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X9 MR K2 y Udriopxe Di F9 V

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Equivalent Concept 2.

CHAPTER

2 Equivalent Concept

EXERCISE I (JEE MAIN)

Oxidation–Reduction

1. A compound contains X, Y and Z atoms. The 6. In which of the following compound, the oxidation
oxidation states of X are +a, Y is −b and Z is state of sulphur is +7?
−c. The molecular formula of the compound is (a) Na2S2O8 (b) H2S2O7
XmYnZr. Therefore, among the given relations,
(c) H2SO4 (d) None of these
which one is correct?
(a) am + bn + cr = 0 (b) am + bn = cr 7. In which of the following compound, iron has the
(c) am + cr = bn (d) bn + cr = am lowest oxidation state?
(a) Fe(CO)5
2. What is the oxidation state of Xe in Ba2XeO6?
(b) Fe2O3
(a) 0 (b) +4
(c) K4[Fe(CN)6]
(c) +6 (d) +8
(d) FeSO4 ⋅ (NH4)2SO4 ⋅ 6H2O
3. When K2Cr2O7 is converted into K2CrO4, the
change in oxidation number of Cr is 8. Which of the following have been arranged in the
order of decreasing oxidation number of sulphur?
(a) 0 (b) 6
(c) 4 (d) 3 (a) H2S2O7 > Na2S4O6 > Na2S2O3 > S8
(b) SO2+ > SO42− > SO32− > HSO4−
4. The formula of brown ring complex is
(c) H2SO5 > H2SO3 > SCl2 > H2S
[Fe(H2O)5(NO)]SO4. The oxidation state of
iron is (d) H2SO4 > SO2 > H2S > H2S2O8

(a) +1 (b) +2 9. The oxidation state of iron in oxygenated


(c) +3 (d) 0 haemoglobin is
(a) +1 (b) +2
5. In the reaction: 3Br2 + 6CO32− + 3H2O → 5Br− +
BrO3− + 6HCO3− (c) +3 (d) Zero

(a) Bromine is oxidized and carbonate is reduced. 10. The oxidation numbers of C in HCN and HNC,
(b) Bromine is oxidized and water is reduced. respectively, are
(c) Bromine is both oxidized and reduced. (a) +2, +2 (b) +2, +4
(d) Bromine is neither oxidized nor reduced. (c) +4, +4 (d) −2, −2

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 1 7/8/2019 2:25:27 PM


11. The oxidation number of carbon in carbon 20. The oxidation state of C in C6H12O6 is equal to the
suboxide (C3O2) is oxidation state of C in
(a) +2/3 (b) +4/3 (a) HCOOH (b) HCHO
(c) +4 (d) −4/3 (c) CH4 (d) CO

12. The oxidation states of the most electronegative 21. An oxide of iron contains 30% oxygen by mass.
element in the products of the reaction, BaO2 with The oxidation state of iron in this oxide is (Fe =56)
dil. H2SO4 are (a) +1 (b) +2
(a) 0 and −1 (b) −1 and −2 (c) +3 (d) +4
(c) −2 and 0 (d) −2 and +1 22. The strongest reducing agent is
(a) H2S (b) H2O
13. The pair of compounds having metals in their
(c) H2Se (d) H2Te
highest oxidation state is
(a) MnO2, FeCl3 23. During developing of an exposed camera film, one
step involves in the following reaction.
(b) [MnO4]−, CrO2Cl2
(c) [Fe(CN) 6]3−, [Co(CN)3] HO OH + 2AgBr + 2OH–
(d) [NiCl4]2−, [CoCl4]−

14. The oxidation number of phosphorus in Mg2P2O7 (Hydroquinol)


is
(a) +5 (b) −5 O O + 2Ag + 2H2O + 2Br–
(c) +6 (d) −7
Which of the following best describes the role of
15. The sum of oxidation states of all carbon atoms in hydroquinol?
toluene molecule is
(a) It acts as an acid.
(a) −1 (b) −7/8 (b) It acts as a reducing agent.
(c) −8/7 (d) −8 (c) It acts as an oxidant.
16. The oxidation number of K in KO2 is (d) It acts as a base.
(a) +4 (b) +1 24. A redox reaction is
(c) +1/2 (d) −1/2 (a) exothermic.
(b) endothermic.
17. The oxidation state of chromium is +6 in
(c) neither exothermic nor endothermic.
(a) K3CrO8 (b) Cr2O3 (d) either exothermic or endothermic.
(c) Cr2(SO4)3 (d) CrO5
25. The decomposition of KClO3 to KCl and O2 on
18. The oxidation states of N in aniline and heating is an example of
nitrobenzene are, respectively, (a) intermolecular redox change
(a) −3, +3 (b) −1, +5 (b) intramolecular redox change
(c) −3, +5 (d) −3, +1 (c) disproportionation or auto redox change
19. Which of the following statements is true about (d) All the above
oxidation state of S in Na2S4O6? 26. Which of the following reaction is non-redox?
(a) All S–atoms are in +2.5 state. (a) 2NaNO3 → 2NaNO2 + O2
(b) All S–atoms are in +2 state. (b) CaO + SiO2 → CaSiO3
(c) Two S–atoms are in 0 state and other two is in (c) Fe + H2 SO 4 → FeSO 4 + H2
+5 state. (d) 4Ag + 8 CN − + O2 + 2H2 O →
(d) Two S–atoms are in −1 state and other two is
4[Ag(CN)2 ]− + 4OH−
in +6 state.

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 2 7/8/2019 2:25:28 PM


27. Which of the following reaction is not a (a) 5:1 (b) 1:5
disproportionation reaction? (c) 2:3 (d) 3:2
(a) Br2 + CO32 − + H2 O → Br − + BrO3− + HCO3−
32. For the process, NO3− → N 2 O, the number of H2O
(b) P4 + OH − + H2 O → PH3 + H2 PO2−
molecules needed for balancing in acid medium
(c) H2 S + SO2 → S + H2 O and the side in which it should be added are
(d) H2 O2 → H2 O + O2 (a) 2, right (b) 2, left
28. Which of the following reaction is an example of (c) 5, right (d) 5, left
comproportionation reaction?
33. In the process, NO 2− → NH3, the number of
(a) Cl2 + OH − → Cl − + ClO3− + H2 O OH– ions and the side in which they should be
(b) CH4 + O2 → CO2 + H2 O added in balancing are
(c) H2 S + SO2 → S + H2 O (a) 7, right (b) 7, left
(d) NaOH + HCl → NaCl + H2 O (c) 4, left (d) 5, right
29. An oxide, X2O3 is oxidized to XO4− by Cr2O72− 34. For the redox reaction,
in acid medium. The number of moles of X2O3
Zn + NO3− → Zn2+ + NH4+
oxidized per mole of Cr2O72− is
(a) 3/4 (b) 3 in basic medium, the coefficients of Zn, NO3− and
OH− in the balanced equation, respectively, are
(c) 3/2 (d) 2/3
(a) 4, 1, 7 (b) 7, 4, 1
30. The number of electrons involved in the reduction
(c) 4, 1, 10 (d) 1, 4, 10
of nitrate ion to hydrazine is
(a) 8 (b) 7 35. The ratio of coefficients of HNO3, Fe(NO3)2 and
(c) 5 (d) 3 NH4NO3 in the following redox reaction,

31. In the disproportionation reaction (unbalanced), Fe + HNO3 → Fe(NO3)2 + NH4NO3 + H2O

Br2 + OH − → Br − + BrO3− + H2 O, respectively


the ratio of Br2 molecules undergoing oxidation (a) 10 : 1 : 4 (b) 10 : 4 : 1
and reduction is (c) 4 : 10 : 1 (d) 4 : 1 : 10

Equivalent Concept
2En
36. An oxide of metal have 20% oxygen, the equivalent (a) (b) 2mEn
weight of oxide is m
(a) 32 (b) 48 E
(c) (d) En
(c) 40 (d) 52 n
39. Equivalent weight of a metal is 18.67. When it
37. On heating in contact with tin, sulphurated
reacts with chlorine, the mass of metal which will
hydrogen (V.D. = 17) is converted into hydrogen
form 162.52 g of metal chloride is
without change in volume. The equivalent weight
of sulphur is (a) 143.83 g (b) 56 g
(a) 32 (b) 16 (c) 14.4 g (d) 5.6 g
(c) 24 (d) 34 40. How many grams of Mg would have to react in
order to liberate 4 NA electrons?
38. An element (X) having equivalent mass E forms an
oxide XmOn. The atomic mass of element should (a) 12 g (b) 24 g
be (c) 48 g (d) 96 g

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 3 7/8/2019 2:25:30 PM


41. Equivalent weight of K2CrO4 when it reacts with 49. In the following unbalanced redox reaction,
AgNO3 to give Ag2CrO4 is
Cu3P + Cr2O72− → Cu2+ + H3PO4 + Cr3+,
(a) infinite (b) M
M M the equivalent weight of H3PO4 is
(c) (d)
2 3 (a) M/3 (b) M/6
42. The equivalent weight of NaHC2O4 in reaction (c) M/7 (d) M/8
with NaOH is 50. The equivalent weight of Cl2 acting as oxidizing
(a) 112 (b) 56 agent is
(c) 224 (d) 84 (a) 72 (b) 35.5
43. The equivalent weight of NaHC2O4 in reaction (c) 7.1 (d) 23.67
with HCl is 51. H2O2 disproportionates into H2O and O2. The
(a) 112 (b) 56 equivalent weight of H2O2 in this reaction is
(c) 224 (d) 8 (a) 34 (b) 17
44. In a reaction, calcium phosphate is producing (c) 68 (d) 8.5
calcium hydrogen phosphate. The equivalent weight 52. The equivalent weight of H2SO4 in the reaction:
of calcium phosphate in this process is (Ca = 40,
P = 31) 2KMnO4 + 3H2SO4 + 10HCl →
2MnSO4 + K2SO4 + 5Cl2 + 8H2O, is
(a) 310 (b) 155
(c) 103.33 (d) 51.67 M
(a) (b) M
2
45. The equivalent weight of MnSO4 is half of its 3M 3M
molecular weight when it is converted to (c) (d)
10 5
(a) Mn2O3 (b) MnO2 53. What would be the equivalent weight of reductant
(c) MnO4− (d) MnO42− in the reaction? (Fe = 56)
46. Equivalent weight of MnO4− in acidic, basic, 2[Fe(CN)6]−3 + H2O2 + 2OH− →
neutral medium is in the ratio of 2[Fe(CN)6]4− + 2H2O + O2
(a) 3 : 5 : 15 (b) 5 : 3 : 1 (a) 17 (b) 212
(c) 5 : 1 : 3 (d) 3 : 15 : 5
(c) 34 (d) 32
47. In the following reaction (unbalanced), equivalent 54. In the Haber’s process, the equivalent weight of
weight of As2S3 is related to its molecular weight, ammonia is
M, by
(a) M (b) M/3
As2S3 + H+ + NO3− →
NO + H2O + AsO43− + SO42− (c) 2M/3 (d) 3M

(a) M/2 (b) M/4 55. Equivalent mass of a bivalent metal is 32.7.
Molecular mass of its chloride is
(c) M/28 (d) M/24
(a) 68.2 (b) 103.7
48. In the following redox reactions, NH3 appears (c) 136.4 (d) 166.3
either in reactant or product. In which case, the
equivalent weight of NH3 is maximum? 56. In the reaction,
(a) N2 + 3H2 → 2NH3 Zn + HNO3 → Zn(NO3)2 + NO + H2O,
(b) 4NH3 + 5O2 → 4NO + 6H2O the equivalent weight of HNO3 is
(c) 2NH3 + 2Na → 2NaNH2 + H2
(a) M (b) 4M/3
(d) Equal in all cases
(c) 8M/3 (d) 2M/3

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 4 7/8/2019 2:25:31 PM


57. Equivalent weight of H2SO4 in the reaction 64. How many grams of H2S will react with 6.32 g
Mg + 2H2SO4 → MgSO4 + SO2 + 2H2O, is KMnO4 to produce K2SO4 and MnO2? (K = 39,
Mn = 55)
(a) 98 (b) 49
(a) 4.08 g (b) 0.85 g
(c) 196 (d) 32.67
(c) 0.51 g (d) 2.04 g
58. A metal carbonate on heating is converted to
metal oxide and is reduced to 60% of its original 65. The oxide of a metal contains 52.91% of the
weight. The equivalent weight of the metal is metal. If the formula of the metal oxide is M2O3,
then what is the atomic mass of the metal?
(a) 5 (b) 25
(a) 8.99 (b) 26.96
(c) 60 (d) 70
(c) 17.97 (d) 53.93
59. A quantity of 0.298 g of the chloride of a metal
yielded 0.348 g of the sulphate of the same metal. 66. The equivalent weight of an element is 25. If its
The equivalent weight of the metal is specific heat is 0.085 cal/K-g, its exact atomic mass
should be
(a) 12 (b) 20
(a) 75.29 (b) 75
(c) 39 (d) 41.5
(c) 50 (d) 50.8
60. NH3 is oxidized to NO by O2 in basic medium.
67. The vapour density of metal chloride is 77. If its
The number of equivalents of NH3 oxidized by
equivalent weight is 3, its atomic mass will be
1 mole of O2 is
(a) 3 (b) 6
(a) 4 (b) 5
(c) 9 (d) 12
(c) 6 (d) 7
68. One gram of the acid C6H10O4 requires 0.768 g
61. The number of moles of Cr2O72− needed to oxidize of KOH for complete neutralization. How
0.136 equivalent of N2H5+ through the reaction many neutralizable hydrogen atoms are in this
N2H5+ + Cr2O72− → N2 + Cr3+ + H2O is molecule?
(a) 4 (b) 3
(a) 0.023 (b) 0.091
(c) 2 (d) 1
(c) 0.136 (d) 0.816

62. A certain amount of a reducing agent reduces 69. A quantity of 1.878 g of a metal bromide when
x mole of KMnO4 and y mole of K2Cr2O7 in heated in a stream of hydrogen chloride gas is
different experiments in acidic medium. If the completely converted to the chloride weighing
change in oxidation state in reducing agent is same 1.00 g. The specific heat of the metal is 0.14
in both experiments, x : y is cal/ºc-g. What is the molecular weight of the
bromide? (Br = 80, Cl = 35.5)
(a) 5 : 3 (b) 3 : 5
(c) 5 : 6 (d) 6 : 5 (a) 45.54 (b) 125.54
(c) 285.54 (d) 205.54
63. When a metal carbonate is treated with excess of
dilute sulphuric acid, the weight of metal sulphate 70. Potassium sulphate is isomorphous with potassium
formed is 1.43 times the weight of carbonate chromate which contains 26.79% by mass of
reacted. What is the equivalent weight of metal? chromium. The atomic mass of chromium is
(a) 23 (b) 20 (a) 24 (b) 32
(c) 39 (d) 12 (c) 51.96 (d) 53.2

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 5 7/8/2019 2:25:31 PM


Volumetric Analysis

71. Equal volumes of 10% (w/v) H2SO4 solution and experiments. The volumes of the acids A and B
10% (w/v) NaOH solution are mixed. The nature required were 10 ml and 40 ml, respectively. How
of the resulting solution will be many volumes of A and B are to be mixed in order
(a) neutral (b) acidic to prepare 1 litre of normal acid solution?
(c) basic (d) unpredictable (a) 179.4, 820.6 (b) 820.6, 179.4
72. A quantity of 0.62 g of Na2CO3 ⋅ H2O is added (c) 500, 500 (d) 474.3, 525.7
to 100 ml of 0.1 N-H2SO4 solution. The resulting 79. A sample of an alloy of silver weighing 0.50
solution would be g and containing 90% silver was dissolved in
(a) acidic (b) alkaline conc. HNO3 and silver was analysed by Volhard
(c) neutral (d) buffer method. A volume of 25 ml of a KCNS solution
was required for complete precipitation. The
73. The volume of 0.10 M-AgNO3 should be added normality of KCNS solution is (Ag = 108)
to 10.0 ml of 0.09 M-K2CrO4 to precipitate all the
chromate as Ag2CrO4 is (a) 4.167 (b) 0.167
(c) 3.136 (d) 0.125
(a) 18 ml (b) 9 ml
(c) 27 ml (d) 36 ml 80. A 0.5 g sample of KH2PO4 is titrated with 0.1 M
NaOH. The volume of base required to do this is
74. What volume of 0.18 N-KMnO4 solution would 25.0 ml. The reaction is represented as
be needed for complete reaction with 25 ml of
0.21 N-KNO2 in acidic medium? H2PO4− + OH− → HPO42− + H2O.
(a) 57.29 ml (b) 11.67 ml The percentage purity of KH2PO4 is (K = 39,
(c) 29.17 ml (d) 22.92 ml P = 31)
75. A 0.1 M-KMnO4 solution is used for the following (a) 68% (b) 34%
titration. What volume of the solution will be (c) 85% (d) 51%
required to react with 0.158 g of Na2S2O3?
81. A solution of H2O2 is titrated with a solution of
S2O32− + MnO4− + H2O
KMnO4. The reaction is
→ MnO2(s) + SO42− + OH−
2MnO4− + 5H2O2 + 6H+
(a) 80 ml (b) 26.67 ml
→ 2Mn2+ + 5O2 + 8H2O
(c) 13.33 ml (d) 16 ml
76. One litre of a solution contains 18.9 g of HNO3 It requires 50 ml of 0.1 M-KMnO4 to oxidize 10
and one litre of another solution contains 3.2 g of ml of H2O2. The strength of H2O2 solution is
NaOH. In what volume ratio must these solutions (a) 4.25% (w/v) (b) 8.5% (w/v)
be mixed to obtain a neutral solution?
(c) 0.85% (w/v) (d) 1.7% (w/v)
(a) 3:8 (b) 8:3
82. For the standardization of Ba(OH)2 solution,
(c) 15:4 (d) 4:15
0.204 g of potassium acid phthalate was weighed
77. What volume of gaseous NH3 at 0°C and 1 atm which was then titrated with Ba(OH)2 solution.
will be required to be passed into 30 ml of N– The titration indicated equivalence at 25.0 ml of
H2SO4 solution to bring down the acid strength of Ba(OH)2 solution. The reaction involved is
this solution to 0.2 N?
KHC8H4O4 + Ba(OH)2
(a) 537.6 ml (b) 268.8 ml → H2O + K+ + Ba2+ + C8H4O42−
(c) 1075.2 ml (d) 371.3 ml
The molarity of the base solution is (K = 39)
78. A 26 ml of N-Na2CO3 solution is neutralized (a) 0.04 M (b) 0.03 M
by the solutions of acids A and B in different (c) 0.02 M (d) 0.01 M

