CONFIDENTIAL

AS/APR 2011/CHM520

Avogradros number (NA) = 6.02214 1023 mol-1

Gas constant (R) = 8.314 J K-1 mol-1 or 0.0821 dm3 atm K-1 mol-1 or 0.0831 dm3 bar K-1 mol-1
1 Pa = 1 N m-2, 1 bar = 105 Pa, 1 atm = 101.325 kPa
RT/F at 25 oC = 0.02569 V mol
ln a = 2.303 log a
Faraday constant (F) = 96485 C mol-1

QUESTION 1
a)

For one mole of an ideal gas, external pressure (Pexternal) = pressure (P) = 200 103 Pa.
The temperature is changed from 100 C to 25.0 C at constant pressure. Molar heat
capacity at constant volume (CV,m) = 3/2 R. Calculate (in unit J)
i) change of internal energy (DU),
ii) change of enthalpy (DH),
iii) heat (q) and
iv) work done (w).
(12 marks)

b)

A pellet of Zn of mass 10.0 g is dropped into a flask containing dilute H2SO4 at a

pressure (P) = 1.00 bar and temperature (T) = 298 K.
i) Write the balanced chemical equation for the reaction that occurs.
ii) Calculate the work done (w) for the process (in unit J).
(8 marks)

QUESTION 2
Calculate the change of entropy of system (DSsys), the change of entropy of surroundings
(DSsurr) and the total change of entropy (DStot), when the volume of 85.0 g of CO initially at
298 K and 1.00 bar increases by a factor of three in
a) an adiabatic reversible expansion,
b) an expansion against external pressure (Pexternal) = 0, and
c) an isothermal reversible expansion.
State whether each process (a to c) is spontaneous.
Given that the molar heat capacity at constant pressure (Cp,m) to be constant at the value
29.14 J mol1 K1 and assume ideal gas behavior.
(20 marks)

Hak Cipta Universiti Teknologi MARA

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AS/APR 2011/CHM520

QUESTION 3
a) Express mean activity coefficient ( g ) in terms of activity coefficient for cation ( g + ) and
activity coefficient for anion ( g - ) for
i) SrSO4,
ii) MgBr2,
iii) K3PO4, and
iv) Ca(NO3)2.
Assume complete dissociation.
(8 marks)
b) Using the DebyeHckel limiting law, calculate the value of mean activity coefficient ( g )
in 5.0 103 molal solutions of
i) KCl,
ii) Ca(NO3)2, and
iii) ZnSO4.
Assume complete dissociation. Given that: A = 0.509 for aqueous solution at 25 oC.
(12 marks)

QUESTION 4
a) For the half cell reaction Hg2Cl2 (s) + 2 e- 2 Hg (l) + 2 Cl- (aq), standard cell potential
(E) = +0.26808 V. Determine the standard molar Gibbs energy of formation (Gf) (Cl-,
aq).
Given that: (Gf) (Hg2Cl2, s) = 210.7 kJ mol-1
(5 marks)
b) Reaction of 4 NO3- + 4 H+ 4 NO + 2 H2O + 3 O2 is referred.
i) Show the electrode half-reactions and standard cell potential (E).
ii) Calculate the equilibrium constant (K) at 298.15 K for the reaction.
(7 marks)
c) The cell potential (E) = +0.260 V for the cell
Pt (s) H2 (g, aH 2 = 1) H+ (aq, aH+ = 1 NaCl (aq, m = 0.300) AgCl (s) Ag (s)
Show the electrode half-reaction, the overall reaction and standard cell potential (E),
reaction quotient (Q) and the Nernst Equation of each cell.
ii) Determine g Cl- assuming that g = g Na + = g Cl- .
i)

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AS/APR 2011/CHM520

Quantities a, g and m denote activity, activity coefficients and concentration.

(8 marks)
QUESTION 5
a) Radium-224 decays by -particle emission.
i) Write the balanced nuclear equation.
ii) Calculate the mass defect (m) (in unit kg).
iii) Determine the energy (in unit J) associated with this decay.
Given that:
1 amu = 1.6606 10-27 kg
1 J = 1 kg m2 s-2
Speed of light (c) = 2.9979 108 m s-1
Table 1 Masses of fundamental particles of matter.
Particle
Mass (amu)
Electron
0.00054858
proton
1.007825
neutron
1.008665
Table 2 Nuclide and its nuclear mass
Particle
Nuclear mass (amu)
224
Ra
223.9719
220
Rn
219.9642
4
He
4.00150
(8 marks)
b) Copper consists of several radioactive isotopes, some of which are listed in Table 3.
i)

Which of these isotopes are stable and which isotope is less stable? Give your
explanation.
ii) Justify the observation that Cu-64 can undergo emission, positron emission, or
electron capture by referring to Figure 1. Write the balanced nuclear equation for
each case.
Table 3 Isotopes of copper
Isotope
Cu-63
Cu-64
Cu-65

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AS/APR 2011/CHM520

Figure 1 Neutron-proton ratio and the belt of stability of nuclides (dots in a region).
(12 marks)

END OF QUESTION PAPER

Hak Cipta Universiti Teknologi MARA

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Faculty of Applied Science, UiTM

Final Exam Apr 2011

Course : Physical Chemistry II, CHM 520

First Examiner : Dr. Chan Chin Han
Second Examiner : Mr Borhanuddin
Answer : 5 questions only

Page 1 of 9

QUESTION 1
Solution:

Mark
[Sub
total]

a)

i)
U = nCV ,m T =

3
8.314 J mol-1 K -1 ( 298 K 373 K ) = 935 J
2

ii) and iii)

CV,m = Cp, m R

[3]

H = nCP ,m T = n ( CV ,m + R ) T

5
8.314 J mol-1K -1 ( 298 K 373 K )
2
= 1.56 103 J
= qP
=

[4]

[2]

1
2

[3]

i)
Zn (s) + H2SO4 (aq) Zn2+ (aq) + SO42- (aq) + H2 (g)

[2]

ii)
w = -PexV and Vf >>> Vi, so dV ~ Vf

iv)

U = q + w

w = U qP = 935 J + 1.56 103 J = 624 J

b)

nRT
V=
Pex

w = Pex

nRT
Pex

w = - nRT
So, n = amount of H2 produced.
Due to, 1 mol of H2 1 mol Zn,
So, n = amount of Zn consumed.

Page 2 of 9

mass
10g
=
molar mass 65.39g mol1
10g
w=
8.315J K 1 mol1 298.15K
1
65.39g mol
w = -379 J
n=

2
Total:

[6]
20

QUESTION 2
Solution:

Mark
[Sub
total]

a) an adiabatic reversible expansion

Stot = Ssys + Ssur
q
Ssurr = surr
Tsurr
Ssys = 0 because the process is reversible.

Ssurr = 0 because q = 0

Stot = Ssys + Ssurr = 0.

The process is not spontaneous. The system and surroundings are at

equilibrium.

[5]

b) an expansion against Pexternal = 0 (Isothermal)

w = -PexV
T and w = 0. Therefore U = q = 0.

Ssys :

S = nR ln

Vf
Vi

85.0 g
8.314 J mol -1 K -1 ln 3
-1
28.01g mol

= 3.03 mol 9.13 J mol-1 K -1 = 27.7 J K -1

Ssurr = 0 because q = 0

Stot = Ssys + Ssurr = 27.7 J K-1 + 0 = 27.17 J K-1 .

The process is spontaneous.

Page 3 of 9

[7]

c) an isothermal reversible expansion

T = 0. Therefore U = 0.
w = q = nRT ln

Vf
Vi

= 3.03 mol 8.314 J mol -1 K -1 298 K ln 3 = 8.25 103J

qreversible 8.25 103J

Ssys : S =
=
= 27.7 J K -1
T
298 K
S surroundings =

q 8.25 103J
=
= 27.7 J K -1
T
298 K

Stot = Ssys + Ssurr = 27.7 J K-1 27.7 J K-1 = 0.

The process is not spontaneous. The system and surroundings are at

equilibrium.

