Chemistry Pre-Medical

4
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HINTS AND SOLUTIONS

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Chemistry
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HINTS AND SOLUTIONS

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Pre-Medical
Pre-Medical : Chemistry
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194 Pre-Medical : Chemistry ALLEN
SOLID STATE

EXERCISE-I 20. Let, Ni+2 in the crystal Ni0.98O be x.

\ Ni+3 in the crystal Ni0.98 will be (0.98 – x)
16. a = 3.04 Å = 3.04 × 10–8 cm
Ni +x2 Ni (0.98
+3
-x ) O
V = a3 = (3.04 × 10–8)3 = 2.81 × 10–23 cm3
By law of conservation of charge
65. d = 5.85 g/cm3 2x + 3 × (0.98 – x) – 2 = 0
a = ? x = 0.94

Z×m 0.94
5.85 = ; Z = 4 (formula units) So, the fraction of Ni+2 ions in the crystal =
N × a3 0.98

; 0.96
4× 58.5
5.85 =
6×1023 × a 3
EXERCISE-III
4× 58.5
a3 = 8. a = 436.6 pm = 4.366 × 10–8 cm
5.85 × 6×1023
M = 133 + 80 = 213 ; Z = 1 (formula unit)
So, a = 4.06 × 10–8 cm
1×213
EXERCISE-II d = 23
6×10 × (4.36)3 ×10–24
18. BCC FCC
= 4.25 g/cm3
4r = 3a 4r = 2a
21
4r 4r
a= a=
0-

3 2
02

2´M
:2

3
ZBCC ´ M æ 4r ö
d BCC NA ç ÷
NA a3 è 3ø 3 3
n

= = =
d FCC ZFCC ´ M 4´M
io

4 2
ss

NA a3 æ 4r ö
3

NA ´ ç ÷
Se

è 2ø
19. Anion A in HCP
No of ions of A in Unit cell = 6
No of Octahedral voids = 6
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75% is occupied by cations C

75
No of cations C = 6 ´
100
3
= 6´
4
9
=
2
C9/2A6
C9A12
Simple ratio C3A4

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 ALLEN Pre-Medical : Chemistry 195

CHEMICAL KINETICS

EXERCISE-I [ A] [ A ]
from (1) = Keq
[A ]
2
- d[N2 O5 ]
5. Given = K1[N2O5],
dt [A]2 = Keq[A2]
or [A] = Keq
1/2
[A2]½
d [NO2 ] d[O2 ]
= K2[N2O5], = K3[N2O5] Put this value in eq(4)
dt dt
r = k' Keq
1/2
[A2]1/2[B2]
Given reaction :
r = k [A2]1/2 [B2]
1
N2O5 ® 2NO2 + O
2 2 1 3
\ order + 1 =
2 2
Rate of Reaction
35. In rate expression r=k[NO2]2, CO is not present
- d[N2 O5 ] 1 d[NO2 ] 1 d[O2 ] it means CO will not present in slowest step of the
= =
dt 2 dt 1 2 dt mechanism.

Put given values

40. Order Rate of Rx.
1
K1[N2O5] = K [N O ] = 2K3[N2O5] 1 r1 = K[A]1
2 2 2 5
21
2 r2 = K[A]2
or 2K1 = K2 = 4K3
3 r3 = K[A]3
0-

20. A + B ® Product
02

K is numerically same & [A] > 1M

Order w.r.t. A and B is one \ r1 < r2 < r3
:2

\ rate law r = K[A][B] 60. Flask I

n
io

put given data in rate law 1 Lit of 1 M solution of A

ss

0.1 = K[0.2] [0.05] .....(1) ¯t

½
Se

0.4 = K[x] [0.05] .......(2) 0.5 M t = 8 hrs.

0.8 = K[0.4] [y] ........(3) ¯ t½

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0.25 M
eq(2)/eq(1) gives value of x &
\ 2t1/2 = 8
eq(3)/eq(1) gives value of y
t1/2 = 4
33. A2 + B2 ® 2AB
Flask II
ˆˆ†
A2 ‡ˆˆ A + A (fast) ......(1) 100 ml of 0.6 M solution of A

A + B2 ® AB + B (Slow) ....(2) ¯ t1/2 = ?

