CHEMISTRY 123 Problem Set #4 Reversibility, Entropy

and Free Energy

Concept questions
1. In an imaginary experiment, you take a steel ball from the freezer and drop it in a
Styrofoam cup of water (an isolated system). You hypothesize that the water temperature
increases and the ball gets colder. Describe AS for this transition of the ball and water.
What can you conclude about your hypothesis?
This change in state requires negative heat flow from the cold body and positive heat flow to the
hot body. The sum of these heat flows divided by the respective temperatures is the total !S,
which is clearly negative. A negative entropy change cannot occur spontaneously in an isolated
system. This would violate the Second Law of Thermodynamics. The process described is
impossible.
2. Along the way to defining the quantity !G, we found that we could represent any state
change at constant P and T in terms of
!H T!S = T (!S + !S
surr
)

where we know that for any natural process the difference between state variables, !H
and T!S must be negative or zero.

The equation above allows us to recast this constraint entirely in terms of entropy: The
change in entropy of the system, !S, plus the change in entropy of the surroundings,
!S
surr
. What must be true of this sum for the state change to be natural (spontaneous)?
What must be true of this sum for the system to be at equilibrium?
For a state change to occur spontaneously, the sum, !S + !S
surr
, must be greater than zero (The
quantity T (!S + !S
surr
) must be less than zero). In other words, the combined entropy change
in the system and the surroundings must be greater than zero.

For the system to be at equilibrium, these two entropy changes must balance to total zero.

3. The T!S part of the entropy change condition of question 2 is obviously governed by T!S
in the system. What state variable change relates to the T!S
surr

term? Explain physically
how a change in this state variable determines an entropy change in the surroundings.
The entropy change in the surroundings is governed by the heat flow associated with the change
in state. For a reversible (equilibrium) process at constant P, !H =T !S
surr
.

4. Ideal solutions that obey Troutons Rule have AS

vap
= 88 J mol
1
K
1
? Water and
methanol fail to obey this rule. Verify this by calculating AS

vap
for water and methanol,
given the data in the table below. Explain why these liquids are special.

Example S

(J mol
-1
K
-1
)
H
2
O
(l)
70.0
H
2
O
(g)
188.7
CH
3
OH
(l)
126.3
CH
3
OH
(g)
239.9

Both methanol and water violate Troutons rule to some degree. AS

liq
for water is 118.7 J mol
-1

K
-1
while AS

liq
for methanol is 113.6 J mol
-1
K
-1
as opposed to 88 J mol
1
K
1
. The larger
deviation for water reflects the further constraint on the number of accessible arrangements
afforded by stronger hydrogen bonding.

Problems
3-6. When 44.0 g of solid carbon dioxide at 1.00 atm pressure are reversibly converted to vapour at
1 atm pressure and 78 C, 25.33 kJ of heat are absorbed by the system. The density of solid
CO
2
is 1.56 g cm
3
.

3. H for this process is (in kJ):
(1) 23.71 (2) +23.71 (3) 25.33 (4) +25.33 (5) +26.95
The answer is (4).
H is the heat transferred into or out of the system in a constant pressure process.

H = q
p
= +25.33 kJ
Note that H is positive because heat is absorbed by the system.

4. S for the process is (in J K
1
):
(1) 130.0 (2) 130.0 (3) 121.5 (4) 121.5 (5) 138.1
The answer is (1).
For a process carried out reversibly:
S =
T
q
rev

=
T
H
rev

(for a constant pressure process, q = H)

S =
K 195
J 25330 +
= +130.0 J K
1
(Entropy has increased, since the final state is a gas, which is more disordered than the initial
state solid form.)

5. G for the process is (in kJ):
(1) 50.66 (2) 50.66 (3) 46.71 (4) 46.71 (5) 0
The answer is (5).
G = 0 if the process is carried out reversibly; i.e., incremental steps are made between the initial
and final states such that the system is always in equilibrium.