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 6 7/8/2019 2:25:32 PM


83. A volume of 12.5 ml of 0.05 M selenium dioxide, How many grams of borax is necessary to
SeO2, reacted with exactly 25.0 ml of 0.1 M – neutralize 25 ml of 0.2 M solution of hydrochloric
CrSO4. In this reaction, Cr2+ is converted to Cr3+. acid? (B = 10.8)
To what oxidation state the selenium is converted (a) 0.4765 g (b) 0.953 g
by the reaction?
(c) 9.53 g (d) 1.906 g
(a) 0 (b) +1
90. A volume of 50 ml of 0.1 M metal salt reacts
(c) +2 (d) +4 completely with 25 ml of 0.1 M sodium sulphite.
84. The chromate ion may be present in waste water In the reaction, SO32− is oxidized to SO42−. If the
from a chrome planting plant. It is reduced to oxidation number of metal in the salt is +3, then
insoluble chromium hydroxide, Cr(OH)3 by what is its new oxidation number?
dithionation, in basic solution: (a) 0 (b) +1
S2O42− + CrO42− + H2O + OH− (c) 2 (d) 4
→ SO32− + Cr(OH)3
91. A 1 g sample of hydrogen peroxide solution
100 litre of water requires 522 g of Na2S2O4. The containing x% of H2O2 by weight requires x
molarity of CrO42− in waste water is ml of KMnO4 solution for complete oxidation
(a) 0.04 (b) 0.03 under acidic conditions. What is the normality of
KMnO4 solution?
(c) 0.02 (d) 2.0
(a) 5.88 N (b) 58.8 N
85. Calcium oxalate is insoluble in water. This
property has been used to determine the amount (c) 0.0588 N (d) 0.588 N
of calcium ion in fluids such as blood. The 92. One gram of ferrous oxalate dissolved in dil. H2SO4
calcium oxalate isolated from blood is dissolved is treated with KMnO4 solution added in drops till
in acid and titrated against a standard KMnO4 a faint pink colour persists in the solution. If 60 ml
solution. In one test, it is found that the calcium of KMnO4 solution is consumed, then calculate
oxalate isolated from a 10 ml sample of blood its molarity (Fe = 56).
requires 25 ml of 0.001 M-KMnO4 for titration. The (a) 0.694 M (b) 0.0694 M
number of milligram of calcium per litre of blood is (c) 0.294 M (d) 0.0294 M
(a) 0.25 (b) 0.50 93. Magnesium hydroxide is the white milky substance
(c) 0.80 (d) 0.40 in milk of magnesia. What mass of Mg(OH)2 is
86. How many grams of KMnO4 will react with 50 ml formed when 15 ml of 0.2 M-NaOH is combined
of 0.2 M-H2C2O4 solution in the presence of H2SO4? with 12 ml of 0.15 M-MgCl2?
(a) 1.58 g (b) 3.16 g (a) 0.087 g (b) 0.079 g
(c) 0.632 g (d) 0.79 g (c) 0.1044 g (d) 0.522 g
87. What volume of 0.05 M-Ca(OH)2 solution is 94. The formula weight of an acid is 82 amu. In
needed for complete conversion of 10 ml of 0.1 a titration, 100 cm3 of a solution of this acid
M-H3PO4 into Ca(H2PO4)2? containing 39.0 g of the acid per litre was
(a) 10 ml (b) 5 ml completely neutralized by 95 cm3 of aqueous
(c) 20 ml (d) 40 ml solution of NaOH containing 40 g of NaOH in
1 L of solution. What is the basicity of the acid?
88. How many grams of oxalic acid crystals, H2C-
(a) 4 (b) 2
2O4 ⋅ 2H2O is needed to react completely with 100
ml of 0.4 M-KMnO4 in the presence of H2SO4? (c) 1 (d) 3
(a) 2.52 g (b) 12.6 g 95. A quantity of 20 g of H3PO4 is dissolved in water
(c) 25.2 g (d) 9.0 g and made up to 1 L. What is the normality of the
89. Borax has the formula Na2B4O7 ⋅ 10H2O. It is a solution, if titration against NaOH is carried only
strong base in aqueous solution because OH− ions up to the second stage of neutralization?
are produced by reaction with water. (a) 0.408 (b) 0.204
2− −
(B4O7 + 7H2O → 4H3BO3 + 2OH ). (c) 0.612 (d) 0.102

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 7 7/8/2019 2:25:32 PM


96. A volume of 25 ml of 0.017 M-HSO3– in strongly 102. The normality of a solution of a mixture containing
acidic solution required the addition of 16.9 ml HCl and H2SO4 is N/5. Twenty millilitres of this
of 0.01 M-MnO4− for its complete oxidation. solution reacts with excess of AgNO3 solution to
In neutral solution, 28.6 ml is required. Assign give 0.287 g of silver chloride. The percentage of
oxidation numbers of Mn in each of the products. HCl in the mixture by mass is (Ag = 108)
(a) 2, 4 (b) 3, 4 (a) 42.69% (b) 57.31%
(c) 2, 3 (d) 3, 4 (c) 40% (d) 33.18%
97. A quantity of 0.84 g of an acid (molecular mass 103. A quantity of 0.10 g of anhydrous organic acid
= 150) was dissolved in water and the volume was requires 25 ml of 0.10 N-NaOH for neutralization.
made up to 100 ml. Twenty five millilitres of this A quantity of 0.245 g of the hydrated acid requires
solution required 28 ml of (N/10) NaOH solution 50 ml of the same alkali. The number of moles
for neutralization. The equivalent weight and of water of crystallization per equivalent of the
basicity of the acid is anhydrous acid is
(a) 75, 2 (b) 150, 1 (a) 1.0 (b) 2.0
(c) 75, 4 (d) 150, 2 (c) 0.5 (d) 4.0
98. A quantity of 0.70 g of a sample of Na2CO3 ⋅ xH2O
104. A volume of 100 ml of H2O2 is oxidized by 100
was dissolved in water and the volume was made to
ml of 1 M-KMnO4 in acidic medium (MnO4−
100 ml. Twenty millilitres of this solution required
reduced to Mn2+). A volume of 100 ml of same
19.8 ml of N/10 HCl for complete neutralization.
H2O2 is oxidized by ‘V’ ml of 1 M-KMnO4 in basic
The value of x is
medium (MnO4− reduced to MnO2). The value of
(a) 2 (b) 1 ‘V’ is
(c) 4 (d) 10 (a) 500 (b) 100
99. The specific gravity of a given H2SO4 solution is (c) 33.33 (d) 166.67
1.76. A quantity of 3.5 ml of the acid is diluted to
1.0 L and 25 ml of this diluted acid required 25.6 105. A quantity of 1 g of metal carbonate was dissolved
ml of N/10 ( f = 0.95) NaOH solution for complete in 25 ml of normal HCl. The resulting liquid
neutralization. The percentage strength (by mass) requires 50 ml of N/10 caustic soda solution to
of the original acid solution is neutralize it completely. The equivalent weight of
metal carbonate is
(a) 61.6% (b) 77.38%
(c) 50% (d) 47.66% (a) 10 (b) 20
(c) 100 (d) 50
100. A volume of 25 ml of (N/10)-Na2CO3 solution
neutralizes 10 ml of a dilute H2SO4 solution. The 106. When 0.91 g of a mixture of Na2SO4 and
volume of water that must be added to 400 ml of (NH4)2SO4 was boiled with 80 ml of 0.1 N-NaOH
this H2SO4 solution in order to make it exactly until no more NH3 is evolved, the excess of NaOH
N/10 is required is 11.6 ml of 0.1 N-HCl. How many
(a) 1000 ml (b) 600 ml grams of Na2SO4 is present in the mixture?
(c) 500 ml (d) 400 ml (a) 0.594 g (b) 0.459 g
(c) 0.549 g (d) 0.945 g
101. A volume of 10 ml of a H2SO4 solution is diluted
to 100 ml. Twenty five millilitres of this diluted 107. A quantity of 10 g of a sample of silver, which is
solution is mixed with 50 ml of 0.5 N-NaOH contaminated with silver sulphide, gave 11.2 ml of
solution. The resulting solution requires 0.265 hydrogen sulphide at 0oC and 1 atm, on treatment
g Na2CO3 for complete neutralization. The with excess of hydrochloride acid. The amount of
normality of original H2SO4 solution is silver sulphide in the sample is (Ag = 108)
(a) 12 N (b) 1.2 N (a) 1.24 g (b) 124 mg
(c) 3 N (d) 0.275 N (c) 5 × 10−3 mol (d) 62 mg

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 8 7/8/2019 2:25:32 PM


108. A 0.2 g sample of iron wire containing 98% iron is The volume of thiosulphate hypo consumed is
dissolved in acid to form ferrous ion. The solution (As = 75)
requires 30 ml of K2Cr2O7 solution for complete (a) 48.1 ml (b) 38.4 ml
reaction. What is the normality of K2Cr2O7
(c) 24.7 ml (d) 30.3 ml
solution? (Fe = 56)
(a) 0.1167 N (b) 0.2333 N 113. S2O32− ion is oxidized by S2O82− ion, the products
(c) 0.0583 N (d) 0.167 N are S4O62− and SO42− ions. What volume of 0.25 M
thiosulphate solution would be needed to reduce 1
109. One litre of a mixture of O2 and O3 at 0oC and g of K2S2O8? (K = 39)
1 atm was allowed to react with an excess of
(a) 36.92 ml (b) 32.69 ml
acidified solution of KI. The iodine liberated
requires 40 ml of M/10 sodium thiosulphate (c) 29.63 ml (d) 62.93 ml
solution for titration. What is the mass percent of 114. V1 ml of permanganate solution of molarity
ozone in the mixture?
M1 reacts exactly with V2 ml of ferrous sulphate
(a) 6.575% (b) 9.6% solution of molarity M2, then
(c) 93.425% (d) 90.4% (a) V1M1 = V2M2 (b) 5V1M1 = V2M2
110. A 71 ml (specific gravity 1.1) of chlorine water (c) V1M1 = 5V1M2 (d) None of these
is treated with an excess of KI. The liberated
115. x g of KHC2O4 requires 100 ml of 0.02 M-KMnO4
iodine requires 26 ml of 0.11 N-Na2S2O3 (sodium
in acidic medium. In another experiment, y g of
thiosulphate or hypo) solution. What is the
KHC2O4 requires 100 ml of 0.05 M-Ca(OH)2. The
percentage of Cl2 (by mass) in the chlorine water?
ratio of x and y is
Chlorine water is a solution of free chlorine in
water. (a) 1 : 1 (b) 1 : 2
(a) 0.26% (b) 0.13% (c) 2 : 1 (d) 5 : 4
(c) 0.065% (d) 1.3%
116. In the mixture of NaHCO3 and Na2CO3, the
111. Household bleach contains hypochlorite ion, volume of a given HCl required is x ml with
which is formed when chlorine dissolves in water. phenolphthalein indicator and further y ml is
To determine the concentration of hypochlorite in required with methyl orange indicator. Hence, the
the bleach, the solution is first treated with a KI volume of HCl for complete reaction of NaHCO3
solution. The iodine liberated can be determined present in the original mixture is
by titration with a standard thiosulphate solution. (a) 2x (b) y
A 25 ml of certain household bleach requires 17.4 (c) x/2 (d) (y − x)
ml of a 0.02 M-Na2S2O3 solution for titration.
The mass of chlorine dissolved in one litre of the 117. A volume of 25 ml of 0.107 M-H3PO4 was titrated
bleach solution is with 0.115 M solution of NaOH to the end
(a) 0.1392 g (b) 0.494 g point identified by indicator bromocresol green.
This requires 23.1 ml. The titration was repeated
(c) 9.88 g (d) 0.278 g
using phenolphthalein as indicator. This time 25
112. One gram of Na3AsO4 is boiled with excess of ml of 0.107 M-H3PO4 requires 46.2 ml of the
solid KI in the presence of strong HCl. The iodine 0.115 M-NaOH. What is the coefficient n in the
evolved is absorbed in KI solution and titrated following reaction?
against 0.2 N hypo solution. Assuming the H3PO4 + nOH− → [H3−nPO4]n− + nH2O
reaction to be
(a) 1, 2 (b) 2, 1
AsO43− + 2H+ + 2I− → AsO33− + H2O + I2 (c) 3, 2 (d) 1, 3

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 9 7/8/2019 2:25:32 PM


118. Calculate the temporary and permanent hardness (a) 56 (b) 100
of water sample having the following constituents (c) 200 (d) 112
per litre.
Ca(HCO3)2 = 162 mg, MgCl2 = 95 mg 120. RH2 (ion exchange resin) can replace Ca2+ in hard
NaCl = 585 mg, Mg(HCO3)2 = 73 mg water as follows.
CaSO4 = 136 mg RH2 + Ca2+ → RCa + 2H+.
(a) 200 ppm, 150 ppm One litre of hard water after passing through RH2
(b) 100 ppm, 150 ppm has pH = 2. Hence, hardness in ppm of Ca2+ is
(c) 150 ppm, 200 ppm (a) 200 (b) 100
(d) 150 ppm, 150 ppm (c) 50 (d) 125

119. A volume of 100 L of hard water requires 5.6 g


of lime for removing temporary hardness. The
temporary hardness in ppm of CaCO3 is

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 10 7/8/2019 2:25:33 PM


EXERCISE II (JEE ADVANCED)

Section A (Only one Correct)


1. Which of the following process is reduction? 9. The oxidation number of cobalt in K[Co(CO)4] is
(a) CH2 = CH2 → CH2 − CH2 (a) +1 (b) +3
| | (c) −1 (d) 0
OH OH
(b) CH3CH2 CH=CH − CH2 − CHO → 10. Phosphorus has oxidation state of +3 in
CH3CH2 CH=CH − CH2 − CH2 OH (a) phosphorus acid
(c) CH3CHO → CCl3CHO (b) orthophosphoric acid
(d) Ag + + 2NH3 → [Ag(NH3 )2 ]+ (c) metaphosphoric acid
2. The oxidation number of sodium in sodium amalgam is (d) pyrophosphoric acid
(a) +2 (b) +1 11. One gas bleaches the colour of the flowers by
(c) −2 (d) zero reduction while the other by oxidation. The gases
3. The oxidation state of molybdenum in its are
oxocomplex [Mo2O4(C2H4)2(H2O)2]2− is (a) CO, Cl2 (b) H2S, Br2
(a) +2 (b) +3 (c) SO2, Cl2 (d) NH3, SO3
(c) +4 (d) +5
12. In a reaction, HNO3 is behaving as reducing agent.
4. The oxidation state of boron in potassium What should be its expected product?
tetrafluoroborate is
(a) H2 (b) NO2
(a) +2 (b) +3 (c) N2O (d) O2
(c) +4 (d) −3
13. Which of these substance is a good reducing
5. The oxidation state of bismuth in lithium
agent?
bismuthate is
(a) HI (b) KBr
(a) +5 (b) +3
(c) FeCl3 (d) KClO3
(c) +2 (d) +4
6. The compound of Xe and F is found to have 14. Which of the following ion cannot act as an
53.5% Xe. What is the oxidation number of Xe in oxidizing agent?
this compound? (Xe = 131, F = 19) (a) MnO4− (b) CrO42−
(a) −4 (b) 0 (c) I− (d) Fe3+
(c) +4 (d) +6
15. Which of the following reaction is redox?
7. The oxidation number of S in (CH3)2SO is
(a) Mg3 N 2 + 6H2 O → 3Mg( OH )2 + 2 NH3
(a) zero (b) +1
(b) CaC 2 + 2H2 O → Ca( OH )2 + C 2 H2
(c) +2 (d) +3
8. Sulphide ions react with Na4[Fe(NO) (c) Ca( OCl )Cl + H2 O → Ca( OH )2 + Cl2
(CN)5] to form a purple-coloured compound
(d) PCl5 + 4H2 O → H3 PO 4 + 5HCl
Na4[Fe(CN)5(NOS)]. In the reaction, the oxidation
state of iron 16. During the oxidation of Mn2+ to MnO4− by PbO2
(a) changes from +2 to +3. in acid medium, the number of moles of acid
(b) changes from +2 to +4. consumed per mole of Mn2+ ion is
(c) changes from +3 to +2. (a) 4 (b) 1/2
(d) does not change. (c) 2 (d) 1/4

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 11 7/8/2019 2:25:34 PM


17. During the oxidation of arsenite ion AsO33– to 25. When copper oxide is strongly heated with
arsenate ion AsO43− in alkaline medium, the hydrogen, it reduces to copper. The loss in its weight
number of moles of hydroxide ions consumed per is 14.9 g and the weight of water formed was 16.78
mole of arsenite ion is g. What is the equivalent weight of oxygen, taking
(a) 2 (b) 3 the equivalent weight of hydrogen as 1.008?
(c) 2/3 (d) 3/2 (a) 8.000 (b) 7.989
(c) 8.064 (d) 16.00
18. Cr(OH)3 + ClO− + OH− → ... + Cl− + H2O. The
missing ion is 26. A quantity of 1 g of metal ion, M2+ was discharged
(a) Cr2O72− (b) Cr3+ by the passage of 1.81 × 1022 electrons. The atomic
mass of the metal is
(c) CrO42− (d) Cr2O3
(a) 33.27 (b) 99.81
19. In a reaction, 4 moles of electrons is transferred to
(c) 66.54 (d) 133.08
one mole of HNO3. The possible product obtained
due to reduction is 27. Phosphoric acid has minimum equivalent weight
(a) 0.5 mole of N2. when 1 mole of it reacts with
(b) 0.5 mole of N2O. (a) 1 mole of NaOH (b) 2 moles of NaOH
(c) 1 mole of NO2. (c) 3 moles of NaOH (d) 4 moles of NaOH
(d) 1 mole of N2O. 28. Equivalent weight of water in a neutralization
reaction between dibasic acid and triacidic base is
20. The number of electrons lost per mole of ethanol
in its oxidation into acetic acid is (a) 9 (b) 18
(a) 4NA (b) 2NA (c) 6 (d) 3
(c) 6NA (d) 8NA 29. Acetic acid on chlorination yields trichloroacetic
acid. Its equivalent weight will be
21. For the process CH3CH2OH → CH3COOH,
the number of H+ ions needed for balancing (a) 60 (b) 40
and the side in which it should be added are, (c) 20 (d) 10
respectively
30. Molecular masses of NH3 and N2 are x1 and x2,
(a) 4, left (b) 4, right respectively. In the reaction,
(c) 2, Left (d) 2, right N2 + 3H2 → 2NH3,
22. In basic medium, Cl2 disproportionates their equivalent weights are y1 and y2. Then
into Cl− and ClOx−. If there is loss and gain of (y1 − y2) is
one mole of electron per mole of Cl2, then the
value of x is ⎛ 2 x − x2 ⎞
(a) ⎜ 1 ⎟ (b) (x1 − x2)
⎝ 6 ⎠
(a) 3 (b) 1
(c) (3x1 − x2) (d) (x1 − 3x2)
(c) 2 (d) 4
31. In the reaction,
23. An amount of 0.2 mole of AO3− gains 1.2 mole
of electron in a process. Assuming that there is no P4 + NaOH + H2O → PH3 + NaH2PO2,
change in oxidation state of oxygen, determine the the equivalent weight of P4 is
oxidation state of ‘A’ in product.
(a) M (b) M/3
(a) +1 (b) −1 (c) M/6 (d) 2M/3
(c) 0 (d) +6
32. In the reaction,
24. The equivalent weights of an element of variable
Pb + PbO2 + H2SO4 → PbSO4 + H2O,
valency are 21 and 14. The atomic mass of the
element may be the equivalent weight of H2SO4 is
(a) 35 (b) 42 (a) M (b) M/2
(c) 70 (d) 126 (c) 2M (d) M/4

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 12 7/8/2019 2:25:35 PM


33. In the reaction, 41. A quantity of 1.0 g of an acid when completely
Cl2 + NaOH → NaCl + NaClO3 + H2O, acted upon by magnesium gave 1.301 g of the
anhydrous magnesium salt. The equivalent weight
the equivalent weight of H2O is of the acid is
(a) M (b) 3M/5 (a) 35.54 (b) 36.54
(c) 6M/5 (d) M/2 (c) 48 (d) 49
34. The equivalent weight of ozone behaving as an 42. A quantity of 3.7 g of an oxide of a metal was
oxidizing agent is heated with charcoal, and CO2 so produced was
(a) 48 (b) 24 absorbed in caustic soda solution whose weight
(c) 16 (d) 32 increased by 1.0 g. The equivalent weight of the
metal is
35. In the reaction,
(a) 11 (b) 40.7
MnO2 + 4HCl → MnCl2 + Cl2 + 2H2O,
(c) 32.7 (d) 73.4
the equivalent weight of HCl is
43. Which has the maximum number of equivalent
(a) M (b) M/2 per mole of the oxidant?
(c) 2M (d) M/4 (a) Zn(s) + VO2+(aq) → Zn2+(aq) + V3+ (aq)
36. In an acidic solution, I− changes to I2. How many (b) Ag(s) + NO2−(aq) → Ag+(aq) + NO2(g)
grams of I2 is produced if, in the same process, 1.5 (c) Mg(s) + V4+(aq) → Mg2+(aq) + V2+(aq)
× 1022 electrons are used up to reduce H3AsO4 to (d) I−(aq) + IO3−(aq) → I3−(aq)
H3AsO3? (I = 128, NA = 6 × 1023)
44. The number of moles of KMnO4 that will be
(a) 1.6 g (b) 6.4 g needed to react completely with one mole of
(c) 4.8 g (d) 3.2 g ferrous oxalate in acidic solution is
37. An ion is reduced to the element when it absorbs (a) 3/5 (b) 2/5
6 × 1020 electrons. The number of equivalents of (c) 4/5 (d) 1
the ion is
45. The number of moles of KMnO4 that will be
(a) 0.1 (b) 0.01 needed to react completely with one mole of
(c) 0.001 (d) 0.0001 sulphite ion in acidic solution is
38. In which of the following reactions, 1 g equivalent (a) 3/5 (b) 2/5
of H3PO4 reacts with 3 g equivalents of NaOH? (c) 4/5 (d) 1
(a) H3PO4 + NaOH → NaH2PO4 + H2O 46. A certain amount of a reducing agent reduces x
(b) H3PO4 + 2NaOH → Na2HPO4 + 2H2O mole of MnO2 and y mole of K2CrO4 in different
(c) H3PO4 + 3NaOH → Na3PO4 + 3H2O reactions in acidic medium. If the changes in
(d) None of the above oxidation states of reducing agent in the reactions
are in 1 : 2 ratio, respectively, then the ratio of x
39. A quantity of 8.6 g of an oxide of a metal reacts and y is
completely with hydrogen gas to yield 1.8 g of (a) 2:3 (b) 1:3
water. The equivalent weight of the metal is
(c) 3:4 (d) 3:2
(a) 23 (b) 37
47. Dichloroacetic acid (CHCl2CO2H) is oxidized
(c) 78 (d) 35
to CO2, H2O and Cl2 by 1.2 equivalents of an
40. A quantity of 20 g of an acid furnished 0.5 moles oxidizing agent. Same amount of the acid can
of H3O+ ions in its aqueous solution. The mass of neutralize ‘X’ moles of NH3 to give ammonium
1 g equivalent of the acid will be dichloroacetate. The value of ‘X’ is
(a) 40 g (b) 20 g (a) 0.4 (b) 0.3
(c) 10 g (d) 100 g (c) 0.2 (d) 0.1