A + B ® AB (fast) ........(3) 0.3 M

t1/2 = 4 hrs.
Rate law will be written for eq(2)
[Q for Ist order reaction t1/2 does not depends on
r = k'[A][B2] .......(4)
concentration]
A ® Intermediate

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196 Pre-Medical : Chemistry ALLEN
72. For t1/4, x = a/4 EXERCISE-II
2.303 a 26. (t1/2)1st order = Independent of Concentration
t1 = log
4 K a-a
4
1
(t1/2)2nd order µ [ ]
A0
2.303 4 2.303
=
K
log =
3 K
[ log 4 - log 3]
[ A ]0
27. ( t1 / 2 )zero =
2K
2.303
=
K
[0.6020 - 0.4771]
\ If [A]0 = doubled, t1/2 = doubled
28. For first order reaction
2.303 0.287
= ´ 0.1249 =
K K 1 é Ao ù For 99% completion,
k= ln ê ú
t ë At û [A]o=100, [A]t=1
73. [A]t = [A]0 – Kt
[A]0 = [A]t + Kt 1 é 100 ù
k= ln
t êë 1 úû
30
= 0.05 mol dm–3 + 0.2 mol dm–3 h–1 × h
60
2.303 log10 100
k=
t
- Ea
89. K = Ae RT

2.303 ´ 2
If T®¥ k=
21
t
0-

Then K = AeO
4.606
02

k=
So K= A t
:2

and log K = log A

4.606
n

t=
io

102. For 10°C rise of temp. 25°C to 35°C rate of given k

ss

reaction is double.
29. N2(g) + 3H2(g) ƒ 2NH3(g)
Se

K2
\ Temp. coefficient of reaction K = 2 d éN ù 1 d ëéH2 ûù 1 d ëéNH3 ûù
1 - ë 2û = - =+
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K2 Ea(T2 - T1 )
log = 0.693
K1 2.303R T1 T2 30. For a first order reaction; t1/2 =
K

Ea (308 - 298) 0.693

log2 = t1/2 = = 301 s
2.303R ´ 298 ´ 308 2.303 ´ 10-3

The time required for 40 g of reactant to reduce

(2.303log2) R ´ 298 ´ 308
Ea = to 10g
10
t75% = 2 × t1/2
t75% = 2 × 301 = 602 s

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 ALLEN Pre-Medical : Chemistry 197
9. For a first order reaction
æK ö Ea æ 1 1 ö
31. log ç 2 ÷ = ç - ÷ r = K [A]
è K1 ø 2.303R è T1 T2 ø
r 1.5 ´ 10-2
Ea = 0 K= = = 3 × 10–2 min–1
éëA ùû 0.5
æK ö
log ç 2 ÷ = 0
è K1 ø 0.693 0.693
t 12 = = = 23.1 min.
K 3 ´ 10-2

K2 21. K1 = K2
= 10° = 1
K1
1016 e -2000 / T = 1015 e -1000 / T
Þ K2 = K1 10 = e1000/T
6 –1
K2 = 1.6 ×10 s at 400K
10 1000 / T
loge = log ee

EXERCISE-III 1000
log e 10 =
T
5. (CH3)2CHN=NCH(CH3)2(g) ® N2(g)+C8H14(g)
Initially P0 O O 1000
T= K
at time t (P0 – P') P' P' 2.303
\ Total pressure of the mixture
=> (P0 – P') + P' + P' = Pt
21

P' = Pt – P0
0-
02

2.303 a 2.303 P0
K= log or log P - P '
:2

t a - x t 0
n
io

2.303 P0
K = log P - ( P - P )
ss

t 0 t 0
Se
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198 Pre-Medical : Chemistry ALLEN
SOLUTION

EXERCISE-I 43. A® solvent B® solute

15. molality of solution = X = ? PA° = 10 torr w = 1gm, W = 20gm
(solvent)
Let moles of solute = n
Ps = 9 torr M = 200 a.m.u., m=?
&moles of solvent = N
P ° - PS n wM
n = =
Xsolute = = 0.2 Ps N mW
n+N
46. Given P°A = 70 torr,
n 1
\ = PS = 84 torr
N 4
XB = 0.2,

moles of solute ( n ) XA = 1– XB = 1–0.2 = 0.8

molality = wt of solvent C H
( 6 6 ) ( kg ) P°B = ?

