XIII (XYZ) PHYSICAL CHEMISTRY REVIEW TEST-6

P A P ER - 2
PART-B
MATCH THE COLUMN [3 × 10 = 30]
There is NEGATIVE marking. 0.5 Marks will be deducted for each wrong match.
INSTRUCTIONS:
Column-I and column-II contains four entries each. Entries of column-I are to be matched with some
entries of column-II. One or more than one entries of column-I may have the matching with the same entries
of column-II and one entry of column-I may have one or more than one matching with entries of column-II.
Q.7 Column I Column II
(A) For the process (P) –ve, +ve
H2O(l) l H2O(s), H & S are
(B) For the endothermic reaction (Q) +ve, –ve
1
2A(s) + O (g) l 2A2O(s)
2 2
S & G are
(C) C(diamond) l C(graphite), favourable (R) +ve, +ve
conditions for formation of diamond are
high pressure and high temperature then
H for formation of diamond and S for
formation of graphite from diamond are
(D) For the given reaction (S) –ve, –ve
N2O4 (g) l 2NO2 (g), Ea(forward)= 57.2 kJ
and Ea(backward) = 3.2 kJ, H & S
for the given reaction
[Ans. (A) S, (B) P, (C) R, (D) R ]
 PART-C

SUBJECTIVE:
There is NO NEGATIVE marking.

Q.11 What would be the pOH of a 0.02 M solution calcium propanoate, Ca(C3H5O2)2
[Ka of propanoic acid (HC3H5O2 = 10–5)] [Use log2 = 0.3 ] [4]
[Ans. 5.2]
[Sol. 2+
Ca(C3H5O2)2 (aq) Ca (aq) + 2CH3CH2COO (aq) –
___ 0.02 2× 0.02
CH3CH2COO– (aq) + H2O(l) l CH3CH2COOH (aq)+ OH– (aq)
C(1–) C C

Q  is neglible w.r.t 1
1
pH = [ pK w + pK a + log [CH3CH2COO– (aq)] ]
2
1
pH = [14 + 5 + log (0.04)]
2
1
pH = [19 – 1.4]  8.8
2
pOH = 5.2 ]

Q.12 H3A is a weak triprotic acid ( K a1 = 10–5 , K a 2 =10–9, K a 3 =10–13 ).

[ A 3 ]
Calculate the value of pX of 0.1 M H3A (aq) solution where pX = – log X & X = . [5]
[ HA 2 ]
[Ans. 10]
[Sol.  is neglible w.r.t 1
[H+] mainly from first step
[H+] = Ka  C  10 5  0.1 = 10–3
1

[ H  ][ A 3 ] 10 3[ A 3 ]
 K a3 =  10–13 =
[ HA 2 ] [ HA 2 ]

[ A 3 ]
X= = 10–10
[ HA 2 ]
 pX = 10 ]
Q.13 At a certain temperature the equilibrium constant Kc is 0.25 for the reaction
A2(g) + B2(g) l C2(g) + D2(g)
If we take 1 mole of each of the four gases in a 10 litre container, what would be equilibrium concentration
of A2(g). [5]
[Ans. 0.13]
1 1
[Sol. Q= 1
1 1
Q Q > Kc so reaction will proceed in backward direction
A2 (g) + B2(g) l C2(g) + D2 (g)
1 .0  x 1 .0  x 1 .0  x 1 .0  x
concentration at equilibrium
10 10 10 10
2
1 x 
 
 10 
0.25 = 2
1 x 
 
 10 

1 x
0.5 =  0.5 + 0.5 x = 1–x
1 x
1.5 x = 0.5
x = 0.333
1 x 1.333
[A2(g) ] =   0.13 ]
10 10

Q.14 Equilibrium constant of T2O (Tritium is an isotope of H) differ from those of H2O at 298 K. Let at
298 K pure T2O has pT (like pH) is 7.60. Find out the pT of a solution prepared by adding 10 ml of
0.2 M TCl to 15 ml of 0.20 M NaOT. (Given log2 = 0.30) [5]
[Sol. TCl + NaOT  NaCl + T2O
M.Moles 2 3
Excess NaOT = 1
1
 [OT–] =  0.04  4×10–2
25
pOT = 2 – log 4  1.4
pT = 15.2 – 1.4  13.80 Ans.]
Q.15 A flask containing 0.5 atm of A2(g) contains some solid AB which undergoes dissociation according to
2AB (s) l A2(g) + B2(g). Kp = 0.06 atm2
Calculate the total pressure (in atm) at equilibrium. [5]
[Ans. 0.70 atm]
[Sol. 2AB(s) l A2(g) + B2(g)
0.5 + x x
Kp = PA 2 .PB2  0.06 = (0.5 + x) x
x2 + 0.5 x – 0.06

