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Anda di halaman 1dari 98

1. Answer (1)

Number of moles of 200 ml of 3 M AgNO3 = 200 × 3 × 10–3

= 0.6

Number of moles of 300 ml of 2M AgNO3 = 300 × 10–3 × 2

= 0.6

Total number of Ag + ions = 0.6 + 0.6

= 1.2 moles

Moles of Cl– released by 200 ml of 10 M

= 200 × 10 × 10–3

= 2 moles

1.2 moles of Ag+ will precipitate 1.2 moles of Cl–

The number of moles of NaCl left unprecipitated = 2 – 1.2 = 0.8 moles

Amount of NaCl left unprecipitated = 0.8 × (23 + 35.5)g = 46.8 g

2. Answer (4)

1 ml H2O is equal to 1 g of H2O because density of water is 1 g/ml.

3. Answer (4)

The change in oxidation number of Cr is +3 to +6. Total e– lost are 6. Hence, equivalent weight of

M

Cr2(SO4)3 = .

6

4. Answer (3)

3% solution of H2O2 means

100 ml H2O2 solution — 3g H2O2

1000 ml H2O2 solution — 30g H2O2

234 22.4 L

at NTP

30 g of H2O2 liberates 9.88 L of O2

30 g of H2O2 = 1000 ml of H2O2 = 9.88 × 103 ml of O2

1 ml of H2O2 = 9.88 ml of O2

volume strength = 9.88

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2 Physical Chemistry Success Achiever (Solutions)

5. Answer (3)

MgCO3 + 2 HCl MgCl2 + CO2 + H2O

MgCl2 + HCl no reaction

Now, 1 mole of MgCO3 1 mole of CO2

1 mole of CO2 1 mole of MgCO3

4 4

moles of CO2 = moles of MgCO3

44 44

= 0.09

= 0.09 × 84 g of MgCO3

= 7.64 g

% of MgCO3 in the mixture = 38.2%

% of MgCl2 in the mixture = 61.8%

6. Answer (3)

x

1000

mol. wt. of KMnO 4 56

60 N

5 5 .6

158 56

60

x 5 5 .6

1000

= 18.96 g

18.96

% purity of KMnO4 = 100 63.2%

30

7. Answer (3)

100 g of solution contain 49 g of H2SO4

49

mol. weight of H2SO 4

M 100

weight of solution

density

100 NH2SO4 50 12

NH2SO4 6N

6N H2SO4 = 3 M H2SO4

49

3 98 1000

100

d

49

3 10 d

98

d = 0.6 g/ml

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Success Achiever (Solutions) Physical Chemistry 3

8. Answer (1)

0.395

Number of moles of KClO4 formed = (molar mass of KClO4 = 138.5)

138.5

= 2.85 × 10–3

Number of moles of KClO3 decomposed to give 2.85 × 10–3 moles of KClO4

4

= 2.85 10 3

3

= 3.8026 × 10–3 moles of KClO3

= 3.8026 × 10–3 × 122.5 g KClO3 = 0.466 g of KClO3

Amount of KClO3 used in 1st reaction = 1.034 g of KClO3

= 8.44 × 10–3 moles of KClO3

Number of moles of O2 formed by 8.44 × 10–3 moles of KClO3

3

= 8.44 10 3

2

= 0.01266

Volume occupied by 0.01266 moles of O2 = 0.01266 × 22.4 L = 283.6 ml

9. Answer (2)

5 FeC2O4 + 3 MnO4– + 24 H+ 5 Fe3+ + 10 CO2 + 3 Mn2+ + 12 H2O

Molecular weight of FeC2O4 = 144 g

1

Number of moles in 1.44 g of FeC2O4 = 1.44 = 0.01 mole

144

From the above balanced equation

5 moles of FeC2O4 are oxidised by 3 moles of KMnO4

3

0.01 mole of FeC2O4 are oxidised by 0.01 = 0.006 moles

5

Volume of 0.01 M KMnO4 solution required

1000

= 0.006

0.01

= 600 ml

10. Answer (1)

Milli equivalent of NaOH = x

Milli equivalent of Na2CO3 = y

y

x 50 0.2

2

2x + y = 10 × 2 = 20

x + y = 72 × 0.2

x + y = 14.4

x = 20 – 14.4

= 5.6

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4 Physical Chemistry Success Achiever (Solutions)

5.6 40

Weight of NaOH in the solution = = 0.224 g

1000

y = 14.4 – 5.6 = 8.8

Number of milli equivalent of Na2CO3 in 25 ml of solution = 8.8

8.8 53

Weight of Na2CO3 of solution = 0.4664 g

1000

WNaOH 0.224

0.48

WNa2CO3 0.4664

KMnO

Fe2

4 Fe3

12. Answer (3)

No. of neutron in 1H2 = 1

4

No. of mole of 1H2 4

1

13. Answer (4)

1 1 1

u= th wt. of C-12 atom = th wt. of O-16 atom = th wt. of C-14 atom

12 16 14

14. Answer (3)

No. of moles of solute does not change on dilution.

15. Answer (4)

Equal volume of gas must have same mole and entities.

16. Answer (1)

Percentage by weight also can be calculated by the empirical formula.

17. Answer (1)

1 5

No. of atom = 5 NA NA

4 4

18. Answer (1)

x A 1000

m

xB 18

x

Total no. of mole of solution

For 1 kg solvent

5.2 5.2

x 0.086

55.5 5.2 60.7

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Success Achiever (Solutions) Physical Chemistry 5

19. Answer (2)

M 1.8

Total volume in litre 5 5

20. Answer (4)

1000 0.8 400

46 23

As per Avogadro’s Law v n (At constant P & T)

22. Answer (2)

23. Answer (2)

Sum of positive and negative charges should be equal.

3(number of atoms of A) + 6 NB = 2 NC

NA = 2

NB = 3

NC = 12

Hence A2(BC4)3

24. Answer (2)

100 ml of 1 M Ca(OH)2 = 100 ml of 2 N Ca(OH)2

10 ml of 20 N H2SO4 = 100 ml of 2 N H2SO4

100 ml of 1 M Ca(OH)2 will neutralize 10 ml of 20 N H2SO4 completely.

Thus, the resulting solution will be neutral.

Number of equilibrium of acid = Number of equilibrium of base

1

Given V.D. of A = ( V.D)B and molecular mass of B = x = 2 × V.D. of B

6

Molecular mass of A = 2 × V.D. of A

1

= 2 VB

6

1

= 2 VB

6

x

=

6

26. Answer (3)

Molecular mass of CH3OH = 12 + 4 + 16 = 32

12

% of C in CH3OH = 100 37.5%

32

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6 Physical Chemistry Success Achiever (Solutions)

12

% of C in CO2 = 100 27.27%

44

48

% of C in CH3CH CHCOOH = 100 55.8%

86

24

% of C in COOH–COOH = 26.6%

90

27. Answer (1)

100 g of solution contain 40 g solute

1000 g of solution contain 400 g solute

Amount of solute left in solution after precipitation = 400 – 200 = 200 g

Weight of the solution after precipitation = 1000 – 200 = 800 g

200

% concentration of new solution = 100 25%

800

12 g of N in 100 g of compound

100

14 g of N in 14 g of compound

12

= 116.67 g

8 g sulphur present in 100 gm organic compounds

32 g sulphur present in 400 gm of organic compound

Hence minimum molecular weight of compound = 400 g/mol

(170 ) ( 58.5 )

11.7 of NaCl = 0.2 moles

NaCl is limiting reagent

Hence 0.2 moles of AgCl is formed.

30. Answer (4)

21

84 1000 1.25 M

Molarity of the solution =

200

1.25 × 25 = x × 1250

x = 0.025 M

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Success Achiever (Solutions) Physical Chemistry 7

31. Answer (1)

1

100 × 0.5 + 200 × × 2 N = 600 × x

4

N

x = 0.25

4

20 ml of 0.25 N solution (acidic) 25 ml of 0.2 N acidic solution

10 ml of 0.2 N NaOH will neutralize 10 ml of 0.2 N acidic solution

15 ml of solution will be left unneutralized

Nature of solution = acidic.

32. Answer (4)

50

32

The mole fraction of methanol = = 0.59

50 50

32 46

33. Answer (1)

34. Answer (4)

35. Answer (2)

MgCO3 MgO CO 2

84 g 40

40

Weight of MgO = 42 20 g

84

M2CO3 + 2HCl 2MCl + H2O + CO2

nM2CO3 nCO2

1

0.01186

MM2CO3

1

MM2CO3 = = 84.3 g/mol

0.01186

A=H B=N

AB3 = HN3 – acid

A3B = NH3 – base

37. Answer (4)

MH2PO4 = M+ and H2PO4– univalent metal

Metal chloride = MCl

38. Answer (1)

81.6

The number of atoms of A = 2.2988

35.5

18.4

The number of atoms of B = 1.15

16

Mole formula = A2.2988 B1.15

= A1.99 B1

= A2B

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8 Physical Chemistry Success Achiever (Solutions)

Amount of MgCl2 in the sample = 50% of 25 g

= 12.5 g

Molecular mass of MgCl2 = 24 + 35.5 × 2

= 24 + 71

= 95 g

95 g of MgCl2 = 24 g of Mg

12.5 g of MgCl2 = 3.157 g of Mg

Amount of MgSO4 in sample = 50% of 25 = 12.5 g

120 g of MgSO4 24 g of Mg

24

12.5 g of MgSO4 = 12.5 = 2.5 g of Mg

120

5.657

% of Mg in sample = 100 22.63%

25

The volume of NaOH neutralized by 30 ml of 0.1 N HCl

40 × 0.1 = 0.2 × x

x = 20 ml

The amount of NaOH left unneutralized by 0.1 N HCl

= 120 – 20

= 100 ml

NH2SO4 0.5 N

0 .5

Molarity of H2SO4 = 0.25 M

2

41. Answer (2)

12

% composition of CH : C 100 92%

13

12 2

% composition of CH2O : C 100 40% H 100 6.7%

12 2 16 30

36

% composition of C3H6O : C 100 62%

36 6 16

36

% composition of C3H4O2 : C 100 50%

36 4 32

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Success Achiever (Solutions) Physical Chemistry 9

mass mole number ratio

6

C 6 = 0.5 1

12

1

H 1 =1 2

1

So, X = 1, Y = 2

Equation for combustion of CXHY

⎛ Y⎞ Y

C XHY ⎜ X ⎟ O2 XCO2 H2 O

⎝ 4⎠ 2

⎛ Y⎞

Oxygen atoms required = 2 ⎜ X ⎟

⎝ 4⎠

As per information,

⎛ Y⎞

2 ⎜ X ⎟ 2Z

⎝ 4⎠

⎛ 2⎞

⎜1 ⎟ Z

⎝ 4⎠

Z = 1.5

Molecule can be written

CXHYOZ

C1H2O3/2

C2H4O3

0.26% zinc means 100 g of compound contains 0.26 g of zinc

100

65.38 g of Zn is present in 65.38

0.26

= 25146

= 2.5146 × 104 g

x + 2(16 + 1) = 171

x = 171 – 34

= 137 g

137

Equivalent mass of metal is = 68.5 g

2

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10 Physical Chemistry Success Achiever (Solutions)

6 M = 12 N H2SO4

12 × 1 = 15 × NH2SO4

12

NH2SO 4

15

= 0.8

MH2SO4 0.4 M

47. Answer (1)

V.D. of gas = 45 g

Molecular mass of gas = 90 g

90 g of a gas occupies 22.4 L

22.4

22.5 g of a gas occupies 22.5 = 5.6 L

90

48. Answer (4)

0.01 M K2Cr2O7 0.06 N K2Cr2O7

W

0.06 × 50 = 1000

152

= 0.456 g

0.456

% purity of sample = 38%

1 .2

49. Answer (1)

The weight loss is due to the evolution of O2 gas

2 KClO3 2 KCl + 3O2

∵ 3 × 32 g O2 is obtained by 2 × 122.5 g KClO3

2 122 .5

0.384 g O2 is obtained by 0.384 = 0.98 g KClO3

3 32

0.98

% of KClO3 decomposed = 100 = 10%

9 .8

50. Answer (3)

Only Na2CO3 reacts with HCl.

M.e. of Na2CO3 = M.e. of HCl

W 1

1000 100

53 10

W = 0.53 g Na2CO3

So, weight of NaCl = 1 – 0.53 = 0.47 g

0.47

% of NaCl = 100 47%

1

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Success Achiever (Solutions) Physical Chemistry 11

51. Answer (1)

(109% of oleum means 109 g of H2SO4 formed when 100 g of oleum is diluted hence amount of water added

= 109 – 100 g = 9 g with water)

80 g 18 g

18 g of water combines with SO3 = 80 g

80

9 g of water combines with SO3 = 9 40

18

% of SO3 = 40%

52. Answer (4)

5.6 L of gas weighs 4.5 g

4.5

112 L of gas weighs 112

5 .6

= 90 g

53. Answer (1)

12.25

0.5 1000 (x is the basicity)

98

x

500

x=2

Acid has been neutralized to HPO42–.

54. Answer (4)

The balanced chemical equation is

1272 1063 g

254 g = 630 g

Thus, HNO3 required for 5 g iodine

630

= 5 12.4 g

254

55. Answer (4)

5 3

AsO34 AsO33 nf 2 ; I I2 nf 1

1.5 1022 1

n 23

mole electrons

6.02 10 40

1

I I2 e

2

1 1

mol mol

80 40

1

wt. of iodine = w = × 254 = 3.2 g

80

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12 Physical Chemistry Success Achiever (Solutions)

11

2FeS2 O2 Fe2 O3 4 SO2

x mol 2 2x mol

11 x

mol

4

11x 1 11x

⇒ mol O2 13.1 x

4 0.21 4

mol of N2 present = 0.79 × 21 x = 16.6 x

mol of air left = 21 x – 2.75 x + 2x = 20.25 x

16.6 x

⇒ %N2 100 81.97%

20.25 x

Aufbau principle violated because ns should be preferentially full filled and only after that np should be filled.

