br H 3O +
H2 /Pd BaSO4 Alkaline KMnO4
(i) C6 H5 CH(OH)C ºº CH ¾® C6 H5 ¾ CH == CH ¾ CHO
X ¾¾¾¾¾® Y¾¾¾¾¾¾® Z
H+
Is the compound Z optically active? Justify your answer. (ii)
(2002)
OH O CH3
59. (a) Identify (A), (B), (C), (D) and (E) in the following schemes 65. The hydrocarbon A, adds one mole of hydrogen in the presence
and write their structures : of a platinum catalyst to form n-hexane. When A is oxidised
vigorously with KMnO4 , a single carboxylic acid, containing
Br2/Cl4
three carbon atoms, is isolated. Give the structure of A and
explain. (1997, 2M)
NaNH2 HgSO4/H2SO4 66. Complete the following, giving the structures of the principal
A B C organic products : (1997, 1M)
H2 NHNCONH2 NaOD/D2 O (excess)
C ¾¾¾¾¾® D ¾¾¾¾¾¾¾® E Ph H
(b) Identify (X), (Y) and (Z) in the following synthetic scheme A
(i) + KNH2
and write their structures. Explain the formation of labelled
formaldehyde (H2C*O) as one of the products when Ph Br
compound (Z) is treated with HBr and subsequently R R
ozonolysed. Mark the C* carbon in the entire scheme.
BaC*O3 + H2SO4 ® (X) gas
B
(ii) + HClO4
[C* denotes C14] [R = nPr]
(i) Mg/ether LiAlH4
H2C == CH ¾ Br ¾¾¾¾® (Y ) ¾¾¾® (Z ) O
(ii) X
(2001)
(iii) H3 O+ C
(iii) + CHBr3 + t-BuOK
60. An alkene (A) C16H16 on ozonolysis gives only one
product (B) C8H8O. Compound (B) on reaction with
NaOH/I2 yields sodium benzoate. Compound (B) reacts 67. An alkyl halide, X, of formula C6 H13 Cl on treatment with
with KOH/NH2NH2 yielding a hydrocarbon (C) C8H10. potassium tertiary butoxide gives two isomeric alkenes Y and Z
Write the structures of compounds (B) and (C). Based on (C6 H12 ) . Both alkenes on hydrogenation gives 2, 3-dimethyl
butane. Predict the structures of X, Y and Z. (1996, 3M)
316 Hydrocarbons
68. Give the structure of the major organic products obtained (iii) CH3 COCH3 (iv) CH3 ¾ CH ¾ CHO
from 3-ethyl-2-pentene under each of the following reaction |
conditions : (1996) CH3
(a) HBr in the presence of peroxide What are the structures of A, B and C ? (1986, 4M)
(b) Br2 / H2O 76. How would you convert acetylene to acetone? (1985, 1M)
(c) Hg(OAc)2 / H2O, NaBH4 77. Give the chemical test to distinguish between 2-butyne and
69. Write down the structure of the stereoisomers formed when 1-butyne. (1985, 1M)
cis-2-butene is reacted with bromine. (1995) 78. Following statements are true, only under some specific
70. An organic compound E (C5 H8 ) on hydrogenation gives conditions. Write the condition for each subquestion in not
compound F (C5 H12 ). Compound E on ozonolysis gives more than two sentences :
formaldehyde and 2-keto propanal. Deduce the structure of (i) 2-methyl propene can be converted into isobutyl bromide
compound E. (1995) by hydrogen bromide.
71. When gas A is passed through dry KOH at low temperature, a (ii) Ethyne and its derivatives will give white precipitate with
deep red coloured compound B and a gas C are obtained. The ammoniacal silver nitrate solution. (1984,1M ´ 2 = 2M)
gas A, on reaction with but-2-ene, followed by treatment with 79. Give reasons for the following in one or two sentences :
Zn / H2 O yields acetaldehyde. Identify A, B and C. (i) Methane does not react with chlorine in the dark.
(1994, 3M) (ii) Propene reacts with HBr to give isopropyl bromide but
72. Give the structures of A, B and C (explanation are not required) does not give n-propyl bromide. (1983,1M ´ 2 = 2M)
(i) A (C4H8 ) which adds on HBr in the presence and in the absence 80. State with balanced equation, what happens when “propene
of peroxide to give same product.
is bubbled through a hot aqueous solution of potassium
permanganate.”? (1982, 1M)
(ii) B (C4H8 ) which when treated with H2O / H2SO4 gives C4H10O
which cannot be resolved into optical isomers. 81. One mole of a hydrocarbon A reacts with one mole of
(iii) C (C6H12 ), an optically active hydrocarbon which on catalytic bromine giving a dibromo compound, C5 H10 Br2 . Compound
hydrogenation gives an optically inactive compound C6H14. A on treatment with cold dilute alkaline potassium
(1993,1M ´ 3 = 3M) permanganate solution forms a compound, C5 H12 O2 . On
ozonolysis A gives equimolar quantities of propanone and
73. Write the balanced chemical equation for the following
ethanal. Deduce the structural formula of A. (1981, 1M)
“Ethylene glycol is obtained by the reaction of ethylene with
potassium permanganate.” (1991, 1M) 82. Write the structural formula of the major product in each of
the following cases
74. Give a chemical test and the reagents used to distinguish (i) Ethene mixed with air is passed under pressure over a
between cyclohexane and cyclohexene. (1991, 1M)
silver catalyst.
75. A white precipitate was formed slowly when silver nitrate (ii) The compound obtained by hydration of ethyne is treated
was added to compound A with molecular formula C6 H13 Cl. with dilute alkali. (1981 , 2 ´ 1 / 2 M = 1M)
Compound A on treatment with hot alcoholic potassium 83. Outline the reaction sequence for the conversion of ethene to
hydroxide gave a mixture of two isomeric alkenes B and C, ethyne (the number of steps should not be more than two).
having formula C6 H12 . The mixture of B and C, on (1981, 1M)
ozonolysis, furnished four compounds
(i) CH3 CHO (ii) C2 H5 CHO 84. Give one characteristic test which would distinguish CH4
from C2 H2 . (1979, 1M)
Answers
Topic 1 17. (a) 18. (a) 19. (a) 20. (a)
1. (b) 2. (c) 3. (b) 4. (b) 21. (d) 22. (c) 23. (b) 24. (b)
5. (d) 6. (c) 7. (b) 8. (c) 25. (d) 26. (a) 27. (a) 28. (d)
9. (a) 10. (d) 11. (c) 12. (d) 29. (c) 30. (b) 31. (b) 32. (a)
13. (b) 14. (c) 15. (d) 16. (b) 33. (a) 34. (c) 35. (d) 36. (d)
17. (8) 37. (a,b,d) 38. (b) 39. (a) 40. (c)
41. (a) 42. (c) 43. (d) 44. (b)
Topic 2 45. (d) 46. (c) 47. (a)
1. (c) 2. (c) 3. (b) 4. (d)
48. 3,4-dibromo-1-butene 49. H 2SO 4 , HgSO 4
5. (d) 6. (c) 7. (c) 8. (a)
9. (a) 10. (b) 11. (c) 12. (a) 50. ethene 51. sp 3 52. 2-butyne
13. (d) 14. (a) 15. (b) 16. (a) 53. Terminal alkyne (ethyne) 54. False 55. (5)
Hints & Solutions
Topic 1 Saturated Hydrocarbons
1. A dihedral angle is the angle between two C ¾ H bonds
projected on a plane orthogonal to the C ¾ C bond. In the given
skew conformation, having Newman’s projection the dihedral and
angle is
H¢¾ C ¾ C ¾ H¢¢ III II
= (H¢¾ C ¾ C ¾ Ha ) + (Ha ¾ C ¾ C ¾ H¢¢)
= 29°+120° = 149°
and
H
H H¢ I
29º (ethane, C2H6)
Ha On moving left to right (III to I)
120º · branching increases
H¢¢ H · surface area decreases
b
H Br
1-bromo-3-chlorocyclobutane
H H
H
CH3
CH3 a+ b CH3 hn
6. + Cl2
H CH3 H 3C Cl
I
2-methyl butane
H H Cl
H
OH a+ b+ d + + +
H OH Cl
Cl
II III IV
H H
H
Out of the four products formed above, II and IV are chiral,
produced in pairs, giving total of six mono-chlorination
3. PLAN This problem is based on boiling point of isomeric alkanes.
As we know more the branching in an alkane, lesser will be its
products.
surface area and lesser will be the boiling point
318 Hydrocarbons
7. Bromination is highly selective, occur at the carbon, where the Due to this method of formation, methane is also known as marsh
most stable free radical is formed : gas.
CH3 ¾ CHD ¾ CH — CH3 + Br · ¾® 17. *
Cl +
½
CH3 Cl I
· Cl
CH3 ¾ CHD ¾ C— CH3 + HBr * * + +
½
CH3 II III IV Cl
(a tertiary free radical) I has one chiral carbon = two isomers
8. Toluene on treatment with Cl 2 in the presence of heat or light II has two chiral carbons and no symmetry = four isomers.
III and IV have no chiral carbon, no stereoisomers.
undergo free-radical chlorination at benzylic position, giving
benzyl chloride
CH3 CH2Cl Topic 2 Unsaturated Hydrocarbons
1. According to the given conditions, the compound should be
hv alkyne with triple bond present at the terminal. The chemical
+ Cl2 + HCl
or heat reactions involved are as follows:
Toluene Benzyl chloride Step 1
CH3 Ag2O
CH3 C CH CH3 C C Ag
½ Prop-1-yne (Precipitates)
9. (CH3)3 CMgCl + D2O ¾® CH3 ¾ C — D + Mg(OD)Cl (A )
½
CH3 Step 2
Hg2+
10. Alkanes are all less dense than water, floats over water. CH3 C CH dil. H SO
2 4
11. C—H bond with sp3-C will be longest in C2H6. OH O
Tauto-
CH3 CH3 CH3 merisation
CH3 C CH2 CH3 C CH3
½ ½ ½ (Propan-2-one)
12. CH3 ¾ C — C — CH2 ¾ CH3 CH3 ¾ C — CH2CH2CH3 (B)
½ ½ ½
CH3 CH3 CH3 NaBH4
2, 2, 3, 3-tetramethyl pentane 2, 2-dimethyl pentane
(no isopropyl group) (no isopropyl group) CH3 CH CH3
CH3 OH
CH3 CH3 (C) (2° alcohol)
½ ½ ½
CH3 ¾ C — CH— CH2CH3 CH3 ¾ CH — CH2CH2CH3 Conc. HCl
+
½ ZnCl2
CH3 Isopropyl group
2, 2, 3-trimethyl pentane 2-methyl pentane CH3 CH CH3
(no isopropyl group)
Cl
13. Boiling point of alkane increases with molar mass. Among Turbidity within 5 minutes
(Insoluble in Lucas reagent)
isomeric alkanes, branching decreases boiling point. Therefore,
n-octane has highest boiling point, higher than In step-1, prop-1-yne reacts with Ag2O to form
2, 2, 3, 3-tetramethyl-butane (an isomer of n-octane). CH3 ¾ C ºº C ¾ Ag, that forms white precipitates.
14. Ethylene absorb H2SO4 forming CH3 ¾ CH2OSO3H and In step 2, prop-1-yne in presence of mercuric sulphate and
dil × H2SO4 produces carbonyl compound (CH3 )2 C == O which
dissolve. Benzene, with warm H2SO4, undergo sulphonation and
produces (CH3 )2CH ¾ OH in presence of NaBH4. 2ºalcohol
dissolve.
on reaction with Lucas reagent produces turbidity in about
Aniline, with H2SO4, forms anilinium sulphate salt and dissolve. 5 min.
Hexane, a hydrophobic molecule, does not react with H2SO4,
remains insoluble. 2. But-2-ene on reaction with alkaline KMnO4 at elevated
temperature followed by acidification will give acetic acid
15. Among alkanes, boiling point increases with molar mass. (CH3COOH). Hot alkaline solution of potassium
Among isomeric alkanes, branching decreases boiling point. permanganate followed by acidification oxidatively cleaved
Therefore, n-hexane has highest boiling point among these. alkenes. The reaction proceed as follows :
16. Methane is produced due to the decay of vegetables or animal Alk. KMnO4 , heat
organisms present in swamps and marsh, by the action of bacteria. CH3 ¾ CH == CH ¾ CH3 ¾¾¾¾¾¾® 2CH3COOH
But-2 -ene H3O+ Acetic acid
Hydrocarbons 319
+ HCl r
Cl < CH —
F3C — — CH2 Slow F3C — CH2 — CH2
Slow H 2O (– I) – Cl
s
CH3—CH=
=CH2 + Cl—Cl CH3—CH—CH2 Fast s
Cl
Chloronium – F3C — CH2CH2Cl
+ Cl Slow
ion
OH CH3 ¾ CH ¾ CH2
½ ½
9. PhCH2 CH3 PhCH2 H Cl NO
C C C C
H H H CH3 17. Cyclohexanol on treatment with concentrated H3PO4 undergo
cis form trans form acid catalysed dehydration giving cyclohexene.
10. CH3 CH3 OH
O3 O conc.H3PO4
Zn/H2O CHO
O3 ½ ½
2 CH3 CHO + 2 OHC C CHO Ph Ph
Zn/H2O 2-phenyl propene 3 °, resonance stabilised
H OH
Since, none of the above dial is chiral, no optically active ½
product is obtained. CH3 ¾ C — CH3
½
13. CH3CH2C ºº CH + Br — CH2CH2CH2CH3 Ph
2-phenyl-2-propanol
¾¾® CH3CH2 — C ºº C— CH2CH2CH2CH3
— HBr 3-octyne 20. Reaction proceeds through carbocation intermediate :
+ H2 O
14. Br2 undergo anti-addition on C == C bonds as: Ph ¾ C ºº C ¾ CH3 + H+ ¾® Ph ¾ C == CH ¾ CH3 ¾®
Br Resonance stabilised
CH3 OH O
H3C H C ½ ½½
CH3
H
C==C
CH3
+ Br H C H
Ph ¾ C == CH ¾ CH3
Unstable enol
e
(Tautomerisation)
Ph ¾ C ¾ CH2 ¾ CH3
22. In addition of HBr to an alkene, in the presence of peroxide, both 28. According to the IUPAC conventions, compound can be
the propagation steps are exothermic : numbered as:
HBr + HO· ¾® H2O + Br ·
1 2 3 4 5 6
H2 C== CH ¾ CH2 ¾ CH2 ¾ C ºº C ¾ H
Propagation Here, C-2 is sp2 and C-3 is sp3-hybridised.
·
ì ·
ï CH3 ·¾ CH == CH2 + Br ¾® CH3 ¾ CH ¾ CH2Br; DH < 0 29. Electrophilic addition on C == C is governed by stability of
ï
íCH3 ¾ CH ¾ CH2Br + HBr ¾® CH3 ¾ CH2 ¾ CH2Br carbocation:
ï + Br ·; DH < 0 H+
ïî CH3—CH==CH— —OH
In case of addition of HCl and HI, one of the propagation step is +
endothermic, reaction fail to occur. CH3—CH2—CH— —OH
-
23. HOCl ¾® HO + Cl +
Cl +
35. Structural formula of 1, 2-butadiene is : Both Statement I and Statement II are correct and Statement II is
correct explanation of Statement I.
H2C == C == CH¾ CH3
40. CH3 ¾ CH2 ¾ CH== CH2 + Br · ¾®
sp2 sp sp2 sp3 ·
CH3 ¾ CH2 ¾ CH ¾ CH2 Br
36. Unsaturated compounds which contain C == C or C ºº C, a secondary radical
decolourises the purple colour of alkaline KMnO4 solution. Therefore, Statement I is correct but Statement II is incorrect.
CH2 ¾ OH 41. CH3 ¾ CH2 ¾ CH == CH2 + Br2 ¾®
HO-
CH2 == CH2 + KMnO4 ¾¾® ½ + MnO2 ¯
purple CH2 ¾ OH CH3 ¾ CH2 ¾ CH ¾ CH2 Br
coloured ½
Br
37. Addition of halogen at double bond occur in antiorientation via has one chiral carbon
cyclic halonium ion intermediate.
Both Statement I and Statement II are correct and Statement II is
(i) correct explanation of Statement I.
r Br
CH3 H Br CH3 H
Br2 CH3 Br –
Passage 1
C C CH3
H H The reaction condition indicates that starting compound is phenyl
H CH3 H 3C H Br acetylene.
trans Meso (M and N)
42.
(ii) r ¾ CH2
CH ¾
H H Br CººC—H OH
Br2 CH3 Pd/BaSO4 (i) B2H6
C C H2 (ii) H2O2, NaOH, H2O
H
CH3 CH3 H
cis CH3 (2-phenyl ethanol)
(X)
H CH3
Br Hydroboration oxidation brings about anti-Markonikoff’s
Br
Br –
H CH3 hydration of alkene.
+
CH3 Br
H H CH3
43.
Br O
O P
C ºº CH
ó
ô
ô ó
í
+ CH3
Br CH3
H3C H C
38. C==C + Br2 CH3 H+/D CH3
C C2H5 MgBr, H2O CH3
H CH3 H OH
trans H
CH3
Statement I is correct. Statement II is also correct. Meso form of
the product is due to anti addition of Br - on cyclic bromonium
Passage 2
ion intermediate, hence Statement II is not correct explanation The final ozonolysis product indicates that the alkene before
of Statement I. ozonolysis is
O
Br
H 3C CH3
CH3 O3
2 C
C C C Zn–H2O
Br– CH3 H 3C CH 3 H 3 C CH3
H C P
H
Also P(C6H10) has two degree of unsaturation and
Br oxymercuration demercuration hydration indicates that it is an
(meso) alkyne. As alkyne, on hydration, gives a carbonyl compound
which on reduction with NaBH4 gives a 2º alcohol.
39. O
O OH
C==C + O3 C C CH3—S—CH3
(i) NaBH4
—C C— + H2O —C—CH2— + — C—CH2—
O O (ii) H
ozonide H
2° alcohol
C ==O + O == C + (CH3 )2 SO
Hydrocarbons 323
The secondary alcohol that can give above shown alkene on acid Hence, using the concept of regioselectivity we come on the
catalysed dehydration is conclusion that final product is correctly represented by
structure (a).
CH3 OH
+ + 48. 3, 4-dibromo-1-butene :
H Me-shift
CH3 — C — CH — CH3 CH3 — C — CH— CH3
–H2O + Br2
Br
CH3
Q 2° carbocation Br
CH3 CH3
+ HgSO
+ –H 49. CH ºº CH + H2SO4 ¾¾®
4
CH3CHO
CH3 —C—CH—CH 3 CH3 — C C — CH3
CH2 ¾ COOK
Electrolysis
CH3 CH3 50. ½ ¾¾¾® CH2 == CH2 + 2CO2
CH2 ¾ COOK ethene
44. Explained in the beginning.
CH3 CH3 O sp 3
HgSO4 (i)NaBH4
51. CH3 ¾ CH== CH ¾ CH3
CH3—C— C—CH3 Q
45. CH3—C—C CH H2SO4 (ii) H +
2- butene
OH Me O
CrO3 O
½½
Y + CH3 ¾ C ¾ CHO
• Thus, X and Y are functional isomers of each other and Y gives
iodoform test due to the presence of CH 3CO group as Indicated. H3C H H3C H
Hence, correct choice is (c). (b) C == C C == C
H2C CH2 ¾¾ H2C CH2
47. PLAN This problem can be solved by using the concept of nucleophilic
substitution reaction, oxidation reaction and reduction reaction natural rubber
including strength of nucleophile and regioselectivity.
Reaction of Scheme 1 can be completed as 57. From oxidation products, structure of starting compound can be
1. NaNH2 deduced as :
H C3 H8 ¾ COOH + HOOC ¾ COOH
II
O butanoic acid oxalic acid O
HO M I
½½
Among two nacked nucleophilic group I and II, II is more + HOOC ¾ (CH2 )8 ¾ CH2 O ¾ C ¾ CH3
nucleophilica and then will react selectively as follows 10-acetoxy decanoic acid
1. CH3CH2—I O 3 / H 2O 2
CH3 CH2 CH2 CH==CH ¾ CH==CH ¾ (CH2 )8
O
O CH3I ¾ CH2 OCOCH3
H2 Lindlar’s Therefore, Bombykol is :
catalyst (produces
cis alkene)
CH3O CH3CH2CH2 ¾ CH== CH ¾ CH== CH ¾ (CH2 )8 ¾ CH2OH
H H Bombykol
H2
CH3 ¾-
( CH2 )14 ¾ CH2OH
CH3O
(A )
324 Hydrocarbons
C2H5
H H alkaline KMnO4 H OH
(i) NaNH Pd/BaSO
58. CH3CH2 ¾ C ºº C ¾ H ¾¾¾¾®
2
CH3CH2 ¾ C ºº C ¾ CH2CH3 ¾¾¾¾®
4
C== C H OH
(ii) CH3 CH2 Br X H2 C2H5 C2H5 C2H5
Y (meso diol)
‘Z ’
O
Br
Br2 NaNH2 HgSO4
59. (a) —C ººCH B —C—CH3
CCl4 H2SO4
A Br B C
O
CH3 O C
H2NHNCONH2 NaOD
—C==N—NH—C—NH2 D CD3
D2O
E D
D
* *
(b) Ba CO3 + H2 SO4 ¾® CO2 + BaSO4
X
O
(i) Mg / ether ½
½ LiAlH4 *
CH2 == CH ¾ Br ¾¾¾® CH2 ==CH ¾ C ¾ OH ¾¾® CH2 == CH ¾ CH2 ¾ OH
(ii) X * Z
(iii) H3O+ Y
CH3
61. Lindlar’s
CH3 catalyst H
H
cis hydrogenation
O OH
D OH
D D CH3
H 2O 2
(b) CH3 C==C + BHR2 – CH3 C—C
HO
CH3 H
H3C H 3C
CH3 CH3 D
R = (CHl 3 )2 CHCH2
Hydrocarbons 325
Br CH2CH3 C2H5
½ ½ ½
HBr
63. C6H5 ¾ CH == CH2 + Br2 ¾® C6H5 ¾ CH ¾ CH2 68. CH3CH == C ¾ CH2 CH3 ¾¾® CH3 ¾ CH ¾ CH ¾ C2H5
½ 3-ethyl-2-pentene peroxide ½
Br Br
A [A]
NaNH2 CH2 CH3
¾¾¾® C6H5 ¾ C ºº C ¾ CH3
CH3 I B Br 2 /H2O ½
+ ¾¾¾® CH3 ¾ CH ¾ C — CH2 ¾ CH3
OH OH2 ½
½ ½ ½
H+ Br OH
64. (i) C6H5 ¾ CH ¾ C ºº CH ¾® C6H5 ¾ CH ¾ C ºº CH
[B]
– H2 O +
H+ C2H5
¾¾® C6H5 ¾ CH ¾ C ºº CH ¾®
H2 O Hg(OAc) 2 /H2 O ½
¾¾¾¾¾® CH3 ¾ CH2 ¾ C — CH2 CH3
C6H5 ¾ CH == CH ¾ CHO e
(Tautomerisation)
C6H5 ¾ CH == C == CH
½
OH
NaBH4
½
OH
unstable enol [C ]
69. H3C CH3
H+ C==C + Br2
(ii) + H cis H
OH O CH3 Br H CH3
H Br
H C C
CH3 C
H + H3C C +
H Br
Br CH3
O CH3 H
Pair of enantiomers
65. Oxidation product indicates that alkene is symmetrical : O CH2
½½ ½½
H+ 70. CH3 ¾ C ¾ CHO + O== C ¾ H ¬¾ CH3 C ¾ CH == CH2
+ KMnO4 2CH3CH2COOH
3-hexene 2-ketopropanal ½ E
‘A’ H
Formaldehyde
Ph H Gas A
71. CH3 ¾ CH == CH ¾ CH3 ¾¾¾® 2CH3 ¾ CHO
Zn - H2 O
66. (i) C==C + KNH2 Ph—C C—Ph
A \ Gas A is ozone (O3 )
Ph Br Also; Gas A + KOH (dry) ¾® B + Gas C
R R deep red coloured
\ 4O3 + 4KOH ¾® 4KO3 + 2H2O + O2
(ii) + HClO4 2R—COOH B C
B 72. (i) A must be a symmetrical alkene :
O Br
Br ½
CH3 CH==CHCH3 + HBr ¾® CH3 CH2 ¾ CH ¾ CH3
CH3 CH3
(iii) + CHBr3 + t-BuOK ½ ½
(ii) CH3 ¾ C == CH2 + H2SO4 + H2O ¾® CH3 ¾ C — CH3
C ½
OH
CH3 CH3 Achiral
Cl (CH3)3COK
CH3 CH2 CH3
67.
H 3C H3C ½ Pt
(iii) CH3 ¾ CH2 ¾ C — CH == CH 2 + H2 ¾®
CH3 CH3 D
‘X’ ‘Y’ ½
H
CH3 CH3 has one chiral carbon CH3
CH3 CH3 ½
H2/Pt CH3CH2 ¾ C — CH 2CH 3
+ H3C H3C ½
CH3 CH3 H
‘Z’
Achiral
326 Hydrocarbons
73. CH2 == CH2 + KMnO4 + H2O ¾® CH2 ¾ CH2 + MnO2 79. (i) Free radical chlorination of alkane require energy which is
½ ½ supplied either in the form of heat or radiation.
OH OH (ii) Addition of HBr proceeds through carbocation intermediates.
Ethylene glycol + -
CH3 ¾ CH == CH2 + H+ ¾® CH3 ¾ CH ¾ CH3 ¾®
Br
74. Baeyer’s reagent (cold, dilute, alkaline permanganate) can be used 2 ° carbocation
to distinguish between alkanes and alkenes. Alkenes decolourises
purple colour of Baeyer’s reagent while alkanes do not. CH3 ¾ CH ¾ CH3
½
75. The alkenes are : Br
Isopropyl bromide
CH3 ¾ CH == O + O == CH ¾ CH(CH3 )2
CH3 CH3 D CH ¾ CH ¾ CH + MnO
80. CH3CH == CH2 + KMnO4 (aq) ¾® 3 2 2
½ ½ ½ ½
CH3 ¾ CH == CH ¾ CH — CH3 ; CH3CH2CH ==O + O == C ¾ CH3 OH OH
I (B )
CH3 81. Ozonolysis products are the key of identification :
½ CH3 CH3
CH3 ¾ CH2 ¾ CH== C — CH3 ½ ½
O3
II (C ) CH3 ¾ C== O + O == CH ¾ CH3 ¬¾¾ CH3 ¾ C== CH ¾ CH3
Since, both alkenes I and II are obtained by b-elimination of Propanone Ethanal Zn -H2 O A
same halides, the halides must be :
CH3 Other products are:
½ CH3
CH3 ¾ CH2 ¾ CH ¾ CH — CH3 ½ dil. KMnO4 Br 2
½ CH3 ¾ C — CH ¾ CH3 ¬¾¾¾¾ A ¾®
Cl -
½ ½ Cold, OH
(A ) OH OH CH3 Br
Heat ( D ) CH I ½ ½
76. H ¾ C ºº C ¾ H + Na ¾¾¾® ¾¾®
3
CH3 ¾ C ºº CH CH3 ¾ C — CH — CH3
O ½
H2 SO4 ½½ Br
¾¾¾® CH3 ¾ C ¾ CH3 O
HgSO4 Acetone 1 Ag
77. 1-butyne (terminal) can be distinguished from 2-butyne 82. (i) CH2 == CH2 + O2 ¾¾® H2C ¾¾ CH2
2 heat Ethylene oxide
(internal) by either Tollen’s test or through Fehling’s test. (oxirane)
AgNO3 +
NH3(aq)
CH3—CH2—C ºº CAg¯ (ii) CH ºº CH + H2SO4 ¾¾®
4 HgSO
CH3 ¾ CHO ¾¾®
dil. OH
White ppt.
CH3—CH2—C ººC—H OH
CuCl2
CH3—CH2—C ºº CCu¯ ½
NH3(aq)
Red ppt. CH3 ¾ CH ¾ CH2 ¾ CHO
(Aldol)
Peroxide
78. (i) CH3 ¾ C == CH2 + HBr ¾¾¾® CH3 ¾ CH ¾ CH2Br NaNH
½ 83. CH2 == CH2 + Br2 ¾® CH2 ¾ CH2 ¾¾¾®
2
½
CH3 CH3 ½ ½ H ¾ C ºº C ¾ H
2-methyl propene Isobutyl bromide Br Br
In the absence of peroxide, HBr would be added giving 84. Acetylene can be distinguished from methane using Tollen’s reagent :
tertiary butyl bromide. NH (aq)
(ii) Tertiary alkynes are slightly acidic, forms silver salt with C2H2 + AgNO3 ¾¾®
3
H ¾ C ºº CAg ¯
White ppt.
ammoniacal solution of silver nitrate :
No such reaction occur with methane.
NH ( aq )
R ¾ C ºº C ¾ H + AgNO3 ¾¾®
3
R ¾ C ºº CAg ¯
White ppt.
(a) Ph (b) Ph
Progress of reaction Progress of reaction
OH
OH
(c) PE (d) PE
(c) Ph (d) Ph
2. Which one of the following is likely to give a precipitate with Progress of reaction Progress of reaction
AgNO3 solution? (2019 Main, 12 April II)
(a) CH2 == CH ¾ Cl (b) CCl 4 6. The major product of the following reaction is
(c) CHCl 3 (d) (CH3 )3 CCl
CH2CH3
3. The major product Y in the following reaction is
(2019 Main, 10 April II) NaOEt
H3C C Cl D
Cl EtONa HBr
X Y
Heat COOCH2CH3
(2019 Main, 12 Jan II)
Br
(a) Br (b) (a) CH3 CH2C == CH2
½
CO2CH2CH3
(b) CO2CH2CH3
HO
(c) (d) ½
CH3 C == CHCH3
Br CH2CH3
Br CH3O
CH2Cl
(i) AlCl3 (anhyd.)
(ii) H2O
(b) HO CH2 CH CH3
(2019 Main, 10 Jan I)
Br
Cl
14. The increasing order of reactivity of the following halides for
the SN 1 reaction is (2017 Main)
CH3O CH3O
(a) (b) I. CH3CH(Cl)CH2CH3
Cl II. CH3CH2CH2Cl
Cl III. p-H3CO ¾ C6H4 ¾ CH2Cl
CH3O (a) (III) < (II) < (I)
(c) (d) CH3O
(b) (II) < (I) < (III)
Cl (c) (I) < (III) < (II)
(d) (II) < (III) < (I)
10. Which hydrogen in compound (E) is easily replaceable
during bromination reaction in presence of light? 15. Which of the following, upon treatment with tert-BuONa
CH3 ¾ CH 2 ¾ CH ==CH 2 (2019 Main, 10 Jan I) followed by addition of bromine water, fails to decolourise
d g b a the colour of bromine ? (2017 Main)
(E) C6H5
O
(a) b-hydrogen (b) d-hydrogen
(a) (b)
(c) g-hydrogen (d) a-hydrogen
Br Br
11. The major product of the following reaction is
Br O
KOH alc. (excess)
D
(c) (d)
Ph Br Br
Br (2019 Main, 10 Jan I) 16. 3-methyl-pent-2-ene on reaction with HBr in presence of
peroxide forms an addition product. The number of possible
stereoisomers for the product is (2017 Main)
(a) Ph (b) Ph (a) six (b) zero
(c) two (d) four
(c) Ph (d) Ph
Alkyl Halides 329
17. The major product obtained in the following reaction is 23. The major product of the following reaction is (2008, 3M)
Br H 3C Br
H tBuOK
C6H5 D
C6H5
(2017 Main)
F
PhSNa
(a) (± ) C6 H5CH(O Bu)CH2C6 H5
t
dimethyl formamide
(b) C6 H5CH == CHC6 H5
(c) (+ ) C6H5CH(Ot Bu)CH2C6 H5 NO2
(d) (- )C6 H5CH(Ot Bu)CH2C6 H5 H3 C SPh H3 C SPh
18. 2-chloro-2-methylpentane on reaction with sodium
F F
methoxide in methanol yields (2016 Main)
(a) (b)
CH3
½
I. C2 H5 CH2 C ¾ OCH3 II. C2 H5 CH2 C == CH2 NO2 NO2
½ ½
CH3 CH3 H3 C Br H3 C SPh
OH O CO2H H Cl CH3
(a) (b) (c) (d) CH3 H CH3
(K) MeO— —NO2
26. Identify the set of reagents/reaction conditions X and Y in the Objective Questions II
following set of transformations– (2002, 3M)
(One or more than one correct option)
X
CH3 ¾ CH2 ¾ CH2 Br ¾® Product ¾®
Y CH ¾ CH ¾ CH
3 3 37. For the following compounds, the correct statement(s) with
½ respect to nucleophilic substitution reaction is(are)
Br
(2017 Adv.)
(a) X = dilute aqueous NaOH, 20°C,Y = HBr/acetic acid, 20°C CH3 CH3
(b) X = concentrated alcoholic NaOH, 80°C,
Y = HBr/acetic acid, 20°C Br Br
H 3C C Br
Br
(c) X = dilute aqueous NaOH, 20°C, Y = Br2 / CHCl 3 , 0°C CH3
(d) X = concentrated aqueous NaOH, 80°C, I II III IV
Y = Br2/CHCl 3 , 0°C
(a) Compound IV undergoes inversion of configuration
27. The compound that will react most readily with NaOH to (b) The order of reactivity for I, III and IV is : IV > I > III
form methanol is (2001, 1M) (c) I and III follow S N 1 mechanism
(a) (CH3 )4 N + I – (b) CH3OCH3 (d) I and II follow S N 1 mechanism
(c) (CH3 )3 S+ I – (d) (CH3 )3 Cl 38. Compound(s) that on hydrogenation produce(s) optically
28. An SN 2 reaction at an asymmetric carbon of a compound inactive compound (s) is/are (2015 Adv.)
always gives (2001) H Br H Br
(a) an enantiomer of the substrate (a) (b) H2C CH3
(b) a product with opposite optical rotation H 3C CH3
(c) a mixture of diastereomers
H Br Br H
(d) a single stereoisomer
(c) H2C (d) H2C CH3
29. The order of reactivities of the following alkyl halides for a CH3
SN 2 reaction is– (2000, 1M) CH3
(a) RF > RCl > RBr > RI (b) RF > RBr > RCl > RI
39. In the following reaction, the major product is (2015 Adv.)
(c) RCl > RBr > RF > RI (d) RI > RBr > RCl > RF
CH3
30. Which of the following has the highest nucleophilicity? CH2 1 equivalent HBr
(2000) H2C
(a) F - (b) OH - (c) CH3- (d) NH2- CH3 CH3
CH3
31. A solution of (+)-2-chloro-2-phenylethane in toluene (a)
H2C
(b)
H3C
racemises slowly in the presence of small amount of SbCl5, Br
Br
due to the formation of (1999)
CH3 CH3
(a) carbanion (b) carbene
(c) free-radical (d) carbocation (c) (d)
H2C Br H3C Br
32. Which of the following is an organometallic compound?
(a) Lithium methoxide (b) Lithium acetate (1997)
40. The compounds used as refrigerant are (1990, 1M)
(c) Lithium dimethylamide (d) Methyl lithium (a) NH3 (b) CCl 4 (c) CF4 (d) CF2Cl 2
(e) CH2F2
33. (CH3 )3 CMgCl on treatment with D2 O produces (1997, 1M)
(a) (CH3 )3 CD (b) (CH3 )3 COD (c) (CD)3 CD (d) (CD)3 COD Assertion and Reason
34. 1-chlorobutane on reaction with alcoholic potash gives 41. An Assertion and a Reason are given below. Choose the
(a) 1-butene (b) 1-butanol (1991, 1M)
correct answer from the following options.
(c) 2-butene (d) 2-butanol
Assertion (A) Vinyl halides do not undergo nucleophilic
35. n-propyl bromide on treatment with ethanolic potassium
substitution easily.
hydroxide produces (1987, 1M)
(a) propane (b) propene (c) propyne (d) propanol Reason (R) Even though the intermediate carbocation is
stabilised by loosely held p-electrons, the cleavage is
36. The reaction condition leading to the best yield of C2 H5 Cl
difficult because of strong bonding. (2019 Main, 12 April II)
are– (1986, 1M) (a) Both (A) and (R) are wrong statements.
UV light
(a) C2H6 (excess) + Cl 2 ¾¾¾® (b) Both (A) and (R) are correct statements and (R) is correct
explanation of (A).
dark
(b) C2H6 + Cl 2 (excess) ¾¾¾® (c) Both (A) and (R) are correct statements but (R) is not the
room temp.
correct explanation of (A).
UV light
(c) C2H6 + Cl 2 (excess) ¾¾¾® (d) (A) is a correct statement but (R) is a wrong statement.
UV light
(d) C2H6 + Cl 2 ¾¾¾®
Alkyl Halides 331
42. List-I contains reactions and List-II contains major products. Column I Column II
A. CH3 ¾ CHBr ¾ CD3 on p. E1 reaction
List-I List-II treatment with alc. KOH gives
P. 1. CH2 == CH ¾ CD3 as a major
+
ONa Br OH product.
B. Ph—CHBr—CH3 reacts faster q. E2 reaction
Q. + HBr
2. than Ph—CHBr—CD3
Br
OMe C. Ph—CH2 ¾ CH2Br on treatment r. E1CB
with C2H5 OD /C2H5 O- gives reaction
R. + NaOMe
3.
Br OMe Ph ¾ CD ==CH2 as the major
product.
S. + MeBr 4. D. PhCH2CH2Br and PhCD2CH2Br s. First order
ONa react with same rate. reaction
5. O
Fill in the Blanks
45. Vinyl chloride on reaction with the dimethyl copper
Match each reaction in List-I with one or more products in gives ………. (1997)
List-II and choose the correct option. (2018 Adv.) 46. The starting material for the manufacture of polyvinyl
(a) P ® 1, 5; Q ® 2; R ® 3; S ® 4 chloride is obtained by reacting HCl with …… (1983, 1M)
(b) P ® 1, 4; Q ® 2; R ® 4; S ® 3 47. The halogen which is most reactive in the halogenation of
(c) P ® 1, 4; Q ® 1,2; R ® 3,4; S ® 4 alkanes under sunlight is … (1981 , 1M)
(d) P ® 4, 5; Q ® 4; R ® 4; S ® 3,4
43. Match the chemical conversion in Column I with the True/False
appropriate reagents in Column II and select the correct 48. Photobromination of 2-methylpropane gives a mixture of
answer using the code given below the lists. (2013 Adv.) 1-bromo-2-methyl propane and 2-bromo-2-methyl propane
in the ratio 9 : 1. (1993, 1M)
Column I Column II
49. During S N 1 reactions, the leaving group leaves the molecule
1. (i) Hg(OAc)2 ; before the incoming group is attached to the molecule.