6. If S of CO
2
(g) is 197.7 J K
1
mol
1
at 78 C, the standard entropy of solid CO
2
is (in J K
1
):
(1) 67.70 (2) 67.70 (3) 327.7 (4) 0 (5) 130.0
The answer is (1).
S = S(g) S(s)

S(s) = S(g) S
= (197.7 130.0) J K
1
= +67.7 J K
1



7. At 279 K and 1 atm pressure, pure benzene crystallizes reversibly with an entropy change of
35.66 J mol
1
K
1
. What is the molar heat of fusion of benzene (in kJ mol
1
) at its melting point?
C
6
H
6
(l) ! C
6
H
6
(s) at 1atm and 279 K, S = 35.66 J K
1
mol
1



T
H
T
q
S
rev

= =

H = TS (note: G = H TS = 0)
= 279 K (35.66 10
3
kJ mol
1
K
1
)
= 9.95 kJ mol
1


Therefore, for C
6
H
6
(s) C
6
H
6
(l), H = +9.95 kJ mol
1

810. Consider the following processes at constant T and P:

Process H S
(1) positive positive
(2) positive negative
(3) negative positive
(4) negative negative

Answer the following questions, using the process numbers as the answer choices:

8. Which processes are ALWAYS spontaneous?
9. Which processes can be both spontaneous or non-spontaneous (i.e. the spontaneity depends
on the temperature)?
10. Which processes are NEVER spontaneous?

8-10: 8: The answer is (3)
9: The answer is (1, 4)
10: The answer is (2)

G = H T S
(1) +, + + + non-spontaneous at low T, spontaneous at high T
(2) + + + never spontaneous
(3) + + always spontaneous
(4) ,+ + spontaneous at low T, non-spontaneous at high T

G < 0 for a spontaneous process.
G > 0 for a non-spontaneous process.
T is in Kelvin and is always positive.

1115. Consider the following data at 298 K:

Ag(s) H
2
S(g) O
2
(g) Ag
2
S(s) H
2
O(g)
H
f

(kJ mol
1
) 20.5 242
S

(J K
1
mol
1
) 42.6 206 205 189

For the reaction
4Ag(s) + 2H
2
S(g) + O
2
(g) 2Ag
2
S(s) + 2H
2
O(g)
at a temperature of 25 C, H = 507 kJ and S = 119 J K
1
.

11. H
f
of Ag
2
S (s) is (in kJ mol
1
):
(1) +475 (2) 32 (3) 64 (4) 285.5 (5) 728.5

The answer is (2).
H = _
moles
H
f
(products) _
moles
H
f
(reactants)

507 kJ = 2 mol H
f
(Ag
2
S) + 2 mol (242 kJ mol
1
)
4 mol (0 kJ mol
1
) 2 mol (20.5 kJ mol
1
) 1 mol (0 kJ mol
1
)

H
f
(Ag
2
S) = 32 kJ mol
1


12. S of Ag
2
S (s) is (in J K
1
mol
1
):
(1) 290.4 (2) 264.2 (3) 145.6 (4) 145.2 (5) 383.6
The answer is (4).
S = _
moles
S(products) _
moles
S(reactants)

119 J K
1
= 2 mol S(Ag
2
S) + 2 mol (+189 J mol
1
K
1
)
4 mol (42.6 J mol
1
K
1
) 2 mol (206 J mol
1
K
1
) 1 mol (205 J mol
1
K
1
)

S(Ag
2
S) = +145.2 J mol
1
K
1


13. G for the reaction is (in kJ):
(1) + 396.3 (2) 471.5 (3) 43302 (4) 75300 (5) 35.6
The answer is (2).
G = H TS
= 507,000 J (298K)(119 J K
1
)
= 471,538 J = 471.5 kJ

14. K for the reaction is:
(1) 2.2 10
83
(2) 1.9 10
2
(3) 3.4 10
70
(4) 5.25 (5) 4.5 10
82

The answer is (5).
G = RT lnK

471,538 J = (8.314 J mol
1
K
1
)(298K) ln K
ln K = 190.32
K = 4.5 10
82


15. If the reaction were to occur at a higher temperature, more Ag
2
S(s) would be formed.
(1) True (2) False
The answer is (2).
H < 0. The reaction is exothermic:

4Ag(s) + 2H
2
S(g) + O
2
(g) 2Ag
2
S(s) + 2H
2
O(g) + heat

16. For the reaction Cl
2
(g) 2Cl(g), S is likely to be:
(1) positive (2) zero (3) negative
The answer is (1).
For each mole of Cl
2
(g) reacted, two moles of Cl(g) atoms are produced. A system with more
particles will be more disordered than one with fewer particles; hence, S is positive.