In np the two electrons with same spin will have all the four quantum numbers same, hence 1 is incorrect.

58. Answer (3)

Possible exchanges in 1 = 2

Possible exchanges in 2 = 10

Possible exchanges in 3 = 20

Possible exchanges in 4 = 16

z2

The number of revolution = 6.55 × 1015 ×

n3

12

= 6.55 × 1015 × = 2.43 × 1014

33

t n3

t1 33 27

= 3 =

t2 4 64

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Success Achiever (Solutions) Physical Chemistry 13

(KE)1 1 – 0 2x – 0

= =

(KE)2 2 – 0 3 x – 0

y 2x – 0

=

4y 3 x – 0

8x – 40 = 3x – 0

5x = 30

5x

0 =

3

64. Answer (3)

Increase in photocurrent implies higher number of emitted electrons per second. Increase in frequency increases

the kinetic energy of emitted electrons only.

65. Answer (4)

We know that 2rn = n

2rn 2.n2a0

= =

n n

= 2na0 = 8a0 (... n = 4)

66. Answer (2)

Number of subshell = 2l + 1

... Each subshell contain 2 electrons.

67. Answer (4)

h

x . p

4

h

0 . p

4

h

p

4 . 0

p

68. Answer (1)

Number of peaks = n – l

69. Answer (1)

n

Exchange energy = nC2 .K = K

2 n–2

n (n – 1)

= K, where n = number of unpaired electrons having similar spin

2

Cu(29) = 1s2 2s2 2p6 3s2 3p6 4s2 3d9 (expected)

= 1s2 2s2 2p6 3s2 3p6 4s1 3d10 (Real)

Expected exchanges for 4s2 3d9 = 16

Real exchanges for 4s1 3d10 = 20

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14 Physical Chemistry Success Achiever (Solutions)

The difference between energies of adjacent energy levels decreases as we move away from nucleus. Thus

in H-atoms.

(E2 – E1) > (E3 – E2) > (E4 – E3) ..................

71. Answer (2)

For d orbital l = 2

h h h

orbital angular momentum = l (l 1) = 2 (2 1) = 6

2 2 2

72. Answer (4)

4s 3d

1 6

s = 6 × = =3

2 2

Spin multiplicity = 2s + 1 = 2 × 3 + 1 = 7

73. Answer (3)

Last electron is filled in 3d orbital.

74. Answer (3)

Energy of unfilled orbital is decided by (n+l) rule

75. Answer (3)

e– is excited to 3rd shell.

76. Answer (4)

Work function of metal depend on ionisation energy.

77. Answer (3)

p 2 4mp 2 ev 2 2

2 mp .ev 1

Spin quantum number have no relation with probability.

79. Answer (3)

All orbital in s orbital have zero orbital angular momentum.

80. Answer (2)

In representation of , sign of wave function are shown.

81. Answer (3)

1

n

⎞

4⎛

sin ⎜ ⎟

2

⎝ ⎠

82. Answer (1)

e4 Z2

I.E.

802h2n2

where is reduced mass.

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Success Achiever (Solutions) Physical Chemistry 15

83. Answer (4)

Cu, Pf, Pd have abnormal E.C. in which Aufbau principle is voilated.

84. Answer (1)

Cr have 3d5 electronic configuration.

85. Answer (3)

Energy in H atom

RHhC R hC

– 2 =– H

n 9

n=3

3s 3p 3d

1 3 5

Total degeneracy = 1 + 3 + 5 = 9

86. Answer (3)

dxy orbital lies in xy plane.

87. Answer (1)

s orbital does not have angular nodes, only p and d orbitals have angular nodes.

88. Answer (3)

Number of nodal planes l

for 4d, n = 4, l = 2

Number of nodal planes = 2

89. Answer (3)

Spectrum depends on electronic environment of an atom.

90. Answer (3)

Visible region belongs to Balmer series. Since the electron transition is from 5th energy level to 3rd energy level.

So no line obtained in Balmer series.

91. Answer (2)

1s2 2s2 2p6 3s2 3p6

l = 0 for s subshell hence total number of electrons having l = 0 is 6.

92. Answer (2)

After filling np level electron enters into (n + 1) s level.

93. Answer (1)

Since 1s is lowest energy level hence it can absorb photon only but cannot emit it.

94. Answer (2)

⎡ ⎤

1 ⎢ 1 1⎥ ⎡1 1 ⎤ R34

–

max = RZ2 ⎢ 2 2 ⎥ = R (2)2 ⎢ – ⎥ = = 3R

⎣ n1 n2 ⎦ ⎣1 4 ⎦ 4

1

max =

3R

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16 Physical Chemistry Success Achiever (Solutions)

h

=

mv

v=

h

Hence, =

m

h

2 =

m

h

=

m

96. Answer (3)

We know that,

nh

mvr =

2

nh

v=

2mr

frequency (number of revolutions per sec)

velocity

=

circumference

v

=

2 r

nh

= 2mr

2r

nh

= s–1

4 2mr 2

97. Answer (4)

1

2p contains 6 electrons out of which only 3 electrons have spin – .

2

l varies from 0 to n – 1 and number of electrons in any energy level = 2 (2l + 1).

Number of orbitals associated with a shell

= n2

= 52 = 25

Number of orbitals = n2 = 52 = 25

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Success Achiever (Solutions) Physical Chemistry 17

For n = 3, l 2.

Thus m cannot have value of 3.

101. Answer (2)

Sc (21) = 1s2 2s2 2p6 3s2 3p6 4s2 3d1

Outermost electron lies in 4s.

Therefore

1

n = 4, l = 0, m = 0, s = ±

2

37 1s22s22p63s23p63d104s24p65s1

So last electron enters 5s orbital

1

Hence n = 5, l = 0, ml = 0, ms

2

h

x.p

4

h

x.m v

4

h

v.mv

4

h

(v)2 =

4m

h

v =

4m

h mh 1 mh

p = mv = m = =

4m 4 2

103. Answer (1)

m1 m2 m2 m

m1 m2 2m 2

RH

Rydberg's constant

2

104. Answer (3)

n2

rn 0.53 Å

Z

105. Answer (1)

L 1

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18 Physical Chemistry Success Achiever (Solutions)

Fact

107. Answer (2)

Follow Schrodinger's wave equation.

108. Answer (2)

From the data

109. Answer (4)

Ionic radius of an element depend on the charge reside on that ion, effective nuclear charge and group to which

it belong.

110. Answer (3)

If IE2 is 7 to 14 times of IE1, then that element will belong with Ist group.

111. Answer (2)

IInd successive ionisation energy is always greater than Ist ionisation energy and difference between these two

differ for element to element.

112. Answer (1)

Ga : 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p1

Ga belong with 13th group, 4th period and p block.

113. Answer (1)

Ionisation energy Electron affinity

Electronegativity =

2

114. Answer (1)

van der Waal radius is larger than metallic radius because in metallic radius, atoms are closer to each other

because metallic bond is stronger than van der Waal bond.

115. Answer (3)

In process of ionisation, energy have to be supplied to remove the outermost electron.

116. Answer (4)

1. Electron affinity of noble gases is negative (means endothermic).

2. Addition of e– to anion is always endothermic.

3. The process of ionisation is endothermic.

117. Answer (4)

Fact

118. Answer (3)

IE1 of Be is more than I.E.1 of B.

119. Answer (4)

I.E. E.A.

E.N.

2

120. Answer (1)

Shielding power is s > p > d > f

121. Answer (3)

Cu belong with XI group.

122. Answer (1)

Fact

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Success Achiever (Solutions) Physical Chemistry 19

123. Answer (3)

Element Electronegativity

F 4.0

O 3.5

Cl 3.2

N 3.0

124. Answer (3)

Charge per unit area is same

125. Answer (2)

Mosley equation is as

k(Z b)

where b is screening constant.

126. Answer (3)

Addition of e– in N is an endothermic process.

127. Answer (1)

Fact

128. Answer (2)

129. Answer (2)

Gallium have smaller size than aluminium.

130. Answer (2)

1

For isoelectronic species, size .

Atomic number

Radius of N3–, O2– and F– follow order

N3– > O2– > F–

As per inequality only option (3) is correct

that is 1.71 Å, 1.40 Å and 1

Mg2+, Na+, O2– and F– all have 10 electrons each.

Energy have to be absorbed to increase the energy of the E.C. and decrease the stability.

132. Answer (2)

With respect to oxygen valency along period generally increase.

Al2O3, SiO2, P4O10, SO3, Cl2O7

133. Answer (4)

Polar bond is present between two atoms which have different electronegativity. If electronegativity is different,

then I.E. and E.A. should be different.

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20 Physical Chemistry Success Achiever (Solutions)

Electronegativity of an atom depend on the electronic configuration, hybridisation and effective nuclear force.

135. Answer (3)

Electron affinity of silicon is higher than carbon because of small size and high electron density of carbon.

136. Answer (2)

Na + e– Na– it is exothermic process while all other are endothermic process.

137. Answer (1)

107 — Unnilseptium.

138. Answer (2)

Technetium.

139. Answer (1)

15th group element = P

16th group element = O

On basis of valency common formula P4O10.

140. Answer (3)

Gallium have smaller size than aluminium this is called scandide contraction.

141. Answer (2)

O > N > B > Be.

142. Answer (2)

Take example of Al and O whose formula is Al2O3.

143. Answer (4)

Mg < C (graphite) < B < Al

144. Answer (4)

He is inert and has weakest van der Waal's forces.

145. Answer (3)

146. Answer (3)

ClF3, XeOF2 and XeF3 are sp3d hybridised with 2 lone pairs hence all have T-shape.

Bond order of C O is 3.5.

148. Answer (4)

5

Bond order = = 1.67,

3

1

Charge per atom = – = – 0.33

3

149. Answer (4)

O 2 O 2 O 2– O 2–2

2 .5 2 1 .5 1

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Higher is the bond order, shorter is the bond length.

sp3 hybridised carbon atom contains 75% p-character.

151. Answer (4)

N N, N O+, C = C.

152. Answer (1)

O

P—Cl

Cl Cl

154. Answer (3)

H

54°44'

C H

H H

155. Answer (3)

Due to intramolecular hydrogen bonding.

156. Answer (2)

Its dipole moment is 3 D.

157. Answer (2)

Due to see-saw shape.

158. Answer (3)

14 carbon atoms are sp2 hybridised and 4 carbon atoms are sp3.

159. Answer (2)

.. ..

O

H H

160. Answer (2)

obs

Percentage ionic character = × 100

th

Fact.

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22 Physical Chemistry Success Achiever (Solutions)

F F

F

F

Structure of I3–

–

I

Due to pentagonal bipyramidal shape.

Hybridisation of iodine is sp 3d 3

So, structure is pentagonal bipyramid.

CH=CH2

Smaller halogen atom more possibility of back bonding.

166. Answer (1)

F Cl

P F

F

Cl

167. Answer (2)

Fact.

168. Answer (4 )

Larger anion, easier polarisation.

169. Answer (3)

Smaller ionic radius, larger hydration radius.

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170. Answer (1)

Larger ionic radius, more ionic mobility (drift velocity per unit electric field).

171. Answer (2)

ClF3 is T-shaped and other are pyramidal.

172. Answer (2)

Cl F Cl F

P F , P Cl

Cl Cl

Cl F

>0 =0

173. Answer (3)

Low heat of sublimation of metal, lower bond energy of non metal element, high lattice energy and high electron

affinity of non metal favour ionic bond formation.

174. Answer (3)

Fact.

175. Answer (2)

All peroxides are polar.

176. Answer (2)

O 2–2 contains zero unpaired electrons.

177. Answer (3)

O

||

P

O O

O

4- bonds O=P—O P=O

O O

P

||

O

178. Answer (4)

1

Polarising power of cation

Size of cation

179. Answer (4)

Peroxide are diamagnetic

The electronic configuration of the given diatomic molecules is

2 2 2 2 2 2

C2 : 1s *1s 2s *2s 2px 2py

2 2 2 2 2 2 2

N2 : 1s *1s 2s * 2s 2p 2p 2pz

x y

2 2 2 2 2 2 2 1 1

O2 : 1s *1s 2s * 2s 2pz 2p 2p * 2p * 2py

x y x

2 2

S2 : 1s *1s 22s *22s 22pz 2p

2 2

2p *22p *22py

x y x

*22pz 3s

2 2

*3s 2

3p 2 2 *13px *13py

z 3p x 3p y

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24 Physical Chemistry Success Achiever (Solutions)

CO has 14 electrons (even) it is diamagnetic

NO has 15e–(odd) it is paramagnetic and has 1 unpaired electron in 2p molecular orbital.

B 2 has 10e – (even) but still paramagnetic and has two unpaired electrons in 2p x and 2p y

(s-p mixing).

O2 has 16 e– (even) but still paramagnetic and has two unpaired electrons in *2px and *2py molecular

orbitals.

Cl

B

Cl Cl

181. Answer (1)

Due to more negative charge on F–

H-bond is one of the dipole-dipole interaction and dependent on inverse cube of distance between the

molecules.

In Ar, London forces exist

183. Answer (1)

When Z 7, sp mixing take place

184. Answer (3)

186. Answer (3)

In valence cell of S is 10e– are present.

187. Answer (1)

Compound Bond angle

OF2 102

H2O 104.5

CH4 109.25

BCl3 120

188. Answer (1)

Fact

189. Answer (2)

190. Answer (2)

O2[AsF6] O2 + [AsF6] –

( 2.5 )

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Electronic configuration Bond order

2–1

He2 * 0.5

1s2 1s1 2

2–1

H2– * 0.5

1s2 1s1 2

2–2

H2–

2 * 0

1s2 1s2 2

2–0

He22 1

1s2 2

Molecule having zero bond order will not be a viable molecule.

It is sp hybridised.

192. Answer (2)

NO contains 15 electrons.

193. Answer (2)

Both bond moments lie in same direction.