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 13 7/8/2019 2:25:35 PM


48. Two acids H2SO4 and H3PO4 are neutralized 55. The ratio of amounts of H2S needed to precipitate
separately by the same amount of an alkali when all the metal ions from 100 ml of 1 M-AgNO3 and
sulphate and dihydrogen orthophosphate are 100 ml of 1 M-CuSO4 is
formed, respectively. Find the ratio of the masses (a) 1:2 (b) 2:1
of H2SO4 and H3PO4.
(c) zero (d) infinite
(a) 1 : 1 (b) 1 : 2
56. A volume of 100 ml of 0.1 M-NaAl(OH)2CO3 is
(c) 2 : 1 (d) 2 : 3
neutralized by 0.25 N-HCl to form NaCl, AlCl3
49. A metal exhibits the valencies of 2 and 3. Its and CO2. The volume of HCl required is
equivalent weight is 28 when it forms a metal oxide
(a) 10 ml (b) 40 ml
of formula MO. What mass of H2SO4 is needed
for complete reaction with 4.8 g of M2O3? (c) 100 ml (d) 160 ml
(a) 8.82 g (b) 4.41 g 57. Purple of Cassius is prepared by reducing AuCl3 to
(c) 13.23 g (d) 11.03 g colloidal gold by SnCl2. A 1 L solution containing
1.97 mg of gold per ml is prepared from 0.05 M
50. The specific heat of a metal is 0.26. The chloride solution of AuCl3 by reduction with appropriate
of the metal (always monomer) has its molecular amount of 0.05 M-SnCl2 solution, the resulting
mass 95. The volume of hydrogen gas that 1.2 g solution being diluted to 1 L with water. The
of the metal will evolve at 0oC and 1 atm, if it is volume of stannous chloride solution required, if
allowed to react with excess of an acid, is its oxidation product is SnCl4(aq), is (Au = 197)
(a) 2.24 L (b) 1.12 L (a) 300 ml (b) 500 ml
(c) 0.56 L (d) 5.611 L (c) 800 ml (d) 100 ml
51. The vapour density of a volatile chloride of a
metal is 74.6. If the specific heat of the metal is 58. The iodide content of a solution was determined by
0.55, then the atomic mass of the metal is titration with cerium (IV) sulphate in the presence
of HCl, in which I− is converted to ICl. A 250 ml
(a) 7.2 (b) 7.46
sample of the solution required 20 ml of 0.05 N-Ce4+
(c) 11.63 (d) 10 solution. What is the iodide concentration in the
52. A quantity of 3 g of impure marble was treated original solution in g/L? (I = 127)
with 200 ml of dil. HCl. After completion of the (a) 0.508 (b) 0.254
reaction a small quantity of the residue was left
(c) 0.762 (d) 0.127
and 560 ml of a gas was evolved at 0oC and 1 atm.
The normality of acid solution is 59. A chemist is preparing to analyse samples that
(a) 0.3 N (b) 0.125 N will contain no more than 0.5 g of uranium. His
(c) 0.25 N (d) 0.5 N procedure calls for preparing the uranium as U4+
ion and oxidizing it by MnO4− in the following
53. What will be present in the solution when 50 ml of acid solution.
0.1M-HCl is mixed with 50 ml of 0.1 M-NaOH
solution? U4+ + MnO4− + H2O → UO22+ + Mn2+ + H3O+
(a) 4.5 millimoles of H+ If he wants to react the total U4+ sample with a
(b) 0.05 millimoles of OH− maximum of 50 ml of KMnO4 solution, then
(c) 0.1 M-NaCl what concentration does he choose? (U = 238)
(d) 10−7 M of H+ ion (a) 0.0336 M (b) 0.0168 M
54. A quantity of 5.88 g of FeSO4 ⋅ (NH4)2SO4 ⋅ xH2O (c) 0.168 M (d) 0.0672 M
was dissolved in 250 ml of its solution. Twenty
millilitres of this solution requires 20 ml of 60. KIO3 reacts with oxalic acid in solution to yield
KMnO4 solution containing 3.16 g of 75% pure K2C2O4, CO2 and I2. How many grams of oxalic
KMnO4 dissolved per litre. The value of ‘x’ is acid will be required to react with one gram of
(K = 39, Mn = 55, Fe = 56) KIO3? (K = 39, I = 127)
(a) 3 (b) 4 (a) 1.262 g (b) 1.622 g
(c) 6 (d) 7 (c) 1.747 g (d) 1.022 g

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 14 7/8/2019 2:25:36 PM


61. What is the mass of oxalic acid, H2C2O4, which can 67. A sample of a metal carbonate MCO3 was
be oxidized to CO2 by 100 ml of MnO4− solution, neutralized by 10 ml of 0.1 N-HCl and the
10 ml of which is capable of oxidizing 50 ml of resulting chloride gave 0.0517 g of phosphate,
1.00 N – I− to I2? M3(PO4)2. The equivalent weight of M is
(a) 2.25 g (b) 52.2 g (a) 20.03 (b) 40.06
(c) 25.2 g (d) 22.5 g (c) 51.7 (d) 8.62
62. What volume of 0.2 M-KMnO4 solution is needed
68. A small amount of CaCO3 completely neutralizes
for complete reaction with 26.56 gm Fe0.9O1.0, in
525 ml of 0.1 N-HCl and no acid is left at the end.
acidic medium? (Fe = 56)
280 After converting all calcium chloride to CaSO4,
(a) 280 ml (b) ml how much plaster of Paris can be obtained?
9
2800 (a) 1.916 g (b) 5.827 g
(c) ml (d) 560 ml
9 (c) 3.57 g (d) 3.81 g
63. A volume of 20 ml of M-KMnO4 solution is
diluted to 150 ml. In this solution, 50 ml of 10 M 69. What volume of 0.40 M-Na2S2O3 would be
H2SO4 is added. 25 ml of this mixture is titrated required to react with the I2 liberated by adding
with 20 ml of FeC2O4 solution. The molarity of excess of KI to 50 ml of 0.20 M CuSO4?
FeC2O4 solution is (a) 12.5 ml (b) 25 ml
(a) 0.0416 (b) 0.208 (c) 50 ml (d) 2.5 ml
(c) 0.625 (d) 0.125
70. To a 25 ml H2O2 solution, excess of acidified
64. A volume of 20 ml of M-K2Cr2O7 solution is
solution of potassium iodide was added. The
diluted to 200 ml. Twenty five millilitres of diluted
iodine liberated required 20 ml of 0.3 N-Na2S2O3
solution is mixed with 50 ml of 4 M-H2SO4
solution. The volume strength of H2O2 solution is
solution. Thirty millilitres of this mixture is
diluted to 150 ml. How many millilitres of 0.02 (a) 1.362 (b) 0.681
M-H2O2 solution is needed to titrate 15 ml of the (c) 2.724 (d) 0.908
diluted solution?
71. An unknown composition of a mixture of carbon
(a) 14 ml (b) 15 ml
disulphide and hydrogen sulphide was burnt in
(c) 30 ml (d) 45 ml sufficient amount of oxygen. The resulting gases
65. A polyvalent metal weighing 0.1 g and having found to exert a pressure of 1.97 atm in a 20 l vessel
atomic mass 51 reacted with dilute H2SO4 to at 400 K. The gaseous mixture required 2.8 M
give 43.9 ml of hydrogen at 0oC and 1 atm. iodine solution and 250 ml of it was required to
The solution containing the metal in this lower reach the end point forming I−. Calculate the mole
oxidation state was found to require 58.8 ml of fraction of CS2 in the original mixture.
0.1 N–permanganate for complete oxidation.
(a) 0.2 (b) 0.4
What are the valencies of the metal?
(c) 0.6 (d) 0.8
(a) 2, 5 (b) 2, 4
(c) 3, 5 (d) 4, 5 72. One gram of a sample of CaCO3 was strongly
66. A solution of Na2S2O3 is standardized heated and the CO2 liberated absorbed in 100 ml
iodometrically against 0.1336 g of KBrO3. This of 0.5 M-NaOH. Assuming 90% purity for the
process required 40 ml of the Na2S2O3 solution. sample, how much ml of 0.5 M-HCl would be
What is the strength of the Na2S2O3? (K = 39, required to react with the solution of the alkali for
Br = 80) the phenolphthalein end point?

(a) 0.04 M (b) 0.02 M (a) 73 ml (b) 41 ml


(c) 0.05 M (d) 0.01 M (c) 82 ml (d) 97 ml

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 15 7/8/2019 2:25:36 PM


73. A volume of 40 ml of 0.05 M solution of sodium (a) Molarity of Na2CO3 = 20V1
sesquicarbonate (Na2CO3 ⋅ NaHCO3 ⋅ 2H2O) is (b) Molarity of NaHCO3 = 10 (V2 − 2V1)
titrated against 0.05 M-HCl solution. x ml of (c) Molarity of Na2CO3 = 10 (V2 + V1)
HCl solution is used when phenolphthalein is the
(d) Molarity of NaHCO3 = 10 (V2 − V1)
indicator and y ml of HCl is used when methyl
orange is the indicator in two separate titrations. 75. In the mysterious deserts of Egypt, large deposits of
Hence, (y − x) is ‘Trona’ (Na2CO3 ⋅ NaHCO3) are found. If a sample
(a) 80 ml (b) 30 ml of ‘Trona’ (containing same inert impurities) is
dissolved in water and titration against 0.1 M-HCl,
(c) 120 ml (d) 40 ml
then which of the following readings are possible
74. A 100 ml mixture of Na2CO3 and NaHCO3 is when x and y ml of HCl are required for titration
titrated against 1 M-HCl. If V1 L and V2 L are against equal volumes of this solution, one using
consumed when phenolphthalein and methyl phenolphthalein and the other using methyl orange
orange are used as indicators, respectively, in two respectively as indicators?
separate titrations, which of the following is true (a) x = 20, y = 20 (b) x = 10, y = 30
for molarities in the original solution?
(c) x = 20, y = 40 (d) x = 20, y = 10

Section B (One or More than one Correct)

1. In the compound NOClO4, the oxidation state of 7. A quantity of 15.8 g of KMnO4 can be
(a) nitrogen is +1 (b) nitrogen is +3 decolourized in acidic medium by (K = 39, Mn =
55, Fe = 56)
(c) chlorine is +5 (d) chlorine is +7
(a) 18.25 g HCl (b) 22.5 g H2C2O4
2. Which of the following is/are peroxide(s)?
(c) 32 g SO2 (d) 38 g FeSO4
(a) PbO2 (b) H2O2
(c) SrO2 (d) BaO2 8. When copper is treated with a certain concentration
of nitric acid, nitric oxide and nitrogen dioxide
3. Which of the following is a non-redox process? are liberated in equal volumes according to the
4 → SO3
(a) SO 2− (b) Cr2O 72− → CrO 2−
4 following equation.

4 → P2O 7
(c) PO 3− → CO2
4−
(d) C2O 2−
4 XCu + YHNO3 → Cu(NO3)2 + NO + NO2 + H2O
4. Which of the following compound does not The coefficients of X and Y are, respectively,
decolourized an acidified solution of KMnO4? (a) 2 and 3 (b) 2 and 6
(a) SO2 (b) FeCl3 (c) 1 and 3 (d) 3 and 8
(c) H2O2 (d) FeSO4
9. The equivalent volume of a gaseous substance is
5. Which of the following statement(s) is/are true 5.6 L at 0oC and 1 atm. The substance may be
regarding the change CN− → CNO−?
(a) CH4 gas in combustion.
(a) Carbon is losing two electrons per atom. (b) O3 gas as oxidizing agent.
(b) The oxidation state of carbon changes from (c) H2S gas as reducing agent.
+2 to +4.
(d) CO2 formed from carbon.
(c) Oxidation state of nitrogen is not changing.
(d) Oxidation state of nitrogen changes from −3 10. A quantity of 0.5 g of a metal nitrate gave 0.43 g
to −1. of metal sulphate.
6. Substances which may be oxidized as well as (a) The equivalent weight of the metal is 38.
reduced are (b) The equivalent weight of the metal is 76.
(a) HCl (b) HClO (c) The atomic weight of metal may be 76.
(c) HClO3 (d) HClO4 (d) The atomic weight of metal may be 19.

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 16 7/8/2019 2:25:38 PM


11. A metal (M) forms a hydrated sulphate, (c) The molarity of acid solution is 0.1 M.
isomorphous with ZnSO4 ⋅ 7H2O. If the sulphate (d) 100 ml of the same acid solution requires 40
contains 20% metal, by weight, which of the ml of 0.05 M-KMnO4 solution for complete
following is/are correct for the metal? oxidation in the presence of H2SO4.
(a) The atomic weight of metal is 24.
(b) The equivalent weight of the metal is 27.75. 16. A bottle of oleum is labelled as 109%. Which
of the following statement is/are correct for this
(c) The metal is bivalent.
oleum sample?
(d) The anhydrous metal sulphate contains 36.6%
(a) It contains 40% of free SO3 by weight.
metal, by mass.
(b) 1.0 g of this sample approximately requires
12. A metal forms two oxides. The higher oxide 22.25 ml of 0.5 M-NaOH solution for
contains 20% oxygen, while 4.29 g of the lower complete neutralization.
oxide when converted to higher oxide, become
(c) 0.5 g of this sample approximately requires
4.77 g. The equivalent weight of metal in
11.12 ml of 0.1 N-Ba(OH)2 solution for
(a) lower oxide is 32. complete neutralization.
(b) lower oxide is 64.4. (d) When 500 g water is added to 100 g of this
(c) higher oxide is 64.4. sample, the resulting solution becomes ⎛ 109 ⎞
⎜⎝ ⎟
(d) higher oxide is 32. m in H2SO4. 49 ⎠
17. A quantity of 5.68 g of pure P4O10 is dissolved
13. The specific heat of a metal is found to be
completely in sufficient water and the solution
0.03. 10 g of the metal on treatment with nitric
is diluted to 250 ml. Which of the following
acid gave 18.9 g of pure dry nitrate. The correct
statement(s) is/are correct? (P = 31)
statement(s) is/are
(a) The diluted solution has molarity 0.32 with
(a) The equivalent weight of the metal is 69.66. respect to H3PO4.
(b) The atomic weight of the metal is 209. (b) 25 ml of the diluted solution exactly requires
(c) The metal is trivalent. 48 ml of 0.5 M-NaOH solution for complete
(d) The metal is an alkali metal. neutralization.
14. A 100 ml mixture of Na2CO3 and NaHCO3 is (c) 15 ml of the diluted solution exactly requires
titrated against 1 M-HCl. If V1 L and V2 L are 36 ml of 0.2 M-BaCl2 solution for complete
consumed when phenolphthalein and methyl precipitation of phosphate.
orange are used as indicators, respectively, in two (d) 40 ml of the diluted solution exactly requires
separate titrations, which of the following is true 48 ml of 0.8 N-KOH solution for the first
for molarities in the original solution? equivalent point.
(a) Molarity of Na2CO3 = 20V1 18. An amount of 0.01 mole of SO2Cl2 is hydrolysed
(b) Molarity of NaHCO3 = 10 (V2 − 2V1) completely in sufficient water (no gas is allowed to
escape out) and the solution is diluted to 200 ml.
(c) Molarity of Na2CO3 = 10 (V2 + V1)
Which of the following statement is/are correct?
(d) Molarity of NaHCO3 = 10 (V2 − V1) (Ag = 108)
15. A volume of 20 ml of an aqueous solution of (a) The solution is 0.05 M in H2SO4.
hydrated oxalic acid (H2C2O4 ⋅ xH2O) containing (b) The solution is 0.1 M in HCl.
6.3 g per litre requires 40 ml of 0.05 M-NaOH (c) A volume of 20 ml of the solution exactly
solution for complete neutralization. Which of the requires 20 ml of 0.2 M NaOH solution for
following statement about the acid solution is/are complete neutralization.
correct? (d) When 100 ml of the solution is treated with
(a) The value of x is 2. excess of AgNO3 solution, 1.435 g of AgCl
(b) The equivalent weight of anhydrous acid is 63. will precipitate out.

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 17 7/8/2019 2:25:38 PM


19. A definite mass of H2O2 is oxidized by excess 20. A quantity of 8.0 g of solid sulphur is first oxidized
of acidified KMnO4 and acidified K2Cr2O7 in to SO2 and then it is divided into two equal parts.
separate experiments. Which of the following is/ One part is sufficient for complete decolourization
are correct statements? (K = 39, Cr = 52, Mn = 55) of 200 ml of acidified KMnO4 solution. Another
(a) Mass of K2Cr2O7 used up will be greater than part is oxidized to SO3 and the SO3 formed is
that of KMnO4. sufficient for complete precipitation of all BaCl2
(b) Moles of KMnO4 used up will be greater than present in 100 ml solution as BaSO4. Which of
that of K2Cr2O7. the following statements is/are correct? (S = 32,
Ba = 138)
(c) Equal mass of oxygen gas is evolved in both
the experiments. (a) The molarity of KMnO4 solution is 0.25.
(d) If equal volumes of both the solutions are (b) The molarity of BaCl2 solution is 0.25.
used for complete reaction, then the molarities (c) The weight of BaSO4 precipitated out is 29.25 g.
of KMnO4 and K2Cr2O7 solutions are in 6 : 5 (d) The same equivalents of KMnO4 and BaCl2
ratio. are reacted.

