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Physical Chemistry Assignment

AUTUMN SESSION 2013

School of Science and Health

Due: 1 pm Thursday 6
th
June 2013.



You must submit a hard copy of the answers, and attach a signed
assignment cover sheet.



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USEFUL FORMULAE AND DATA



w = - nRT ln (V
2
/V
1
) S = nR ln (V
2
/V
1
) G = nRT ln (P
2
/P
1
)
G
0
= H
0
- TS
0
G = G
0
+ RT lnK G
0
= -FE
0

E = E
0
(RT/F) lnK

a
A
=
A
[A] log

= - |z
+
z
-
| 0.509 I
1/2

I = (m
+
z
+
2
+ m
-
z
-
2
) R = 8.314 J K
-1
mol
-1
N
A
= 6.022 x 10
23
mol
-1

h = 6.626 x 10
-34
J s k
B
= 1.381 x 10
-23
J K
-1
F = 96500 C mol
-1


CH
3
CH
2
OH
(g)
CH
3
COOH
(g)
CH
3
CH
2
OOCCH
3(g)
H
2
O
(g)

H
0
/ kJ mol
-1
-231 -435 -443 -242
S
0
/ J K
-1
mol
-1
283 285 363 189

Fe
2+
(aq)
+ 2 e Fe
(s)
E
0
= - 0.41 V
Al
3+
(aq)
+ 3 e Al
(s)
E
0
= -1.66 V
ClO
3
-
(aq)
+ 3 H
+
+ 2 e HClO
2(aq)
+ H
2
O E
0
= 1.21 V
fumarate
2-
+ 2 H
+
+ 2 e
-
succinate
2-
E
0
= 0.03 V
pyruvate
-
+ 2 H
+
+ 2 e
-
lactate
-
E
0
= -0.18 V

lnA
t
lnA
0
= -k
1
t 1/A
t
- 1/A
0
= k
2
t




3


1 Suppose 100 g of ethane (C
2
H
6
) expands isothermally at 350
0
C from 50 mL to 2 L.
Calculate the heat and work done by the system, and the change in Entropy if:
i) the process is via a reversible path (sketch the pathway)
ii) the process is non-reversible (sketch the pathway)
iii) which pathway will require the least work and why?
iv) why are these processes done isothermally?
v) why can a real process never convert completely heat to work?
(10 marks)

2 Calculate the enthalpy and entropy change for the following reaction:
CH
3
CH
2
OH
(g)
+ CH
3
COOH
(g)
CH
3
CH
2
OOCCH
3(g)
+ H
2
O
(g)

(5 marks)

3 The Gibbs Free Energy for the reaction: A + B C was measured as a function of
temperature:
G
0
/ kJ mol
-1
26.6 28.1 29.7 31.3
T
0
C 0 20 40 60

a) Calculate the enthalpy and entropy changes for the reaction
b) Comment on the signs of the change in entropy, enthalpy and the effect of increase in
temperature on the equilibrium constant.
c) Predict the equilibrium constant at 100
0
C.
d) If the initial concentrations are A = 1 M, B = 0.1 M, C = 0.01 M at 100
0
C, will the system
produce reactants or products as the reaction comes to equilibrium? Why?
(15 marks)

4 a) Calculate the standard cell potential for ONE of the reactions (acidic conditions):

Fe
(s)
+ ClO
3
-
(aq)
Fe
2+
(aq)
+ HClO
2(aq)



succinate ion
O
O
-
O
-
O
O
O
-
O
-
O
fumarate ion
OH
O
O
-
lactate ion
+
O
O
O
-
pyruvate ion
+

b) Calculate the change in Gibbs Free Energy for this reaction.
c) Calculate the equilibrium constant at 298.15
0
C. Comment on its magnitude.
(10 marks)


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5 a) Discuss the general features of the Debye-Hckel theory of electrolyte solutions.
b) Calculate the reduction potential for 0.1 M Al
2
(SO
4
)
3
.
(10 marks)

6 a) A radioactive isotope of technetium is produced at Lucas Heights for use in medical
imaging and it has a half life of 61 days. What percent of the initial sample remains
after 2 weeks?

b) The kinetics data for a reaction with the following stoichiometric equation was
measured:
CH
3
COOCH
3(aq)
+ OH
-
(aq)
CH
3
COO
-
(aq)
+ CH
3
OH
(aq)


t / s 0 50 100 150 200
[Ester] / mol L
-1
0.500 0.051 0.027 0.018 0.013

i) Find the overall order of the reaction, the rate constant, and the half-life of the reaction
ii) Comment on the order found from experiment compared to the stoichiometry of this
reaction?

(15 marks)
7 A mechanism for the reaction:

2A + B 2D

is:

2A C

C 2A

B + C 2D


Derive a theoretical rate equation for the production of D from this mechanism using the
steady state approximation, and predict effects on the observed kinetics if k
3
<< k
1
.
(5 marks)
k
1
k
2
k
3


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8 Give a short answer for two of the following questions:

a) Explain thermodynamic factors such as activity, Gibbs energy, potential and voltage-
gated channels for controlling the flow of ions across biological membranes.

b) Explain hydrophobic interaction in biomolecular and thermodynamic terms. Use
examples of biological molecules.

c) What experimental procedures can be used to measure U and H for a reaction? Sketch
the apparatus.

d) Explain how Collision Theory gives information about the pre-exponential factor and
activation energy of reactions.
(5 marks)





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