194. Answer (4)

In pyrolle lone pair of N is resonance stabilised.

195. Answer (4)

It is sp3 hybridised and tetrahedral.

In CH4, bond angle is highest

N

197. Answer (1)

Fact.

198. Answer (1)

LiH contains 76% (approx.) ionic character.

199. Answer (2)

In aqueous medium movement of ion becomes easier.

200. Answer (4)

Factual

201. Answer (1)

In NO2 , there are no l.p – b.p repulsions and bond angle of O — N — O is 180º.

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26 Physical Chemistry Success Achiever (Solutions)

Molecule/ion Hybridization

NO2– sp2

NO3– sp2

NO2 sp2

NO2 sp

In (3) there is maximum charge separation.

203. Answer (3)

3 2 1 1

NH4 N2 H4 NH2 OH N2 O

204. Answer (4)

(1), (2) and (3) are unstable.

205. Answer (3)

PV = nRT

He 1 × 2 = n1 × R × 300 …(i)

H2 1 × 2 = n2 × R × 300 …(ii)

Divide equation (i) by (ii)

n1

1

n2

n1 = n2

In vessel B, number of atoms will be 2 times that present in vessel A. Because H2 is diatomic while He is

monoatomic.

206. Answer (3)

At constant pressure (parallel to V axis)

V1 > V 2 > V 3

Since V T hence T1 > T2 > T3.

207. Answer (2)

V

= constant

T

Charle’s law.

208. Answer (1)

Molecular weight of C2H6 = 30 gm

Molecular weight of H2 = 2 gm

Since H2 is lighter hence it diffuses faster into balloon containing C2H6 hence balloon will be enlarged.

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209. Answer (3)

W

PV = RT

M

200 0 .5

0.821 0.0821 400

1000 M

M = 100

Molecular weight of C2F4 = 2 × 12 + 4 × 19 = 100.

210. Answer (3)

1

P

V

(3) is not correct representation.

211. Answer (3)

b = 4Vm

where Vm is volume of a gas molecule.

212. Answer (1)

2 2 2 2

1 2 3 4 30

Vrms = 7 .5 .

4 4

⎛ ⎞

⎜ P a ⎟( V b) RT

⎜ 2⎟

⎝ V ⎠

PV = RT

Which is equation of ideal gas.

Both a and b for Cl is more than C2H6.

If thermal energy >> molecular attraction then molecules will be largely separated and will be present in

gaseous state.

At low temperature and high pressure molecules of gas come closer and hence it favour liquefaction of gas.

2a

Ti

Rb

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28 Physical Chemistry Success Achiever (Solutions)

a

TB

Rb

8a

TC

27Rb

Ti

2

TB

Ti 2 54

6.75

TC 8 8

27

TC 8

0.296

TB 27

TB

3.375

TC

TC

Hence T is least.

B

At high temperature gas approaches ideal behaviour and curve starts becoming flat.

219. Answer (3)

Gas cannot be liquefied at a temperature higher than critical temperature and a pressure lower than critical

pressure.

220. Answer (1)

3O2 2O3

Let x lit oxygen converted to ozone.

2

Volume of ozone produced = x

3

Volume of oxygen remaining = 1 – x

2

1 x x 0.8 litre

3

x

1 0 .8

3

x

1 0 . 8 0 .2

3

x = 0.6 litre

2

Volume of ozone = 0.6 0.4 litre

3

Volume of oxygen remaining = 1 – x = 1 – 0.6 = 0.4 litre.

Since volume are equal hence mole fraction of both will be 0.5.

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221. Answer (3)

v 100

r= 10

t 10

x 100

(1) 2 .5

t 40

x 25

(2) 2 .5

t 10

x 100

(3) 10

t 10

x 5

(4) 2 .5

t 2

In option (3) rate of diffusion of O2 is same as that of rate of diffusion of H2 which is never possible because

H2 is lighter and O2 is heavier hence rate or diffusion of H2 will be faster and that of O2 will be slower.

222. Answer (3)

Collision frequency (pressure)2

Hence at 5 atm, collision frequency will be 25z.

223. Answer (2)

8a

Tc

27Rb

a

Vc = 3b and Pc 2 .

27b

224. Answer (4)

At high temperature, a and b both negligible hence PV = RT.

PV

Compressibility factor (Z)

RT

(For one mole of real gas)

van der Waal equation

a

(P )(V b) RT

V2

At low pressure

V b V

⎛ a ⎞

⎜⎝ P 2 ⎟⎠ V RT

V

a

PV RT

V

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a

PV RT

V

PV a

1

RT VRT

a

So, Z 1

VRT

a

At high pressure can be neglected

V2

⎛ a ⎞

⎜ p + 2 ⎟ (Vm b) = RT

⎝ Vm⎠

p(Vm – b) = RT

pb

Z = 1+

RT

At critical temperature density of liquid and gas phase become equal hence meniscus will disappear.

226. Answer (2)

rA vA / t MB

rB vB / t MA

2 MB

1 MA

1 MA

2 MB

MA 1

MB 4

Pwet gas = Pdry gas + aqueous tension

Pdry gas = Pwet gas – aqueous tension.

228. Answer (3)

PVm = RT

RT

Vm =

P

Vm will be maximum at higher temperature and lower pressure.

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229. Answer (2)

At Boyle’s temperature, a real gas behave like ideal.

230. Answer (4)

Vm, real > V m, ideal Z > 1 repulsive forces are dominant this is only possible when gas is highly

compressed, for this experimental temperature should be more than Tc.

231. Answer (1)

Z < 1 Intermolecular force of attraction is dominant, so liquefaction is possible.

232. Answer (1)

‘a’ is large when force of attraction is large.

233. Answer (3)

2a

Ti

Rb

234. Answer (4)

When temperature Texp < Ti, cooling occurs.

235. Answer (3)

When Texp < Tc, repulsive forces do not develop.

236. Answer (3)

2a 2 27

Ti 304.2 2053.3 K 1780.3C

Rb 8

237. Answer (2)

8

Tc 33 9.8 K 263.2C

27

So, for liquefaction temperature must be maintained below –264°C.

238. Answer (1)

2

⎛n⎞

Pressure correction ⎜ ⎟

⎝v⎠

and P n, so pressure correction increases with pressure.

239. Answer (4)

PV = K

log P + log V = log K

log P = log K – log V (y = c + mx)

240. Answer (2)

On comparing, m = –1 = tan

= tan–1(–1) = 135°

241. Answer (4)

P1V1 P2 V2

T1 T2

242. Answer (1)

PV = constant

1

d

V

At sea level pressure is more hence volume less and density more.

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Postulate of kinetic theory of gases.

244. Answer (2)

3

KE = KT

2

T = constant

hence KE = constant

245. Answer (3)

Postulate of kinetic theory of gases.

246. Answer (2)

Due to viscous force (frictional force) liquid comes to rest.

247. Answer (1)

At constant pressure the volume of a given sample of an ideal gas varies with temperature as follows

⎛ t ⎞

Vt V0 ⎜1 ⎟

⎝ 273 ⎠

248. Answer (2)

V = kT

log V = log T + log k

y = mx + c

m=1 c = log k

graph (2) is correct.

249. Answer (1)

Reciprocal of viscosity is called fluidity.

250. Answer (2)

The film of a soap bubble has small thickness and there is air both inside and outside the film.

251. Answer (1)

⎛ V⎞

P1 ⎜ ⎟

PV P1V ⎝ 2⎠

n

RT1 RT1 RT2

P P1 P1 2PT2

⇒ or P1

T1 T1 2T2 2T2 T1

252. Answer (3)

P1V1 = P2V2

g(h1 + 10) × V = g × 10 × 8V. [∵ P = gh]

h1 = 70 m

253. Answer (1)

1

2x + y = 50 H2 + O H 2O

2 2

5

15 mL O2 is in excess C 2H2 + O 2CO2 + H2O

x

2 2 2x

1

CO O2 CO2

y 2 y

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254. Answer (4)

If during neutralisation acid/base or both are weak than it is possible.

255. Answer (3)

For non spontaneity

G > 0

H – TS > 0

If H = +ve and S = –ve

Then, G = H – T (–S)

G = + H + TS

G = +ve

G > 0

256. Answer (3)

When rod cools, energy is given to surrounding hence entropy of universe increase and entropy of rod

decreases.

257. Answer (3)

⎛ E ⎞

For Ideal gas, ⎜ ⎟ = 0.

⎝ P ⎠ T

When T 0 Randomness is zero S = 0.

259. Answer (2)

H = (Bond energy of Reactants) – (Bond energy of product)

= (BEH—H + BEO = O) – (2 × BEOH + BEO—O)

= (x + y) — (2w + z)

= x + y – 2w – z

260. Answer (3)

Density is an intensive property as it does not depend upon amount of substance.

261. Answer (3)

ng = (1 + 3) – 2 = 4 – 2

ng = 2

ng > 0

H > E

262. Answer (2)

9

C2H5SH + O 2 2CO 2 3H2 O SO 2

2 ( g) (l) ( g)

( g)

At 298K, H2O will be in liquid state and CO2 and SO2 will be in gaseous state.

263. Answer (2)

Entropy is a state function i.e. change in entropy depends upon the initial and final states of the system, not

on how that change is brought about.

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An increase in number of moles of gaseous phase shows more increase in entropy.

265. Answer (2)

A reversible process is carried out infinitesimally slowly so that all changes occurring in the direct process

can be exactly reversed and the system remains almost in a state of equilibrium with the surrounding at every

state of the process.

266. Answer (1)

In order to calculate average energy for C—H bond formation we should know the following data. C(graphite)

C(g), Ho = enthalpy of sublimation of carbon.

( g) ( g)

If a gas was to expand by a certain volume reversibly, then it would do a certain amount of work on the

surrounding. If it was to expand irreversibly it would have to do the same amount of work on the surrounding

to expand in volume, but it would also have to do work against frictional forces. Therefore amount of work has

greater modulus but –ve sign.

WIrreversible > WReversible

(Tf)Irreversible > (Tf)Reversible

268. Answer (1)

1

C O 2 CO 2

2

(s) ( g) ( g)

1 1

ng = 1 – =

2 2

1

H – U = ng RT = × R × 298 = 149R

2

15

C6H6 (l) O2 (g) 6CO2 (g) 3H2O(l)

2

15 3

n g 6

2 2

H = U + ngRT

⎛ 3⎞ 3

= 3263.9 ⎜ ⎟ 8.314 298 10

⎝ 2⎠

= –3263.9 + (–3.71)

= –3267.6 kJ mol–1

As no heat can enter or leave the system work is done at the cost of internal energy which falls and so does

the temperature (joule Thomson effect).

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270. Answer (2)

Bond energy of O—H bond = 109 kcal/mol means that when 1 mole of O—H bonds are formed, 109 kcal energy

is released (because dissociation of bond absorb energy). Formation of one mole of water is equivalent to

formation of 2 moles of O—H bond (H—O—H).

Hence energy released = 2 × 109 = 218 kcal.

I. H2O(l) H+(aq) + OH–(aq); H = 57.32 kJ

1

II. H2(g) + O (g) H2O(l); H = –286.20 kJ

2 2

Adding I & II we get,

1

H2(g) + O (g) H+(aq) + OH–(aq)

2 2

H = 57.32 – 286.2

= –228.88 kJ

G = H – TS

The process would be

Reversible if G = – ve

Irreversible if G = +ve

Equilibrium if G = 0

Given H = – 25000 cal and S = 90 cal

at 300K, G = H – TS

= – 25000 – 300 × 90 = – 52000

G is –ve (reversible).

G = H – TS

If H and S are both positive, then G may be negative at high temperature hence reaction becomes

spontaneous at high temperature

For expansion against vacuum work done PdV = 0.

For expansion of an ideal gas the change in internal energy E = 0 as there is no force of attraction amongst

gas molecules or no work has to be done to overcome the intermolecular force. Under adiabatic condition no

heat enters or leaves this further confirms E = 0.

H = E + PV

H = 0 + 0 = 0

H = 0

273. Answer (4)

These are well known criterion of spontaneity.

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S = = = =

T 300 300 3

At equilibrium G = 0

H 276.5 3

Teq = = = 414.75 K

S 2

Adiabatic curve is more steeper.

276. Answer (4)

At low temperature system is spontaneous.

277. Answer (4)

Enthalpy change is path independent.

278. Answer (3)

In Bomb calorimeter reaction is carried out at constant volume, V = 0 hence heat measured is E.

279. Answer (3)

Variation of heat of reaction with temperature is known as Kirchhoff’s equation.

280. Answer (2)

CH4 + 2O2 CO2 + 2H2O, H = x

3

CH3OH + O CO2 + 2H2O, H = y

2 2

1

CH4 + O CH3OH H = –ve

2 2

H = x – y = –ve

x–y<0

y > x

281. Answer (4)

For endothermic reaction the minimum value of activation energy is equal to H.

282. Answer (2)

Formation of oxides of Nitrogen is in general endothermic.

283. Answer (1)

Since heat of neutralisation of strong acid and strong base is equal to formation of water.

NaOH + HCl NaCl + H2O + q

where q = heat of neutralisation

Na+ + OH– + H+ + Cl– Na+ + Cl– + H2O + q

H+ + OH– H2O + q

284. Answer (4)

G = H – TS

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285. Answer (3)

Qrev – Wrev

S = =

T T

P1

nRT ln

S = P2

T

P1

S = nR ln P

2

Fact.

