INDIAN INSTITUTE OF TECHNOLOGY KHARAGPUR

DEPARTMENT OF CHEMISTRY

Autumn Mid-semester Examination Session: 2020-2021

Subject No. CY11003 Time: 60 min Full Marks: 30
----------------------------------------------------------------------------------------------------------------
INSTRUCTIONS
1. All symbols used in this question paper have usual meaning
2. Report numerical answers rounded off two places after decimal (e.g. 4.214 = 4.21,
4.215 = 4.22, 4.245 = 4.25)
3. Use R = 8.314 JK–1 mol‒1; F = 96487 C mol–1; 1 atm = 101325 Pa; 1 bar = 105 Nm-2
__________________________________________________________________________

(1) For the reversible reaction X ⇋ Y at 298 K, ΔrHo = – 54.07 kJ mol–1 and ΔrSo = 10.0 JK–1
mol–1. If Keq is the thermodynamic equilibrium constant for the reaction, then the value of
log10Keq is ___________.

(A) 40 (B) 20 (C) 10 (D) 5

(2) For an electrochemical cell,M | M+| X– | X,EoM+/M = 0.44 V and EoX/X– = 0.33 V. The
correct statement about the cell is

(A) M + X  M+ + X– is the spontaneous reaction

(B) M+ + X– M + X is the spontaneous reaction
(C) ECell = 0.77 V
(D) ECell = – 0.77 V

(3) The standard EMF of a cell with one electron change is 0.59 V at 298 K. The equilibrium
constant of the corresponding reaction is

(A) 1.0 × 1010 (B) 1.0 × 105 (C) 1.0 × 1020 (D) 1.0 × 1030

(4) Identify the INCORRECT statement about the phase diagram of a substance X as
shown in the figure.

(A) Density of X increases on melting at

its normal melting point.
(B) 2 𝜇𝑠𝑜𝑙𝑖𝑑 = 𝜇𝑙𝑖𝑞𝑢𝑖𝑑 + 𝜇𝑔𝑎𝑠 at the
triple point.
(C) Sublimation of solid X is observed
on applying 100 kPa pressure at 150
K.
(D) X in liquid phase has the lowest
chemical potential at 250 K and
11.3 MPa compared to solid/gas
phase.
(5) Match the curves 1,2, and 3 (left panel) showing three different variations of Gibbs free
energy as a function of pressure to the processes indicated in the phase diagram (right panel).

(A) 1: CD; 2: AB; 3: XY

(B) 1: XY; 2: LW; 3: CD
(C) 1: AB; 2: NM; 3: LW
(D) 1: LW; 2:NM; 3: AB

(6) The following steps were used while deriving an expression for the Gibbs free energy of
mixing for 𝑛𝐴 and 𝑛𝐵 moles of the ideal gases A and B respectively at a given temperature, 𝑇
and pressure, 𝑝.

Identify the correct statement on the derivation steps shown above.

(A) The gases A and B are kept separately each at a temperature 𝑇 and pressure 𝑝0 in
Steps 1 and 2.
(B) A and B are present in their respective pure phases in Steps 1 and 2.
(C) Dalton’s law of partial pressure has been used in Steps 1, 3 and 4.
(D) The Gibbs free energy of mixing is ∆𝑚𝑖𝑥 𝐺 = 𝑥𝐴 𝑅𝑇 ln 𝑥𝐴 + 𝑥𝐵 𝑅𝑇 ln 𝑥𝐵
(7) Autoclaves that are used to sterilize surgical tools require a temperature of 120 oC to kill
bacteria. At the normal boiling point (100 oC ) of water, ΔvapH is 40656 J mol–1. If water is
used for this purpose, the pressure (in atm) at which the autoclave must operate is _____.

(A) 19.5 (B) 195 (C) 1.95 (D) 95

(8) Between 0 and 90°C, the potential of the cell:

Pt (s) H 2 ( g , f  1atm) HCl (aq, m  0.100 ) AgCl (s) Ag ( s)

is described by the equation:

E (V)=0.3551—3.422x10‒5t-3.2347x10‒6t2+6.314x10‒9t3
where t is the temperature in degree Celsius. The value of ∆G (in kJ mol–1) for the cell
reaction at 50 oC may have any value in the range of _______________.