Section C (Comprehensions)
Comprehension I
For the reaction: MnBr2 + PbO2 + HNO3 → HMnO4 + Pb(BrO3)2 + Pb(NO3)2 + H2O
(Atomic masses: Mn = 55, Br = 80, Pb = 208)
1. The equivalent weight of MnBr2 is 3. The equivalent weight of HNO3 is
(a) 107.5 (b) 215 (a) 63 (b) 55.6
(c) 12.65 (d) 19.55 (c) 31.5 (d) 111.18
2. The equivalent weight of PbO2 is
(a) 120 (b) 240
(c) 14.11 (d) 21.82

Comprehension II
It was found that 100 g of silver combined with all the chlorine in 56 g of arsenious chloride. The vapour density of
arsenious chloride is 6.25 (air = 1). The specific heat of arsenic is 0.08. Given that one litre of air at 0oC and 1 atm
weighs 1.3 g (Ag = 108).
4. What is the exact atomic weight of arsenic? 6. What is the molecular formula of arsenious
(a) 74.94 (b) 24.98 chloride?
(c) 80.00 (d) 182.47 (a) AsCl3 (b) As2Cl6
5. What is the equivalent weight of arsenic in the (c) As2Cl5 (d) AsCl5
arsenious chloride?
(a) 74.94 (b) 24.98
(c) 14.49 (d) 49.96
Comprehension III
A quantity of 0.4 g of oxygen and 4.0 g of a halogen combine separately with the same amount of metal.
7. What is the equivalent weight of halogen if the ele- (a) 40 (b) 80
ment exhibits the same valency in both compounds? (c) 20 (d) 160
(a) 40 (b) 80 9. The atomic weight of the halogen can never have the
(c) 20 (d) 160 value
8. What is the equivalent weight of halogen if the (a) 40 (b) 80
valency of element in the halide is twice that in oxide? (c) 20 (d) 160

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 18 7/8/2019 2:25:39 PM


Comprehension IV
KMnO4 oxidizes Xn+ ion to XO3− in acid solution. 2.5 × 10−3 mole of Xn+ requires 1.5 × 10−3 mole of MnO4−.
10. What is the value of n? (a) 71 (b) 112
(a) 3 (b) 2 (c) 97 (d) 41
(c) 1 (d) 4 12. How many mole of KMnO4 is needed per mole of
Xn+ to oxidize it to XO 3− in strong basic medium?
11. What is the atomic mass of X, if the mass of 1
g-equivalent of XCln in this reaction is 56? XCln (a) 1 (b) 3
is the molecular form of x+n. Assume no change (c) 0.6 (d) 2
in oxidation state of chlorine.

Comprehension V
One gram of a moist sample of a mixture of potassium chloride and potassium chlorate was dissolved in water and
made up to 250 ml. Twenty-five millilitres of this solution was treated with SO2 to reduce the chlorate to chloride and
excess SO2 was removed by boiling. The total chloride was precipitated as silver chloride. The weight of the precipitate
was 0.1435 g. In another experiment, 25 ml of the original solution was heated with 30 ml of 0.2 N solution of ferrous
sulphate and unreacted ferrous sulphate required 37.5 ml of 0.08 N solution of an oxidizing agent for complete oxidation.
(K = 39, Ag = 108)
13. What is the molar ratio of the chlorate to chloride (a) 1.0% (b) 1.5%
in the given mixture? (c) 1.75% (d) 3.5%
(a) 1 : 1 (b) 1 : 2 15. What is the mass percent of potassium chloride in
(c) 2 : 1 (d) 2 : 3 the moist sample?
14. What is the mass percent of moisture present in (a) 37.25% (b) 61.25%
the moist sample? (c) 3.725% (d) 74.5%

Comprehension VI
A forensic chemist needed to determine the concentration of HCN in the blood of a suspected homicide victim and de-
cided to titrate a dilute sample of the blood with iodine using the following reaction.
HCN(aq) + I3−(aq) → ICN(aq) + 2I−(aq) + H+(aq)
A diluted blood sample of volume 15.0 ml was titrated to the stoichiometric point with 5.0 ml of an I3− solution. The molar
concentration of the I3− solution was determined by titrating it against arsenic (III) oxide, As4O6, which in solution forms
arsenious acid, H3AsO3. A volume of 10.0 ml of the triiodide solution was needed to reach the stoichiometric point on a
0.1188 g sample of As4O6 in the following reaction.
H3AsO3(aq) + I3−(aq) + H2O(l) → H3AsO4(aq) + 3I−(aq) + 2H+(aq)
(Atomic mass of As = 75)

16. What is the molar concentration of the triiodide 18. How many grams of HCN is present in the blood
solution? of victim if the total volume of blood present in
(a) 0.03 M (b) 0.12 M the victim is 6.0 l?
(c) 0.06 M (d) 0.00012 M (a) 0.24 g (b) 6.48 g
17. What is the molar concentration of HCN in the (c) 3.24 g (d) 2.16 g
blood sample?
(a) 0.04 M (b) 0.03 M
(c) 0.12 M (d) 0.36 M

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 19 7/8/2019 2:25:39 PM


Comprehension VII
In the presence of fluoride ion, Mn2+ can be titrated with MnO4−, where both reactants being converted to a complex of
Mn(III). A 0.458 g of sample containing Mn3O4 was dissolved and all manganese was converted to Mn2+. Titration in
the presence of fluoride ion consumed 30.0 ml of KMnO4 that was 0.125 N against oxalate. (Mn = 55)
19. The correct balanced reaction, assuming that the 20. What is the percentage of Mn3O4 in the sample?
complex is MnF4−, is (a) 50.00% (b) 40.00%
(a) Mn2+ + MnO4− + H+ + F− → MnF4− + H2O (c) 62.50% (d) 75.00%
(b) 4Mn2+ + MnO4− + 8H+ → 5Mn3+ + 4H2O
21. What is the normality of KMnO4 solution against
(c) 4Mn2+ + MnO4− + 8H+ + 20F− → 5MnF4− + Mn2+?
4H2O
(a) 0.125 N (b) 0.1 N
(d) Mn2+ + MnO4− + H+ → MnF4− + H2O
(c) 0.01 N (d) 0.156 N

Comprehension VIII
Chromium exists as FeCr2O4 in the nature and it contains Fe0.95O1.00 as an impurity. To obtain pure chromium from
FeCr2O4, the ore is fused with KOH and oxygen is passed through the mixture when K2CrO4 and Fe2O3 are produced. A
quantity of 2 g of ore required 280 ml of O2 at 0oC and 1 atm for complete oxidation of ore. K2CrO4 is then precipitated
as BaCrO4 after addition of Barium salt. To the remaining solution, 10 ml of 1 M-K4Fe(CN)6 is added when Fe3+ ions
reacts with it to form KFe [Fe(CN)6], after called ‘Prussian Blue’. To determine excess of K4Fe(CN)6 in solution, 6 ml
of 0.4 N-Fe2+ is added when all the K4Fe(CN)6 is precipitated as K2Fe[Fe(CN)6]. (Fe = 56)
22. What is the percentage of Fe0.95O1.00 in the ore? (a) 77.53% (b) 97.73%
(a) 6.92% (b) 3.46% (c) 78.41% (d) 87.9%
(c) 13.84% (d) 93.08% 24. How many millimoles of Prussian blue is formed?
23. What per cent of total iron present in the ore is in (a) 8.9 (b) 8.8
+2 state? (c) 0.0088 (d) 7.85

Comprehension IX
Chile saltpeter, a source of NaNO3 also contains NaIO3. The NaIO3 can be used as a source of iodine, produced in the
following reactions.
IO3− + 3HSO3− → I− + 3H+ + 3SO42−
and 5I− + IO3− + 6H+ → 3I2 + 3H2O

One litre of Chile saltpeter solution containing 5.94 g NaIO3 is treated with stoichiometric quantity of NaHSO3.
Now an additional amount of the same solution is added to the reaction mixture to bring about the second reaction.
(I = 127) 25. How many grams of NaHSO3 is required in step I for complete reaction?
(a) 9.36 g (b) 3.12 g (c) 5000 ml (d) 400 ml
(c) 6.24 g (d) 14.04 g
27. How many grams of I2 can be produced per litre
26. What additional volume of Chile saltpeter must be of Chile saltpeter?
added in step II to bring in complete conversion of
(a) 4.572 g (b) 2.286 g
I− to I2?
(c) 5.486 g (d) 3.810 g
(a) 1000 ml (b) 200 ml

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 20 7/8/2019 2:25:39 PM


Comprehension X
A volume of 50 ml of solution containing 1 g each of Na2CO3, NaHCO3 and NaOH was treated with N-HCl.
28. What will be the titre reading if only (a) 67.7 ml (b) 55.8 ml
phenolphthalein is used as an indicator? (c) 46.3 ml (d) 23.5 ml
(a) 43.8 ml (b) 21.9 ml 30. What will be the titre reading if methyl
(c) 34.4 ml (d) 57.9 ml orange is added after the first end point with
29. What will be the titre reading if only methyl orange phenolphthalein?
is used as indicator from the very beginning? (a) 30.8 ml (b) 21.3 ml
(c) 33.2 ml (d) 51.9 ml

Section D (Assertion–Reason)
The following questions consist of two statements. Statement II: Equivalent weight of any substance
Mark the answer as follows. depends on its nature in the chemical reaction
concerned.
(a) If both statements are CORRECT, and Statement
II is the CORRECT explanation of Statement I. 7. Statement I: Equivalent weight of any element
(b) If both statements are CORRECT, and Statement II represents the parts by weight of the element
is NOT the CORRECT explanation of Statement I. which combines with or displaces 1 part by weight
of hydrogen or 8 parts by weight of oxygen or 35.5
(c) If Statement I is CORRECT, but Statement II is
parts by weight of chlorine.
INCORRECT.
Statement II: The atomic weights of hydrogen,
(d) If Statement I is INCORRECT, but Statement II
oxygen or chlorine are taken as reference for the
is CORRECT.
determination of equivalent weights of all other
1. Statement I: I− can never act as an oxidizing agent. elements.
Statement II: Oxidizing agent undergoes reduction.
8. Statement I: The number of g-equivalents of all
2. Statement I: In propane, all carbon atoms are in the reactants reacted in any chemical reaction is
the same oxidation state. always the same.
Statement II: The oxidation state is −8/3 per Statement II: In any chemical reaction, the total
carbon atom. mass of reactants reacted is always equal to the
3. Statement I: When O3 reacts with KI, O3 is reduced total mass of products formed.
into O2. 9. Statement I: Equal volumes of 0.3 M-H2SO4
Statement II: There is no change in oxidation state solution and 0.2M–H3PO4 solution will require
of oxygen in this reaction. the same volume of the same NaOH solution for
4. Statement I: In CIF3, chlorine has the oxidation complete neutralization.
number −1. Statement II: H2SO4 is dibasic and H3PO4 is a
Statement II: Electron affinity of chlorine is tribasic acid.
greater than that of fluorine.
10. Statement I: When a solution of Na2CO3 is titrated
5. Statement I: The equivalent weight of any substance with HCl solution, the volume of acid solution
is its molecular weight divided by some factor, required for the end point in case of methyl orange
depending on the nature of the substance. indicator is double than that required in case of
Statement II: The equivalent weight of any phenolphthalein indicator.
substance is always less than its molecular weight. Statement II: In case of phenolphthalein indicator,
6. Statement I: The molecular weight of any substance the sudden change in colour is observed when
is unique but the equivalent weight is not unique. Na2CO3 is completely converted into H2CO3.

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 21 7/8/2019 2:25:40 PM


11. Statement I: When 10 ml of 0.5 M–NaHCO3 Statement II: The oxidation state of Mn changes
solution is titrated with 0.25 M–HCl solution from +7 state to +2, +4 and +6 states, respectively,
using phenolphthalein indicator, 20 ml of acid in acid, neutral and strong basic medium.
solution is consumed at the end point.
14. Statement I: When 20 ml of 0.5 M-CuSO4 solution
Statement II: End point cannot be detected when
is treated with excess of KI solution, the liberated
NaHCO3 solution is titrated with HCl solution
I2 exactly requires 20 ml of 0.5 M-Na2S2O3
using phenolphthalein indicator.
solution for titration.
12. Statement I: Equal volumes of 1 M–HCl solution Statement II: For both the solutions (CuSO4
and 1 M–NaOH solution is required for complete and Na2S2O3), their molarity and normality are
reaction with the same mass of KHC2O4. equal.
Statement II: KHC2O4 is amphoteric and it can
15. Statement I: For the sequential reactions: A →
lose or gain one proton.
B and B → C (both occurring completely), the
number of g-equivalents of A and C must be
13. Statement I: The number of g-equivalents in the
equal.
same mass of KMnO4 is in 5 : 3 : 1 ratio in acid,
neutral and strong basic medium, respectively. Statement II: The relation between the number
of g-equivalents of A and C depends on the
equivalent weight of B in both the reactions.

Section E (Column Match)


1. In Column I, some reactions are given and in 3. Match the columns.
Column II, the type of some reactions on the basis
of oxidation and reduction processes are given. Column I Column II
Match the reactions with their correct type. (Oxidation number of (Oxidation number)
underlined element)
Column I Column II (A) NH4NO3 (P) 0
(A) 3CaO + 2P2O5 → Ca3(PO4)2 (P) Dispropor- (B) CH2 O (Q) −2
tionation
(C) Ni(C O)4 (R) +2
(B) 2Cu+ → Cu + Cu2+ (Q) Compropor-
(D) Cl2O5 (S) +5
tionation
(T) −3
(C) NH4NO2 → N2 + 2H2O (R) Non-redox
(D) CH4 + 2O2 → CO2 + 2H2O (S) Combustion
4. In Column I, one mole of some oxidizing agents is
(T) Redox given. Match them with the moles of the reducing
agents needed for complete reaction, given in
2. Some compounds are given in Column I. Column II.
Match them correctly with the terms given
in Column II.
Column I Column II
Column I Column II (A) KMnO4 (H ) +
(P) 3.0 mole of
(A) SO2 (P) Oxidizing agent FeSO4
(B) SO3 (Q) Reducing agent (B) KMnO4 (OH−) (Q) 0.5 mole of I2 to
(C) H2O2 (R) Undergoes disproportionation HIO3
in air (C) MnO2 (H+) (R) 1.0 mole of K2C2O4
(D) NaF (S) Neither an oxidizing nor a (D) K2CrO4 (H+) (S) 1.5 mole of K2SO3
reducing agent

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 22 7/8/2019 2:25:40 PM


5. Some redox reactions are given in Column I. Match 8. Match the columns.
them with the correct mole ratio of oxidizing to
Column I Column II
reducing agents given in Column II.
(Equivalent weight (Chemical change)
Column I Column II of HCl)
(A) MnO4− + C2O42− → MnO2 + CO2 (P) 2 : 1 (A) Greater than its (P) Neutralization reaction
molecular weight
(B) ClO− + Fe(OH)3 → Cl− + FeO42− (Q) 3 : 1 (B) Equal to (Q) MnO2 + HCl → MnCl2
(C) HO2− + Cr(OH)3− → CrO42− + HO− (R) 2 : 3 molecular weight + Cl2 + H2O
(C) Less than (R) HClO → HCl
(D) N2H4 + Cu(OH)2 → N2O + Cu (S) 3 : 2
molecular weight

6. Match the columns. (S) HCl → HClO3


(T) Cu + HCl → H2[CuCl4]
Column I Column II
+ H2
(A) Equivalent volume of (P) 5.6 L at 0oC and
Cl2 gas 1 atm 9. Match the columns.
(B) Volume of O2 (Q) 11.2 L at 0oC
Column I Column II
needed for complete and 1 atm
(Solution needed for
combustion of 5.6 L
complete reaction)
methane at 0oC and 1
atm (A) 100 ml of 0.3 M (P) 100 ml of 0.3 M
o – H2C2O4 solution – KOH solution
(C) Equivalent volume of (R) 22.4 L at 0 C
O2 gas and 0.5 atm (B) 50 ml of 0.6 M – (Q) 120 ml of 0.1 M
(D) Equivalent volume of o
(S) 11.2 L at 0 C KHC2O4 solution – KMnO4 solution in
SO2 gas as oxidizing and 0.5 atm the presence of H2SO4
agent (C) 50 ml of 0.6 M – (R) 60 ml of 0.1 M
HCl solution – KMnO4 solution in
7. Match the columns. the presence of H2SO4
(D) 100 ml of 0.2 M – (S) 100 ml of 0.6 M –
Column I Column II
H3PO4 solution KOH solution
(Process) (Equivalent weight
of Cl2)
(A) Cl2 → Cl− (P) 71

(B) Cl2 → ClO3 (Q) 35.5
(C) Cl2 → Cl− + ClO3− (R) 42.6
− −
(D) Cl2 → Cl + ClO (S) 7.1

10. Match the columns.

Column I Column II (Solution needed for complete reaction)


(A) 50 ml of 0.5 M-Na2CO3 solution using (P) 50 ml of 0.5 M-H2SO4 solution
methyl orange indicator.
(B) 50 ml of 0.5 M-Na2CO3 solution using (Q) 50 ml of 0.5 M-HCl solution
phenolphthalein indicator.
(C) 50 ml of 0.5 M-NaHCO3 solution using (R) 25 ml of 0.5 M-H2SO4 solution
methyl orange indicator.
(D) 50 ml of 0.5 M-NaOH solution using (S) 50 ml of 1.0 M-HCl solution
phenolphthalein indicator.

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 23 7/8/2019 2:25:40 PM


Section F (Subjective)
Single-digit Integer Type 10. The basic solution of Na4XeO6 is powerful oxidants.
How many millimoles of Mn(NO3)2 ⋅ 6H2O reacts
1. The value of n in the following processes: with 62.5 ml of a 0.04 M basic solution of Na4XeO6
AO n4 − + 2e → HAO2n − is that contains an excess of sodium hydroxide if the
products include Xe and a solution of sodium
2. AO2 disproportionates into AO4− and An+ ion. If permanganate? (Mn = 55)
the mole ratio of AO2 undergone oxidation and
11. A newly developed method for water treatment
reduction is 2 : 3, the value of n is
uses chlorine dioxide ClO2 rather than Cl2 itself.
3. A volume of 1.12 L dry chlorine gas at 0oC and 1 ClO2 can be obtained by passing Cl2(g) into
atm was passed over a heated metal when 5.55 g concentrated solution of sodium chlorite NaClO2.
of chloride of the metal was formed. If the atomic NaCl is the other product. If this reaction has
mass of the metal is 40, then its valency is a 90% yield, then how many moles of ClO2 are
produced from 5 L of 2.0 M-NaClO2?
4. The equivalent weight of Br2 is 96 in the following
12. A quantity of 1.245 g of CuSO4 ⋅ xH2O was
disproportionation reaction.
dissolved in water and H2S was passed into it
Br2 + OH− → Br− + H2O + ? (Oxidized product) till CuS was completely precipitated. The H2SO4
produced in the filtrate required 10 ml of M-NaOH
The oxidation state of Br in the oxidized product solution. Calculate the value of x. (Cu = 63.5)
is (Br = 80)
13. A mixture of CS2 and H2S when oxidized yields a
5. HCHO disproportionates to HCOO− and CH3OH mixture of CO2, SO2 and H2O(g), which exerts a
in the presence of OH− (Cannizzaro’s reaction). pressure of 7.2 atm, when collected in 82.1 L vessel
2HCHO + OH− → HCOO− + CH3OH at 327ºC. To oxidize SO2 in the mixture, 7 L of 2 N
– iodine was required. Moles of CS2 in the
If the equivalent weight of HCHO is E, then the mixture is
E
value of is 14. A mixture of Xe and F2 was heated. A sample of
10
white solid thus formed reacted with hydrogen to
6. When a solid element is reacted with chlorine, give 56 ml of Xe at 0oC and 1 atm and HF formed
a gaseous chloride of vapour density 68.75 is required 60 ml of 0.25 M-NaOH for complete
formed. If this reaction is performed at constant neutralization. If the molecular formula of the
temperature and pressure, the volume of the solid formed is XeFx, then the value of x is
system reduces by one third. If the equivalent
weight of the solid element is E, then the value of 15. One litre of a sample of ozonized oxygen
⎛ 12 ⎞ at 0oC and 1 atm on passing through a KI
⎜⎝ × E ⎟⎠ is solution, liberated iodine which required 9 ml
31
of a thiosulphate solution. A volume of 12 ml
7. V litre of SO2 at 0oC and 1 atm is required to of a ‘5.675 volume’ hydrogen peroxide solution
reduce 16.9 g of HClO3 to HCl. The number of liberated iodine from another iodide solution,
moles in ‘5 V’ litre of SO2 at 273oC and 2 atm is which required 24 ml of the same thiosulphate
8. The approximate mass (in g) of N2H4 can be solution. The volume percent of ozone in the
oxidized by 24 g of K2CrO4 is (Cr = 52) ozonized oxygen sample is approximately