287. Answer (2)

Factual

288. Answer (2)

P1V1 = P2V2

3 2.5

P2 15 bar

0.5

W = –Pext V = –15 × (–2.0) = 30 dm3 bar

2H2O2(l)

2H2O(l) + O2(g)

w = – Pext (4V)

= – nO2 RT

= – 124.5 kJ

work done by O2(g) = 124.5 kJ

228

P–H bond energy = 76 kcal / mol1

3

H H

P P

H H

4(P – H) + (P – P) = 355

or 4 × 76 + (P – P) = 355

(P – P) .E = 51 kcal/mol–1

290. Answer (1)

R

Cp – Cv = R Cv

1

nR

∫ dW nC ∫ dT 1 T T

v 2 1

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38 Physical Chemistry Success Achiever (Solutions)

For occurrence of a reaction,

(rH – TrS) < 0

rH < TrS

283

T 103

87

T > 3253 K (2980°C)

G° = H° – TS°

= – 29.8 + 298 × 0.1

= – 29.8 + 29.8 = 0

Apply relation between G° and Keq

K eq 1

2NO(g) + O2(g) 2

G

°

reaction ⎣

= ⎡⎢ G° ⎤

⎥product

formation ⎦

– ⎡⎢ G ° ⎤

⎣ formation ⎥

⎦reactant

⇒ –RT ln K P = 2× G° – 2 G °

NO 2 NO

⇒ G ° 2 G ° RT ln K P

NO 2 NO

2×86600 – R 298 ln K P

⇒ G °

NO 2

=

2

2

Amount of heat released

3.6

= (393.5) 103 J

12

= 1.18 × 105 J

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Success Achiever (Solutions) Physical Chemistry 39

C2H5OH(l) + 3O2(g) 2CO2(g) + 3H2O(l)

Bomb calorimeter gives U of the reaction

So, as per question

U = –1364.47 kJ mol–1

ng = –1

H = U + ngRT

1 8.314 298

1364.47

1000

= –1366.93 kJ mol–1

= rG + 0

kf

K 1

kb

296. Answer (2)

Let B.EC–H = x, B.EC–C = y

4x = 360 …(1)

6x + y = 620

y = (620 – 540) = 80

297. Answer (3)

Number of eqs. of KOH = 1

For maximum heat, there must be complete neutralisation.

Number of eqs. of H2SO4 = (0.5 × 2) V

V = (0.5 × 2) V

V = V

57.1 kJ

t

mc

S = 2.303nR log 10

= 2.303 × 2 × 8.314

= 38.29 JK–1

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40 Physical Chemistry Success Achiever (Solutions)

V2

S nRln

V1

100

S 2.303 2 8.314 log

10

S = 38.3 J/mole/K

H2O(l), 10C

S

H2O(l),0C H2O(s),0C

1 S2

S = S1 + S2

273 ⎛ 1440 ⎞

= 2 2 2.303 log 2⎜ ⎟

283 ⎝ 273 ⎠

= –11.84 cal K–1

300. Answer (3)

= 312 + 342 – 681.8

= –27.8

301. Answer (4)

1

Wirr = 2(70 20) 101 = –2416 cal

4.18

302. Answer (3)

303. Answer (4)

E remains constant, as it is a state function.

304. Answer (1)

4763.9 ⎞

K = 5.88 × 10–2 exp ⎛⎜ –

⎝ 8.314 573 ⎟⎠

ln 2

⇒ t1 35 s

2

K

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305. Answer (3)

⎛ E⎞

S nF ⎜ 2 96500 1.5 104 = 28.95 JK–1 mol–1

⎝ T ⎟⎠ P

1st I.E. is for gaseous atoms only.

307. Answer (3)

In free expansion, W.D = 0.

308. Answer (1)

Fact.

309. Answer (3)

1

H2(g) + S (g) H2S(g) K1 ...(I)

2 2

H2(g) + Br2(g) 2HBr(g) K2 ...(II)

1

Br2(g) + H2S(g) 2HBr(g) + S (g) K ...(III)

2 2

(III) = (II) – (I)

K2

K= K

1

1

HgO(s) Hg(g) + O (g)

2 2

Total pressure at equilibrium = P

Molar ratio of Hg : O2 = 2 : 1

2 1

PHg = P PO2 = P

3 3

1/ 2

KP = PHg × PO2 1/ 2 ⎛2 ⎞ ⎛1 ⎞

= ⎜ P⎟ ⎜ P⎟

⎝3 ⎠ ⎝3 ⎠

2

KP = P3/2

33 / 2

311. Answer (1)

1– 2 at equilibrium

1–

pN2O4 = × 0.5 atm

1

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42 Physical Chemistry Success Achiever (Solutions)

2

pNO2 = × 0.5 atm

1

pN2 O

2

KP =

p N2 O 4

2

4 2 (0.5)2 (1 ) 2

2= =

(1 )2 (1 – ) 0.5 1 – 2

1 – 2 = 2

22 = 1

1

2 =

2

= 0.707

= 71%

312. Answer (3)

CO Cl2 COCl2

0.1 0 .1 0.3

0.5 0.5 0.5

0.3

0.5

KC = = 15

0.1 0.1

5 5

More the value of equillibrium constant less is the stability of the oxide of nitrogen.

314. Answer (1)

KP = KC (RT ) ng

ng = np – nr = 1 – 2 = – 1

KP 1

= (RT)–1 =

KC RT

1

SO2 (g) O (g) SO3 (g)

2 2

KP = KC(RT)x

⎛ 1⎞ 3 1

= 1 ⎜⎝ 1 ⎟⎠ 1

2 2 2

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315. Answer (2)

AgCl(s) Ag+(aq) + Cl–(aq) ...(i)

Ag+ + 2NH3 [Ag (NH3)2]+ ...(ii)

Due to removal of Ag+ through reaction (ii), equilibrium (i) shifts in forward direction.

316. Answer (1)

At 25°C pKb for NH3 = 4.7 (in aqueous solution)

[NH4Cl] = 0.1 M

[NH3] = 0.01 M

for basic buffer

[conjugate acid B] 0 .1

pOH = pKb + log = 4.7 + log = 4.7 + log 10 = 5.7

[ weak base BOH] 0.01

pH + pOH = 14

pH = 14 – 5.7 = 8.3

1 1

pH = 7 +

2

pK a – pK b = 7 + 3.2 – 3.4 = 6.9

2

1 0

N2O 4 (g) 2NO 2 (g)

1 – 0.2 0 .4

Total moles at equilibrium = 1.2

at t = 0, PV = nRT

1 × V = 1 × RT1

V = RT1

at equilibrium

P2V = n2RT2

P2 = RT2 = RT × RT2 = = 2.4 atm

V 1 300

318. Answer (2)

Fact.

319. Answer (3)

Solution will be neutral hence pH = 7.

320. Answer (2)

[Sr2+] [Cl–]2

(IP) KSP

2

⎛1 –2 ⎞ ⎛ 1 –3 ⎞

IP = ⎜ 10 ⎟ ⎜ 10 ⎟

⎝2 ⎠ ⎝2 ⎠

1

IP = × 10–8 which is greater than KSP.

8

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44 Physical Chemistry Success Achiever (Solutions)

pH = 13

[H+] = 10–13 mole ion/lit

1 mole ion have = 6 × 1023 ions

1 × 10–13 mole ion have = 6 × 1023 × 1 × 10–13

= 6 × 1010 ions per litre

Hence number of ions in 1 ml solution = 6 × 107.

322. Answer (4)

Aqueous solution of FeCl3 is acidic, as on hydrolysis it produces H+ ions according to following equation

Fe+3 + H2O [Fe(OH)2]+2 + H+

This is known as cationic hydrolysis.

323. Answer (2)

According to this equation the concentration of CrO4–2 ions will be half of concentration of Ag+ ions.

[ CO32 ] = 10–4 M

K sp 5.1 109

[Ba2+] = = = 5.1 × 10–5 M

[CO32 ] 104

[50 1]

Final concentration of [SO4– –] = = 0.1 M

[500]

Ksp of BaSO4,

[Ba2+][SO42–] = 1 × 10–10

10 10

[Ba2+][0.1] = = 10–9 M

0.1

Concentration of Ba2+ in final solution = 10–9 M

Concentration of Ba2+ in the original solution.

M1V1 = M2V2

M1 (500 – 50) = 10–9 (500)

M1 = 1.11 × 10–9 M

So, option (3) is correct.

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324. Answer (2)

The pH of Buffer is given by

[Salt]

pH = pKa + log10

[ Acid]

pKa = 4.76

[Acid] = 10 ml of 1.0 M

[Salt] = 20 ml of 0.5 M

But total volume is made up 100 ml

[Acid] = 0.1 M

[Salt] = 0.1 M

[Acid] = [Salt]

pH = pKa

Hence pH of Buffer solution will be 4.76.

325. Answer (4)

Each reaction has a definite value of the rate constant at a particular temperature i.e. KP is constant at constant

temperature.

326. Answer (1)

Backward reaction is dissociation reaction and hence endothermic. The forward reaction will therefore be

exothermic. Further it is acccompanied by decrease in number of gaseous moles. Hence its equilibrium will

be affected by temperature and pressure.

327. Answer (3)

t0 5 5 0

2SO 2 O2 2SO 3

60 3

at equilibrium 5 – 5 5 – 1 .5

100

5–3 3 .5

2

328. Answer (3)

P4 (s) 6Cl2 (g) 4PCl 3 ( g)

at equilibrium 1 – x 1 – 6x 4x

1 – x 1 – 6x

The reaction in which value of K is more goes fastest to completion.

330. Answer (3)

On doubling the volume, pressure decreases and the reaction shifts in the direction of increasing number of

moles.

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3

⎡4⎤

[C]3 ⎢2⎥

⎣ ⎦

Q= = = 16

[ A ] [B] 1 2

2 2

Thus to have Q = KC. The concentration of C must increase i.e. reaction should proceed from left to right.

B + C, G° = 2494.2 J

2A

2494.2 = –2.303 × 8.314 × 300 log KC

–0.434 = log KC

KC = anti log (–0.434)

KC = 0.367

1 1

Now A = , B = 2 and C =

2 2

1

⎛ ⎞

CB ⎜⎝ 2 ⎟⎠

2

Now QC = = =4

A 2 ⎛ 1⎞

2

⎜ ⎟

⎝2⎠

pH = 12

pOH = 2

[OH–] = 10–2 M

10 –2

Ca(OH)2 = M = 10–2 N

2

= 10–1 equivalent in 100 ml = 1 milliequivalent

333. Answer (4)

K for the reaction is given by K = [CO2]

Because concentration of solids taken to be unity. Since [CaCO3] and [CaO] do not figure in the expression

there will be no effect of addition of CaCO3.

334. Answer (2)

0 .1 0.03 0 0 0

2KCN AgNO 3 Ag(CN)2– KNO 3 K

0.1 — 0.06 0 0.03 0.03 0.03

[Ag(CN)2]– = 0.03

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0.03 0 0.04

Now [ Ag(CN)2 ] – Ag 2CN– (left from KCN)

0.03 – a a 0.04 a

0.03 0.04

(0.04)2 a

KC = 4 × 10–19 =

0.03

a = 7.5 × 10–18

335. Answer (1)

Initial 0 .2 0 .6 0

N2 3H2 2NH3

At equilibrium 0.2 – a 0.6 – 3a 2a

0.8 40 0.8 40 1

Total mixture is 0.8, 40% of its reacts i.e. reacts to give mole of NH3 or NH3 formed

100 100 2

is 0.16 mole

2a = 0.16

a = 0.08

Initial mole = 0.8

Final mole = (0.2 – 0.08) + (0.6 – 0.24) + 0.16

= 0.12 + 0.36 + 0.16 = 0.64

0.64 4

Ratio of final to initial mole = = 0.8 =

0 .8 5

336. Answer (2)

1 0 0

NH4HS NH 3 + H2S

( s) ( g) (g)

1– x x x

Total mole of gaseous substances = 2x

1

x H2S = x NH3 =

2

P

pH2S = pNH3 =

2

p2

KP = pNH3 × pH2S = = 64

4

p2 = 256

p = 16 atm.

X(g) Y(g)

XY(s)

P P

2P = 10 bar, KP = P2 = 25

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CuS Cu+2 + S–2

Ksp [CuS] = S2 = 10–31

S = 3.16 × 10–16

Ag2S 2Ag+ + S–2

KSP (Ag2S) = (2S)2 × S = 4S3 = 10–44

S = 1.36 × 10–15 = 13.6 × 10–16

HgS Hg+2 + S–2

KSP (HgS) = S2 = 10–54

S = 1 × 10–27

338. Answer (2)

At 50% neutralisation

[CH3COOH] = [CH3COONa]

pKa = 14 – pKb = 4.74

pH = pKa = 4.74

At complete neutralisation CH3COONa solution is alkaline due to hydrolysis and concentration is halved due

to dilution by equal volume NaOH.

0.01

Hence [CH3COONa] = M

2

pKa log C

pH = 7 + +

2 2

log 0.005

= 7 + 2.37 + = 8.22

2

339. Answer (4)

HA + BOH BA + H2O

B + A– + H2O BOH + HA

C (1 – h) C (1 – h) Ch Ch

mol / L mol / L mol / L mol / L

h2 Kw

Kh = , Kh =

(1 – h) 2 (1 – h) 2

1 10 –14 h2

=

5 10 – 7 5 10 – 7 (1 – h)2

1 10 –7 h

–7 =

5 10 1– h

5h = 1 – h

1

h =

6

h = 0.166

h = 16.6%

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340. Answer (3)

C = 0.1

HA H + A –

C (1 – ) C C

pH = – log10 [H+]

2 = – log10 C

2 = – log10 0.1

log10 0.1 = –2

0.1 = 10–2

10 –2

= = 10–1 = 0.1

10 –1

... n = 0 for H + I 2HI

g 2 2

342. Answer (3)

A & C are weak base and it salt with strong base hence will form basic buffer.

343. Answer (3)

At the half neutralisation point of an acid pH = pKa.

344. Answer (3)

H2 + I2 2HI

[HI] 2

K=

[H2 ] [I2 ]

At the initial number of moles of H2 and I2 were same therefore at equilibrium [H2] = [I2]

[HI] 2

47.6 = K =

[I2 ] 2

[I2]2 < [HI]2

[I2] < [HI]

A B C D

Initially : 1 1 1 1 [D]eq = 1.818 M

Q=1

Q < keq

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A B C D

Equilibrium : 1–x 1–x 1+x 1+x

(1 x)2

102

(1 x)2

1 x

= 10

1 x

1 + x = 10 – 10x

11x = 9

9

x= = 0.818

11

So, equilibrium concentration of 'D' = 1.818 M.