PS = XA P°A + XB P°B
1 mol
= ´ 1000 47. (Tb)solution = 100.15° C
( ´ 78 gm )
4
\ DTb = 100.15 – 100 = 0.15

0.02 DTb = molality (m) × Kb ...... (1)

21
16. ppm concentration = ×106 = 40ppm
500
0-

moles
molality (m) =
02

wt. of solvent (w) (kg)

w 5
18. = =1.5
:2

M =
mV(L) 34 ×0.1
by diluting above solu. by equal vol. of water wt
n

of solvent becomes double

io

29. Given C6H6 (A) C6H5CH3 (B)

ss

at 88°C PA0 = 900torr PB0 = 360torr moles m

\ molality (m1) = =
Se

2W 2
XA =? XB = (1 – XA)

at 88° C PM = 760torr \ DTf = molality (m1) × Kf ..... (2)

eq. (2)/(1)
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(mixture boils at 88° C and at B.P., vapour pres-

sure equals to atmospheric pressure)
DTf m1 ´ K f m / 2 ´ Kf
40. PS = Xsolvent P° DTb = Þ m ´ Kb
m ´ Kb

Ps 2 2 49. Given, K = 5.2 K mol–1 100 gm H2O

= =
P° 1 + 2 3
100 ´ 10
or K = 5.2 K mol–1 gm H2O
10
N
42. PS = P0
n+N
5.2
K = K mol -1 kg
given Xsolute = 0.1 10
\ Xsolvent = 1 – 0.1 = 0.9
or Kb = 0.52 K kg mol–1
DTb = molality × Kb

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 ALLEN Pre-Medical : Chemistry 199
51. F. pt of pure C6H6 = 5.45° C 107. When HgI2 is added to the aq. solu. of KI. following
reaction will take place
F. pt of solu. of tetrachloroethane in
2 KI (aq) + HgI2 ¾¾® K2HgI4
C6H6 = 3.55° C
2 mol 1 mol
\ Depression in F. pt DTf = (5.45–3.55)
(4 mol ions) 2K+ + HgI42–
& DTf = molality × Kf
(3 mol ions)
68. wt of glucose = 3 gm; wt of water=60 gm
Q No. of particles decreases in solu.
\ wt of solution = 3 + 60 = 63 gm; \ C.P. ¯ & F. pt ­
density of solution = 1 gm/ml

\ vol of solution = 63 ml
EXERCISE-II
p = CRT
25. If, intermolecular attractive forces between A – A
æ 3 ´ 1000 ö and B – B are stronger than those A – B then
p= ç ÷ ´ 0.0821 ´ (15 + 273 ) it show positive deviation from ideal behaviour.
è 180 ´ 63 ø

87. p = i (CRT) 25. X H2 O = 0.02

pNa2 SO4 = p glu cos e \ Xgas = 0.98

Ptotal = 1.2 atm
i(0.004RT) = 1(0.010RT)
partial pressure of dry-air = PT × mole fraction of dry-air
21
0.01 Partial pressure of dry-air = 1.2 atm × 0.98
i = = 2.5
0.004
0-

= 1.176 atm.
02

27. 2 M solution of NaOH menas 2 mole NaOH is

a=
( i - 1) present in 1 L solution;
:2

( n - 1) density = 1.28 g/ml

n

mass of solution = volume of solution × density

io

æwö
ss

88. 5.8% ç ÷ NaCl solution means = 1200 × 1.28

èvø
Se

= 1280 g
100 ml solution contains 5.8 gm NaCl mass of solvent = mass of solution – mass of solute
= 1280 – 80
5.8 ´ 1000
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molarity of solution = = 1M NaCl

58 ´ 100 = 1200 g

NaCl ionised in solution 1 mol. gives 2 mol ions. 2 20 10 5

molality = ´ 1000 = = = = 1.67 m
1200 12 6 3
\ It's O.P. is corrosponding to 2 M solution.
96. p = i (CRT)
for KNO3 i = 2 EXERCISE-III
(strong electrolytes µ =1) 2. 10% strength of glucose solution means 10 gm of
for CH3COOH i < 2 glucose is present in 100 ml solution.
(weak electrolyte µ << 1) \ 2 gm mole (2 × 180 gm) of glucose is
CH3COOH
present in 100 ´ 360 ml solution= 3.6 litre
\ P1 > P2 10

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200 Pre-Medical : Chemistry ALLEN
12. mole fraction in solution XA = 0.4 13. C6H6 (A) C6H5CH3 (B)