Cl
P. (ii) NaBH4 (1990, 2M)
50. The reaction of vinyl chloride with hydrogen iodide to give
ONa OEt 1-chloro-1-iodoethane is an example of anti-Markownikoff’s
Q. 2. NaOEt rule. (1989, 2M)
51. Iodide is better nucleophile than bromide. (1985)
OH
52. Carbon tetrachloride is inflammable. (1985, 1/ 2M)
R. 3. Et-Br
53. Carbon tetrachloride burns in air when lighted to give
phosgene. (1983, 1M)
S.
4. (i) BH3 ; Integer Answer Type Question
(ii)H2 O2 / NaOH
54. In the following monobromination reaction, the number of
OH
possible chiral product(s) is (are)...
Codes CH 2 CH 2 CH 3
P Q R S Br 2 (1.0 mole)
H Br
(a) 2 3 1 4 300°C
(b) 3 2 1 4 CH3
(c) 2 3 4 1 (1.0 mole) (Enantiomerically pure)
(d) 3 2 4 1
55. The total number of alkenes possible by dehydrobromination
of 3-bromo-3-cyclopentylhexane using alcoholic KOH is
(2011)
332 Alkyl Halides
Answers
1. (c) 2. (d) 3. (b) 4. (c) 33. (a) 34. (a) 35. (b) 36. (a)
5. (b) 6. (b) 7. (d) 8. (d) 37. (a, d) 38. (b,d) 39. (d) 40. (a,d)
9. (c) 10. (c) 11. (d) 12. (d) 41. (c) 42. (b) 43. (a)
13. (b) 14. (b) 15. (a) 16. (d) 44. A ® q, B ® q, C ® r, D ® p, s
17. (b) 18. (d) 19. (a) 20. (d) 45. propene 46. ethyne 47. chlorine 48. False
21. (b) 22. (b) 23. (a) 24. (a) 49. True 50. True 51. True 52. False
25. (a) 26. (b) 27. (a) 28. (d) 53. False 54. (5) 55. (5)
29. (d) 30. (c) 31. (d) 32. (d)
Hints & Solutions
1. Heating of 2-chloro-1-phenylbutane with EtOK/EtOH gives 3. The given reaction takes place as follows :
1-phenyl but-1-ene(X).
Cl
Reaction of X with Hg(OAc)2 / H2O followed by NaBH4 gives H
EtONa/D
1-phenyl butan-1-ol (Y). b-H for b-elimination
Saytzeff elimination –HCl
Reaction involved is as follows: CH2
H b-H for
Cl –+ Hoffmann elimination
EtOK
EtOH Markownikov’s
Ph Ph centre for Brs
+
OH
1. Hg (OAc)2,H2O 3-methyl but-2-ene 3-methyl-but-1-ene
major (X) minor
2. NaBH4
Ph (Saytzeff product) (Hoffmann product)
(Y )
Electrophilic addition
HBr
Mechanism (Markownikov’s rule)
OAc Br
Cl
s
Br +
OEt
+ Hg OAc
Ph dehydro- Ph 2-bromo-3-methyl 2-bromo-2-methyl
H halogenation butane (minor) butane (major) (Y)
Oxymercuration 4. In the given question, the substrate is a 2º-halide (bromide) and the
medium, CH3OH (as well as a poor nucleophile) is protic in nature,
OAc
So, the reaction will follow mainly S N1 pathways via the formation
of a carbocation intermediate (I).
Hg+
Ph
H Me Me r Me r
Me
–Br CH3OH
C H C CH r
rds –H
Me H Me (2°)
Fast
H H C2H5 H Br H (I)
H 2O
Me
CH—CH—Me
Ph CH CH Hg OAc Me
OCH3
OH C2 H5 (Minor)
OH C2H5 (Y)
5. The potential energy (PE) diagram for S N1 reaction is
2. (CH3 )3CCl gives a precipitate with AgNO3 solution because Carbocation
it forms stable carbocation. (i.e. tertiary) that readily combines intermediate
with AgNO3 to give precipitates of AgCl.
CH3
½ + PE R++X–
CH3 ¾ C ¾ Cl + AgNO3 ¾® (CH3 )3 C + AgCl –
+Nu
½ (White ppts.)
CH3 R¾ X
R ¾ Nu
CH2 == CH ¾ Cl forms unstable carbocation. Progress of reaction
Hence, it does not readily react with AgNO3.
334 Alkyl Halides
S N1 reaction has two steps. In the first step, the carbon halogen Key Idea Both alc. KOH and NaNH2 in liquid NH3 are
bond breaks heterolytically, with the halogen retaining the 8.
dehydrohalogenating reagents. On comparative terms
previously shared pair of electron. In the second step, the NaNH2/liquid NH3 is stronger in action.
nucleophile reacts rapidly with the carbocation formed in the
first step. The reaction proceeds as :
In the above graph, the alkyl halide is the only species that Alc. KOH
CH3 CH2 CH CH2
CH3 CH2 CH CH2
participates in the rate limiting step. Here, the rate of reaction
depends on the concentration of the alkyl halide and does not Br Br Br
depend on the concentration of nucleophile. NaNH2/liquid NH3
–
6. Presence of strong base (EtO- ) and heat indicates elimination. CH3 CH2 C CH
H+
CH3CH2C CNa+
Thus, the compound undergo dehydrohalogenation and alkene Thus, option (d) is the correct answer.
is produced. As per the position of Cl in substrate, following 2 9. The given reactant in presence of Cl2/CCl4, given vicinal
alkenes are formed as product: dihalide. Chlorine adds up to alkene via electrophilic addition
(i) CH3CH2 C == CH2 reaction involving cyclic chlorinium ion formation.
½ Cl
COOCH2CH3
H3CO H3CO
Cl2/CCl4
(ii) CH3 CH == C ¾ CH3
Cl
½
COOCH2CH3 The vicinal dihalide in presence of anhyd. AlCl3 results in the
In accordance with Saytzeff rule formation of carbocation that rearranges itself to form a cyclic
compound.
CH3 CH == C ¾ CH3 will be the major product
Cl
½
COOCH2CH3 H3CO
+ AlCl3
(Anhyd.)
Cl Cl
7. Key Idea The excess of HBr and high temperature in given H3CO
reaction serves for dual purpose: + –
r + AlCl
4
(i) Hydrolysis of ether via SN 2 mechanism, i.e. Zeisel’s
method.
(ii) Markownikoff addition at double bond of the branch.
CH3O CH3O
The road map of complete reaction is as follows:
–H+
Cl Cl
H
CH3 O CH CH CH3
10. The compound (E ) has two allyl-hydrogen atoms (g ). When E
H+ HBr excess/Heat reacts with Br2 / hn, it readily undergoes allylic free radical
+
substitution and forms 3, 3-dibromobut-1-ene
CH3 O CH CH2 CH3 d g b a Br / hn
C H3 ¾ C H2 ¾ C H == C H2 ¾ ¾2 ¾®
–HBr
Br– But-1-ene
Br
| Br / hn
CH3 O CH CH2 CH3 C H3 ¾CH ¾ C H ==C H2 ¾ ¾ ¾®
2
d g b a –HBr
Br 3-bromo-but-1-ene
Br
H+ |
Br–
C H3 ¾ Cg ¾ C H == C H2
d b a
H |
d– +
Br
BF d BB d–
Br C O CH CH2 CH3 3,3- dibromobut-1-ene
BF
H H H d+ 11. The reaction follows a, b-elimination mechanism to give a more
Br
Transition state substituted stable alkene as a major product. As the substrate is a
a, g -dibromo (1, 3-) compound it gives a conjugated diene.
SN2 Reaction
(Zeisel’s Method)
Br
CH3Br + HO CH CH2 CH3 HOs H Alc. KOH
D
Br Ph H
–2HBr
(It is very stable because
Product
Br sOH the conjugated diene system
Here, BB = Bond breakage present. It is further conjugated
with the benzene ring.)
BF = Bonf formation
Alkyl Halides 335
12. In the given reaction, AlCl3 act as Lewis acid and helps in 15. To show decolourisation, compound must be unsaturated.
generation of carbocation. The resulting carbocation (1°) O – + O
tert-BuONa
rearranges itself to stable carbocation (3°).
MeO Br O—tBu
Cl (Saturated)
AlCl3(anhy.) (cannot decolourise Br2 water)
C6H5 – + C6H5
r s
MeO Cl AlCl3 tert–BuONa
MeO s
–AlCl4
H r Br
(Unsaturated)
(1°) (decolourise Br2 water)
MeO O – + O
a-Hs shift r
tert–BuONa
(H2O)
Br
(Unsaturated)
3° carbocation, more stable (decolourise Br2 water)
Protic medium, H2O supports the O O
rearrangement of carbcation
– +
Intramolecular ArSE2 pathway tert–BuONa
r
Me O MeO
–Hr Br
(Unsaturated)
(decolourise Br2 water)
H
16. The number of stereoisomers in molecules which are not
13. Complete reaction can be represented as divisible into two equal halves and have n number of
asymmetric C-atoms = 2n.
Br
Na+OMe
– 3-methyl-pent-2-ene on reaction with HBr in presence of peroxide
+ NaBr + MeOH forms an addition product i.e. 2-bromo-3-methyl pentane. It has
MeOH
H two chiral centres. Therefore, 4 stereoisomers are possible
Thus, the given reaction is dehydrohalogenation which is a Br
b-elimination proceeding through E2 mechanism.
2 4 2 4
1 3 HBr 1 3
5 5
Mechanism The reaction proceeds through the formation of Peroxide
following transition state with simultaneous removal of Br and 3-methylpent-2-ene Anti-Markownikoff's addition
H atoms. Four stereoisomers are possible
Na+ Na+Br– (As molecule has two chiral
centres and asymmetric).
BF (Product)
BB Br 17. An alkyl halide in presence of a bulkier base removes a proton
Here, BB = Bond breakage from a carbon adjacent to the carbon bonded to the halogen. This
BF
BF = Bond formation reaction is called E2 ( b-elimination reaction).
– Br
(Product) BB H
BF
OMe H C6H5
(Transition t-BuO–K+ H
State) C6H5 C==C
C6H5 H C6H5
MeOH (Product)
H + tert-BuOH + Br–
14. (i) The rate of S N 1 reaction depends only upon the concentration H
of the alkyl halide.
-
(ii) S N 1reaction proceeds through the formation of carbocation. 18. Key Idea Strong nucleophile ( OMe) in polar solvent (MeOH)
The reactivity is decided by ease of dissociation of alkyl halide. gives elimination products over substitution products but all
R ¾ X q RÅ + X È products are possible in different yields.
Higher the stability of R + (carbocation), higher would be the
Cl OCH3
reactivity towards S N1 reaction. -+
p - H3CO ¾ C6H4 ¾ CH2Å is the most stable carbocation due CH3—C—CH2CH2CH3
MeONa
CH3—C—CH2—CH2—CH3 +
to resonance and then CH3 CHCH2CH3 (2° carbocation) while MeOH
Å Å
CH3 CH3
CH3CH2 CH2(1°) is least stable.
(Less yield)
Thus, the correct increasing order of the reactivity of the given
halides towards the S N 1reaction is CH3 —C == CH—CH2—CH3+ CH2 ==C—CH2—CH2—CH3
CH3CH2CH2Cl < CH3 CHCH2CH3 < p-H3COC6H4CH2Cl
| CH3 CH3
Cl (More yield)
(II) (I) (III)
336 Alkyl Halides
C2H5Cl ¾¾®
NaI C2H5I + NaCl CH3 H CH3
acetone
+
Free redical fluorination is highly explosive reaction, so not CH3O— —NO2 H shift
preferred for the preparation of fluoride. +
30. CH-3 , being the strongest base, has highest nucleophilicity. 40. Both NH3 and CF2Cl 2 are used as refrigerant.
Cl
½ + 41. Vinyl halide (CH2 ==CH ¾ Cl) do not undergo nucleophilic
31. C6H5 ¾ C ¾ CH3 + SbCl 5 l C6H5 ¾ C ¾ CH3 + SbCl6- T substitution reactions. This is because it forms highly unstable
½ ½ Å
H H carbocation (CH2 == CH). It cannot delocalise its p-electron. In
(I) vinyl halide C ¾ Cl bond possess double bond character also.
he planar carbocation (I), when return back, forms racemic s r
mixture of the starting compounds. CH2 CH Cl CH2 CH Cl
R. OH (i) Hg(OAC) 2 Mercuration- 54. Given compound undergoes free-radical bromination under
(ii) NaBH4 demercuration adds given conditions, replacing H by Br.
(1) H2O by
Markownikoff’s rule
C* is chiral carbon.
without rearrangement CH2CH2CH3 CH2CH2CH3
S. (i) BH3 Hydroboro-oxidation Br2
H Br H Br
(ii) H2O 2 /OH- adds H2O by
anti-Markownikoff’s
OH (4) rule
CH3 CH2Br
I. Chiral
Thus, P — (2), Q — (3), R — (1), S — (4) Br
Alc. KOH CH2CH2CH3
44. A. CH3 ¾ CHBr ¾ CD3 ¾¾¾® CH2 == CH ¾ CD3 CH—CH2CH3
E2
Br Br
E2 reaction is a single-step reaction in which both H Br
deprotonation from b-C and loss of leaving group from a-C CH3
occur simultaneously in the rate-determining step. CH3
C-D bond is stronger than C—H bond, C—H is preferably II. Achiral III. Chiral
broken in elimination. Br
B. Ph ¾ CHBr ¾ CH3 reacts faster than Ph ¾ CHBr ¾ CD3 in CH2—CH2CH2CH3
E2 reaction because in latter case, stronger C—D bond is to CH2— CH—CH3
H Br
be broken in the rate determining step. H Br
C2 H5 OD CH3
C. Ph ¾ CH2 ¾ CH2Br ¾¾¾¾®
-
Ph ¾ CD == CH2 CH3
C2 H5 O
IV. Chiral V. Chiral
Deuterium incorporation in the product indicates E1CB
mechanism (III) has two chiral centres and can have two structures.
C2 H5 O- -
CH2CH3 CH2CH3
Ph ¾ CH2 ¾ CH2Br l Ph ¾ CH ¾ CH2Br
carbanion H Br H Br
C2 H5 OD
H Br Br H
l Ph ¾ CHD ¾ CH2Br
I
D CH3 CH3
C2 H5 O- ½ (III) A (III) B
I ¾¾¾® Ph ¾ C ¾ CH2 ¾ Br ¾® Ph ¾ C == CH2 (IV) has also two chiral centres and can have two structures.
-
½
D CH3 CH3
D. Both PhCH2CH2Br and PhCD2CH2Br will react at same
H Br H Br
rate in E1 reaction because C—H bond is broken in fast non
rate determining step. Also E1 reaction follow first order H Br Br H
kinetics.
CH3 CH3
45. Propene is produced (IV)A (IV)B
(CH3 )2 Cu + CH2 == CHCl ¾® CH3 ¾ CH== CH2 It has plane of symmetry thus, achiral.
46. Vinyl chloride is obtained by the reaction of HCl with ethyne. Thus, chiral compounds are five. I, III A, III B, IV B and V.
47. Chlorine is most reactive. 55. The substrate has three different types of B—H, therefore, first
three structural isomers of alkenes are expected as :
48. 2-bromo-2-methylpropane is formed as major product.
H H
49. In SN 1 reaction, leaving group is detached in the first step Br
forming carbocation intermediate. H
KOH
50. True + +
51. Larger the size of donor atom, greater is its polarisability, 3 types of B-H
I II III
stronger is the nucleophile.
52. False The last two alkenes II and III are also capable of showing
geometrical isomerism, hence two geometrical isomers for each
53. CCl 4 is fire retardent, used as fire-extinguisher. of them will be counted giving a total of five isomers.
Alkyl Halides 339
methyl shift ½ Due to the above resonance phenomena, C—X bond acquire
¾¾¾¾® CH3 ¾ C ¾ CH2 CH3 partial double bond character and becomes difficult to break in
+ the rate determining step of SN 2 reaction.
I
CH3 Alc. KOH
64. C6H5CH2 ¾ CH ¾ CH3 ¾¾¾® C6H5 ¾ CH == CH ¾ CH3
D
E1 ½
CH3—C==CH—CH3 Br
¯ HBr
I CH3 C6H5 ¾ CH ¾ CH2 ¾ CH3
SN 1 ½
CH3—C—CH2CH3 Br
CH3 CH3
OC2H5 Alc. KOH ½
65. (i) H3C ¾¾¾ CH2CH3 ¾¾¾® CH3 ¾ C == CHCH3
Alc. KOH E2
58. C6H5CH2 ¾ CH ¾ C6H5 ¾¾¾® C6H5 ¾ CH == CH ¾ C6H5 Cl
E2
½ OH
Cl
Aq. NaOH ½
(ii) CH3CH2CHCl 2 ¾¾¾® [CH3CH2 ¾ CH ¾ OH]
CH3 boil unstable
½ E2 CH3 -H O
59. CH3 ¾ C ¾ Br + CH3 O- ¾¾® CH2 == C ¾¾¾®
2
CH3CH2CHO
½ CH3
CH3 66. (i) H2O < CH3OH < HO- < CH3O-
CH3 (ii) CH3F < CH3Cl < CH3Br < CH3I
CH3
½ SN 2 ½ 67. Chloroform in presence of air and sunlight, oxidises slowly to
CH3 ¾ C ¾ O- + CH3 Br ¾¾® CH3 ¾ C ¾ OCH3 form a highly poisonous compound called phosgene
½ ½ hn
CH3 CH3 2CHCl 3 + O2 ¾¾® 2COCl 2 + 2HCl
(Phosgene)
NC O OH OH
Br OMe
OH I (a) (b)
(a) (b)
NC OMe O
NC OH OH (c) (d)
I OH
(c) (d)
OH
O
½
7. CH3CH 2 ¾ C ¾ CH3 cannot be prepared by
(a) (b) OH ½
Ph (2019 Main, 12 Jan I)
HO O
(a) CH3 CH2 COCH3 + PhMgX
(c) (d) (b) PhCOCH3 + CH3 CH2 MgX
(c) PhCOCH2 CH3 + CH3 MgX
O O (d) HCHO + PhCH(CH3 ) CH2 MgX
Alcohols and Ethers 341
HO Cl I
(c) OH (d)
(a) (b)
I OH
Cl
12. The acidic hydrolysis of ether (X) shown below is fastest
HO
(d) when (2014 Adv.)
(c)
17. When phenyl magnesium bromide reacts with tert butanol, 23. In CH3 CH2 OH, the bond that undergoes heterolytic cleavage
which of the following is formed? (2005, 1M) most readily is (1988, 1M)
(a) Tert butyl methyl ether (a) C ¾ C (b) C ¾ O
(b) Benzene (c) C ¾ H (d) O ¾ H
(c) Tert butyl benzene
24. Hydrogen bonding is maximum in (1987, 1M)
(d) Phenol
CH3 (a) ethanol (b) diethyl ether
H+ Br2/CCl4 (c) ethyl chloride (d) triethyl amine
18. [F ] C4H8Br2
/ H 2O 25. HBr reacts fastest with (1986, 1M)
H 3C OH 5 such products
are possible (a) 2-methyl propan-2-ol (b) propan-1-ol
(c) propan-2-ol (d) 2-methyl propan-1-ol
How many structures of F is possible? (2003, 1M)
26. An industrial method of preparation of methanol is
(a) 2 (b) 5 (c) 6 (d) 3
(1984, 1M)
19. Compound ‘A’ (molecular formula C3H8O) is treated with (a) catalytic reduction of carbon monoxide in presence of
acidified potassium dichromate to form a product ‘B’ ZnO-Cr2 O3
(molecular formula C3H6O) ‘B’ forms a shining silver mirror (b) by reacting methane with steam at 900°C with nickel
on warming with ammoniacal silver nitrate. ‘B’ when treated
catalyst
with an aqueous solution of H2NCONHNH2 and sodium
(c) by reducing formaldehyde with LiAlH4
acetate gives a product ‘C’. Identify the structure of ‘C’.
(d) by reacting formaldehyde with aqueous sodium
(a) CH3 CH2 CH == NNHCONH2 (2002, 3M)
hydroxide solution
(b) H3 C ¾ C == NNHCONH2
½ 27. Diethyl ether on heating with conc. HI gives two moles of
CH3 (a) ethanol (b) iodoform (1983, 1M)
OH OH Me OH Me OH
(a) (b)
22. The products of combustion of an aliphatic thiol (RSH) at
298 K are (1992)
(a) CO2 ( g ), H2 O( g ) and SO2 ( g )
(b) CO2 ( g ), H2 O( l ), and SO2 ( g )
(c) CO2 ( l ), H2 O( l ) and SO2 ( g ) (c) Me OH (d) Me OH
(d) CO2 ( g ), H2 O( l ) and SO2 ( l )
Alcohols and Ethers 343
32. The correct statement(s) about the following reaction Compound J upon reaction with KOH gives benzyl alcohol
sequence is (are) and a compound L, whereas K on reaction with KOH gives
(i) O2 CHCl 3 / NaOH only M.
Cumene (C9 H12 ) ¾¾¾®
+
P ¾¾¾¾® O
(ii) H 3O
H3C Ph
NaOH M=
Q (major) + R (minor), Q ¾¾¾® S
PhCH 2 Br (2016 Adv.) Ph H
(2008, 3 ´4M = 12M)
(a) R is steam volatile
(b) Q gives dark violet colouration with 1% aqueous 36. The structures of compounds J , K and L respectively, are
FeCl 3 solution (a) PhCOCH3 , PhCH2COCH3 and PhCH2COO- K+
(c) S gives yellow precipitate with (b) PhCHO, PhCH2CHO and PhCOO- K+
2, 4-dinitrophenylhydrazine (c) PhCOCH3 , PhCH2CHO and CH3COO- K+
(d) S gives dark violet colouration with 1% aqueous (d) PhCHO, PhCOCH3 and PhCOO- K+
FeCl 3 solution
37. The structure of compound I is
33. The following ether, when treated with HI produces
(1999, 3M) Ph CH3 H3C Ph
(a) (b)
—O—CH2— + HI H Ph H Ph
O
Assertion and Reason (c) ; PhCH2MgBr
Read the following question and answer as per the direction Ph H
given below :
O CH2
(a) Statement I is correct; Statement II is correct; Statement II
(d) ;
is a correct explanation of Statement I.
Ph H Ph MgBr
(b) Statement I is correct; Statement II is correct; Statement II
is not the correct explanation of Statement I.
Fill in the Blanks
(c) Statement I is correct; Statement II is incorrect.
39. Glycerine contains one ……… hydroxyl group. (1997, 1M)
(d) Statement I is incorrect; Statement II is correct.
35. Statement I Solubility of n-alcohol in water decreases 40. Aliphatic ethers are purified by shaking with a solution of
with increase in molecular weight. ferrous salt to remove ……… which are formed on prolonged
standing in contact with water. (1992, 1M)
Statement II The relative proportion of the hydrocarbon
part in alcohols increases with increasing molecular weight 41. A …… diol has two hydroxyl groups on …… carbon atoms.
(1986, 1M)
which permit enhanced hydrogen bonding with water.
(1988 , 2M) 42. Ethanol vapour is passed over heated copper and the product is
treated with aqueous NaOH. The final product is ………
Passage Based Questions (1983, 1M)
44. The yield of a ketone when a secondary alcohol is oxidised is 54. When t-butanol and n-butanol are separately treated with a
more than the yield of aldehyde when a primary alcohol is few drops of dilute KMnO4 in one case only, the purple
oxidised. (1983, 1M) colour disappears and a brown precipitate is formed. Which
of the two alcohols gives the above reaction and what is the
Subjective Questions brown precipitate? (1994, 2M)
45. O 55. Compound X (molecular formula, C5 H8 O) does not react
—OH
appreciably with Lucas reagent at room temperature but
+
gives a precipitate with ammoniacal silver nitrate with excess
H /D (i) O3 NaOH
X Y of MeMgBr, 0.42 g of X gives 224 mL of CH4 at STP.
(ii) Zn/CH3COOH Treatment of X with H2 in presence of Pt catalyst followed by
boiling with excess HI, gives n-pentane. Suggest structure
Identify X and Y. (2005, 2M) for X and write the equation involved. (1992, 5M)
46. An organic compound P having the molecular formula 56. Arrange the following in increasing order of boiling point :
C5H10O when treated with dil H2SO4 gives two compounds, n-butane, n-butanol, n-butylchloride, iso-butane. (1988, 1M)
Q and R both gives positive iodoform test. The reaction of
C5H10O with dil, H2SO4 gives reaction 1015 times faster than 57. How may be the following transformation be carried out (in
ethylene. Identify organic compound of Q and R. Give the not more than six steps)?
reason for the extra stability of P. (2004) “Ethyl alcohol to vinyl acetate.” (1986, 3M)
47. Cyclobutylbromide on treatment with magnesium in dry 58. Write down the main product of the following reaction :
ether forms an organometallic compound (A). The I /NaOH
organometallic reacts with ethanal to give an alcohol (B) Ethanol ¾¾¾¾®
2
(1985, 1M)
after mild acidification. Prolonged treatment of alcohol (B)
with an equivalent amount of HBr gives 1-bromo-1- 59. Give a chemical test to distinguish between methanol and
methylcyclopentane (C). Write the structures of (A), (B) and ethanol. (1985, 1M)
explain how (C) is obtained from (B). (2001, 5M) 60. Suggest a reason for the large difference between the boiling
48. Explain briefly the formation of products giving the points of butanol and butanal, although they have almost the
structures of the intermediates. same solubility in water. (1985, 2M)
HCl 61. An alcohol A, when heated with conc. H2 SO4 gives an alkene
(i)
OH Cl B. When B is bubbled through bromine water and the product
obtained is dehydrohalogenated with excess of sodamide, a
+ CH2Cl + etc. new compound C is obtained. The compound C gives D when
CH3 CH3 treated with warm dilute H2 SO4 in presence of HgSO4 . D can
also be obtained either by oxidising A with KMnO4 or from
HCl
(ii) acetic acid through its calcium salt. Identify A, B, C and D.
OH Cl (1983, 4M)
only (1999, 3M)
62. State the conditions under which the following preparations
49. Write the structures of the products : are carried out. Give necessary equations which need not be
HI (excess) balanced.
(CH3 )2 CH ¾ OCH3 ¾¾¾®
heat (1998, 2M) (i) Ethanol from acetylene
50. Give reasons for the following in one or two sentences. (ii) Lead tetraethyl from sodium-lead alloy
“Acid catalysed dehydration of t-butanol is faster than that of (iii) Methyl chloride from aluminium carbide (1983, 3M)
n-butanol. (1998, 2M) 63. A compound ‘X’ containing C, H and O is unreactive
51. 2, 2-dimethyloxirane can be cleaved by acid (H+ ). Write towards sodium. It does not add with bromine. It also does
mechanism. (1997, 2M) not react with Schiff’s reagent. On refluxing with an excess
of HI, ‘X’ yields only one organic product ‘Y’. ‘Y’ on
52. A compound D(C8 H10 O) upon treatment with alkaline
solution of iodine gives a yellow precipitate. The filtrate on hydrolysis yields a new compound ‘Z’ which can be
acidification gives a white solid E (C7 H6 O2 ). Write the converted into ‘Y’ by reaction with red phosphorus and
structures of D, E and explain the formation of E. (1996, 2M) iodine. The compound ‘Z’ on oxidation with potassium
permanganate gives a carboxylic acid. The equivalent weight
53. 3, 3-dimethylbutan-2-ol losses a molecule of water in the of acid is 60. What are the compounds ‘X’, ‘Y’ and ‘Z’ ?
presence of concentrated sulphuric acid to give Write chemical equations leading to the conversion of ‘X’ to
tetramethylethylene as a major product. Suggest a suitable ‘Y ’. (1981, 3M)
mechanism. (1996, 2M)
Alcohols and Ethers 345
64. An organic liquid ‘A’ containing C, H and O with boiling Integer Type Question
point 78°C, possessing a rather pleasant odour, on heating
with concentrated sulphuric acid gives a gaseous product ‘B’ 65. The number of hydroxyl group(s) in Q is (2015 Adv.)
with the empirical formula, CH2 . ‘B’ decolourises bromine Aqueous dilute
H+ KMnO4 (excess)
water as well as alkaline permanganate solution and takes up H P Q
Heat 0°C
one mole of H2 (per mole of B) in presence of finely divided HO
nickel at high temperature. Identify the substances A and B. H 3C CH3
(1979 , 2M)
Answers
1. (d) 2. (c) 3. (a) 4. (c) 25. (a) 26. (a) 27. (c) 28. (d)
5. (d) 6. (b) 7. (d) 8. (a) 29. (c) 30. (b) 31. (b) 32. (b,c)
9. (b) 10. (c) 11. (d) 12. (c) 33. (a,d) 34. (c,e) 35. (c) 36. (d)
13. (b) 14. (b) 15. (c) 16. (b) 37. (a) 38. (b) 39. secondary 40. Peroxides
17. (b) 18. (d) 19. (a) 20. (c) 41. vicinal; same 42. aldol 43. False 44. False
21. (a) 22. (b) 23. (d) 24. (a) 65. (4)
Key Idea PBr3 reagent is used for the substitution of —Br As conc. HBr is in excess. So, reaction will take place at both the
4. substituents.
group while alc. KOH reagent is used to carry out
elimination reaction. Mechanism
Step 1 Protonation of ether to form oxonium ion.
The given reaction proceed in following manner:
H
Step I In presence of PBr3, alcohols undergo substitution |r
s
reactions to give halides. Reagent PBr3 is usually generated O—CH3 O—CH3 + Br
H—Br
insitu by the reaction of red phosphorus with bromine.
PBr3
OH Br CH=
=CH2 CH=
=CH2
Oxonium ion
|
SN2
Alc. KOH Br-+ Slow
Br Br
CH=
=CH2 CH=
=CH2
O O
Cyclohex-2-en-1-one
OH
5. Major product obtained in the given reaction is
CH3—Br +
O CH=
=CH2
C—CH2 — Br O
EtOH, 25°C
d– d+ d – d+
O Intramolecular H H C H + PhCH CH2 MgX Ph CHCH2 CH2 O MgX
cyclisation
CH3 CH3
H3O+
6. Key Idea Ethers are least reactive functional groups. The
cleavage of C ¾ O bond in ethers take place under drastic Ph CH (CH2)2 OH
conditions with excess of HX .
CH3
The major product obtained in the reaction is as follows :
The obtained product is not the required substance. While option
OCH3 OH (a), (b) and (c) can readily prepare the required substance.
Conc. HBr (excess)
Heat The reactions are as follows :
CH=
=CH2 Br—CH— CH3
Alcohols and Ethers 347
Ether group O O
electrophile that further undergoes ArSE 2 reaction to give the remains unaffected
by dil. HCl (hot)
required product. OH OH C C OH
AlCl3 Me
HO HO
H—Cl O
–AlCl s O H OH C C OH
4
–H2O (COOH)2/Polymerisation
O O
Intramolecular
ArSE2 reaction O
H O
O O
HO –HCl
–AlCl3 O n
AlCls4
H OCH3
It does not show SN reaction
with HCl because of double bond 11. Key idea The reaction given is a nucleophilic substitution
nature of the O—C bond, (due reaction in which cleavage at C¾O bond is visible. The
to +R-effect of the —OH group.) product formation can be visualised with the help of
following analysis.
9. The most suitable reagent to carry out given transformation is
I2/NaOH These two atoms are directly
attached to benzene ring.
OH Hence, development of
a O
½ any charge on these atoms is
stabilised by the ring itself due
C H3 C H== C H ¾ C H2 ¾ C H ¾ C H3 ¾Strong
¾¾¾¾¾¾
oxidation, [O]
¾® to conjugation (Resonance)
6 5 4 3 2 1 (Oxidative cleavage) O b
O If any one properly visualise the fact written with figure
½½ above, than a conclusion can be made that C¾O bonds
C H3 ¾ C H== C H ¾ C H2 ¾ C ¾ OH marked (a) and (b) in the figure will undergo heterolysis
6 5 4 3 2
during the reaction.
+CHI3 ¯ + CO2
348 Alcohols and Ethers
: :
O O + –H O OCH2R
O HI I Acetal
Resonance
Heat + I + CH3OH stabilisation
O
OH
Mechanism O
Step I The reaction begins with the attack of H + of HI on
+
oxygen to form oxonium ion as 15. All dihydroxy benzene will have higher boiling points than
+ monohydroxy benzene. Also, among dihydroxy benzenes, 1,
O O 2,-di-hydroxy benzene has lowest boiling point due to
HI
D H intramolecular H-bonding.
O O O
Oxonium ion
Step II This oxonium ion undergoes lysis and addition of I- to H
form two products as O
+
O H
I– I + CH OH
H 3 (intramolecular H-bonding in
O O 1,2-dihydroxy benzene)
.
Although both reactions are giving the same product, Now if the given product is
carbocation I is more stable than II. Me N3
*
22. Thiol, (RSH), on combustion produces CO2 (g ), SO2 (g ) and
H2O(l ). At 298 K, H2O will be in liquid phase.
23. OH ¾® O- + H+ (has maximum electronegativity and which is too enantiomerically pure i.e. 100% either
difference) dextrorotatory or leavorotatory form, then the ‘X’ must be
Me OH
24. Ethanol is capable in forming intermolecular H-bonds : *
H O—H O—H
C2H5—O C2H5 C2H5 Note The configuration at carbon * atom in ‘X’ becomes inverted
due to SN 2 mechanism which is visible in the product as well.
25. Reaction proceeds via carbocation intermediates :
CH3 CH3 Thus, the probable reactions will be
½ - H2 O ½ Me OH Me Br
CH3 ¾ C — OH + H+ ¾¾® CH3 ¾ C + PBr3
½ ½ Et2O
CH3 CH3
(2-methylpropan -2-o1) (3 ° carbocation) Me Br Me I
CH3 NaI
- ½ Me2CO
+ NaBr
Br
¾¾® CH3 ¾ C — Br
½ Me I Me N3
CH3
NaN3
ZnO-Cr 2 O3 HCONMe2
26. CO + H2 ¾¾¾® CH3OH
heat
32. CH3
27. CH3 ¾ CH2 ¾ O ¾ CH2 ¾ CH3 + HI ¾® 2C2H5I
CH3
CH CH3 O—O—CH
28. 2-methyl propan-2-ol is a tertiary alcohol, will react fastest with CH3
Lucas reagent :
O2 H3 O +
CH3 CH3
½ ½
HCl
CH3 ¾ C — OH ¾¾® CH3 ¾ C — Cl
½ ZnCl 2 ½ OH
CH3 CH3 O
SN1 reaction
+ CH3—C—CH3
29. On heating with concentrated H2SO4, ethanol would undergo Acetone CHCl3/NaOH
Phenol D , Reimer-Tiemann
dehydration to produce ethene. reaction
(P)
30. Ethanol is soluble in water due to its ability to form
intermolecular H-bonds with water : OH O O H O H
31. Key idea All the reactions involved in the problem are H CHO
Nucleophilic substitution of second order i.e., SN 2 which have , NaOH
the speciality of inversion of configuration at the carbon atom
involved. (Q) Major
(Q) Major
CHO
Of the reactions given (R) Minor
Reaction 1 in its generalised format is seen as
PBr
ROH ¾¾¾¾¾¾¾¾®
3
RBr O—Na Br CH2—Ph O—CH2Ph
In diethyl ether (Et 2O)
CHO
Reaction 2 is simple halogen exchange reaction called Williamson's CHO
Finkelstein reaction. Its generalised format is synthesis
In acetone( Me2 CO )
RX + NaI ¾¾¾¾¾¾® RI + NaX (S )
where X =Cl or Br (a) R is not steam volatile, but Q is steam volatile thus, incorrect.
Reaction 3 in its generalised format seen as (b) Q has enolic group thus, gives violet colour with 1% aqueous
HCONMe2 FeCl 3 solution thus, correct.
RI + NaN3 ¾¾¾¾® RN3 + NaI
350 Alcohols and Ethers
Phenol does not react further with HI. 39. Secondary : HO OH C–2(OH) is secondary
··
OH
34. CH3CH2Br + O == N ¾ O- ¾® CH3CH2NO2 + CH3CH2ONO 40. Peroxides : H2O2 + Fe2+ ¾® H2O + Fe3+
ambident nitroethane ethyl nitrite
nucleophile
41. Vicinal, same
OH
35. R—OH ¬ Hydrophilic
Cu ½ NaOH
Hydrophobic 42. C2H5OH ¾® CH3CHO ¾¾® CH3 ¾ CH ¾ CH2 ¾ CHO
D H 2O
aldol
Increasing molecular weight increases hydrocarbon (R)
proportion that lowers the solubility in water. 43. Ethanol is weaker acid than water, not neutralised with NaOH.
Passage 1 44. 2°-alcohol on oxidation yields ketone while 1°alcohol on
oxidation produces aldehyde which can further be oxidised to
Compound J must be benzaldehyde because it on treatment acid.
with KOH undergoing Cannizzaro’s reaction producing
+
benzyl alcohol and pot-benzoate (L). —OH CH2 +
H+ Ring – H+
KOH 45.
C6 H5 ¾ CHO ¾¾® C6 H5 ¾ CH2 OH + C6 H5 COOK( L) expansion
J benzyl alcohol X
O
Also M is aldol condensation product formed from H
acetophenone O3
[X ]
O Zn/CH3COOH
O
½½ KOH
Y
Ph ¾ C ¾ CH3 ¾¾® O
acetophenone ( K )
O NaOH
CH3 O CH3
½
—Ph aldol
½½ - H2 O
Ph ¾ C — CH2 ¾ C ¾ Ph ¾¾®
½ O
OH Ph M +
dil. H2SO4/H
Ph 46. CH3CH2OH + CH3—C—CH3
ÞI = C== CH ¾ Ph O
H3C P CH3 Q R
I2/NaOH
OH Both gives positive iodoform test.