PPCl3 PCl2

PCl5(g) PCl3(g) + Cl2(g) KP =

PPCl5

PCO PCl2

COCl2(g) CO(g) + Cl2(g) KP =

PCOCl2

If CO is introduced, the dissociation of COCl2 will decrease and PCl2 will decrease. This will favour dissociation

of PCl5 because both reactions are attained in same vessel.

346. Answer (1)

t0 1 0

N2 O 4 2 NO 2

t eq 1 – x 2x

2x = 50% of 1 + x

2x = 0.5 (1 + x)

2x = 0.5 + 0.5 x

x = 0.33

KC = = =

[N2O 4 ] 1 – 0.33 0.66

KC = 0.66

347. Answer (3)

40 ml of 0.1 M ammonia solution = 40 × 0.1

= 4 milliequivalent ammonia solution

20 ml of 0.1 M HCl = 20 × 0.1

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= 2 milliequivalent of HCl

4 2 0

NH4 OH HCl NH4 Cl H2O

4–2 0 2

2

[NH4 Cl] 2

pOH = pKb + log [NH OH] = 4.74 + log = 4.74

4 2

pH = 14 – 4.74 = 9.26

348. Answer (4)

[Ag(H2O)2]+(aq) + NH3(aq) [Ag(NH3)(aq) (H2O)]+ + H2O(I) ...(1)

K1 = 2.0 × 103

[Ag(NH3) (H2O)]+ + NH3(aq) [Ag(NH3)2]+(aq) + H2O(aq) ...(2)

K2 = 8.3 × 103

adding (1) and (2)

[Ag(H2O)2]+(aq) + 2NH3(aq) [Ag(NH3)2]+(aq) + 2H2O(I) : K

On addition of reactions equilibrium constants are multiplied

K = K1K2 = 2 × 103 × 8.3 × 103 = 16.6 × 106

349. Answer (4)

HCl ionises as

HCl

H+ + Cl–

2H+ + SO 4–2

H2SO4

Since pH of both is same, H+ concentration has to be equated.

Hence 0.1M 0.05 M H2SO4

350. Answer (2)

AgCl Ag+ + Cl–

KSP = S2

S= K SP = 1.5 10 –10

= 1.225 × 10–5 × 143.5 g/litre

= 17.58 × 10–4 g/litre

351. Answer (2)

Kw 1 10 –14

Kn = K = = 2 × 10–10

a 5 10 – 5

0.02

ASC– + H2O HASC OH –

x x

0.02 – x

0.02

[HASC][OH– ] x.x x2

Kn = – = =

[ ASC ] 0.02 – x 0.02

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x2

2 × 10–10 =

0.02

x = 2 × 10–6

[OH–] = 2 × 10–6

1 10 –14

[H+] = = 5 × 10–9

2 10 – 6

pH + pOH = 14

12 + pOH = 14

pOH = 2

[OH–] = 10–2 mole/litre

10 –2

Number of OH– in 250 ml =

4

= 0.25 × 10–2 = 2.5 × 10–3

1

Soluble mole of Ca(OH)2 = × 2.5 × 10–3 = 1.25 × 10–3

2

353. Answer (2)

A + B 2C + D + Heat

2 moles 3 moles

Reaction is exothermic.

Reaction involved increase in volume (number of moles). So it is most favoured at low temperature and low

pressure.

354. Answer (1)

1 mole 0 0

NH2 COONH 4 2NH3 CO 2

1– 2

Total number of moles = 1 – + 2 + = 1 + 2

Average molar mass = 2 × 16 = 32

(1 – ) 78 (2 17) 44

32 =

1 2

32 = =

1 2 1 2

32 + 64 = 78

= 0.71875 = 0.72

355. Answer (1)

[Ag2O](s) = [Ag](s) = 1

KP = p O 2

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356. Answer (4)

1

pH = pKW (for pure H2O)

2

1

pH = × 13.26 = 6.63

2

CO (Carbon monoxide) is a lewis base. The C atom tends to donate a pair of e–.

SiCl4 can accept lone pair of electron in d-orbital of silicon hence it can act as Lewis acid.

* Although the most suitable answer is (4). However, both option (4) & (2) can be considered as correct

answers.

e.g. hydrolysis of SiCl4

Cl Cl

H

Si + H2O Si O

Cl Cl Cl H

Cl

Cl Cl

Cl

Cl Si OH + HCl

Cl

Hence option (2), AlCl3 and SiCl4 is also correct.

0.1435

Moles of AgCl formed = 103 mole

143.5

= 5 × 10–4 moles

1000

Strength of H2SO4 = 5 10 4 98 2.45 gL1

20

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54 Physical Chemistry Success Achiever (Solutions)

1

H2 O H2 O2

2

1 0 0

1

2

∑ n 1

2

2 1 2

XH2O ; XH2 ; XO2

2 2 2

PH2 PO1/22

KP

PH2O

1

1

⎛ 2 ⎞ ⎛ ⎞2

⎜⎝ ⎟ P ⎜⎝ ⎟ P2 3/2 P1/2

2 ⎠ 2 ⎠

⇒ KP

2 1 1 2 1/2

P

2

1 3

N2 H2 NH3 , n 1

2 2

362. Answer (3)

H 2 ⎡⎣S2 ⎤⎦

k1k 2

H2S

0.12 S2

1021 ⇒ S2 10 20

0.1

In presence of external H+,

2

2H S , K a 1 K a2 K eq

H2S

H 2 S2

1 10 7 1.2 1013

H2S

0.22 S2

1.2 10 20

0.1

[S2–] = 3 × 10–20

NH4Cl is the salt of weaker base and strong acid, so will be acidic. NaCl neutral and NaCN will be basic as

this is the salt of strong base and weak acid HCN.

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CH3COOK + H2O CH3COOH + KOH

Basic

FeCl3 – Acidic solution

Al(CN)3 – Salt of weak acid and weak base

Pb(CH3COO)2 – Salt of weak acid and weak base

CH3COOK is salt of weak acid and strong base.

Hence solution of CH3COOK is basic.

Ksp = 22 33 S2+3 = 108(S)5

365. Answer (1)

HCO3 H

H2CO3

2

H CO3

366. Answer (4)

s1 K a1 s1 10 4 103

⇒

s2 K a2 s2 4 10 10 2

Ksp = 10–11 = [Mg2+][OH–]2 = 0.1[OH–]2

[OH–] = 10–5 (Minimum conc. for precipitation)

pH = 9

368. Answer (3)

In water, solubility will be maximum as in other cases, there is common-ion effect. In 0.05 M AgNO3, it will

be least.

369. Answer (1)

Q < K Reaction goes forward

370. Answer (1)

⎛ 11.45 103 ⎞

Kc = ⎜ 103 mole/L

⎜ 8.314 298 ⎟⎟

⎝ ⎠

= 4.6 × 10–3 M

371. Answer (3)

1

K p =

(K p )2

1

=

(4 103 )2

106

=

16

= 6.25 × 104 atm

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Volume occupied by diamond is less.

373. Answer (2)

As ‘K’ is increasing on increase of ‘T’.

374. Answer (1)

Hº Sº

log K

2.303 RT R

H

⎛A ⎞

Equilibrium constant K ⎜ f ⎟ e RT

⎝ Ab ⎠

⎛A ⎞ H ⎛ 1 ⎞

ln K ln ⎜ f ⎟ R ⎜⎝ T ⎟⎠

⎝ Ab ⎠

y= C+ m x

Comparing with equation of straight line,

H

Slope =

R

Since, reaction is exothermic, H° = –ve, therefore, slope = +ve.

ln K

A

B 1

(0, 0) T(K)

Apply mass balance

376. Answer (4)

In the expression of Q, all activity terms are taken at unit pressure or unit concentration.

377. Answer (3)

Weaker acid has stronger conjugate base.

378. Answer (3)

In benzaldehyde, 5 carbon atoms have –1 oxidation number, 1 carbon atom has zero oxidation number and

1 carbon atom has +1 oxidation number.

H

(+1)C = O

(0)

(–1) (–1)

(–1) (–1)

(–1)

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379. Answer (1)

The sum of oxidation number of all the carbon atoms = 5(–1) + 0 + 3 = –2.

O–H

(+3)C = O

(0)

(–1) (–1)

(–1) (–1)

(–1)

380. Answer (4)

6 2 3 4

H

Cr 3 Fe 3 C O 2

K 2 Cr 2 O 7 Fe C 2 O 4

(nf 6 ) (nf 3 )

3 K2Cr2O7 + 6 FeC2O4 Cr3+ + Fe3+ + CO2

∵ 6 mole FeC2O4 required 3 mole of K2Cr2O7

3 1

1 mole FeC2O4 required 1 mole of K2Cr2O7

6 2

381. Answer (2)

–

8 e

N2H4 (N2H4 ) 8 ( y )

2 x 4 8

x 2

+2 –2 0

Cu S Cu + SO2

–

+2 e

–

–6 e

So, 1 mole of CuS loses 4 mole of electrons.

M

Equivalent weight of CuS =

4

383. Answer (4)

0 –3

N2 N H3

One mole of N2 loses 6 mole of electrons and one mole of NH3 gains 3 mole of electrons. Hence, equivalent

M1 M2

weight of N2 and NH3 will be and respectively. If an element is present in its lowest oxidation state

6 3

then it behaves as reducing agent only. So, NH3 acts as reducing agent only.

384. Answer (2)

If an element is present in its highest oxidation state then it behaves as oxidising agent only and if an element

is present in its lowest oxidation state then it behaves as reducing agent only. S has highest oxidation state

+6 and lowest oxidation state –2. So, H2SO4 acts as oxidising agent only and H2S acts as reducing agent

only.

385. Answer (1)

The structure of K3CrO8 is

O O

Cr – +

O O—O K

– O

O

+ –

K O+

K

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58 Physical Chemistry Success Achiever (Solutions)

In the reaction, only two chlorine atom change its oxidation number (–1) to zero.

2

So, n-factor for HCl = 0 .5

4

M 36.5

Equivalent weight of HCl = 73

0 .5 0.5

Balanced reaction is

3 Cl2 + 6 OH– 5 Cl– + ClO3– + 3H2O

388. Answer (4)

Cu2+, Sn4+ and Fe3+ are placed below hydrogen in electrochemical series. So, it is reduced by hydrogen but

Al3+ is placed above hydrogen in electrochemical series.

389. Answer (3)

Less electronegative halogen does not displace more electronegative halogen from the salt but I2 displaces

chlorine and bromine from oxysalt because in this case, displacement of halogen is done by reduction.

390. Answer (4)

2+ –1 +3 +4

Fe S 2 Fe2O3 + SO2

–

–1 e

–

–2 × 5e

M

Total 11 mole of electrons are lost by 1 mole of FeS2. Hence, equivalent weight of FeS2 = .

11

391. Answer (4)

Equivalents of KMnO4 = 0.5 × 5 (nf = 5) = 2.5

In 4th option,

Equivalents of FeSO4 = 2.5 × 1 (nf = 1) = 2.5

392. Answer (4)

M

Br2 Br–, equivalent mass of Br2 =

2

M

Br2 BrO3– equivalent mass of Br2 =

10

M M 6M

Net equivalent mass of Br2 =

2 10 10

10 5

n-factor of Br2 =

6 3

393. Answer (2)

O O

– (+5) (0) (0) (+5) –

O —S—S—S—S—O

O O

In which, two sulphur atoms have (+5) oxidation number and two sulphur atoms have zero oxidation number.

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Fluorine is most electronegative element and it does not show positive oxidation state.

Silver can’t displace Cu from CuCl2 because Ag is placed below than Cu in electrochemical series.

395. Answer (2)

Electrolysis makes a non-spontaneous change spontaneous.

396. Answer (2)

Factual

397. Answer (1)

Factual

398. Answer (4)

Here energy evolved (–G) is converted in electrical energy.

399. Answer (1)

Factual

400. Answer (4)

Electrochemical series is the arrangement of increasing order of standard reduction potentials.

401. Answer (1)

Oxidation potential of Li is highest and of H is zero.

402. Answer (3)

= 0.41 – (–0.74)

= 1.15 V

1 atm

Pt(s)

1 M HCl

This is schematic diagram of S.H.E.

404. Answer (1)

This is as per the law of conservation of mass and law of conservation of charge.

405. Answer (3)

As oxidation potential of metalloids must be less than metals and greater than non-metals.

406. Answer (3)

Oxidation potential under standard conditions will be positive and constant irrespective of concentration.

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60 Physical Chemistry Success Achiever (Solutions)

6 2 4

H

Cr 3 Sn Cl 4

K 2 Cr2 O 7 Sn Cl 2

( nf 6 ) (nf 2 )

H

Cr 3 SnCl 4

K 2Cr2 O 7 3SnCl 2

1

1 mole SnCl2 will be oxidised by 1 mole K Cr O

3 2 2 7

1

So, mole of K2Cr2O7 required = mole

3

408. Answer (1)

Na2 B4 O7

2 × 1 + 4x – 14 = 0

4x = +12

x = +3

409. Answer (3)

In H2SO4, S has highest oxidation number i.e. +6 and in SO2, S has oxidation number +4 which lies in

between range of S (–2 to +6).

410. Answer (4)

+1 –2 +2 2+ +4

Cu2 S Cu + SO2

–

+2 e

–

–6 e

M

Total 8 e– are lost by one molecule of Cu2S. So, equivalent weight of Cu2S = .

8

411. Answer (3)

1 2

CH3 CH CH2

412. Answer (3)

4 4

CO2 , n 4 4 8

CH4

Total 4 alternate corners, 4 alternate edges and 2 alternate faces are present in a cubic unit cell.

1 1

Number of ‘A’ atoms = 4

8 2

1

Number of ‘B’ atoms = 4 1

4

1

Number of ‘C’ atoms = 2 1

2

Hence, formula of unit cell = A1/2BC and simplest formula of compound is AB2C2.

