CM1502 Tutorial 2

1
1)
For the process going from A to B to C, what is S
at point A, B and C?
[C
p,m
: H
2
O (s) = 37.7 JK
-1
mol
-1
(273K); H
2
O (l) =
75.3 JK
-1
mol
-1
(298 K); H
2
O (g) = 37.5 JK
-1
mol
-1

(373 K) and H
fus
at 273 K is 6.0 kJmol
-1
and
H
vap
at 373 K is 40.8 kJmol
-1
.] For calculations,
assume that point A is 0.1 K.
Point A
S = 0 JK
-1
Point B
S
298 K
= C
p,s
ln(T
2
/T
1
) + H/T + C
p,l
ln(T
3
/T
2
)
= 37.7 ln(273/0.1) + 6000/273 + 75.3 x ln(298/273)
= 298.3 + 22.0 + 6.6
= 326.9 JK
-1
Point C
S
393 K
= S
298 K
+ C
p,l
ln(T
4
/T
3
) + H/T + C
p,g
ln(T
5
/T
4
)
= 326.9 + 75.3 x ln (373/298) + 40800/373 K
+ 37.5 x ln (393/373)
= 326.9 + 16.9 + 109.4 + 2.0 = 455.2 JK
-1
Assume C
p
constant over the T range
3
2) A Carnot cycle uses 1.00 mol of a monatomic perfect gas as the working
substance from an initial state of 10.0 atm and 327C. It expands isothermally to
a pressure of 1.00 atm using 11.49 kJ of heat (step 1), and then
adiabatically to a temperature of 27C (step 2). This expansion is followed by
an isothermal compression (step 3) releasing 5.74 kJ of heat, and then an
adiabatic compression (step 4) back to the initial state. Determine S for
each stage of the cycle and for the cycle as a whole. Calculate the efficiency of
this cycle.
S = q
H
/ T
H
= 11.49 kJ / (327 + 273) K = 11490 J / 600 K
= 19.15 JK
-1
300 K = T
C
11.49 kJ
5.74 kJ
S = 0 as q = 0
S = 0 as q = 0
10.0 atm, 600 K = T
H
1.0 atm, 600 K
S = q
C
/ T
C
= -5.74 kJ / (27 + 273) K = -5740 J / 300 K
= -19.13 JK
-1
4
For whole cycle, S = q
H
/ T
H
+ q
C
/ T
C

= 19.15 + -19.13 = 0.02 JK
-1
0 JK
-1
Efficiency () = 1 T
C
/ T
H

= 1 (27 + 273) / (327 + 273) = 1 300 / 600 = 0.5
5
3) Metallic aluminium is an effective reagent for the reduction of oxides of some other
metals, as in the thermite reaction:

2Al (s) + Fe
2
O
3
(s) Al
2
O
3
(s) + 2Fe (s) (G
f
(Al
2
O
3
(s))= -1576.5 kJmol
-1
)

For each of the following oxides, decide which cannot be reduced by aluminium:
(a) CuO (G
f
= -127.2 kJmol
-1
),
(b) ZnO (G
f
= -318.2 kJmol
-1
),
(c) CaO (G
f
= -604.2 kJmol
-1
).
kJ 1194.9
0) 2 2 . 127 3 ( 0) 3 5 . 1576 1 ( G
0



(a) 2Al (s) + 3CuO (s) Al
2
O
3
(s) + 3Cu (s)
kJ 621.9
0) 2 2 . 318 3 ( 0) 3 5 . 1576 1 ( G
0


2Al (s) + 3ZnO (s) Al
2
O
3
(s) + 3Zn (s) (b)
(c) 2Al (s) + 3CaO (s) Al
2
O
3
(s) + 3Ca (s)
kJ 1 . 236
0) 2 2 . 604 3 ( 0) 3 5 . 1576 1 ( G
0


CaO cannot be reduced by Al.
6
H
f
/ kJ mol
-1
G
f
/ kJ mol
-1

CuO(s) -155.2 -127.2
H
2
(g) 0 0
Cu(s) 0 0
H
2
O (g) -241.8 -228.6
4) Small amounts of hydrogen can safely be removed from gaseous mixtures by
reaction with cupric oxide at 200
o
C:

CuO (s) + H
2
(g) Cu (s) + H
2
O (g)

Find G
o
, H
o
, S
o
and K for this reaction at 298K using the data in the table.
Calculate the equilibrium constant at 200
o
C, assuming that H
o
is independent of
temperature.

kJ 6 . 86
0) 1 2 . 155 1 ( ) 8 . 241 1 0 1 ( H
0


kJ 4 . 101
0) 1 2 . 127 1 ( ) 6 . 228 1 0 1 ( G
0


0 0 0
S T H G
0
S 298 86.6 101.4
1 0
JK 49.7 S


7
vant Hoffs Law is used when we want to
calculate K at a different T.
ln (K
2
/K
1
) = (-H/R)(1/T
2
1/T
1
)
G
298 K
= RT lnK

-101400 = (8.314 x 298) lnK

K = 5.95 x 10
17

ln (K
2
/5.95 x 10
17
) = (86600/8.314)(1/473 1/298)
K
2
= 1.44 x 10
12

8
5) (a) Describe what is meant by microscopic states of a system.




(b) Calculate the number of microscopic states present in 1 mole of KCl (s) given
that S
m
at 298 K is 82.59 JK
-1
mol
-1
. (Your answer can take the form W = e
x
)










(c) What does the third law of thermodynamics state about microscopic states at 0
K and hence what is the entropy of a system at 0 K?
Each possible arrangement of the positions of particles, in the whole
system, is called a microstate."
Boltzmann equation: S = (R/N
A
) ln W = k ln W

82.59 JK
-1
mol
-1
= (8.314 JK
-1
mol
-1
/6.022 x 10
23
mol
-1
) ln W

ln W = 5.98 x 10
24



24
10 x 5.98
e W
S = k ln W = k ln 1 = 0 JK
-1
There is only one microstate at 0 K.
Third law: As a system approaches absolute zero temperature (0 K), all
processes cease and the entropy (disorder) of the system approaches a
minimum value (zero).