3N2H4 + 4CrO42− + 4H2O 16. A certain mass of anhydrous oxalic acid is


→ 3N2 + Cr(OH)4− + 4OH− converted into H2O, CO2 and CO, on heating in
the presence of H2SO4. The CO formed reacts
9. A sample of pure KHC2O4.H2C2O4.2H2O requires completely with iodine pentoxide to liberate
30 mol of NaOH for titration. How many moles iodine. The iodine thus liberated required 200 ml
of KMnO4 will the same sample react with, in acid of 0.2 N thiosulphate. The mass (in g) of oxalic
medium? acid taken was

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 24 7/8/2019 2:25:41 PM


17. When ammonium vanadate is heated with oxalic 19. A quantity of 1.0 g sample of Fe2O3 solid of 55.2
acid solution, a substance Z is formed. A sample per cent purity is dissolved in acid and reduced by
of Z was treated with KMnO4 solution in hot heating the solution with zinc dust. The resultant
acidic solution. The resulting liquid was reduced solution is cooled and made up to 100 ml. An
with SO2, the excess SO2 boiled off and the liquid aliquot of 25 ml of this solution requires 17 ml of
again titrated with same KMnO4. The ratio of 0.0167 M solution of an oxidant for titration. The
the volumes of KMnO4 used in the two titrations number of electrons taken up by the oxidant in the
was 5 : 1. What is the oxidation state of vanadium reaction of the above titration is
in substance Z? Given that KMnO4 oxidizes all
oxidation state of vanadium to vanadium (+5) and 20. A quantity of 1.16 g CH3(CH2)nCOOH was burnt
SO2 reduces V (+5) to V (+4). in excess of air and the resultant gases (CO2 and
H2O) were passed through excess NaOH solution.
18. A solution of 0.2 g of a compound containing Cu2+ The resulting solution was divided into two equal
and C2O42− ions on titration with 0.02 M-KMnO4 parts. One part requires 50 ml of N-HCl for
in the presence of H2SO4 consumes 22.6 ml of the neutralization using phenolphthalein indicator.
oxidant. The resultant solution is neutralized with Another part required 80 ml of N-HCl for
Na2CO3 acidified with dilute acetic acid and treated neutralization using methyl orange indicator. The
with excess KI. The liberated iodine requires 11.3 value of n is
ml of 0.05 M-Na2S2O3 for complete reduction. If
the molar ratio of Cu2+ to C2O42− in the compound
is 1 : x, then the value of x is

Four-digit Integer Type

1. A transition metal X forms an oxide of formula 36 ml of 0.12 N – KMnO4 separately. Assume all
X2O3. It is found that only 50% of X atoms in this H-atoms are replaceable and x, y and z are in the
compound are in the +3 oxidation state. The only simple ratio of g-atoms. The value of xyzn is
other stable oxidation states of X are +2 and +5.
What percentage of X atoms is in the +2 oxidation 6. A solution is made by mixing 200 ml of 0.1
state in this compound? M-FeSO4, 200 ml of 0.1 M-KMnO4 and 600 ml of
1 M-HClO4. A reaction occurs in which Fe2+ and
2. An amount of 0.1 moles of OH− ions is obtained MnO4− convert to Fe3+ and Mn2+. If the molarity
from 8.50 g of hydroxide of a metal. What is the of H+ ion in the final solution is ‘x’ M, then the
equivalent weight of the metal? value of 1000x is
3. A quantity of 2.7 g of an alloy of copper and
silver was dissolved in moderately conc. HNO3 7. The saponification number of fat or oil is defined
and excess of HCl was added to this solution as the number of mg of KOH required to saponify
when 2.87 g of a dry precipitate is formed. 1 g oil or fat. A sample of peanut oil weighing
Calculate the percentage of copper in the alloy. 1.5 g is added to 25.0 ml of 0.4 M-KOH. After
(Cu = 63.5, Ag = 108) saponification is complete, 8.0 ml of 0.25 M-H2SO4
is needed to neutralize excess of KOH. What is the
4. Peroxides like oxides are basic. They form saponification number of peanut oil?
hydrogen peroxide upon treatment with an acid.
What volume (in ml) of 0.25 M-H2SO4 solution is 8. A quantity of 1.6 g of pyrolusite ore was treated
required to neutralize a solution that contains 7.2 g with 50 ml of 1.0 N-oxalic acid and some sulphuric
of CaO2? acid. The oxalic acid left undecomposed was raised
5. A volume of 30 ml of a solution containing 9.15 to 250 ml in a flask. A volume of 25 ml of this
g per litre of an oxalate KxHy(C2O4)z.nH2O is solution when titrated with 0.1 N-KMnO4 required
32 ml of the solution. The percentage of available
required for titrating 27 ml of 0.12 N-NaOH and
oxygen in the ore is

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 25 7/8/2019 2:25:41 PM


9. Calculate the amount (in mg) of SeO32− in As2S3 + 2I2 + 2H2S → As2S5 + 4H+ + 4I−
solution, where 20 ml of M/40 solution of KBrO3
As2S5 + 4H+ + 2I− → As2S3 + 2I2 + 2H2S
was added to a definite volume of SeO32− solution.
The bromine evolved was removed by boiling and The mole percent of As2S3 in the original mixture
excess of KBrO3 was back titrated with 7.5 ml is (As = 75)
of M/25 solution of NaAsO2. The reactions are
(Se = 79) 15. The element Se dispersed in 2 ml sample of
SeO3 2− −
+ BrO3 + H → SeO4 + 2−
+ Br2 + H2O detergent for dandruff control was determined
by suspending it in the warm ammonical solution
BrO3 + AsO2 + H2O → Br + AsO43− + H+
− − −
that contained 45 ml of 0.02 M-AgNO3.
10. If 91 g of V2O5 is dissolved in acid and reduced to 6Ag+ + 3Se(s) + 6NH3 + 3H2O
V2+ by treatment with zinc metal, then how many → 2Ag2Se(s) + Ag2SeO3(s) + 6NH4+
grams of I2 could be reduced by the resulting V2+
solution, as it is oxidized to V4+? (V = 51, I = 127) The mixture was now treated with excess nitric
acid which dissolved the Ag2SeO3 but not Ag2Se.
V2O5 + 10H+ + 6e− → 2V2+ + 5H2O The Ag+ from Ag2SeO3 and the excess of AgNO3
V2+ + I2 + H2O → 2I− + VO2+ + 2H+ consumed 10 ml of 0.01 N-KSCN in Volhard
titration. How many milligrams of Se was
11. A 200 ml sample of a citrus fruit drinks containing contained per ml of sample? (Se = 80)
ascorbic acid (vitamin C) was acidified with H2SO4
and 10 ml of 0.025 M-I2 was added. Some of the 16. One gram of commercial AgNO3 is dissolved in
I2 was reduced by the ascorbic acid to I−. The 50 ml of water. It is treated with 50 ml of a KI
excess of I2 required 2.5 ml of 0.01 M-Na2S2O3 for solution. The silver iodide thus precipitated is
reduction. What was the vitamin C content of the filtered off. Excess of KI is titrated with M/10-
drink in microgram vitamin per ml drink? KIO3 solution in the presence of 6 M-HCl till
C6H8O6 + I2 → C6H6O6 + 2HI all iodide ions are converted into ICl. It requires
5H2O + S2O32− + 4I2 → 2SO42− + 8I− + 10H+ 50 ml of M/10-KIO3 solution. A 20 ml of the
same stock solution of KI requires 30 ml of M/10-
12. A 0.2 g sample of chromite was fused with excess KIO3 under similar conditions. The percentage of
of Na2O2 and brought into solution according to AgNO3 in the sample is (Ag = 108)
the following reaction.
Reaction: KIO3 + 2KI + 6HCl → 3ICl + KCl + 3H2O
2Fe(CrO2)2 + 7Na2O2
→ 2NaFeO2 + 4Na2CrO4 + 2Na2O 17. A 4.0 g sample containing Fe3O4, Fe2O3 and an
inert impure substance is treated with excess
The solution was acidified with dil. HCl and
of KI solution in the presence of dilute H2SO4.
1.96 g Mohr’s salt (molar mass = 392 g/mol) was
The entire iron is converted to Fe2+ along with
added. The excess of Fe2+ required 40 ml of 0.05
the liberation of iodine. The resulting solution
N-K2Cr2O7 for titration. What is the percent of Cr
is diluted to 100 ml. A 20 ml of dilute solution
in sample? (Cr = 52, Fe = 56)
requires 11.2 ml of 0.5 M – Na2S2O3 solution to
13. A 10 g mixture of Cu2S and CuS was treated reduce the iodine present. A 50 ml of the diluted
with 400 ml of 0.4 M – MnO4− in acid solution solution, after complete extraction of iodine,
producing SO2, Cu2+ and Mn2+. The SO2 was requires 12.80 ml of 0.25 M – KMnO4 solution
boiled off and the excess of MnO4− was titrated in dilute H2SO4 medium for the oxidation of Fe2+.
with 200 ml of 1 M – Fe2+ solution. The percentage The percentage of Fe2O3 in the original sample is
of CuS in original mixture is (Cu = 64)
18. An aqueous solution containing 1.07 g KIO3 was
14. A mixture containing As2S3 and As2S5 requires treated with an excess of KI solution. The solution
20 ml of 0.05 N iodine for titration. The resulting was acidified with HCl. The liberated I2 consumed
solution is then acidified and excess of KI was 50 ml of thiosulphate solution to decolourize the
added. The liberated iodine required 1.24 g hypo, blue starch-iodine complex. The molarity of the
Na2S2O3 ⋅ 5H2O, for complete reaction. The sodium thiosulphate solution is x M, then the
reactions are as follows. value of 1000x is (K = 39, I = 127)

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 26 7/8/2019 2:25:42 PM


19. Hydrogen peroxide solution (20 ml) reacts 20. If 20 ml of 0.1 M solution of sodium
quantitatively with a solution of KMnO4 (20 ml) sesquicarbonate (Na2CO3 ⋅ NaHCO3) is titrated
acidified with dilute H2SO4. The same volume of against 0.05 M – HCl, using (i) phenolphthalein
the KMnO4 solution is just decolourized by 10 and (ii) methyl orange as indicators, then what
ml of MnSO4 in neutral medium simultaneously difference in titre values (in ml) would be recorded?
forming a dark brown precipitate of hydrated
MnO2. The brown precipitate is dissolved in 10 ml
of 0.2 M sodium oxalate under boiling condition
in the presence of dilute H2SO4. The strength of
H2O2 solution in mg per 100 ml solution is

Answer Keys Exercise I


Oxidation–Reduction
1. (d) 2. (d) 3. (a) 4. (a) 5. (c) 6. (d) 7. (a) 8. (a) 9. (c) 10. (a)
11. (b) 12. (b) 13. (b) 14. (a) 15. (d) 16. (b) 17. (d) 18. (a) 19. (c) 20. (b)
21. (c) 22. (d) 23. (b) 24. (d) 25. (b) 26. (b) 27. (c) 28. (c) 29. (a) 30. (b)
31. (b) 32. (c) 33. (a) 34. (c) 35. (b)

Equivalent Concept
36. (c) 37. (b) 38. (a) 39. (b) 40. (c) 41. (c) 42. (a) 43. (a) 44. (b) 45. (b)
46. (d) 47. (c) 48. (c) 49. (d) 50. (b) 51. (a) 52. (c) 53. (a) 54. (b) 55. (c)
56. (b) 57. (a) 58. (b) 59. (c) 60. (a) 61. (a) 62. (d) 63. (d) 64. (c) 65. (b)
66. (b) 67. (d) 68. (c) 69. (c) 70. (c)

Volumetric Analysis
71. (c) 72. (c) 73. (a) 74. (c) 75. (b) 76. (d) 77. (a) 78. (a) 79. (b) 80. (a)
81. (a) 82. (c) 83. (a) 84. (c) 85. (a) 86. (c) 87. (a) 88. (b) 89. (b) 90. (c)
91. (d) 92. (b) 93. (a) 94. (b) 95. (a) 96. (a) 97. (a) 98. (a) 99. (b) 100. (b)
101. (a) 102. (d) 103. (c) 104. (d) 105. (d) 106. (b) 107. (b) 108. (a) 109. (a) 110. (b)
111. (b) 112. (a) 113. (c) 114. (b) 115. (b) 116. (d) 117. (a) 118. (c) 119. (b) 120. (a)

Answer Keys Exercise II


Section A (Only one Correct)
1. (b) 2. (d) 3. (b) 4. (b) 5. (b) 6. (d) 7. (a) 8. (d) 9. (c) 10. (a)
11. (c) 12. (d) 13. (a) 14. (c) 15. (c) 16. (c) 17. (a) 18. (c) 19. (b) 20. (a)
21. (b) 22. (b) 23. (b) 24. (b) 25. (b) 26. (c) 27. (c) 28. (b) 29. (d) 30. (a)
31. (b) 32. (a) 33. (b) 34. (b) 35. (c) 36. (d) 37. (c) 38. (d) 39. (d) 40. (a)
41. (b) 42. (c) 43. (d) 44. (a) 45. (b) 46. (c) 47. (c) 48. (b) 49. (a) 50. (b)
51. (a) 52. (c) 53. (d) 54. (c) 55. (c) 56. (d) 57. (a) 58. (b) 59. (b) 60. (a)
61. (d) 62. (a) 63. (b) 64. (b) 65. (a) 66. (b) 67. (a) 68. (d) 69. (b) 70. (a)
71. (b) 72. (c) 73. (a) 74. (b) 75. (b)

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 27 7/8/2019 2:25:42 PM


Section B (One or More than one Correct) 9. (d) 10. (a), (c)
11. (b), (c), (d) 12. (b), (d)
1. (b), (d) 2. (b), (c), (d) 13. (a), (b), (c) 14. (b)
3. (a), (b), (c) 4. (b) 15. (a), (d) 16. (a)
5. (a), (b), (c) 6. (b), (c) 17. (a), (b), (c) 18. (a), (b), (c), (d)
7. (a), (b) 8. (b) 19. (a), (b), (c), (d) 20. (a), (c), (d)

Section C
Comprehension I Comprehension VI

1. (c) 2. (a) 3. (b) 16. (b) 17. (a) 18. (b)


Comprehension II Comprehension VII

4. (a) 5. (b) 6. (b) 19. (c) 20. (a) 21. (b)


Comprehension III Comprehension VIII

7. (b) 8. (a) 9. (c) 22. (a) 23. (b) 24. (b)


Comprehension IV Comprehension IX

10. (b) 11. (c) 12. (b) 25. (a) 26. (b) 27. (d)
Comprehension V Comprehension X

13. (a) 14. (b) 15. (a) 28. (c) 29. (b) 30. (b)

Section D (Assertion – Reason)


1. (a) 2. (d) 3. (b) 4. (d) 5. (c) 6. (a) 7. (c) 8. (b) 9. (a) 10. (c)
11. (d) 12. (a) 13. (a) 14. (a) 15. (d)

Section E (Column Match)


1. A → R; B → P, T; C → Q, T; D → S, T
2. A → P, Q; B → P; C → P, Q, R; D → S
3. A → S, T; B → P, Q; C → P, Q, R; D → Q, S
4. A → Q; B → P, S; C → R; D → P, S
5. A → R; B → S; C → P; D → Q
6. A → Q, R; B → Q, R; C → P, S; D → P, S
7. A → Q; B → S; C → R; D → P
8. A → Q, T; B → P; C → R, S
9. A → Q, S; B → P, Q; C → P, R; D → S
10. A → P, S; B → Q, R; C → Q, R; D → Q,R

Section F (Subjective)
Single-digit Integer Type

1. (3) 2. (2) 3. (2) 4. (5) 5. (3) 6. (4) 7. (3) 8. (3) 9. (8) 10. (4)
11. (9) 12. (5) 13. (2) 14. (6) 15. (9) 16. (9) 17. (0) 18. (2) 19. (6) 20. (4)
Four-digit Integer Type

1. (0033) 2. (0068) 3. (0020) 4. (0400) 5. (1322)


6. (0568) 7. (0224) 8. (0009) 9. (0127) 10. (0254)
11. (0132) 12. (0026) 13. (0080) 14. (0020) 15. (0024)
16. (0085) 17. (0040) 18. (0600) 19. (0340) 20. (0080)

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 28 7/8/2019 2:25:42 PM


HINTS AND EXPLANATIONS

EXERCISE I (JEE MAIN)

Oxidation–Reduction

1. m × ( + a ) + n × ( −b ) + r × ( −c ) = 0 ⇒ ma = bn + cr. 17. Oxidation state of Cr in K3CrO8 is +5. In CrO5 ,


it is +6. K3CrO8 has four peroxide ( O2−
2 ) linkage
2. 2 ( +2 ) + x + 6 ( −2 ) = 0 ⇒ x = +8.
while CrO5 has only two peroxide linkage.
3. Oxidation state of Cr in both compounds is +6. H O
++2
18. –1N–1
N –
4. In this compound, NO is present as NO + . –1 H
–1 +1
O

5. Oxidation state of Br in Br2 , Br − and BrO3− is 0, Oxidation state of N = –3 Oxidation state of


–1 and +5, respectively. N = +3
O O
6. The maximum oxidation state of S in any of its
– +5 O O +5 –
compound is +6. 19. O S S S S O

7. The oxidation state of Fe in Fe (CO )5 , Fe2 O3 , O O

K 4 ⎡⎣Fe ( CN )6 ⎤⎦ and FeSO 4 . ( NH4 )2 SO 4 .6H2 O 20. Empirical formula of C 6 H12 O6 and HCHO is
same.
are 0, +3, +2 and +2, respectively.
+6 +2.5 +2 0
70
8. (a) H2 S2 O7 , Na 2 S4 O6, Na 2 S4 O3, S8 N Fe 56 2
21. = = ⇒ Formula = Fe2 O3
+4 +6 +4 +4 NO 30 3
(b) SO2 +, SO24 −, SO32 − , HSO 4− 16
+6 +4 +2 −2 ∴ Oxidation state of Fe = +3.
(c) H2SO5 , H2SO3 , SC 2 , H2 S
+6 +4 −2 +6 22. The reducing power of non-metal hydrides
(d) H2 SO 4 , SO2, H2 S , H2 S2 O8 increase from top to bottom in a group

9. On oxygenation, Fe2+ present in haemoglobin 23. Hydroquinol undergoes removal of hydrogen, i.e.,
oxidizes to Fe3+ . oxidation and hence, it acts as a reducing agent.
+ –
10. H+1 –1C+3 –3N H+1 –1N–3 +3C
24. Redox reactions may involve absorption or release
of heat.
Oxidation state of C = +2 Oxidation state of
C = +2 25. Oxidation and reduction is occurring due
to different elements and hence, it is not a
4
11. 3x + 2 ( −2 ) = 0 ⇒ x = + . disproportionation.
3 +4 +4
12. H2SO 4 + BaO2 → BaSO 4−2 + H2 O2−1 26. CaO + SiO2 → Ca SiO3
Base Acid Salt
+7 +6
13. MnO −4 , Cr O2 Cl2 These are highest oxidation 27. H2S + SO2 → S + H2 O
states of Mn and Cr, respectively.
Same element but belonging to different
14. 2 ( +2 ) + 2 x + 7 ( −2 ) = 0 ⇒ x = +5. molecule undergoes oxidation and reduction and
hence, it is not disproportionation. In fact, it is
15. Toluene = C 7 H8 ⇒ 7 x + 8 ( +1) = 0 ⇒ 7 x = −8. comproportionation.
16. Oxidation state of K in all of its compound is +1. 28. Referer Question No. 27.

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 29 7/8/2019 2:25:49 PM


29. 3X 2 O3 + 4Cr2 O72 − + 26H+ → 31. Oxidation: Br2 + 12OH− → 2BrO3− + 6H2 O + 10e −
6 XO 4− + 8Cr3+ + 13H2 O Reduction: Br2 + 2e − → 2Br − 1× 5
Method II: (After equivalent concept) Net reaction:
neq of X 2 O3 = neq Cr2 O7−2 6Br2 + 12OH− → 2BrO3− + 10Br − + 6H2 O
3 32. 2 NO3− + 10H+ + 8e − → N 2 O + 5H2 O
or n × 8 = 1 × 6 ⇒ nx2o3 =
4
33. NO2− + 5H2 O + 6e − → NH3 + 7OH−
30. 2 NO3− + −
+ 16H + 14e → N 2 H4 + 6H2 O
34. 4 Zn + NO3− + 7H2 O → 4 Zn2 + + NH+4 + 10OH −
14
∴ Number of e − per NO3− ion = = 7.
2 35. 4Fe + 10HNO3 → 4Fe( NO3 )2 + NH4 NO3 + 3H2 O
Method II: Oxidation state of N changes from +5
to –2 and hence, there is a gain of 7e − per NO3−
ion.