(A) ‒33.3 to ‒33.4 (B) –35.5 to –36.1 (C) –43.1 to ‒44.6 (D) –73.0 to ‒77.1

(9) For a gas that obeys the equation of state Vm = RT/P + B(T), (∂H/∂P)T is equal to ______

 dB(T ) 
[ A}B (T )  T  
 dT 
 dB(T ) 
[ B ]B (T )  T  
 dT 
 dB(T ) 
[C ]B (T )  T 2  
 dT 
 dB(T ) 
[ D]T  
 dT 

(10) To show that the melting point of a solid varies linearly with pressure, the following
steps were written down. Which of the steps shown is INCORRECT?

Step Derivation
1 𝑇2
𝑑𝑝 ∆𝐻𝑓𝑢𝑠 𝑑𝑇
= ∫
𝑑𝑇 ∆𝑉𝑓𝑢𝑠 𝑇
𝑇1
2 ∆𝐻𝑓𝑢𝑠 𝑇2
∆𝑝 = ln ( )
∆𝑉𝑓𝑢𝑠 𝑇1
3 𝑇 ∆𝑇
For small variations in temperature, ln (𝑇2 ) ≈
1 𝑇1
4 ∆𝐻𝑓𝑢𝑠 ∆𝑇
∆𝑝 =
∆𝑉𝑓𝑢𝑠 𝑇1
5 ∆𝑝 ∝ ∆𝑇
 (A) 1 and 2
(B) 2 and 3
(C) 4
(D) 1

(11) On isothermal compression from 1 bar to 5 bar at 300 K, the change in chemical
potential of 1.0 mole of a substance, X in its gas phase is 10 times of that in its liquid phase.
Assuming X behaves ideally in the gas phase, the molar volume of liquid X (in 𝒎3 ) is found
to be 1.0 × 10−𝑛 . The value of 𝑛 is __________.

(12) The densities of water and ice at –5 oC are 0.999 g cm–3 and 0.917 g cm–3, respectively.
The ΔCp,m and ΔGm for the freezing of super cooled water at –5 oC are 37.3 J K–1mol–1 and
109.84 J mol–1, respectively. The maximum reversible work (wrev,max) (in J mol–1) that can be
obtained from freezing of super cooled water at atmospheric pressure is ___________.

(13) The ideal gas reaction 𝐶𝑂(𝑔) + 𝐻2 𝑂(𝑔) ⇌ 𝐶𝑂2 (𝑔) + 𝐻2 (𝑔) is carried out in a closed
vessel immersed in a temperature and pressure reservoir. N2 gas at 𝑇1 and 𝑝1 is passed
through a throttle into the reservoir as shown in the figure below.

The partial pressures (in MPa) of the reaction mixture at 𝑇1 = 1000 𝐾 are: 0.5 (𝐶𝑂), 0.4
(𝐻2 𝑂), 0.4 (𝐶𝑂2), 0.2 (𝐻2 ). Under the given conditions, the equilibrium constant, 𝐾𝑒𝑞 = 1.6
and 𝜇𝐽𝑇 (𝑁2 ) = −0.2 × 10−5 𝐾 𝑃𝑎−1 .

(a) The temperature (in K) at which the reaction takes place is__________.

(b) The pressure (in MPa) at which the reaction takes place is __________.

(c) If 1 stands for forward reaction and 2 stands for backward reaction, the favoured
direction of the reaction is________.

∆𝑟 𝐺
(d) The reaction Gibbs energy, 𝑖𝑠 𝑒𝑞𝑢𝑎𝑙 𝑡𝑜 _______
𝑅𝑇
(14) Replace the unknown quantities (𝑿𝟏 , 𝑿𝟐 , 𝑿𝟑 , 𝑿𝟒 ) in the following equations by the
serial numbers of measurable quantities shown in Table I.

𝑿𝟏 = _____________ (1/2/3/4)

𝜕𝑈
(𝑖) 𝐶𝑝 = ( 𝜕𝑇 ) + 𝑝 𝑉 𝑿𝟏
𝑝 𝑿𝟐 = _____________ (1/2/3/4)
𝜕𝑈
(𝑖𝑖) ( 𝜕𝑇 ) = 𝑿𝟐 + 𝑿𝟏 𝑿𝟑 𝑉
𝑝 𝑿𝟑 = _____________ (1/2/3/4)
𝜕𝑈 𝑿𝟏 𝑇
(𝑖𝑖𝑖) ( ) = −𝑝
𝜕𝑉 𝑇 𝑿𝟒
𝑿𝟒 = _____________ (1/2/3/4)

Table I

Sl No 1 2 3 4
Measurable Isothermal Specific heat at Isobaric Internal pressure,
quantity compressibility, constant volume, expansion 𝜋𝑇
𝜅 𝐶𝑣 coefficient, 𝛼