414. Answer (2)

Orthorhombic crystal system has simple, body centred, end centred and face centred unit cell.

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415. Answer (4)

416. Answer (4)

Only Ba forms body centred structure, Ca and Sr forms face centred structure while Be forms hexagonal close

packed structure.

417. Answer (3)

= = = 9.11 × 105 gm–3 = 0.91 g cm–3

3

a3NA 2 452 1012 m / 3 6.023 1023 mol1

419. Answer (2)

In Fe3O4, O2– ions form the ccp lattice, one Fe2+ is present in octahedral void. While Fe3+ ions are equally

distributed in between octahedral and tetrahedral voids. So, only 12.5% tetrahedral voids are occupied.

420. Answer (1)

421. Answer (1)

422. Answer (3)

ZA

d

V(in cm 3 ) N0

4 27 4 27

d 8 3 23 = = 2.8 g/c.c

24

( 4 10 ) 6.023 10 64 10 6.023 10 23

All the correct statements.

424. Answer (1)

425. Answer (1)

1

Number of ‘A’ atoms = 8 1

8

1

Number of ‘B’ atoms = 6 3

2

1

Number of ‘C’ atoms = 12 1 4

4

After passing tetrad axis, 2 face atoms and 1 body atom is removed. Now,

1

Number of ‘A’ atoms = 8 1

8

1 1

Number of ‘B’ atoms = 6 2 2

2 2

Number of ‘C’ atoms = 4 – 1 = 3

Hence, formula of unit cell is AB2C3.

426. Answer (2)

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8

ZA

8

5

ZB

2

So formula of compound is AB5/2

i.e., A2B5

In Frenkel defect, ions occupy the interstial site like interstitial defect and create a vacancy in the lattice site

like vacancy defect. So, it is the combination of vacancy as well as interstitial defect.

In Frenkel defect, cation is dislocated from its normal lattice site to an interstitial site.

429. Answer (1)

In case of BCC structure,

3a

r r– (a = cell edge length, r+ + r– = inter ionic distance)

2

3 3.5

r r–

2

r+ + r– = 3.031 Å

—

Cl

– Cl

—

Cl –

Cl

+

Cs

—

Cl –

Cl

— Cl

Cl

2rCl 2rCs 3 a

3a

rCl rCs

2

431. Answer (4)

In a cubic crystal, 9 plane of symmetry, 13 axis of symmetry and 1 centre of symmetry is present.

Factual type.

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433. Answer (3)

1 1

Number of O2– ions = 8 6 4

8 2

(12.5% T.V ) ( 50% O.V.)

434. Answer (2)

The length of face diagonal = a 2

= 80 2

So, a = 80 pm (a = cell edge length)

In NaCl type structure,

a 80

r r 40 pm

2 2

a 361

r= 127.6 pm

2 2 2 2

By ABC,

a

2a2 = 16r2

1 2 C B

r2 a

8

1

r a

2 2

a

Distance of closest approach = 2r =

2

670.3

r+ = pm – 181 pm = 154 pm

2

436. Answer (3)

Factual type.

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CrO2 is strongly attracted towards magnetic field so it is ferromagnetic.

For fcc,

a

x

2

3

⎛ a ⎞ a3

⎜

Volume of fcc unit cell = ⎜ ⎟

⎟

⎝ 2⎠ 2 2

The length of body diagonal is a 3 . Two tetrahedral voids are present on each body diagonal at the distance

a 3

.

2

440. Answer (3)

The simplest unit of hcp structure is hexagon. Other statements are correct.

441. Answer (4)

For bcc,

a 3 5 3

r 2.165 Å

4 4

r = 216.5 pm

In BCC,

4

edge length = r

3

4

4.29 = r

3

4.29

r= 3 1.86 Å

4

443. Answer (3)

Total 4 body diagonals are present in a cube. 1 middle tetrahedral void is present on each body diagonal is

common for all. So, total number of tetrahedral voids are 9.

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444. Answer (1)

rNa

From r 0.75

K

rNa

Putting the value of rNa in 0.55 then we get

rCl –

0.75 rK

0.55

rCl–

rK 0.55

0.733

rCl– 0.75

So, 2(r r – ) 2(0.55 1) 1.118

Na Cl

(Side for unit cell for KCl = 2(rK rCl– ) , Side for unit cell for NaCl = 2(rNa rCl– ))

Triclinic is the most irregular system. The cell dimensions of this system are a b c and

90°.

446. Answer (4)

All statements are correct for fluorite structure.

447. Answer (4)

1 mole AlCl3 develops 2 mole of cation vacancies in the doping in NaCl.

10 5

Number of cation vacancies = 2 6.023 10 23 = 1.2046 × 1017

100

448. Answer (3)

In this defect, some Fe2+ ions are converted into Fe3+ ions. Due to charge balance number of Fe atoms

decrease. Hence, it is found as Fe0.95O not FeO.

449. Answer (2)

Both Al3+ ions are present in octahedral voids. Other statements are correct.

450. Answer (3)

In the unit cell of NaCl, Na+ ions are present in octahedral voids and Cl– ions are present on ccp lattice. When

one body diagonal plane is placed in the unit cell, then 4 corner ions, 2 edge ions, 2 face ions and 1 body

ions are removed. Now,

⎛1 ⎞ 1

Number of Na+ ions = 4 ⎜ 2 1⎟ 2

⎝4 ⎠ 2

⎛1 1 ⎞ 1

Number of Cl– ions = 4 ⎜ 2 4 ⎟ 2

⎝ 2 8 ⎠ 2

451. Answer (2)

3 ⇒ 1 3 1.103

27.94 a2 a2 27.94

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Fact

453. Answer (2)

Volume of any lattice is

V = abc(1 – cos2– cos2– cos2– 2cos cos cos)1/2

V1 = Vtetragonal = a2c

(because a = b c, = = = 90°)

3

V2 = Vhexagonal = a2c

2

(because a = b c, = = 90°, = 120°)

V1 2

V2 3

MnO2 has rutile structure.

455. Answer (1)

No. of T-voids = 2 × no. of atoms

No. of O-voids = no. of atoms.

456. Answer (4)

Reverse osmosis involves moment of solvent particles through semipermeable membrane from concentrated

solution to dilute solution.

457. Answer (3)

For isotonic solution C1 = C2 (at constant temperature).

458. Answer (1)

98 1000 1.6

N= 32

49 100

459. Answer (2)

9.1 × 10–31 kg = 1 e–

1

1 kg = e

31

9.1 10

∵ 6.023 × 1023 e– = 1 mole

1 1 1

e

31 23 31

9.1 10 6.023 10 9.1 10

Number of moles (n) = 0.018 × 108 = 1.8 × 106 moles

n

Molarity = v

2

1.8 106

M=

0.5

M = 3.6 × 106 M.

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460. Answer (4)

According to Raoults law for non-volatile solution.

PB P ⎡ A solute ⎤

xA ⎢ ⎥

PB ⎣B solvent ⎦

PB gain in weight of CaCl2 .

Because in positive deviation solvent-solvent interaction is greater than solute-solvent interaction.

462. Answer (4)

463. Answer (1)

Elevation in boiling point is inversely proportional to molecular length of solute.

464. Answer (4)

465. Answer (2)

meq of HCl = meq of NaOH

Mass

1000 NVml …(i) (N = 0.5 N, V = 100 ml)

Eq mass

∵ molality = M.m mass of solvent (g)

⎛ g ⎞ 1000

5 ⎜⎜ ⎟⎟

⎝ Eq mass ⎠ w

g

1000 w 5 …(ii)

Eq mass

⎡N 0.5 N ⎤

w × 5 = 0.5 × 100 ⎢ ⎥

⎣ V 100 ml ⎦

w = 10 g.

(mass of solvent )

a3Na

M=

N

=

4

= 74.7 g mol–1

467. Answer (1)

468. Answer (2)

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470. Answer (3)

471. Answer (1)

nRT

Osmotic pressure () =

v

i1n1RT i2n 2RT

1 = and 2 =

v v

= 1 + 2

⎛ i1n1RT ⎞ ⎛ i2n2RT ⎞

= ⎜⎜ v ⎟⎟ ⎜⎜ v ⎟⎟

⎝ ⎠ ⎝ ⎠

and v1 + v2 = v

⎛ i1n1 i2n 2 ⎞

= ⎜⎜ v

⎟RT

⎟

⎝ ⎠

T ⎡ ini in2 ⎤

⎢ ⎥

v ⎣v v ⎦

⎛ i1n1 i2n 2 ⎞

⎜ ⎟

or = ⎜ v v ⎟RT .

⎝ 1 2 ⎠

472. Answer (4)

18

pº –ps nsolute 180 18

ps nsolvent 178.2 17.82

18

760 – ps 18

ps 1782

ps = 752.4 torr

PB P in A ⎡ A solute ⎤

…(i) ⎢ ⎥

PB in A nB ⎣B solvent ⎦

∵ solution is concentrated

P°B = 760 mm-Hg P = 750 mm-Hg

5.85

nA = = 0.1 mole

58.5

180

nB = = 10 moles

18

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for AB A B

1

i=1+

760 (1 )0.1 10

1 0.1(1 )

(dilute solution)

76 10

100

1+=

76

= 0.315.

3

Al 2 (SO 4 ) 4 2Al 3SO 4 2

2 moles

1 mole 3 moles

nsolute

molality = w 1000

solvent

⎡ w ⎤

⎢d v ⎥

⎢ ⎥

n ⎢ w 250 1⎥

3= 1000 ⎢ w 250 g ⎥

250 1

⎢ ⎥

⎣ ⎦

3

n= mole

4

3 2 3 3

mole of Al2SO4 producing = mole

4 1 4 2

3 23 23

number of Al3+ ions = 6.023 10 9.03 10 ions.

2

For MgCl2, = 50% i.e. 0.5

2

MgCl2 Mg 2Cl

1 2

i1 = 1 + 2

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i1 = 1 + 1

i1 = 2

for CH3COOH, = 50% i.e. = 0.5

1

CH3 COOH (CH3 COOH)2

1

2

2

i2 = 1 Total value of

2

i2 = 1 – 0.25 i = i1 + i 2

i2 = 0.75 i = 2 + 0.75

i = 2.75

477. Answer (1)

478. Answer (3)

479. Answer (3)

Addition of acid in to water is exothermic and H < 0 then solution will be non ideal showing negative deviation.

Ethanol has H-Bonding, n-heptane tries to break the H-bonds of ethanol, hence, V.P. increases. Such a

solution shows positive deviation from Raoult's Law.

At –56.6°C, solid and liquid are in the same phase.

Solvent is the component which have same physical state as that solution.

484. Answer (3)

3

For AlCl3 Al 3Cl

1 3

i1 = 1 + 3 ( = 100%)

i1 = 4

NaCl Na Cl

1

i=1+ ( = 100%)

i=2

1 = i1RT

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2 = i2cRT

1 i1

2 i2

1 4

2 2

1 : 2 = 2 : 1.

485. Answer (1)

The solution which shows maximum freezing point must have minimum number of solute particles.

(1) [Co(H2O)6]Cl3 [Co(H2O)6]3+ + 3Cl–, i = 4

(2) [Co(H2O)5Cl]Cl2 H2O [Co(H2O)5Cl]2+ + 2Cl–, i = 3

(3) [Co(H2O)4Cl2]Cl 2H2O [Co(H2O)4Cl2]+ + Cl–, i = 2

(4) [Co(H2O)3Cl3] 3H2O [Co(H2O)3Cl3], i = 1

So, solution of 1 molal [Co(H2O)3Cl3] 3H2O will have minimum number of particles in aqueous state.

Hence, option (4) is correct.

When benzoic acid dissolved in benzene it gets dimerises and molecular mass of its diemer is 244 amu.

1000 1000

m 55.56

18 1000

489. Answer (3)

PB P ⎡ A solute ⎤

xA …(i) ⎢ ⎥

PB ⎣B solvent ⎦

xA xA

m = x 55.55 xA 1

B 0.054

xA ⎛ 1 ⎞

3 = x 55.55 x A ⎜1 ⎟ 1

B ⎝ 0.054 ⎠

xA 1

= 0.054 xA

xB 19.5

xA

xB …(i) xA = 0.05

0.054

∵ xA + xB = 1 P°B – P = xA × P°B

P°B – P = 0.05 × 760 = 38.97 mm-Hg.

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Vapour pressure of solution, PS = 183 torr

Molar mass of solvent, MA = 58 g/mole

P°A – PS nB

as we know =

PS nA

185 – 183 WB MA

⇒ = ×

183 MB WA

2 1.2 58

⇒ = ×

183 MB 100

1.2 58

⇒ MB = × ×183

2 100

= 63.68 g / mole

491. Answer (1)

SO2 + NaOH NaHSO3

meq. of NaOH = meq of NaHSO3

g

NV 1000(NaHSO 3 )

(NaOH) eq mass

g

0.1 1 100 1000

104

3 3

PB P ⎡ A solute ⎤

xA ⎢ ⎥

PB ⎣B solvent ⎦

1.04

PB P

104

PB 36 (dilute solution)

18

PB P 0.01

PB 2

0.01

(P°B – P) = 1 (atm)

2

P P

B = 0.005 atm

(lowering of vapour pressure)

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492. Answer (2)

RT0 2

Kb

1000 Hv

2

2 (373)

Kb

9.72 3

1000 10

18

Kb = 0.52° mole/kg

Tb = Kb × m

Tb = 0.52 × 0.1 = 0.052°.

493. Answer (2)

1

C 6H5 COOH C H COOH

1

n 6 5

1

n

i = 1

n

⎛ 1⎞ ⎡ 100%⎤

i = 1 ⎜ 1 ⎟ ⎢ ⎥

⎝ n⎠ ⎣ ⇒ 1 ⎦

⎛ 1⎞

i = 1 ⎜1 ⎟ …(i)

⎝ n ⎠

Tf (obserbed)

i=

Tf (calculated)

Tf

i …(ii)

Kfm

12.2 1000

m=

122 100

m = 1 molal

0.93

i=

1.86 1

1

i=

2

Putting the value of ‘i’ in equation (i)

⎛ 1⎞

i 1 ⎜1 ⎟

⎝ n⎠

1 ⎛ 1⎞

1 ⎜1 ⎟

2 ⎝ n ⎠

n = 2.