\ XB = 1–XA = (1–0.4) = 0.6 PA0 = 160 torr PB0 = 60 torr

V.P. of mixture moles of A = moles of B

PM = XAP°A +XBP°B (nA) (nB)

PM = 0.4 × 100 + 0.6 × 200 =160mm

nA 1 1
XA = n + n = XB =
Let mole fraction of vapour A above solution be A B 2 2
= yA, Partial V.P. of A
mole fraction in vapour state YB = ?
XA P°A = YA PM
YBPM = XBPB0
(acc. to Raoult's law) (acc. to dalton's law)

0
X B PB
X A PA0 PM = XAPA0=XBPB0 YB =
\ yA = PM
PM

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02
:2
n
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ss
Se

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 ALLEN Pre-Medical : Chemistry 201

ELECTROCHEMISTRY

EXERCISE-I 0.0591
E = Eo - log éë Zn2+ ùû
2
k ×1000
9. L eq =
N When [Zn2+]1 = 1 M
When [Zn2+]2 = 0.1 M
1 G* ×1000 E1 = E°
L eq = ×
R N
0.0591
E2 = Eo - log éë0.1ùû = (E° + 0.03)
2
Lceq
14. a=
L¥eq \ Eocell = 0.5400 V

\ potential of Zn/Zn2+ is increased by 0.03V

k ×1000
L ceq =a× L ¥eq = 0.9 × 425 =
N 1
50. H+ + e– ¾¾¾® H
2 2
3.825 ×1000
\ Normality = = 10 N
0.9× 425
0.0591 1
E = Eo - log (E° = 0)
1 éëH + ùû
1000
17. Lm = k ´
M
0.0591
E=+ log éë H+ ùû
21
For saturated solution 1
0-

1000 When pH = 0 ; [H+] = 1M

M=S= k´ L
02

m E1 = 0
:2

For BaSO4 Ksp = S2 When pH = 7 ; [H+] = 10–7 M

n

46. For the reaction E2 = +0.0591 log 10–7

io

Cl2(g) + 2Br–(aq) ¾¾¾® 2Cl–(aq) + Br2 E2 = –7 × 0.0591 = –0.4137 V

ss
Se

2.303 RT
éCl - ùû [ Br2 ]
2 53. E ocell = log Kc
0.0591 nF
E cell = Eocell - log ë 2
2 PCl2 éë Br - ùû
0.0591
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E ocell = log1012
2
[0.01] [ 0.01]
2
0.0591
E cell = 0.29 - log = 6 × 0.0591 = 0.354 V
[0.01]
2
2
54. Given :
49. Let initial concentration of [Zn2+], be 1 M (i) OCl– + 2H+ + 2e– ¾® Cl– + H2O
after 10 times dilution concentration of ; E1o = 0.94V ; DG1o = -2FE1o

1
[Zn2+] = = 0.1 1
10 (ii) Cl– ¾® Cl + e– ; E2o = -1.36V
2 2
for the potential of Zn/Zn2+
Zn ¾¾¾® Zn2+ + 2e– ; DGo2 = -1FEo2

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202 Pre-Medical : Chemistry ALLEN
61. Given :
1
(iii) OCl– + 2H+ + e– ¾® Cl + H2O ; E3o = ?
2 2 (i) Fe+2 + 2e– ¾® Fe ; E1o = –0.441V

; DGo3 = -1FEo3 ; DG1o = -2FE1o

Equation (i) + equation (ii) will gives equation (iii)

(ii) Fe+3 + e– ¾® Fe+2 ; Eo2 = 0.771V
-2FE1o - FE2o = -1FE3o
; DG2o = -1FEo2

\ Eo3 = 2E1o + Eo2

(iii) Fe + 2Fe+3 ¾® 3Fe+2 ; E3o = ? ;
56. Concentration of [H+] in negative electrode (Anode)
C1 = 10–8 M ; DGo3 = -2FE 3o

Concentration of [H+] in positive electrode (Cathode) 2×Equation (ii) – equation (i) will give equation (iii)
C2 = 0.001 M
2DGo2 - DG1o = DGo3
1
At anode : H (g) ¾¾¾® H+(C1) + e–
2 2 2( -FEo2 ) - (–2FE1o ) = -2FEo3