Equivalent Concept

36. neq of oxygen = neq of oxide 44. Ca3 ( PO 4 )2 + 2H+ → 2CaHPO 4 + Ca 2 +


20 100 M
or = ⇒ E = 40. Equivalent weight of Ca3 (PO 4 )2 = .
8 E 2
37. Sulphurated hydrogen (g) 45. Change in oxidation state of Mn should be 2 units.
+ Sn(S) → Tin Sulphide (s) + H2 ( g ) M M M
46. E1 : E2 : E3 = : : = 3 : 15 : 5
x mole x mole 5 1 3
= x × 34 g = x×2 g 47. As 2S3 + 20H2 O + 28e − → 2 AsO34− + 3SO24 − + 40H+
No change in volume means no change in mole of M M M
gases. 48. (a) E = (b) E = (c) E =
3 5 1
Mass of sulphur combined with 2x gm hydrogen +5
= 34 x − 2 x = 32 x g. 49. Cu 2 P −3 → H3 PO 4
32 x 50. Cl2 → Cl −
∴ Esulphur = × 1 = 16
2x 1
51. H2 O 2 → H2 O + O 2
38. Atomic mass = Equivalent mass × Valency 2
n The reaction is balanced on the loss and gain of
=E× ×2 one electron per H2 O2 molecule.
m
39. neq metal = neq metal chloride 52. Reaction is balanced on the loss or gain of 10e − .

w 162.52 53. H2 O2 is acting as reductant. Its equivalent weight


or = ⇒ w = 56 g.
18.67 18.67 + 35.5 34
is = 17.
40. 4N A electrons means 4 equivalents. Hence, mass 2
of Mg needed = 4 × 12 = 48 gm 54. N 2 + 3H2 → 2 NH3
M Reaction is balanced by the loss or gain of 6e − .
41. K 2 CrO 4 is behaving as salt and hence, E = .
2
M 55. MCl2 = 32.7 × 2 + 35.5 × 2 = 136.4
42. NaHC 2 O 4 is behaving as acid and hence, E = .
1
56. 3Zn + 8HNO3 → 3Zn ( NO3 )2 + 2 NO + 4H2 O
M
43. NaHC 2 O 4 is behaving as base and hence, E = . Reaction is balanced by the loss or gain of 6e − .
1

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 30 7/8/2019 2:25:56 PM


57. Reaction is balanced by the loss or gain of 2e − . 2 × V.D. 2 × 77
67. Valency = = =4
58. neq metal carbonate = neq metal oxide E + 35.5 3 + 35.5
100 60 ∴ Atomic mass = 3 × 4 = 12
or = ⇒ E = 25
E + 30 E + 8 68. neq C 6 H10 O 4 = neq KOH
59. neq metal chloride = neq metal sulphate
1 0.768
0.298 0.348 or × Basicity = ×1
or = ⇒ E = 39 146 56
E + 35.5 E + 48 ⇒ Basicity of C 6 H10 O 4 = 2
60. neq NH3 = neq O2 = 1 × 4 = 4
69. neq metal bromide = neq metal chloride
61. neq Cr2 O72 − = neq N 2 H5+ 1.878 1.00
or = ⇒ Equivalent mass of
⇒ n × 6 = 0.136 E + 80 E + 35.5
⇒ n = 0.0226 metal, E = 15.18.
62. x×5 = y×6 ⇒ x : y = 6 :5 Now, approximate atomic mass of metal
6.4
63. neq metal carbonate = neq metal sulphate = = 45.71
0.14
w 1.43w 45.71
or = ∴ Valency = = 3 (Integer)
E + 30 E + 48 15.18
∴ E = 11.86 ∴ Exact atomic mass of metal bromide
64. neq H2S = neq KMnO 4 = 15.18 × 3 = 45.54
w 6.32 × 3 ∴ Molecular mass of metal bromide
or ×8 = ⇒ w = 0.51 g = 45.54 + 3 × 80 = 285.54
34 158
65. neq metal = neq oxygen 70. The chemical formula of potassium sulphate
is K 2SO 4 and hence, potassium chromate is
52.91 47.09 K 2 CrO 4 .
or = ⇒ E = 8.99
E 8 Molecular mass = 2 × 39 + A + 4 × 16 = 142 + A
∴ Atomic mass of metal = 8.99 × 3 = 26.97
26.79
6.4 From question, (142 + A) × = A ⇒ A = 51.96.
66. Approximate atomic mass = = 75.29 100
0.085
Atomic mass 75.29
Now, Valency = ≈
Equivalent mass 25
≈ 3 ( integer )
∴ Exact atomic mass = 25 × 3 = 75.

Volumetric Analysis
10

100 = x
71. neq of H2SO 4 in V ml solution = Hence, 0.01 eq. of Na 2SO 4 will form and the
49
resulting solution will be neutral.
10
V× 73. neq AgNO3 = neq K 2 CrO 4
100 = y
neq of NaOH in V ml solution =
40 V × 0.1 10 × 0.09
or ×1 = × 2 ⇒ V = 18 ml
As y > x , the resulting solution should be basic. 1000 1000
0.62 74. neq KMnO 4 = neq KNO2
72. neq of Na 2 CO3 .H2 O = × 2 = 0.01
124 V × 0.18 25 × 0.21
or = ⇒ V = 29.17 ml
100 × 0.1 1000 1000
and neq of H2SO 4 = = 0.01.
1000

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 31 7/8/2019 2:26:06 PM


75. neq KMnO 4 = neq Na 2S2 O3 84. neq CrO 4−2 = neq S2 O24 −
V × 0.1 0.158 522
or ×3 = × 8 ⇒ V = 26.67 ml or 100 × M × 3 = × 2 ⇒ M = 0.02
1000 158 179
85. neq CaC 2 O 4 = neq KMnO 4
76. neq HNO3 = neq NaOH
25 × 0.001
V1 × 18.9 V × 3.2 or n × 2 = ×5
or ×1 = 2 × 1 ⇒ V1 : V2 = 4 : 15 1000
63 40
∴ Moles of Ca = Moles of CaC 2 O 4 = 62.5 × 10 −6
77. neq NH3 = neq H2SO 4 in 10 ml of blood.
∴ Milligram of Ca per litre blood
V 30 × (1 − 0.2 )
or ×1 = ⇒ V = 537.6 ml 62.5 × 10 −6 × 40
22400 1000 = × 1000 = 0.25
10
78. neq Na 2 CO3 = neq acid ‘A’ 86. neq KMnO 4 = neq H2 C 2 O 4
26 × 1 10 × N A w 50 × 0.2
or = ⇒ N A = 2.6 N or ×5 = × 2 ⇒ w = 0.632 g
1000 1000 158 1000
and neq Na 2 CO3 = neq acid ‘B’ 87. neq Ca (OH)2 = neq H3 PO 4
26 × 1 40 × N B
or = ⇒ N B = 0.65 N V × 0.05 10 × 0.1
1000 1000 or ×2 = × 1 ⇒ V = 10 ml
1000 1000
Now, VN = VA N A + VB N B 88. neq H2 C 2 O 4 ⋅ 2H2 O = neq KMnO 4
or 1000 × 1 = VA × 2.6 + (1000 − VA ) × 0.65 w 100 × 0.4
⇒ VA = 179.49 ml. or ×2 = × 5 ⇒ w = 12.6 g
126 1000
79. neq Ag = neq KCNS 89. neq Na 2 B4 O7 .10H2 O = neq HCl
90 w 25 × 0.2
0.5 × or ×2 = ⇒ w = 0.953 g
or 100 = 25 × N ⇒ N = 0.167 381.2 1000
108 1000
90. neq metal salt = neq Na 2SO3
80. neq KH2 PO 4 = neq OH −
50 × 0.1 25 × 0.1
w 25 × 0.1 or × (3 − x ) = ×2⇒ x = 2
or ×1 = ⇒ w = 0.34 g 1000 1000
136 1000 91. neq H2 O 2 = neq KMnO 4
0.34 x
∴ % Purity = × 100 = 68% 1×
0.5 100 x×N
or ×2 = ⇒ N = 0.588
81. neq KMnO 4 = neq H2 O2 34 1000
50 × 0.1 w 92. neq FeC 2 O 4 = neq KMnO 4
or ×5 = × 2 ⇒ w = 0.425 g
1000 34
1 60 × M
0.425 or ×3 = × 5 ⇒ M = 0.0694
∴ Strength = × 100 = 4.25% ( w v ) 144 1000
10
15 × 0.2
82. neq KHC8H4 O 4 = neq Ba (OH)2 93. neq of NaOH = × 1 = 3 × 10 −3
1000
0.204 25 × M 12 × 0.15
or ×1 = × 2 ⇒ M = 0.02 neq of MgCl2 = × 2 = 3.6 × 10 −3
204 1000 1000
83. neq SeO2 = neq Cr 2 + Hence, NaOH is a limiting reagent.
12.5 × 0.05 25 × 0.1 Now, the mass of Mg ( OH )2 formed = 3 × 10–3 ×
or × (4 − x ) = ×1 ⇒ x = 0 29 = 0.087 g.
1000 1000

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 32 7/8/2019 2:26:13 PM


94. neq acid = neq NaOH 102. neq HCl = neq AgCl
39 40 25 × N 0.287
× 100 × 95 or = × 1 ⇒ N HCl = 0.08
or 1000 ×n = 1000 × 1 ⇒ n = 1.997  2 1000 143.5
82 40 and N H2SO4 = 0.2 − 0.08 = 0.12.
20 ∴ Mass per cent of
95. Normality = × 2 = 0.408 N
98 0.08 × 36.5
96. Acidic solution: HCl = × 100 = 33.18%
0.08 × 36.5 + 0.12 × 49
25 × 0.017 16.9 × 0.01 103. neq anhydrous acid = neq NaOH
×2 = × (7 − x ) ⇒ x = 2
1000 1000
0.10 25 × 0.1
Neutral Solution: or = ⇒ E = 40
E 1000
25 × 0.017 28.6 × 0.01 and neq hydrated acid = neq NaOH
×2 = × (7 − y ) ⇒ y = 4
1000 1000
97. neq acid = neq NaOH 0.245 50 × 0.1
or = ⇒ x = 0.5
E + 18x 1000
⎛ 28 ⎞ 1
0.84 ⎜⎝ × 100⎟⎠ × 100 × 1 V ×1
25 10 104. ×5 = × 3 ⇒ V = 166.67 ml
or ×n = ⇒ Basicity, N = 2 1000 1000
150 1000
150 105. neq HCl = neq metal carbonate + neq caustic soda
and equivalent weight of acid = = 75
2 1
98. neq Na 2 CO3 ⋅ xH2 O = neq HCl 50 ×
25 × 1 1 10
or = + ⇒ E = 50
1000 E 1000
⎛ 19.8 ⎞ 1
⎜ × 100⎟ ×
0.70 ⎝ 20 ⎠ 10 106. neq NaOH = neq ( NH4 )2 SO 4 + neq HCl
or ×2 = ⇒x=2
106 + 18x 1000
80 × 0.1 w 11.6 × 0.1
or = ×2+ ⇒ w = 0.451 g
99. neq H2SO 4 = neq NaOH 1000 132 1000

⎛ 25.6 ⎞ 1 ∴ Mass of Na 2SO 4 = 0.91 − 0.451 = 0.459 g


⎜⎝ × 1000⎟ × × 0.95
w 25 ⎠ 10
or ×2 = 107. neq Ag 2S = neq H2S
98 1000
⇒ w = 4.77 g w 11.2
or ×2 = × 2 ⇒ w = 0.124 g
w 248 22400
∴ % Strength of acid = × 100 = 77.38%
3.5 × 1.76
108. neq Fe2 + = neq K 2 Cr2 O7
100. neq Na 2 CO3 = neq H2SO 4
98
1 0.2 ×
25 × or 100 × 1 = 30 × N ⇒ N = 0.1167
or 10 = 10 × N ⇒ N = 0.25 56 1000
1000 1000
109. neq O3 = neq I 2 = neq Na 2S2 O3
Now, for dilution, 400 × 0.25 = V × 0.1
⇒ V = 1000 ml. 1
40 ×
or n × 2 = 10 × 1 ⇒ n = 2 × 10 −3
∴ Volume of water added = 1000 − 400 = 600 ml. O3
1000
101. neq H2SO 4 = neq NaOH + neq Na 2 CO3 1
and total moles of gases = = 4.46 × 10 −2
25 × N 50 × 0.5 0.265 22.4
or = + ×2
1000 1000 106 ∴ Moles of O2 = 4.46 × 10 −2 − 2 × 10 −3 = 4 26 × 10 −2
∴ Normality of diluted solution, N = 1.2 ∴ Mass percent of
Now, V1N1 = V2 N 2 ⇒ 10 × N1 = 100 × 1.2 2 × 10 −3 × 48
O3 = × 100 = 6.575%
⇒ N1 = 12 N 2 × 10 × 48 + 4.26 × 10 −2 × 32
−3

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 33 7/8/2019 2:26:21 PM


y×N
110. neq Cl2 = neq I 2 = neq Na 2S2 O3 or = a ×1+ b ×1 (2)
1000
w 26 × 0.15 35.5 × 26 × 0.11
or ×2 = ⇒w= g From (1) and (2), we get:
71 1000 1000
w VHCl only forms NaHCO3 (original ) = ( y − x ) ml.
∴ Mass percent of Cl2 = × 100 = 0.13%
71 × 1.1 117. Bromocresol green:
111. neq HClO = neq I 2 = neq Na 2S2 O3 25 × 0.107 23.1 × 0.115
×n = ×1 ⇒ n  1
17.4 × 0.02 0.174 1000 1000
or n × 2 = ×1 ⇒ n = .
1000 1000 Phenolphthalein:
25 × 0.107 46.2 × 0.115
Cl2 + H2 O → HCl + HClO ×n = ×1 ⇒ n  2
1000 1000
⎛ n ⎞
∴ Mass of Cl2 per litre = ⎜ × 1000⎟ × 71 = 0.494 g
⎝ 25 ⎠ 118. Temporary hardness is due to Ca ( HCO3 )2 and
112. neq Na3 AsO 4 = neq I 2 = neq hypo Mg (HCO3 )2 .

or
1
×2 =
V × 0.2
⇒ V = 48.1 ml neq CaCO3 = neq Ca (HCO3 )2 + neq Mg (HCO3 )2
208 1000
w 162 × 10 −3 73 × 10 −3
113. neq S2 O32 − = neq K 2S2 O8 or ×2 = ×2+ ×2
100 162 146
V × 0.25 1 ⇒ w = 150 × 10 −3 g
or ×1 = × 2 ⇒ v = 29.63 ml
1000 270
150 × 10 −3
114. neq MnO 4− = neq FeSO 4 ∴ Temporary hardness = × 106
1000
V1 × M1 V × M2 = 150 ppm.
or ×5 = 2 × 1 ⇒ 5V1M1 = V2 M 2 Permanent hardness is due to MgCl2 and CaSO 4.
1000 1000
115. n eq KHC 2 O 4 = neq KMnO 4 neq CaCO3 = neq MgCl2 + neq CaSO 4
x 100 × 0.02 w 95 × 10 −3 136 × 10 −3
or ×2 = ×5 (1) or ×2 = ×2+ ×2
M 1000 100 95 136
neq KHC 2 O 4 = neq Ca (OH)2 ⇒ w = 200 × 10 −3 g.
y 100 × 0.5 200 × 10 −3
or ×1 = ×2 (2) ∴ Permanent hardness = × 106
M 1000 1000
x 1 = 200 ppm.
∴ =
y 2 ⎛ 5.6 ⎞
× 1000
⎜ 100 ⎟
116. Let NaHCO3 = a mole, Na 2 CO3 = 6 mole. 119. Temporary hardness = ⎜ ⎟ × 200
56
In the presence of phenolphthalein, neq HCl = ⎜ ⎟
⎝ ⎠
neq Na2CO3
= 100 ppm.
x×N 2
or
1000
= b ×1 (1)
(
120. Ca 2 + =)
10
2
= 5 × 10 −3 M

In the presence of methyl orange, ⎛ 5 × 10 −3 ⎞


∴ Hardness = ⎜ × 106 ⎟ × 40 = 200 ppm
neq HCl = neq NaHCO3 (original ) + ⎝ 1000 ⎠
neq NaHCO3 (formed )

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 34 7/8/2019 2:26:29 PM


EXERCISE II (JEE ADVANCED)

Section A (Only one Correct)

1. Addition of hydrogen is reduction. 16. 2Mn2 + + 5PbO2 + 4H+ → 2MnO 4− + 5Pb2+ + 2H2 O

2. Sodium amalgam is an alloy (mixture of sodium 17. AsO33− + 2OH− → AsO34− + H2 O + 2e −


and mercury).
18. ‘Cr’ should be in +6 oxidation state in the product.
3. 2 x + 4 ( −2 ) + 2 × 0 + 2 × 0 = −2 ⇒ x = +3 For basic medium, the product should be CrO2− 4 .
+5
4. KBF4 : ( +1) + x + 4 ( −1) = 0 ⇒ x = +3 19. N O3− + 4e − → Oxidation state of N in the product
should be +1.
5. LiBiO2 : ( +1) + x + 2 ( −2 ) = 0 ⇒ x = +3
20. CH3CH2 OH + H2 O ⇒ CH3COOH + 4H+ + 4e −
53.5 46.5
6. N Xe : NF = : = 1 : 6 ⇒ XeF6
131 19 21. CH3CH2 OH + H2 O ⇒ CH3COOH + 4H+ + 4e −
∴ Oxidation state of Xe = +6. 22. The oxidation state of ‘Cr’ in ClO −x must be +1 and
O hence, x = 1.
7. H3C S CH3 S is more E N than C, but less E N 23. 1 mole of AO3− should gain 6 moles of electron.
than O.
AO3− + 6H+ + 6e − → A x + + 3H2 O

8. Oxidation state of Fe is +2 in both as NO and
NOS− are the ligands. From charge conservation, (–1) + (+6) + (−6) = +x
⇒ x = −1.
9. CO is a neutral oxide. A
24. E = ⇒ A = 21 V1 = 14 V2
V
10. Phosphorus acid: H3 PO3 , oxidation state of
P = +3. As V1 and V2 must be integer, A should be 42, 84,
126, etc.
Orthophosphoric acid: H3 PO 4 , oxidation state of
P = +5. 25. Mass of oxygen present = 14.9 g and mass of
hydrogen combined with oxygen to form water =
Metaphosphoric acid: HPO3 , oxidation state of P 16.78 – 14.9 = 1.88 g.
= +5.
14.9
∴ Equivalent weight of oxygen = × 1.008 = 7.989
Pyrophosphoric acid: H4 P2 O7 , oxidation state of 1.88
P = +5. 26. M2 + + 2e − − → M
A gm 2 NA e
11. Informative 2N A
∴ 1g → × 1 = 1.81 × 1022 ⇒ A = 66.54.
12. Reducing agent undergoes oxidation. In HNO3 , A
H and N are in their maximum oxidation state and 27. For minimum equivalent weight, the basicity of
hence, oxidation is possible only for ‘O’. acid should be maximum.
13. I − is a strong reducing agent. 28. In the neutralization reactions, one mole of H2 O
− is formed from 1 mole of H+ and 1 mole of OH−
14. Oxidizing agent must undergo reduction. I can ions and hence, equivalent weight of water = 18.
never be reduced.
29. CH3COOH + 3Cl − → CCl3COOH + H + 6e −
15. In Ca (OCl ) Cl, the oxidation state of ‘Cl’ is +1
60
and –1 but in the product Cl2 , it becomes zero. ∴ ECH COOH = = 10
3
6

