Question 1 (15 marks)

C01
a
12

b
8

1 mol of gas B expands adiabatically against a constant external pressure that equals to the
final pressure, Pf = 4 atm. The initial state of the gas is Ti = 27 C and Pi = 10 atm. Assume the
gas to be ideal with heat capacity of:
CP,m =28.58+1.7610-2 T
with CP,m is in (J K-1 mol-1) and T is in Kelvin.
(a)

Determine the final temperature of the system, Tf in C.

(12 marks)

(b)

Calculate the enthalpy, H (in kJ) and entropy, S (in J K-1) of the process.

(8 marks)

SOLUTION:
Part (a):
Given: Ti =27 C = 300 K, Pi = 10 atm, n = 1 mol, Pexternal = Pf = 4 atm
dU = dq Pexternal dV; since dq = 0 dU = PdV

= = = ( )

= = ,

(1)

(2)

CP,m CV,m = R CV,m = CP,m R

CV,m = [(28.58 + 1.76 x 10-2T) 8.3145] = (20.2655 + 1.76 x 10-2 T) J K-1 mol-1
Ideal gas, PV = nRT

Initial: =
; Final: =

From (1):

= ( ) = (

) = ( )

= (1)(8.3145)(4) ( 4 30010) = (1)(8.3145)(4) ( 4 301)

...

= (8.3145 ) + 997.74
From (2):

(1) (20.2655

+ 1.76 102 )

= [20.2655( ) + (12) 1.76 102 ( 2 2 )]

= [20.2655( 300) + 0.00898 ( 2 3002 )]

(3)

 = [20.2655 6079.65 + 0.00898 2 808.2]

....

(4)

Eqn (3) = Eqn (4),

[20.2655 6079.65 + 0.00898 2 808.2] = (8.3145 ) + 997.74
0.00898 2 + 28.58 7885.59 = 0
Solving quadratic equation:
28.58 28.582 (4 0.00898 (7885.59))
=

2 0.00898

Taking the positive root: Tf =255.42 K = -17.58 C

Part (b):

(i) For ideal gas: = = ,

= [(1)(28.58)( ) + (1)(0.00898) ( 2 2 )]
= [28.58(255.42 300) + 0.00898 (255.422 3002 )]
H = -1496.6 J = -1.5 kJ

(ii) For ideal gas: = =

ln

28.58 + 0.0176
4
(
) (1)(8.3145) ln

10

= [28.58 ln + 0.0176( )] (7.618)

255.42
= [28.58 ln
+ 0.0176(255.42 300)] + 7.618
300
S = 2.24 J K-1
= (1)

Question 2 (20 marks)

CO2
a

12

The data below show the temperature variation of the equilibrium constant of the reaction

Ag CO (s) 5 Ag O(s) + CO (g)

2

T [K]

350

400

450

500

Kp

3.98 104

1.41 102

1.86 101

1.48

a) Draw a graph to demonstrate the relationship between the temperature and equilibrium
constant.

(Tips:

K P Tf

d lnK

use

K P 298.15

the
Tf

integrated

form

of

vant

H
1
dT

R 298.15 T

rxn
2

Hoff

equation;
(12 marks)

b) Based on the graph in part (a); determine the standard reaction enthalpy of the
decomposition, Hrxn. (Tips: assume that Hrxn is independent of temperature).
(3 marks)
c) State either the above reaction is endothermic or exothermic? Why?

(2 marks)

d) In general, list three factors that affect the position of chemical equilibrium? (3 marks)

SOLUTION:
a)

T [K]
Kp
1/T
ln K p

350
3.98E-04

400
1.41E-02

0.002857

0.002500

-7.8291

-4.2616

450
1.86E-01

500
1.48

0.002222 0.002000
-1.6820

0.3920

Hrxn
lnK P Tf lnK P 298.15K
R

Tf 298.15K
1/T [1/K]

1.0
0.00.0000

0.0005

0.0010

0.0015

ln Kp

-1.0
-2.0
-3.0

-4.0
-5.0
-6.0

-7.0
-8.0

y = -9579x + 19.595

0.0020

0.0025

0.0030

Question 3 (20 marks)

C03
a
15

b
5

The data in the following table have been obtained for the potential of the cell

Pt(s) | H2(g, f = 1 atm) | HCl(aq, m) | AgCl(s) | Ag(s)

as function of m at 25C. Given the cell reaction,
2AgCl(s) + H2(g) 2Ag(s) + 2H+(aq) + 2Cl(aq)

m (mol kg1)

E (V)

m (mol kg1)

E (V)

m (mol kg1)

E (V)

0.00100

0.59715

0.0200

0.43024

0.500

0.27231

0.00200

0.54425

0.0500

0.38588

1.000

0.23328

0.00500

0.49846

0.100

0.35241

1.500

0.20719

0.0100

0.46417

0.200

0.31874

2.000

0.18631

a) Determine E using a graphical method.