½
and H = Ph ¾ C — CH2 ¾ Ph Br OH
½ Mg (i) CH3CHO
CH3 47. —CH—CH3
ether (ii) H+/H2O
3 °-alcohol ‘B’
O
½½ - H+ + Ring expansion
+ H–shift
36. J = C6 H5 CHO, K = Ph ¾ C ¾ CH3 , L = PhCOOK + —CH—CH3
2° Br
Ph
37. I = C== CH ¾ Ph + Br–
H3 C
3° ‘C’
Alcohols and Ethers 351
+
H+ Lucas reagent
48. CH2 55. Compound ‘X’ ¾¾¾¾¾® No reaction at room
(i) OH temperature.
Cl–
Ammoniacal Excess of
C5H8 O ¾¾¾¾¾® ppt, X ¾¾¾¾® CH4;
AgNO3 CH3 MgBr
Cl
H2 /Pt
+ Cl– X ¾¾¾® n-pentane
CH2 CH2Cl HI excess
H+
Above information suggest that X has a terminal triple bond and
+ Cl–
it contain primary —OH group.
(ii)
OH 2° Cl Ag(NH3 )+2
Þ H ¾ C ºº C ¾ CH2 ¾ CH2 ¾ CH2OH ¾¾¾®
HI X
49. (CH3 )2 CH ¾ O ¾ CH3 ¾® CH3 ¾ CH ¾ CH3 + CH3I
½ Ag ¾ C ºº C ¾ CH2CH2CH2OH
I
56. Isobutane < n-butane < n-butylchloride < n-butanol
50. Acid catalysed dehydration proceeds via carbocation Conc.H SO
intermediate. Also, greater the stability of reactive intermediate, 57. CH3CH2OH ¾¾¾¾¾®
2 4
CH2 == CH2
D
faster the reaction :
Br 2 NaNH2
CH3 CH3 ¾® CH2 ¾ CH2 ¾¾¾® H ¾ C ºº C ¾ H
½ H+
½ ½ ½
CH3 ¾ C — OH ¾¾® CH3 ¾ C — CH3 Br Br
½ - H2 O
+
CH3 (3 ° highly stable)
Hg(CH3COO) 2
(t - butanol) ¾¾¾¾¾® CH2 ==CH ¾ OCOCH3
CH3COOH vinyl acetate
n-butanol forms less stable (1°) carbocation.
I /NaOH
H 58. C2H5OH ¾¾¾®
2
CHI3 + HCOONa
iodoform
O O+ 59. CH3 ¾ CH2 OH + I2 + NaOH ¾® CHI3 ¯ (Iodoform test)
51. H+ – H+
H3C H 3C yellow
H3C H 3C OH2
Iodoform test is not given by methanol.
2,2-dimethyloxirane
CH3 OH 60. Butanol forms intermolecular H-bonds, has higher boiling point
than butanal.
H3C—C——CH2 O
½½ D
OH 61. (CH3COO)2 Ca ¾® CH3 ¾ C ¾ CH3 + CaCO3
52. E = C6H5COOH (benzoic acid) D
O
O ½½
½½ I2
H2 SO4
CH3 ¾ C ºº CH ¾¾® CH3 ¾ C ¾ CH3
Þ D = C6H5 ¾ C ¾ CH3 ¾¾® C6H5 ¾ COONa + CHI3 C HgSO4 D
NaOH
CH3 OH CH3
½ ½ H+
½ + OH
53. CH3 ¾ C — CH ¾ CH3 ¾¾® CH3 ¾ C — CH ¾ CH3 ½ Br 2
Conc.
½ ½ CH3 ¾ CH ¾ CH3 ¾¾® CH3 ¾ CH== CH2 ¾®
CH3 CH3 H2 SO4 B H2 O
2°
Br
CH3 ½
Methyl ½ – H+ HC CH3 CH3 ¾ CH ¾ CH2
¾¾® CH3 ¾ C — CH — CH3 ¾® 3 C == C ½
shift ½ H3C CH3 Br
+
CH3 X
NaNH2
KMnO4 CHO + MnO2¯ X ¾¾® CH3 ¾ C ºº CH
H 2O C
54. OH brown
n-butanol
352 Alcohols and Ethers
CH3CH2OH
CH3 ¾ CH3
Heat
(ii) 4 C2H5Br + 4 (Na / Pb) ¾® (C2H5 )4 Pb CH2 == CH2 + Br2 ¾ H2O ¾® CH2 ¾ CH2
sodium -lead tetraethyl lead (brown) ½ ½
alloy Br Br
colourless
H O
(iii) Al 4C3 ¾¾®
2
Al(OH)3 + CH4 CH2 == CH2 + alk. KMnO4 ¾® CH2 ¾ CH2
hn purple ½ ½
CH4 + Cl 2 ¾® CH3Cl + HCl OH OH
colourless
63. Compound X must be a symmetrical ether :
65. +
HI Na
R ¾ O¾ R ¾® 2R ¾ I ¾® No reaction, not an alcohol H
H Methyl shift
X Y Heat
HO
Schiffs’ H 3C CH3 CH3
¾¾¾® No reaction, not an aldehyde. H3C
reagent
H2 O [O] –H
R ¾ I ¾® R ¾ OH (Z ) ¾® Acid Heat
EW = 60
½ I2 / P CH3 H3C
¯ CH3 CH3
R—I ‘P’
OH
Þ Acid is CH3COOH and Z = CH3CH2OH KMnO4(dil)
HO
Þ X = C2H5 ¾ O ¾ C2H5, Y = CH3 ¾ CH2 ¾ I 0°C
OH
HI
H3C OH CH3
CH3CH2 ¾ O ¾ CH2CH3 ¾® 2CH3CH2I
‘Q’
X Y
OtBu
5. An organic compound neither reacts with neutral ferric
(d) OHC chloride solution nor with Fehling solution. It however,
CHO reacts with Grignard reagent and gives positive iodoform
2. In the following reaction, test. The compound is (2019 Main, 8 April I)
HCl
Carbonyl compound + MeOH - acetal O
Rate of the reaction is the highest for: (2019 Main, 9 April II) CH3 O
(a) (b) CH3
(a) Acetone as substrate and methanol in excess
H
(b) Propanal as substrate and methanol in stoichiometric amount OH
(c) Acetone as substrate and methanol in stoichiometric amount O
(d) Propanal as substrate and methanol in excess O OH
3. The major product obtained in the following reaction is C2H5 CH3
(2019 Main, 8 April II) (c) (d)
CH3 O CH3 C2H5
O
NaOH O
OHC D
CH3
6. In the following reactions, products A and B are
H3C (2019 Main, 12 Jan I)
(a) H (b) H O O
Dil. NaOH
O CH3 O CH2 H 3C H [A ]
H3 C CH3
CH3 CH3 H3O+
[A] D [B]
O O
(c) (d) CH3 CH3
(a) A= CH3 ; B= CH3
O O HO
354 Aldehydes and Ketones
O O O
CH3 CH3 OH OH
CH2 C OCH3
(b) A= CH3 ; B= CH3 CH2 CH2 OH
HO (a) (b)
O
O
OH CH3
O OH
C O
H H CH2 C H CH2 CH2 OH
HC
(c) A= 3 ; B= (c) (d)
H 3C H3C
CH3 CH3
O 10. The correct sequence of reagents for the following
O
OH conversion will be (2017 Main)
C H2C
H H O HO CH3
A= H3C ; B=
(d)
H 3C H 3C
CH3 CH3
(d) Q P R S CH3
CH3 CH3
9. The major product ‘X’ formed in the following reaction is ½
(2019 Main, 10 Jan I)
½
CH3
½
O (c) (d)
O
CH2 C OCH3 NaBH4
X
½
MeOH CH3
Aldehydes and Ketones 355
13. The major product in the following reaction is (2014 Adv.) 17. Cyclohexene on ozonolysis followed by reaction with zinc
O dust and water gives compound E. Compound E on further
(i) CH3MgBr, dry ether, 0°C treatment with aqueous KOH yields compound F.
Cl
(ii) Aqueous acid Compound F is (2007, 3M)
CH3
O —CHO —CHO
(a) (b)
(a) H3C
CH3
OH —COOH
(c) (d)
COOH
(b)
H2C CH3
CH3
18. The smallest ketone and its next homologue are reacted with
NH2OH to form oxime (2006)
(c) (a) two different oximes are formed
CH2 (b) three different oximes are formed
O
(c) two oximes are optically active
CH3
(d) all oximes are optically active
(d)
CH3 19. Butan-2-one can be converted to propanoic acid by which of
O
the following ? (2006)
14. The most suitable reagent for the conversion of (a) NaOH, NaI/H+
R ¾ CH2 ¾ OH ® R ¾ CHO is (2014 Main)
(b) Fehling’s solution
(a) KMnO4 (c) NaOH, I2/H+
(b) K 2 Cr2 O7
(d) Tollen’s reagent
(c) CrO3
(d) PCC (pyridinium chlorochromate) CHO
15. The major product H in the given reaction sequence is CH3COONa
20. + (X )
s 95% H2 SO4
CH3 ¾ CH2 ¾ CO ¾ CH3 ¾¾®
CN G ¾¾¾¾® H MeO
COOH
(a) CH3 ¾ CH == C ¾ COOH
½
CH3 (2012)
MeO
(b) CH3 ¾ CH == C ¾ CN
What is X ?
½
CH3 (a) CH3 COOH (b) BrCH2 COOH
(c) (CH3 CO)2 O (d) HOC ¾ COOH
OH
21. The order of reactivity of phenyl magnesium bromide with
½
(c) CH3 ¾ CH2 ¾ C ¾ COOH the following compounds is (2004, 1M)
½ O O O
CH3 ½½ ½½ ½½
23. The appropriate reagent for the following transformation: Objective Questions II
O (One or more than one correct option)
CH2CH3 33. Reagent(s) which can be used to bring about the following
CH3
transformation is (are) (2016 Adv.)
HO HO
O O O O
(a) Zn (Hg), HCl (b) NH2 NH2 , OH– C O C
(c) H2 /Ni (d) NaBH4
O H O OH
24. Which of the following has the most acidic hydrogen?
(2000, 1M) COOH COOH
(a) 3-hexanone (b) 2, 4-hexanedione (a) LiAlH 4 in ( C2 H5 )2 O (b) BH 3 in THF
(c) 2, 5-hexanedione (d) 2, 3-hexanedione (c) NaBH 4 in C2 H5 OH (d) Raney Ni/H 2 in THF
25. The enol form of acetone, after treatment with D2 O, gives 34. The major product of the following reaction is (2015 Adv.)
(1999, 2M)
O
OD O (i) KOH, H2O
½ ½½ (ii) H+, Heat
(a) H3 C ¾ C ==CH2 (b) D3 C ¾ C ¾ CD3 CH3
O
OH OD
½ CH3 CH3
½
O O
(c) H2 C==C ¾ CH2 D (d) D2 C==C ¾ CD3
(a) (b)
26. Which of the following will react with water? (1998, 2M)
(a) CHCl 3 (b) Cl 3 CCHO O
(c) CCl 4 (d) ClCH2 CH2 Cl O CH3
27. Which of the following compounds is oxidised to prepare (c) CH3 (d)
methyl ethyl ketone? (1987, 1M)
(a) 2-propanol (b) 1-butanol
(c) 2-butanol (d) t-butyl alcohol 35. After completion of the reactions (I and II), the organic
compound (s) in the reaction mixtures is/are (2013)
28. The compound that will not give iodoform on treatment with
alkali and iodine is (1985, 1M) O
Br2 (1.0 mol)
(a) acetone (b) ethanol
(c) diethyl ketone (d) isopropyl alcohol Reaction I H3C CH3 Aqueous/NaOH
==
O O H 3C OH
H3C
37. A new carbon–carbon bond formation is possible in
(1998, 2M) O
(a) Cannizzaro’s reaction O
(b) Friedel-Crafts’ reaction
(c) Clemmensen’s reduction
44. The compounds P and Q respectively are
(d) Reimer-Tiemann reaction CH3
H3C H
38. Which of the following will undergo aldol condensation? CH H C
(a) Acetaldehyde (1998, 2M)
(a) H3C C and
(b) Propanaldehyde O
O
(c) Benzaldehyde CH3
(d) Trideutero acetaldehyde H
H
39. Among the following compounds, which will react with CH H C
(b) H3C C and
acetone to give a product containing C==N¾ ? O
O
(a) C6 H5 NH2 (b) (CH3 )3 N (1998, 2M)
H3C CH2 H H 3C H
(c) C6 H5 NHC6 H5 (d) C6 H5 NHNH2 CH C C
(c) and
40. Which of the following is an example of aldol condensation? CH3 O O
Dil.NaOH
(a) 2CH3 CHO ¾¾¾® CH3 CH(OH)CH2 CHO (1989, 1M)
H3C CH2 H H H
OH CH C C
Dil.NaOH ½ (d) and
(b) 2CH3 COCH3 ¾¾¾® H3 C ¾ C ¾ CH2 COCH3 CH3 O O
½ 45. The compound R is
CH3
O O
Dil . NaOH
(c) 2HCHO ¾¾¾® CH3 OH + HCOONa
H 3C C H 3C C
Dil .NaOH (a) C H (b) C H
(d) C6 H5 CHO + HCHO ¾¾¾® C6 H5 CH2 OH +HCOONa H 3C H 3C
H 2C CH
41. Which of the following compounds will react with ethanolic OH H 3C OH
KCN? (1984, 1M)
(a) Ethyl chloride (b) Acetyl chloride CH3 O CH3 O
(c) Chlorobenzene (d) Benzaldehyde CH CH
C C
42. Which of the following compounds will give a yellow (c) H3C CH H (d) H3C CH H
precipitate with iodine and alkali ? (1984, 1M)
H2C CH
(a) 2-hydroxy propane OH H3C OH
(b) Acetophenone
(c) Methyl acetate 46. The compound S is
(d) Acetamide CH3 O
O
43. Base catalysed aldol condensation occurs with (1984, 1M)
CH C
(a) propionaldehyde H3C H H3C C
(a) CH (b) C H
(b) benzaldehyde H3C
(c) 2-methyl propionaldehyde H 2C H2C
CN CN
(d) 2, 2-dimethyl propionaldehyde
358 Aldehydes and Ketones
(a) H3C Br
(c) (d)
(b) H3C
O C2H5 CH3
Br
48. The structures of the products Q and R, respectively, are
(c) H3C Br
O
(d) H3C Br
H
(a) CH3
COCH3 51. The structures of compounds J and K , respectively, are
CH3
H3C H 3C CH3 (a) H3C COOH and SOCl2
O
(b) H3C COOH and SO2Cl2
H
(b) (c) H3C and SOCl2
CHO
CH3 COOH
H 3C H 3C CH3
(d) H3C COOH
and CH3SO2Cl
O
H
52. The structure of product L is
(c) (a) H3C CHO
CHO
Me Et Et
Me
O (b) H3C CHO
Me
CH3 (c) H3C
(d)
CHO CHO
Me Me Et
(d) H3C CHO
Aldehydes and Ketones 359
Match the Column 59. In the scheme given below, the total number of
intramolecular aldol condensation products formed fromY is
53. Match each of the compounds given in Column I with the
reaction(s) that they can undergo, given in Column II. 1. O3 1. NaOH(aq)
Y
2. Zn, H2O 2. heat
Column I Column II (2010)
A. Br p. Nucleophilic
substitution Subjective Questions
HCl
O 60. (A), C6H12 ¾¾® (B), C6H13Cl + (C ), C6H13Cl
Alcoholic KOH
B. q. Elimination (B) ¾¾¾¾¾® (D), (an isomer of (A))
OH
O zonolysis
(D) ¾¾¾¾® (E), (positive iodoform and negative
Fehling’s solution test)
C. CHO r. Nucleophilic addition
Ozonolysis
(A) ¾¾¾¾® (F) + (G), (positive Tollen's test for both)
Conc. NaOH
OH (F) + (G) ¾¾¾¾® HCOONa + A primary alcohol
D. s. Esterification with Identify the compounds (A) to (D). (2003)
Br
acetic anhydride
61. A compound C9H7O2Cl exists predominantly in enol form
NO2 (A) and also in keto form (B). On oxidation with KMnO4 it
gives m-chlorobenzoic acid as one of the products. Identify
t. Dehydrogenation the compounds (A) and (B). (2003)
54. Match the compounds/ions in Column I with their 62. An alkene (A) C16 H16 on ozonolysis gives only one product
properties/reactions in Column II. (2007, 6M) (B) C8 H8 O. Compound (B) on reaction with NaOH / I2 yields
sodium benzoate. Compound (B) reacts with KOH/NH2 NH2
Column I Column II yielding a hydrocarbon (C ) C8 H10 . Write the structures of
A. C6 H5 CHO p. gives precipitate with compounds (B) and (C ). Based on this information two
2, 4-dinitrophenylhydrazine isomeric structures can be proposed for alkene (A). Write
their structures and identify the isomer which on catalytic
B. CH3 C ºº CH q. gives precipitate with AgNO3 hydrogenation (H2 / Pd – C) gives a racemic mixture.
–
(2001, 5M)
C. CN r. is a nucleophile
63. Identify A, B and C, and give their structures.
D. I- s. is involved in cyanohydrin
O
formation CH3
CH3 Br2
Fill in the Blanks A +B
NaOH
55. Fehling’s solution A consists of an aqueous solution of O H+
C(C7H12O)
copper sulphate, while Fehling’s solution B consists of an heat (2000)
alkaline solution …… (1990, 1M) 64. An organic compound A, C6 H10 O, on reaction with CH3 MgBr
followed by acid treatment gives compound B. The compound
True or False B on ozonolysis gives compound C, which in presence of a
56. The reaction of methyl magnesium iodide with acetone base gives 1-acetyl cyclopentane D. The compound B on
followed by hydrolysis gives secondary butanol. (1987, 1M) reaction with HBr gives compound E. Write the structures of
A, B, C and E. Show, how D is formed from C. (2000, 5M)
57. Benzaldehyde undergoes aldol condensation in an alkaline
medium. (1982 , 1M) 65. What would be the major product in the following reaction ?
Ph
Integer Answer Type Questions base
isomers of molecular formula (C8 H9 NO). When D is 73 Complete the following reaction with appropriate structure :
boiled with alcoholic KOH, an oil F (C6H7 N) separates CH3 CH2
out. F reacts rapidly with CH3COCl to give back D. On the (i) KCN/H2SO4
C==O ¾¾¾¾¾®
other hand, E on boiling with alkali followed by (ii) LiAlH4
acidification gives a white solid G (C7 H6O2). Identify H (1996, 1M)
A-G.
(b) Carry out the following transformation in not more than 74. Complete the following reaction with appropriate structure.
three steps. NaOC 2 H5 in absolute
1-butyne ¾® 2-pentanone (1999, 3M) C6H5CHO + CH3COOC2H5 ¾¾¾¾¾¾¾¾® A
C2 H5 OH heat (1995, 1M)
67. Write the intermediate steps for each of the following
reactions 75. Write the structure of the major organic product expected
from the following reaction. (1992, 1M)
H3O+
(i) C6H5CH(OH)C ºº CH ¾¾® C6H5CH == CHCHO
KOH
MeO CHO + HCHO
–
H
(ii)
76. Arrange the following in the increasing order of expected
OH O CH3 enol content.
68. Complete the following reactions with appropriate structures CH3 COCH2 CHO, CH3 COCH3 , CH3 CHO,
of products/reagents. CH3 COCH2 COCH3 (1992, 1M)
70. Acetophenone on reaction with hydroxylamine hydrochloride 79. Answer the followings with suitable equations wherever
can produce two isomeric oximes. Write structures of the necessary
oxime. (1997, 2M) (i) suggest a reagent to distinguish acetaldehyde from acetone.
71. Complete the following, giving the structures of the principal (ii) what happens when excess chlorine is passed through
organic products, boiling toluene in the presence of sunlight? (1987, 2M)
O
80. Complete the following with appropriate structures
NaOH
? CH CH—CHO
(i) + Ph3P CH2 A
(1986, 1M)
81. How may the following transformation be carried out (in not
(ii) ClCH2CH2CH2COPh + KOH + MeOH ¾® B more than six steps) “benzaldehyde to cyanobenzene”?
O (1986, 2M)
C6H5 82. Give reason in one or two sentences for the following:
H 3O +
(iii) H3C + NaOH C “Hydrazones of aldehydes and ketones are not prepared in
O (1997, 2M) highly acidic medium”. (1986, 1M)
72. Suggest appropriate structures for the missing compounds.
83. Write down product of the following reaction
(the number of carbon atoms remains the same throughout
NaOH
the reaction) Propanal ¾¾¾®
heat (1985, 1M)
CH3
84. Arrange the following in order of their increasing reactivity
Dil. KMnO4 HIO4 HO– towards HCN :
A B C
CH3CHO, CH3COCH3 , HCHO, C2H5COCH3 (1985, 1M)
85. Write down the reactions involved in the preparation of the treated with bromine in presence of phosphorus yields a
following using the reagents indicated against in parenthesis: compound C which on hydrolysis gives a hydroxyl acid D.
“Acetoxime from acetaldehyde.” This acid can also be obtained from acetone by the reaction
with hydrogen cyanide followed by hydrolysis. Identify the
[K2Cr2O7 / H+ , Ca(OH)2 and NH2OH, HCl] (1984, 2M) compounds A, B, C and D. (1982 , 2M)
86. Show with balanced equation, what happens, when the 88. Outline the reaction sequence for the conversion of methanal
following are mixed : to ethanol (the number of steps should not be more than
“Chloral is heated with aqueous hydroxide” (1984, 2M)
three). (1981, 2M)
87. An alkene A on ozonolysis yields acetone and an aldehyde. 89. Write the structural formula of the main organic product
The aldehyde is easily oxidised to an acid B. When B is formed when methanal reacts with ammonia. (1981, 1/2M)
Answers
1. (a) 2. (d) 3. (c) 4. (d) 37. (b,d) 38. (a,b,d) 39. (a,d) 40. (a,b)
5. (d) 6. (b) 7. (b) 8. (c) 41. (a,b,d) 42. (a,b) 43. (a,c) 44. (b)
9. (b) 10. (a) 11. (a) 12. (b) 45. (a) 46. (d) 47. (b) 48. (a)
13. (d) 14. (d) 15. (a) 16. (c) 49. (b) 50. (d) 51. (a) 52. (c)
17. (a) 18. (b) 19. (c) 20. (c) 53. A ® p, q, t B ® p, s, t C ® r, s D ® p.
21. (c) 22. (a) 23. (b) 24. (b) 54. A ® p, q, s B ® q, r C ® q, r, s D ® q, r.
25. (b) 26. (b) 27. (c) 28. (c) 55. Sodium potassium tartarate
29. (b) 30. (c) 31. (c) 32. (c) 56. False 57. False
33. (c) 34. (a) 35. (c) 36. (a,c,d) 58. (5) 59. (1)
Less acidic
2. Key Idea Aldehydes are more reactive than ketones in H s
nucleophilic addition reactions. O
D HO H 2O 4
5 3
For the reaction, –H2O – OH
s 1 2
HCl (option-c)
Carbonyl compound + MeOH Acetal - O Major
O H More acidic O
Rate of reaction is the highest for propanal as substrate and b-H for b-elimination
methanol in excess. Propanal is an aldehyde and more reactive
than ketones. When MeOH is taken in excess then reaction
362 Aldehydes and Ketones
4. –I
O
6. The reactant in presence of dil × NaOH undergoes intramolecular
O
H b-elimination aldol condensation reaction.
Cl s r /D
tBuOK As a result of this, b-hydroxyketone (A) is obtained which on
Acidic hydrogen H
–HCl
hydrolysis followed by heating produces a , b-unsaturated
This benzylic –H activates ketone (B)
r
p-position by +ve H (Conc. H2SO4) O O O O
for ArSO2 Electrophilic addition
dil.
H H H 3C H NaOH s H
O O H 3C CH3
2°
r
r 1° O O O
2°, but less stable carbocation
1°, but more stable
carbocation
because of –I effect of O
D H2O
s
ArSE 2 ArSE 2 –H2O HO O
H H (B) H (A ) H
r O r O
LiAlH4 (excess)
Major product CH3
5- membered ring Minor product
(option-d)
(less stable) (option-c)
NO2 NH2 OH
5. According to the given conditions, compound (d) neither reacts Compound
(b)
with neutral ferric chloride solution nor with Fehling solution. It
however reacts with Grignard reagent and gives positive 8. (A) ® Q; B ® (P) ; C ® (S), D ® (R)
iodoform test.
(A) Lysine (R=–(CH2)4–NH2)
● As the compound does not contain any phenolic ¾ OH
½
group into an alcohol but cannot reduce an isolated O3
½
C == C and an ester group too. D
Zn.H2O2
Carbonyl
group O O O O
O OH
½½ ½½
CH2 C OCH3 CH2 C OCH3 CH3 ¾ C ¾ CH2 ¾ CH2 ¾ CH2 ¾ C ¾ CH3
NaBH4
Heptan -2, 6 dione
Ester MeOH
group
CH3
Isolated ½
C C
½
(b) O3
10. D
Zn.H2O2
½
O O O HO CH3 CH3
O
[Ag (NH3)2]OH Esterification CH3MgBr
CH3OH, H+ 6 ½½5 4 3 2 1
(Excess)
Tollen’s reagent
CH3 ¾ C ¾ CH2 ¾ CH2 ¾ CH ¾ CHO
½
CHO COOH COOCH3 OH
CH3
5-keto-2-methyl hexanal
Before final product is formed, intermediate is
HO CH3
CH3
½
½
O3
(c) D
½ Zn.H2O2
O CH3 CH3
O CH3
11. ½½ ½
O O CH3 ¾ C ¾ CH2 ¾ CH ¾ CH2 ¾ CHO
5-keto- 3-methyl hexanal
–
OH CH3
H
½
(d) CH3
½
OH OMgX CH3
O O aq. acid
Cl intramolecular
CH3 nucleophilic
HCHO O CH3
CH3 substitution reaction
Acetal CH2OH + HCOO– + Mg X Cl
formation (By oxidation)
(By reduction)
364 Aldehydes and Ketones
PCC
14. R — CH2OH ¾ ¾¾® R — CH == O O CH2OH
½½ ½
Pyridinium chlorochromate is the mild oxidising agent which H ¾ C ¾ H + – CH ¾ CHO r
causes conversion of alcohol to aldehyde stage. While others ½
causes conversion of alcohol to acid. CH2OH
15. The first step is cyanohydrin reaction O- CH2OH CH2OH
O ½ ½ H 2O
½
½½ H ¾ C ¾ C ¾ CHO ¾® HOCH2 ¾ C ¾ CHO
-
CH3 ¾ CH2 ¾ C ¾ CH3 + CN ¾® ½ ½ ½
H CH2OH CH2OH
O- OH
½ H2O ½ CH2OH O O-
CH3 ¾ CH2 ¾ C ¾ CN ¾¾® CH3 ¾ CH2 ¾ C ¾ CN ½ ½½ ½
½ ½ Step IV HOCH2 ¾ C ¾¾¾ C ¾ H + H ¾ C ¾ OH
CH3 CH3 ½ ½
(I) CH2OH H
In the second step the ¾ CN of intermediate (I) is first
OH
hydrolysed and then dehydrated on heating in the presence of OH
Cannizzaro reaction
conc. H2SO4. + HCOO–
OH OH HO
½ H2SO4 ½ OH
CH3 ¾ CH2 ¾ C ¾ CN ¾¾¾® CH3CH2 ¾ C ¾ COOH
½ ½ In the last step, formaldehyde is oxidised and the other aldehyde
CH3 CH3 is reduced giving the desired products.
(I) 17. O
D
¾® CH3 ¾ CH == C ¾ COOH O3
H
½ H
CH3 Zn-H2O
O
E
16. The given reaction is an example of repeated aldol condensation
followed by Cannizzaro reaction.
KOH CHO
-
Step I CH3CHO + OH- ¾® CH2 ¾ CHO + H2O
H2O
O
Intramolecular aldol
½½ - condensation reaction
H ¾ C ¾ H + CH2 ¾ CHO r
18. Three different oximes are formed out of which two are optically
O- OH
active i.e.exists as a pair of enantiomers while other is optically
½ ½
H 2O
H ¾ C ¾ CH2 ¾ CHO ¾® CH2 ¾ CH2 ¾ CHO inactive.
½ 19. CH3
NaOH
H H 3C CHI3 + CH3CH2COONa
I2/H2O
- O
Step II HOCH2 ¾ CH2 ¾ CHO + HO r
H+
- CH3CH2COOH
HO ¾ CH2 ¾ CH ¾ CHO + H2O
O
½½ - 20. X is (CH3CO)2 O and it is an example of Perkin’s reaction.
H ¾ C ¾ H + CH ¾ CHO r
½ 21. The reactivity of carbonyl compound towards nucleophilic
CH2OH
addition of Grignard’s reagent depends on extent of steric
O- OH hindrance at a-carbon. Greater the steric hindrance smaller the
½ H 2O
½ reactivity. Hence, reactivity order is
H ¾ C ¾ CH ¾ CHO ¾¾® CH2 ¾ CH ¾ CHO
½ ½ ½ CH3CHO > CH3 ¾ CO ¾ CH3 > Ph ¾ CO ¾ Ph
H CH2OH CH2OH II I III
O
Step III HOCH2 ¾ CH ¾ CHO + HO- r
½ 22. —CHO + H—C—H
NaOH
—CH2OH
CH2OH
H 2O
-
HOCH2 ¾ C ¾ CHO + H2O + H— COONa
½
CH2OH This is an example of cross Cannizzaro reaction in which
formaldehyde is always oxidised.
Aldehydes and Ketones 365
23. O 32. Grignard’s reagent reacts with both aldehydes and ketones
while other three reagents reacts only with aldehydes, not with
NH2–NH2 CH2CH3
CH3 ketones.
HO–
33. Only ¾ CHO group is to be reduced to ¾ CH2OH.
HO HO
It can be done using NaBH4 in C2H5OH.
(Wolff-Kishner reduction)
24. O IV O
O O O O C O
+ H+ H
– O III
II
Highly resonance
H stabilised COOH
I
OH O
½ ½½ (a) LiAlH4 / (C2H5 )2 O reduces I, II and III into ¾ CH2OH, and
25. CH2 == C ¾ CH3 + D2O r D3C ¾ C ¾ CD3
IV into diol.
All a-H will be replaced by deuterium.
(b) BH3 / THF show same properties as (a).
26. H O (c) NaBH4 / C2H5OH reduces III into ¾ CH2OH.
Cl (d) Raney nickel, same as (a) and (b), thus (c) is correct
Cl3C—CHO + H2O Cl—C—–CH reagent.
Cl 34. CH3
H O
O O O
Highly stable hydrate
HO–
OH O CH3
Aldol type
½ [O] ½½ O
27. CH3 ¾ CH ¾ CH2 ¾ CH3 ¾¾® CH3 ¾ C ¾ CH2 ¾ CH3 Condensation
2- butanol catalyst Ethyl methyl ketone CH3 CH3
O O O
H+
28. Compounds that contain either CH3 ¾ CO or CH3 ¾ CH ¾ D
group gives iodoform test : ½ –H2O
OH
O a, b-unsaturated ketone
½½
CH3 ¾ C ¾ CH3 CH3 ¾ CH ¾ H CH3 ¾ CH ¾ CH3 35. Plan When acetone reacts with Br2 in basic medium, bromoform is
formed.
Acetone ½ ½
OH OH Reaction I CH3COCH3 + 3Br2 + 4NaOH
Ethanol Isopropyl alcohol 1 mol 3 mol
1 1 mol
Above three compounds has the desired group for iodoform test. mol
3
Diethyl ketone does not has the required group for iodoform
¾® CH3COONa + CHBr3 + 3NaBr + 3H2O
test. (T ) (U )
29. Aldehydes lacking presence of a-H undergo Cannizzaro When CH3COCH3 and Br2 are in equimolar quantity, all the Br2
reaction. When treated with aqueous base CH3CHO does not (limiting reactant) is converted into desired products and
undergo Cannizzaro reaction because it has a-H and in the 2/3 mole of CH3COCH3 remains unreacted, being in excess.
presence of aqueous base it undergoes aldol condensation. When acetone reacts with Br2 in acidic medium, there is
30. CH3 ¾ CHO + Fehling’s solution ¾¾® Cu 2O ¯ monobromination of acetone.
Red Reactions II
O CH COOH
CH3COCH3 + Br2 ¾¾¾¾®
3
CH3COCH2Br + HBr
½½
31. For iodoform test, CH3 ¾ C ¾ group is required 1 mol 1 mol (P )
CH3COCH3 and Br2 react in 1 : 1 mole ratio and (P) is formed.
O
In reaction I, (U ) and (T ) are formed and acetone (reactant)
+ NaOH + I2 remains unreacted. In reaction II, (P) is formed.
H3C CH3
2-pentanone
36. All those carbonyl compounds containing a-H to sp2 carbon
COONa + CHI3¯ show keto-enol tautomerism.
Yellow
366 Aldehydes and Ketones
37. In both Friedel-Craft’s reaction and Reimer-Tiemann reaction 43. For base catalysed aldol condensation, there must be at least one
new carbon-carbon bond is formed. a-H to carbonyl group.
CH3 CH3 ¾ CH2 ¾ CHO,
AlCl3 Propionaldehyde
+ CH3Cl (2 a -H)
CH3 CH3
Friedel-Crafts' alkylation ½ ½
OH OH CH3 ¾ CH ¾ CHO , CH3 ¾ C — CHO
CHO 2-methyl propionaldehyde ½
+
(1 a -H) CH3
H
+ CHCl3 + NaOH 2, 2-dimethyl propionaldehyde
(no a -H)
Ph Ph Ph Ph
n-butyl–CH—Et A= C == C + C == C
(6) n-propyl–C—Et H3C CH3 H3C CH3
(±) racemic
OH mixture I II
O NaBH4 H
(7) Iso-propyl–C—Et Iso-propyl–CH—Et H
O (±)racemic Ph + Enantiomer
OH II + H2/Pd
mixture CH3
= Racemic mixture
Ph CH3
While in case of (4) and (5) they do not produce enantiomer
due to the presence of stereogenic centre on ketone.
63.
59. O O O O
CH3
O3 OH–
CH3
CH3 Br2
Zn-H2O
NaOH
COONa + CHBr3
O O ‘B’
Only product
Y ‘A’ O
CH3 CH3 Cl CH3
½ ½ ½ H+
60. CH2 == CH ¾ C — CH3 CH3 ¾ CH — C — CH3 Heat
+ CO2
½ ½
CH3 CH3 C
A B
64. O
Cl CH3 CH3
OH– C
½ ½ ½
CH3 ¾ CH — C — CH3 CH3 ¾ C == C — CH3 C CH3
Aldol
½ ½
CH3 CH3 D
C D CHO O
O CH3 CH3 CH3
½½ ½ Þ C= B=
CH3 ¾ C ¾ CH3 CH3 ¾ C — CHO HCHO
E ½ G
CH3 MeMgBr H+
A (C6H10O) ¾¾¾® ¾¾® B
F
O
61.
H
O O O Þ + CH3MgBr
CHO
H A HO CH3 CH3
H+
Cl Cl
A B B
COOH
KMnO4
65. Ph Ph
Base
_
O O
Cl Br Br
Enolisation
62. B + NaOH / I2 ¾® C6H5COONa + CHI3
Ph
O
CH2CH3 O
C
N2H4/OH–
Þ B= CH3
Aldehydes and Ketones 369
66. (a) G is benzoic acid C6H5 ¾ COOH , B and C are two 68. O
stereomeric oximes which undergo Beckmann’s rearrangement O CH—Ph
on treatment with acid to give amides D and E. (i) NaOH
O (ii) C6H5CHO
½½ OH-
C6H5 ¾ C ¾ NHCH3 ¾¾® C6H5COOH + CH3NH2 CH—Ph
E H2 O G (i) LiAlH4
O
H5C6 OH (ii) H+, heat
+
H
C==N C6H5—C—NHCH3
H 3C E 69. Aldehyde A does not has any a-H but undergo ozonolysis to
give two moles of compound B and benzaldehyde. Compound B
C on oxidation gives oxalic acid, so A is
O
H5C6 O3
H+ C6H5 ¾ CH == CH¾ C ºº C ¾ CHO ¾®
C==N CH3—C—NHC6H5 A
H 3C OH
D C6H5 ¾ CHO + 2COOH
½
B KOH CHO
CH3COOH + C6H5NH2
H2O B
F
F + CH3COCl ¾® C6H5NHCOCH3 Ag +
D B ¾¾® COOH
O ½
½½ COOH
Þ A = C6H5 ¾ C ¾ CH3
70.
(b) CH3 ¾ CH2 ¾ C ºº CH O
H5C6 OH
O
B2 H6 ½½ (i) CH3 MgBr
C6H5—C—CH3 + H2NOH C==N
¾¾¾® CH3CH2CH2 ¾ C ¾ H ¾¾¾¾¾® H 3C
H2 O2 /OH- (ii) H3 O +
OH H5C6
½
CH3CH2CH2 ¾ CH ¾ CH3 + C==N
O H 3C OH
[O] ½½ O CH2
¾® CH3CH2CH2 ¾ C ¾ CH3
2-pentanone.
72. 76. CH3 ¾ CO ¾ CH2 ¾ COCH3 has highest enol content due to
CH3 CH3 CH3 resonance and formation of six membered ring through
intramolecular H-bonding
Dil. KMnO4 OH HIO4 O O O H
OH O O O
CH3 CH3 CH3 H3C CH3
A B
O (A) H3C CH3
(I)
HO–
B Also, enol content depends upon the number of substituents on
aldol double bond, greater the number of substituents, greater the
stability, higher the enol content.