17. For the reaction,
N
2
(g) + O
2
(g) ! NO(g),
K = 1.11 10
2
at 1800 K, and 2.02 10
2
at 2000 K. The enthalpy of reaction at 2000 K is nearest
to (in kJ):
(1) 89.6 (2) 90.3 (3) 90.3 (4) 89.6 (5) 0.0896
The answer is: (4).
G = H TS = RT lnK

Assume H and S are independent of T; i.e. S(T
1
) = S(T
2
).

ln K
1
=
R
S
RT
H
1

+

ln K
2
=
R
S
RT
H
2

+



ln K
1
ln K
2
=
!
"
#
$
%
&

1 2
T
1
T
1
R
H


ln
'
'
(
)
*
*
+
,
2
1
K
K
=
!
"
#
$
%
&

1 2
T
1
T
1
R
H


H =
1 2
2
1
T
1
T
1
K
K
ln R

'
'
(
)
*
*
+
,

=
K 1800
1
K 2000
1
10 02 . 2
10 11 . 1
ln
J 1000
kJ 1
K mol J 314 . 8
2
2
1 1

'
'
(
)
*
*
+
,

= 89.6 kJ mol
1


18. Consider the following data (values are tabulated at 25 C and 1 atm pressure):

NO(g) O
3
(g) NO
2
(g) SO
2
(g) O
2
(g) SO
3
(g)
H
f
(kJ mol
1
) +90.39 +142.1 +33.9 296.8 0.0 394.6
G
f
(kJ mol
1
) +86.5 +163.0 +51.8
S (J mol
1
K
1
) +248.3 +204.8 +255.8

(a) Calculate G, H, S, and K at 25 C for the reaction,
NO (g) + O
3
(g) ! NO
2
(g) + O
2
(g)
G = +51.8 + 0 86.5 163.0 = 197.7 kJ
H = +33.9 + 0 90.39 142.1 = 198.5 kJ

G = H TS

1
1
K J 0 . 3
K kJ 00299 . 0
298
) 7 . 197 ( ) 5 . 198 (
T
G H
S

=
=

=

=


G = RT lnK

8 . 79
) 298 )( 314 . 8 (
) 10 7 . 197 (
RT
G
K ln
3
+ =

=

=


K = 4.5 10
34


(b) For the reaction,
SO
2
(g) + O
2
(g) ! SO
3
(g)
calculate H, S, G, and K at 25 C. Assuming that H and S do not change with
temperature, also calculate K at 327 C.

H = 394.6 (296.8) (0) = 97.8 kJ
S = +255.8 (+248.3) (204.8) = 94.9 J K
1

At 25 C (298 K):

G = H TS
= 97.8 298(94.9 10
3
) = 69.5 kJ

05 . 28
) 298 )( 314 . 8 (
) 10 5 . 69 (
RT
G
K ln
3
+ =

=

=

K = 1.52 10
12


At 327 C (600 K):

G = H TS
= 97.8 600(94.9 10
3
) = 40.86 kJ

19 . 8
) 600 )( 314 . 8 (
) 10 86 . 40 (
RT
G
K ln
3
+ =

=

=


K = 3.6 10
3


19. Suppose you have to investigate the thermodynamic feasibility of converting coal and hydrogen
at 25 C either to a synthetic natural gas such as propane, C
3
H
8
, or to the industrially useful
acetylene, C
2
H
2
. For simplicity, the properties of coal are assumed to be the same as those of
graphite. The relevant thermodynamic data are given in the following table:

C(s,graphite) H
2
(g) C
3
H
8
(g) C
2
H
2
(g)
H
f,298
(kJ mol
1
) 0 0 103.75 226.51
S
298
(J mol
1
K
1
) 5.68 130.46 269.65 200.64

(a) Calculate the enthalpies, entropies, and free energies of formation of (i) propane and (ii)
acetylene from graphite and hydrogen.
(i) 3C(s) + 4H
2
(g) C
3
H
8
(g)

H = 103.75 kJ mol
1

S = +269.65 3(5.68) 4(130.46)
= 269.23 J K
1
mol
1

G = H TS
= 103.75 298(269.23 10
3
)
= 23.52 kJ mol
1


(ii) 2C(s) + H
2
(g) C
2
H
2
(g)

H = +226.51 kJ mol
1

S = +200.64 2(5.68) (130.46)
= +58.82 J K
1
mol
1

G = H TS
= +226.51 298(58.82 10
3
)
= +208.98 kJ mol
1


(b) Calculate the equilibrium constants at 25 C for the reactions of graphite and hydrogen to form
propane and to form acetylene.


(i) 3C(s) + 4H
2
(g) C
3
H
8
(g)
493 . 9
) 298 )( 314 . 8 (
) 10 52 . 23 (
RT
G
K ln
3
+ =

=

=


K = 1.33 10
4


(ii) 2C(s) + H
2
(g) C
2
H
2
(g)
35 . 84
) 298 )( 314 . 8 (
) 10 98 . 208 (
RT
G
K ln
3
=
+
=

=


K = 2.33 10
37


(c) From the results of (a) and (b) decide whether either of these processes is thermodynamically
feasible, and, if so, discuss what other factors would be involved in making them practical.

Formation of propane is thermodynamically feasible (G < 0). Formation also depends on
kinetics (relative to formation of other possible products).
Formation of acetylene is not thermodynamically feasible (G > 0).

20. Dinitrogen tetroxide, N
2
O
4
, dissociates reversibly into nitrogen dioxide, NO
2
, according to the
following reaction:
N
2
O
4
(g) ! 2NO
2
(g)
Some thermodynamic data for these compounds at 25 C are as follows:

Compound H
f
(kJ mol
1
) S (J mol
1
K
1
)
N
2
O
4
9.66 303.9
NO
2
33.15 240.4

(a) Calculate the standard free energy change, G, at 25 C for the above reaction.
H = 2(33.15) (9.66) = +56.64 kJ
S = 2(240.4) (303.9) = +176.9 J K
1

G = H TS
= 55.64 298(176.9 10
3
)
= +3.92 kJ

(b) Calculate the equilibrium constant for the reaction at 25 C.
G = RT lnK
58 . 1
) 298 )( 314 . 8 (
) 10 92 . 3 (
RT
G
K ln
3
=
+
=

=


K = 0.205

(c) At what temperature will the equilibrium constant for the reaction be equal to one? (Assume H
and S do not vary with temperature.)
K = 1, lnK = 0, G = RT lnK = 0
Also, G = H TS = 0
K 320
K J 9 . 176
J 10 64 . 56
S
H
T
1
3
=

=


=

(d) Calculate G for one mole of reaction if each gas were at 100 atmospheres partial pressure
(assume ideal behaviour).
kJ 3 . 15
41 . 11 92 . 3
100
) 100 (
ln ) 298 )( 10 314 . 8 ( 99 . 3
P
P
ln RT G
Q ln RT G G
2
3
O N
2
NO
4 2
2
=
+ + =
+ + =
+ =
+ =

21. Assume that all gases are ideal. For ideal gases, PV = nRT, and R = 8.314 J K
1
mol
1
. One
possible way to make dinitrogen trioxide (N
2
O
3
) is through the following reaction:
NO(g) + NO
2
(g) ! N
2
O
3
(g)
At 298.15 K, the basic thermodynamic quantities are given below:

Substance AH
f
(kJ mol
1
) S (J mol
1
K
1
) AG
f
(kJ mol
1
)
NO(g) 91.3 210.8 87.6
NO
2
(g) 33.2 240.1 51.3
N
2
O
3
(g) 82.8 314.6