Total:

Page 4 of 9

[8]

20

PART B - QUESTION 3
Solution:

Mark
[Sub
total]

a)
To the case of a compound MpXq that dissolves to give a solution of p
cations and q anions.

= ( p q
+

1 / p+q

i) SrSO4: = ( + )

ii) MgBr2: = ( +

)
)

iii) K3PO4: = (

3
+

2
1

2
1

iv) Ca(NO3)2: = ( +

2
2

[8]

b)
I m = 1 i mi zi2
2

log = z + z A I m
i) KCl
m
1
I = ( v+ z+2 + v z2 ) = ( m+ z+2 + m z2 )
2
2
1
I = ( 0.0050 mol kg 1 + 0.0050 mol kg 1 ) = 0.0050 mol kg 1
2
I
ln = 1.173 z+ z
= 1.173 0.0050 = 0.08294
mol kg -1

= 0.92

Page 5 of 9

[4]

ii) Ca(NO3)2
1
m
v+ z+2 + v z2 ) = ( m+ z+2 + m z2 )
(
2
2
1
I = ( 0.0050 mol kg -1 + 22 0.0050 mol kg -1 ) = 0.0125 mol kg -1
2
I
ln = 1.173 z+ z
= 1.173 2 0.0125 = 0.26229
mol kg 1

= 0.77

I=

iii) ZnSO4
m
1
I = ( v+ z+2 + v z2 ) = ( m+ z+2 + m z2 )
2
2
1
I = ( 4 0.0050 mol kg 1 + 4 0.0050 mol kg 1 ) = 0.020 mol kg 1
2
I
ln = 1.173 z+ z
= 1.173 4 0.020 = 0.6635
mol kg -1

[4]

= 0.52
Total:

Page 6 of 9

[4]
20

PART B - QUESTION 4
Solution:
a)

Mark
[Sub
total]

GRo = nFE o = 2G of ( Cl- , aq ) G of ( Hg 2 Cl 2 , s )

G of ( Cl- , aq ) =

G of ( Hg 2 Cl 2 , s ) nFE o

2
210.7 kJ mol-1 2 mol 96485 C mol-1 0.26808 V
G of ( Cl- , aq ) =
= 131.2 kJ mol -1
2

b) i)

NO3- + 4H+ +3e- NO + 2H2O

2 H2O O2 + 4H+ + 4 e-

E = +0.957 V
E = 1.229 V

1
1

The overall reaction is

4NO3- + 4H+ 4NO + 2H2O + 3O2

E = 0.272 V

[5]

ii)
nF o
12 96485 C mol-1 0.272 V
E =
RT
8.314 J K -1mol-1 298.15 K
= 127.047

ln K =

K = 6.67 10

2
1

56

[7]

c) i)

The half cell and overall reactions are

AgCl + e- Ag + Cl1/2 H2 H+ + eAgCl + 1/2 H2 Ag + H+ + Cl-

Q=

E = +0.22233V
E = 0
E = +0.22233V

aCl aH+

aH 2

E = E

RT aCl aH+
ln
nF
aH 2

, n =1

Page 7 of 9

[3]

ii)

= Na = Cl ,
+

a =

m
, m = 1 mol/kg.

E = Eo
ln =

RT aH + aCl
RT
RT mCl
= Eo
ln
ln aCl = E o
ln o
nF
nF
nF
m
aH 2

nF ( E o E )

ln

mCl

RT
m
-1
1 96, 485 C mol ( 0.22233 V 0.260 V )
ln 0.30 = 0.2630
ln =
8.314 J mol-1 K -1 298 K
= 0.769

1
1

Total:

[5]
20

QUESTION 5
Solution:

Mark
[Sub
total]

a) i)
224
220
4
88 Ra 86 Rn + 2 He

ii)
m = (mass 220Rn + 4He) mass 224Ra
m = (219.9642 + 4.00150 223.9719) amu = -0.0062 amu

[2]

AND
m = ( 0.0062amu )

1g
= 1.0296 10 26 g = 1.0296 10 29 kg
6.022 10 23 amu

E = mc 2
2
E = (- 1.0296 10-29 kg )(3.00 108m/s ) = 9.27 10 13 kg m 2 s 2

[3]

1
1

1 J = 1 kg m2 s-2

E = 9.27 10 13 J

b) i)
Cu-63: stable
No. of proton = 29 (odd)
No. of neutron = 34 (even)
Stable nuclide with an odd number of protons and even number of
Page 8 of 9

1
1

[3]

neutrons.
Cu-65: stable
No. of proton = 29 (odd)
No. of neutron = 36 (even)
Stable nuclide with an odd number of protons and even number of
neutrons.
Cu-64: less stable
No. of proton = 29 (odd)
No. of neutron = 35 (even)
Stable nuclide with an odd number of protons and odd number of
neutrons.

1
1

ii)
emission
64
64
0
29 Cu 30 Zn + 1 e
Zn-64 is even-even isotope, close to the belt of stability and is likely to
be stable.
positron emission
64
64
0
29 Cu 28 Ni + +1 e
Ni-64 is even-even isotope, close to the belt of stability and is likely to
be stable.
electron capture
64
64
0
29 Cu + -1 e 28 Ni
Ni-64 is even-even isotope, close to the belt of stability and is likely to
be stable.
Total:

Page 9 of 9

[6]

1
1

1
1

1
1

[6]
20

CONFIDENTIAL

AS/JUL 2010/CHM520

Avogradros number (NA) = 6.02214 1023 mol-1

Gas constant (R) = 8.314 J K-1 mol-1 or 0.0821 dm3 atm K-1 mol-1 or 0.0831 dm3 bar K-1 mol-1
1 Pa = 1 N m-2, 1 bar = 105 Pa, 1 atm = 101.325 kPa
RT/F at 25 oC = 0.02569 V mol
ln a = 2.303 log a
Faraday constant (F) = 96485 C mol-1

QUESTION 1
a)

Calculate change of enthalpy (H) (in unit J) and the change of internal energy (U) (in
unit J) for the transformation of one mole of an ideal gas from 27.0 C and 1.00 atm to
327 C and 17.0 atm if molar heat capacity at constant pressure (Cp,m) = 20.9 + 0.042T in
units of J K-1 mol-1.
(9 marks)

b)

In the adiabatic expansion of one mole of an ideal gas from an initial temperature of 25
C, the work done on the surroundings is 1200 J. If molar heat capacity at constant
volume (CV,m) = 3/2 R, calculate:
i) heat (q) (in unit J),
ii) work done (w) (in unit J),
iii) final temperature (T) (in unit K)
iv) change of internal energy (U) (in unit J), and
v) change of enthalpy (H) (in unit J).
(11 marks)

QUESTION 2
a) Are change of entropy of fusion (Sfusion) and change of entropy of vaporization
(Svaporization) always positive or negative? Explain your answer.
(4 marks)
b) Are change of enthalpy of fusion (Hfusion) and change of enthalpy of vaporization
(Hvaporization) always positive or negative? Explain your answer.
(4 marks)
c) Calculate change of entropy (S) if the temperature of 1 mol of an ideal gas with molar
heat capacity at constant volume (CV,m) = 3/2 R is increased from 150 to 350 K under
conditions of
i) constant pressure and
ii) constant volume.
(7 marks)
d) Calculate the normal boiling point (Tb) (in unit of K) of Br2, using values of standard
molar enthalpy of formation (Hf), standard molar entropy (S) and standard molar
Gibbs energy of formation (Gf) from Table 1.
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CONFIDENTIAL

AS/JUL 2010/CHM520

Table 1 Standard molar properties at 298.15 K

Substances
Hf / kJ mol-1
S / J K-1 mol-1
Br2 (g)
30.91
245.46
Br2 (l)
0
152.23
HBr (g)
-36.40
198.70

Gf / kJ mol-1
3.11
0
-53.45
(5 marks)

QUESTION 3
a) Why are activity coefficients ( ) calculated using the DebyeHckel limiting law always
less than one? Explain your answer.
(3 marks)
b)