C
73. KCN + H2SO4 ¾® KHSO4 + HCN Therefore, CH3COCH2CHO forms next most stable enol
O O OH
½½ R ½½ HCN
½ H+
82. R ¾ C ¾ R + PhNHNH2 ¾® C ==N ¾ NHPh 87. CH3 ¾ C ¾ CH3 ¾¾® CH3 ¾ C — CN ¾¾®
R Hydrazone ½ H2 O
CH3 OH
In acidic medium, hydrazine reacts to form salt and hydrazone is
½
hydrolysed back to aldehyde/ketone. CH3 ¾ C — COOH
OH- ½
83. CH3CH2CHO ¾¾® CH3 ¾ CH2 ¾ CH == C ¾ CHO CH3
heat ½ D
CH3 Br CH3
Aldol followed by ½ ½
dehydration Þ C = CH3 ¾ C — COOH , B = CH3 ¾ CH — COOH
½
84. Steric hindrance at carbonyl carbon determine the reactivity CH3
towards nucleophilic addition reaction. Greater the steric
hindrance, smaller the reactivity. CH3 CH3
½ ½
C2H5COCH3 < CH3COCH3 < CH3CHO < HCHO Þ A = CH3 ¾ C== CH ¾ CH ¾ CH3
H+ Ca(OH) 2 O
85. CH3CHO ¾¾® CH3COOH ¾¾® (CH3COO)2 Ca
K 2 Cr 2 O7 ½½ E ther
O 88. H ¾ C ¾ H + CH3MgBr ¾¾® CH3CH2OMgBr
heat ½
½ H2 NOH
(CH3COO)2 Ca ¾® CH3 ¾ C ¾ CH3 ¾¾® H+
¾¾® CH3CH2OH
H2 O
H3C
C == N ¾ OH 89. N
H3C acetoxime
6CH2O + 4NH3 N ‘‘(CH2)6N4’’
86. Cl 3C ¾ CHO + NaOH(aq) ¾® Cl 3C ¾ CH2OH N N
Cannizzaro reaction
Hexamine
+ Cl 3C ¾ COONa
8. When benzene sulphonic acid and p-nitrophenol are treated List–I List–II
with NaHCO3 , the gases released respectively, are (2006, 3M)
P. Ph 1. I2 , NaOH
(a) SO2 , NO2 (b) SO2 , NO (c) SO2 , CO2 (d) CO2 , CO2
HO
9. An enantiomerically pure acid is treated with racemic Me
Ph + H2SO4
mixture of an alcohol having one chiral carbon.The ester OH
formed will be (2003, S, 1M) Me
(a) optically active mixture (b) pure enantiomer
Q. Ph 2. [Ag(NH 3 )2 ] OH
(c) meso compound (d) racemic mixture
H 2N
10. Benzoyl chloride is prepared from benzoic acid by H
Ph + HNO2
(a) Cl 2 , hn (b) SO2 Cl 2 (2000, S, 1M) OH
(c) SOCl 2 (d) Cl 2 , H2 O Me
CH2OH H2SO4(cat.) O
CO2Et CHCl3
O
O O CO2H Cl
(a) (b)
(a) (b)
Cl
CO2Et COOH
O O
OH OH
O Cl O
(c) (d)
OEt O (c) (d)
O O COOH Cl
O
374 Carboxylic Acids and Their Derivatives
3. The increasing order of the reactivity of the following with 8. Different possible thermal decomposition pathways for
LiAlH 4 is (2019 Main, 12 Jan II) peroxyesters are shown below. Match each pathway from
O O Column t I with an appropriate structure from Column II and
(A) (B) select the correct answer using the code given below the lists.
(2014 Adv.)
C2H5 NH2 C2H5 OCH3 P
R· + R¢O·
O O O –CO2
(C) (D) O Q
C2H5 Cl C2H5 O C2H5 O R· + R¢O· R· + X·
–CO2
R O R¢ + Carbonyl compound
(a) ( A ) < ( B ) < ( D ) < (C )
(b) ( A ) < ( B ) < (C ) < ( D ) (Peroxyester) R
RCO· 2+ R¢O· R· + X¢·
–CO2
(c) ( B ) < ( A ) < ( D ) < (C ) + Carbonyl
compound
(d) ( B ) < ( A ) < (C ) < ( D ) S
RCO2· + R¢O· R· + R¢O·
4. The major product obtained in the following reaction is –CO2
(2019 Main, 10 Jan II)
CO2Et
NaOEt/D Column I Column II
O
O O
O O P. Pathway P 1. O
C6H5CH2 O CH3
(a) (b)
CO2Et
O
CO2Et Q. Pathway Q 2. O
C6H5 O CH3
O O
(c) (d) O
CO2Et
O CH3
R. Pathway R 3. C6H5CH2 O
CO2Et CH3
CH2C6H5
5. The decreasing order of ease of alkaline hydrolysis for the
following esters is (2019 Main, 10 Jan I) O
O CH3
COOC2H5 Cl COOC2H5 S. Pathway S 4. C6H5 O
CH3
I II C6H5
Codes
O2N COOC2H5 CH3O COOC2H5
P Q R S
III IV (a) 1 3 4 2
(b) 2 4 3 1
(a) III > II > IV > I (b) III > II > I > IV
(c) 4 1 2 3
(c) II > III > I > IV (d) IV > II > III > I (d) 3 2 1 4
6. The compounds A and B in the following reaction are, 9. A compound with molecular mass 180 is acylated with
respectively CH 3 COCl to get a compound with molecular mass 390. The
HCHO+HCl AgCN number of amino groups present per molecule of the former
A B
compound is (2013 Main)
(2019 Main, 9 Jan I)
(a) 2 (b) 5
(a) A = Benzyl alcohol, B = Benzyl isocyanide
(c) 4 (d) 6
(b) A = Benzyl alcohol, B = Benzyl cyanide
(c) A = Benzyl chloride, B = Benzyl isocyanide 10. Which of the following reactants on reaction with
(d) A = Benzyl chloride, B = Benzyl cyanide conc. NaOH followed by acidification gives the following
7. The major product of following reaction is lactone as the only product? (2006, 5M)
O
(i) AIH( i - Bu) 2
R ¾ C ºº N ¾¾¾¾¾¾¾®?
(ii) H 2O (2019 Main, 9 Jan I)
O
(a) RCHO (b) RCONH2
(c) RCOOH (d) RCH2 NH2
Carboxylic Acids and Their Derivatives 375
COOCH3 COOH 17. Identify the binary mixture(s) that can be separated into
(a) (b) individual compounds, by differential extraction, as shown
in the given scheme. (2012)
COOH CHO
NaOH (aq)
CHO COOH
Binary mixture containing
(c) (d) Compound 1 and Compound 2 NaHCO3 (aq)
CHO COOH
Compound 1 + Compound 2
11. Benzamide on treatment with POCl 3 gives (2004, S, 1M) Compound 1 + Compound 2
(a) aniline (b) benzonitrile
(c) chlorobenzene (d) benzyl amine (a) C6 H5 OH and C6 H5 COOH
CH3MgBr (b) C6 H5 COOH and C6 H5 CH2 OH
12. Ethyl ester ¾¾¾® P, the product ‘P’ will be
(excess) (2003, S, 1M) (c) C6 H5 CH2 OH and C6 H5 OH
H3C CH3 H3C C2 H 5 (d) C6 H5 CH2 OH and C6 H5 CH2 COOH
(a) (b)
H3C OH H5C2 OH 18. Reaction of RCONH2 with a mixture of Br2 and KOH gives
R ¾ NH2 as the main product. The intermediates involved in
H5C2 C2 H 5 H5C2 C2 H 5 this reaction are (1992, 1M)
(c) (d)
(a) RCONHBr
H5C2 OH H7C3 OH (b) RNHBr
13. The product of acid hydrolysis of P and Q can be (c) R ¾ N == C == O
distinguished by (2003, S, 1M)
(d) RCONBr2
OCOCH H3C
3
P : H2C== ; Q: Assertion and Reason
CH3
OCOCH3 Read the following questions and answer as per the direction
(a) Lucas reagent (b) 2, 4-DNP given below :
(c) Fehling’s solution (d) NaHSO 3 (a) Statement I is true; Statement II is true; Statement II is a
correct explanation of Statement I.
14. Hydrogenation of benzoyl chloride in the presence of Pd on (b) Statement I is true; Statement II is true; Statement II is not
BaSO4 gives (1992, 1M) the correct explanation of Statement I.
(a) benzyl alcohol (b) benzaldehyde (c) Statement I is true; Statement II is false.
(c) benzoic acid (d) phenol (d) Statement I is false; Statement II is true.
15. Acetamide is treated separately with the following reagents. 19. Statement I p-hydroxybenzoic acid has a lower boiling
Which one of these would give methyl amine ? (1983, 1M) point than o-hydroxybenzoic acid.
(a) PCl 5 (b) NaOH + Br2 Statement II o-hydroxybenzoic acid has intramolecular
(c) Sodalime (d) Hot conc. H2 SO4 hydrogen bonding. (2007, 3M)
Objective Questions I 20. Statement I Acetic acid does not undergo haloform reaction.
Statement II Acetic acid has no alpha hydrogen. (1998, 2M)
(One or more than one correct options)
16. With reference to the scheme given, which of the given Passage Based Questions
statement(s) about T, U, V and W is/are correct? (2012)
Passage 1
O
The reaction of compound P with CH3 MgBr (excess) in (C2 H5 )2 O
O followed by addition of H2 O givesQ. The compoundQ on treatment
with H2 SO4 at 0° C gives R. The reaction of R with CH3 COCl in the
H3C
T presence of anhydrous AlCl 3 in CH2 Cl 2 followed by treatment with
LiAlH4 (excess) H2O produces compound S . [Et in compound P is ethyl group]
CrO3/H+ (CH3CO)2O
V U W (H3C)3C
(a) T is soluble in hot aqueous NaOH CO2Et Q R S
(b) U is optically active
P
(c) Molecular formula of W is C10H18 O4
(d) V gives effervescence on treatment with aqueous NaHCO3
376 Carboxylic Acids and Their Derivatives
O
21. The product S is (2017 Adv.)
15 *
(a) NH2, NH2, NH2, formaldehyde (H2 CO) as one of the products when
compound (Z) is treated with HBr and subsequently
D D ozonolysed. Mark the C* carbon in the entire scheme.
15
NH2 * *
Ba CO3 + H2 SO4 ¾® X ( C = C14 gas )
15
(b) NH2, NH2 (i) Mg/ether
4 LiAlH
CH2 == CH ¾ Br ¾¾¾¾® Y ¾¾¾® Z
(ii) X
D (ii) H3 O+ (2001 Main, 5M)
15
(c) NH2, NH2 36. Write the structures of the products A and B.
O
15 ½½ 18 H3O+
(d) NHD, NH2 CH3 ¾ C ¾ O C2H5 ¾¾® A+ B (2000 Main, 3M)
37. Explain briefly the formation of the products giving the
structures of the intermediates
Fill in the Blank O
28. Formic acid when heated with conc. H2 SO4 produces O
OC2H5
………………… (1983, 1M)
C OC2H5
NaOEt Br (i) OH–
H 2C
True/False C OC2H5
(ii) H+
COOH
29. The boiling point of propanoic acid is less than that of n-butyl
alcohol, an alcohol of comparable molecular weight. O
(1991, 1M) COOH
(1999, 5M)
30. Hydrolysis of an ester in the presence of a dilute acid is
38. Write the structures of the products :
known as saponification. (1983, 1M)
(CH3CO) 2 O, heat
CH3 CH2 NH2 ¾¾¾¾¾¾® (1998)
Integer Type Question
39. An ester A (C4H8O2), on treatment with excess methyl
31. The total number of carboxylic acid groups in the product P
magnesium chloride followed by acidification, gives an
is (2013 Adv.)
alcohol B as the sole organic product. Alcohol B, on
O O oxidation with NaOCl followed by acidification, gives acetic
(i) H3O+ , D
acid. Deduce the structures of A and B. Show the reactions
O (ii) O3
P involved. (1998)
(iii) H2O2 40. Complete the following, giving the structures of the principal
O O organic products
Me
Subjective Questions (i) + (COOEt)2 + EtONa A
CH2Cl NO2
32. conc. H2SO 4
+ (ii) (COOH)2 + (CH2OH)2 ¾¾¾¾® ¾® B
KCN C2H5ONa/EtOH H3O /D
(A) (B) (C) H O+
Heat
DMF C6H5CHO (iii) H3CCOCOC6H5 + NaOH ¾¾®
3
C (1997, 2M)
SOCl2
(D) 41. A hydrocarbon A of the formula C8 H10 , on ozonolysis gives
CH3NH2
Identify A to D. (2004, M)
compound B (C4 H6 O2 ) only. The compound B can also be
obtained from the alkyl bromide C (C3 H5 Br) upon treatment
33. Compound A of molecular formula C9 H7 O2 Cl exists in keto with magnesium in dry ether, followed by carbon dioxide
form and predominantly in enolic form B. On oxidation with and acidification. Identify A, B and C and also give equations
KMnO4 , A gives m-chlorobenzoic acid. Identify A and B. for the reactions. (1996, 3M)
(2003 Main, 2M)
42. Complete the following sequence of reactions with
34. (±) 2-phenylpropanoic acid on treatment with (+) 2-butanol appropriate structures
gives (A) and (B). Deduce their structures and also establish
Red-P A
CH3 ¾ CH2 ¾ COOH ¾¾¾®
stereochemical relation between them. (2003)
Br 2
35. Identify X and Y in the following synthetic scheme and
(i) Alc. KOH (excess)
write their structures. Explain the formation of labelled A ¾¾¾¾¾¾¾® B
(ii) H+ (1995, 2M)
378 Carboxylic Acids and Their Derivatives
43. Which of the following carboxylic acids undergoes and 1.36 Å and both the carbon-oxygen bonds in sodium
decarboxylation easily ? Explain briefly. formate have the same value, i.e. 1.27Å.” (1988, 2M)
(i) C6H5COCH2COOH 51. Write balanced equations for the following reaction :
(ii) C6H5COCOOH “Acetamide is reacted with bromine in the presence of
(iii) C6H5CH(OH)COOH potassium hydroxide.” (1987, 1M)
(iv) C6H5CH(NH2) COOH (1995, 2M) 52. A liquid X, having a molecular formula C6 H12 O2 is hydrolysed
44. Predict the major product in the following reaction : with water in the presence of an acid to give a carboxylic acid
(i) CH MgBr (excess) Y and an alcohol Z. Oxidation of Z with chromic acid gives Y.
3
C6H5 ¾ CH2COCH3 ¾¾¾¾¾¾¾® (1994, 1M) What are the structures of X, Y and Z ? (1986, 3M)
(ii) H+
53. An ester A (C4H8O2) on treatment with excess of methyl
45. In the following reactions, identify the compounds A, B, C magnesium chloride followed by acidification, gives an alcohol
and D. B as the sole organic product. Alcohol B, on oxidation with
(i) PCl5 + SO2 ¾® A + B NaOCl followed by acidification, gives acetic acid. Deduce
(ii) A + CH3COOH ¾® C + SO2 + HCl structures of A and B. Show the reactions involved. (1998)
(iii) 2C + (CH3 )2 Cd ¾® 2D + CdCl2 (1994, 1M ´ 4 = 4M) 54. Complete the following with appropriate structures :
46. Complete the following sequence of the reactions with C H OH
(CH3CO)2 O ¾¾¾®
2 5
CH3COOH + ? (1986, 1M)
appropriate structures
55. Arrange the following in order of their increasing ease of
Fuming 1. NaOH (Fuse) hydrolysis : (1986, 1M)
(i) —SO3H +
H2SO4 2. H CH3COOC2H5 , CH3COCl, (CH3CO)2 O, CH3CONH2
P 2O 5
+
H , H 2O 56. Give reasons in one or two sentences for the following :
(ii) —CONH2 “Formic acid is a stronger acid than acetic acid.” (1985, 1M)
D
(1992, 1M) 57. Write down the reactions involved in the preparation of the
47. In the following identify the compounds/reaction following using the reagents indicated against in parenthesis.
conditions represented by the alphabets A, B, and C : “Propionic anhydride from propionaldehyde”
PCl NH
[AgNO3 , NH4 OH, P2 O5 ] (1984, 2M)
5 3
C6 H5 COOH ¾¾® A ¾¾® 58. Give reasons for the following in one or two sentences.
P2 O5 H2 /Ni ‘‘Acetic acid can be halogenated in the presence of P and Cl 2 ,
B ¾¾® C6 H5 CN ¾¾® C (1991, 2M)
but formic acid cannot be halogenated in the same way.’’
48. Arrange the following as stated: Why? (1983, 1M)
“Increasing order of acidic strength.”
59. State with balanced equation, what happens when, “Acetic
ClCH2COOH, CH3CH2COOH, ClCH2CH2COOH, anhydride reacts with phenol in presence of a base.” (1982, 1M)
(CH3 )2 CHCOOH, CH3COOH (1991, 1M)
60. Write the structural formula of main organic product formed
49. How will you bring about the following conversion? when ethyl acetate is treated with double the molar quantity of
“Ethanoic acid to a mixture of methanoic acid and diphenyl methyl magnesium bromide and the reaction mixture is poured
ketone.” (1990, 2M)
into water. (1981, 1/2 M)
50. Give reasons for : 61. Write the chemical equation to show what happens when,
“Carbon-oxygen bond lengths in formic acid are 1.23 Å “Ethyl acetate is treated with sodium ethoxide in ethanol and
the reaction mixture is acidified”. (1981, 2 M)
Answers
Topic 1 5. (b) 6. (c) 7. (a) 8. (a)
1. (b) 2. (c) 3. (d) 4. (d) 9. (b) 10. (c) 11. (b) 12. (a)
5. (b) 6. (d) 7. (c) 8. (d) 13. (c) 14. (b) 15. (b) 16. (a,c,d)
9. (d) 10. (c) 11. (d) 12. (a) 17. (b,d) 18. (a,c) 19. (d) 20. (c)
13. (d) 21. (a) 22. (c) 23. (b) 24. (a)
Topic 2 25. (d) 26. (d) 27. (b)
1. (d) 2. (d) 3. (a) 4. (b) 28. H2O and CO gas 29. False 30. False
31. (2)
Hints & Solutions
Topic 1 Carboxylic Acids NOTE
l
Ordinary carboxylic acid require soda-lime catalyst for
COOH
1. Heating of (CH2)4 (adipic acid) with a dehydrating agent, decarboxylation.
COOH l
Final step of decarboxylation in the above shown mechanism
decarboxylates ( ¾CO2 ) to give a ketone (cyclopentanone), not involve tautomerism, therefore, for decarboxylation of b-keto
an anhydride. acid by above mechanism, the acid must contain an a-H].
O
½½ NH3 SO3H SO3Na
4. CH3CH2 ¾ C ¾ OH ¾®
(A ) 8. + NaHCO3
O
D ½½ + H2O + CO2
CH3CH2COONH4 ¾® CH3 ¾ CH2 ¾ C ¾ NH2
(B ) (C ) OH ONa
Br 2 , KOH + NaHCO3
¾¾¾¾¾¾¾® CH3 ¾ CH2 ¾ NH2
Hoffmann’ s bromamide
reaction O 2N O2N
+ H2O + CO2
5. It is a b-keto acid which undergo decarboxylation in very mild
condtion, i.e. on simple heating. This occur through a six O O-
member cyclic transition state as ½½ H ½
- H+
9. R ¾ C ¾ OH + O R ¢ ¾¾® R ¾ C — OH
OH ··
H ½
O O D Tautomerism OR ¢
–CO2
R C CH2
C C Reaction occur at planar sp2 carbon giving racemic mixture of
R CH2 O O
product.
Six membered cyclic R C CH3
transitionstate of a 10. C6H5COOH + SOCl 2 ¾® C6H5 ¾ COCl
b-keto acid
*
11. CH3 ¾ CH2 ¾ COOH + NaHCO3 ¾® CH3CH2COONa
*
+ H2 O + CO2
380 Carboxylic Acids and Their Derivatives
12. Ethanol is the weakest acid among these, hence it is most basic. The reaction proceed as
13. (d) Ph
Ph Ph Ph O
HO Me Pinacol
For P, i.e. + H2SO4 Pinacolone
HO OH Me
Ph OH + H2SO4 Me Me rearrangement Ph
Me
Me (Phenyl shift)
The correct match is 1 i.e., I2 , NaOH and 5 i.e., NaOBr
H Both
The reactions proceed as aO haloform
/N
I2 reactions
Ph Me Ph O
Pinacol
+ H2SO4
HO OH Pinacolone Me Me Ph O NaOBr
Ph Me rearrangement Ph
(Methyl shift) Me
OH
Ph
Both
X
H
aO
haloform
Ph
/N
reactions
I2
For S, i.e. Br H
Ph + AgNO3
OH
NaOBr
Me
Ph O The correct match is 2, 3.
Me OH The reaction proceed as
Ph Ph
‘ X’ Br H
Ph H
Ph OH + AgNO3
For Q, i.e. + HNO2
NH2 OH Me
dibromination
Ph Me rearrangement
The correct match is 2 i.e. [Ag(NH3)2]OH and 3 i.e., Fehling’s Ph
solution.
O
The reactions proceed as Me
Ph H Ph O Ph H
Deamination
+ HNO2 Rest procedure is same as seen for Q above i.e., via oxidation.
H2N rearrangement Me H
Ph Me OH (Methyl shift) Ph OH
t ion ½ D
NaOH
o lu 14. CH3CHO + HCHO ¾¾® H ¾ C — CH2 ¾ CHO ¾®
'ss
lin
g ½ Aldol
h Both H
Fe oxidation
Reactions OH
[Ag(NH3)2]OH
(Tollens's HCN ½
reagent) CH2 == CH ¾ CHO ¾¾® CH2 == CH ¾ CH ¾ CN
Ph O Cyanohydrin
Me
OH OH OH
Ph
‘X’ ½ H+ ½
CH2 == CH ¾ CH ¾ CN ¾® CH2 == CH ¾ CH ¾ COOH
Ph Ph H2 O
Thus, both benzyl cyanide and benzyl isocyanide are the products of reaction but benzyl isocyanide being the major product gives the correct
option as (c).
7. Key Idea DIBAL-H is diisobutyl aluminium hydride, [(CH3 )2 CHCH2 ]2 AlH. It is a selective reducing agent. It reduces carboxylic acids,
carboxylic acid derivatives and nitriles into aldehydes. It is an electrophilic reducing agent.
O
O
P. 1. C6H5H2C CH3
O C6H5 — CH2+ CO2+ CH3O
O
O CH3
O CH3 C6H5 — CH2+ CO2+ Ph—CH2 — C — CH3 Ph —CH2+ CH3—CO—CH3
Q. 3. C6H5H2C O
CH2C6H5 CH3
O O
CH3
O CH3 C6H5 — CO2+ CH3—C—CH3 Ph + CH3—CO—Ph + CH3 + CO2
R. 4. C6H5 O
–CO2
C6H5 C6H5
O
C6H5 —CO2+ CH3O
O
S. 2. C6H5 O CH3 C6H5+ CO2
Carboxylic Acids and Their Derivatives 383
H+
17. For separation by differential extraction one of the component
O must form salt with the given base so that the salt will be
extracted in aqueous layer leaving other component in organic
layer.
O (a) Both phenol and benzoic acid forms salt with NaOH, hence
½½ this mixture can’t be separated.
POCl 3
11. C6H5 ¾ C ¾ NH2 ¾¾® C6H5 ¾ CN (b) Benzoic acid forms salt with NaOH while benzyl alcohol
does not, hence the mixture can be separated using NaOH.
O OMgBr Also benzoic acid forms salt with NaHCO3 but benzyl
½½ CH3 MgBr
½ alcohol does not, hence NaHCO3 can be used for
12. CH3 ¾ C ¾ OC2H5 ¾¾¾® CH3 ¾ C — CH3 separation.
excess
½ (c) Neither benzyl alcohol nor phenol forms salt with NaHCO3,
CH3 mixture cannot be separated using NaHCO3.
CH3 (d) C6H5CH2COOH forms salt with NaOH, C6H5CH2OH does
½ not, hence mixture can be separated using NaOH.
H 2O C6H5CH2COOH forms salt with NaHCO3. C6H5CH2OH
¾® CH3 ¾ C — OH
does not, hence mixture can be separated using NaHCO3.
½
CH3 O O
½½ -
½½
OH O 18. R ¾ C ¾ NH2 + OH + Br2 ¾® R ¾ C ¾ NHBr
H+ ½ ½½ (A )
13. P ¾¾® CH3 ¾ C == CH2 r CH3 ¾ C ¾ CH3 O O
H2 O
NaOH ½½ ½
½ -
¾¾® CHI3 ¯ R ¾ C ¾ NHBr + OH- ¾® R ¾ C ¾ N ¾ Br
I2 Yellow (B )
H+ ¾® R ¾ N == C == O + Br -
Q ¾¾® CH3 ¾ CH== CH ¾ OH r CH3 CH2 OH (C )
H 2O
Fehling solution 19. p-hydroxy benzoic acid has higher boiling point than o-hydroxy
¾¾¾¾¾® Cu 2 O ¯ benzoic acid because former prefers intermolecular H-bonding
Red while the latter prefer intramolecular H-bonding.
H O
COCl CHO
H2 HOOC— —O C— —OH
14. Pd/BaSO4 ‘‘Rosenmund H—O
reduction’’ intermolecular H-bonding
OH
O
½½ C
15. CH3 ¾ C ¾ NH2 + Br2 + NaOH ¾® CH3NH2 “Hofmann’s O
bromamide reaction”.
H
O
intramolecular H-bonding
384 Carboxylic Acids and Their Derivatives
O
½½ COOH COOH COOH
20. Compounds with CH3 ¾ C ¾ or CH3 ¾ CH(OH)–group gives
haloform reaction but this reaction is given only by aldehydes, H—C H 2O + O H—C—OH OH—C—H
ketones and alcohols, so acetic acid does not give haloform +
reaction. However acetic acid has three a-H, therefore, C—H dilute alkaline HO—C—H H—C—OH
KMnO4
statement I is true but statement II is false.
COOH COOH COOH
Passage-1
(fumaric acid) (T) d (+) (U) l (–)
OH
(I) CH3MgBr(ex) T and U (in 1 : 1 molar ratio) form optically inactive (racemic
OEt+ (ii) H2O mixture) due to external compensation.
Q
24. PLAN Ni / H2 reduces (C == C) bond.
O H+/0°C
Benzene undergoes Friedel-Crafts reaction Zn-Hg/HCl reduces
carbonyl group (Clemmensen reduction)
CH3COCl
AlCl3 O
R(F.C. Alkylation) CHCOOH CH2COOH CH2C
Ni/H2 D O
O
S(F.C. Acylation) HOOCHC CH2COOH CH2C
O
22. (a) succinic anhydride (V)
22. (c) O
O
23. PLAN A lkenes decolourise Br2 water anhydrous C
dil× KMnO4 CH2—C AlCl3 CH2
c i s -isomer ¾¾¾¾® M e s o isomers by s y n addition + O
dil× KMnO4 CH2—C CH2COOH
t r a n s -isomer ¾¾¾¾® d (+ ) and l(- ) isomers by s y n
a d d it io n t h u s , r a c e m ic m ix t u r e . O
Formation of anhydride from dicarboxylic acid indicates Å
c i s -isomer. Zn–Hg/HCl H3PO4
P and Q are isomers of dicarboxylic acids. Clemmensen
Br water HO
P , Q ¾¾¾¾®
2
decolourised O
O
P and Q have ( C ==C ) bond (W)
D
P ¾® anhydride O
Thus, P is cis-isomer.
25. Cl— —C—NH2 + KOH + Br2
CHCOOH Br—CHCOOH CHCO
Br2 Water D
O O
(i)
CHCOOH Br—CHCOOH CHCO
Cl— —C—NHBr
COOH COOH
an intermediate (ii)
H—C H 2O + O H—C—OH 26. Rearrangement of (iii) to (iv) is the rate determining step :
O
H—C dilute alkaline H—C—OH
KMnO4 Slow Cl—
Cl— —C – —N==C==O + Br–
COOH COOH
N—Br
(P) (S)
(iii) (iv)
(maleic acid) Optically inactive due to
internal compensation of
rotation (meso-isomer) 27. The rate determining step of Hofmann’s bromamide reaction is
unimolecular rearrangement of bromamide anion (iii) and no
cross-products are formed when mixture of amides are taken.
Carboxylic Acids and Their Derivatives 385
15
KOH
33. Compound A of molecular formula C9 H7 O2Cl exist in keto and
—CONH2 + —CONH2 predominantly in enolic form B. Hence, A must be a carbonyl
Br2
compound which contain a-H. Enolic forms of B predominates
D (i) 15 because of presence of intramolecular H-bonding.
—NH2 + —NH2 Cl Cl Cl
[O] tautomerism
D
D
28. HCOOH + H2SO4 ¾® H2O + CO COOH
conc. O O
29. Propanoic acid has higher boiling point than n-butanol because H H
of more exhaustive H-bonding in former case. CHO O
30. Saponification is hydrolysis of ester in presence of dilute base 34. The two stereoisomers of 2-phenyl propanoic acid in the
rather in presence of dilute acid. racemic mixture are :
31. PLAN R eactant is cyclic anhydride and chang es to dicarboxylic acid *
COOH COO CH(CH3 )Et
on hydrolysis. ½ * ½
CH3 C H(OH)Et
Also there is decarboxylation on heating if there is keto group H ¾ C — Ph ¾¾¾¾¾¾® H ¾ C — Ph
w.r.t ¾ COOH group. Ozonolysis cleaves (C== C) bond and ½ ½
H2O2 oxidises ¾ CHO to ¾ COOH group. CH3 CH3
O O O O (A )
*
(i) H3O+ OH COOH COOCH(CH3 )Et
O ½ *
CH3C H(OH)Et
½
OH
and Ph ¾ C — H ¾¾¾¾¾® Ph ¾ C — H
O O O O ½ ½
CH3 CH3
Anhydride
O O (B )
D decrbo- Here A and B are diastereomers.
xylation O3 OHC O
OHC (i) Mg/ether ½½
35. H2C == CH ¾ Br ¾¾¾¾® H2C == CH ¾ C ¾ OH
(ii) X *
O O (iii) H3O+ Y
O
LiAlH4 *
H2O2 HOOC
¾¾® H2 C==CH ¾ CH2 OH
Z
HOOC O O
½½ 18 H3O+ ½½ 18
O 36. CH3 ¾ C ¾ OC2H5 ¾¾® CH3 ¾ C ¾ OH + C2H5 ¾ OH
(P)
(A ) (B )
Thus, number of ¾COOH groups in P = 2.
CH2Cl CH2CN O
O
OH O
C6H5 C6H5
H3O+/D COOH
C6H5—CH—CH—C6H5 C==C (i) OH–
O CH3 COOC2H5 (ii) H+
HOOC H
CN (C ) H5C2O—C—CH—CH—COOC2H5
(B) COOH
C6H5 C6H5 O
SOCl2
C==C (CH3 CO) 2 O ½½
CH3NH2 38. CH3CH2NH2 ¾¾¾¾® CH3CH2NH ¾ C ¾ CH3
CH3HN—C H Heat
O (D )
386 Carboxylic Acids and Their Derivatives
O CH3 OH
½ O
½½ MeMgBr /H2 O ½½ ½
39. H ¾ C ¾ O ¾ CH — CH3 ¾¾¾¾¾® CH3 ¾ CH ¾ OH (i) CH3 MgBr
44. C6H5CH2 ¾ C ¾ CH3 ¾¾¾¾® C H ¾ CH ¾ C — CH3
A excess ½ (ii) H+
6 5 2
CH3 ½
B
CH3
NaOCl
45. (i) PCl 5 + SO2 ¾® POCl 3 + SOCl 2
¾¾¾® CH3COOH + CHCl 3 B A
– (ii) SOCl 2 + CH3COOH ¾® CH3COCl + SO2 + HCl
CH3 CH2
EtO – (COOEt)2 (A )
40. (i) O
½½
NO2 NO2 (iii) 2CH3COCl + Cd(CH3 )2 ¾® 2CH3 ¾ C ¾ CH3 + CdCl 2
O SO3H SO3H OH
CH2—C—COOEt
fuming NaOH
46. (i)
H2SO4 fusion
NO2 SO3H OH
A
CONH2 CN COOH
HO
O O
COOH CH2 H+
(ii) + P2O5 H+
(ii)
COOH CH2 H2O
HO O O
B
CH3 O
O O ½½
½½ ½½ NaOH
½ PCl 5
47. C6H5COOH ¾¾® C6H5COCl ¾¾® C6H5 ¾ C ¾ NH2 NH3
(iii) CH3 ¾ C ¾ C ¾ C6H5 ¾¾® C6H5 ¾ C ¾ COOH A B
H2 O ½
OH P2O5 H2 /Ni
C ¾¾® C6 H5 ¾ CN ¾¾® C6 H5 CH2 NH2
C
41. B is C3H5COOH and A is C3H5 ¾ C ºº C ¾ C3H5
48. Electron withdrawing inductive effect increases acid strength
Also A on ozonolysis gives B indicates that there is no olefinic while electron donating inductive effect decreases acid strength.
bond in C3H5-unit of A and it is cyclopropyl group.
+ I-effect
50. Both formic acid and sodium formate exhibit the phenomenon Hydrolysis is an example of nucleophilic acyl substitution,
of resonance as : hence the reactivity towards hydrolysis is :
O O- CH3CONH2 < CH3COOC2H5 < (CH3CO)2 O < CH3COCl
½½ · · ½ +
H ¾ C ¾ O ¾ H ¬® H ¾ C == O ¾ H O O
·· ·· ½½ ½½
O O- 56. CH3 ¾ C ¾ OH < H ¾ C ¾ OH
does not affect acidity.
½½ ½ +I -effect
H ¾ C ¾ O- ¬® H ¾ C == O decreases acid-strength
52. X is an ester and both its acid and alcohol fragments have same OH O CH3
OH–
number of carbons. Hence, X is : 59. + (CH3CO)2O
+ O
H
CH3CH2COOCH2CH2CH3 ¾¾® CH3CH2COOH
X H2 O O OMgBr
Y
½½ ½
+ CH3CH2CH2OH 60. CH3 ¾ C ¾ OC2H5 + 2CH3MgBr ¾® CH3 ¾ C ¾ CH3
[O]
Z ½
Z ¾¾® CH3CH2COOH CH3
Y OH
O CH3 ½
H 2O
½½ ½ MeMgCl H+ /H2 O ¾¾® CH3 ¾ C — CH3
53. H ¾ C ¾ O ¾ CH — CH3 ¾¾¾® ¾¾¾®
A
excess ½
CH3
OH
½ C H O- -
CH3 ¾ C — CH3 61. CH3COOC2H5 ¾¾®
2 5
CH2COOC2H5
½
H O
½½ O
B ½½
CH3 ¾ C ¾ OC2 H2
B + NaOCl ¾® CHCl 3 + CH3COOH ¾¾¾¾¾¾® CH3 ¾ C ¾ CH2 ¾ COO2H5
Claisen condensation
O
C2H5 OH ½½ O
54. (CH3CO)2 O ¾¾¾® CH3COOH + CH3 ¾ C ¾ OC2H5 ½½
H+
¾¾¾® C2H5OH + CH3 ¾ C ¾ CH2COOH
55. Among acid derivatives, the reactivity towards nucleophilic H2 O
acyl substitution is in the order of :
Amide < Ester < Anhydride < Acid chloride
OH COCH3
(a) CH3N OH OH
10. The correct structure of product ‘P’ in the following reaction is 13. Major product of the following reaction is
NEt 3 Cl
Asn -Ser + (CH3CO)2 O ¾® P
(Excess) Cl NH2
(2019 Main, 10 Jan I) (i) Et3N
+ H 2N
O O O (ii) Free radical
polymerisation
O NH2 O
H (2019 Main, 9 Jan I)
N Cl O O
(a) H3C N OH Cl
H (a) n (b)
O NH2
OCOCH3 N
O n
O
OCOCH3 H
O O HN NH2
N Ol
(b) H3C N H OH Cl Cl
H NHCOCH3 (c) (d)
O
n n
O
OCOCH3 HN O
O O NH2 NH2
H N
N O H
(c) H3C N OH O
H NH2
O 14. The increasing order of basicity of the following compounds is
O NH2
I. NH
O II.
O NHCOCH3 NH2
O IV.
III. NHCH3
(d) H3C N NH
NH (2018 Main)
H OH
O OCOCH3 (a) (I) < (II) < (III) < (IV)
(b) (II) < (I) < (III) < (IV)
11. The major product formed in the reaction given below will be (c) (II) < (I) < (IV) < (III)
NH2 (d) (IV) < (II) < (I) < (III)
NaNO2
15. The order of basicity among the following compounds is
Aq. HCI, 0-5°C
(2017 Adv.)
(2019 Main, 10 Jan I) O NH2
17. Considering the basic strength of amines in aqueous solution, 23. The correct order of basicities of the following compounds is
which one has the smallest pK b value? (2014 Main) NH
(a) (CH3 )2 NH (b) CH3NH2 H3C ¾ C , CH3 ¾ CH2 ¾ NH2 ,
(c) (CH3 )3 N (d) C6H5NH2 NH2 2
1
18. On heating an aliphatic primary amine with chloroform and
ethanolic potassium hydroxide, the organic compound formed is O
½½
(a) an alkanol (b) an alkanediol (2014 Main) (CH3 )2 NH, H3C ¾ C ¾ NH2
(c) an alkyl cyanide (d) an alkyl isocyanide 4 (2001, 1M)
3
19. The gas leaked from a storage tank of the Union Carbide plant in (a) 2 > 1 > 3 > 4 (b) 1 > 3 > 2 > 4 (c) 3 > 1 > 2 > 4 (d) 1 > 2 > 3 > 4
Bhopal gas tragedy was (2013 Main) 24. A positive carbylamine test is given by (1999, 2M)
(a) methyl isocyanate (a) N, N-dimethylaniline (b) 2, 4-dimethylaniline
(b) methylamine
(c) N-methyl-o-methylaniline (d) p-methylbenzylamine
(c) ammonia
(d) phosgene 25. p-chloroaniline and anilinium hydrochloride can be
distinguished by (1998, 2M)
20. The major product of the following reaction is (2011)
(a) Sandmeyer reaction (b) NaHCO3
O
(c) AgNO3 (d) Carbylamine test
C (i) KOH 26. Carbylamine test is performed in alc. KOH by heating a
NH mixture of (1984, 1M)
C (ii) Br— —CH2Cl (a) chloroform and silver powder
(b) trihalogenated methane and a primary amine
O (c) an alkyl halide and a primary amine
O (d) an alkyl cyanide and a primary amine
C 27. Acetamide is treated separately with the following reagents.