(15). Assuming Cp,m (75 J K–1mol–1) of water is constant the change in entropy (J K–1) when
54g of hot water at 67 oC is poured into 108 g of cold water at 7 oC in an insulated container
is ___________.
Answer Key:

Question No. Answer Marks

1 C 1
2 B 1
3 A 1
4 C 1
5 D 1
6 B 1
7 C 1
8 A 1

9 B 1
10 D 1
11 3 4
12 109 to 110 4
13 (a) 1005 1x4 = 4
(b) 1.5
(c) 1.0
(d) ‒1.38 to
‒1.39
14 3,2,4,1 4
15 2.8 to 2.9 4
 Q. 1. ΔG0 = ΔH0 – TΔS0 = -54.07 – 298 x 0.01 = -57.05 kJ

RT ln Keq = - ΔG0

2.303 RT log10Keq = - ΔG0

log10Keq = - ΔG0 / 2.303RT

57.05
= = 10
2.303 𝑋 0.008314 𝑋 298

Q.2. As EoM+/M > EoX/X–,

Spontaneous reactions: M+ + e → M
X- - e → X

Overall reaction: M+ + X– M + X

Q. 3 ΔG0 = -RT ln K = -nFE0

Here, n =1

So, E0 = 2.303 RT log10 K / F

= 0.059 log10 K (at 298 K)

E0 = 0.59 V

So, log10 K = 0.59 / 0.059 = 10

∴ K = 1 x 1010
Q.4. Solution

𝒅𝒑 ∆𝑺𝒕𝒓𝒂𝒏𝒔
(A) Correct. Using Clapeyron’s equation, 𝒅𝑻 = . For melting, ∆𝑆 > 0. For
∆𝑽𝒕𝒓𝒂𝒏𝒔
𝑑𝑝
X, 𝑑𝑇 > 0 . Thus, like CO2, ∆𝑉 > 0. So, the density of X decreases on melting
at 𝑝 = 1 𝑏𝑎𝑟 = 105 𝑃𝑎.

(B) Correct, as 𝜇𝑠𝑜𝑙𝑖𝑑 = 𝜇𝑙𝑖𝑞𝑢𝑖𝑑 = 𝜇𝑔𝑎𝑠 at the triple point.

(C) Incorrect. At 100 kPa and 150 K, there is no point on the Solid-gas
coexistence curve.

(D) Correct. At this state point, X exists at critical pressure but at a temperature
lower than its critical temperature. So its most stable phase is liquid phase.

Ans. (C)

Q.5. Solution

The G vs p curves represent isothermal compression of gas (1), liquid (2) and solid (3).

(D) : LW, 2: NM and 3: AB.

Q. 6. Solution
(A) Incorrect. A and B are kept separately at 𝑇 and 𝑝 in steps 1 and 2.

(B) Correct. A and B are kept separately at 𝑇 and 𝑝 in their respective pure phases in steps 1
and 2.

(C) Incorrect. Dalton’s law has been used only in the steps 3 and 4.

(D) Incorrect. ∆𝑚𝑖𝑥 𝐺 = −𝑛𝑅𝑇 (𝑥𝐴 ln 𝑥𝐴 + 𝑥𝐵 ln 𝑥𝐵 )

Ans. (B)
Q.7

Solution

ln (Pf/Pi)= -∆Hm (vaporization)/R x[1/Tf-1/Ti]

ln (Pf/Pi)= -(40656 J mol-1 /8.314 JK--1mol-1)x [1/393-1/373] =0.667

Pf/Pi =1.95

Pf=1.95xPi =1.95x1 atm=1.95 atm ANSWER: C

Q.8

Solution

1/2H2(g)+AgCl(s)→H+ (aq)+Ag(s)+Cl-(aq)►n=1,

E=0.3551—0.3422x10-4t-3.2347x10-6t2+6.314X10-9t3

E=0.3551—0.3422x10-4x500C-3.2347x10-6 x(500C) 2+6.314X10-9 x(500C)3

E=0.3460915 V

We have considered two value of E:

For E=0.3460 and F=96485 C mol-1: ∆G=-nFE→∆G=-1x96485x0.3460=-33.383 kJ

mol-1

For E=0.3460 and F=96500 C mol-1: ∆G=-nFE→∆G=-1x96500x0.346=-33.389 kJ

mol-1

For E=0.3461, F=96485 C mol-1: ∆G=-nFE→∆G=-1x96485x0.3461=-33.393 kJ

mol-1

For E=0.3461, F=96500 C mol-1: ∆G=-nFE→∆G=-1x96500x0.3461=-33.393 kJ

mol-1

Based on this, it is suggested to consider range of ∆G as

may be considered as
∆G= - 33.3 to -33.4 kJ mol-1 Answer: [A]