Why is it not possible to measure the activity coefficient ( + ) of Na+ (aq)? Explain your
answer.
(2 marks)

c) Calculate the molar solubility (S) of BaSO4 [solubility constant (Ksp) = 1.08 1010]
i) in pure H2O and
ii) in an aqueous solution with ionic strength (Im) = 0.0010.
hint: MX

M+ + X-, K sp = a+ a

Given that:
S = number moles of solute in 1 L of a saturated solution in units of mol L-1.

a =

m
, m = 1 mol kg-1. Quantities a, and m denote activity, activity
m

coefficients and concentration.

log = z+ z A I m . Quantities zi = charge ion i and A = 0.509 for aqueous

solution at 25 oC.
(15 marks)

QUESTION 4
a) Reaction of 4 NiOOH + 2 H2O 4 Ni(OH)2 + O2 is referred.
i) Show the electrode half-reactions and standard cell potential (E).
ii) Calculate the equilibrium constant (K) at 298.15 K for the reaction.
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CONFIDENTIAL

Given that: NiOOH + H2O + e- Ni(OH)2 + OH-

AS/JUL 2010/CHM520

E = +0.52 V
(7 marks)

b) Consider the Daniell cell for the indicated molalities:

Zn (s) ZnSO4 (aq, 0.3000 m) CuSO4 (aq, 0.2000 m) Cu (s)
The activity coefficient ( ) has the value 0.1040 for CuSO4 and 0.08350 for ZnSO4 at
the indicated concentrations.
i) Show the electrode half-reactions, the overall reaction and standard cell potential
(E), reaction quotient (Q) and the Nernst Equation of each cell.
ii) Calculate cell potential (E) by setting the activity (a) equal to the molality (m).
iii) Calculate E by using the above values of the .
iv) How large is the relative error for E calculated in ii) and iii) if the concentrations,
rather than the activities, are used?
(13 marks)
QUESTION 5
a) For , and radiation, answer the following questions. Explain your answer for each
case.
i) Which has the greatest ability to penetrate through matter?
ii) Which has the greatest ability to ionize matter?
iii) Which suffers the greatest deflection in a magnetic field?
iv) How does a ray differ from and X-ray?
(8 marks)
b) Without doing detailed calculations, determine which of the radioactive nuclides in
Table 2:
i) has the greatest activity (A), for a 1-million-atom sample,
ii) would undergo a 75 % reduction in activity in about 2 days.
Explain your answer in i) and ii).
Table 2 Nuclide and its half-life (t0.5)
Nuclide
t0.5
15
O
122 s
18
F
109.8 min
28
Mg
21 h
44
Sc
3.93 h
33
P
25.3 d
(6 marks)

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CONFIDENTIAL

AS/JUL 2010/CHM520

c) The mass defect (m) in the formation of a nucleus of neon-20 is 0.173 amu.
i) What is the nuclear mass of this nuclide (in unit of amu)?
ii) What is its atomic mass (in unit of amu)?
Given that:
Table 3 Masses of fundamental particles of matter.
Particle
Mass (amu)
Electron
0.00054858
proton
1.007825
neutron
1.008665
(6 marks)

END OF QUESTION PAPER

Hak Cipta Universiti Teknologi MARA

CONFIDENTIAL

Faculty of Applied Science, UiTM

Final Exam Nov 2010

Course : Physical Chemistry II, CHM 520

First Examiner : Dr. Chan Chin Han
Second Examiner : Mr Borhanuddin
Answer : 5 questions only

Page 1 of 9

QUESTION 1
Solution:

Mark
[Sub
total]

a)
1

Tf

H = n CP ,m dT
Ti

20.9 + 0.42 dT
K
300 K
600 K

= 20.9 ( 600 K 300 K ) J + 0.21T 2

600 K
300K

= 6.27 10 J + 56.7 10 J

= 63.0 103 J

U = H ( PV ) = H nRT

[5]

2
1

= 63.0 103 J 8.314 J K -1mol 1 300 K

= 60.5 103 J

[4]

1
1+1

[1]
[2]

b)
i) to iv)
U = q + w, q = 0 for adiabatic process

q = 0 because the process is adiabatic

U = w = 1200 J
U = nCV ,m (T f Ti )

Tf =

U + nCV ,mTi

nCV ,m

1200 J + 7.5 8.314 J mol-1 K 1 298 K

=
1.5 8.314 J mol -1 K -1
= 202 K

vi)
CV,m = Cp, m R

H = n

[3]

1
2

C(T f Ti ) = n ( CV ,m + R ) (T f Ti )

P ,m

= 2.5 8.314 J mol-1 K 1 ( 202 K 298 K )

= 2.00 103 J

1
Total:

Page 2 of 9

[5]
20

QUESTION 2
Solution:

Mark
[Sub
total]

a)
Sfusion = positive
Solid liquid, degree of randomness increases.
2
Svaporization = positive
Liquid gas, degree of randomness increases.

b)
Hfusion = positive
Solid liquid, attractive forces must be overcome.

vaporization = positive
Liquid gas, attractive forces must be overcome.

[4]

[4]

c)
i) at constant pressure
CV,m = Cp, m R
S = nCP ,m ln

350 K
3

= 1 mol + 1 8.314 J mol-1 K -1 ln

= 17.6 J K -1
Ti
150 K
2

Tf

ii) at constant volume

Tf
3
350 K
S = nCV ,m ln
= 1 mol 8.314 J mol-1 K -1 ln
= 10.6 J K -1
Ti
2
150 K

d)
Br2 (l, 1 atm) Br2 (g, 1 atm)

G = H TS ,
at equilibrium, G = 0,
H
Tb =
S
H = nH (products) nH (reactants)

H = nH (Br2 , g ) nH (Br2 , l) = 30.91 0 = 30.91kJ

Page 3 of 9

[7]

S = nS (products) nS (reactants)

S = nS (Br2 , g ) nS (Br2 , l) = 245.46 152.23 = 93.23J K 1

Tb =

H 3.091 10 4 J
=
= 331.5K
S
93.23J K 1

2
Total:

Page 4 of 9

[5]
20

PART B - QUESTION 3
Solution:

Mark
[Sub
total]

a)

the charge on an electrolyte lowers the chemical potential of the

electrolyte (due to the charges interact attractively with the solvent,
lowering the energy.)
when compared with an analogous solution of uncharged solute
molecules.

b)
It is impossible to create a solution of pure Na+ in water.
A counter ion is always required to give a solution that is
electrically neutral,
and this anion will always affect the measurement.

2
1

[3]

1
1

[2]

c) i)

m
, m = 1 mol/kg

m
1
Im =
m z2
2 i i i

a =

log = z+ z A I m
a) BaSO 4 (s) Ba 2+ (aq) + SO 2-4 (aq)

+ = 1,

=1

z+ = 2,

z = 2

c B 2+
K sp = ao
c

cBa2+ = cSO2-

cSO42 o
c

2
-10
= 1.08 10

CBa2+
K sp = o
C

Assume: = 1

2
-10
= 1.08 10

cBa 2+ = 1.039 10-5 mol L-1

Page 5 of 9

[4]

when = 1

cBa 2+ = 1.039 10-5 mol L-1

m
( + z+2 + z2 )
2
1.039 10-5
=
( 4 + 4 ) = 4.157 10-5 mol kg -1
2

I=

ln = 1.173 4 4.157 10-5 = 0.03025

[2]

= 0.97020
when = 0.970230
I=

cBa 2+ = 1.0711 10-5 mol L-1

1.0711 10-5
( 8 ) = 4.2846 10-5 mol kg -1
2

ln = 1.173 4 4.2846 10-5 = 0.03071

= 0.9698
when = 0.9698
I=

[2]

cBa 2+ = 1.0716 10-5 mole L-1

1.0716 10-5
( 8 ) = 4.2866 10-5 mol kg -1
2

ln = 1.173 4 4.2866 10-5 = 0.03072

= 0.9697

1
1

solubility = 1.07 10 mol L

-5

-1

[3]

3 iterations are sufficient.