 0.5  (0.5) 2  4(0.06)  0 .5  0 .7

x=   0.1
2 2

Ptotal = PA 2  PB2  0.6 + 0.1

 0.70 atm ]

Q.16 0.50 mol of an ideal gas initially at a temperature of 300 K and at a pressure of 2 atm is expanded
isothermally in three steps. In each step, the pressure is dropped suddenly and held constant until equilibrium
is reestablished. The pressure at each of the three stages of expansion are 1.6, 1.2 and 1 atm.
Calculate the work done ( |w| ) (in atm-litre) in this process. [Use R = 0.08 atm-litre/mol.K] [6]
[Ans. 7.4 atm litre]
[Sol. Since pressure is constant is each step
nRT 0.5  0.08  300
V1 = P   6 litre
1 2
0.5  0.08  300 0.5  0.08  300
V2 = P2   7.5 litre
1 .6
0.5  0.08  300 12
V3 = P3   10 litre
1.2
12 12
V4 = P   12 litre
4 1.0
Wtotal = w1 + w2 + w3
here w1 = – P2 (V2–V1)  – 1.6 × (1.5)
 –2.4 litre
w2 = – P3 (V3 – V2)  – 1.2 × (2.5)  – 3 litre atm
w3  –P4 (V4–V3)  –1 × (2)  – 2 litre atm
 wtotal = w1 + w2 + w3  –2.4 – 3.0 – 2.0
wtotal  – 7.4 atm litre
| wtotal|  7.4 atm litre ]
Q.17 Calculate the heat produced ( |q| ) in kJ when 280 gm of CaO is completely converted to CaCO 3 by
reaction with CO2 at 27°C in a container of fixed volume.
Given at 27°C : H of (CaCO3 ; s) = – 1207 kJ/mol

H of (CaO ; s) = –635 kJ/mol

fH°(CO2 ; g) = – 394 kJ/mol [Use R = 8.3 K–1mol–1] [6]
[Ans. 877.55 kJ]
[Sol. CaO (s) + CO2(g)  CaCO3(s)
rH° = H of (CaCO3) – H of (CaO) – H of (CO2)
= – 1207 – (–635) – (–394)
rH° = – 178 kJ/mol
 rE = H – ngRT
(1)  8.3  300
rE = – 178 –
1000
280
nCaO =  5.0
56
 qv = E  n. rE = 5 × (–175.51)
 877.55 kJ Ans.]

Q.18 Thermal decomposition of H2O2 follows first order kinetics. Three flask, each containing 20 mL of
2.8 V H2O2 were taken for kinetic study. Into the first flask, 20 mL of a KI solution was added after
1.0 hour, heated gently to expel-off liberated iodine and finally titrated against 0.5 M chromic acid
solution, 10 mL of chromic acid was required to reach end point. After three hour from beginning,
20 mL of KI solution of same strength was added to the second flask, heated gently and finally titrated
against chromic acid solution of same strength. After a very long time, similar experiment was repeated
with the third flask and required 40 mL of 0.5 N chromic acid solution. What was the volume of chromic
acid required for second experiment? Given ln2= 0.693 [8]
[Sol. Normality of chromic acid = 0.5 × 3 = 1.5 N
Normality of KI = 1N (From third experiment)
Ist flask: meq of KI left = 10 × 1.5 = 15
meq of KI = H2O2 = 20 – 15 = 5
2 .8 10
Initial meq of H2O2 = 20 × = 10  k = ln ; k = 0.693
5 .6 5
IInd flask: Let x meq of H2O2 left undecomposed.
10 10
3k = ln  ln(2)3 = ln ; x = 1.25 = meq of KI consumed
x x
meq of KI reduced with chromic acid = 20–1.25 = 18.75
18.75 = 1.5 × V
V = 12.50 mL
Vol. of chromic acid required = 12.50 mL ]