Q.9

Solution  H   V 
   V T 
 P  T  T  P
RT
 Vm   B (T )
P
 V  R dB
   
 T  P P dT
 H   V  RT  R dB 
   V T    B(T )  T   
 P  T  T  P P  P dT 
 H   dB(T ) 
   B (T )  T  
 P  T  dT 
Answer: B

Q.10. Solution
𝑑𝑝
Step 1 is incorrect. The starting point is Clapeyron’s equation 𝑑𝑇
∆𝑆𝑡𝑟𝑠 ∆𝐻𝑓𝑢𝑠
𝑝2 ∆𝐻𝑓𝑢𝑠 𝑇2 𝑑𝑇 = =
from where one should write ∫𝑝 𝑑𝑝 = ∫
∆𝑉𝑓𝑢𝑠 𝑇1 𝑇
. ∆𝑉𝑡𝑟𝑠 𝑇∆𝑉𝑓𝑢𝑠
1

All other steps are correct.

Answer: (D)
Q.11. Solution
𝑑𝜇 𝑇 = 𝑉𝑚 𝑑𝑝

Assuming ideal behaviour of X in its gas phase,

𝑑𝑝
𝑑𝜇 𝑇 = 𝑉𝑚 𝑑𝑝 = 𝑅𝑇
𝑝
𝑝2
2
𝑑𝑝
∫ 𝑑𝜇 𝑇 = 𝑅𝑇 ∫
1 𝑝
𝑝1

𝑝2
∴ ∆𝜇 𝑇 (𝑔) = 𝑅𝑇 ln ( ) = (8.314 𝐽𝐾 −1 𝑚𝑜𝑙 −1 ) × (300 𝐾) × ln(5)
𝑝1

∴ ∆𝜇 𝑇 (𝑔) = 4014.26 𝐽 𝑚𝑜𝑙 −1

Also, in the incompressible liquid phase, 𝑑𝜇 𝑇 = 𝑉𝑚 (𝑙) 𝑑𝑝 gives ∆𝜇 𝑇 (𝑙) = 𝑉𝑚 (𝑙) (𝑝2 −
𝑝1 )

∴ ∆𝜇 𝑇 (𝑙) = 𝑉𝑚 (𝑙) × (4 𝑏𝑎𝑟) = 𝑉𝑚 × (4 × 105 𝑁 𝑚−2 )

∆𝜇𝑇 (𝑔)
Given, = 10
∆𝜇𝑇 (𝑙)

∴ ∆𝜇 𝑇 (𝑙) = 𝑉𝑚 (𝑙) × (4 × 105 𝑁 𝑚−2 ) = (4014.26 𝐽 𝑚𝑜𝑙 −1 ) × 10−1

4014.26 × 10−1 4014.26

Thus, 𝑉𝑚 (𝑙) = 𝑚3 = × 10−6 𝑚3 = 1.003 × 103 × 10−6 𝑚3
4 ×105 4

∴ 𝑉𝑚 (𝑙) = 1.003 × 10−3 𝑚3 ≈ 1.0 × 10−3 𝑚3

Answer: 3
Q. 12.

Ans: T = 268 K; Tf = 273 K; ΔCp,m = 37.3 J K–1mol–1;

wrev,max= – ΔGm (l → s, 268= 109.84 J mol–1; wrev = – ΔAm;

ΔA = ΔU – TΔS = ΔU – (ΔH – ΔG) = ΔG – PΔV;

ΔAm= ΔGm – PΔVm;

ΔVm =Vm(s) – Vm(l) = (18 g mol–1) {1/(0.917 g cm–3) – 1/(0.999 g cm–3)}

ΔVm = 1.612 cm3mol–1 = 1.612 × 10–6 m3mol–1;

ΔAm= (–109.84 J mol–1) – (101325Jm–3) (1.612 × 10–6 m3mol–1)

ΔAm = –109.84 J mol–1 – 0.16 J mol–1

ΔAm = –110.0 J mol–1

wrev,max = 110.0 J mol–1

Q. 13 Solution

Total pressure of the reaction mixture = ((0.5 + 0.4 + 0.4 + 0.2) 𝑀𝑃𝑎 = 1.5 𝑀𝑃𝑎

Since the reaction vessel is in thermal and mechanical equilibrium with the N2 gas in LHS
compartment,
the pressure of N2 gas after passing through the throttle, 𝑝2 = 1.5 𝑀𝑃𝑎 (b)