(a) N—CH2— —Br Which of these would give methylamine? (1983, 1M)
C (a) PCl 5 (b) Sodalime
O (c) NaOH + Br2 (d) Hot, conc. H2SO4
O 28. The compound which on reaction with aqueous nitrous acid at
C
low temperature produces an oily nitrosamine, is
(b) (a) methylamine (b) ethylamine (1981, 1M)
N— —CH2Cl
(c) diethylamine (d) triethylamine
C
O Objective Question II
O (Only one more than one correct option)
C 29. The major product of the reaction is (2015, Adv.)
(c) N H 3C CO2H
NaNO2, aq. HCl
C 0°C
CH3 NH2
O —CH2— —Br
O H3C NH2 H3C CO2H
(a) (b)
C
(d) N CH3 OH CH3 OH
C
H3C CO2H H 3C NH2
O— —CH2Cl (c) (d)
CH3 OH CH3 OH
Match the Columns 38. Arrange the following in increasing order of basic strength:
methylamine, dimethylamine, aniline, N-methylaniline.
32. Match each of the compounds in Column I with its characteristic (1988, 1M)
reaction(s) in Column II. (2016, Adv.)
39. Give a chemical test and the reagent used to distinguish between
Column I Column II the following : “Ethylamine and diethylamine”. (1988, 1M)
(A) CH3 CH2 CH2 CN (p) Reduction with Pd - C/ H2 40. For nitromethane molecule, write structures
(B) CH3 CH2 OCOCH3 (q) Reduction with SnCl 2 / HCl (i) showing significant resonance stabilisation
(ii) indicating tautomerism (1986, 1M + 1M = 2M)
(C) CH3 CH == CHCH2 OH (r) Development of foul smell
on treatment with chloroform 41. State the equation for the preparation of following compounds :
and alcoholic KOH. n-propyl amine from ethyl chloride. (1982, 2 ´ 1M = 2M)
Answers
1. (a) 2. (b) 3. (c) 4. (c) 5. (a) 6. (c) 7. (c) 8. (b)
9. (c) 10. (a) 11. (*) 12. (b) 13. (d) 14. (c) 15. (d) 16. (c)
17. (a) 18. (d) 19. (a) 20. (a) 21. (d) 22. (b) 23. (b) 24. (d)
25. (c) 26. (b) 27. (c) 28. (c) 29. (c) 30. (b,d) 31. (more)
32. A ® p, q, s, t; B ® p, s, t; C ® p; D ® r 42. (a) 43. (b)
Hints & Solutions
1. The mechanism of the given reaction is as follows: 5. n-butylamine (CH3CH2CH2CH2NH2 ) can be prepared by
O Gabriel phthalimide reaction. This method produces only
OH
H—C—OEt
primary amines without the traces of secondary or tertiary
CH3—CH—CH2CH2—NH2 amines. In this method, phthalimide is treated with ethanolic
Et3N
[–NH2 is stronger —EtOs
KOH, it forms potassium salt of phthalimide which on heating
nucleophile than with alkyl halide followed by alkaline hydrolysis forms
—OH] OH
r corresponding primary amines.
CH3—CH—CH2CH2—NH—CH=
=O CO CO
NH+ Alc. KOH –H O N –K +
H 2
CO CO
OH EtOs
nBu—X
CH3—CH—CH2CH2—NH—CHO
COO–Na+ CO
NaOH(aq.)
The basic mechanism of the reaction is acyl S N 2 because the + n Bu—NH2 N—R
nucleophile, CH3 (OH)CH2CH2 NH2 attacks the sp2 carbon of –
COO Na + CO
1° amine
the ester (H ¾ CO2Et) and gets substituted. N-alkyl
phthalimide
2. The reaction for the production of ethylamine from
N -ethylphthalimide can be takes place as follows: Triethylamine, t-butylamine and neo-pentylamine cannot be
prepared by Gabriel phthalimide reaction.
O H HN
6. Basic strength can be compared by the reaction of an
Hydrazinolysis
alkanamine and ammonia with proton.
N—C2H5
NH2—NH2 H H
(Hydrazine) | |
H HN R—N + H+ R—N+—H
O | |
(N-ethylphthalimide) O H H
H H
NH | |
| + C2H5—NH2 H—N + H+ H—N+—H
NH | |
Ethylamine
(An aliphatic
H H
O 1°-amine)
Basicity of an amine in aqueous solution depends upon the
This reaction is the second step of Gabriel phthalimide synthesis solubility of ammonium cation formed by accepting proton
for the preparation of aliphatic 1°-amines and amino acid. In this from water. The stability of ammonium cation depends upon the
step concentrated alkali can also be used in place of hydrazine. following factors.
(a) + I effect (b) Steric effect
3. Hinsberg’s reagent is C6H5SO2Cl (benzene sulphonyl chloride). (c) Solvation effect
This reagent is used to distinguish between primary, secondary In first case, on increasing the size of alkyl group + I effect
and tertiary amines. increases and the positive charge of ammonium cation gets
4. O O dispersed more easily, Therefore, order of basicity is 2º amine >
I CN 1º amine > ammonia. In second case, substituted ammonium
Step I
KCN cation is also stabilised by solvation with water molecules.
DMSO Greater the size of ion, lesser will be the solvation and less
stabilised is the ion.
[A]
Step II H2/Pd
OH2
O H
| C2H5 H----OH2
CH2NH2 +
C2H2—N+—H----OH2 > N
| C2H5 H----OH2
H
2° amine
[B] OH2
1° amine
Step I involves the nucleophilic substitution reaction in which I
(Iodine) is substituted by
Considering both steric and solvation effect, it can be concluded
¾ CN group. In step II, H2/Pd reagent is used for reduction
that greater the number of H-atoms on the N-atom, greater will
process. Here, ¾ CN group reduces itself to ¾CH2NH2. be the H-bonding and hence more stable is the ammonium
Aliphatic Compounds Containing Nitrogen 393
cation. But in case of ¾C2H5 group, + I effect predominates or CH3 CH(CONH2 )CH3 (b).
over H-bonding. Therefore, order is 2º amine > 1° amine > Carbylamine test given by (a) and (b)
ammonia i.e. (C2H5 )2 NH > C2H5NH2 > NH3. D
CH3 CH2 CH2 NH2 + CHCl 3 + 3KOH ¾¾ ®
7. Key Idea The reaction involves: CH3 (CH2 )2 NC + 3KCl + 3H2
A. Deamination in step (i) NH2
B. Oxidation in step (ii) ½
D
C. Hydroysis in step (iii) CH3 ¾ CH ¾ CH3 + CHCl 3 + 3KOH ¾¾ ®
The complete pathway of reactions is as follows: NC
H 3C O ½
NH2
CH3 ¾ CH ¾ CH3 + 3KCl + 3H2
(i)
O As (b) is not among the given options So, it is ruled out and
H 3C O compound (X) is CH3CH2CH2CONH2.
NaNO2/H+
OH 9. NaBH4 is a selective reducing agent. It can reduce C==O
Deamination O
group into alcohol, N-methyl imine group, Me ¾ N == CH ¾
H 3C O into 2°-amine but cannot reduce an isolated C == C.
(ii) OH O OH
O N
NaBH4
O NH
H3C H3C H3C
CrO3/H+ O
OH N-methyl isolated Keto
Oxidation C C group
O imine
NH2 O
O
Br2
Þ CH3CH2CH2—C—NH2 CH3CH2CH2—NH2
NaOH
–Na2CO3 11. No option is the correct answer.
Amines in presence of NaNO2 + dil. HCl undergoes
H2N—C NH2
diazotisation. The diazotised product readily loses nitrogen gas
Br2/NaOH
Þ CH3—CH—CH3 CH3—CH—CH3 with the formation of carbocation. The resulting carbocation
–Na2CO3
rearranges itself to give the expanded ring.
So, ‘X ’ can be CH3 CH2 CH2 ¾ CONH2 (a)
394 Aliphatic Compounds Containing Nitrogen
14. Key Idea Among the given compounds the basic nature
(Major)
depends upon their tendency to donate electron pair.
NH
12. Rate of acetylation : ¾ NH2 > ¾ OH because N-bases are Among the given compounds in , Nitrogen is
stronger than O-bases. Size of N-atom is larger than O-atom and sp2-hybridised. This marginally increases the electronegativity
at the same time, N atom is less electronegative than O-atom. of nitrogen which in turn decreases the electron donation
··
tendency of nitrogen. Thus making compound least basic.
So, N-atom of the ¾ N H2 group can donate its lone pair of
NH2
electrons (Lewis basicity) more easily than that of O atom of the Among the rest NH is totally different from others as in
··
¾ O H group. this compound lone pair of one nitrogen are in conjugation with
p bond i.e. As a result of this conjugation the cation formed after
OH OH protonation becomes resonance stabilised
s
CH3 CH3COO
Protonation
H 2N C HN—COCH3 + +
H 2N NH2 H 2N NH2
HN NH2
O—COCH3 H Equivalent resonance
s
O—C—CH3
OH
This equivalent resonance in cation makes HN NH2 most
CH3COOH + basic among all.
NHCOCH3 NH2
Absorbed Categorisation is very simple between rest two as
by pyridine
N N CH3
(primary amine) is less basic than (secondary
H amine)
13. The analysis of both the substrates : Hence, the correct order is
Vinylic centre (II) < (I) < (IV) < (III) i.e. option (c) is correct.
Cl 15. IV is most basic as conjugate acid is stabilised by resonance of
(+R) two ¾ NH2.
r
NH NH2 NH2
O Cl H+
Acyl SN2 centre r
H2N NH2 H2 N NH2 H2N NH2
Acts as NH2
H2N nucleophile
(1°-amine) r
This N-atom can H2N NH2
O
not act as nucleophile
NH2 + R III is least basic as
Amide group H+ r
H N N H N N H
So, the reaction can take place as follows:
Destablised by -I-effect of sp2-carbons.
Aliphatic Compounds Containing Nitrogen 395
16. Hofmann-bromamide degradation reaction is given as: Bromine is not substituted in the above reaction as it is in
RCONH2 + 4NaOH + Br2 ¾® RNH2 resonance with benzene ring giving partial double bond
(1° amine) character to C—Br bond, hence difficult to break.
–
:
+ Na2 CO3 + 2NaBr + 2H2O +
: :
ClCH2 Br: ClCH2 Br
Hence, four moles of NaOH and one mole of Br2 are used.
+ -
17. This problem can be solved by using the concept of effect of 21. CH3NH2 + CHCl 3 + KOH ¾® CH3 ¾ N ºº C + KCl + H2O
steric hindrance, hydration and H-bonding in basic strength of isocyanide
amines. Order of basic strength of aliphatic amine in aqueous O
solution is as follows (order of K b ) ½½
·· ·· ·· ·· POCl 3
(CH3 )2 NH > CH3 NH2 > (CH3 )3 N > C6H5 NH2 22. C6H5 ¾ C ¾ NH2 ¾¾® C6H5 ¾ C ºº N + H2O
O O p-methyl benzylamine
(a primary amine) H3C— —CH2—NC
O– O
(isocyanide)
N N
Carbylamine test is not given by secondary or tertiary amine.
O O– + +
25. C6H5 NH3Cl - + AgNO3 ¾® C6H5 N H3NO3- + AgCl (s) ¯
The conjugate base formed above act as nucleophile in the anilinium
subsequent step of reaction. As shown above, the nucleophile hydrochloride
exist in three resonating form, one may think of oxygen being No such precipitate of AgCl(s) would be formed with
the donor atom in the nucleophilic attack. However, nitrogen act p-chloroaniline.
as donor as it is better donor than oxygen. KOH
26. R ¾ NH2 + CHCl 3 ¾¾® R ¾ NC ‘Carbylamine test’
O isocyanide
SN 2 (foul smell)
N–+ CH2 Br The above test is characteristic of primary amine and used to
distinguish primary amine from other amines.
Cl
O O O
½½ NaOH
N CH2 Br 27. CH3 ¾ C ¾ NH2 + Br2 ¾¾® CH3NH2
acetamide methylamine
O (Hofmann’s bromamide reaction)
396 Aliphatic Compounds Containing Nitrogen
Cl
CH3 Cl
(I) (II) (III)
(a) III < I < II (b) II < I < III (c) (d)
(c) III < II < I (d) I < III < II n
n
3. Increasing order of reactivity of the following compounds for
SN 1substitution is (2019 Main, 9 April II)
CH3
CH2 Cl OH
H3C Cl OH
CH3
(A ) (B) 6. The increasing order of reactivity of the following
compounds towards aromatic electrophilic substitution
Cl Cl reaction is (2019 Main, 9 April I)
H3CO Cl OMe Me CN
(C) (D)
(a) (A) < (B) < (D) < (C)
(b) (B) < (C) < (D) < (A)
(c) (B) < (A) < (D) < (C)
(d) (B) < (C) < (A) < (D) A B C D
Benzene and Alkyl Benzene 399
(a) A < B < C < D (b) B < C < A < D 9. Among the following four aromatic compounds, which one
(c) D < A < C < B (d) D < B < A < C will have the lowest melting point? (2019 Main, 12 Jan I)
(c) (d)
Cl Cl N
CH2 OH CHO 11. In the following sequence of reactions (2015 Main)
KMnO 4 SOCl 2 H 2 / Pd
Toluene ¾¾® A ¾¾® B ¾¾® C, the product C is
(c) (d) BaSO 4
12. Match the four starting materials given in Column I with the corresponding reaction schemes provided in Column II and select the
correct answer using the code given below the lists.
Column I Column II
A. H H p. Scheme I
(i) KMnO4 , HO- , heat (ii) H + , H 2O
(iii) SOCl 2 (iv) NH 3
? ¾¾¾¾¾¾¾¾¾¾¾¾
¾® C7 H6N2O3
B. OH q. Scheme II
(i) Sn / HCl (ii) CH 3COCl (iii) Conc. H 2SO4
(iv) HNO3 (v) Dil. H 2 SO4 , heat (vi) HO-
? ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾¾® C6H6N2O2
OH
C. NO2 r. Scheme III
(i) Red hot iron, 873 K (ii) fuming HNO3 , H 2SO4 , heat
(iii) H 2S × NH 3 (iv) NaNO2 , H 2SO4 (v) hydrolysis
? ¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾
¾® C6H5NO3
D. NO2 s. Scheme IV
(i) Conc. H 2SO4 ,60°C
(ii) Conc. HNO3 , conc. H 2SO4 (iii) Dil × H 2SO4 , heat
? ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾® C6H5NO4
CH3
Codes
A B C D A B C D
(a) p s q r (b) r p s q
(c) r s q p (d) s p r q (2014 Adv.)
400 Benzene and Alkyl Benzene
NO2 O
C
O NO2
Cl CN OH SH
I II III IV
NO2 AlCl
17. + Cl — CH2 CH2 — CH3 ¾¾¾®
3
NO2 O NO2
(a) + CH3CH2CHO
C
O
(b) + CH3COCH3
Benzene and Alkyl Benzene 401
O O O Conc. H2SO4
HN HN (a)
D
H 3C CH3 H3C CH3
(a) Heated iron tube
(b) (b) Me —— H
873 K
O
Br Br (1) Br2, NaOH
(2) H3O+
O (c)
HN (3) Sodalime, D
H 3C CH3
(c) O O
CHO
Br
O (d) Zn/Hg, HCl
HN
H3C CH3 OHC CHO
(d)
27. Among the following reactions(s), which gives(give)
Br tert-butyl benzene as the major product? (2016 Adv.)
Å NO2 NO2
Å
Conc. HNO3
(c) (d) (ii)
Conc. H2SO4
s NO2
32. Toluene, when treated with Br2 /Fe, gives p-bromotoluene as
the major product because the CH3 group (1999, 3M)
(a) is para-directing
Pd/C
(b) is meta-directing (d)
(c) activates the ring by hyperconjugation 3.0 mol
H2
(d) deactivates the ring
33. A new carbon–carbon bond formation is possible in (1998)
(a) Cannizzaro’s reaction (b) Friedel-Craft’s alkylation
(c) Clemmensen reduction (d) Reimer-Tiemann reaction
True or False
34. An electron donating substituent in benzene orients the
incoming electrophilic group to the meta-position. not
(1987, 1M)
35. In benzene, carbon uses all the three p-orbitals for
hybridisation. (1987, 1M)
39. Give reasons for the following : 48. Identify the major product in the following reactions :
(i) tert-butylbenzene does not give benzoic acid on treatment HNO3/H2SO4
with acidic KMnO4. (i) —COO—
mononitration
(ii) Normally, benzene gives electrophilic substitution
reaction rather than electrophilic addition reaction (ii) C6H5COOH + CH3MgI ? + ? (1993, 2M)
although it has double bond. (2000)
49. Write the structure of the major organic product expected
40. Show the steps to carry out the following transformations. from the following reaction
(i) Ethylbenzene ® benzene
AlCl3
(ii) Ethylbenzene ® 2-phenylpropionic acid + (CH3)2CHCH2Cl
(1992, 1M)
41. Write the structures of the products.
50. Give reasons in two or three sentences only for the following:
Br 2 /Fe
CH3 CONHC6 H5 ¾¾¾® (1998, 2M) Phenyl group is known to exert negative inductive effect, but
each phenyl ring in biphenyl (C6 H5 ¾ C6 H5 ) is more
42. Give reasons for the following in one or two sentences reactive than benzene towards electrophilic substitution.
“Nitrobenzene does not undergo Friedel-Craft’s alkylation.” (1992, 1M)
(1998, 2M)
51. Arrange the following in increasing order of reactivity
43. Complete the following, giving the structures of the principal towards sulphonation with fuming sulphuric acid.
organic products. (1997)
Benzene, toluene, methoxy benzene, chlorobenzene.
Me (1988, 1M)
47. Give reason for the following ‘In acylium ion the structure
R ¾ C ºº O+ is more stable than R ¾ C+ == O’ (1994, 1M) r r
404 Benzene and Alkyl Benzene
Answers
1. (c) 2. (a) 3. (c) 4. (a) 21. (a) 22. (d) 23. (d) 24. (a)
5. (a) 6. (c) 7. (a) 8. (d) 25. (c) 26. (a,b,d) 27. (b,c,d) 28. (b)
9. (b) 10. (b) 11. (d) 12. (c) 29. (b,c) 30. (b,c,d) 31. (b,c,d) 32. (a,c)
13. (d) 14. (c) 15. (d) 16. (b) 33. (b,d) 34. False 35. False 54. (12s, 3p)
17. (c) 18. (b) 19. (c) 20. (d) 58. (5)
CH3 O CH3 O
AlCl3 CH3
CH3 O O
Cl – AlCl s4 –HCl r
r
–AlCl3
Intramolecular
ArSE 2-reaction H
CH3 –
AlCl4
2. Key Idea In electrophilic aromatic substitution (Ar SE 2) reaction, the aromatic (benzene nucleus here) compound (substrate) acts as
a nucleophile which gets attacked by an electrophile in the rate determining step (rds).
Higher electron density on the nucleophile, i.e. benzene nucleus will fasten the rate of the reaction. Electron-donating groups (EDG) will
increase electron density in benzene nucleus by any or both of their +R/+M and hyperconjugative (HPC) effects. Now, let us consider the
given substrate.
O
3. Reactivity of substitution nucleophilic unimolecular (S N1) reaction depends on the formation of carbocation. Greater the stability of
carbocation, greater will be its ease of formation of alkyl halide and faster will be the rate of reaction. So, the correct order of (S N1) reactivity is
CH2Cl CH2—Cl
Cl
OCH3
(+R)
(C) (D) (A ) (B)
In compound C, the carbocation formed is stabilised by activating group ( ¾ OCH3 ). Compound D forms benzyl carbocation (C6H5 ¾ CH2+ )
that is stabilised by resonance. Compound A produces a primary carbocation that further rearranges itself to secondary carbocation.
Nus Rearrangement
r r
Cl 1° carbocation 2° carbocation
Compound B produces primary carbocation which is least stable among all the given options.
Benzene and Alkyl Benzene 405
Alc. KOH
8.
CH3
Cl
Cl Cl
The alkene produced undergoes polymerisation via free radical
mechanism. This process involve three steps, i.e. initiation,
Cl
propagation and termination.
hn/benzylic free radical
substitution with Cl2
Polymerisation n Cl2(1 eqv.) Cl2(2 eqv.) Cl2(excess)
9. Melting point of a compound depends on size and force of attraction between the molecules. Compound (c) has largest size and also possess
weak intermolecular association due to dipole - dipole interactions.
Compound (a) is a dicarboxylic acid and possess high melting point due to intermolecular hydrogen bonding.
As a result, it exist as associated molecule. Compound (d) is an alcohol and possess intermolecular H-bonding. No interactions are present in
hydrocarbon (naphthalene) compound (b).
Hence, melting point is lowest for naphthalene (- ~ 80°C), i.e. compound (b).
10. Aromaticity of a compound can be decided by Huckel’s rule. In cyclopentadienyl cation (b), resonance takes place as follows:
H Resonance
hybrid
Huckel’s rule as it has conjugated 4p-electron (4 np, n = 1) system. Rest of the species are aromatic as each of them belongs to 6p-electron
[(4 n + 2) p, n = 1] system.
11. CH3 COOH COCl CHO
12. PLAN This problem can be solved by using the various concepts synthesis of benzene, electrophilic substitution reaction and directive influence of various
substituents, including oxidation and reduction.
Þ —OH and —NH2 are o/p-directing groups.
Þ N-acetylation is more favourable than C-acylation.
Þ N-sulphonation is more favourable than C-sulphonation.
Þ NO2 is a meta-directing group.
Þ H2S× NH3 reduces only one NO2 group selectively in the presence of two NO2 groups.
Using above concepts the correct sequence of reaction can be written as
NO2 NH2
NaNO2
Red hot Fuming HNO3 / H2SO4 H2S .NH3
A. 3CH CH H2SO4
iron 873K
D selective reduction
NO2 NO2 Here, N-sulphonation is
N+2HSO4– OH more favourable in
comparisons to
C-sulphonation.
Hydrolysis
NO2 NO2
OH OH OH OH
+
O 2N O2N
Conc. H2SO4 NO2 Dil.H2SO4
B.
60°C Here, nitration takes D
OH OH place at o-position of OH OH
less hindered side.
SO3H SO3H
Benzene and Alkyl Benzene 407
NH2 NHCOCH3
NO2 NO2
OH–
Both — OCH3 and — CH3 are activating ortho/para directing groups but — OCH3 is stronger activator, electrophile attack to ortho of
— OCH3.
O O NO2
C C
O HNO3 O
II H2SO4
I S
Ring II is activated while ring I is deactivated in SE Ar reaction. Therefore, electrophile attack at para to ring-II, the less hindered position.
408 Benzene and Alkyl Benzene
H
Cl
17.
AlCl3
+ ClCH2CH2CH3 P 24. Toluene is most reactive among these. Nitro and carboxylic groups
Friedel-Craft’s
reaction
are deactivating in aromatic electrophilic substitution reaction.
O2/heat 25. Toluene is most readily sulphonated among these because
Q + Phenol,
H3O+ methyl group is electron donating (+ I effect), activate benzene
O ring for electrophilic aromatic substitution.
(1) and (2) reactions of option (c) combined to give haloform 28. CH3 CH3
reaction while (3) reaction given in this option is O
OH
decarboxylation reaction i.e., + O2 CH3
+ CH2 — CHCH3 H CH3
COCH3
Cumene hydroperoxide
(1) Br2/NaOH Cumene
(2) H3O+ Cumene hydroperoxide formed above is an intermediate in the
H3COC COCH3 synthesis of phenol.
–
COONa+
29. According to Huckel rule, the compounds which have
4 n (n = 0, 1, 2, 3¼) delocalised p-electrons in a close-loop are
+ 3CHBr3¯ anti-aromatic and characteristically unstable. Compound B
+– – satisfy the criteria of anti-aromaticity as :
NaOOC COONa+ Bromoform
The above product of haloform reaction on decarboxylation gives
4p
benzene as
–
COONa+ Compound C is anti-aromatic in its resonance form :
(Sodalime) –
NaOH/CaO O O
+ – – –3Na2CO3
NaOOC COONa+
Benzene
+
The reaction given in option (d) is Clemmensen reduction i.e.,
anti-aromatic
Zn - Hg
C == O ¾ ¾ ¾® CH2 + H2O Compound A has 4p-electrons which are also delocalised but do
HCl
not constitute close loop, hence non-aromatic.
Hence, the final product of this reaction is also mesitylene which Compound D is aromatic, characteristically stable.
can be seen as
CHO CH3 –
O O
Zn-Hg/HCl
+
OHC CHO H3C CH3 Tropyllium ion, aromatic
Mesitylene
Order of stability Aromatic > Non-aromatic > Anti-aromatic
27. (a) 30. Aromatic molecule must.
NaOC2H5
Br (b) have (4 n + 2)p electrons. (c) be planar.
(d) be cyclic.
C2H5O- (a strong nucleophile) causes E1 reaction to form
isobutene as the major product. 31. A compound is considered to be aromatic, if it follows three
rules:
(a) Must be cyclic and planar.
(b) Cl AlCl3 1, 2-hydride
(b) Must have conjugated system in it.
shift 3° carbocation
1° carbocation (Major) (c) It must follow Huckel rule which states that number of
p-electrons = (4 n + 2)
+
H
(c) (X)
(C) Þ 8p-e- system [ 4 np , n = 2 ]Þ Anti-aromatic
OH +
BF3,Et2O (D) Þ The sp3-carbon does not support conjugation and
(d)
sp3 also devoids planarity.
Þ Non-aromatic
410 Benzene and Alkyl Benzene
OH OH NO2
CHO
– H+ Nitro group is meta directing as well as strongly deactivating.
+ CHCl3 + OH
H2O
Reimer-Tiemann
reaction
F OH
—Br + Ag+ + + AgBr
(b) (i) + NaOH + F–
O2N O2N anti-aromatic
5-bromo-1,3-cyclopentadiene (unstable)
CH3 CH3
Nitro group from para position activate aromatic nucleophilic O
substitution.
Br2
F N—
38. Fe
(ii) + NaOH No reaction
deactivated activated
H3C O
CH2NO2
—NO2 is not in resonance with benzene ring, does not activate N— —Br
the aromatic nucleophilic substitution reaction, hence fluoride is
not formed.
Benzene and Alkyl Benzene 411
39. (i) Oxidation of side-chain alkyl group of benzene occur 42. Nitro group is a very strong deactivating group, the very slow
through free radical mechanism and it initiates at a -C as. Friedel-Craft’s reaction does not takes place in presence of nitro
group.
½ ½
Ph — C— H ¾® Ph — C · + H · 43. CH3 CH3 CH3
½ ½ CH3 C—CH3
In tertiary butyl benzene, there is no a - H, required to AlCl3
+ CH3—C—CH2Br CH3
initiate free radical oxidation reaction, hence not oxidised
with KMnO4. H CH3
CH3
C—CH3 +
+ KMnO4 No oxidation
CH3
takes place
CH3 C CH3
tert butyl benzene
(no a-H) CH3
(ii) Pi-electrons of double bonds are involved in aromatic
44. In presence of light, free radical reaction takes place at — CH3
delocalisation (aromaticity), hence electrophilic addition do
not occur as it would destroy aromatic stability. However, group while in presence of FeBr3, electrophilic substitution
electrophilic substitution do not destroy aromaticity. occur in the ring.
CH3 CH2Br
E H Br2/heat
E+ Addition
H+ + + HBr or light
Br
aromaticity retained electrophilic loss of aromaticity Br2/FeBr3 CH3
(occur preferably) substitution (not occur)
CH3
+
CH2CH3 COOH
K2Cr2O7 Br
40. (i)
Br
OCH3 O OCH3
CaO/NaOH
(i) AlCl3 Zn(Hg)
Heat 45. + O
(ii) H3O+ HCl
CH2CH3 CH—CH3
Br2 NaCN O
(ii) O COOH
heat Br
Friedel-Craft’s
CH3 reaction
OCH3
CH—CH3 C—COOH
+
H /H2O
H3PO4
CN H Final product
NHCOCH3 NHCOCH3
Br2/Fe COOH
41. CH3
Br
C—CH3
H2SO4
NHCOCH3 46. (i) + (CH3)2CHCH2OH
CH3
+
Br H
NHCOCH3 is ortho/para directing although deactivating group. CH2CH3 C—CH3
Therefore, Ortho/pare bromoderivatives are fomed or (i) Br2/heat
treatment.
(ii)
(ii) NaCN CN
412 Benzene and Alkyl Benzene
+ +
47. R — C ºº O ¬® R — C==O CaC2 + 2H2O ¾® Ca(OH)2 + C2H2
I II Acetylene
I is more stable resonance structure of acylium ion than Cu
3C2H2 ¾¾® C6H6
II on the following grounds. D Benzene
It has more covalent bonds. (ii) —CH3 in toluene is ortho/para directing group, first
It has complete octet of both carbon and oxygen. oxidised to —COOH in order to make it meta directing and
O then nitrated.
HNO3/H2SO4
—C—O— CH3 COOH COOH
48. (i) mononitration
—C—O— —NO2 O
C—CH2CH3
(ii) C6H5COOH + CH3MgI ¾® CH4 + Mg(OOCC6H5 )I AlCl3
53. + CH3CH2COCl
CH3 CH3
49.
AlCl3 + Hydride Friedel-Craft’s acylation
CH3—C—CH2Cl CH3—C—CH2 H
shift
H H H H
1° carbocation 54. It has 12 sigma and 3 pi-bonds.
CH3 H H
CH3
C—CH3 H
C6H6
CH3—C—CH3
+ CH3 55. CH3CH2OH + PCl 5 ¾® POCl 3 + HCl + CH3CH2Cl
3° carbocation
(more stable) AlCl 3
C6H6 + CH3CH2Cl ¾¾® C6H5— CH2CH3
+ –
50. — —
— Friedel-Craft’s reaction
—
— – p-xylene
SO3H OH
The above resonance activate an aromatic ring for electrophilic
KOH
substitution reaction. H3C— —CH3 H3C— —CH3
51. Both — CH3 and — OCH3 are activating groups but chloro is fusion
deactivating group in electrophilic aromatic substitution
reaction. 57. Pi-bonds of benzene are involved in aromaticity, not open for
Also — OCH3 activate more than — CH3 due to resonance electrophilic addition reaction. Rather, it undergo electrophilic
effect by the former group. Therefore, the overall order of substitution reaction.
reactivity is:
Chlorobenzene < benzene < toluene < methoxy benzene 58. The aromatic systems are
52. (i) Lime is heated with coke at high temperature and then, r s
hydrolysed to form acetylene. This acetylene on passing red r
hot tube polymerises to form benzene :
, , , ,
2000 °C
CaO + 3C ¾¾¾® CaC2 + CO
Lime Coke
(d) —N==N—NH—
(b) N N O
CH3O H H
S
5. The major product obtained in the following reaction is
(B)
NH2
N N (i) CHCl3/KOH
(ii) Pd/C/H2
O2N H H
S
(C) CN O (2019 Main, 8 April II)
N N
H H
NCH3 NCH3
H H
H 3C (a) (b)
S
(D)
N N CN O CN OH
H H (2019 Main, 12 April I) H H
NCHCl2 NCH3
(a) (A) < (C) < (D) < (B)
(c) (d)
(b) (C) < (A) < (D) < (B)
(c) (B) < (D) < (A) < (C)
(d) (B) < (D) < (C) < (A) CN OH H 2N OH
414 Aromatic Compounds Containing Nitrogen
6. The major product in the following reaction is 9. The major product of the following reaction is
(2019 Main, 8 April II) (2019 Main, 11 Jan I)
NH2 O
N + N H
NCH3 N
(a) (b)
N N O OH
N N (c) CHO (d)
H NH2
CH3
NHCH3 NH2 10. What will be the major product in the following mononitration
reaction ? (2019 Main, 10 Jan II)
N N N N
(c) (d)
N N +
H N N N HNO3
H H Conc.H2SO4
CH3
OH
12. The increasing basicity order of the following compounds is
8. The increasing order of reactivity of the following compounds CH 2CH3
towards reaction with alkyl halides directly is
(2019 Main, 12 Jan I)
½
(A) CH3CH 2NH 2 (B) CH3CH 2NH
O O CN
NH2
NH2 NH2 CH3 CH3
NH ½ ½
(C) H3C ¾ N ¾ CH3 (D) Ph ¾ N ¾ H
O
(A) (B) (C) (D) (a) (D) < (C) < (B) < (A)
(a) (A) < (C) < (D) < (B) (b) (A) < (B) < (C) < (D)
(b) (B) < (A) < (C) < (D) (c) (A) < (B) < (D) < (C)
(c) (B) < (A) < (D) < (C) (d) (D) < (C) < (A) < (B) (2019 Main, 9 Jan II)
(d) (A) < (B) < (C) < (D)
Aromatic Compounds Containing Nitrogen 415
13. The tests performed on compound X and their inferences are : 18. The major product of the following reaction is (2017 Adv.)
OH
Test Inference
(a) 2, 4- DNP test Coloured precipitate (i) NaNO2/HCl/0°C
(ii) (aq. NaOH)
(b) Iodoform test Yellow precipitate
(c) Azo-dye test No dye formation NH2
– +
Compound ‘X ’ is OH ONa
H 3C CH3 H3C CH3
N N (a) (b)
COCH3
(a) CHO
(b) N N NH2
N N OH OH
NH2 OH NH2
CH3
NH
(a) (b) NH The product E is (2015 Main)
CH3 COOH
CH3
(a) (b) H3C CH3
NH NH
(c) (d)
CH3
15. Arrange the following amines in the decreasing order of CN
CH3
basicity: (2019 Main, 9 Jan I)
(c)
(d)
N N N
(I)
H H CH3
(II) (III)
20. Amongst the compounds given, the one that would form a
(a) I > II > III (b) III > II > I (c) I > III > II (d) III > I > II brilliant coloured dye on treatment with NaNO 2 in dil. HCl
16. The correct decreasing order for acid strength is followed by addition to an alkaline solution of b-naphthol is
(2019 Main, 9 Jan I) NHCH3
N(CH3)2
(a) FCH2COOH > NCCH2COOH (a) (b)
> NO2CH2COOH > ClCH2COOH
(b) CNCH2COOH > O2NCH2COOH NH2 CH2NH2
> FCH2COOH > ClCH2COOH (c) (d)
(c) NO2CH2COOH > NCCH2COOH H3C (2011)
> FCH2COOH > ClCH2COOH
(d) NO2CH2COOH > FCH2COOH 21. The species having pyramidal shape is (2010)
> CNCH2COOH > ClCH2COOH (a) SO3 (b) BrF3 (c) SiO2-
3 (d) OSF2
17. Which of the following compounds will give significant amount 22. In the following reaction,
of meta-product during mononitration reaction? (2017 Main)
OH OCOCH3 NH2 NHCOCH3 O
N Conc. HNO3
(a) (b) (c) (d) H X
Conc. H2SO4
416 Aromatic Compounds Containing Nitrogen
The structure of the major product X is (2007, 3M) 25. Benzene diazonium chloride on reaction with phenol in
weakly basic medium gives (1998, 2M)
O
(a) (a) diphenyl ether (b) p-hydroxy azobenzene
NO2 (c) chlorobenzene (d) benzene
N
H 26. Examine the following two structures of anilinium ion and
choose the correct statement from the ones given below :
O 2N (1993, 1M)
O +
(b) NH3 NH3
N +
H
O I II
(c) (a) II is not an acceptable canonical structure because
N carbonium ions are less stable than ammonium ions
H (b) II is not an acceptable canonical structure because it is
NO2 non-aromatic
(c) II is not an acceptable canonical structure because the
O nitrogen has 10 valence electrons
(d)
(d) II is an acceptable canonical structure
O2N N
H 27. Chlorobenzene can be prepared by reacting aniline with
(a) hydrochloric acid (1984, 1M)
(CH3)2NH (b) cuprous chloride
23. F NO2 (A) (c) chlorine in the presence of anhyd AlCl 3
DMF,D
(d) nitrous acid followed by heating with cuprous chloride
(i) Fe/HCl
(ii) NaNO2/HCl/0°C
(B), B is Objective Questions II
(iii) H2/Ni (One or more than one correct option)
(2003, 1 M)
28. Aniline reacts with mixed acid (conc. HNO 3 and
CH3
(a) H2N N conc. H 2SO 4 ) at 288 K to give P (51%),Q (47%) and R
CH3 (2%). The major product(s) of the following sequence is (are)
(1) Sn /HCl
(1) Ac2 O, pyridine (2) Br2 /H 2 O (excess)
(b) H2N NH2 R ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾® S ¾¾¾¾¾¾¾¾¾®
(2) Br2 , CH 3 CO 2 H
(3) H 3 O+ (3) NaNO 2 , HCl /273-278 K
(4) NaNO 2 , HCl /273-278 K (4) H 3 PO 2
CH3 (5) EtOH, D
(c) O2N N Major product(s) (2018 Adv.)
CH3
Br Br
(d) O2N NH2 Br Br
(a) (b)
24. The most unlikely representation of resonance structures of Br Br
p-nitrophenoxide ion is (1999, 2M)
_ _ _
Br Br
O + O O + O (d) Br
N N (c) Br
(a) (b) Br Br Br Br
Br
O– O 29. The product(s) of the following reaction sequence is (are)
O O O– + O (2017, Adv.)
N N NH2
(i) Acetic anhydride/Pyridine
(ii) KBrO3/Br
(c) (d)
– (iii) H3O+, Heat
(iv) NaNO2/HCl, 273-278 K
(v) Cu/HBr
O– O
Aromatic Compounds Containing Nitrogen 417
Br Br
33. When nitrobenzene is treated with Br2 in the presence of FeBr3 ,
(a) (b) (c) (d) the major product formed is m-bromonitrobenzene. Statements
which are related to obtain the m-isomer, are (1992, 1M)
30. In the following reactions, the major product W is (2015 Adv.)
(a) the electron density on meta carbon is more than that on ortho
OH
NH2 and para positions
NaNO2,HCl , NaOH (b) the intermediate carbonium ion formed after initial attack of
0°C
V W
Br + at the meta position is less destabilised
(c) loss of aromaticity when Br + attacks at the ortho and
para positions and not at meta position
OH
(d) easier loss of H+ to regain aromaticity from meta position
(a) (b) than from ortho and para positions
N=
=N OH N=
=N
Assertion and Reason
Read the following questions and answer as per the direction given
HO below :
OH
(a) Statement I is correct; Statement II is correct; Statement
II is the correct explanation of Statement I.