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 35 7/8/2019 2:26:37 PM


30. N2 + 3H2 → 2 NH3 (No. of e − involved = 6) 42. neq metal oxide = neq CO2
n − factor =6 2 3
3.7 1.0 ⎛° +4 ⎞
x x or = ×4 ⎜ C → CO2 ⎟
∴ E NH3 = 1 and E N 2 = 2 . EM + 8 44 ⎝ ⎠
3 6
31. P4 + 3NaOH + 3H2 O → PH3 + 3NaH2 PO2 ∴ EM = 32.7
The reaction is balanced by the loss and gain of 43. neq = n × n-factor and n-factor is maximum for
3 moles of electron per mole of P4 and hence, ⎛ 1⎞
M IO3− ⎜⎝ +5 to − ⎟⎠ .
EP4 = . 3
3 44. neq KMnO 4 = neq FeC 2 O 4
32. Pb + PbO2 + 2H2SO 4 → 2PbSO 4 + 2H2 O
(FeC 2 O 4 → Fe3+ + CO2 )
The reaction is balanced by the loss and gain of 3
2 moles of electron per mole of Pb and hence, or n × 5 = 1 × 3 ⇒ n = .
5
2M
EH2SO4 =
2
= M. 45. neq KMnO 4 = neq SO32 − (SO 2−
3 → SO24 − )
33. 3Cl2 + 6 NaOH → 5NaCl + NaClO3 + 3H2 O 2
or n × 5 = 1 × 2 ⇒ n = .
The reaction is balanced by the loss and gain of 5
5 moles of electron per mole of NaClO3 and hence, 46. neq R.A. = neq MnO2 ⇒ n × 1 = x × 2
3M
E H2 O = . and neq R.A. = neq K 2 CrO 4 ⇒ n × 2 = y × 3.
5
34. O3 + 2H+ + 2e − → O2 + H2 O ∴x: y = 3:4
48
∴ EO3 = = 24. 47. CHCl2 COOH + 3H2 O →
2
35. The reaction is balanced by the loss and gain of 2CO2 + H2 O + Cl2 + 6H+ + 6e −
2 moles of electron per mole of MnO2 and hence, neq CHCl2 COOH = neq O.A.
4M
EHCl = = 2M . or n × 6 = 1.2 ⇒ n = 0.2.
2
36. neq I 2 = neq H3 AsO 4 Now, neq CHCl2 COOH = neq NH3

w 1.5 × 1022 or 0.2 × 1 = x × 1 ⇒ x = 0.2.


or ×2 = ⇒ w = 3.175 g.
254 6 × 1023 98 98
20
48. M H2SO4 : M H3PO4 = EH2SO4 : EH3PO4 = : =1 : 2
6 × 10 2 1
37. neq = = 0.001 AM
6 × 1023 49. 28 = ⇒ Atomic mass of metal, AM = 56.
38. 1 g equivalent always reacts with 1 g equivalent of 2
other substance. Now, neq H2SO 4 = neq M2 O3
39. neq metal oxide = neq water w 4.8
or ×2 = × 6 ⇒ w = 8.82 g
8.6 1.8 98 160
or = × 2 ⇒ EM = 35
EM + 8 18 6.4
50. Approximate atomic mass of metal = = 24.62.
20 0.26
40. Mass of acid = × 1 = 40 g
0.5 Let the metal chloride be MCl V .
41. Let the acid be H n A. 24.62 + V × 35.5 ≈ 95 ⇒ V  2
neq acid = neq magnesium salt ∴ Exact atomic mass of metal = 95 − 2 × 35.5 = 24.
1.0 1.301 Now, neq metal = neq H2
or = ⇒ E An − = 35.54
1 + E An − 12 + E An − VH2
1.2
∴ Equivalent weight of acid = 1 + 35.54 = 36.54. or ×2 = × 2 ⇒ VH2 = 1.12 L
24 22.4 L

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 36 7/8/2019 2:26:49 PM


6.4
51. Approximate atomic mass of metal = = 11.63. 61. neq H2 C 2 O 4 = neq MnO 4− = neq I −
0.55
w 500 × 1.0
Let the metal chloride be MCl V . Then, or ×2 = ⇒ w = 22.5 g
90 1000
2 × 74.6  11.63 + V × 35.5 ⇒ V ≈ 4.
62. neq Fe0.9 O = neq KMnO 4
Again, 2 × 74.6 = A + 4 × 35.5 ⇒ A = 7.2.
26.56 V × 0.2
52. neq HCl = neq CO2 or × 0.7 = × 5 ⇒ V = 280 ml
66.4 1000
200 × N 560 63. neq KMnO 4 = neq FeC 2 O 4
or = × 2 ⇒ N HCL = 0.25 N
1000 22400
⎛ 20 × 1⎞
25 × ⎜
53. The resulting solution becomes neutral. ⎝ 200 ⎟⎠ 20 × M
or ×5 = ×3
54. neq FeSO 4 ⋅ ( NH4 )2 SO 4 ⋅ x H2 O = neq KMnO 4 1000 1000
⇒ M FeC2 O4 = 0.208 M
⎛ 20 ⎞ 3.16 75
⎜ × 250⎟ × × 64. 20 × 1 = 200 × M1 ⇒ M1 = 0.1 M
5.88 ⎝ 25 ⎠ 1000 100
or ×1 = ×5 0.1
284 + 18x 158 20 × 0.1 = 75 × M 2 ⇒ M 2 = M
⇒ x = 6. 3
0.1 1
55. 2 Ag + + H2S → Ag 2S ↓ +2H+ 30 × = 150 × M3 ⇒ M3 = M
3 150
Cu 2 + + H2S → CuS ↓ +2H+ Now, neq K 2 Cr2 O7 = neq H2 O2
∴ Ratio of amount of H2S = 1 : 2 1
15 ×
150 × 6 = V × 0.02 × 2 ⇒ V
56. NaAl (OH)2 CO3 + 4HCl → or H2 O2 = 15 ml
1000 1000
NaCl + AlCl3 + CO2 + 3H2 O
65. neq metal = neq H2
neq NaAl (OH)2 CO3 = neq HCl
0.1 43.9
100 × 0.1 V × 0.25 or ×x = ×2⇒ x  2
or ×4 = ⇒ V = 160 ml 51 22400
1000 1000
Now, neq Mx + = neq MnO 4−
57. neq Au = neq SnCl2
0.1 58.8 × 0.1
or × ( y − x) = ⇒ y5
1.97 V × 0.05 51 1000
or ×3 = × 2 ⇒ V = 300 ml
197 1000 66. neq Na 2S2 O3 = neq K BrO3
− 4+
58. neq I = neq Ce 40 × M 0.1336
or ×1 = ⇒ M Na2S2 O3 = 0.02 M
250 × M 20 × 0.05 1 1000 167
or ×2 = ⇒ M I− = M
1000 1000 500 67. neq HCl = neq M3 (PO 4 )2
g 1 10 × 0.1 0.0517
∴ Concentration in = × 127 = 0.254 or = ⇒ EM = 20.03
L 500 1000 EM + 31.67
1
59. neq U 4 + = neq KMnO 4 68. neq HCl = neq CaSO 4 ⋅ H2 O
2
0.5 50 × M 525 × 0.1 w
or ×2 = × 5 ⇒ M = 0.0168 or = × 2 ⇒ w = 3.81 g
238 1000 1000 145

60. 2IO3− + 6H2 C 2 O 4 → C 2 O24 − + 10CO2 + I2 + 6H2 O 69. Cu 2 + + I − → Cu + + I 2


neq Na 2S2 O3 = neq I 2 = neq Cu 2 +
nKIO3 nH2C2 O4 1 1 w
= ⇒ = × ⇒ w = 1.262 g
2 6 214 3 90 V × 0.4 50 × 0.2
or ×1 = × 1 ⇒ VNa2S2 O3 = 5 ml
1000 1000

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 37 7/8/2019 2:26:58 PM


70. neq H2 O2 = neq I 2 = neq Na 2S2 O3 ∴ Final solution contains NaOH = (50 − 18) ×
25 × M 20 × 0.3 6 10–3 = 32 × 10–3 mole and Na 2 Co3 = 9 × 10 −3 mole.
or ×2 = ⇒ M H2 O2 = M
1000 1000 50 Now, neq HCl = neq NaOH + neq Na 2 CO3
6
∴ Volume strength = × 11.35 = 1.362 V × 0.5
50 or × 1 = 32 × 10 −3 × 1 + 9 × 10 −3 × 1
1000
71. CS2 + 3 O2 → CO2 + 2SO2
x mole x mole 2x mole
⇒ VHCl = 82 ml
3 73. Phenolphthalein:
H2S + O2 → H2 O + SO2
y mole 2 x × 0.05 40 × 0.05
y mole y mole
×1 = × 1 ⇒ x = 40
1000 1000
1.97 × 20
3x + 2 y = = 1.2 (1) Methyl orange:
0.082 × 400
y × 0.05 40 × 0.05
Now, neq SO2 = neq I 2 ×1 = × 3 ⇒ y = 120
1000 1000
250 × 2.8
or (2 x + y ) × 2 = × 2 ⇒ 2 x + y = 0.7 (2) 74. Let M Na2CO3 = xM ; M NaHCO3 = y M
1000
100 × x
From (1) and (2), x = 0.2 ; y = 0.3 Now, V1 × 1 × 1 = × 1 (Phenolphthalein)
x 1000
Now, X CS2 = = 0.4
x+ y 100 × x 100 × y
and V2 × 1 × 1 = ×2+ ×1 ( M e t h y l
0.9 1000 1000 orange)
72. nCO2 formed = = 9 × 10 −3
100
∴ x = 10V1 and y = 10 (V2 − 2V1 )
100 × 0.5
nNaOH = = 50 × 10 −3 75. In presence of phenolphthalein, n-factor = 1.
1000
In presence of methyl orange, n-factor = 3.
2 NaOH+ CO2 → Na 2 CO3 + H2 O
−3
18 ×10 9 ×10 −3 9 ×10 −3

Section B (One or More than one Correct)


15.8
1. NO + and ClO 4− ⇒, Oxidation state of N = +3, 7. KMnO 4 = × 5 = 0.5 eq
Cl = +7. 158
18.25
HCl = × 1 = 0.5 eq
2. PbO2 is an oxide. 36.5
3. (a) Oxidation state of S = +6 in both. 22.5
H2 C 2 O 4 = × 2 = 0.5 eq
90
(b) Oxidation state of Cr = +6 in both. 32
SO2 = × 2 = 1.0 eq
(c) Oxidation state of P = +5 in both. 69
38
FeSO 4 = × 1 = 0.25 eq
4. As KMnO 4 reduces, the compound must oxidize. 152
Fe +3 cannot oxidize.
8. 2Cu + 6HNO3 →

5. C N Oxidation state of C = +2, N = –3 2Cu( NO3 )2 + NO + NO2 + 3H2 O

O C N –
O C N 9. Equivalent volume is the volume occupied by
1g-equivalent of the gas.
O.S. of C= +4, O = –2, N = –3 1 1
(a) 1g-equivalent of CH4 = mole = × 22.4 L
6. ‘Cl’ should be in intermediate oxidation state. 8 8
= 2.8 L

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 38 7/8/2019 2:27:07 PM


1 6.3
(b) 1g-equivalent of O3 =
mole = 11.2 L 15. Molarity of oxalic acid solution =
2 90 + 18x
1
(c) 1g-equivalent of H2S = mole = 11.2 L ⎛ 6.3 ⎞
20 × ⎜
2 ⎝ 90 + 18x ⎟⎠ 40 × 0.05
1 Now, ×2 = ×1 ⇒ x = 2
(d) 1g-equivalent of CO2 = mole = 5.6 L 1000 1000
4 126 90
EH2C2 O4 .2H2 O = = 63 but EH2C2 O4 = = 45
10. neq metal nitrate = neq metal sulphate 2 2
0.5 0.43 6.3
or = ⇒ EM = 38 Molarity = = 0.05 M
EM + 62 EM + 48 126

11. The chemical formula of sulphate is MSO 4 ⋅ 7H2 O. Now, neq acid = neq KMnO 4
20 100 × 0.05 V × 0.05
(A + 222) × = A ⇒ A = 55.5 or ×2 = × 5 ⇒ V = 40 ml.
100 1000 1000
As the valency of metal is 2, the equivalent weight 16. (a) 109% oleum means 100 g oleum (H2SO 4 + SO3)
55.5
= = 27.75 exactly requires 9 g water to produce exactly
2 109 g of pure H2SO 4 .
80 20
12. Higher oxide: = ⇒ EM = 32. H2 O + SO3 → H2SO 4
EM 8 18 g 80 g

Lower oxide ( 4.29 g ) → Higher oxide ( 4.77 g ) ∴ 9 g → 40 g


80 ∴ Percentage of free SO3 = 40%
Mass of metal = 4.77 × = 3.816 g
100
(b) 1 g of oleum contains 0.4 g of SO3 and hence,
Mass of oxygen = 4.29 – 3.816 0.6 g of H2SO 4 .
= 0.474 g
Now, neq SO3 + neq H2SO 4 = neq NaOH
3.816 0.474
Lower oxide: = ⇒ EM = 64.4 0.4 0.6 V × 0.5
EM 8 or ×2+ ×2 = × 1 ⇒ V = 44.49 ml
80 98 1000
6.4
13. Atomic weight (approx.) = = 213.33 (c) neq SO3 + neq H2SO 4 = neq Ba (OH)2
0.03
10 18.9 2.0 3.0 V × 0.1
Now, = ⇒ EM = 69.66 or ×2+ ×2 = ⇒ V = 111.22 ml
EM EM + 62 80 98 1000
213.33 (d) 100 g of oleum requires 9g of water to give
Now, Valency ≈ ≈ 3 (Integer value)
69.66 109 g of H2SO 4 . Hence, the final solution
∴ Atomic weight (exactly) = 69.66 × 3 = 208.98 contains 109 g of H2SO 4 and 491 g of water.
109 /98
14. Let molarities of Na 2 CO3 and NaHCO3 be xM ∴ Molality = × 1000 = 2.265 m.
and yM, respectively. 491
5.68
Phenolphthalein: 17. (a) Moles of P4 O10 = = 0.02
284
100 × x
× 1 = V1 × 1 × 1 ⇒ x = 10V1 P4 O10 ⎯⎯⎯⎯
aqueous
→ 4 H3 PO 4
1000
Methyl orange: ∴ Molarity of H3 PO 4 solution
100 × x 100 × y 0.02 × 4
×2+ × 1 = (V2 × 1) × 1 = × 1000 = 0.32 M
1000 1000 250
⇒ y = 10 (V2 − 2V1 ) 25 × 0.32 V × 0.5
(b) ×3 = × 1 ⇒ V = 48 ml
1000 1000

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 39 7/8/2019 2:27:16 PM


15 × 0.32 V × 0.2 WKMnO4 WK 2Cr2 O7
(c) ×3 = × 2 ⇒ V = 36 ml or ×5 = ×6
1000 1000 158 294
40 × 0.32 V × 0.8 ⇒ WKMnO4 < WK 2Cr2 O7
(d) ×1 = ⇒ V = 16 ml
1000 1000
V × M KMnO4 V × M K 2Cr2 O7
18. SO2 Cl2 + 2H2 O → H2SO 4 + 2HCl or ×5 = ×6
0.01mole 0.01mole 0.02 mole 1000 1000
0.01 M KMnO4 6
(a) [H2SO 4 ] = × 1000 = 0.05 M ⇒ =
200 M K 2Cr2 O7 5
0.02
(b) [HCl] = × 1000 = 0.1 M 8.0
200 20. Moles of S = = 0.25
32
20 × 0.05 20 × 0.1 V × 0.2
(c) ×2+ ×1 = ×1 0.25 200 × M
1000 1000 1000 (a) ×2 = × 5 ⇒ M KMnO4 = 0.25 M
2 1000
⇒ VNaOH = 20 ml. 0.25/ 2
(b) MBaCl2 = × 1000 = 1.25 M
100 × 0.1 w 100
(d) = ⇒ WAgCl = 1.435 g
1000 143.5 0.25
(c) MBaSO4 = × 234 = 29.25 g
19. neq H2 O2 = neq KMnO 4 = neq K 2 Cr2 O7 = neq O2 2

or nKMnO4 × 5 = nK 2Cr2 O7 × 6
⇒ nKMnO4 > nK 2Cr2 O7

Section C (Comprehensions)
Comprehension I
215
1. EMnBr2 =  12.65 The reaction is balanced by the loss or gain of 34
17 electrons. Hence,
240
2. EPbO2 = = 120 30 × 63
2 EHNO3 = = 55.6
34
3. 2MnBr2 + 17PbO2 + 30HNO3 →
2HMnO 4 + 2Pb (BrO3 )2 + 15Pb ( NO3 )2 + 14H2 O

Comprehension II
6.4
4. Atomic weight (approx.) = = 80 5. E As = 24.98
0.08
neq Ag = neq arsenious chloride 6. Molecular mass of arsenious chloride = 6.25 ×
(22.4 × 1.3) = 182.
100 56
or ×1 = ⇒ E AS = 24.98 Let the formula be ( AsCl3 )x .
108 E As + 35.5

Now, Valency =
80
3 x (74.94 + 3 × 35.5) = 182 ⇒ x = 1.0
24.98
∴ Molecular formula = AsCl3
∴ Exact atomic mass = 24.98 × 3 = 74.94

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 40 7/8/2019 2:27:22 PM


Comprehension III

Let the oxide be M2 O x and the halide be MX y . From (1) and (2) , we get:
E x
=
0.4 w 80 y
For oxide: = ×x (1)
8 A 7. x = y ⇒ E = 80
4.0 w 8. y = 2 x ⇒ E = 40
For halide: = ×y (2)
E A
9. A = E .n ⇒ As valency should be an integer, A
must be an integer multiple of 40.

Comprehension IV

10. neq KMnO 4 = neq X n + ∴ M = 56 × (5 − n ) = 168


Hence, atomic mass of X = 168 − 2 × 35.5 = 97.
or 1.5 × 10 −3 × 5 = 2.5 × 10 −3 × (5 − n ) ⇒ n = 2.
M 12. neq KMnO 4 = neq X n +
11. E=
n-factor or n × 1 = 1 × 3 ⇒ n = 3

Comprehension V
Let the sample contains x mole KCl and y mole KClO3 . From Equation (1), we get: x = 5 × 10 −3
SO
KClO3 ⎯⎯⎯
2
→ KCl 13. nKClO3 : nKcl = y : x = 1 : 1
y y
mole mole
10 10
14. mKCl = x × 74.5 = 0.3725 g
Now, mole of AgCl formed,
x y 0.1435 mKClO3 = y × 122.5 = 0.6125 g
+ = ⇒ x + y = 0.01 (1)
10 10 143.5 ∴ mmoisture = 1 − (0.3725 + 0.6125) = 0.015 g,
For second experiment, i.e., 1.5%
neq KClO3 + neq O.A. = neq FeSO 4 0.3725
15. Mass percent of KCl = × 100 = 37.25%
1
y 37.5 × 0.08 30 × 0.2
or ×6+ = ⇒ y = 5 × 10 −3
10 1000 1000

Comprehension VI

16. neq As 4 O6 = neq I3− 17. nHCN = n I3−

0.1188 10 × M 15 × M 5 × 0.12
or ×8 = × 2 ⇒ MI − = 0.12 M or = ⇒ M HCN = 0.04 M
396 1000 3 1000 1000

18. Mass of HCN = (6 × 0.04 ) × 27 = 6.48

Comprehension VII

19. 4Mn2 + + MnO −4 + 20F− + 8H+ → 5MnF4− + 4H2 O 20. Let the moles of Mn3 O 4 = x. Hence, moles of
Mn2+ formed = 3x.