Change in pressure in Joule-Thomson expansion, ∆𝑝 = (1.5 − 4) 𝑀𝑃𝑎 = −2.5 𝑀𝑃𝑎

Thus, change in temperature,

∆𝑇 = 𝜇𝐽𝑇 ∆𝑝 = (−0.2 × 10−5 𝐾 𝑃𝑎−1 ) × (−2.5 × 106 𝑃𝑎) = 5.0 𝐾

Temperature at which the reaction takes place, 𝑇2 = 1005.0 𝐾 (a)

𝑝𝐶𝑂2 𝑝𝐻2 0.4×0.2
The reaction quotient, 𝑄 = = = 0.4
𝑝𝐶𝑂 𝑝𝐻2 𝑂 0.5×0.4
Since 𝑄 < 𝐾𝑒𝑞 , the forward reaction will be favoured. So, the answer to (c) is 1
∆𝑟 𝐺 𝑄 0.4
= ln (𝐾) = ln (1.6) = −1.39 (d)
𝑅𝑇

Q.14. Solution
𝜕𝐻 𝜕𝑈 𝜕𝑉
(i) 𝐶𝑝 = ( 𝜕𝑇 ) where 𝐻 = 𝑈 + 𝑝𝑉. Thus 𝐶𝑝 = ( 𝜕𝑇 ) + 𝑝 (𝜕𝑇 ) .
𝑝 𝑝 𝑝

𝜕𝑉 𝜕𝑈
By definition, (𝜕𝑇 ) = 𝛼 𝑉. Thus, 𝐶𝑝 = ( 𝜕𝑇 ) + 𝑝𝑉𝛼. Therefore, 𝑋1 = 𝛼 with sl no. 3
𝑝 𝑝

𝜕𝑈 𝜕𝑉 𝜕𝑈
(ii) 𝑑𝑈 = 𝐶𝑣 𝑑𝑇 + 𝜋𝑇 𝑑𝑉. ∴ ( ) = 𝐶𝑉 + 𝜋𝑇 ( ) so that ( ) = 𝐶𝑉 + 𝛼𝜋𝑇 𝑉
𝜕𝑇 𝑝 𝜕𝑇 𝑝 𝜕𝑇 𝑝

Therefore, 𝑋2 = 𝐶𝑣 with sl no. 2

and 𝑋3 = 𝜋𝑇 with sl no. 4

(iii) 𝑑𝑈 = 𝑇𝑑𝑆 − 𝑝𝑑𝑉 so that

𝜕𝑈 𝜕𝑆 𝜕𝑝
(𝜕𝑉 ) = 𝑇 (𝜕𝑉) − 𝑝 = 𝑇 (𝜕𝑇) − 𝑝 using Maxwell’s relation
𝑇 𝑇 𝑉

𝜕𝑝 𝛼 𝝏𝑼 𝜶𝑻
But (𝜕𝑇) = . Thus ( 𝝏𝑽) = − 𝒑.
𝑉 𝜅 𝑻 𝜿

Therefore, 𝑋4 = 𝜅 with sl no. 1

Answer: 𝑋1 = 3, 𝑋2 = 2, 𝑋3 = 4, 𝑋4 = 1

Q.15.

Ans:

n(1) = 54/18 = 3 moles; n(2) = 108/18 = 6 moles; n(2)/ n(1) = 6/3 = 2;

Ti(1) = 340 K; Ti(2) = 280 K; Let final temperature is Tf;

q(1) = – q(2) or n(1) Cp,m (Tf – Ti(1)) = – n(2) Cp,m (Tf – Ti(2))

or Tf = Cp,m {n(1) Ti(1) + n(2) Ti(2)}/{2Cp,m (n(1) + n(2))}

or Tf = {Ti(1) + n(2)/n(1)Ti(2)}/{1 + n(2)/(n(1))}= {Ti(1) + 2Ti(2)}/(1 + 2)

Tf = (340 + 2×280) K/3 = 300 K;

ΔS = ΔS(1) + ΔS(2) = n(1) Cp,mln(Tf /Ti(1)) + n(2) Cp,mln(Tf /Ti(2))

Or ΔS = (3 mol) (75 J K–1mol–1) ln(300/340) + (6mol) (75 J K–1mol–1) ln(300/280)

Or ΔS = (– 28.162 J K–1 + 31.047 J K–1) = 2.89 J K–1;