ii)
b) I = 0.0010 mol kg -1
ln = 1.173 4 0.0010 = 0.148374

= 0.8621
2`

cBa2+
2
K sp = o ( 0.8621) = 1.08 10-10
c

cBa2+ = 1.2110-5 mol kg -1

1
Total:

Page 6 of 9

[4]
20

PART B - QUESTION 4
Solution:
a)

Mark
[Sub
total]

The half cell reactions are

NiOOH + H2O + e- Ni(OH)2 + OH4OH- O2 + 2H2O + 4e-

E = +0.52V
E = 0.401V

The overall reaction is

4 NiOOH + 2 H2O 4 Ni(OH)2 + O2

E = + 0.12V

nF o
4 96485 C mol-1 0.12 V
ln K =
E =
RT
8.314 J K -1mol-1 298.15 K
= 18.683

2
2

K = 1.30 108

[7]

b) i)

Oxidation: Zn (s) Zn2+ (aq) + 2 eReduction: Cu2+ (aq) + 2 e- Cu (s)

Overall: Zn (s) + Cu2+ (aq) Zn2+ (aq) + Cu (s)

E = 0.7618 V
E = 0.337 V
E = 1.099 V

2+
aZn
Q = 2+
aCu
o
o
Ecell
= Ecell

1
1

2+
RT aZn
ln 2+
nF aCu

, n = 2

[4]

[3]

[4]

ii)
Activities equal to molalities:

(8.3145 J mol K ) ( 298.15 K ) ln 0.300 = 1.094 V

= 1.099

0.200
( 2 ) ( 96, 485 C mol )
-1

o
cell

-1

-1

iii) Using :
m
a = , m = 1 mol/kg. Quantities a, and m denote activity,
m
activity coefficients and concentration.

Page 7 of 9

(8.3145 J mol K ) ( 298.15 K ) ln 0.0835 0.300 = 1.097 V

= 1.099

0.104 0.200
( 2 ) ( 96, 485 C mol )
-1

o
cell

-1

-1

iv)
Relative error:
11.094 V 1.0971 V
100% = 0.27%
1.097 V

Total:

[2]

20

QUESTION 5
Solution:

Mark
[Sub
total]

a) i)
1
1

[2]

1
1

[2]

1
1

[2]

1
1

[2]

has the greatest penetrating power through matter.

= 42 He 2+ , = 10 e , = energy having neither mass nor charge. (most
energetic)
ii)

has the greatest ionizing power.

= 42 He 2+ , with charge of 2+.

iii)

suffers the greatest defection in magnetic field.

= 10 e , its mass is much lighter than that of .

iv)

ray is emitted from the nucleus while

X-ray is produced in the electron shell. The X-ray is usually more
energetic.

Page 8 of 9

b) i)
15
O

0.693
N
t0.5
The shortest t0.5 would be the greatest activity.
A = N =

ii)
28
Mg with t0.5 = 21 h

[3]

t0.5
t0.5
100% 1
50% 2

25%

25 % left 2 t0.5
If 2 days 2 t0.5
Then, t0.5 1 day.

c) i)
Mass of proton = 1.0073 amu 10 = 10.073 amu
Mass of neutron = 1.0087 amu 10 = 10.087 amu
m = 0.173 amu

[3]

m = mass of (proton + neutron) nuclear mass

nuclear mass = mass of (proton + neutron) m
nuclear mass = (20.160 -0.173) amu = 19.987 amu

[3]

ii)

nuclear mass = atomic mass - mass of extranuclear electrons

Atomic mass = nuclear mass + mass of extranuclear electrons

Atomic mass = 19.987 amu + (10 5.48610-4 amu) = 19.992 amu

Total:

Page 9 of 9

[3]
20

CONFIDENTIAL

AS/APR 2010/CHM520

Avogradros number (NA) = 6.02214 1023 mol-1

Gas constant (R) = 8.314 J K-1 mol-1 or 0.0821 dm3 atm K-1 mol-1 or 0.0831 dm3 bar K-1 mol-1
1 Pa = 1 N m-2, 1 bar = 105 Pa, 1 atm = 101.325 kPa
RT/F at 25 oC = 0.02569 V mol, ln a = 2.303 log a
Faraday constant (F) = 96485 C mol-1

QUESTION 1
a) Two ideal gas systems undergo reversible expansion starting from the same pressure
(P) and volume (V). At the end of the expansion, the two systems have the same
volume. The pressure in the system that has undergone adiabatic expansion is lower in
the system that has undergone isothermal expansion. Explain this result without using
equations.
(4 marks)
b)

A cup of water at 278 K (the system) is placed in a microwave oven and the oven is
turned on for one minute, during which it begins to boil. State positive, negative or zero
for the following quantities. Explain your answer for each case.
i) Heat (q)
ii) Work (w)
iii) Change of internal energy (U)
(6 marks)

c)

One mole of an ideal gas at an initial pressure (Pi) of 2.00 bar undergoes adiabatic
expansion from an initial temperature (Ti) of 450 K to a final temperature (Tf) of 300 K.
i)
ii)

Calculate work done (wad) (in unit J).

Write an expression for the work done (w) in the isothermal reversible expansion of
the gas at 300 K from an initial pressure of 2.00 bar.
iii) What value of the final pressure (Pf) (in unit bar) under isothermal reversible
expansion would give the same value of wad under adiabatic expansion?
Assume that molar heat capacity at constant pressure (Cp,m) = 5/2 R.
(10 marks)

QUESTION 2
a) Classify the following processes as spontaneous or not spontaneous. Explain your
answer for each case.
i) The reversible isothermal expansion of an ideal gas.
ii) The vaporization of superheated water at 102 C and 1 bar.
iii) The constant pressure melting of ice at its normal freezing point by the addition of an
infinitesimal quantity of heat.
iv) The adiabatic expansion of a gas into a vacuum.
(8 marks)
Hak Cipta Universiti Teknologi MARA

CONFIDENTIAL

CONFIDENTIAL

AS/APR 2010/CHM520

b) Calculate the change in entropy (S) if 1 mol of liquid water is heated from 0 to 100 C
under constant pressure. Molar heat capacity under constant pressure (Cp,m) for water is
75.291 J K1 mol1.
The melting point (Tm) of water at the pressure of interest is 0 C and the enthalpy of
fusion (Hfus) is 6.0095 kJ mol1. The boiling point (Tb) is 100 C and the enthalpy of
vaporization (Hvap) is 40.6563 kJ mol1. Calculate S for the transformation H2O
(s, 0 C) H2O(g, 100 C).
(10 marks)
c) Under what conditions is dG 0 ; a condition that defines the spontaneity of a process?
(2 marks)
QUESTION 3
a) Calculate ionic strength (Im), mean activity coefficient ( ), and activity ( aAlCl3 ) for a
0.0250 molal solution of AlCl3 at 298 K. Assume complete dissociation.
Given that: A = 0.509 for aqueous solution at 25 oC.
(10 marks)
b)

Conductivity measurements were one of the first methods used to determine the
ionization constant of water (Kw). The ionization constant of water is given by the
following equation:

[ ] [

H + OH

K w = a + a =
H
OH
1M 1M
m
Given that: a = , m = 1 mol/kg. Quantities a, and m denote activity, activity
m
coefficients and concentration. Assume that 1 and water is a weak electrolyte with
degree of dissociation of .

i) Using the expression provided, show that the molar conductivity of pure water
( ) can be written as (H 2O ) = (1M )K w1 2 o H + + o OH - . Quantity o denotes
molar ionic conductivity at infinite dilution.
ii) Kohlrausch and Heydweiller measured the conductivity of water in 1894 and
determined that (H 2 O ) = 5.5 106 S m1 at 298 K. Using the information provided
in Table 1, determine Kw.