(a) What is the heat of reaction under constant pressure at 298.15 K under standard conditions?
q
p
= AH
AH = _
moles
AH
f
(products) _
moles
AH
f
(reactants)
= 82.8 (91.3 + 33.2)
= 41.7 kJ

(b) Calculate AS, AE, and AG for this reaction at 298.15 K?
AS = _
moles
S(products) _
moles
S(reactants)
= 314.6 (210.8 + 240.1) = 136.3 J K
1


AG= AH TAS
= 41.7 298.15 (136.3 10
3
) = 1.1 kJ

AE = AH A(PV)
= AH A(nRT)
= AH (An)RT
= 41.7 (1) 8.314 298.15 10
3
= 39.2 kJ

(c) Evaluate the standard Gibbs free energy of formation, AG
f
, of N
2
O
3
(g) at 298.15 K.
AG = _
moles
AG
f
(products) _
moles
AG
f
(reactants)

1.1 = AG
f
(N
2
O
3
) (87.6 + 51.3)
AG
f
(N
2
O
3
) = 137.8 kJ mol
1


(d) Evaluate the equilibrium constant, K, at 298.15 K.
AG = RT lnK

lnK = AG/(RT)

lnK = (1.1)/(8.314 298.15 10
3
) - 0.44

K - e
0.44
- 1.6

(e) Write an expression for the equilibrium constant in terms of activities and in terms of partial
pressures.
a
N2O3(g)
P
N2O3(g)

K = -
a
NO(g)
a
NO2(g)
P
NO(g)
P
NO2(g)


(f) Could this reaction be used to mass produce N
2
O
3
at 298.15 K? Give reasoning for your answer.
Yes. Because AG = 1.1 kJ < 0.

(g) Will increasing the temperature favour the production of N
2
O
3
? Give reasoning for your answer.
No.
AH = 41.7 kJ < 0
Decreasing T favours exothermic reaction.

(h) If a chemical factory operating under standard conditions is built in a desert near the equator in
Australia, where the temperature stays above 35 C during the entire year, will N
2
O
3
be produced
spontaneously by using this reaction? Assume that AS and AH

do not change with the
temperature. Give reasoning for your answer.

AG = AH TAS < 0 for spontaneous process.

AH < TAS, AS = 136.3 J K
1
< 0
T < AH/AS = T
0
for spontaneous process.

T
0
= AH/AS = 41.7/(136.3 10
3
) - 305.9 K = 32.8 C

When T = 35 C > T
0
= 32.8 C, AG > 0
Thus, non-spontaneous.



Alternatively, use the vant Hoff equation and equilibrium constant.

AG = RT lnK < 0 for spontaneous process

Hence, lnK = AG/(RT) > 0 for spontaneous process

For lnK > 0, K > 1 for spontaneous process

Lets calculate K
2
at T
2
= 35 C = 308.15 K,
with K
1
at T
1
= 25 C = 298.15 K and AH = 41.7 kJ,
using the vant Hoff equation:
ln(K
1
/K
2
) = (AH/R) (T
2
1
T
1
1
)

ln(K
1
/K
2
) = 41.7/(8.314 10
3
) (308.15
1
298.15
1
) - 0.55
K
1
/K
2
- e
0.55
- 1.73

K
2
- K
1
/1.73 - 1.6/1.73 - 0.9 < 1
Thus, non-spontaneous.

22. The standard free energy change (AG) for the hydrogenation of ethylene, shown below, is
101 kJ at 25 C. Assume all gases are ideal; PV nRT.

CH
2
=CH
2
(g) + H
2
(g) CH
3
CH
3
(g)

(a) By inspection of the above reaction, predict the sign of the standard entropy change (AS) for
this reaction at 25 C:
(1) negative (2) positive (3) zero (4) cannot be determined from the given data
The answer is (1).
Two units of gas turn into one unit of gas. Thus, the entropy decreases.