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For MX2 salt

Van’t Hoff factor = 1 + 2 = 2

= 0.5

Tb = Kbm

logTb = logKb + logm log Tb

y = mx + c

m=1 (tan = 1, = 45°) log m

496. Answer (4)

Solute solvent interaction is equal to solute-solute and solvent-solvent interaction.

497. Answer (4)

For dilute solution

nA

xA ~ n (nA + nB ~ nB)

B

PB P in A

ix A .

PB nB

For isotonic solution

A = B

CART = CBRT

CA = CB.

499. Answer (2)

P A x A

x A

( vapour phase )

P A x A PB x B

50 0.5

xA =

50 0.5 100 0.5

25

xA =

75

xA = 0.33.

500. Answer (1)

Volume strength of H2O2 = 5.6 × normality

volume strength = 5.6 × 4.5 = 25.2.

501. Answer (3)

The solution which flow into the blood stream are of the same osmotic pressure as that of blood otherwise

due to difference in osmotic pressure blood cells may swell and burst.

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502. Answer (2)

Partial pressure of water

R.H 100

Saturated partial pressure of water

503. Answer (2)

Fact

504. Answer (3)

P XA PA0 XBPB0

505. Answer (3)

2A

A2

3A

A3

1 0

1

1 3

2

2

⇒ i 1 ⇒ i 1

2 3

1 2 1

1 0.5 1 0.33

2 3 3

0.2 / 60

0.45 = i(5.12) 1000

20

i = 0.527

CH3COOH2

2CH3 COOH

1–

2

i 1–

2

0.527 = 1 –

2

= 0.473

2

= 0.946

% association = 94.6%

8.314 383.7 92

2

RTb2 M1

Kb ⇒ Hv = 34 kJ mol–1

1000Hv 1000 3.32 103

507 Answer (2)

i = 5 for K4[Fe(CN)6) and i = 5 for Mohr salt.

Tf = i Kfm

i for Na2SO4 is 3(100% ionisation)

0.01

Tf = 3 × 1.86 ×

1

Tf = 0.0558 K

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i CRT

509. Answer (2)

0.2 mol I2 and 0.8 mol C6H6

WC6 H6 0.8 78

0.2 1000

m 3.2

0.8 78

510. Answer (4)

6

Cr 2 O72 2Cr O24

G1 = – 2Fx1, G2 = + x2F, G3 = – FE°

G3 = – G1 – G2 = – (– 2Fx1) – (x2F) = – FE°

E° = (x2 – 2x1) V

3+ E0 = ? 2+ E0 = – 0.439 V

Fe (1)

Fe (2)

Fe

0

E = – 0.036 V

(3)

– n1E01 – n2E02 = – n3E03

– E0 + 2 × 0.439 = +3 × 0.036

E0 = +0.77 V

Ksp = 4x3, (x is solubility of Ag2CrO4)

[Ag+] = 2x

0.0591 1

E = 0.80 – log

1 2x

513. Answer (2)

AgNO3 will react with copper.

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514. Answer (3)

Standard free energies of reactant and product are same.

Go = 0

515. Answer (4)

516. Answer (4)

Value of ‘n’ is not given

517. Answer (4)

2.303 RT

E= – log Q

nF

2H+

H2

PH2

Q=

[H ]2

518. Answer (4)

519. Answer (4)

Fact.

520. Answer (2)

Only H2O is electrolysed.

521. Answer (4)

Change in oxidation number of N is 6

22.4

Veqv = = 3.73 L

6

522. Answer (1)

2H2O + 2e– H2 + 2OH– ...(i)

2H2O O2 + 4H+ + 4e– ...(ii)

2x

From (i) 1 mol of H2 = 22.4 LH2 is obtained by 2 units xL of H2 units costing Rs.x

22.4

hence, 1 units costs = Rs. 11.2

from (ii) : 22.4 L at NTP costs = 4 units

= 4 × 11.2

xL costs = 2x

523. Answer (3)

NO2 NO

2e– +

nf 2

n=2

1 Eq nitrogen benzene require 1F

1

Net charge = = 1.25 F

0 .8

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It is 2.26V.

525. Answer (1)

The cell can be formed as Fe|Fe3+; OH–|Fe(OH)3(s)|Fe

The electrode reactions can be written as

Fe(s) Fe3+ + 3e–

Fe(OH)3(s) + 3e– Fe(s) + 3OH–

Overall reaction is i.e., by adding

i.e. E° = E0 – E0

OH– /Fe(OH)3 /Fe Fe2 /Fe

OH– /Fe(OH)3 /Fe

E° = log10 –36.4

0.3 3

0.75V

Larger cation, more ionic mobility.

527. Answer (2)

Eocell = EFe

o

2

/ Fe

o

– E Cr 3

/ Cr

Li has maximum reducing power.

529. Answer (3)

WAg WMg

=

E Ag EMg

M 0.01

K= = (C1 – 2C2 + C3) ×

1000 1000

According to Debye Huckle onsager equation,

C A C

Here A = B

C B C

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531. Answer (2)

Pb(s) + CaC2O4(s) PbC2O4(s) + Ca+2 + 2e–

532. Answer (2)

Temperature coefficient becomes minimum.

533. Answer (3)

Example : Pt | Sn+2, Sn+4

534. Answer (1)

0.0591

E = Eo – log [H+]2 = Eo + 0.0591 × pH

2

E1 – E2 = 0.0591 [(pH)1 – (pH)2]

535. Answer (2)

After electrolysis aqueous NaCl is converted into aqueous NaOH

0.250 35 60

The quantity of electricity passed = F = 5.44 × 10–3 F

96500

5.44 10 –3

Molarity of NaOH = 1.36 10 –2

0.4L

pH = 12.13

536. Answer (3)

G

=

H

3

CH3OH(l) + O (g) CO2(g) + 2H2O(l)

2 2

Greaction = Gproducts – Greactant

= [–394.4 – 2 × 237.2] – [–166.2]

= –702.6 kJ

G

We know, efficiency of a fuel cell, 100

H

–702.6

= 100

–726

97%

M C 2

= ,K=

1–

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80 Physical Chemistry Success Achiever (Solutions)

– +

CHCOOH + H2O CH3COO + H3O

c 48.15

x (degree of ionisation) = = 0.1232

0 390.7

Ka(ionisation constant) = = = 1.78 × 10–5

(1– x) (1– 0.1232)

Equivalent conductance c = normality

97.1 (ohm–cm2equiv–1) =

0.1(equivalent cm –3 ) 1.50

current = 0.02913 × 5 = 0.1456A

For 0.2 M solution

R = 50

= 1.4 S m–1 = 1.4 × 10–2 S cm–1

1 1

cm

1.4 10 2

l

Now, R

a

l R

50 1.4 10 2

a

R = 280

=?

l

50 1.4 10 2

a

l

R

a

1 1 l

R a

1 1

= 50 1.4 10 2 = 70 10 2 = 2.5 × 10–3 S cm–1

280 280

Now, m = = 5 S cm2 mol–1 = 5 × 10–4 S m2 mol–1

M 0.5

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539. Answer (3)

dE S

=

dT nF

E > 0, Q < 1.

1

H e –

H2

2

1

0.059 PH2 2

E0 log

1 [H ]

0.059 21/2

E log

1 1

Therefore E is negative.

E = Z × 96500

Fact.

1

H2O O + 2e–, H2O2 O2 + 2e–

2 2

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82 Physical Chemistry Success Achiever (Solutions)

27.66 of B2H6 = 1 mole of B2H6 which requires three moles of oxygen (O2) for complete burning

6H2O 6H2+ 3O2 (On electrolysis)

Number of faradays = 12 = Amount of charge

12 × 96500 = i × t

12 × 96500 = 100 × t

12 96500

t second

100

12 96500

t hour

100 3600

t = 3.2 hours

wq

551. Answer (3)

electrolys is 1

NaH Na H2 (g)

2

( cathode) anode

On electrolysis only in case of Ca2+ salt aqueous solution H2 gas discharge at Cathode.

Case of Cr

At cathode : Cr3+ + 2e– Cr

So, Cr is deposited.

Case of Ag

At cathode : Ag+ + e– Ag

So, Ag is deposited.

Case of Cu

At cathode : Cu2+ + 2e– Cu

Case of Ca2+

1

At cathode : H2O + e– H + OH–

2 2

E

w= ×i×t

96500

553. Answer (4)

0.0591 [Cu 2 ]1

E1 – E2 = log

2 [Cu 2 ] 2

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554. Answer (2)

Go = – nF Eocell = – 2 × 96500 × 1.10 J

555. Answer (4)

1

H2

+

H +e

–

2

K = [H+] = C1

E = E° – 0.0591 logC1

E decreases if C1 increases

1

Cl–

Cl2 e

–

2

1 1

K

–

[Cl ] C2

E = E° + 0.0591 logC2

E increases if C2 increases

Ag +

Ag + e

–

K = C3

E = E° – 0.0591logC3

E decreases if C3 increases

556. Answer (2)

557. Answer (4)

For spontaneous cell reaction, E > 0.

2 7

2

4

–n3E°3 = – n1E°1 – n2E°2

+3E°3 = 2 × 1.26 – 1 × 0.336

E°3 = 0.728 V

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84 Physical Chemistry Success Achiever (Solutions)

Cu does not react with dilute H2SO4.

560. Answer (2)

E

w= ×it

96500

⎛ 127 ⎞

⎜ ⎟

⎝ 1 ⎠

10 = × i × 60 × 60

96500

i = 2.11 A

561. Answer (2)

It requires no gaseous reactant.

562. Answer (1)

Eo = +0.22 – 1.36 = –1.14 V

1

0.059

⇒ E Eo

1

log PCl2 2

–w max = G = –nFE = (–1) (–1.14) × 96500 × 10–3

=110 kJ mol–1

563. Answer (4)

2 × 1.6 × 10–19C is carried by 1 molecule of Zn2+

1

2 × 10–5 C is carried by = 2 10 5

2 1.6 1019

1 1

moles

1.6 1014 N0

1

1.6 6.023 1014 1023

= 10–10

564. Answer (2)

1000 sp.conduc tance

0 (BaSO4 )

conc.(Normality)

1000 8 10 –5

Normality =

400

Normality

Molarity = 10 –4 M

2

Ksp = S2 = 10–8 M2

565. Answer (3)

E 0.5208 V

Cu /Cu

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+ –

Ag Ag + e ; E°Ag/Ag+ = –0.80V

– –

AgI+e Ag + I ; E°I– / AgI/Ag+ = –0.15V

Ag + I–

+

AgI E°Cell = –0.95V

0.0591

ECell = log k sp

1

–0.95

log K sp

0.0591

Ksp = 8.42 × 10–17

567. Answer (2)

0.059 ⎛ D ⎞

Ecell 0.003 log ⎜ ⎟ 0 at equilibrium

2 ⎝ H ⎠

⎛ D ⎞

0.006 0.059log ⎜ ⎟

⎝ H ⎠

⎛ D ⎞ D

0.102 log ⎜ ⎟ ⇒ 100.102 1.2

⎝ H ⎠ H

568. Answer (3)

569. Answer (3)

570. Answer (1)

The fraction of collision with sufficient energy i.e., e – E a / RT becomes unity only at Ea = 0.

571. Answer (4)

2.303 ⎛ a ⎞

k= log ⎜⎜ ⎟⎟

t ⎝a– x ⎠

at time (t/2) seconds

0.6932 2.303 ⎛ a ⎞

log ⎜⎜ ⎟⎟

t ( t / 2) ⎝a– x ⎠

0.6932 ⎛ a ⎞

log ⎜⎜ ⎟⎟

2 2.303 ⎝a– x ⎠

⎛ a ⎞

log ⎜⎜ ⎟⎟ 0.15

⎝a– x ⎠

⎛ a ⎞

⎜⎜ ⎟⎟ 1.413

⎝a– x ⎠

a = 1.413a – 1.413x

0.413a = 1.413x

x 0.413

a 1.413

0.413

% fraction of element decayed = 100 = 29%

1.413

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86 Physical Chemistry Success Achiever (Solutions)

1

t 1/ 2 & where n is order of reaction

n –1

a

for zero order reaction n = 0

t1/2 & a

573. Answer (4)

On decreasing the volume of vessel the to half conc. of A and B are increased by factor of

2 times

rate will be increased by a factor of 4 times

Rate = k[A] [B]

For the completion of 75% reaction 2 half life requires

2 t1/2 = 50

t1/2 = 25 mins

ln 2

t1/2 =

k

2.303 0.301

k=

6.93

2.303 ⎛ a ⎞

log ⎜

⎝ a – 0.99a ⎟⎠

Also, t =

k

2.303 ⎛ 1 ⎞

t = 2.303 0.301 6.93 log ⎜⎝ 0.01⎟⎠ = 46.05 minutes

Rate = k[0.1]m [0.2]n = 2 × 10–3 …(i)

m n –3

k[0.1] [0.4] = 4 × 10 …(ii)

m n –3

k[0.2] [0.2] = 2 × 10 …(iii)

dividing equation (i) by (ii)

n

1 ⎡ 1⎤

n=1

2 ⎢⎣ 2 ⎥⎦

m

⎡ 1⎤

⎢2⎥ 1 m=0

⎣ ⎦

Rate = k[A]0 [B]

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2A B C D

Rate of Reaction =

2 dt dt dt dt

d[C]

Or, k[A]x [B]y

dt

⇒

1.2 10 3 k[0.1]x [0.2]y

y

⎡ 1⎤

⇒ 1 ⎢ ⎥

⎣2⎦

⇒ y0

⇒

2.4 10 3 k[0.2]x [0.1]y

1 x

⎡ 1⎤ ⎡ 1⎤

⇒ ⎢2⎥ ⎢2⎥

⎣ ⎦ ⎣ ⎦

⇒ x 1

d[C]

Hence = k[A]1[B]0 .

dt

Temperature cofficient is the ratio of rate constant when the temperature differ by 10°

75 32 K

65 16 K

55 8K

45 4K

35 2K

25° K

Since the value of rate constant will be increased by 32 times therefore the rate will be increased by 32 times.