[ ( ) (

Hak Cipta Universiti Teknologi MARA

)]

CONFIDENTIAL

CONFIDENTIAL

Table 1.
Cation

H3O or H
NH4+
K+
Na+
Ag+
Ca+
Mg2+

Anion

( cm mol )
350.0
73.5
73.5
50.1
62.1
118.0
106.1
-1

AS/APR 2010/CHM520

-1

( cm2 mol-1)
199.2
78.1
76.3
76.8
71.4
40.8
159.6
(10 marks)
-1

OH
BrClINO3CH3COOSO42-

QUESTION 4
a) A current of 2.00 A is applied to a metal wire for 30 s. How many electrons pass through
a given point in the wire during this time?
Given that: 96500 C 1 mol e.
(4 marks)
b) Reaction of Hg2Cl2 (s) 2 Hg (l) + Cl2 (g) is referred.
i) Show the electrode half-reactions and standard cell potential (E).
ii) Calculate change of molar Gibbs free energy for the reaction
equilibrium constant (K) at 298.15 K for the reaction.

(G )

rxn

and the

Given that: Hg2Cl2 (s) + 2 e 2 Hg (l) + 2 Cl- (aq) E = + 0.26808 V

(8 marks)
c) Determine solubility constant (Ksp) for AgBr at 298.15 K using the electrochemical cell
described by Ag (s) AgBr (s) Br- (aq) Ag+ (aq) Ag (s).
Given that: AgBr + e- Ag + Br-

E = + 0.07133 V
(8 marks)

QUESTION 5
a) Complete the following nuclear equations and identify X in each case:
i)

235
92

1
U + 01n 87
35 Br + 3 0 n + X

ii)

235
92

72
U + 01n 160
62 Sm + 30 Zn + 4X

iii)

235
92

135
U + 01n 99
40 Sr + 52Te + 2X

(6 marks)

Hak Cipta Universiti Teknologi MARA

CONFIDENTIAL

CONFIDENTIAL

AS/APR 2010/CHM520

b) Nuclear waste disposal is one of the major concerns of the nuclear industry. In choosing
a safe and stable environment to store nuclear wastes, consideration must be given to
the heat released during nuclear decay. Consider the decay of 90 Sr (89.907738 amu):
1st decay:
The

90

90
38

Sr 9039Y + -10

half-life (t0.5) is 28.1 yr

Y (89.907152 amu) futher decays as follows:

2nd decay:

90
39

0
Y 90
40 Zr + -1

t0.5 = 64 h

Zirconium-90 (89.904703 amu) is a stable isotope.

i) By referring to Table 2, calculate the following for the 1st and the 2nd decays:
The mass defect (m) (in unit amu and kg)
The energy released (in unit J) for the decays
Given that:
1 amu = 1.6606 10-27 kg
1 J = 1 kg m2 s-2
Speed of light (c) = 2.9979 108 m s-1
Table 2
Particle
Electron
proton
neutron

Mass (amu)
0.00054858
1.007825
1.008665

ii) Starting with one mole of

90

Sr , calculate the number of moles (n) of

90

Sr that

will decay in one year.

iii) Calculate the amount of heat released (in unit kJ) corresponding to the number of
moles of 90 Sr decays to 90 Zr in ii).
(14 marks)

END OF QUESTION PAPER

Hak Cipta Universiti Teknologi MARA

CONFIDENTIAL

Faculty of Applied Science, UiTM

Final Exam Apr 2010

Course : Physical Chemistry II, CHM 520

First Examiner : Dr. Chan Chin Han
Second Examiner : Ms Hjh Mashiah Domat Shaharudin
Answer : 5 questions only

Page 1 of 11

QUESTION 1
Solution:

Mark
[Sub
total]

a)
In the system undergoing adiabatic expansion, all the work done must come
through the lowering of U, and therefore of the temperature.
By contrast, some of the work done in the isothermal expansion can come at
the expense of the heat that has flowed across the boundary between the system
and surroundings.
b) i)
q is positive
because heat flows across the system-surrounding boundary into the system.

[4]

1
1

ii)
w is negative
because the vaporizing water does work on the surroundings (expansion).
(w = PV)

1
1

iii)
U is positive
because the temperature increases and some of the liquid is vaporized.
(U = nCp,mT)

1
1

[6]

c)
i)

CV,m = Cp, m R

U = q + w, q = 0 for adiabatic process

3
wad = U = n(Cp, m R)T = 8.314J mol1 K 1 150K = 1.87 103 J
2
ii)

The total work of reversible expansion is

w = Vif PdV
V

Isothermal reversible expansion: (of a perfect gas)

PV = nRT
nRT
, T is constant
P=
V

w = Vif PdV
V

Page 2 of 11

[4]

dV
V
V
w = nRT ln f
Vi
For ideal gas:
P1V1 = nRT1 and P2V2 = nRT2
P1V1 nRT1
, when T1 = T2
=
P2V2 nRT2
Vf Pi
=
Vi Pf
w = nRT Vif
V

w = nRTln

Pi
Pf

[3]

iii)

ln

Pi
w
= ad
Pf
nRT

(2bar ) =
ln

1.87 103 J
(1mol) 8.314J mol-1 K -1 (300K )

Pf
(2bar ) = 0.472
Pf

[3]

Pf = 4.24 bar

Total:

20

QUESTION 2
Solution:

Mark
[Sub
total]

a)
i) is not spontaneous because the system and surroundings are in
equilibrium.

ii) is spontaneous because the equilibrium phase under the stated

conditions is a gas.

iii) is not spontaneous because the process is reversible.

iv) is spontaneous because at equilibrium, the density of a gas is

uniform throughout its container.

Page 3 of 11

[8]

b)
The heat input is the same for a reversible and an irreversible process.
S heating :

dq = dqreversible = nCP ,m dT

T
C
S = n P ,m dT = nCP ,m ln f
T
Ti
= 1 mol 753 J mol-1 K -1 ln

1
1

373.15 K
273.15 K

[4]

= 23.49 J K -1

S fusion =

H fusion
T fusion

Svaporization =

6009 J
= 22.00 J K -1
273.15 K

H vaporization
Tvaporization

40656 J
= 108.95 J K -1
373.15 K

Stotal = S fusion + Svaporization + Sheating = ( 22.00 + 108.95 + 23.49 ) J K -1

[6]

[2]

= 154.4 J K -1

c)
This is the case at constant T and P if no non-expansion work is
possible.
Total:

Page 4 of 11

20

PART B - QUESTION 3
Solution:

Mark
[Sub
total]

a)
I m = 1 i mi zi2
2
Im = 1

{[(0.025 3 ) + (0.075 1 )]}

2
2

I m = 0.15

log = z + z A I m
log = (3)( 1) 0.509 0.15 = 0.59

1
1
1

[3]

1
1
1

[3]

= 0.256
m
, m = 1 mol/kg

m
m
m
so, a = and a + = + +
m
m
a =

To the case of a compound MpXq that dissolves to give a solution of p cations

and q anions.
m+ = pmi and m- = qmi , mi = electrolytes stoichiometric molality.

[(a ) ][(a ) ]
p

[(a ) ][(a ) ]
p

p
q

p m+
q m
= ( + ) ( )
m
m

p
q

p pmi
q qmi
= ( + ) ( )
m
m

[(a ) ][(a ) ] = (
p

p
q
p
q mi
+ ) ( ) ( p ) (q )

[(a ) ][(a ) ] = (
p

[(a ) ][(a ) ]
p

p+q

mi

p+q
( p ) p (q )q
)

m
= ( p ) (q ) ( ) i
m

, where ( )

( + ) ( )
p

p+q

p+q

[a(Al ) ][a(Cl ) ]= (1) (3) [(0.256)(0.0250)]

3+ 1

p+q

1+ 3

[a(AlCl3 )] = 1.51 108

Page 5 of 11

1
1

[4]

b) i)
The conductivity of a weak electrolyte is given as
= o

The degree of disassociation is given by the equilibrium expression

H + OH

, [H+] = [OH-] = 1 M
K w = a + a =
H
OH
1M 1M

[ ] [

Kw =

2
(1M )2

1
1

= (1M )K w1 2

And, o is given as

( )

o (H 2O ) = o H + + o OH

Combining the above expressions yields the relationship of interest:

(H 2O ) = (1M )K w1 2 o H + + o OH

[ ( )

ii)

)]

( )

o H + = 0.3050S m 2 mol1 , o OH = 0.0199S m 2 mol1

[5]

(H 2O ) = 5.5 106 S m-1

Substituting these values in the expression derived in part (a) of this
question and rearranging to isolate Kw yields:

(H 2O )
Kw =
+

(1M ) o H + o OH

[ ( )

)]

o
Kw =
+

(1M ) o H + o OH

[ ( )

1
2

)]

5.5 10 6 S m -1
Kw =
2
-1
2
-1
(1M ) 0.0350 S m mol + 0.0199 S m mol

K w = 1.00 108
K w = 1.00 10

mol L 1 m

mol2 m 6 1000 L
2

14

1
[5]

Page 6 of 11


m
Kw =
(1 M ) ( H + ) + ( OH )

5.5 10 ? S m ?
=
2
?
2
?
1 M ( 0.0350 S m mol + 0.0199 S m mol
mol 2 L2
=1.00 10
mol2 m 6
?