(15 marks)

b) Calculate for HCl at m = 0.00100, 0.0100, and 0.100.

(5 marks)

SOLUTION:
a) Cell reaction: 2AgCl(s) + H2(g) 2Ag(s) + H+ (aq) + 2Cl (aq)

RT
RT
2
lnaH a Cl E
lnaH a Cl
2F
F
2

aH a Cl a m
E E

2RT m
2RT
ln
E
ln
F mo
F

Low concentration limit use the Debye-Hckel result

ln 0.50926log10

m
m
1.172614ln
mo
mo

For dilute solutions

2RT m
2RT
m
E
ln
1.172614 ln
F
F
mo
mo

0.2360

E+(2RT/F)ln(m/m )

E E

From graph, E = 0.2237

0.2320
0.2280
y = 0.035x + 0.2237

0.2240
0.2200
0.0000

0.1000

0.2000 0.3000
(m/m )^1/2

b) Given E we can now find from

Plot, E+(2RT/F) ln(m/mo) (y-axis) vs (m/mo) (x-axis), intercept E

Use data up to m = 0.1 Debye-Hckel model is no valid for
more concentrated solutions

m/m
0.001
0.002
0.005
0.010
0.020
0.050
0.100

(m/m)1/2
0.031623
0.044721
0.070711
0.100000
0.141421
0.223607
0.316228

E
0.579150
0.544250
0.498460
0.464170
0.430240
0.385880
0.352410

Question 4 (20 marks)

E+(2RT/F)ln(m/m)
0.224212
0.224909
0.226203
0.227531
0.229218
0.231943
0.234090

ln

m
F

E E ln
RT
mo

E = 0.2237

m/m
ln
0.001 -0.010654
0.010 -0.075511
0.100 -0.203036

0.989
0.927
0.816

0.4000

a
10

C04
b
5

c
5

Consider the schematic reaction,

A k B
a) If the reaction is 3.5-th order with respect to [A], solve the derivative of integrated rate
law expression for this reaction?

(10 marks)

b) Explain what k is, and how to determine its value from the above reaction?

(5 marks)

c) Derive and evaluate the half-life expression for this reaction.

(5 marks)

SOLUTION:

Question 5 (20 marks)

a
4

C05
b
3

c
13

a. What is the difference between a homogeneous and a heterogeneous catalyst? (4 marks)

b. What are the inherent assumptions in the Langmuir model of surface adsorption?
(3 marks)
c. The adsorption of nitrogen on mica measured at different pressures is as follows
Vads (cm3g-1)

P (Torr)

0.494

2.110-3

0.782

4.610-3

1.16

1.310-3

Langmuir equation can be written as

1
1 1
1
=
( )+
Vads KVm P Vm

where Vm is the maximum adsorption and K is equilibrium constant.

Using Langmuir isotherm, determine the
i.

Langmuir parameters

(7 marks)

ii.

Fractional coverage, at each pressure.

(6 marks)

Fractional coverage, is defined as ratio of adsorbed volume to the volume of

maximum absorption

SOLUTION:
a. For a homogeneous catalysis both the catalyst and the substrate exist in the same phase.
1.5 marks
Heterogeneous catalysis occurs when the catalyst and the substrate molecules exist in
different phases. 1.5 marks
b. Langmuir assumptions:
1. Adsorption finishes once one monolayer of coverage results.
2. The surface is uniform and all adsorption sites are equivalent.
3. The occupancy of a site will not affect the adsorption or desorption processes in
adjacent sites.
c.
i.

Plot 1/Vads versus 1/P as follows: 4marks

Vads (cm3g-1)
0.494
0.782
1.16

1/Vads
2.024
1.279
0.862

P (Torr)
2.110-3
4.610-3
1.310-2

1/P
476.19
217.39
76.92

Best fit to the data by a straight line yields:

1
1
=0.0029 ( ) + 0.642
Vads
P
The maximum adsorption volume is,
Vm =

1
intercept of y-axis
Vm =

1
0.642

Vm=1.56 cm3g-1 2marks

The equilibrium constant, K
1
( )
1
=
0.0029(1.56)
=

K=2.21 torr-1 2marks

ii.

=Vads/Vm
Vads (cm3g-1)
0.494
0.782
1.16

0.317
0.501
0.744

P (Torr)
2.110-3
4.610-3
1.310-3