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88 Physical Chemistry Success Achiever (Solutions)

t1/2 a

t1/2 = ka

log t1/2 = log k + log a

y = c + mx

m=1

= 45°

578. Answer (3)

k = A e –Ea / RT

when Ea = 0

The k = A, it means rate constant is independent of temperature

k rate constant at 330 K will be 4.5 × 105 s–1

579. Answer (1)

x 10

k= for zero order reaction = = 10

t 1

20

In second case k = = 10

2

30

In third case k = = 10

3

Since rate constant (k) is equal in each case therefore reaction follows the zero order mechanism.

580. Answer (1)

k1

Value of k1 is the least, therefore the conversion A B is the slowest and rate determing step of the

reaction.

581. Answer (4)

r1 = k[A] – 1st order reaction

r2 = k[A]2 – 2nd order reaction

r3 = k[A]3 – 3rd order reaction

When the rate constant k is same for three reaction it is clear that

r1 = r2 = r3 when [A] = 1

r1 > r2 > r3 when [A] < 1

r1 < r2 < r3 when [A] > 1

582. Answer (3)

Ea

Energy

P

H

R z

Reaction progress

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583. Answer (3)

( excess)

order of reaction = 1

molecularity = 1 + 1 = 2

584. Answer (2)

Since the half life of first order reaction is independent of initial conc.

585. Answer (2)

CH3COOC2H5 + NaOH CH3COONa + C2H5OH

Rate = k[CH3COOC2H5 ] [OH– ]

Order of reaction is 2

586. Answer (4)

At intersection of two curve the concentration of A and B are equal (i.e., half of the reactant converted into

products) therefore it represent the half life of A.

587. Answer (2)

Rate = k[A][B]2 since [A] is taken in excess therefore its concentration remain almost constant

Rate = k[B]2 k × [A] = k

Order of reaction = 2

588. Answer (2)

Positive catalyst increases the rate of chemical reaction by lowering of activation energy of system.

589. Answer (2)

k = A e –Ea / RT

Ea

ln k = ln A –

RT

y = c + mx

Ea

slope of graph = –

R

590. Answer (1)

t 0 PA 90 0 0

tt 90 – x 2x x

x = 45

2.303 90

k= log

10×60 90 – 45

0.6932

= 10×60

= 1.155 × 10–3 s–1

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90 Physical Chemistry Success Achiever (Solutions)

Assume the order of reaction with respect to acetaldehyde is x.

Condition-1 :

Rate = k[CH3CHO]x

1 = k[363 × 0.95]x

1 = k[344.85]x ...(i)

Condition-2 :

0.5 = k[363 × 0.67]x

0.5 = k[243.21]x ...(ii)

Divide equation (i) by (ii),

x

1 ⎛ 344.85 ⎞

⎜ ⎟ ⇒ 2 (1.414)x

0.5 ⎝ 243.21 ⎠

x=2

592. Answer (3)

H = x

and the activation energy of reverse reaction is also x.

593. Answer (2)

Rate = k[NO2] 2

Rate of reaction is independent of concentration of CO.

594. Answer (2)

Rate of reaction = [A]a

[A]I = 2.2 M r1 = 2.4 M s–1

2 .2 2 .4

[A]II = = 1.1 M r2 = 0.6 or

2 4

On reducing the conc. of A to half the rate of reaction is decreased by 4 times.

595. Answer (2)

596. Answer (1)

Rate constant depends only on temperature.

598. Answer (3)

Rate = k[ester] [H+ ]

K H2SO 4 K [H ]H2SO 4

KHCl = K[H+] HCl

Since [H+] is obtained from H2SO4 is more than HCl therefore K H2SO4 K HCl .

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599. Answer (3)

Since concentration of increases time to time but not linearly.

600. Answer (1)

1 d [I– ] d [I ]

– 2

2 dt dt

0.004 M min –1

dt 10

d [I2 ]

0.002 M min –1

dt

0.693

Rate = K[H2O2] = 0.05

25

1 0.693

Rate of formation of H2O2 = 0.05 = 6.93 × 10–4 mol min–1

2 25

Rate = k[A]

8.75 × 10–5 = k(0.5)

k = 17.5 × 10–5 s–1 = 1.75 × 10–4 s–1

602. Answer (4)

Since the concentration of H2O2. If (first order reaction) decreases with the time as (at = a0 e –kt ) therefore graph

(4) is correct.

603. Answer (2)

t = 144 = 1.44 × 100

1

= 1.44 t1/2, tav =

1

=

1

N N ·

e = 0 ⇒ 0 e e

t

N N

N0

N=

e

604. Answer (4)

2.303 a 2.303

t= log = 2

k a 0.99a k

2.303 2

t=

k

⎛ 1⎞

t = 2.303 2 · ⎜ ⎟ = 4.604 tav = 4.6

⎝k ⎠

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92 Physical Chemistry Success Achiever (Solutions)

Ea = = 67.5 kJ mol–1

K 2 K a 1.0 10 2 3.0 10 2

606. Answer (3)

Rate = k[A]x [B] y

R = k[A]x [B]y …(i)

R

= k[2A]x [2B]y …(ii)

2

R

= k[2A]x [B]y …(iii)

4

Dividing equation (ii) by (iii)

2 = [2] y

y=1

dividing equation (i) and (iii)

x

⎛ 1⎞

4 = ⎜ ⎟ x = –2

⎝2⎠

607. Answer (2)

CA 2, CB 4

608. Answer (3)

1

t1/ 2 n –1

a

t1/2 × an – 1 = constant

n=2

609. Answer (3)

0.6932

t1/2 =

k

2.303 100 2.303

t = log log1000

k 0 .1 k

6.909

=

k

t = 10 t1/2

ln 2

t1/2 =

k

2.303 0.301

k =

6.93

2.303 ⎛ a ⎞

log ⎜

⎝ a – 0.99a ⎟⎠

Also, t =

k

2.303 ⎛ 1 ⎞

t = 2.303 0.301 6.93 log ⎜⎝ 0.01⎟⎠

= 46.05 minutes

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610. Answer (3)

k2

e(E1 – E 2 ) / RT

k1

E1 – E 2 2

2 .5

RT 2 10 3 400

–

k2

e 2 .5

k1

k 2 e 2 .5 k 1

1 + k2 [NH3 ] k2 NH3

k 1[NH3 ]

rate = constant

k 2 [NH3 ]

This follows the zero order kinetics therefore rate is independent of conc. of NH3 .

initial pressure P0 0 0

0

After reaction P – P 2P P

P0 – P + 2P + P = Pt

2P = Pt – P0

⎛ Pt – P0 ⎞ 2.303 ⎛ P0 ⎞ P0 2.303 ⎛ 2 P0 ⎞

P = ⎜ ⎟ = log ⎜ ⎟ = 2.303 log = log ⎜ ⎟

⎝ 2 ⎠ t ⎜ 0 ⎟ t ⎡ 0 ⎛ P – P0 ⎞⎤ t ⎜ 3 P0 – P ⎟

⎝ P –P ⎠ ⎝ t ⎠

⎢P – ⎜⎜ t ⎟⎥

⎟⎥

⎢⎣ ⎝ 2 ⎠⎦

After the expiry of 40 mins the reactant A decomposes to 75% therefore

Initial pressure 400 0 0

⎛ 3⎞ 3 3

After t 40 mins 400⎜1– ⎟ 400 400

⎝ 4⎠ 4 4

⎛ 3⎞ 3 3 3

= 400 ⎜1– ⎟ 400 400 = 400 400 = 400 + 300 = 700 mm of Hg

⎝ 4⎠ 4 4 4

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94 Physical Chemistry Success Achiever (Solutions)

Let N0 and N be the number of atoms of the radioactive substance present at the start and after 5 minutes

respectively rate of disintegration at the start = N0 = 275 and the rate of disintegration after 5 minute = N

N0 475

= 270 dividing both,

N 270

N0

Or, 1.76

N

2.303 N

We know that log10 0

t N

2.303

log10 1.76 = 0.113 minute–1

5

0.693 0.693

Half life period = 6.1 minute

0.113

615. Answer (4)

7500 0.012 0.35

Weight of radioactive potassium = = 0.0315 g

100 100

0.693 Weight

Activity = t1/2 Atomic weight Avogadro’s number

0.693 0.0315

Activity = 9

6.023 1023 = 4.81 105 dpm

1.3 10 365 24 60 40

616. Answer (2)

% of y = 100 = 100 = –2 = = 16.66%

k1 k 2 –3

2.5 10 1.25 10 –2 1 . 50 10 1 .50

617. Answer (2)

K1

Cyclohexene

Bicyclohexane

K2

Methyl cyclopentene

K1 1.26 104

Percentage of cyclohexene = 100 = 100 = 77%

K1 K 2 1.26 104 3.8 10 5

% of methy cyclopentene = 23%

618. Answer (2)

kf = 4 × 10–4

kb = 2 × 104

kf 4 10 –4

keq = 2 10 – 8

kb 2 10 4

619. Answer (1)

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Success Achiever (Solutions) Physical Chemistry 95

from equation (i) and (ii) we get

Ea (E – 20)

– – a

500 R 400 R

– 4 Ea = – 5 Ea + 100

Ea = 100 kJ mol –1

–Ea /RT

k1 = Ae 1

–Ea /RT

k2 = Ae 2

1

k2

e RT Ea1 – Ea2

k1 =

k Ea – Ea2 10 103

ln 2 = 1 = 4

k1 RT 8.314 300

Rate = k[N2O5 ]

2.4

[N2O5 ] = 0 .8

3

0.693 0.693

K

t1/2 22

If K 1 and K2 are the rate constants of the reactions leading to 222th and Fr223, respectively we have

0.693

K1 + K2 =

22

K1 2

K 2 98

K2 = 0.03087–1y–1

K1 = 0.00063–1y–1

⎡ ⎛ N ⎞⎤

⎢ ln ⎜ N ⎟⎥

⎠ ⎥ ⇒ N0 24 ⇒ N 48 g

t t1

2

.⎢ ⎝ 0

⎣⎢ ln 2 ⎦⎥ N

0

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96 Physical Chemistry Success Achiever (Solutions)

0.693 2.303 4 1

9

log

4.5 10 t 4

t log 3

0.693 2

= 0.1

0.693

624. Answer (4)

Rate = k[A]n

r1 = k[A]n

8r1 = k 4n.[A]n

2n = 3 n = 1.5

625. Answer (3)

X is intermediate.

626. Answer (2)

Ea

K1 K 2 102 3 102

= 67.5 kJ mol–1

627. Answer (4)

x ap

Apply . At high P, 1 + bp bp.

m 1+ bp

Based on definition of peptization.

629. Answer (3)

Size of clay particles is greater than 100 nm.

630. Answer (4)

The size of crystalline particles are very small as compare to diameter of pores of membrane.

631. Answer (2)

Fluorescein and Eosin are examples.

632. Answer (1)

633. Answer (3)

634. Answer (3)

635. Answer (3)

Higher the critical temperature higher the adsorption of gas.

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Success Achiever (Solutions) Physical Chemistry 97

636. Answer (4)

637. Answer (4)

Catalyst decreases activation energy hence rate constant increases.

Ea

–

K Ae RT

A

K Ea

e RT

As Ea decreases, K increases

Hence rate of reaction increases.

638. Answer (4)

639. Answer (2)

Colloids of metal and their sulphides are prepared by special methods not by simple mixing.

640. Answer (3)

Lyophilic colloids not easily coagutated and are highly stable.

641. Answer (3)

Kraft temp. = Temp. above which micell is formed.

642. Answer (2)

643. Answer (3)

Brownian motion is zig-zag motion responsible for stabilisation of colloids and it prevent the colloidal particle

to settle down.

644. Answer (2)

2AuCl3 + 3HCHO + 3H2O

2Au(sol) + 3HCOOH + 6HCl

645. Answer (2)

Cellulose is a polymer having very large particle size.

646. Answer (3)

Fauzasite is natural, Na56[(AlO2)56(SiO2)136] 250 H2O.

647. Answer (2)

Chemisorption is irreversible.

648. Answer (3)

KI KI

AgNO3 AgI [AgI] I—

649. Answer (2)

For adsorption, S < 0, H < 0, G < 0.

Physisorption is an exothermic process with H –20 kJ/mol

More contact with catalyst, faster rate of hydrogenation.

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98 Physical Chemistry Success Achiever (Solutions)

In Bergious process Fe2O3 is used as catalyst.

652. Answer (1)

Brownian movement is independent to nature of solute.

653. Answer (2)

Due to very high difference between refractive indices of dispersed phase and dispersion medium.

For Tyndall effect refractive index of dispersion phase and dispersion medium must differ significantly.

Secondly, size of dispersed phase should not differ much from wavelength used.

Proteins in acidic medium is positively charged and in basic medium, negatively charged. Au and CdS are

negatively charged.

655. Answer (4)

4

Z=

D

656. Answer (1)

Ferric hydroxide is positively charged colloid.

657. Answer (1)

Gold numbers

Potato starch = 25

Gum Arabic = 0.15

Haemoglobin = 0.03

Gelatin = 0.001

658. Answer (4)

Both emulsions show different properties in given tests.

659. Answer (2)

It can describe only physisorption.

660. Answer (2)

It is an example of induced catalysis.

661. Answer (1)

Micelle formation takes place only above a certain temperature, hence, H = +ve

662. Answer (1)

Fact

663. Answer (4)

Fact

664. Answer (1)

Fact

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