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 41 7/8/2019 2:27:29 PM


0.125 Now, mass of Mn3 O 4 = x × 229 = 0.229 g
Now, for KMnO 4 solution, molarity =
= 0.025 M. 5
0.229
∴ Percentage of Mn3 O 4 = × 100 = 50%
Now, neq KMnO 4 = neq Mn2 + 0.458
21. Normality = 0.025 × 4 = 0.1N.
30 × 0.025
or × 4 = 3x × 1 ⇒ x = 10 −3
1000

Comprehension VIII
Let the ore contains x mole of FeCr2 O 4 and y mole of From (1) and (2), we get:
Fe0.95 O1.00 . y = 2 × 10 −3 , x = 6.9 × 10 −3
Now, neq FeCr2 O 4 + neq Fe0.95 O1.00 = neq O2
22. Mass per cent of
or x × 7 + y × 0.85 =
280
× 4 ⇒ 7 x + 0.85 y = 0.05 (1) 2 × 10 −3 × 69.2
Fe0.95 O1.00 = × 100 = 6.92%
22400 2
Now,
10 × 1 23. Let in Fe0.95 O1.00 , ‘z’ Fe-atom are in +2 state.
Moles of K 4 ⎡⎣Fe ( CN )6 ⎤⎦ taken = = 0.01
1000 z × ( +2 ) + (0.95 − z ) × ( +3) = 2.00 ⇒ z = 0.85
neq Fe 2+
= neq K 4 ⎡⎣Fe (CN )6 ⎤⎦ Hence, per cent of total iron in +2 state
6 × 0.4 x + y × 0.85
or = n = 2 ⇒ n = 0.0012 . = × 100
1000 x + 0.95 y
∴ Moles of K 4 ⎡⎣Fe ( CN )6 ⎤⎦ reacted with = 97.73%
3+
Fe = 0.01 − 0.0012 = 0.0088 24. Moles of Prussian blue = moles of Fe3+
Now, neq Fe 3+
= neq K 4 ⎡⎣Fe (CN )6 ⎤⎦
= x + 0.95 y = 8.8 × 10 −3
or ( x + 0.95 y ) × 3 = 0.0088 × 3 ⇒ x + 0.95 y = 0.0088 (2)

Comprehension IX
1 5.94
25. Moles of NaHSO3 needed = 3 × moles of NaIO3 = × = 6 × 10 −3
5 198
5.94 6 × 10 −3
= 3× = 0.09 ∴ Volume of solution required = = 0.2 L
198 5.94 / 198
∴ Mass of NaHSO3 needed = 0.09 × 104 = 9.36 g.
27. Mass of I 2 produced = 6 × 10 −3 × 3 × 254 = 4.572 g
26. Moles of SO3− needed in 2nd reaction.
∴ Mass of I 2 produced per litre of solution
1
= × moles of I − formed in 1st reaction 4.572
5 = = 3.81 g
(1 + 0.2)
Comprehension X
28. neq HCl = neq Na 2 CO3 + neq NaOH 29. neq HCl = neq Na 2 CO3 + neq NaHCO3 + neq NaOH

V ×1 1 1 V ×1 1 1 1
or = ×1+ × 1 ⇒ VHCl = 34.43 ml or = × 2 + ×1+ ×1
1000 106 40 1000 106 84 40
⇒ VHCl = 55.77 ml

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 42 7/8/2019 2:27:40 PM


30. neq HCl = neq NaHCO3 formed + neq NaHCO3 , V ×1 1 1
or = × 1 + × 1 ⇒ VHCl = 21.34 ml
present initially. 1000 106 84

Section D (Assertion–Reason)
1. I − can never be reduced. 9. V × 0.3 × 2 = V × 0.2 × 3
2. The oxidation state of terminal C-atoms are –3 10. In the presence of methyl orange, the colour change
and middle C-atoms are –2. appears when Na 2 CO3 converts completely in
H2 CO3 .
3. I − can not be reduced and hence, reduction of O3
occurs. 14. Copper converts from Cu 2+ to Cu + .
O3 + 2H+ + 2e − → O2 + H2 O 15. neq A = neq C only when n-factor of B is same in
4. Oxidation state of Cl = +3 both reactions.

5. n-factor may be fractional.

Section E (Column Match)


4. 6. Equivalent volume is the volume of gas
Column I Column II corresponding to 1 g-equivalent of the gas.
(A) neq = 1 × 5 (P) neq = 3 × 1 7.
(B) neq = 1 × 3 (Q) neq = 0.5 × 10
(A) n-factor = 2
(C) neq = 1 × 2 (R) neq = 1 × 2
(D) neq = 1 × 3 (S) neq = 1.5 × 2 (B) n-factor = 10

2 × 10 5
(C) n-factor = =
2 + 10 3
5. 2×2
(D) n-factor = =1
Column I Column II 2+2

(A) neq MnO 4− = neq C 2O24 − ⇒ 8.


(O.A.) (R.A.)
n1 × 3 = n2 × 2 ⇒ n1 : n2 = 2 : 3 (P) n-factor = 1
(B) neq ClO = neq Fe (OH)3 ⇒

(Q) n-factor =
1
(O.A.) (R.A.) 2
n1 × 2 = n2 × 3 ⇒ n1 : n2 = 3 : 2 (R) n-factor = 2
(S) n-factor = 6
(C) neq HO2 = neq Cr (OH)3 ⇒

(O.A.) (R.A.) 1
(T) n-factor =
n1 × 2 = n2 × 4 ⇒ n1 : n2 = 2 : 1 2

(D) neq N 2H4 = neq Cr (OH)2 ⇒


(R.A.) (O.A.)
n1 × 6 = n2 × 2 ⇒ n2 : n1 = 3 : 1

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 43 7/8/2019 2:27:44 PM


9. Milliequivalents: 10. Milliequivalents:

Column I Column II Column I Column II


(A) 100 × 0.3 × 2 = 60 for P, (P) 100 × 0.3 × 1 = 30 (A) 50 × 0.5 × 2 = 50 (P) 50 × 0.5 × 2 = 50
Q, R, S (B) 50 × 0.5 × 1 = 25 (Q) 50 × 0.5 × 1 = 25
(B) 50 × 0.6 × 1 = 30 for P, S (Q) 120 × 0.1 × 5 = 60 (C) 50 × 0.5 × 1 = 25 (R) 25 × 0.5 × 2 = 25
50 × 0.6 × 2 = 60 for (D) 50 × 0.5 × 1 = 25 (S) 50 × 1.0 × 1 = 50
Q, R
(C) 50 × 0.6 × 1 = 30 for P, (R) 60 × 0.1 × 5 = 30
Q, R, S
(D) 100 × 0.2 × 3 = 60 for (S) 100 × 0.6 × 1 = 60
P, Q, S

Section F (Subjective)
Single-digit Integer Type

1. AO n4 − + (9 − 2 n )H+ + 2e − → HAO2n− + ( 4 − n )H2 O Mass of chloride formed


From charge conservation, 2 275
= n × 68.75 × 2 = ng
3 3
( − n) + (9 − 2n) + ( −2) = −2 ⇒ n = 3.
275 62
∴ Mass of element used = n − 71n = ng
2. 5AO2 + 4H+ → 2 AO 4− + 3A n + + 2H2 O 3 3
From charge conservation,
Now, equivalent weight of element,
(+4) = ( −2) + 3n ⇒ n = 2. 62 n / 3 31
E= × 35.5 =
3. neq Cl2 = neq metal chloride 71n 3
7. neq SO2 = neq HClO3
1.12 5.55
or ×2 = ⇒ Equivalent weight of
22.4 E + 35.5 V 16.9
or ×2 = × 6 ⇒ V = 13.44 L
metal, E = 20 22.4 84.5

∴ Valency = =
A 40
= 20 PV 2 × (5 × 13.44 )
E 20 Now n = = =3
RT 0.0821 × 546
160 2 × n 8. neq N 2 H4 = neq K 2 CrO 4
4. = ⇒ n = 10 ⇒ Oxidation state of Br in
96 2 + n
unknown product = 5 w 24
or ×4 = × 3 ⇒ w = 2.97 g  3 g
30 32 194
5. E= = 30
⎛ 2 × 2⎞ 9. neq KHC 2 O 4 ⋅ H2 C 2 O 4 ⋅ 2H2 O = neq NaOH
⎜⎝ ⎟
2 + 2⎠
or n × 3 = 30 × 1 ⇒ n = 10
6. M (s ) + Cl2 (g ) → Chloride (g )
Now, neq KHC 2 O 4 ⋅ H2 C 2 O 4 ⋅ 2H2 O = neq KMnO 4
As the volume reduced by one-third, moles of
or 10 × 4 = n × 5 ⇒ n = 8
2
chloride formed = × Moles of Cl2 reacted.
3 10. neq Mn ( NO3 ) ⋅ 6H2 O = neq Na 4 Xe O6
Mass of chorine used = n × 71 g.
62.5 × 0.04
or n × 5 = × 8 ⇒ n = 4 × 10 −3
1000

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 44 7/8/2019 2:27:50 PM


11. Cl2 + 2 NaClO2 ⇒ 2ClO2 + 2 NaCl 17. Ammonium Vanadate ⎯⎯⎯
oxalic
→ Z ⎯⎯⎯⎯
4

KMnO
acid ⎛ x +⎞
90 ⎜⎝ V ⎟⎠
neq NaClO2 × = neq ClO2
100 +5 +4 +5
SO KMnO
90 V ⎯⎯2⎯
→ V ⎯⎯⎯⎯
4
→V
or 5 × 2 × =n⇒n=9
100 neq Z = neq KMnO 4 ⇒ n × (5 − x ) = V1 × N
12. neq CuSO 4 ⋅ xH2 O = neq H2SO 4 = neq NaOH
neq V 4 + = neq KMnO 4 ⇒ n × 1 = V2 × N
1.245 10 × 1
or ×2 = × 1 ⇒ x = 4.97  5 V1 5
159.5 + 18x 1000 From question, = ⇒x=0
V2 1
13. CS2 + O2 → CO2 + 2SO2
x mole x mole 2 x mole
18. Let Cu 2+ = a mole and C 2 O2−
4 = b mole.
3
H2S + O2 → H2 O (g ) + SO2 22.6 × 0.02
y mole 2 y mole y mole neq C 2 O24 − = neq MnO 4− ⇒ b × 2 = ×5
1000
7.2 × 82.1
From the question, 3x + 2 y = = 12 neq Cu 2 + = neq I 2 = neq Na 2S2 O3 ⇒
0.0821 × 600
and (2 x + y ) × 2 = 75 × 2 11.3 × 0.05
a ×1 = ×1
1000
Hence, x = 2 and y = 3.
∴a:b=1:2
x
14. XeFx + H2 → Xe + x HF 0.552
2 a mole a x mole 19. Moles of Fe2 O3 = ⇒
56 160
a=
22400 0.552
Moles of Fe2+ formed = 2 ×
60 × 0.25 160
and ax × 1 = ×1 ⇒ x = 6
1000 Now, neq Fe2+ = neq Oxidizing agent

15. neq H2 O2 = neq I 2 = neq Na 2S2 O3 ⎛ 17 ⎞


2 × 0.552 ⎜⎝ × 100⎟⎠ × 0.0167
5.675 25
12 ×
or ×1 = × nf
11.35 × 2 = 24 × M × 1 ⇒ M = 0.5 160 1000
or ⇒ n-factor, n f  6
1000 1000
Now, neq O3 = neq I 2 = neq Na 2S2 O3
CH3 (CH2 ) n COOH → ( n + 2 ) CO2 ⎯⎯⎯
NaOH
20. excess

V 9 × 0.5 a mole a ( n + 2 )mole
or ×2 = × 1 ⇒ V = 0.504 L
22.4 1000 (n + 2) Na2 CO3 + x mole NaOH left
0.0504 a ( n + 2 ) mole
∴ Percentage of O3 = × 100 = 5.04%  5%
1
In presence of phenolphthalein:
16. H2 C 2 O 4 → H2 O + CO + CO2 a (n + 2) 50 × 1
x mole x mole x ×1+ ×1 = (1)
2 1000
SCO + I 2 O5 → 5CO2 + I 2
x mole x In presence of methyl orange:
mole
5
a (n + 2) 80 × 1
neq I 2 = neq Na 2S2 O3 x ×1+ ×2 = (2)
2 1000
x 200 × 0.2 a (n + 2) 1.16
or ×2 = ⇒ x = 0.1 From (1) and (2), = 0.03 and a =
5 1000 2 60 + 14 n
∴ Mass of H2 C 2 O 4 = 0.1 × 90 = 9 g ∴n=4

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 45 7/8/2019 2:27:58 PM


Four-digit Integer Type

1. 1( +3) + x ( +2 ) + 1(1 − x ) ( +5) + 3 × ( −2 ) = 0 7. Moles of KOH used in saponification


2 25 × 0.4 8.0 × 0.25
⇒x= = − × 2 = 6 × 10 −3
3 1000 1000
2
∴ Mass of KOH used = 6 × 10 −3 × 56 = 0.336 g
∴ Percentage of ‘x’ in +2 state = 3 × 100% = 33.33%
2 0.336 × 103
∴ Saponification number = = 224
1.5
2. neq OH − = neq Metal hydroxide
8.50 8. neq Oxalic acid = neq MnO2 + neq KMnO 4
or 0.1 × 1 = ⇒ E = 68
E + 17 50 × 1.0 320 × 0.1
or = nMnO2 × 2 +
3. neq Ag = neq AgCl 1000 1000
−3
⇒ nMnO2 = 9 × 10
w 2.87
or ×1 = × 1 ⇒ w = 2.16 g
108 143.5 MnO2 → MnO + ’O’
available oxygen
∴ Mass of Cu = 2.7 − 2.16 = 0.54 g
∴ Percentage of available oxygen
0.54
∴ Percentage of Cu = × 100 = 20% 9 × 10 −3 × 16
2.7 = × 100 = 9 %
1.6
4. neq H2SO 4 = neq CaO2
V1 × 1 / 40
9. neq SeO32 − = neq BrO3− ⇒ n × 2 = ×5 (1)
V × 0.25 7.2 1000
or ×2 = × 2 ⇒ V = 400 ml
1000 72 neq AsO2− = neq BrO3−
5. neq NaOH = neq Oxalate 1 1
7.5 × V2 ×
⇒ 25 × 2 = 40 × 6 (2)
9.15
30 × 1000 1000
27 × 0.12 M ×y
or = (1)
1000 1000 and V1 + V2 = 20 (3)
neq KMnO 4 = neq Oxalate From (1), (2) and (3), we get:
9.15 n = 10 −3
30 ×
36 × 0.12 M × 2z
or = (2) ∴ Mass of SeO32 − = 10 −3 × 127 g = 127 mg
1000 1000
From charge conservation, 91
10. Moles of V2 O5 = = 0.5
x + y = 2z (3) 182
∴ Moles of V 2+ formed = 0.5 × 2 = 1.0
and molar mass, M = 39x + y + 88z + 18n (4)
Now, neq V 2 + = neq I2
Solving (1), (2), (3) and (4), we get: x : y : z = 1 : 3 : 2
and n = 2. 2
or 1.0 × 2 = × 2 ⇒ w = 254 g
254
6.
11. neq I 2 = neq C 6 H8 O6 + neq Na 2S2 O3
5Fe2 + + MnO 4− + 8H+ →5Fe3+ +Mn2 + +4H2 O
200 × 0.1 600 ×1.0
M 200 × 0.1M
1000 1000
M
10 × 0.025 w 2.5 × 0.01
1000 or ×2 = ×2+ ×8
1000 176 1000
⇒ w = 0.0264
600 8 20 568
⎡H + ⎤
⎣ ⎦ final = 1000 − 5 × 1000 = 1000 M ∴ Vitamin C content =
0.0264
× 106 = 132 mg/mL
200

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 46 7/8/2019 2:28:04 PM


∴ x = 8.
12. neq Mohr salt = neq Na 2 CrO 4 + neq K 2 Cr2 O7 x
∴ Percentage of CuS = × 100 = 80%
1.96 40 × 0.05 10
or × 1 = 2a × 3 +
392 1000 14. Let the mixture contains x moles of As 2S3 and
y moles of As 2S5 .
∴ Moles of Fe (CrO2 )2 = a = 5 × 10 −4
neq As 2S3 = neq I 2
2a × 52
∴ Mass of Cr – present = × 100% = 26% 20 × 0.05
0.2 or x × 4 = ⇒ x = 2.5 × 10 −4
1000

13. neq CuS + neq Cu 2S + neq Fe2 + = neq MnO 4− Now, neq As 2S5 = neq I 2 = neq Na 2S2 O3 ⋅ 5H2 O
1.24
x 10 − x 200 × 1 900 × 0.4 or ( x + y ) × 4 =× 1 ⇒ y = 1.0 × 10 −3
or ×6+ ×8+ ×1 = ×5 248
96 160 1000 1000
x
∴ Mole percent of As 2S3 = × 100 = 20%
x+ y

15. 3 Se (s ) + 6 Ag + + 6 NH3 + 3H2 O → 2 Ag 2Se + Ag 2SeO3 + 6 NH4+

x mole 45 × 0.02 0 0
1000
= 9 × 10 −4 mole

0 (9 × 10 −4 − 2 x ) 2x
mole
x
mole
mole 3 3

(
From the question, 9 × 10 −4 − 2 x + 2 × ) x 10 × 0.01
3
=
1000
(n
Ag +
= nSCN − )
∴ x = 6 × 10 −4
6 × 10 −4 × 80
∴ Mass of Se per ml gm = 24 mg
2
16. neq KI = neq KIO3 = Moles of AgNO3 present
1 5 × 10 −3 × 170
30 × ∴ Percentage of AgNO3 = × 100 = 85%
20 × M 10 1
or ×2 = ×4
1000 1000
17. Let the original sample contains x moles of Fe3 O 4
⇒ Molarity of KI solution = 0.3 M and y mole of Fe2 O3 .
50 × 0.3 As, neq Fe3 O 4 + neq Fe2 O3 = neq I 2 = neq Na 2S2 O3
Now, moles of KI taken = = 15 × 10 −3
1000
and moles of KI reacted with ⎛ 11.2 ⎞
⎜⎝ × 100⎟ × 0.5
1 20 ⎠
50 × or x × 2 + y × 2 = ×1
10 1000
KIO3 = 2 × = 10 × 10 −3
1000 ⇒ 2 x + 2 y = 28 × 10 −3 (1)
∴ Moles of KI reacted with Now, moles of Fe2+ formed = 3x + 2 y
−3 −3 −3
AgNO3 = 15 × 10 − 10 × 10 = 5 × 10
As, neq Fe2 + = neq KMnO 4

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 47 7/8/2019 2:28:09 PM


⎛ 12.8 ⎞ 2MnO 4− + 3Mn2 + + 2H2 O → 5MnO2 + 4H+
⎜⎝ × 100⎟ × 0.25
50 ⎠ 2
× 2 ×10 −3 mole 2 ×10 −3 mole
or (3x + 2 y ) × 1 = ×5 (2) 5
1000 = 0.8 ×10 −3 mole

⇒ 3x + 2 y = 32 × 10 −3 2MnO 4− + 6H+ + 5H2 O2 → 2Mn2 + + 8H2 O + 5O2


−3 5
0.8 ×10 mole × 0.8 ×10 −3 mole
From (1) and (2), we get: 2
= 2 ×10 −3 mole
x = 4 × 10 −3 and y = 10 × 10 −3. = 2 ×10 −3 × 34 g

Now, the percentage of Fe2 O3 in sample ∴ Mass of H2 O2 per 100 ml of solution


y × 160
= × 100 = 40% 68 × 10 −3
4 = × 100 g = 340 mg
20
18. IO3− + 5I − + 6H+ → 3I 2 + 3H2 O
1.07 −3
= 5 ×10 mole 15 ×10 −3 mole 20. In the presence of phenolphthalein,
214
20 × 0.1 V × 0.05
Now, neq I 2 = neq Na 2S2 O3 ×1 = 1 × 1 ⇒ V1 = 40 ml
1000 1000
50 × M In the presence of methyl orange,
or 15 × 10 −3 × 2 = × 1 ⇒ M = 0.6
1000
20 × 0.1 V × 0.05
×3 = 2 × 1 ⇒ V2 = 120 ml
19. C 2 O24 − +MnO2 + 4H+ →2CO2 + Mn2 + +2H2 O 1000 1000
10 × 0.2 2 × 10 −3 mole
1000 ∴V2 −V1 = 80 ml
= 2 × 10 −3 mole

M02 Advanced Problems in Physical Chemistry xxxx 01.indd 48 7/8/2019 2:28:11 PM

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