(b) The above reaction is:
(1) endothermic (2) exothermic (3) neither (4) cannot be determined from the given data
The answer is (2).
AG = 101 kJ < 0
AS < 0 (result from (a))
Thus, AH = AG + TAS < 0, exothermic

(c) If the temperature is increased, the equilibrium will shift:
(1) to the right (2) to the left (3) neither way (4) cannot be determined from the given data
The answer is (2).
Increasing T favours endothermic reaction. Because the forward reaction is exothermic, the
reverse reaction is endothermic. Then, the equlibirum will shift to the left (in the reverse
direction) as T increases.

(d) Calculate the Q for the reaction when the three gases are present at a partial pressure of 1 atm
each.
a
C2H6(g)

Q =
a
C2H4(g)
a
H2(g)


P
C2H6(g)
1
- = = 1
P
C2H4(g)
P
H2(g)
11

(e) Calculate the free energy change (AG) for the reaction when the three gases are present at a
partial pressure of 1 atm each.
AG = AG + RT lnQ
= AG + RT ln1
= AG
= 101 kJ

(f) Under the conditions of 25(e):
(1) The reaction is at equilibrium.
(2) The reaction will shift to the right.
(3) The reaction will shift to the left.
(4) Shifts cannot be determined from the given data.
The answer is (2).
AG = 101 kJ < 0, the forward reaction is spontaneous.

23. The white pigment TiO
2
(s) can be prepared by the hydrolysis of titanium tetrachloride in the gas
phase according to the reaction:
TiCl
4
(g) + 2H
2
O(g) ! TiO
2
(s) + 4HCl(g)
At 25 C, its equilibrium constant K = 1.55 10
15
, and the AH
f
data are given below:

TiCl
4
(g) H
2
O(g) TiO
2
(s) HCl(g)
AH
f
(kJ mol
1
) 763.2 241.8 944.7 92.3

This reaction is carried out at 25 C. Assume all gases are ideal (PV = nRT).
(a) Calculate AH
(b) Calculate AG
(c) Calculate AE
(d) Calculate AS
(e) Calculate K for this reaction at 100 C. What assumptions have you made in your calculation?
(f) Write the expression for K in terms of activities.
(g) At constant temperature, if 0.3 atm HCl(g) are added to the system after equilibrium is reached,
K will (circle one):
(1) increase (2) decrease (3) stay the same (4) cannot be determined from the given data
Give reasoning for your answer.
With the expression k, do you put
all the compounds--s/l/g?
(a) AH = _
moles
AH
f
(products) _
moles
AH
f
(reactants)
= (92.34 944.7) (241.82 763.2) = 67.1 kJ

(b) AG = RT lnK
= 8.314 10
3
298.15 ln(1.5510
15
) = 86.7 kJ

(c) AH = AE + A(PV)

AE = AH A(PV) (ignoring volume change of solid)
= AH A(nRT) (assuming ideal gas)
= AH (An)RT (at constant T)
= 67.1 (43) 8.314 298.15 10
3
= 69.6 kJ

(d) AG = AH TAS
AH AG
AS =
T
67.1 (86.7)
= = 0.0657 kJ K
1
= 65.7 J K
1

298.15

(e) Assume AH and AS to be independent on the change of T.
At 25 C, T
1
= 298.15 K, K
1
= 1.5510
15

At 100 C, T
2
= 373.15 K, K
2
= ???

ln(K
1
/K
2
) = (AH/R) (T
2
1
T
1
1
)
= (67.1 10
3
8.314) (373.15
1
298.15
1
) = 5.441

K
1
/K
2
= e
5.441


K
2
= K
1
e
5.441
= (1.5510
15
) e
5.441
= 6.7 10
12


Or: at 100 C, T = 373.15 K,
AG = RT lnK = AH TAS = 67.1 373.15 65.7 10
3
= 91.6 kJ

AG 91.6
lnK = = = 29.5
RT 8.314 373.15 10
3


K = e
29.5
= 6.7 10
12


(f) a
TiO2(s)
a
4
HCl(g)

K =
a
TiCl4(g)
a
2
H2O(g)


(g) The answer is (3)
K is a function of T only. If T stays the same, K remains the same.

K IS A
FUNCTION OF
ONLY
TEMPERATURE