(c) N=
=N (d)
N=
=N (b) Statement I is correct; Statement II is correct; Statement
II is not the correct explanation of Statement I.
(c) Statement I is correct; Statement II is incorrect.
(d) Statement I is incorrect; Statement II is correct.
31. In the reaction shown below, the major product(s) formed is/are
(2014 Adv.) 34. Statement I Aniline on reaction with NaNO2/HCl at 0°C
NH2 followed by coupling with b-naphthol gives a dark blue coloured
precipitate.
Acetic Statement II The colour of the compound formed in the
anhydride
NH2 Product(s) reaction of aniline with NaNO2/HCl at 0°C followed by
CH2Cl2 coupling with b-naphthol is due to the extended conjugation
O (2008, 3M)
N
H CH3 35. Statement I In strongly acidic solution, aniline becomes more
reactive towards electrophilic reagents.
O
Statement II The amino group being completely protonated in
(a)
NH2 + CH3COOH strongly acidic solution, the lone pair of electrons on nitrogen is
no longer available for resonance. (2001, 1M)
O
NH2
Match the Column
(b) H 36. Match the compounds in Column I with their characteristic
N CH3 + CH3COOH test(s)/reaction(s) given in Column II. (2008, 6M)
O O Column I Column II
H
N CH3 Sodium fusion
Å s extract of the
O (A) H2N ¾ NH3 Cl (p) compound gives
(c) H Prussian blue
N CH3 + H2O
colour with FeSO4
O O Å
r s O2N NHNH3Br
NH3CH2COO (B) Gives positive
(q) FeCl3 test
NO2
(d) H
N CH3
O O
418 Aromatic Compounds Containing Nitrogen
Column I Column II 44. What would be the major product in the following reaction?
O
Å Gives white
(C) HO NH3Cl precipitate with
(r) Br2/Fe
AgNO3
N—
Reacts with (2000, Main, 1M)
Å
O2N NHNH3Br aldehydes to form
(D) the corresponding 45. How would you bring about the following conversion (in 3 steps)?
(s)
hydrazone
NO2 derivative Aniline ¾® Benzylamine (2000, 3M)
38. In an acidic medium, ……… behaves as the strongest base. I (1994, 4M)
(nitrobenzene, aniline, phenol) (1981, 1M)
47. Following reaction gives two products. Write the structures of
the products.
Subjective Questions
Br 2 /Fe
39. Convert CH3 CONHC6 H5 ¾¾¾® (1998, 2M)
NO2 NO2
48. Write the structure of foul smelling compound obtained when
aniline is treated with chloroform in the presence of KOH.
(1996, 1M)
to
49. Complete the following with appropriate structure:
OH
NH2
in not more than four steps. Also mention the reaction conditions
and temperature. (2004, 4M)
NO2 (i ) NaNO2 and HCl at 5°C
¾¾¾¾¾¾¾¾¾® A
40. Which of the following is more acidic and why? (ii ) Anisole (1995, 1M)
+ +
NO2
NH3 NH3
50. How will you bring about the following conversions?
“Benzamide from nitrobenzene” (1994, 2M)
(A )
N=
=N —NH2 + HCl
H3C S
>
N
H N
H For an effective coupling, the solution must be so alkaline
that the concentration of diazonium ion is too low. It must not
(D)
be so acidic that the concentration of free amine or phenoxide
H3CO ion is too low. That is why amines couple fastest in mild
S
acidic solution and phenols couple fastest in mild alkaline
N
H N
H solution.
(B)
420 Aromatic Compounds Containing Nitrogen
s NaOH
5. [ Ar ¾ N ºº N ]+ OH - Ar ¾ N == N ¾ OH
1° NH2 responds
H+ Does not couple
NH2 NººC NaOH - +
CHCl3/KOH
(Carbylamine reaction)
- Ar ¾ N == N ¾ O Na
H+ Does not couple
(SN2 attack)
OEt Ni/H2/D OEt
NH2 CºN DIBAL–H
NH2 –EtOH
Note This C C¢ N N 1
are missing in all 2 CH
the option given. N –H2O NH2
N N (Nucleophilic addition
3
elimination reaction)
4
CH3
(Option-b) 10. Here, in mononitration the electrophile produced from mixed
+
7. Coupling of benzene diazonium chloride with 1-naphthol in acid (HNO3 + conc.H2SO4 ) is N O2.
alkaline medium will give the following coupling reaction.
OH OH O –R
A +R
PhN2+ N
B
OH –
H
N==N Ring-(A) is activated, i.e. becomes more nucleophilic by the + R
· ·
- + effect of the ¾ N H ¾ group and it becomes o / p-directing
In the presence of OH ion, Ar N 2 exists in equilibrium with an
towards the electrophile, NO+2 in the ArS E 2 reaction. For
unionised compound (Ar ¾ N == N ¾ OH) and salts Å
+ –
s mononitration, N O2 will preferably come at p-position,
[ ArN == N ] ¾OH derived from it, which do not couple.
Aromatic Compounds Containing Nitrogen 421
whereas the ring-(B) gets deactivated by -R- effect of the Aromatic amines (D) are always weaker bases than aliphatic
O amines, because of the conjugation of lp of electrons of N
½½ (+ R-effect) with the benzene ring.
¾ C ¾ group, So, the correct order is (D) < (C) < (A) < (B).
r
O2N O r 13. It is a 3°-amino group (—NMe2) though
NO2
aromatic which will not respond to
C rds of ArSE2 CH3
N diazotisation (NaNO2 + dil. HCl/5°C).
NH CH3 So, formation of diazonium ion and its
further reaction with alkaline phenol or
H b-napthol at 5-10°C to produce a
O precipitate of azo-dye will not take place.
O2N
r C (b) It is a keto group C==O and so it
NH Fast,–Hr
responds to 2, 4-DNP test with Brady’s
CH3 —— C==O reagent (2, 4-dinitrophenyl hydrazine) to
O2N O give a reddish orange precipitate.
O
C
NH It is a keto-methyl group —C—CH3 and
hence, it responds to iodoform test to
give a yellow precipitate of iodoform
11. Using retro-synthesis, to get the required compounds, A , B and (CHI3).
% s-character is most basic. Among the rest, pyridine (I) and aromatic amine, on treatment with NaNO2 in dil. HCl forms the
pyrrole (II) the lone pair of electrons of N in pyrrole (II) is corresponding diazonium chloride salt.
involved in delocalisation and follows (4 n + 2) p aromatic + –
NH2 N2 Cl
(n = 1) system. So, the N-atom of pyrrole (II) will show least
NaNO2
basicity. Thus, the order of basicity is as follows: HCl
H3C H 3C
> >
N N N
OH
H H
(III) (I) (II) b-naphthol
N N CH3
16. All the given compounds are a-monosubstituted acetic acid
derivatives and the a-substitutions have been made by strong–I OH
groups/atoms. More powerful the - I group, stronger will be the
acid.
-I power of different groups is as follows : 21. F—S==O S
—
¾ NO2 > ¾ CN > ¾ F > ¾ Cl. F O
F F
Thus, the correct decreasing order for acid strength is: S is sp3-hybridised Pyramidal
NO2CH2COOH > NCCH2COOH > FCH2COOH SO3 is planar (S is sp2-hybridised), BrF3 is T-shaped and SiO2-
3 is
> ClCH2COOH. planar (Si is sp2-hybridised).
17. Aniline in presence of nitrating mixture O
(conc. HNO3 + conc. H2 SO4) gives significance amount 22. ½½
(» 47%) of meta-product because in presence of H2SO4 its N Conc. HNO3
protonation takes place and anilinium ion is formed. I ½ Conc. H2SO4
NH2 NH3HSO4
H
II O2N
H2SO4 O
½½
Aniline Anilinium ion
N
½
Here, anilinium ion is strongly deactivating group and H
meta-directing in nature. So, it gives meta-nitration product.
Ring-I is activated while ring-II is deactivated towards
NH2 NH3HSO4 electrophilic aromatic substitution reaction.
H3C
Conc.H2SO4 (CH3)2NH
23. F NO2 N— NO2
+Conc.HNO3 DMF
NO2 H3C
18. Diazo coupling occur at para-position of phenol.
H3C
OH OH OH (i) Fe/HCl
N— NH2
(ii) NaNO2
(i) NaNO2/HCl/0°C (iii) H2/Ni H 3C
(ii) NaOH
+ O O
NH2 N2Cl– N N N
19. NH2
+
N2 Cl
-
CN Nitrogen has five bonds and 10 valence
24. electrons, not an acceptable resonance structure.
NaNO2/HCl D
0-5°C CuCN/KCN –
diazotisation O
+
CH3 CH3 25. C6H5N2Cl– + C6H5OH
CH3
4-methyl aniline D E
4-methyl diazonium chloride 4-methyl benzocyanide
—N==N— —OH
20. As we know, benzenediazonium salt forms brilliant coloured
dye with b-naphthol, the compound under consideration must be
p-hydroxy azobenzene
p-toluidine (c) as it is a primary aromatic amine. Primary
Aromatic Compounds Containing Nitrogen 423
So, Br
26. In structure II, nitrogen is associated with five bonds and 10
valence electrons, hence not acceptable. NO2 NH2 NH2
Sn/HCl Br2
H H2O (Excess)
Br Br
H—N—H Br Br Br
(S) NaNO2+HCl
+ 273-278K
Br Br
–
N2+Cl
N-has five bonds H3PO2
and 10 valence electrons
Br Br Br Br
CuCl
27. C6H5NH2 + HNO2 ¾® C6H5N2OH ¾® C6H5 ¾ Cl Br Br
Major product
Conc. HNO3 +
28. Given, Aniline ¾ ¾ ¾ ¾ ¾¾ ® P + Q + R 1, 3, 4, 5-tetrabromobenzene
Conc. H 2SO4 (51%)
(47%) (2%) Hence, only (d) is the correct answer.
Then P, Q and R will be 29. NH 2 NHAc
NH2 NH2 NH2 NH2
Ac2O/Pyridine
NO2
Conc. HNO3+
+ +
Conc. H2SO4
KBrO3 + HBr ¾® Br2
NO2 Ac is CH3CO (acetyl), it protects ¾ NH2 group from being
NO2 oxidised.
P (51%) Q (47%) R (2%)
NHAc NHAc NH2
(i) Ac 2O, pyridine
(ii) Br2 , CH 3COOH Br2 water H 3O +
Its given R ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾¾® S + CH3COOH
(iii) H 3O+
(iv) NaNO2 , HCl / 273-278 K
(v) EtOH, D
Br Br
O O NH2 N2Cl Br
NH2 HN C CH3 HN C CH3
NaNO2/HCl CuBr/HBr
NO2 NO2 NO2 (Sandmeyer
273-278 K
Ac2O Br2 reaction)
(Diazotisation)
Pyridine CH3COOH
Br Br Br
(R)
Br + –
30. NH2 N2Cl
NaNO2 –HCl b-naphthol
H3 O+
–CH3COOH 0°C NaOH
(Hydrolysis)
V N==N––Ph
+ –
N2Cl NH2 OH
NO2 NO2 NO2
EtOH NaNO2/HCl
D 273-278K W
(Diazotisation)
31. PLAN This problem includes concept of acetylation reaction and
Br Br Br regioselectivity of chemical reaction.
(S)
Regioselectivity means which group will react selectivity in the
Now from S to major products its given. presence of two or more than two functional groups. Here,
(i) Sn / HCl among two functional group ¾ NH2 and ¾ CONH2,
(ii) Br 2 / H2O (Excess)
S ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾¾® Major product NH2 is more nucleophilic, hence NH 2 group will undergo
(iii) NaNO 2 , HCl / 273-278K reaction faster than CONH2.
(iv) H3PO 2
424 Aromatic Compounds Containing Nitrogen
0 °C
34. C6H5NH2 + NaNO2 / HCl ¾® C6H5N+2 Cl – NaNO2
OH HBF4, heat
b-naphthol F NH2
COOH
FeCl3(aq)
violet colouration
OH
NH2 NC
+ CHCl3 + KOH
COOH COOK
foul smell
O O
C C CH2CH2CH2CH3
CH2CH2CH3 Cl2 CH2CH2CH3A Na-Hg
43. FeCl3 HCl
Cl Cl Cl
Cl Cl
NO2 (A) (B)
O O
__ Br2
44. N __ __
Fe N Br
HCl/0 °C
NO2
O
NaNO2(aq)
NO2
H+ NaNO2 + I2
46. —NH—C—CH3 —NH2 —N2Cl–
H2O HCl/0°C Heat Fe
I I
O O O
Benzamide
NO2 NO2
Br Br
Fe HNO3
52. + Br2
H2SO4
NO2
53. No reaction. Tertiary amine does not react with nitrous acid.
NH2 NH2 N2Cl– Br
Br Br NaNO Br Br CuBr Br Br Zn—HCl
Fe 2
54. + Br2 (excess)
HCl/0°C
HCl/0°C
NH2
O
Base
55. NH2 + COCl NH—C—
CH3 CH3
5. Which of the following compounds reacts with ethyl
OH OH magnesium bromide and also decolourises bromine water
solution (2019 Main, 11 Jan II)
(c) (d) CN OCH3
H 3C H 3C CH2—CO2CH3 CH
(a) (b) CH2
2. Increasing rate of S N1reaction in the following compounds is
OH CN O
I I
MeO
(c) (d)
(A) (B)
I
6. Which of the following compounds will produce a
I
precipitate with AgNO3 ? (2019 Main, 11 Jan I)
(C) (D)
Br Br Br
H3C H3CO Br
(2019 Main, 10 April I)
(a) (b) (c) (d)
(a) (A) < (B) < (C) < (D) (b) (B) < (A) < (C) < (D)
(c) (A) < (B) < (D) < (C) (d) (B) < (A) < (D) < (C) N
3. p-hydroxybenzophenone upon reaction with bromine in carbon 7. The major product of the following reaction is
tetrachloride gives (2019 Main, 9 April II) Cl
O (i) HBr
O
Br (ii) alc.KOH
Br (b) O (2019 Main, 11 Jan I)
(a)
HO Cl Cl
HO OH
O Br O
Br (a) (b) (c) (d)
(c) (d)
O O O
HO HO OH
4. The organic compound that gives following qualitative analysis 8. The major product of the following reaction is
is (2019 Main, 9 April I) OH
Test Inference Br2 (excess)
(i) Dil. HCl Insoluble
(ii) NaOH solution Soluble
SO3H (2019 Main, 11 Jan I)
(iii) Br2 /water Decolourisation
428 Aryl Halides and Phenols
OH OH O CH3
OH O
Br
(a) (b) (a) and CH3—OH (b) H3 C CH3
and
Br Br
Br SO3H
OH OH
OH OH O
Br Br Br Br H3 C CH3
(c) (d) (c) and H3C CH3 (d) and
OCH3 OH HO
(c) (d) Br
(ii) EtOH
10. The increasing order of the pK a values of the following (2019 Main, 9 Jan I)
compounds is (2019 Main, 10 Jan I) Br OEt
OH OH OH OH OEt
(a) (b)
CO2H
O CH3
12. The products formed in the reaction of cumene with O2
followed by treatment with dil. HCl are (2019 Main, 9 Jan II) O
Aryl Halides and Phenols 429
SO3H Br Br Br Br
NO2 NO2 Br
SO3H Br
(P) (Q)
H 3C Br H 3C SPh
OH OH
SPh SPh Br
(c) (d)
Br Br Br Br
Br SO3H
NO2 NO2 (R) (S)
25. In the following reaction, the product (s) formed is/are 28. When phenol is reacted with CHCl 3 and NaOH followed by
OH acidification, salicylaldehyde is formed. Which of the following
species are involved in the above mentioned reaction as
CHCl3 intermediates ? (1995, 2M)
?
OH– O OH
(2013 Adv.)
H CHCl2
CH3 –
(a) CCl2 (b)
OH O
OHC CHO
O O–
H CHCl2
H3C CHCl2
CH3 (Q) (c) CHCl (d)
(P)
OH
OH OH
CHO 29. Aryl halides are less reactive towards nucleophilic substitution
reaction as compared to alkyl halide due to (1990, 1M)
(a) the formation of less stable carbonium ion
H 3C CHCl2 (b) resonance stabilisation
(R) CH3 (c) longer carbon halogen bond
(S) (d) sp2-hybridised carbon bonded to halogen
(a) P (major) (b) Q (minor) (c) R (minor) (d) S (major)
OH Assertion and Reason
Read the following questions and answer as per the direction
NaOH(aq)/Br2
26. In the reaction, given below :
(a) Statement I is correct; Statement II is correct Statement II is
the correct explanation of Statement I
the intermediate(s) is/are (2010)
s O (b) Statement I is correct; Statement II is correct Statement II is
O
not the correct explanation of Statement I
Br (c) Statement I is correct; Statement II is incorrect
(a) (b) (d) Statement I is incorrect; Statement II is correct
ONa ONa
NO2
CH2Cl CHCl2
(a) (b) 45. Explain briefly the formation of the products giving the
structures of the intermediates.
CH3 CH3
NaNH2
ONa ONa —OMe —OMe
NH3
CCl3 CH2OH
¾
¾
(c) (d) Br
H 2N
46. Complete the following, giving the structures of the principal
organic products
CH3 CH3
36. Which one of the following reagents is used in the above 47. How will you prepare m-bromoiodobenzene from benzene
reaction ? (in not more than 5-7 steps) ? (1996, 2M)
(a) aq NaOH + CH3Cl (b) aq NaOH + CH2Cl 2
(c) aq NaOH + CHCl 3 (d) aq NaOH + CCl 4 48. Explain the following in one or two sentences only :
“Phenol is an acid, but it does not react with sodium
Integer Type Questions bicarbonate.” (1987, 1M)
37. The number of resonance structures for N is (2015, Adv.) 49. Complete the following with appropriate structures :
OH OH OH
NaOH
N CHO
?
Major product Br
Br2
(B ) –I effect
from m-position
4. Phenol (ArOH) is insoluble in dil. HCl and readily soluble in
(BN) NaOH solution. It reacts with Br2/water to give 2, 4,
6-tribromophenol. It readily decolourises the yellow colour of
I CH3
Br2 water. Reactions involved are as follows :
r Þ More stable OH
s
–I
rds
H3 C H3 C Dil. HCl
(C ) · no reaction
Additional
three hyperconjugation
Phenol
(C ¢)
(Acidic in nature)
Aryl Halides and Phenols 433
– +
OH ONa
(b) —Br + Br
CH3 CH3 CH3 12 The given process is cumene process (Hock process) to
s r
OH O Na d+ d– OCH3 synthesise phenol and acetone industrially.
NaOH (aq) CH3 I In Hock p rocess, Ph — group migrate and release H2O.
Acid-base reaction SN2 reaction
–H2O Å
–NaI 2-methoxy-1- + H
—O—O—H —O—O O
methyl benzene
H
10. Acidic strength is inversely proportional to pK a value. The O2 hn H+ Ph-group
5 atm migration
acidity of phenols is due to greater resonance stabilisation of
phenoxide ion relative to phenol. Therefore, any substituent Cumene H 2O
which stabilises the phenoxide ion more by dispersal of negative OH O
charge will tend to increase the acidity of phenol. Electron
OH
withdrawing groups ( ¾ NO2 ) increases the acidic strength of Hydrolysis
+
phenol whereas electron donating group ( ¾ OCH3 ) decreases
the acidic strength of phenol. In case of ¾ NO2 group attached
to phenol, the dispersal of negative charge is more pronounced 13. Key Idea The reaction involves hydrolysis or nucleophilic
at o- and p-position than at m-position. substitution in first step followed by oxidation and dehydration
Thus, order of acidic strength of nitrophenol is: in last step. The most important fact is that, the Br group
p-nitrophenol > o-nitrophenol and the correct order of the pK a attached directly to aromatic ring will not undergo substitution
values of give option is in step 1.
OH OH OH OH The road map of the given reaction is as follows:
O
11. It is an aromatic electrophilic substitution reaction (ArS E 2).
O
The reaction follows Ar S E2 (Aromatic electrophlic H OH H2SO4/D
–H2O
substitution pathway) as shown below :4
(Intramolecular
Br dehydration) Br
it makes ring activating and p-directing
It becomes ring activating 14 The road map of the given reaction is :
and m-directing
Br
Br
Isolated C=C
H—O HO—AlCl3 HO—AlCl3 *
Br2 /CCl4
*
H3C Anti-addition (electrophilic)
AlCl3 –H /+H of Br2 with the isolated
Friedel-Craft's O (non-aromatic) C==C
EtOH (Polar protic
acetylation – medium as well
SN1,–Br as nucleophile)
O reaction
O 2°-benzyl
OEt carbocation (Stable)
O Stabilises the complex by Å
* Br Br
hyperconjugation EtOH
* Å
*
–H
Racemised ± as well as
O O O—AlCl3
inverted (+ and –)
-AlCl3 OH
O 15. Followed by
O –H2O O + CO2 + NaOH acidification X
H (CH3CO)2O
conc. H2SO4
HO (Catalytic amount)
CH3 H2O
?
OH O
The very first reaction in the above road map looks like Kolbe’s
reaction which results to salicylic acid as
O O OH OH
(i) CO2, NaOH
H (ii) Acidification
COOH
Salicylic acid
(X)
Aryl Halides and Phenols 435
The salicylic acid with acetic anhydride [(CH3CO)2 O] in the 17. PLAN This problem can be solved by using the concept of synthesis of
presence of catalytic amount of conc. H2SO4 undergoes dye using electrophilic aromatic substitution reaction.
acylation to produce aspirin as In basic (alkaline) solution naphthol exists as naphthoxide ion
O which is a strong o, p-directing group.
CH3 C OH O
O O KOH
OH + CH3 C
OCCH3
Conc.
O H2SO4
+ CH3COOH III
COOH -d -d
COOH O
-d
Acetyl salicylic
acid (Aspirin) -d
Aspirin is a non-narcotic analgesic (Pain killer). Thus, formation of dye can be shown as
16. Given, N N¾Ph
OH OH
OH [Ph—N N]Cl–
NaOH Alkaline solution
+ Methyl A
chloroformate Br2
B Thus, (d) is the correct choice.
H3C Br H3C SPh
In the above road map, first reaction appears as acid base
reaction followed by SN AE (Nucleophilic substitution through
Addition and Elimination). Both the steps are shown below 18. F F
PhS–
(i) Acid base reaction DMF
OH O–
–
OH
+ H 2O NO2 NO2
S N 2 reaction bring about inversion of configuration.
(ii) S N AE
19. C6H5OH + C2H5O– ¾® C6H5O–
O
O C2H5I
O– O C O CH3 ¾¾® C6H5— OC2H5
Cl C OCH3
CH3 CH3
In the product of SN AE the attached group is ortho and liq. NH3
para-directing due to following cross conjugation 20. + KNH2 (Benzyne mechanism)
O NH2
d–
6 O1 C O 2 CH3 Cl
5 1
4 2 OH OH
d– 3 d– CS2
21. + Br2
Cross conjugation due to which lone pair of oxygen 1 will be 1000 temp.
Br
easily available to ring resulting to higher electron density at 2,
4, 6 position with respect to group. However from the stability In carbon disulphide, no phenoxide ion exist, therefore only
point of view ortho positions are not preferred by substituents as monobromination takes place.
group ¾ O ¾ C ¾ O ¾ CH3 is bulky. OH OH
||
O Br Br
Hence, on further bromination of SN AE product para bromo 22. + Br2–H2O
derivative will be the preferred product i.e.
O C O CH3 O C O CH3 Br
precipitate
O O
+ Br2 + HBr Br2 + H2O ¾® HBrO + HBr
It is a reversible reaction, but equilibrium is significantly shifted
Br to left, also indicated as Br2 (aq).
436 Aryl Halides and Phenols
23. PLAN This problem includes concept of effect of steric and electronic
Os OH
effect on reactivity of organic compounds. O
Steric effect of halogens are as follows Cl 2 < Br2 < I2 H CHCl2
s +
Electronic effect of phenolic group directs the approaching + : CCl2 CCl2 +H +
electrophile towards ortho and para positions. Tertiary butyl –H
group has large size so it causes steric effect around aromatic
nucleus. On the basis of above factors the products of the given CH3 CH3 CH3
reactions are as follows: H
OH OH O O
I
X2 = I2 CHO C
OH– H
C(CH3)3 or
OH OH
X2 = Br2
Br CH3 CH3
( S)
C(CH3)3 C(CH3)3 Major as stable due to intramolecular H-bonding.
Br
Os O O O
OH
X2 = Cl2 Cl Cl
:CCl2 H 2O
C(CH3)3
s
Cl s
CH3 CH3 CH3 CCl2 CH3 CHCl2
Hence, orientation in electrophilic substitution reaction is Q (minor)
decided by
(a) The steric effect of the halogen Thus, (b) and (d) are correct.
(b) The steric effect of the tert-butyl group
26. — OH in phenol is ortho/para directing group.
(c) The electronic effect of the phenolic group
So, (a), (b) and (c) are correct choices. O– O– O
24. PLAN ¾ OH group is activating group and is o- and p-directing. Br2 s
Also, ¾ SO3H is a better leaving group and is knocked out by
Br - .
OH OH Br Br
Br2 water Br Br
(3 equivalents) Br2 water O O
Br2
SO3H SO3H –
ortho-attack Br Br Br
OH OH
O O– O– O–
Br Br Br Br Br
r + SO3
O + +
Br S —O—H
Br Br Br Br
O (major)
para-attack
27.
25. PLAN Phenolic compounds in alkaline solution react with chloroform
—O—CH2— —OH +
(CHCl 3) at a temperature lower than that of CHCl 3 to form + HI
ortho-isomer as the major product (due to greater stability
resulting from intramolecular hydrogen bonding).
– s –Cl – —CH2I
HO + H—CCl3 a H2O ¾ CCl3 CCl2
dichloro
carbene
Aryl Halides and Phenols 437
28. O– O O O O O
H
+ CCl2 CCl
– 2 (VI) (V) (IV)
dichlorocarbene (III)
O– O O O
CHCl2
VII IX (VIII)
All the above shown nine resonance structures are different.
29. + 38. Ortho-nitrophenol : Due to intramolecular H-bonding.
X X
O
– H Intramolecular H-bonding in
ortho-nitrophenol
+ O–
N
Above resonance makes X- a poor leaving group. Also, the O
carbon bearing X is sp2- hybridised.
39. Phenoxide ion 40. Nucleophilic
30. Bromo group is deactivating due to dominance of inductive 41. Phenoxide ion :
effect over resonance effect. However, orientation is determined
by mesomeric effet of —Br. OH O–
31. + r H+ +
OH OH O—H
Resonance stabilised
+ H H conjugate base
+ E+ E E
OH O– OH
resonance stabilisation COO– COOH
NaOH H+
of intermediate carbocation 42. (i)
CO2
32. Statement I is incorrect, aryl halides do not undergo
Kolbe’s reaction
nucleophilic substitution reaction with ease. Cyanide ion (CN - ) OCOCH3
is a strong nucleophile. COOH
(CH3CO)2O
33. Statement I is incorrect, aryl halides do not usually undergo
nucleophilic substitution with ease. Statement II is correct, Heat
resonance introduces partial double bond character to C—X Aspirin
bond.
O– O ONa COOH COOH COOH
H CHCl2
34. – HNO3 Sn/HCl
+ CCl2 CCl2 (ii)
H2SO4
NO2 NH2
CH3 CH3 CH3 COOH
Intermediate
NaNO2/HBF4
35. Dichlorocarbene is the electrophile as shown above.
· D
36. CHCl 3 + NaOH ¾® · CCl 2 (Dichlorocarbene) F
electrophile meta-fluorobenzoic acid
37. O O Br Br OCH3
OH
NaOH
HNO3 CH3ONa Zn/HCl
43.
N (I) (II) H2SO4 Heat
NO2 NO2
438 Aryl Halides and Phenols
Br 50. The compound must contain a hydroxy group on the ring with
– NH3 NH–2 – all three ortho/para positions vacant :
+ NH2
OH OH
NH2
Benzyne more stable Br Br
carbanion is formed
+ Br2—H2O
2Cu CH3 CH3
46. 2 Me— —I
Heat
Br
51. Intramolecular H-bonding in ortho-nitrophenol lowers its
CH3— — —CH3 +2CuI
boiling point. No such intramolecular H-bonding is possible
with p-nitrophenol and rather it is associated together by
Ullmann’s reaction intermolecular H-bonding which increases the boiling point.
NO2 O
H
+ O–
47. + Conc. HNO3/conc.H2SO4 N
O
ortho-nitrophenol
Cl CH3
OH OH
COOH COOH O CH3
(a) and methanol (b) and methanol CH3 CH3
(c) (d)
CH3
OH O
Cl
OH OH O
(a) CH3OH and HCO2H 9. The major product obtained in the following conversion is
COOH (2019 Main, 11 Jan II)
CH3 O
(b) CH3OH and
O
Br2 (1 eqv.)
CH2OH MeOH
(c) HCOOH and
O
CH2OH COOH O CH3 O
CH3
(d) and O
Br O OMe
(a) (b)
6. The major product of the following reaction is
(2019 Main, 12 Jan II) OMe Br
O O O
NaBH4 CH3 O CH3 O
EtOH Br
O O
OH O
(c) (d)
(a) (b) Br
O O
O OH O
(2019 Main, 12 Jan I)
CHO CHO (b) H3C
(a) (b)
O O
OH O
O
CHO (c) H3C H
CH NH
(c) (d) O OH
OH OH
(d) H
OH H3C
CHO
Aromatic Aldehydes, Ketones and Acids 441
12. The major product obtained in the following reaction is 16. Which of the following reactants on reaction with
O conc. NaOH followed by acidification gives following
O lactone as the main product ? (2006, 5M)
DIBAL-H
O
COOH (2017 Main)
OH OH O
OCOCH3 SO3H
The major product C would be (2014 Main)
OCOCH3 OH (c) ; SO3 (d) ; NaOH
COOH COCH3
(a) (b) CH3 CH3
Hg 2+ / H+
18. Ph ¾ C ºº C ¾ CH3 ¾¾¾® A , A is (2003, 1M)
COCH3
O
OH OCOCH3
Ph Ph
(a) (b) O
COOCH3
(c) (d) H3C H3C
COOH
O–
15. Compound ( A ) , C8 H9 Br gives a white precipitate when Ph Ph
warmed with alcoholic AgNO 3 . Oxidation of (A) gives an
acid (B), C8 H6 O4 . (B) easily forms anhydride on heating. (c) (d) OH
Identify the compound (A). (2013 Main) H 3C H3C
CH2Br C2H5
CHO OHC
(a) (b)
Br (i) NaOH/100°C
19.
CH3 (ii) H+/H2O
CH2Br
CHO OHC
CH2Br
(c) (d) Major product (2003, 1M)
CH3
CH3
442 Aromatic Aldehydes, Ketones and Acids
H H3C CH3
½
C ¾ O– 24. Positive Tollen’s test is observed for
½ OH
(c) O–
O 2N H O CHO Ph
Ph O
H H
½ H O
C ¾ O– Ph Ph
½ Br
(d)
O– (a) (b) (c) (d)
MeO
25. The aldehydes which will not form Grignard product with
21. In the Cannizzaro’s reaction given below : one equivalent Grignard reagents are (2019 Main 12 Jan II)
HO O
Passage
Br In the following reactions sequence, the compound J is an
COBr intermediate.
(c) (d) (CH3 CO) 2 O (i) H2 , Pd/C
I ¾¾¾¾¾® J ¾¾¾¾¾¾® K
Br CH3 COONa (ii) SOCl 2
(iii) anhyd. AlCl 3
27. The compound Z is
J (C9 H8 O2 ) gives effervescence on treatment with NaHCO3
and positive Baeyer’s test. (2012)
(a) (b)
30. The compound K , is
O O
OH
(a) (b)
O O
(c) (d)
(c) (d) O
O
O
Paragraph A 31. The compound I, is
An organic acid P ( C11 H12 O2 ) can easily be oxidised to a dibasic
acid which reacts with ethylene glycol to produce a polymer O H OH
dacron. Upon ozonolysis, P gives an aliphatic ketone as one of the
products. P undergoes the following reaction sequences to furnish (a) (b)
R via Q. The compound P also undergoes another set of reactions to
produce S . (2018 Adv.)
O CH3 H H
(1) H2/Pd-C H
(2) NH3/D (1) H2/Pd-C (1) HCl
(3) Br2/NaOH (2) SOCl2 (2) Mg/Et2O (c) (d)
S P Q R
(4) CHCl3/KOH, D (3) MeMgBr,CdCl2 (3) CO2(dry ice)
(5) H2/Pd-C (4) NaBH4 (4) H3O+
True/False
33. Benzaldehyde undergoes aldol condensation in an alkaline
medium. (1982 , 1M)
CO2H CO2H
(c) (d)
444 Aromatic Aldehydes, Ketones and Acids
COCl CO2Me
H2 DIBAL-H
III. IV.
Pd-BaSO4 Toluene, -78°C
H2 O
Answers
1. (d) 2. (b) 3. (c) 4. (b) 21. (b) 22. (a) 23. (b,c) 24. (a,b,c)
5. (c) 6. (a) 7. (a) 8. (d) 25. (b,d) 26. (c) 27. (a) 28. (a)
9. (b) 10. (a) 11. (c) 12. (a) 29. (b) 30. (c) 31. (a)
13. (d) 14. (a) 15. (d) 16. (c) 32. C6H5 ¾ CH(OAc)2 33. False 37. (a)
17. (a) 18. (a) 19. (b) 20. (d)
38. (d) 39. (b) 40. (4)
Hints & Solutions
1. The major products of the given reaction are as follows: Further, heating of product leads to intramolecular cyclisation.
OH OH
COCl
(1) CHCl3/aq. NaOH OH C==O
D
(2) HCHO, conc. NaOH and HCOOH
(3) H3O+
HO HO
Cl Cl
In step-I, substituted phenol undergoes Reimer-Tiemann 3. (i) C9H10O shows positive iodoform test thus, ¾ C ¾ CH3
reaction in presence of CHCl3 / aq. NaOH group is present. ||
OH OH
O
CHO (ii) C9H10O on strong oxidation (KMnO4 / KOH), gives acid
(1) CHCl3/aq. NaOH
(C8H6O4 ), indicating it can be a dicarboxylic acid. So, ‘A’
contains ¾COCH3 and one ¾CH3 group which get
oxidised into ¾COOH and ¾COOH respectively.
Cl Cl
(iii) In the preparation of phenolphthalein from phenol, phthalic
The aldehyde obtained in above equation does not possess anhydride is used. So, ‘B’ can be phthalic acid (benzene-1,2-
a-hydrogen. In presence of formaldehyde and conc. NaOH it dicarboxylic acid) which readily forms anhydride.
undergoes Cannizaro reaction. In this reaction, one molecule of
Thus, the reaction sequence is as follows :
aldehyde is reduced to alcohol while another molecule is
oxidised to salt of carboxylic acid. CH3
I2/NaOH
OH O–Na+ + CHI3
CH3 (Iodoform test) – +
CHO COONa Yellow ppts.
Conc.
OH CH3
+ HCHO NaOH + HCOO–Na+ C O
O C
Cl Cl A(C9H10O) (i) [O] OH
+ CO2
KMnO4/KOH OH
Upon hydrolysis, following reaction takes place r C
(ii) H3O
O–Na+ OH O
Phthalic acid
H3O+ B(C8H6O4)
OH OH
+ HCOO–Na+ + HCOOH H
D –H2O
(2 mol)/
Cl Cl Conc. H2SO4
O
HO HO
OH OH
¾ OH group of carboxylic acid get substituted by ¾Cl in (Phenolphthalein
presence of SOCl2 (Thionyl chloride). an indicator)
The given reaction takes place as follows : 7. Key Idea Grignard reagent usually attacks on > C == O group
O O as :
s r
( C == O + RMgX ¾®
NaOCl '
Ph—C—CH3 Ph—C—ONa + CHCl3
r
H3O (It is missing in the ( C ' OMgX ¾¾¾®
Hydration ( C ' OH
Keto-methyl ' (R
group
statement of the question) - Mg (OH) X ' ( R
(Ionic salt)
O
The question is related to above reaction only with the condition
Ph—C—OH that the consumption of RMgX will be more than 1 equivalent in
Benzoic acid
(X)
some of the given cases.
O O Among the given compounds B, i.e.
SOCl CHO CHO
2
Ph—C—OH Ph—C—Cl
– SO2 [Acyl SN2
(X) Benzoyl
– HCl pathway]
chloride H2N— HO2C and D, i.e. HOH2C
–HCl
Aniline
O contain additional groups which can give active hydrogens.
Grignard reagents produce alkanes whenever come in contact
—NH—C—Ph with any group or compound which can give active hydrogen as:
Benzanilide
Dry OR
(Y ) ¾® R¢ H + Mg '
ROH + R ¢ MgX ¾ ¾ (
ether X
5. The given reaction is a crossed Cannizzaro reaction which is a These reactions are equivalent to acid-base reactions. So, in both
redox reaction too. Oxidation number of carbon atom of the of these compounds more than one equivalent will be required to
¾CHO groups of Ph¾CHO and H¾CHO are +1 and zero form Grignard products. Remember these compounds will give
respectively. So, HCHO is the stronger reducing agent than 2 type of products as:
PhCHO. As a result, HCHO is oxidised to HCOONa (by
(i) from the >C == O group
donation of hydride, H- ) and PhCHO (H- acceptor) is reduced
to PhCH 2OH. (ii) from the group which release active hydrogen
+1 0 50% NaOH The additional reactions involved are:
Ph ¾ C HO + HC HO ¾¾¾¾® CHO
-1 +2 - +
CHO
Dry
Ph ¾ C H2OH + HC OONa (i) + RMg X RH +
ether
½ + HO2C C
¯ H3 O d+ d–
PhCH2OH + HCOOH X MgO
(Major products) O
The reaction proceed via following mechanism. CHO CHO
Dry
OH (ii) + RMg X + RH
ether
– | s HOH2C
OH Slowest XMgOH2C
H2C=
=O Slower H—C—O
d+ d– | Ph—CH=
=O
H 8. DIBAL-H (Diisobutylaluminium hydride) is a reducing agent
More polar and less
– with formula [l-Bu 2AlH ] . At ordinary temperatures, nitriles
crowding for H shift
nucleophilic addition give imines which are readily converted in aldehydes by
OH
| hydrolysis whereas lactones are reduced directly to aldehydes.