At cathode : H+(C2) + e– ¾¾®

1
H (g)
\ E o2 – E1o = Eo3
2 2
21
EXERCISE-II
Cell reaction H+(C2) ¾¾® H+(C1)
0-

Here n = 1 27. Calculate E°cell corresponding to each compound

02

under going disproportionation reaction. The

:2

0.0591 éC1 ù
Ecell = Eocell - log ë û reaction for which E°cell comes out +ve is
1 ëéC2 ûù spontaneous.
n
io
ss

0.0591 10 -8 HBrO ¾® Br2 E° = 1.595, SRP (cathode)

E cell = 0 - log -3
Se

1 10
HBrO ¾® BrO3– E° = –1.5V, SOP (Anode)
60. For the cell reaction
Zn(s) + Ni2+(a = 0.1) ¾® Zn2+ (a = 1.0) + Ni(s) 2HBrO ¾® Br2 + BrO3–
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According to Nernst's equation

E°cell = SRP (cathode) – SRP (Anode)
0.0591 éZn2 + ù
Ecell = Eocell - log ë 2 + û = 1.595 – 1.5
n éë Ni ùû

= 0.095 V
0.0591 é1ù
0.5105 = Eocell - log ë û
2 ëé0.1ûù E°cell > 0 Þ DG° < 0 [spontaneous]

\ Eocell = 0.5400 V

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 ALLEN Pre-Medical : Chemistry 203

2.303 RT (2) (3)

28. Ecell = Eocell – log10 Q eq. (1) = eq. (4) + eq. – eq.
nF 2 2

at equlibrium Ecell = 0, Q = Keq.

x y
\ l°CH3 COOH = z + -
0.0591 2 2
0 = E ocell - log10 K eq.
1
(x – y)
Eocell = +0.0591 log10 Keq. l° CH3COOH = + z(S × cm 2 mol -1 )
2
0.59 = + 0.0591 log10 Keq.
+10 = log10 Keq. 1
31. Reducing power of metal µ
SRP
Keq. = 10+10
29. 2Fe3+ (aq) + 2I–(aq) ® 2Fe2+(aq) + I2(aq) K > Al > Cr > Ag.
n =2

DGo = –nFE° EXERCISE-III

= – 2 × 96500 × (0.24) 4. For first solution (0.2 M)
= – 46320 J
1
= – 46.32 kJ mol–1 k= × G* = 1.4
R
30. CH3COOH ® CH3COO– + H+ ...(1)
\ cell constant (G*) = 1.4 × 50 = 70 m–1
H2SO4 ® 2H+ + SO4–2 ...(2)
For second solution (0.5 M)
21
K2SO4 ® 2K+ + SO4–2 ...(3)
CH3COOK ® CH3COO– + K+ k ×1000 G* ×1000
0-

...(4)
Lm = =
M R×M
02

According to Kohlrausch's law-

:2

l°CH3 COOH = l°CH + l°H+

3 COO
–
70×10–2 ×1000
\ Lm = = 5 S cm2 mol–1
n

280× 0.5
io
ss

= 5 × 10–4 S m2 mol–1
Se
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204 Pre-Medical : Chemistry ALLEN
SURFACE CHEMISTRY

EXERCISE-I EXERCISE-II
11. According to Hardy Schulze rule : The coagulating
x 1
8. log = logk + logP power of an ion depend on both magnitude and sign
m n
of the charge of the ion.
y = C + MX
12. In negatively charged colloid [AgI] I – , I – is
1 preferentially adsorbed.
slope (M) = = tan45º = 1
n AgNO3 + KI ® AgI + KNO3
1 When KI is in excess, I– will be adsorbed on the
= 1 surface of AgI and [AgI] I– is formed
n
Intercept (logK) = 0.30 x
K = Antilog (0.30) = 2 13. Freundlich adsorption isotherm is = K(P)1/ n
m
x In it, value of 1/n lies in between 0 to 1. So, correct
so = 2× (0.2)1 = 0.4
M
33. AgNO3 + KI ¾® AgI + KNO3 x
option is = KP 0.3
For (negatively charged) colloidal solution millimoles m
of KI should be more than AgNO3

47. Lower will be gold number higher will be the

protective power of protective colloid.
21
48. Since gold sol becomes 10 times so amount of
haemoglobin also becomes 10 times means
0-

= 10 × 0.03
02
:2
n
io
ss
Se

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ALLEN

Se
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IMPORTANT NOTES

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Pre-Medical : Chemistry
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