= 1.00 10 ?

1 m3

1000 L

Total:

Page 7 of 11

20

PART B - QUESTION 4
Solution:
a)

Mark
[Sub
total]

Current (I) is equal to the amount of charge (Q) that flows per unit time
(t):
Q = It

= ( 2.00 A )( 30 s )

1
1

= 60.0 C
Coulombs of charge can be converted to number of electrons using the
charge per electron as follows:
96500 C 1 mol e.
Avogradros number (NA) = 6.02214 1023 mol-1
So, 1 e = 1.60210-19 C

1 e
20
( 60.0 C )
= 3.75 10 e
? 9

1.60
10
C

[4]

b) i)

Hg2Cl2(s) +2e- 2Hg(l) +2Cl-(aq)

2Cl-(aq) Cl2(g) + 2e-

E = + 0.26808 V
E = 1.35827 V

Hg2Cl2(s) 2Hg(l) +Cl2(g)

E= 1.09019 V

ii)
o
Greaction
= nFE o = 2 96485 C mol-1 1.09019 V =210.4 kJ mol-1

2 96485 C mol-1 1.09019 V

nF o
ln K =
E =
8.314 J K -1mol-1 298.15 K
RT
= 85.002

K = 1.21 1037

c)

The half cell and overall reactions are

R: Ag Ag+ + eE = 0.7996 V
L: AgBr + e Ag + Br
E = + 0.07133 V
Overall
AgBr Ag+ + Br-

E = 0.72827 V

Ksp = [Ag+][Br-]

[(

Q = a Ag

1
1
1

)][a(Br )], Q = K

sp

Page 8 of 11

[8]

At equilibrium E = 0,

RT
lnQ
nF
nFE
lnQ =
RT
0 = E

1 ( 0.72827V )
= 28.35
0.02569V
K sp = Q = 4.88 1013

lnQ =

Total:

[8]

20

QUESTION 5
Solution:

a)
i)
ii)
iii)

235
92 U
235
92 U
235
92 U

Mark
[Sub
total]

+ 01 n

+ 01 n

1
0n

87
146
1
35 Br + 57 La + 3 0 n
72
1
160
62 Sm + 30 Zn + 4 0 n
135
1

99
40 Sr + 52Te + 2 0 n

[6]

b) i)
In the 90Sr decay (1st decay), the mass defect is:
m = (mass 90Y + mass e) mass 90Sr

= [(89.907152 amu + 5.4857 104 amu) 89.907738 amu]

= 3.743 105 amu

AND
= (3.743 105 amu)

1g
6.022 10

23

amu

= 6.216 1029 g = 6.216 1032 kg

The energy change is given by:

E = (m)c2

= (6.126 1032 kg)(3.00 108 m/s)2

= 5.59 1015 kg m2/s2 = 5.59 1015 J

Page 9 of 11

[3]

Similarly, for the 90Y decay (2nd decay), we have

m = (mass 90Zr + mass e) mass 90Y

= [(89.904703 amu

104 amu) 89.907152 amu]

3
= 1.900 10 amu

AND
= (1.900 103 amu)

1g
6.022 1023 amu

= 3.156 1027 g = 3.156 1030 kg

and the energy change is:

E = (3.156 1030 kg)(3.00 108 m/s)2 = 2.84 1013 J

[3]

ii)
This calculation requires that we know the rate constant for the decay. From
the half-life, we can calculate .
=

0.693
0.693
=
= 0.0247 yr 1
28.1 yr
t1
2

To calculate the number of moles of 90Sr decaying in a year, we apply the

following equation:

dn
= n
dt

nt 1
t
no dn = 0 dt
n
no
= number of atoms present at time 0.
nt
= number of atoms present at time t.

[lnn]nnot = [dt ]to

n
ln t = t
no
ln

Nt
= t
N0

ln

x
= (0.0247 yr 1 )(1.00 yr)
1.00

where x is the number of moles of 90Sr nuclei left over. Solving, we obtain:
x = 0.976 mol 90Sr

Thus the number of moles of nuclei which decay in a year is

(1.00 0.976) mol = 0.024 mol

Page 10 of 11

[5]

This is a reasonable number since it takes 28.1 years for 0.5 mole of 90Sr to
decay.
iii)
Since the halflife of 90Y is much shorter than that of 90Sr, we can safely
assume that all the 90Y formed from 90Sr will be converted to 90Zr. The
energy changes calculated in part (i) refer to the decay of individual nuclei. In
0.024 mole, the number of nuclei that have decayed is:
0.024 mol

6.022 1023 nuclei

= 1.4 1022 nuclei
1 mol

Realize that there are two decay processes occurring, so we need to add the
energy released for each process calculated in part (i). Thus, the heat released
from 1 mole of 90 Sr waste in a year is given by:
The energy released in the above two decays is 5.59 1015 J (1st decay) and
2.84 1013 J (2nd decay). The total amount of energy released is:
(5.59 10

15

J) + (2.84 10

13

13

J) = 2.90 10

heat released = (1.4 1022 nuclei)

J.

2.90 1013 J
= 4.06 109 J = 4.06 106 kJ
1 nucleus

[3]

This amount is roughly equivalent to the heat generated by burning 50 tons of

coal! Although the heat is released slowly during the course of a year,
effective ways must be devised to prevent heat damage to the storage
containers and subsequent leakage of radioactive material to the surroundings.
Total:

Page 11 of 11

20

CONFIDENTIAL

AS/APR 2009/CHM520

Avogradros number (NA) = 6.02214 1023 mol-1

Gas constant (R) = 8.314 J K-1 mol-1 or 0.0821 dm3 atm K-1 mol-1 or 0.0831 dm3 bar K-1 mol-1
1 Pa = 1 N m-2, 1 atm = 101.325 kPa
RT/F at 25 oC = 0.02569 V mol, ln a = 2.303 log a
Faraday constant (F) = 96485 C mol-1
QUESTION 1
a) State True or False for the statement below and explain you answer.
i) The P-V work in a mechanically reversible process in a closed system always equals
-PV. Quantities P and V denote pressure and volume, respectively.
ii) For every cyclic process, the final state of the system is the same of the initial state.
(6 marks)
b) A strip of magnesium of mass 15 g is dropped into a beaker of dilute hydrochloric acid.
The atmospheric pressure is 1.0 atm and the temperature 25 C.
i) Write the balanced chemical equation for the above reaction.
ii) Calculate the work done (w) (in unit J) by the system as a result of the reaction.
(6 marks)
c) The constant-pressure heat capacity (Cp) of a sample of a perfect gas was found to vary
with temperature according to the expression Cp/(J K1) = 20.17 + 0.3665(T/K). When the
temperature (T) is raised from 25 to 200 C at constant pressure Calculate (in unit kJ):
i) Heat (q)
ii) Work (w)
iii) Change of internal energy (U)
iv) Change of enthalpy (H)
(8 marks)
QUESTION 2
Consider a system consisting of 2.0 mol CO2 (g), initially at 25 C and 10 atm and confined
to a cylinder of cross-section 10.0 cm2. It is allowed to expand adiabatically against an
external pressure of 1.0 atm until the piston has moved outwards through 20 cm. Assume
that carbon dioxide may be considered a perfect gas with constant-volume molar heat
capacity (CV,m) = 28.8 J K1 mol1. Calculate:
a)
b)
c)
d)
e)
f)