H—C==O + Ph—CH2—Os H
Fast
Os
Ö
Al (DIBAL–H) Al (DIBAL–H)
| Al
+ + H
H—C==O + PhCH2OH N
CN N
C
6. Reducing agents like LiAlH4, NaBH4, i.e. complex hydrides C H
O
usually does not affect olifenic or p-bonds. Thus, if NaBH4 is O
O O
O
O
applied to a compound like then its ( C == O bond will be O
' H2O
OH
CHO CHO CHO
+H+ DIBAL–H
(Hs)
reduced only and we get as the OH O O
final product. H
Thus, option (a) is correct answer. O –O
H O
Aromatic Aldehydes, Ketones and Acids 447
KMnO4 SOCl2
+ SO2 + HCl
COOH
(Toluene) (Benzoic Acid) (Benzoyl chloride)
11. In aldol condensation, generally aldehydes react at a faster rate ‘A’ ‘B’
than ketones towards base. In the given case CH3CHO will lose H2/Pd BaSO4
O
O H
C C
a-hydrogen faster than CH3 due to one more
Following four products are possible in the reaction: 14. It is a Kolbe Schmidt reaction.
+ +
H ONa COONa COOH O
½ ½ ½
(i) CH3—C—CH2—CHO (Self Aldol condensation OH OC ¾ CH3
of CH3CHO) H+/Ac2O
+ CO2 125°C
OH 5 atm
H (Cross Aldol condensation of ‘B’ Aspirin
CH3CHO and CH3COC6H5 (pain killer)
(ii) CH3—C—CH2—C—C6H5 in which >C=O group of ‘ C’
CH3CHO is carbanion
OH acceptor). The second step of the reaction is an example of acetylation
reaction.
448 Aromatic Aldehydes, Ketones and Acids
15. Compound A gives a precipitate with alcoholic AgNO3, so it 20. Dioxoanion is better hydride donor. Electron donating group at
must contains Br in side chain. On oxidation, it gives C8 H6O4, ortho/para position further promote H– transfer.
which shows the presence of two alkyl chains attached directly –
O
with the benzene nucleus. Since, compound B gives anhydride
on heating, the two alkyl substituent must occupy adjacent (1, 2) O
C—H
position. Thus, A must be
+ C—R
CH2 Br O–
H3CO H O
–
CH3
C
and the reactions are as follows :
CH2Br CH2 OR + O–
Alcoholic H3CO –
+ AgBr O
AgNO3
CH3 CH3
‘A’
+ H— C —R
Oxidation O
COOH H
D
O -
O O
COOH
‘B’ ½½ ½
O
Phthalic anhydride
21. Ph ¾ C ¾ H + HO- ¾® Ph ¾ C ¾ H
½
16. CHO COOH OH
OH– I
Intramolecular O- O
CHO Cannizzaro reaction CH2OH ½ ½½ Slow
Ph ¾ C ¾ H + C ¾ Ph ¾¾¾¾¾®
O ½ ½ hydride transfer
OH H
I
H+ O O-
O
½½ ½
Ph ¾ C ¾ OH + Ph ¾ C ¾ H
Ester formation
½
17. H
H3C— —SO3H + CH3COONa
Base 22. Cl Cl Cl
4-methyl benzene sulphonic
acid
H3C— —SO3Na + CH3COOH + KOH +
CHO COOK CH2OH
H+ + Cannizzaro’s
18. Ph — C ºº C— CH3 ¾® Ph — C==CH— CH3 reaction
Stable carbocation 23.
O O3
(b) CH3 CH CH2 CH3 CHO+H2CO
H2O ½½ Zn–H2O
(R)
¾¾® Ph — C — CH2CH3 (P) Gives Cannizzaro
but not haloform reaction
CHO OHC
O
NaOH O3
19. Zn–H2O
C CH3+H2CO
(S)
(Q) Gives haloform reaction
CHO OHC but not Cannizzaro reaction
COOH HOH2C
O3
+ (c) CH CH CH3 CHO+CH3CHO
H Zn–H2O
(R)
H 2O P
CH3 CH3
CH2OH Gives Cannizzaro
HOOC but not haloform reaction
H 3C H 3C CH3COO–Na+
C—H + CH3COOH
(i) O3 + (CH3CO)2O 180°C
CHO
(ii) Zn– H2O
R Cinnamic acid
Note Besides CH3COO- Na+, quinoline, pyridine, Na 2CO3,
H 3C CHO triethylamine can also be used as bases in this reaction.
NH3 CH NH
Reaction 3 It is simple addition of bromine to unsaturated acid
(X) formed through reaction 2.
In the above reaction, NH3 prefer to attack at aliphatic aldehyde CH CHCOOH CHBr CHBr
group than an less reactive aromatic aldehyde group.
Br2 COO–Na+
O OH
Na2CO3
H3C
H 3C C N—H
H Cinnamic acid
Tautomerism
Xs NH2 Na2CO 3 works as a base in the reaction to trap H+ to be released
– H2O OH
O CH—CH—Br
H3C
N COO–Na+
by — COOH of the reactant. is also formed
‘S’
26. Given, in the reaction as the minor product.
1 2 Reaction 4 It is decarboxylation and dehydrohalogenation of
CO+HCl Ac2O
Benzene X product produced by reaction 3 as
anhy. AlCl3/CuCl NaOAc (Major) CHBr CHBr C CH
3
Br2 + COO–Na+
C
+ Na2CO3 + KBr
d
2 /P
437 K
H
6 Moist KOH C CH
4
O
4
3P
473 K
H
Br2/NaOH
O
NH N C NH2
(Hofmann
bromamide) CH3—C— —OH Gives positive iodoform
H2/Pd–C CHCl3/KOH test.
(Carbylamine) C
O O Br
37. C6H5 ¾ CH3 ¾®
2
C6H5 ¾ CH2Br + HBr
hv (Free radical bromination)
PCl5
O
HOOC Cl—C || NaOH / Br2
38. C6H5 ¾ C ¾ CH3 ¾¾¾¾® C6H 5COONa + CHBr3 (P )
(II) (i ) Bromoform
B O
O O
O || ||
39. C6H 5CHO+ CH3 ¾ C ¾ O ¾ C ¾ CH3
H2 N2H4
N CH 3 COOK
Pd/BaSO4 ¾¾¾¾¾¾® C6H5 ¾ CH == CH ¾ COOH
Perkin's condensation (Cinnamic acid)
H—C N
D
Cinnamic acid shows cis-trans isomerism.
O
C
40. I. Gattermann-Koch reaction.
36. Intramolecular H-bonding in ortho hydroxy benzaldehyde is II.
responsible for decrease in melting and boiling points. CHCl2 CH(OH)2
H2O
O H 100°C (SN1)
CHO
gem-diol
O
–H2O
H
Intramolecular III. Rosenmund’s reduction.
H-bonding
IV. Acid chloride, anhydride and ester undergo controlled
reduction with di-iso-butylaluminium hydride (DIBAL-H) at
p-hydroxy benzaldehyde molecules are associated by
- 78°C to give aldehydes.
intermolecular H-bonding, has higher melting and boiling
points.
12. Which of the following tests cannot be used for identifying 20. Which one of the following bases is not present in DNA?
amino acids ? (2019 Main, 10 Jan II) (a) Quinoline (b) Adenine (2014 Main)
(a) Barfoed test (b) Ninhydrin test (c) Cytosine (d) Thymine
(c) Xanthoproteic test (d) Biuret test 21. Synthesis of each molecule of glucose in photosynthesis
13. The correct sequence of amino acids present in the involves (2013 Main)
tripeptide given below is (2019 Main, 9 Jan II) (a) 18 molecules of ATP (b) 10 molecules of ATP
(c) 8 molecules of ATP (d) 6 molecules of ATP
Me Me Me OH
H O 22. The following carbohydrate is
N OH
H2N N C H OH
O H
HO H O
OH O OH
HO H HO
(a) Thr - Ser - Leu (b) Leu - Ser - Thr H H (2011)
(c) Val - Ser - Thr (d) Thr - Ser - Val (a) a ketohexose (b) an aldohexose
14 The increasing order of pK a of the following amino acids (c) an a-furanose (d) an a-pyranose
in] aqueous solution is Gly, Asp, Lys, Arg 23. The correct statement about the following disaccharide is
(2019 Main, 9 Jan I) CH2OH
(a) Asp < Gly < Arg < Lys (b) Arg < Lys < Gly < Asp
H O H2COH O H
(c) Gly < Asp < Arg < Lys (d) Asp < Gly < Lys < Arg H
H
OH H H HO
15. Glucose on prolonged heating with HI gives (2018 Main) OCH2CH2O CH2OH
HO
(a) n-hexane (b) 1-hexene
H OH OH H (2010)
(c) Hexanoic acid (d) 6-iodohexanal (a) (b)
16. The predominant form of histamine present in human blood (a) Ring (a) is pyranose with a-glycosidic link
is (pK a , Histidine = 6.0 ) (2018 Main) (b) Ring (a) is furanose with a-glycosidic link
H H (c) Ring (b) is furanose with a-glycosidic link
N N r (d) Ring (b) is pyranose with b-glycosidic link
NH2 NH3
(a) (b)
r 24. Two forms of D-glucopyranose, are called (2005, 1M)
N N (a) enantiomers (b) anomers
H
H H (c) epimers (d) diastereomers
N NH2 N r
NH3 25. Which of the following pairs give positive Tollen’s test ?
(c) (d) (2004, 1M)
r
N N (a) Glucose, sucrose (b) Glucose, fructose
H
(c) Hexanal, acetophenone (d) Fructose, sucrose
17. Which of the following compounds will behave as a
reducing sugar in an aqueous KOH solution? (2017 Main) Objective Question II
(One or more than one correct option)
HOH2C O CH2OH HOH2C O CH2OH
26. The Fischer presentation of D-glucose is given below.
(a) HO (b) HO CHO
OCOCH3 H OH
OH OH HO H
HOH2C H OH
O O CH OCH H OH
HOH2C CH2OH 2 3
CH2OH H
Integer Answer Type Questions
O O
H OH HO H 30. The total number of distinct naturally occurring amino acids
H (d) CH2OH
(c) obtained by complete acidic hydrolysis of the peptide
OH HO H HO shown below is (2014 Adv.)
HO H H OH
O
H H OH H H
O O H O H O N
27. For ‘invert sugar’, the correct statement(s) is (are) N
N N N
N N
(Given: specific rotations of ( + ) - sucrose, (+) - maltose,
L-( - ) -glucose and L-( + ) -fructose in aqueous solution are N CH2 O
H
O H CH2 O
+ 66 °, +140 °, - 52 °and 92° , respectively) (2016 Adv.) H
(a) Invert sugar is prepared by acid catalysed hydrolysis O
of maltose
(b) Invert sugar is an equimolar mixture of D-(+) -glucose
31. A tetrapeptide has ¾ COOH group on alanine. This produces
and D-(-)- fructose glycine (Gly), valine (Val), phenyl alanine (Phe) and alanine
(c) Specific rotation of invert sugar is - 20 ° (Ala), on complete hydrolysis. For this tetrapeptide, the
(d) On reaction with Br2 water, invert sugar forms number of possible sequences (primary structures) with
saccharic acid as one of the products ¾ NH2 group attached to a chiral centre is (2013 Adv.)
28. The correct statement(s) about the following sugars X and Y 32. The substituents R1 and R2 for nine peptides are listed in the
is/are: (2009) table given below. How many of these peptides are
CH2OH
H positively charged at pH = 7.0 ? (2012)
H O O
HOH2C H H3N ¾ CH ¾ CO ¾ NH ¾ CH ¾ CO ¾ NH ¾ CH
H
OH H H HO H
CH2OH R1 R2
OH O
¾ CO ¾ NH ¾ CH ¾ COO
H OH OH H
X H
CH2OH
O Peptide R1 R2
H H
I H H
H
CH2OH II H CH 3
OH H
H O O III CH 2COOH H
OH
H IV CH 2CONH 2 (CH 2 ) 4 NH 2
H OH
OH H V CH 2CONH 2 CH 2CONH 2
OH H VI (CH 2 ) 4 NH 2 (CH 2 ) 4 NH 2
H OH VII CH 2COOH CH 2CONH 2
Y
VIII CH 2OH (CH 2 ) 4 NH 2
(a) X is a reducing sugar and Y is a non-reducing sugar IX (CH 2 ) 4 NH 2 CH 3
(b) X is a non-reducing sugar and Y is a reducing sugar
(c) The glucosidic linkages in X and Y are a and b, respectively 33. When the following aldohexose exists in its
(d) The glucosidic linkages in X and Y are b and a, respectively D-configuration, the total number of stereoisomers in its
pyranose form, is (2012)
Assertion and Reason CHO
Read the following questions and answer as per the direction CH2
given below : CHOH
(a) Statement I is correct; Statement II is correct;
Statement II is a correct explanation of Statement I. CHOH
(b) Statement I is correct; Statement II is correct; Statement CHOH
II is not the correct explanation of Statement I.
(c) Statement I is correct; Statement II is incorrect. CH2OH
(d) Statement I is incorrect; Statement II is correct. 34. A decapeptide (Molecular weight 796) on complete
29. Statement I Glucose gives a reddish-brown precipitate hydrolysis gives glycine (Molecular weight 75), alanine and
with Fehling’s solution. phenylalanine. Glycine contributes 47.0% to the total
Statement II Reaction of glucose with Fehling’s solution weight of the hydrolysed products. The number of glycine
gives CuO and gluconic acid. (2007, 3M) units present in the decapeptide is (2011)
456 Biomolecules and Chemistry in Everyday Life
CH—C 38. Following two amino acids lysine and glutamine form
s dipeptide linkage. What are two possible dipeptides?
H 2N O (2003, 2M)
Subjective Questions H2 N ¾ CH ¾ COOH
½
36. Which of the following disaccharide will not reduce CH2 CH2 CH2 CH2 NH2
Tollen’s reagent? (2005, 2M)
CH2OH CH2OH
H2 N ¾ CH ¾ COOH
HO O
H H
O OH ½
CH2 CH2 COOH
(a)
H HO H HO
O 39. Aspartame, an artificial sweetener, is a peptide and has the
H H
OH H
following structure
OH H
CH2OH CH2OH CH2 C6H5
O O OH
½
OH H H H2 N ¾ CH ¾ CONH ¾ CH ¾ COOCH3
(b) ½
H HO OH H
O CH2 ¾ COOH
H H
OH H H OH (i) Identify the four functional groups.
(ii) Write the Zwitter ionic structure.
37. The structure of D-glucose is as follows :
(iii) Write the structures of the amino acids obtained from
CHO the hydrolysis of aspartame.
H OH (iv) Which of the two amino acids is more hydrophobic?
(2001, 5M)
HO H
40. Give the structures of the products in the following reaction
H OH
H+
Sucrose ¾® A + B (2000, 2M)
H OH
OH
41. Write the structure of alanine at pH = 2 and pH = 10.
(2000, 2M)
6. The structure of nylon-6 is 12. The correct match between item (I) and item (II) is
O H O H Item - I Item - II
|| | || |
(A) Norethindrone (P) Antibiotic
(a) ¾ ]n (b) ¾
[ (CH 2 )6 ¾ C ¾ N ¾ [ C ¾ (CH 2 )5 ¾ N ¾
]n
(B) Ofloxacin (Q) Antifertility
O H O H (C) Equanil (R) Hypertension
|| | || | (S) Analgesics
(c) ¾
[ (CH 2 )4 ¾ C ¾ N ¾
]n (d) ¾
[ C(CH 2 )6 ¾ N ¾
]n
(2019 Main, 11 Jan I)
(2019 Main, 8 April II) (a) (A) ® (Q); (B) ® (R); (C) ® (S)
7. The two monomers for the synthesis of (b) (A) ® (Q); (B) ® (P); (C) ® (R)
nylon 6, 6 are (2019 Main, 12 Jan II) (c) (A) ® (R); (B) ® (P); (C) ® (S)
(a) HOOC(CH 2 )4 COOH, H 2N(CH 2 )4 NH 2 (d) (A) ® (R); (B) ® (P); (C) ® (R)
(b) HOOC(CH 2 )6 COOH, H 2N(CH 2 )4 NH 2 13. The correct match between Item - I and Item - II is
(c) HOOC(CH 2 )4 COOH, H 2N(CH 2 )6 NH 2
Item I (Drug) Item II (Test)
(d) HOOC(CH 2 )6 COOH, H 2N(CH 2 )6 NH 2
A. Chloroxylenol P. Carbylamine test
8. Poly-b-hydroxybutyrate-Co-b-hydroxyvalerate (PHBV) is a B. Norethindrone Q. Sodium hydrogen carbonate test
copolymer of …… (2019 Main, 12 Jan I) C. Sulphapyridine R. Ferric chloride test
(a) 3-hydroxybutanoic acid and 2-hydroxypentanoic acid D. Penicillin S. Bayer’s test
(b) 2-hydroxybutanoic acid and 3-hydroxypentanoic acid (2019 Main, 9 Jan I)
(c) 3-hydroxybutanoic acid and 4-hydroxypentanoic acid (a) A®R;B®P;C®S;D®Q
(d) 3-hydroxybutanoic acid and 3-hydroxypentanoic acid (b) A®R;B®S;C®P;D®Q
9. The homopolymer formed from 4-hydroxybutanoic acid is (c) A®Q;B®P;C®S;D®R
O O O
(d) A®Q;B®S;C®P;D®R
14. The formation of which of the following polymers involves
(a) —OC(CH2)3—O— (b) —C(CH2)2C—
n n hydrolysis reaction? (2017 Main)
O O O (a) Nylon-6
(c) —C(CH2)3—O— (d) —C(CH2)2C—O—n (b) Bakelite
n
(c) Nylon-6, 6
(2019 Main, 11 Jan II) (d) Terylene
10. The correct match between Item I and Item II is 15. Which of the following statements about low density
Item I Item II polythene is false? (2016 Main)
A. Allosteric effect P. Molecule binding to the active site (a) It is a poor conductor of electricity
of enzyme. (b) Its synthesis required dioxygen or a peroxide initiator
B. Competitive Q. Molecule crucial for as a catalyst
inhibitor communication in the body. (c) It is used in the manufacture of buckets, dustbins etc.
C. Receptor R. Molecule binding to a site other (d) Its synthesis requires high pressure
than the active site of enzyme.
16. Which of the following is an anionic detergent?(2016 Main)
D. Poison S. Molecule binding to the enzyme
covalently.
(a) Sodium lauryl sulphate
(b) Cetyltrimethyl ammonium bromide
(a) A ® P; B ® R; C ® S; D ® Q (c) Glyceryl oleate
(b) A ® P, B ® R; C ® Q; D ® S (d) Sodium stearate
(c) A ® R; B ® P; C ® S; D ® Q 17. On complete hydrogenation, natural rubber produces
(d) A ® R; B ® P; C ® Q; D ® S (2019 Main, 11 Jan II) (2016 Adv.)
11. The polymer obtained from the following reaction is: (a) ethylene-propylene copolymer
(2019 Main, 11 Jan I) (b) vulcanised rubber
(i) NaNO2 /H3O
+ (c) polypropylene
NH2 (d) polybutylene
HOOC (ii) Polymerisation
18. Which polymer is used in the manufacture of paints and
O O lacquers? (2015 Main)
H
(a) —C—(CH2)4—N—n (b) —O—(CH2)4—C—n (a) Bakelite
(b) Glyptal
O O O (c) Polypropene
H (d) Polyvinyl chloride
(c) —OC(CH2)4O— (d) —HNC(CH2)4—C—N—
n n
458 Biomolecules and Chemistry in Everyday Life
19. Match the polymers in Column I with their main uses in AcO AcO AcO
Column II and choose the correct answer: HH OH H OH H OO
(c) H H
Column I Column II OAc H O OAc H O OAc H
O H
(A) Polystyrene 1. Paints and lacquers
H OAc H OAc H OAc
(B) Glyptal 2. Raincoats
(C) Polyvinyl chloride 3. Manufacture of toys AcO AcO AcO
(D) Bakelite 4. Computer discs OH H OH H OO
HH H H
Codes (d)
H H O H H O H H
A B C D A B C D O H
(a) 2 1 3 4 (b) 3 1 2 4 OAc OAc OAc OAc OAc OAc
(c) 2 4 3 1 (d) 3 4 2 1
20. OCOCH3
Objective Question II
(One or more than one correct option)
COOH is used as 25. Under hydrolysis conditions, the compounds used for
preparation of linear polymer and for chain termination,
respectively are (2012)
(a) Insecticide (b) Antihistamine (a) CH3 SiCl3 and Si(CH3 )4 (b) (CH3 )2 SiCl2 and (CH3 )3 SiCl
(c) Analgesic (d) Antacid
(c) (CH3 )SiCl2 and CH3 SiCl3 (d) SiCl4 and (CH3 )3 SiCl
21. Which of the following is not an antacid? (2015 Main)
(a) Aluminium hydroxide (b) Cimetidine 26. The correct functional group X and the reagent/reaction
(c) Phenelzine (d) Ranitidine conditions Y in the following schemes are (2011)
(i) Y
22. Which one is classified as a condensation polymer? X—(CH2)4—X Condensation polymer
(2014 Main) O
O
(a) Dacron (b) Neoprene (ii) C—(CH2)4—C
(c) Teflon (d) Acrylonitrile HO heat OH
23. Among cellulose, poly (vinyl chloride), nylon and natural (a) X = COOCH3, Y = H2/Ni/heat
rubber, the polymer in which the intermolecular force of (b) X = CONH2, Y = H2/Ni/heat
attraction is weakest is (2009) (c) X = CONH2, Y = Br2/NaOH
(a) nylon (d) X = CN, Y = H2/Ni/heat
(b) poly (vinyl chloride)
(c) cellulose Match the Columns
(d) natural rubber 27. Match the chemical substances in Column I with type of
24. Cellulose upon acetylation with excess acetic anhydride/ polymers/type of bond in Column II. (2007, 6M)
H2 SO4 (catalytic) gives cellulose triacetate whose structure Column I Column II
is (2008, 3M) A. Cellulose p. Natural polymer
AcO B. Nylon-66 q. Synthetic polymer
OO C. Protein r. Amide linkage
AcO H H D. Sucrose s. Glycoside linkage
(a) O OAcH
H O H
AcO H Subjective Questions
O OAcH H H OAc
HH O 28. Monomer A of a polymer on ozonolysis yields two moles of
OAc HCHO and one mole of CH3COCHO. (2005)
O
OAcH H H
(a) Deduce the structure of A.
H OAc (b) Write the structure of ‘all cis’ – form of polymer of
AcO
OO compound A.
AcO H H 29. Name the heterogeneous catalyst used in the polymerisation
(b) O OH H
O H of ethylene. (2003)
AcO H H
OH H H H OH 30. Give the structures of the products in the following reaction.
HH O O (2000, 2M)
OH NOH
O
OH H H H
H OH H+ Polymerisation
C *—D—n*
Answers
Topic 1 Topic 2
1. (a) 2. (b) 3. (a) 4. (d) 1. (a) 2. (a) 3. (a) 4. (c)
5. (b) 6. (b) 7. (d) 8. (d) 5. (d) 6. (b) 7. (c) 8. (d)
9. (a) 10. (d) 11. (a) 12. (a) 9. (c) 10. (d) 11. (b) 12. (b)
13. (c) 14. (d) 15. (a) 16. (d) 13. (b) 14. (a) 15. (c) 16. (a)
17. (a) 18. (b) 19. (a) 20. (a) 17. (a) 18. (b) 19. (b) 20. (c)
21. (a) 22. (b) 23. (a) 24. (b) 21. (c) 22. (a) 23. (d) 24. (a)
25. (b) 26. (d) 27. (b,c) 28. (b,c) 25. (b) 26. (a, b, c, d)
29. (c) 30. (1) 31. (4) 32. (4) 27. A ® p, s; B ® q, r; C ® p, r; D ® s
33. (8) 34. (6) 35. (2)
3. Key Idea Chiral centre is also called stereo-centre or 5. The peptide that gives positive cerric ammonium nitrate and
stereogenic center. carbylamine tests is ser - lys. The structures of serine and lysine
are,
Linear structure of glucose is as follows :
CHO
HO ¾ CH2 ¾ C H ¾ COOH H2N ¾ (CH2)4 ¾ C H ¾ COOH
| |
H OH NH2 NH2
HO H Serine Lysine
H OH 6. Statement-(b) is not true for sucrose. It is linked through a
H OH glycosidic linkage between C-1 of a-glucose and C-2 of
CH2OH
b-fructose. Since, the reducing groups of glucose and fructose are
involved in glycosidic bond formation, sucrose is a non-reducing
Fischer formula Number of stereo-centre (C* ) = 4. sugar.
Cyclic structure of glucose are as follows : CH2OH
CH2OH CH2OH O
H H HOH2C O
H H
O O a b
H H H H H OH OH H
HO Glycosidic
linkage H HO CH2OH
HO OH H OH HO OH H H
H OH
H OH a-D-glucose OH H
H OH
a-D-glucose b-D-glucose b-D-fructose
Haworth formula Number of stereo-centre (C* ) in each anomer = 5. On hydrolysis with acids or enzyme, sucrose gives equimolar
mixture of D-(+)-glucose and D-(–)-fructose.
4. Amylopectin is the water-soluble component of starch. It is a HCl
branched-chain polymer of a-D-glucose. The main chain C12H22O11 + H2O ¾¾® C6H12O 6 + C6H12O 6
consists of an a - 1, 4¢- glycosidic linkages between a - D- D-(+) -glucose D-(–)-fructose
460 Biomolecules and Chemistry in Everyday Life
CHO COOH 15. HI is a strong reducing agent. It reduces both primary and
secondary alcoholic groups of glucose along with the carbonyl
H OH H OH group to produce n-hexane as
HO H HO H
+ Cu2++ 2H2O + Cu2O +4H+ CHO Carbonyl group CH3
H OH (Cu (II)-acetale) H OH
(Red ppt.) Secondary
H OH H OH HI
alcoholic (CH2)4
(CHOH)4 group D
CH2OH CH2OH (Prolonged)
(D-glucose) (D-gluconic acid) CH2OH Primary CH3
alcoholic
group
(ii) Glucose n-hexane
(Ninhydrin Test)
Violet 16. Our blood is slightly basic in nature with pH range from
Ninhydrin/ D
colouration 7.35-7.4. The structure of histamine is given below :
Amino acid (Xanthoprotic Test) Yellow Aliphatic
(Protein) Conc. HNO3 H amino group
colouration
(Biuret Test) Imidazole N NH2
Violet ring
CuSO4 (aq)+NaOH
colouration N
13. Formation of the tripeptide (Val-Ser-Thr) can be shown as: Basic nitrogen of imidazole ring
Me Me Me OH It is produced by decarboxylation of histidine having following
CH O CH
structure. It is clearly visible from the above structure that
CH OH H HN C CH OH histamine has two basic centres namely aliphatic amino group
H2N C CH OH H HN C and basic nitrogen of imidazole ring. The aliphatic amino group
O CH2 O has pK a around 9.4. In blood with pH around 7.4 the aliphatic
OH amino group of histamine become protonated to give a single
Valine (Val) Serine (Ser) Threonine (Thr) charged cation as shown below
–2H2O H
Me Me Me OH N +
CH O CH NH3
CH NH C CH OH
H2N C C N
CH NH
Nature of O
Nature HOH2C CH2OH
‘R’ in the amino group of R the amino
acids HO O
1. + Basic More basic (due
NH2 to the presence
¾ (CH2)3¾ NH ¾ C OH
of acetamidine
NH2 (a-hydroxyketone)
group)
(Arginine : Arg)
Hemiacetal can be easily reduced by oxidising agent such as
2. O Acidic Acidic Tollen’s reagent.
CH2 C
O– O
HOH2C CH2OH
(Aspartic acid: Asp) Tollen’s
O positive silver
3. ¾H (Glycine) : Gly Neutral Neutral OH reagent
mirror test.
+
4. ¾ ( CH2 ) 4 ¾ NH3 Basic Basic
OH
(Lysine : Lys) (Reducing sugar)
462 Biomolecules and Chemistry in Everyday Life
18. NH2 H O H O
Cystine HO S COOH C1 C1
C S
H C2 OH HO C2 H
O NH2
COOH HO C3 H H C3 OH
Cysteine
HS
NH2 H C4 OH HO C4 H
NH2 Cytosine
O
N H C5 OH HO C5 H
Methionine S C
H 3C OH ,
O N 6CH2OH 6CH2OH
NH2 H D-glucose L-glucose
28. X is acetal, has no free hemiacetal, hence a non-reducing sugar 32. The amino acid remain completely in Zwitter ionic form at its
while Y has a free hemiacetal group, it is reducing sugar. Also, isoelectric point. Amino acids with additional acidic group have
glucosidic linkage of X is ‘a’ while that of Y is b-linkage. their isoelectric pH less than 7.0 and increasing pH above
isoelectric point makes them anionic.
29. Statement I is correct Presence of — CHO group in glucose is
tested by Fehling’s solution test where a reddish-brown On the other hand, amino acids with additional basic group have
precipitate of Cu 2O is formed. their isoelectric pH greater than 7.0 and decreasing pH below
isoelectric point (by adding acid solution) makes them cationic.
Hence, Statement II is incorrect. The given peptide with followings R1 and R2 are basic, will
30. PLAN This problem can be solved by performing hydrolysis of peptide remain protonated (cationic) at pH = 7.0.
and deciding the nature of product.
Chemical reaction and product formed after hydrolysis of given Peptide R1 R2
peptide can be represented as IV CH 2CONH 2 (CH 2 ) 4 NH 4
O
VI (CH 2 ) 4 NH 2 (CH 2 ) 4 NH 4
H
H O H O N VIII CH 2OH (CH 2 ) 4 NH 4
O O
N N IX (CH 2 ) 4 NH 2 CH 3
N NH—C NH N
CH2 O O H CH2 O Thus, 4 is the correct integer.
N
H
33. The D-form of given sugar is
O
CHO
H3O+
CMe3 CH2OH
+ CH2
+ –
H3N—CH2—CO2+ + O2C—CH—NH3 H O OH
(A) (B) CHOH Cyclisation H
+ * *
H3N CO2 H
HO—C—CHNH—CH2—C—OH CHOH
OH H
CH2 + O CH2 O OH *
H
H
CH2OH D-Pyranose
D- Sugar
(C ) (D )
Configurations at the three chiral carbons (starred) can be changed
(A) is glycine which is only naturally occurring amino acid. While
maintaining D-configuration. Hence, the total number of
(B), (C) and (D) are not the naturally occurring amino acids.
steroisomers of D-pyranose = 23 = 8
Hence, correct integer is (1).
Thus, the correct integer is 8.
31. PLAN A peptide linkage is hydrolysed to two free amino acids.
34. A decapeptide has nine peptide (amide) linkage as
O O O O O O
|| O O O O O
H2N ¾ CH ¾ C ¾ NH ¾ CH ¾ COOH
| |
R R¢ —CONH—
bond
Peptide
Therefore, on hydrolysis, it will absorb nine water molecules.
O Hence, total mass of hydrolysis product = 796 +18 × 9 = 958
* || *
H2N ¾ CH ¾ C ¾ OH + H2N ¾ CH ¾ COOH
| | Þ mass of glycine in hydrolysis product = 958 ´ 47 = 450
R R¢ 100
Þ number of glycine molecule in one
C* is chiral carbon tetrapeptide has four amino acids joined by 450
three peptide linkage. molecule of decapeptide = =6
75
¾ COOH group is on alanine part, thus it is at fixed C-terminal
position in each combination. 35. — OO- and —NH2 are two basic groups in lysine.
Glycine is optically inactive thus it cannot be on the N¾ 36. In structure (a), one ring has a free hemiacetal group, will
terminal side. Thus, possible combinations are hydrolyse into open chain in aqueous solution and therefore will
reduce Tollen’s reagent. Structure (b) has only acetal groups,
Phe-Gly-Val-Ala, Phe-Val-Gly-Ala,
will not hydrolyse in aqueous solution into open chain, will not
Val-Gly-Phe-Ala, Val-Phe-Gly-Ala
reduce Tollen’s reagent
Thus, in all four combinations are possible.
464 Biomolecules and Chemistry in Everyday Life
Aspartame
OH OH
(i) Aspartame has amine, acid, amide and ester groups. CH2
O CH2C6H5
+ ½½ ½
(ii) H3 N ¾ CH ¾ C ¾ NH ¾ CH ¾ COOCH3 Novolac
n
½
CH2 ¾ COO -
H+
(D) O
(iii) Aspartame ¾¾® H2N ¾ CH ¾ COOH + NH
H2 O
½
550 K
O 20 atm —C—NH—(CH2)5—
CH2 COOH –H2O Nylon-6 n
I Caprolactum (II)
CH2C6H5
½
Thus, the correct match is as follows :
H2N ¾ CH ¾ COOH + CH3OH (A) ® (III), (B) ® (I), (C) ® (IV), (D) ® (II)
II
3. Nylon-6, 6 (an amide) is a condensation copolymer because it is
(iv) II is more hydrophobic due to the presence of phenyl group.
obtained by condensation between adipic acid and
H+ hexamethylenediamine.
40. Sucrose ¾¾® D-glucose + D-fructose
H2 O
Biomolecules and Chemistry in Everyday Life 465
HO—C—CH2CH2CH2—O H + HO —C—(CH2)3—O H
Caprolactum 4-hydroxy butanoic acid
–H2O
O O
O O
—C—NH—(CH2)5 —C—NH—(CH3)5—
-----—C—(CH2)2CH2—O—C—(CH2)2CH2—O----
or
Ester linkage
O
The homopolymer obtained can also be represented as
—NH—(CH2)5—C—
n O
Nylon-6 ½½
—
[ C — (CH2)3 O —]n
Nylon-6 is prepared by ring opening polymerisation of
caprolactum. It is heated about 533 K in an inert atmospheric 10. (A) Molecule binding to a site other than the active site of
nitrogen about 4-5 hrs. Nylon-6 fibres are tough, possessing enzyme is called allosteric effect.
high tensile strength, as well as elasticity and lustre. They are (B) Molecule binding to the active site of enzyme is called
wrinkle proof and highly resistant to abrasion and chemicals competitive inhibitor.
such as acids and alkalis.
(C) Molecule crucial for communication in the body is called
7. Nylon-6,6 has following structure: receptor.
é O O ù (D) Molecule binding to the enzyme covalently is called poison.
ê ½½ ½½ ú
ú
ê N ¾ (CH2)6 ¾ N ¾ C ¾ (CH2)4 ¾ C ¾ Thus, the correct match is : A ® R, B ® P, C ® Q, D ® S
¾
ê ½ ½ ú 11. Given amino acid on reaction with NaNO 2 / H3O+ gives
ê H H ú
ë ûn diazotisation reaction which further evolves ¾ N 2 gas along
6 C-atoms 6 C-atoms with formation of carbocation. On further reaction with water, it
form HOOC ¾ (CH2 ) ¾ OH that undergoes polymerisation to
As it is a condensation polymer hence, each of its monomeric
give polymer.
unit must contain 6 carbon atoms in them. Hence, a combination
466 Biomolecules and Chemistry in Everyday Life
NaNO2/H3O+
O
H H CH3
HOOC—(CH2)4—NH2 HOOC—(CH2)4—N2 S
(Diazotisation) (D) R C NH
Aliphatic diazonium ion CH3
(Unstable)
–N2 N COOH
+ O
HOOC—(CH2)3—CH2 H
Penicillin
O –H –H2O NaHCO3(aq)
(Sodium
Becomes soluble
Polymerisation with effervescence
C—(CH2)4—O H HOOC—(CH2)4—OH hydrogen
carbonate) of CO2 gas
OH OH (Q)
–H2O
H O—(CH2)4—C == O Thus, the correct match is: A ® R; B ® S; C ® P; D ® Q
O O O
14. Nylon-6 or perlon is prepared by polymerisation of amino
-----O—(CH2)4—C—O—(CH2)4—C---- or —O—(CH2)4—C—
n caproic acid at high temperature. Caprolactam is first
(An ester group) (Polymer)
hydrolysed with water to form amino acid which on heating
12. The correct match is: undergoes polymerisation to give nylon-6.
A ® (Q) B ® (P) C ® (R) O
O
(A) Norethindrone It is an antifertility drug(Q ) containing NH Hydrolysis + –
synthetic progesterone derivative. [Other similar drug, is H3N—(CH2)5—C—O
ethinylestradiol (novestrol)].
Caprolactam D Polymerisation
(B) Ofloxacin It is an antibiotic (P ), O
i.e produced wholly or partly by chemical synthesis with low
concentration of microorganism.[Some other similar drugs : [ HN— (CH2)5—C —
]n
Penicillin, chloramphenicol, salvarsan etc.] Nylon-6
(C) Equanil (meprobamate) It is a mild tranquilizer for
relieving hypertension. It relieve anxiety, stress, excitement by 15. High density polythene is used in the manufacture of buckets,
inducing a sense of well being. dustbins etc.
(Other similar drug is chlordiazepoxide.) 16. Sodium lauryl sulphate [(CH3 (CH2 )10 CH2OSO-3 Na + )] =
Anionic detergent
13 Cetyltrimethyl + ammonium
Phenolic é CH3 ù
OH –OH group ê ½ ú
FeCl3 ê CH (CH ) ¾ N ¾ CH ú Br - = Cationic detergent
(A)
(Ferric chloride)
Violet colouration ê 3 2 15
½
3
ú
(R) ê CH ú
H 3C CH3 ë 3 û
Cl
Glyceryl oleate [(C17 H32COO)3 C3H5 ] = Non-ionic detergent
Chloroxylenol (Dettol) Sodium stearate [C17 H35COO- Na + ] = Anionic soap
17. Natural rubber is formed by polymerisation of isoprene.
OH
H 3C CººCH
H Dil. KMnO4/5°C/OH – CH2 C—CH CH2 CH2—C CH—CH2
H Pink colour of
—
(Baeyer’s test)
(B) (S)
KMnO4 gets CH3 CH3
H H discharged
O Polymerise
Norethindrone Ethylene
C C
—CH2—CH— CH2—CH2— —CH2—C CH—CH2—
Propylene
(Double bond)
H2/Pt
CH3 CH3
O
n n
Natural rubber
(C) H 2N S N Ethylene-propylene copolymer
H N
O
Primary Sulphapyridine This co-polymer is formed from propylene and ethylene.
amine (–NH2) CHCl3 + KOH (alc.)