Heat (q) (in unit J)

Work (w) (in unit J)
Change of internal energy (U) (in unit J)
Change of temperature (T) and the final temperature (Tf) (in unit K)
Initial volume (Vi) and final volume (Vf) (in unit dm3)
Change of entropy for the system (Ssys) (hint: constant volume cooling followed by
isothermal expansion)
(20 marks)

Hak Cipta Universiti Teknologi MARA

CONFIDENTIAL

CONFIDENTIAL

AS/APR 2009/CHM520

QUESTION 3
a) The mobility () of a chloride ion in aqueous solution at 25 C is 7.91 10-8 m2 s-1 V-1.
Calculate the molar ionic conductivity ().
(3 marks)
b) The mobilities () of H+ and Cl- at 25 C in water are 3.623 10-7 m2 s-1 V-1 and 7.91 108
m2 s-1 V-1, respectively.
i) What proportion of the current [or transport number (I)] is carried by the protons in 103
M HCl (aq)?
ii) What fraction of the current do protons carry when the NaCl is added to 10-3 M HCl?
The final concentration of NaCl in the solution is 1.0 mol dm-3. The concentration of
10-3 M HCl does not vary after addition of NaCl is assumed. (hint: concentration (c)
as well as mobility governs the transport of current)
Given that of Na+ is 5.19 10-8 m2 s-1 V-1.
(7 marks)
c) The molar conductivity () of KBr solutions as a function of concentration (c) at 25 oC is
given in Table 1.
Table 1
c /10-3 M
0.25
0.36
0.50
0.75
1.00
1.60
2.00
5.00
10.00

/ S cm2 mol-1
150.16
149.87
149.55
149.12
148.78
148.02
147.64
145.47
143.15

i)

Write the relationship between the cell constant (Kcell) and the electrolytic
conductivity ().
ii) Write the relationship between and the .
1
iii) Verify that the follows the Kohlrausch law = o c 2 and determine

graphically the molar conductivity at infinite dilution (o) for KBr (in unit S cm2 mol1
).
iv) Determine the coefficient .
v) Use scientific calculator to calculate the slope, intercept and r2 for the figure
presented in iii).
(10 marks)

Hak Cipta Universiti Teknologi MARA

CONFIDENTIAL

CONFIDENTIAL

AS/APR 2009/CHM520

QUESTION 4
a) The cell of Ag | AgBr (s) | KBr (aq, 0.050 mol kg1) || Cd(NO3)2 (aq, 0.010 mol kg1) | Cd is
referred.
i) Show the electrode half-reactions, the overall reaction and standard cell potential
(E), reaction quotient (Q) and the Nernst Equation of the cell.
ii) Use the DebyeHckel limiting law to calculate activity coefficient ( ) of anion and

cation; and mean activity coefficient ( ) of anion and cation. Given that: A = 0.509
for aqueous solution at 25 oC.
iii) Use the Nernst equation to estimate the cell potential (E) at 25C of the cell which is
referred.
Given that:

AgBr (s) + e Ag (s) + Br- (aq),

E = 0.07 V.
(14 marks)

b) State True or False for the statement below and explain you answer.
i)

Doubling the coefficients in a chemical reaction will square the value of the
equilibrium constant (Kc).
ii) Doubling the coefficients in a chemical reaction will double the change in standard
Gibbs free energy (G).
iii) Doubling the coefficients in a chemical reaction will not change the standard cell
potential (E)
(6 marks)
QUESTION 5
a) Complete the following nuclear equations and identify X in each case:
i)

235
92

1
U + 01n 140
56 Ba + 3 0 n + X

ii)

235
92

90
U + 01n 144
55 Cs + 37 Rb + 2X

(4 marks)
b)

For 42

He (4.0026 amu), calculate the following by referring to Table 2:

i) The mass of total proton and neutron (in unit amu)

ii) The mass defect (m)
iii) The nuclear binding energy (BE) (in unit J) and the binding energy per nucleon
Given that:
1 amu = 1.6606 10-27 kg
1 J = 1 kg m2 s-2
Speed of light (c) = 2.9979 108 m s-1
(10 marks)

Hak Cipta Universiti Teknologi MARA

CONFIDENTIAL

CONFIDENTIAL

Table 2
Particle
Electron
proton
neutron

c) Tritium

AS/APR 2009/CHM520

Mass (amu)
0.00054858
1.007825
1.008665

( H ) is radioactive and decays by electron emission. Its half-life (t

3
1

1
1

3
1

0.5)

is 12.5 yr.

17

In ordinary water, the ratio of H to H atoms is 1.0 10 to 1.

i) Write a balanced nuclear equation for tritium decay.
ii) How many tritium atoms and disintegrations per minute will be observed in a 1.00
kg sample of water?
(6 marks)

END OF QUESTION PAPER

Hak Cipta Universiti Teknologi MARA

CONFIDENTIAL

Faculty of Applied Science, UiTM

Final Exam Nov 2009

Course : Physical Chemistry II, CHM 520

First Examiner : Dr. Chan Chin Han
Second Examiner : Ms Hjh Mashiah Domat Shaharudin
Answer : 5 questions only

Page 1 of 11

QUESTION 1
Solution:
a)

Mark
[Sub
total]

i)
False
In equilibrium, Pex = P, so

dw = -PexdV; dw = -PdV
1
The total work of reversible expansion is

w = Vif PdV
V

Isothermal reversible expansion: (of a perfect gas)

PV = nRT

nRT
, T is constant
V
V
w = Vif PdV
P=

dV
V
V
w = nRT ln f
Vi
w = nRT Vif
V

ii)
True

In a thermodynamic cycle, the overall change in a state function (from

the initial state to the final state and then back to the initial state again) is
zero.

Page 2 of 11

[6]

b) i)
Mg (s) + 2 HCl (aq) H2 (g) + MgCl2 (aq)

ii)
The external, opposing pressure is 1.0 atm and Vi 0,

Molar mass for Mg = 24.31 g mol-1

15 g
n=
= 0.617 mol
24.31 g mol1

w = PV , Pf = Pex
nRT
Vf =
Pf

w = Pex ( Vf Vi ) P exVf == Pf

nRT
= nRT
Pf

w = (0.617 mol) 8.314J K 1 mol1 (298.15K )

w = 1529J

c)
i)
T
H = Tif CpdT

[6]

H = 298 [20.17 + 0.3655(T/K )]d(T/K )

473

[ ]

0.3665 2
H = (20.17 )(473 298) +
T
2
H = 28.3kJ

473
298

ii)
q = H = 28.3 kJ
iii)
w = PV , Pf = Pex
w = (PV) , PV = nRT
w = nRT
w = -(1 mol) (8.314 J K-1 mol-1) (473 K 298 K)
w = -1.45 kJ

[3]

[1]

iv)
U = q + w
U = 28.3 -1.45 = 26.8 kJ
Total:

Page 3 of 11

[2]

1
1

[2]
20

QUESTION 2
Solution:

Mark
[Sub
total]

a)
q = 0 for adiabatic process
1
b)
w = PexV

106 m3
= 20J
w = 1.01 105 Pa (20cm ) 10cm 2
3
cm
Note: 1 Pa m3 = 1 J

[1]

[2]

c)
U = q + w
U = 0 - 20 = -20 J

[1]

d)
U = nCV,mT

20J
= 0.347 K
T =
(2mol) 28.8J K 1 mol1

Tf = Ti + T = 298.15 0.347 = 297.803 K

[3]

e)
Vi =

Vi

nRT
Pi

(
2.0mol)(0.08206dm3 atm K 1 mol1 )(298.15K )
=
= 4.893dm3

10atm

Vf = Vi + V = 4.892 + 0.2 = 5.093 dm3

f)
Ssys = S1 + S2
Cooling the system from 298.15 K to 297.803 K at 4.893 dm3 (constant
volume cooling)
dq rev
f
, dqrev = CV,mdT
S 2 = i
T
C dT
T
S 2 = Tif n V, m
T

Page 4 of 11

[3]

T
S 2 = nCV, m ln f
Ti
J 297.803K

1
S 2 = (2mol) 28.8
ln
= 0.0671J K

.
K
mol
298
15
K

[3]

Isothermal reversible compression of an ideal gas from 10 to 1 atm at

297.803 K
PV = nRT
nRT
, T is constant
P=
V
V
w = Vif PdV

V dV
w = nRT Vif
V
Vf
w = nRT ln
Vi

U = 0, qrev = -wrev
V
qrev = nRT ln f
Vi

qrev
, when T = constant
T
V
S1 = nR ln f
Vi

S1 =

J 5.093dm3

= 0.666J K 1
S1 = (2mol) 8.314
ln
3

.
K
mol
4
893
dm

Ssys = S1 + S2

[5]

Ssys = ( 0.0671 + 0.666 )J K 1

Ssys = 0.60J K 1

1
Total:

Page 5 of 11

[2]
20

PART B - QUESTION 3
Solution:

Mark
[Sub
total]

a)
= zF

= (1) 7.91 10 m s V
8

)(96485C mol ) = 7.63 10

1

S m mol
2

1
2

[3]

b) i)

I+ = z++pcFEA for I+ and the equivalent term for I-.

z+ p+
z q
t+ =
t =
z+ p+ + z q
z + p+ + z q

In the special case where z+ = z- and necessarily, p = q,

t+ =

tH + =
ii)

+
+ +

t =

+ +

3.623
= 0.82
3.623 + 0.791

( )
(
) ( )
c (H )
=
c (H + Na ) + c (Cl )
(1.0 10 )(3.623)
=
(1.0 10 )(3.623) + (1.0)(0.519) + (1.001)(0.791) = 0.0028

I+ H+
; I+ = z++pcFE, so I+ = constant +c
t+ =
I + H + + Na + + I Cl
t+

+ +

+ +

t+

1
2

c) i)

=
ii)

K cell
, R = resistance
R

Page 6 of 11

[3]

[4]

iii)

c /10-3 M

c (mol L-1)

0.25
0.36
0.50
0.75
1.00
1.60
2.00
5.00
10.00

0.00025
0.00036
0.00050
0.00075
0.00100
0.00160
0.00200
0.00500
0.01000

c1/2
(mol1/2 L-1/2)
0.01581
0.01897
0.02236
0.02739
0.03162
0.04000
0.04472
0.07071
0.10000

/ S cm2
mol-1
150.16
149.87
149.55
149.12
148.78
148.02
147.64
145.47
143.15

For strong electrolyte in dilute solution;

= c 12 (Kohlrauschs law)
o

o = molar conductivity at infinite dilution (extrapolation at

vs

c = 0 of a plot

c.

152

Interceipt= 151.41
slope = -83.30
r = 0.9996

(S cm2 mol-1)

150

148

146

144

142
0.00

0.02

0.04

0.06

0.08

0.10

0.12

c1/2 ( mol1/2 L-1/2)

o = 151.41 S cm mol
2

-1

iv) K = -83.30

v)
From the calculation of scientific calculator.
Interceipt= 151.41
slope = -83.30
r = 0.9996

Total:

Page 7 of 11

[10]

20

PART B - QUESTION 4
Solution:

Mark
[Sub
total]

a) i)
R: Cd2+ (aq) + 2e Cd (s)
L: 2AgBr (s) + 2e 2Ag (s) + 2Br- (aq),

E = -0.40 V
E = 0.07 V

Overall,
R L: Cd2+ (aq) + 2Ag (s) + 2Br- (aq) Cd (s) + 2AgBr (s)

E = -0.47 V (R-L)

Q=

[3]

[a(Cd )][a (Br )]

2+

E = E

RT
1
ln
2+
2

a Br
2 F a Cd

)][ ( )]

[(

)][ ( )]}

m
, m = 1 mol/kg
m
m
m
so, a = and a+ = + +
m
m
2+

a Br = m and a Cd = + m+

{[ (

RT
E=E +
ln a Cd 2 + a 2 Br
2F

[2]

ii)

a =

( )

( )

Br = (KBr ) and + Cd 2 + = [Cd(NO)2 ]

For anion Br-:

I m = 1 i mi zi2
2
Im = 1

{[(0.050 1 ) + (0.050 1 )]}

2

I m = 0.05

log = z + z A I m

log = (1)( 1) 0.509 0.05 = 0.11

= + = = 0.769 ; (Br ) = (KBr )

Page 8 of 11

[3]

For anion Cd2+:

I m = 1 i mi zi2
2
Im = 1

{[(0.010 2 ) + (0.020 1 )]}

2
2

I m = 0.03

log = z + z A I m

log = (2 )( 1) 0.509 0.03 = 0.176

= + = = 0.838 ; + (Cd

iii)

2+

) = [Cd(NO) ]

[2]

{[ (

)][ ( )]}
( )
( )
= = = 0.769 ; (Br ) = (KBr )
= = = 0.838 ; (Cd ) = [Cd(NO) ]

RT
ln a Cd 2 + a 2 Br
2F
a Br = m and a Cd 2 + = + m+
E = E +

2+

RT
2
ln [+ m+ ][ m ]
2F
0.02569 V mol
2
2
E = ( 0.47 V ) +
ln [(0.838)(0.01)] (0.769 ) (0.05)
2mol

E = ( 0.47 V ) + ( 0.145V ) = 0.62V

E = E +

]}

2
1

b) i)
True.
A+BC

Kc =

[C]
[A][B]

[4]

When 2A + 2B 2C

K"c =

[C]2 = K 2
c
[A]2 [B]2

ii) True
A+BC

G = x

When 2A + 2B 2C

G" = 2 x = 2G

iii) True
E is an intensive property.
They do not depend on how many times the reaction occurs.
Page 9 of 11

1
1

[6]

As long as the concentrations of ions and gases are 1 M or 1 atm, E is a

constant and not dependent on the coefficients in the balanced equation.
Total:

20

QUESTION 5
Solution:

Mark
[Sub
total]

a)
i)

235
92 U

+ 01 n

140
56 Ba

+ 3 01 n +

ii)

235
92 U

+ 01 n

144
55 Cs

90
37 Rb

93
36 Kr

+ 2 01 n

b) i)
4
2 He

2 11 p + 2 01 n (There are 2 protons and 2 neutrons in the helium

nucleus.)
1

The mass of 2 protons is:

(2)(1.007825 amu) = 2.015650 amu
the mass of 2 neutrons is:
(2)(1.008665 amu) = 2.017330 amu

The predicted mass of 42 He is 2.015650 + 2.017330 = 4.032980 amu

ii)
the mass defect is:
m = 4.032980 amu 4.0026 amu = 0.0304 amu

iii)
The energy change (E) for the process is
E = (m)c2
= (0.0304 amu)(3.00 108 m/s)2
= 2.74 1015

amu m 2

s2

Lets convert to more familiar energy units (J/He atom).

2.74 1015 amu m 2
1s

1.00 g
6.022 10

23

amu

1 kg
1J

= 4.55 1012 J
1000 g 1 kg m 2
s2

Page 10 of 11

[4]

nuclear binding energy per nucleon =

nuclear binding energy

number of nucleons

For the helium-4 nucleus,

nuclear binding energy per nucleon =

4.55 1012 J/He atom

= 1.14 1012 J/nucleon
4 nucleons/He atom

[10]

c)
i)
3
1H

3
2 He

0
1

The number of tritium (T) atoms in 1.00 kg of water is:

(1.00 103 g H 2 O)

1 mol H 2 O
6.022 1023 molecules H 2 O 2 H atoms
1 T atom

18.02 g H 2 O
1 mol H 2 O
1 H2O
1.0 1017 H atoms

= 6.68 108 T atoms

The number of disintegrations per minute will be:

rate = (number of T atoms) = N =

0.693
N
t1
2

0.693
1 yr
1 day
1h
8

rate =
6.68 10 T atoms
12.5 yr 365 day 24 h 60 min

1
1

[6]

rate = 70.5 T atoms/min = 70.5 disintegrations/min

Total:

Page 11 of 11

20