Foul smell
(Carbylamine
of isocyanide n CH2 == CH + nCH2 == CH2 ¾® —CH2—CH CH2—CH2—
test) (P)
½
CH3 CH3
n
Biomolecules and Chemistry in Everyday Life 467
18. (a) Bakelite is used for making gears, protective coating and electrical fittings.
(b) Glyptal is used in the manufacture of paints and lacquers.
(c) PP is used in the manufacture of textile, packaging materials etc.
(d) Polyvinyl chloride (PVC) is used in the manufacture of rain coats, hand bags, leather clothes etc.
19. (a) Polystyreme- manufacturing toys (b) Glyptal- Paints and lacquers
(c) Polyvinyl chloride (PVC)- Raincoats (d) Bakelite- computer discs
Thus, the correct match is A ® (1), B ® (1), C ® (2), D ® (4)
20. The given structure is of aspirin which is used as analgesic.
21. Aluminium hydroxide Al(OH)3, cimetidine and ranitidine are antacids while phenelzine is not.
H CH(NO2)
N N
Me2N S C
S C
N NHMe
N N NHCN O
H
H
Ranitidine
Cimetidine
Phenelzine is a tranquilizer, not an antacid.
H
N ¾ NH2
H OH CH2OH
CH2OAc CH2OAc CH2OAc
C C H H C O O O O
24. H
H O H
H
O H
H
O
OH H (CH3CO)2O
C C C C
O OH H H
OAc H H OAc H H OAc H
H O
H C O C C
H OH H OAc H OAc H OAc
CHOH
Tri-acetylated cellulose Tri-acetylated cellulose
25. CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3
Polymerisations (CH3)3 XSiCl
(CH3)2SiCl2 + H2O HO—Si—OH HO—Si—O—Si—O —Si—OH CH3 —Si—O —Si— O—Si—O —Si—O —Si— CH3
—O—(CH2)6—O—C—(CH2)4—C—
n
Ester, condensation polymer
468 Biomolecules and Chemistry in Everyday Life
O O
HOOC—(CH 2 ) 4 —COOH
(d) When X = CN NC — (CH2 )4 — CN ¾ ¾¾ ® H2N(CH2 )6 NH2 ¾¾¾¾¾¾¾® —HN—(CH2)6—NH—C—(CH2)4—C—
H 2 / Ni
Heat Heat n
In author’s opinion (a) and (b) should also be the answer. Nylon, condensation polymer
O O O O
Heat
(a) HOCH2—(CH2)4—CH2OH + HO—C— (CH2)4—C—OH —O—(CH2)6 —O—C—(CH2)4—C—
n
Polyester, a condensation polymer
O O
H2/Ni
(b) H2N—C—(CH2)4—C—NH2 H2NCH2—(CH2)4—CH2NH2
Heat
O O O O
Heat
H2NCH2—(CH2)4—CH2NH2 + HO—C—(CH2)4—C—OH —NH—(CH2)6 —NH—C—(CH2)4—C—
n
Nylon, a condensation polymer
Answers
1. (b) 2. (c) 3. (b) 4. (b) 13. (a) 14. (d) 15. (a) 16. (d)
5. (a) 6. (d) 7. (d) 8. (c) 17. (b) 18. (a) 19. (d) 20. (c)
9. (d) 10. (d) 11. (a) 12. (d) 21. (a) 22. (c)
N2(g ) + O2 (g )
In petrol and
¾diesel
¾¾ ¾¾® 2NO(g ) + CH2 == CHCH == O+ H2O
engines
Acrolein
When the concentration of these pollutants is sufficiently high, a 3. In sunlight oxidising smog or photochemical smog or
chain reaction initiate because of the interaction of sunlight with Los-Angeles smog is formed. This smog is brown in colour. It
oxides of nitrogen. occurs in warm, dry and sunny climate. In presence of sunlight,
2NO(g ) + O2 (g ) ¾ ¾ ¾® 2NO2 (g )
Sunlight
NOx (N-oxides), O2 and unburnt hydrocarbons of air combine to
produce photochemical smog which mainly contains peroxyacetyl
NO2(g ) ¾¾
hn
® NO(g ) + [ O] O
Nascent
oxygen ||
nitrate (PAN). CH3 ¾ C ¾ O ¾ O ¾ NO2 (PAN)
O3 (g ) + NO(g ) ¾® NO2 (g ) + O2 (g )
Brown gas 4. The lowest region of atmosphere is troposphere which extends
2. The correct set of species responsible for the photochemical upto the height of 10 km (approx) from sea level. We live in the
smog is NO, NO2, O3 and hydrocarbons. Photochemical smog tropospheric region. It contains air, water vapour and dust which
appears in warm, dry and sunny climate which are obtained by can form clouds with the help of strong air movement.
the action of sunlight on unsaturated hydrocarbons and nitrogen Above the troposphere, stratospheric region extends upto 50 km
oxides. Following reactions are involved during the formation from sea level. It contains mainly N2 , O2 , O3 and little water
of photochemical smog. vapour. O3 in the stratosphere absorbs 99.5% of the sun’s harmful
(i) N2 (g ) + O2 (g ) ¾¾¾® 2NO(g ) UV raditions and thus protects the lives on the earth.
(Originates from
burning of fossil fuels) 5. The atmosphere between the heights 10 to 50 km above the sea
Sunlight level is stratosphere. Atmosphere is not of the same thickness at
(ii) 2NO(g ) + O2 (g ) ¾¾¾® 2NO2 (g ) heights.
hn
NO2 (g ) ¾¾¾® NO(g ) + [ O ] 6. The effect of release of CO2 gas into atmosphere is global
Nascent oxygen warming.
(iii) O (g ) + O2 (g ) - O (g ) 3
Reacts rapidly with NO
Environmental Chemistry 471
7. According to W.H.O. and US environmental protection agency 12. The amount of oxygen required by bacteria to break down the
guidelines, maximum allowable concentration of metals in organic matter present in a certain value of a sample of water is
drinking water are as follows : called biochemical oxygen demand (BOD). The amount of
BOD in the water is a measure of the amount of organic material
Metal Maximum concentration in the water, in terms of how much oxygen will be required to
(ppm or mg dm-3) break it down biologically. Clean water would have BOD value
Cd 0.005 of less than 5ppm whereas highly polluted water would have
Mn 0.05 (option-c) BOD value of 17 ppm or more.
Al 0.2
BOD value of clean water = 4 ppm
BOD value of highly polluted water = 18 ppm
Fe 0.2
Cu 3.0 (option-d) 13. N2 molecule has minimum role in the formation of photochemical
Zn 5.0 (option-a) smog. While CH2 == O, O3 and NO has major role. When
fossil fuels are burnt, a variety of pollutants are emitted. Two
8. Ozone is destroyed by CFCs in the upper stratosphere. of them are hydrocarbons (unburnt) and NO. When these
These compounds ultimately reach the stratosphere where they pollutants build upto high levels, a chain reaction occurs from
get broken down by powerful UV radiations and release their interaction with sunlight. The reactions involved in the
chlorine free radical. The chlorine free radicals react with ozone formation of photochemical smog are as follows:
and cause its depletion by converting it into chlorine monoxide NO2( g ) ¾¾ hn
® NO( g )+ O( g )
radical and molecular oxygen. O( g )+ O2( g ) dO3( g )
hn ·
CF2Cl2 (g ) ¾¾® Cl (g ) + C F2Cl(g ) NO( g ) + O3 ( g ) ¾® NO2( g ) + O2( g )
hn · O 3 reats with unburnt hydrocarbons to produce chemicals such
CFCl3 (g ) ¾¾® CFCl2 (g ) + C l(g ) as formaldehyde, acrolein and PAN.
· · 3CH4 + 2O3 ¾® 3CH2 == O + 3H2O
C l(g ) + O3 (g ) ¾¾® Cl O(g ) + O2 (g ) + CH2 ==CCH == O + CH3 C OONO2
Ozone holes increase the amount of UV radiation reaching the ½½
earth. These radiations can cause skin cancer, sunburns, ageing of O
(PAN)
skin.
9. Using plastic bags is wrong with respect to responsibility as a 14. Acid rain (pH = 3.5 - 5.6) constitutes strong acids like HNO3,
human being to protect our environment. Plastic bags are H2SO4 and H2SO3 which slowly react with marble (CaCO3 ) of
non-biodegradable in nature. It remains in the environment as Taj Mahal and make it disfigured and discoloured. Here, CaCO3
such and does not degraded by bacteria. If it is not disposed (marble) gets dissolved in acids.
properly then it may lead serious threat to the environment. The 2 H Å (aq)
activities that can be used to protect our environment are as CaCO3 (s) ¾¾¾® Ca 2 + (aq) + H2O(l ) + CO2 (g )
(Acid rain)
follows:
l
Restricting the use of vehicles. 15. Organic pigments (colourents) present in flower buds retain
l
Avoiding the use of flood lighted facilities. their colour in the oxidised form of the pigment as their nature is
itself oxidising in nature. When they comes in contact with
l
Setting up compost tin in gardens. moist SO2 (acid rain) of higher concentration, they get
10. Sun emits UV-radiations, which according to following EM decoloured and stiff.
categorisation have the wavelength range from 1 nm to 400 nm. SO2 + H2O ¾® H2SO4
H2SO4 ¾® H+ + HSO-4
Type Wavelength range
HSO-4 ¾® H+ + SO24 -
Radio wave > 0.1 m
Microwave 0.1 m to 1 mm Due to the release of H+ ion (acid), the flower get decoloured
and stiff.
Infrared wave 1 mm to 700 nm
As a result, flower eventually falls off from plants.
Visible rays 700 nm to 400 nm
Ultraviolet rays 400 nm to 1 nm 16. Molecular formula of peroxyacetyl nitrate (PAN) is
O
-3
X-rays 1 nm to 10 nm ½½
Gamma rays < 10- 3 nm CH3 ¾ C ¾ O ¾ O ¾ NO2. It is a secondary pollutant. It is
present in photochemical smog (oxidising or Los Angeles
Thus, option (d) with 200-315 nm range is the correct option.
smog). PAN is a powerful lachrymator or tear producer and it
11. Freons or CFCs or chlorofluoro carbons, i.e. CF2Cl2 is not the also causes breathing troubles.
common component of photochemical smog. This smog is
produced as the result of tropospheric pollution while freons are 17. Dissolved oxygen (DO) is the oxygen dissolved in water either
the components of stratospheric pollution. These are infact from atmosphere or by photosynthesis. The lower the
considered as the major cause of ozone layer depletion. concentration of DO in a water sample, the more polluted is the
water sample.
472 Environmental Chemistry
The concentration range of dissolved oxygen (DO) in cold water sample of water. Clean water or drinking water has a BOD value
reaches upto 10 ppm, but that in normal water (at room < 5 ppm.
temperature) is within 5 ppm. So, water filled with A, BOD = 10 ppm is polluted and water
18. CH4 is not present in the stratosphere and also it cannot diffuse filled with B, BOD = 20 ppm, is also polluted. But, B is more
polluted than A.
or escape into the stratosphere like freon-12 (CF2Cl2) from the
atmosphere. 20. In clean air, rain water picks up some acidic oxides like CO 2 and
In the stratosphere, ozone layer depletion take place mainly by SO 2 (obtained from volcanic eruptions). These substance make
chlorofluorocarbons (CFCs) like CF2Cl2 and the mechanism of the rain slightly acidic (pH = 5.6 - 6).
ozone layer depletion can be shown as:
· · 21. According to EEC (European Environment Commission),
hn
(i) CF2Cl2(g ) ¾¾® C l(g ) + C F2Cl(g ) [Option, (d)] excess of NO -3 (> 50 ppm) in drinking water may lead to
· methemoglobinemia (‘Blue baby syndrome’). It also may cause
(ii) C l(g) + O3 (g ) ¾® ClO· (g ) + O2 stomach-cancer.
(iii) ClO· (g ) + O(g ) ¾® Cl· (g ) + O2 (g ) [Option (b)] 22. For drinking water, the maximum recommended levels of some
·
metals, set by European Environment Commission (EEC) is
(iv) C l(g ) + H2O(g ) ¾® HOCl(g ) + H· (g )
[Present in the
stratosphere] Metal Max. concentration in ppm
· Zn 5
hn
(v) HOCl(g ) ¾¾® OH(g ) + Cl· (g ) [Option (c)]
Mn 0.05
Þ One Cl· can destroy or deplete 105 O3 molecules.
Fe 0.2
As (i) reaction is involved in the formation of photochemical
smog, not in ozone layer depletion. So option (a) is correct. Cu 3
19. BOD is defined as the amount of oxygen required by bacteria to As the concentration of Mn in the given water sample is more
break down the organic matter present in a certain volume of a than the recommended concentration. Thus, it makes water
unsuitable for drinking.
JEE ADVANCED
Solved Paper 2019
Paper 1
Section 1 (Maximum Marks : 12)
l This section contains FOUR (04) questions.
l Each question has FOUR options. ONLY ONE of these four options is the correct answer.
l For each question, choose the option corresponding to the correct answer.
l Answer to each question will be evaluated according to the following marking scheme:
Full Marks : + 3 If ONLY the correct options is chosen.
Zero Marks : 0 If none of the options is chosen. (i.e. the question is unanswered)
Negative Marks : - 1 In all other cases.
1. The correct order of acid strength of the following 4. Molar conductivity (L m) of aqueous solution of sodium
carboxylic acids is stearate, which behaves as a strong electrolyte, is
O recorded at varying concentrations (C) of sodium
O OH stearate. Which one of the following plots provides the
I H II H correct representation of micelle formation in the
OH H solution?
O
III MeO IV H3C OH (critical micelle concentration (CMC) is marked with
OH an arrow in the figures)
O
(a) III > II > I > IV
(b) I > II > III > IV Lm
Lm CMC
(c) II > I > IV > III
(d) I > III > II > IV (a) (b)
CMC
2. The green colour produced in the borax bead test of a
chromium (III) salt is due to
(a) Cr 2 O 3 (b) CrB ÖC ÖC
(c) Cr(BO 2 )3 (d) Cr2 (B 4O 7 )3
3. Calamine, malachite, magnetite and cryolite,
respectively, are CMC
Lm Lm CMC
(a) ZnCO 3 , CuCO 3 , Fe 2O 3 , Na 3 AlF6 (c) (d)
(b) ZnSO 4 , CuCO 3 , Fe 2O 3 , AlF3
(c) ZnSO 4 , Cu(OH)2 , Fe 3O 4 , Na 3 AlF6
(d) ZnCO 3 , CuCO 3 × Cu(OH)2 , Fe 3O 4 , Na 3 AlF6
ÖC ÖC
2 JEE Advanced Solved Paper 2019
5. Choose the reaction(s) from the following options, for (c) x1 will deflect towards negatively charged plate
which the standard enthalpy of reaction is equal to the (d) x3 is g-ray
standard enthalpy of formation.
8. Which of the following statement(s) is(are) correct
(a) 2C(g ) + 3 H2 (g ) ¾® C 2H6 (g ) regarding the root mean square speed (U rms) and
(b) 2H2 (g ) + O 2 (g )¾® 2H2O(l ) average translational kinetic energy (E av) of a molecule
3 in a gas at equilibrium?
(c) O 2 (g ) ¾® O 3 (g )
2 (a) Urms is inversely proportional to the square root of its
1
(d) S8 (s ) + O 2 (g ) ¾® SO 2 (g ) molecular mass
8
(b) Urms is doubled when its temperature is increased four times
6. A tin chloride Q undergoes the following reactions (not (c) Eav is doubled when its temperature is increased four times
balanced) (d) Eav at a given temperature does not depend on its molecular
mass
Q + Cl - ¾® X
Q + Me3N ¾® Y 9. Choose the correct option(s) for the following set of
Q + CuCl 2 ¾® Z + CuCl reactions.
(i) MeMgBr Conc. HCl
X is a monoanion having pyramidal geometry. Both Y C6H10O Q S
(ii) H2O
(major)
and Z are neutral compounds.
20 % H3PO4, 360 K
Choose the correct option(s).
(i) H2, Ni HBr, benzoyl peroxide
(a) There is a coordinate bond in Y T R U
(major) (ii) Br2, hn (major) D
(b) The central atom in Z has one lone pair of electrons (major)
10. Which of the following statement(s) is(are) true? (a) Both Y and Z are coloured and have tetrahedral shape
(a) The two six-membered cyclic hemiacetal forms of (b) Y is diamagnetic in nature while Z is paramagnetic
D-(+ ) -glucose are called anomers (c) In both Y and Z, p-bonding occurs between p-orbitals of
(b) Oxidation of glucose with bromine water gives glutamic acid oxygen and d-orbitals of manganese
(c) Monosaccharides cannot be hydrolysed to given (d) In aqueous acidic solution, Y undergoes disproportionation
polyhydroxy aldehydes and ketones reaction to give Z and MnO 2
(d) Hydrolysis of sucrose gives dextrorotatory glucose and
laevorotatory fructose 12. Each of the following options contains a set of four
molecules. Identify the option(s) where all four
11. Fusion of MnO 2 with KOH in presence of O 2 produces molecules posses permanent dipole moment at room
a salt W. Alkaline solution of W upon electrolytic temperature.
oxidation yields another salt X . The manganese (a) SO 2 , C 6H5Cl, H2Se, BrF5 (b) BeCl 2 , CO 2 , BCl 3 , CHCl 3
containing ions present in W and X , respectively, are Y
(c) NO 2 , NH3 , POCl 3 , CH3Cl (d) BF3 , O 3 , SF6 , XeF6
and Z. Correct statement(s) is (are)
13. Among B 2H 6, B 3N 3H 6, N 2O, N 2O 4, H 2S2O 3 and H 2S2O 8, 16. For the following reaction, the equilibrium constant K c
the total number of molecules containing covalent . ´ 10 17 .
at 298 K is 16
bond between two atoms of the same kind is .............
Fe2 + (aq) + S2 - (aq) - FeS (s)
14. On dissolving 0.5 g of a non-volatile non-ionic solute to 39 g When equal volumes of 0 .06 M Fe 2+
(aq) and
of benzene, its vapour pressure decreases from 650
0 .2 M S2 - (aq) solutions are mixed, the equilibrium
mmHg to 640 mmHg. The depression of freezing point
of benzene (in K) upon addition of the solute is ............ concentration of Fe2 + (aq) is found by Y ´ 10 - 17 M. The
(Given data : Molar mass and the molal freezing point value of Y is ...........
depression constant of benzene are 78 g mol - 1 and 17. At 143 K, the reaction of XeF4 with O 2F2 produces a
. K kg mol - 1 , respectively).
512 xenon compound Y . The total number of lone pair(s) of
electrons present on the whole molecule of Y is ............
15. Consider the kinetic data given in the following table
for the reaction A + B + C ¾® Product 18. Schemes 1 and 2 describe the conversion of P to Q and
R to S, respectively. Scheme 3 describes the synthesis of
Rate of T from Q and S. The total number of Br atoms in a
Experiment [A] [B] [C]
reaction
No. (mol dm- 3 ) (mol dm- 3 ) (mol dm- 3 ) molecule of T is ..............
(mol dm- 3s - 1 )
Scheme 1 NH2
1 0.2 0.1 0.1 6.0 ´ 10 - 5 (i) Br2(excess), H2O
(ii) NaNO2, HCl, 273 K
(iii) CuCN/KCN
2 0.2 0.2 0.1 6.0 ´ 10 - 5 (iv) H3O+, D
Q
(major)
(v) SOCl2, pyridine
3 0.2 0.1 0.2 . ´ 10 - 4
12 P
Scheme 2
4 0.3 0.1 0.1 9.0 ´ 10 - 5 (i) Oleum
(ii) NaOH, D
S
(iii) H+
(major)
-3 (iv) Br2, CS2, 273 K
The rate of the reaction for [ A] = 0 .15 mol dm , R
[ B] = 0 .25 mol dm - 3 and [C ] = 0 .15 mol dm - 3 is found Scheme 3
to be Y ´ 10 - 5 mol dm - 3s - 1 . The value of Y is ............ (i) NaOH, D
S T
(ii) Q
(major)
Paper 2
Section 1 (Maximum Marks : 32)
l This section contains EIGHT (08) questions.
l Each question has FOUR options for correct answer(s). ONE OR MORE THAN ONE of these four option(s) is (are) correct
options(s).
l For each question, choose the correct options(s) to answer the question.
l Answer to each question will be evaluated according to the following marking scheme:
Full Marks : + 4 If only (all) the correct option(s) is (are) chosen.
Partial Marks : + 3 If all the four options are correct but ONLY three options are chosen.
Partial Marks : + 2 If three or more options are correct but ONLY two options are chosen, both of which are correct
options.
Partial Marks : + 1 If two or more options are correct but ONLY one option is chosen and it is a correct option.
Zero Marks : 0 If none of the options is chosen (i.e. the question is unanswered).
Negative Marks : - 2 In all other cases.
l For example: in a question, if (A), (B) and (D) are the ONLY three options corresponding to correct answer, then
choosing ONLY (A), (B) and (D) will get +4 marks; choosing ONLY (A) and (B) will get +2 marks;
choosing ONLY (A) and (D) will get +2 marks; choosing ONLY (B) and (D) will get +2 marks;
choosing ONLY (A) will get +1mark; choosing ONLY (B) will get +1mark;
choosing ONLY (D) will get +1mark;
choosing no option (i.e. the question is unanswered) will get 0 marks; and
choosing any other combination of options will -1mark.
1. Choose the correct option(s) for the following reaction 2. Choose the correct option(s) that give(s) an aromatic
sequence compound as the major product.
CHO Hg2+,
(i) dil. H2SO4 (i) SOCl2 Br
(ii) AgNO3, NH4OH pyridine NaOEt
Q (a)
(iii) Zn-Hg, conc. HCl (ii) AlCl 3
MeO
Zn-Hg
conc. HCl UV, 500 K
R S (b) + Cl2 (excess)
CO2H
(b) 3. The ground state energy of hydrogen atom is
MeO MeO
-13.6 eV. Consider an electronic state Y of He+ whose
O
Q R energy, azimuthal quantum number and magnetic
quantum number are -3.4 eV, 2 and 0, respectively.
Which of the following statement(s) is(are) true for the
(c) MeO MeO state Y?
O (a) It is a 4d state
R S
OH (b) The nuclear charge experienced by the electron in this state
is less than 2e, where e is the magnitude of the electronic
CO2H charge
(d) (c) It has 2 angular nodes
MeO
MeO (d) It has 3 radial nodes
Q S
JEE Advanced Solved Paper 2019 5
4. Consider the following reactions (unbalanced). (b) Natural rubber is polyisoprene containing trans alkene units
(c) Cellulose has only a-D-glucose units that are joined by
Zn + Hot conc. H 2SO 4 ¾® G + R + X glycosidic linkages
Zn + conc. NaOH ¾® T + Q (d) Nylon-6 has amide linkages
G + H 2S + NH 4OH ¾® Z (a precipitate) + X + Y
7. The cyanide process of gold extraction involves
Choose the correct option(s).
(a) The oxidation state of Zn in T is +1 leaching out gold from its ore with CN - in the presence
(b) R is a V-shaped molecule of Q in water to form R. Subsequently, R is treated with
(c) Bond order of Q is 1 in its ground state T to obtain Au and Z. Choose the correct option(s).
(d) Z is dirty white in colour (a) Q is O 2 (b) Z is [Zn(CN)4 ]2-
(c) T is Zn (d) R is [Au(CN)4 ]-
5. With reference to aqua-regia, choose the correct option(s).
(a) Aqua-regia is prepared by mixing conc. HCl and conc. HNO 3 8. Which of the following reactions produce(s) propane
in 3 : 1 (v / v ) ratio as a major product?
(b) The yellow colour of aqua-regia is due to the presence of (a) H3C Cl Zn, dil. HCl
NOCl and Cl 2
(c) Reaction of gold with aqua-regia produces an anion having Br
Au in +3 oxidation state (b) H3C Br Zn
(d) Reaction of gold with aqua regia produces NO 2 in the
absence of air (c) H3C COONa NaOH, CaO, D
9. The decomposition reaction 11. Total number of hydroxyl groups present in a molecule
D of the major product P is ………
2N 2O 5(g) ¾® 2N 2O 4 (g) + O 2 (g) is started in a closed
cylinder under isothermal isochoric condition at an
(i) H2, Pd-BaSO4, quinoline
initial pressure of 1 atm. After Y ´ 10 3 s, the pressure P
(ii) Dil. KMnO4, (excess), 273 K
inside the cylinder is found to be 1.45 atm. If the rate
constant of the reaction is 5 ´ 10 -4 s -1 , assuming ideal
gas behaviour, the value of Y is ………
10. The mole fraction of urea in an aqueous urea solution 12. Total number of cis N ¾ Mn ¾ Cl bond angles (that is
Mn ¾ N and Mn ¾ Cl bonds in cis positions) present in
containing 900 g of water is 0.05. If the density of the
a molecule of cis [Mn(en)2 Cl 2 ] complex is ………
solution is 1.2 g cm -3 , then molarity of urea solution is
(en = NH 2CH 2CH 2NH 2 )
…… (Given data : Molar masses of urea and water are
60 g mol -1 and 18 g mol -1 , respectively) 13. The amount of water produced (in g) in the oxidation of
1 mole of rhombic sulphur by conc. HNO 3 to a
compound with the highest oxidation state of sulphur
is …… (Given data : Molar mass of water = 18 g mol -1 )
Answer the following by appropriately matching the lists Which of the following options has the correct
based on the information given in the paragraph. combination considering List-I and List-II?
(a) (II), (R) (b) (I), (P)
15. Consider the Bohr’s model of a one-electron atom
(c) (I), (T) (d) (II), (Q)
where the electron moves around the nucleus. In the
following List-I contains some quantities for the nth 17. List-I includes starting materials and reagents of
orbit of the atom and List-II contains options showing selected chemical reactions. List-II gives structures of
how they depend on n. compounds that may be formed as intermediate
List-I List-II products and/or final products from the reactions of
List-I.
(I) Radius of the n th orbit (P) µ n -2
List-I List-II
(II) Angular momentum of the electron in the nth (Q) µ n -1
(I) CN (i) DIBAL-H (P)
orbit CHO
(ii) Dil. HCl
(III) Kinetic energy of the electron in the nth orbit (R) µ n0 O (iii) NaBH4 CO2H
(iv) Conc. H2SO4
(IV) Potential energy of the electron in the nth (S) µ n1 O
orbit OH
(II) (i) O3 (Q)
(T) µ n2 (ii) Zn, H2O
H OH H OH S Se
, ,
HO H Br2 HO H O O H H
H OH Water H OH m¹0 m¹0 m¹0
(polar) (polar) (polar)
H OH H OH F
F F
CH2OH CH2OH
m1 m2
D-(+)-glucose Gluconic acid Br
, Cl Be Cl
(c) Monosaccharides can not be hydrolysed into polyhydroxy F F mnet» 0
m¹0
aldehydes and ketones. (non-polar)
(polar)
(d) Hydrolysis of sucrose gives D-glucose and L-fructose. Cl
Invertase m1 m2
C12H 22O11 + H 2O ¾¾¾¾® C6 H12O 6 + C6H12O 6 ,
D-glucose L-fructose O C O B Cl
or dextrorotatory or laevorotatory
mnet 0 m 0
Cl
Hence, options (a, c, d) are correct. (non-polar) (non-polar)
D 1 Cl
11. (a, c, d) MnO 2 + 2KOH + O 2 ¾® K 2MnO 4 + H 2O N N Cl
2 (W) potassium
manganate H C Cl , , , O P Cl ,
O O H H H
+ 2– Cl
K2MnO4 (aq) 92K (aq) + MnO 4 (aq) Cl m¹0
m¹0 m¹0 m¹0
(W) (Y) (polar)
(polar) (polar) (polar)
O F
é
3
sp- hybridisation, F
é Mn tetrahedral (manganate ion) é H
B O
F F
–
O O Green coloured H C Cl , , , Xe
O complex F F O O
H m¹0 m=0
MnO 2- m¹0 F F
4 ion has one unpaired electrons, therefore it gives (polar) (non-polar)
(polar) F
d-d transition to form green colour. Y complex has m»0
paramagnetic nature due to presence of one unpaired electron. (non-polar)
In aqueous solution, Thus, options (a, c) are correct.
Electrolytic oxidation 13. (4.00) N 2O, N 2O 4 , H 2S2O 3 and H 2S2O 8 molecules are
K 2MnO 4 + H 2O ¾¾¾¾¾¾¾®H 2 + KOH + KMnO 4
( W) ( X) containing covalent bond between two atoms.
S
O
sp3, tetrahedral
KMnO4(aq)
D
K+ + MnO4- éMn (purple coloured é
é N ºº N ¾® O , S
O O
(Z) (N2O) N¾N ,
O O complex ion)
HO OH O O
O O (N2O4)
MnO -4 ions gives charge transfer spectrum in which a fraction of (H2S2O3)
electronic charge is transferred between the molecular entities. O O
H H
Electrolytic H
Q MnO 24- ¾¾¾® MnO 4- +e -
(Y) oxidation ( Z) S S , B B
In acidic medium, Y undergoes disproportionation reaction. HO O¾O OH H H
O O H
3MnO 24- (aq) + 4H+ ¾® 2MnO -4 + MnO 2 + 2H 2O (H2S2O8) (B2H6)
(Y) (Z)
H
MnO 2-
4 and MnO -4 both ions form p-bonding between |
(Y) ( Z) H B H
p-orbitals of oxygen and d-orbitals of manganese. N N
Thus, options (a, c, d) are correct.
12. (a,c) Key Idea Dipole moment of a bond depends on the B B
difference in the electronegativities of bonded atoms. H N H
More is the difference in the electronegativities, greater (B3N3H6)
will be the dipole moment. Also,
For symmetrical molecule, m = 0 B 2H 6 and B 3N 6H 6 have polar bond, but do not have same kind
of atom.
For unsymmetrical molecule, m ¹ 0
10 JEE Advanced Solved Paper 2019
14. (1.02) Key Idea First calculate, molar mass of solute using the 16. (8.9) Given, equilibrium constant (K c) at 298 K = 1.6 ´ 1017
p ° - ps nsolute
formula, = and then calculate DTf Fe2+ (aq) + S2- (aq) 1 FeS (s)
p° nsolute + nsolvent
by applying the formula; DTf = K f ´ m. At initial concentration 0.06 M 0.2 M –
(Before mixing)
At initial concentration 0.03 M 0.1 M –
When 0.5 g of non-volatile solute dissolve into 39 gm of (After mixing)
benzene then relative lowering of vapour pressure occurs. At equilibrium 0.03- X 0.1 – 0.03 = 0.07
–
Hence, vapour pressure decreases from 650 mmHg to
3
640 mmHg. [Here, K c >>10 , thus limiting reagent will be consumed
Given, vapour pressure of solvent (p°) = 650 mmHg almost completely, 0.03 - X = 0 \ X = 0.03]
From equilibrium constant,
Vapour pressure of solution (ps) = 640 mmHg
[FeS]
Weight of non-volatile solute = 0.5 g KC =
[Fe2+][S2- ]
Weight of solvent (benzene) = 39 g
1
From relative lowering of vapour pressure, KC = [For FeS(s) = 1 mol L -1 ]
nsolute X ´ 0.07 (Pure solid)
p ° - ps
= xSolute = 1
p° nsolute + nsolvent 17
1.6 ´ 10 =
0.5 X ´ 0.07
650 - 640 1
= molar mass X= 17
= 8.9 ´ 10-17
650 0.5 39 1.6 ´ 10 ´ 0.07
+
molar mass 78 Given, X = Y ´10-17 = 8.9 ´10-17
0.5 \ Y = 8.9
10 molar mass
= 17. (19) XeF4 reacts with O 2F2 to form XeF6 × O 2F2 is fluoronating
650 0.5
+ 0.5 reagent.
molar mass
143 K
0.5 + 0.5 ´ molar mass = 65 ´ 0.5 XeF4 + O 2F2 ¾¾® XeF6 + O 2
\ Molar mass of solute = 64 g (Y)
+ N2 –
From exp-Ist, Cl is displace
Rate = 6.0 ´ 10-5 mol dm -3 s -1 by CN–ion
Br
6.0 ´ 10-5 = k[0.2]1 [01
. ]1 Br 2, 4, 6 tribromo
¾¾¾®
Br Br Br
(S) (T)
(Major)
T compound has total number of Br atom =4
Paper 2
1. (a, b)
C C CH2 CHO C CH CH2 CHO
(i) Hg2+, dil. H2SO4
Hydration of Alkyne OH
CH3O CH3O
Keto–enol
Tautomerism
(ii) AgNO3+NH4OH
C CH2 CH2 C O– C CH2 CH2 CHO
(Tollen's reagent)
CH2
Clemmensen reduction CH2 substitution reaction
CH3O CH2 CH3O C
(S)
O
(R)
2. (c, d) Key Idea An aromatic compound must be cyclic and planar. It must follow ( 4 n + 2 ) e - rule and have the conjugated system in it.
(a) Br OEt
NaOEt Dimerise
+
Substitution product Ellimination product (Non-aromatic)
(b) Benzene react with Cl 2 (excess) in presence of UV light and 500 K of temperature to form benzene hexachloride (non-aromatic).
Cl
Cl Cl
UV
+ Cl2 (excess) 500 K
Cl Cl
Cl
(Non-aromatic)
12 JEE Advanced Solved Paper 2019
(c) CH3 (iii) Red hot iron tube 0 +3
(i) Alc. KOH
CH3C CH Au+ HNO 3 +4HCl ¾® AuCl –4 + H 3O + + NO + H 2O
Br (ii) NaNH2 873 K (Trimerisation)
Br Oxidation
CH3
Hence, option (c) is correct.
(d) Reaction of gold with aqua-regia produces NO gas in
absence of air.
CH3 CH3 Hence, option (d) is incorrect.
(Aromatic)
6. (a, d) The explanation of given statements are as follows:
H (a) Teflon is prepared by heating tetrafluoroethene in
s Na+ presence of persulphate catalyst at higher pressure.
Persulphate
(d) NaOMe nCF2 ==CF2 catalyst
CF2 CF2
–MeOH
Thermoplastic Polymer
(Aromatic ion) (PTFE)
Thus, (c) and (d) options are correct. Thus, option (a) is correct.
(b) Natural rubber is polyisoprene containing cis alkene units.
3. (a, c) Given, ground state energy of hydrogen atom = - 136
. eV
CH2 CH2 n
Energy of He + = - 34
. eV, Z = 2
nCH2 C CH CH2 C C
. ´ Z2
136
Energy of He + , E = - eV CH3 H
n2 CH3 cis-ployisoprene unit
- 136. ´ (2)2 . ´4
136 Isoprene (natural rubber)
. eV =
- 34 Þ n= Þ n= 4
n2 34
. Thus, option (b) is incorrect.
Given, azimuthal quantum number () l = 2(d – subshell (c) Cellulose has only b-D-glucose units that are joined together
by glycosidic linkages as shown in the following structure:
Magnetic quantum number (m) = 0
\ Angular nodes ()l =2 OH OH OH OH
Radial node = n - l - 1 = 4 - 2 - 1 = 1 O
O O
nl = 4d state O OH O
O OH 1 4 OH OH O
Hence, options (a), (c) are correct. O
,
S C O
NH D, H2O –n H 2 O
[H2N(CH2)5COOH] C (CH2)5 NH
O O D
Nylon-6 n
Thus, option (b) is correct.
Caprolactam
When Zn is react with conc. NaOH then H 2 gas is evolved and
Na2ZnO2 is obtained. Thus, option (d) is correct.
Zn + 2NaOH (conc.) ¾® Na2ZnO2 + H 2 7. (a, b, c) Cyanide process of gold extraction involves leaching
out gold from its ore with CN - in the presence of O 2 (Q) in
( T) ( Q)
In ground state, H—H (Q) (bond order = 1)
Thus, option (c) is correct. water to form [Au(CN)2 ]- (R).
The oxidation state of Zn in T(Na 2ZnO 2) is +2 When [Au(CN)2 ]- reacts with Zn (T), it froms [Zn(CN)4 ]2- (Z)
Thus, option (a) is incorrect. and Au.
ZnSO4 + H 2 S + NH 4 OH ¾® ZnS¯ + 2H 2 O + (NH 4 )2 SO4 The corresponding reactions are as follows :
( G) ( Z) ( X) (Y)
ZnS (Z) compound is dirty white coloured. H O + O2 ( Q)
4 Au (s) + 8 CN - (aq) ¾¾¾¾®
2
4[Au(CN)2 ]- + 4OH - (aq)
Thus, option (d) is correct. (R)
5. (a, b, c) The explanation of given statements are as follows: 2[Au(CN)2]- (aq) + Zn(s) ¾® [Zn(CN)4 ]2- (aq) + 2 Au(s)
( R) ( T)
(a) Aqua-regia is prepared by mixing conc. HCl and conc.
HNO 3 in 3:1 (v/v) ratio and is used in oxidation of gold Hence, options (a, b, c) are correct.
and platinum. Hence, option (a) is correct.
8. (a, c) The given reactions takes place as follows:
(b) Yellow colour of aqua-regia is due to its decomposition
into NOCl (orange yellow) and Cl 2 (greenish yellow). (1)
Hence, option (b) is correct. Cl Zn, dil. HCl
CH3 CH2 CH3
(c) When gold reacts with aqua-regia then it produces AuCl -4 (a) CH3 (Propane)
anion complex in which Au has +3 oxidation state.
JEE Advanced Solved Paper 2019 13
Br
11. (6)
Br Zn
CH3 CH CH2 + ZnBr2
(b) CH D (i) H2, Pd–BaSO4
3
(Elimination (Propene)
reaction) Quinoline (reduction)
(Triple bond converts into
CH3 NaOH, CaO, D
CH3 CH2 CH3+ CO2 double bond)
Electrolysis
(c) COONa (Propane)
C OH (Complete hydrolysis
(T ) Hence, correct match of II is (P , S ,U).
of —CN give —COOH
O and ester also get hydrolysed
into —COOH and alcohol ) Hence, correct matching from list-I and list-II on the basis of
CH2 CH2 OH given option is (II), P , S , U.
(iv) conc. H2SO4
H 2O +
D O
(Q) CH2 OH
(R)
Hence, correct match of (III) are T , Q, R.