TRAPP: CHAP03 2006/3/8 17:27 PAGE 53 #1

3
The Second Law
Answers to discussion questions
D3.1 We must remember that the Second Lawof Thermodynamics states only that the total entropy of both the
system (here, the molecules organizing themselves into cells) and the surroundings (here, the medium)
must increase in a naturally occurring process. It does not state that entropy must increase in a portion
of the universe that interacts with its surroundings. In this case, the cells grow by using chemical energy
from their surroundings (the medium) and in the process the increase in the entropy of the medium
outweighs the decrease in entropy of the system. Hence, the Second Law is not violated.
D3.3 All of these expressions are obtained from a combination of the First Law of Thermodynamics with
the Clausius inequality in the form TdS dq, as was done at the start of Justication 3.2. It may be
written as
dU p
ex
dV +dw
add
+TdS 0
where we have divided the work into pressurevolume work and additional work. Under conditions of
constant energy and volume and no additional work, that is, an isolated system, this relation reduces to
dS 0
which is equivalent to S
tot
= S
universe
0. (The universe is an isolated system.)
Under conditions of constant entropy and volume and no additional work, the fundamental relation
reduces to
dU 0.
Under conditions of constant temperature and volume, with no additional work, the relation reduces to
dA 0,
where A is dened as U TS.
Under conditions of constant temperature and pressure, with no additional work, the relation reduces to
dG 0,
where G is dened as U +pV TS = H TS.
TRAPP: CHAP03 2006/3/8 17:27 PAGE 54 #2
54 SOLUTIONS MANUAL
In all of the these relations, choosing the inequality provides the criteria for spontaneous change.
Choosing the equal sign gives us the criteria for equilibrium under the conditions specied.
D3.5 The Maxwell relations are relations between partial derivatives all of which are expressed in terms of
functions of state (properties of the system). Partial derivatives can be thought of as a kind of shorthand
for an experiment. Therefore, the partial derivative (S/V)
T
tells us how the entropy of the system
changes when we change its volume under constant-temperature conditions. But, as entropy is not a
property that can be measured directly (there are no entropy meters), it is important that the derivative
(and hence the experiment) be transformed into a formthat involves directly measurable properties. That
is what the following Maxwell relation does for us.
_
S
V
_
T
=
_
p
T
_
V
.
Pressure, temperature, and volume are easily measured properties.
D3.7 The relation (G/p)
T
= V shows that the Gibbs function of a system increases with p at constant T in
proportion to the magnitude of its volume. This makes good sense when one considers the denition of
G, which is G = U + pV TS. Hence, G is expected to increase with p in proportion to V when T is
constant.
Solutions to exercises
Assume that all gases are perfect and that data refer to 298.15 K unless otherwise stated.
E3.1(a) Assume that the block is so large that its temperature does not change signicantly as a result of the heat
transfer. Then
S =
_
f
i
dq
rev
T
[3.2] =
1
T
_
f
i
dq
rev
[constant T] =
q
rev
T
(a) S =
25 10
3
J
273.15 K
= 92 J K
1
(b) S =
25 10
3
J
373.15 K
= 67 J K
1
.
E3.2(a)
S
m
(T
f
) = S
m
(T
i
) +
_
T
f
T
i
C
V,m
T
dT [3.19, with C
V,m
in place of C
p,m
].
If we assume that neon is a perfect gas then C
V,m
may be taken to be constant and given by
C
V,m
= C
p,m
R; C
p,m
= 20.786 J K
1
mol
1
[Table 2.6]
= (20.786 8.314) J K
1
mol
1
= 12.472 J K
1
mol
1
.
TRAPP: CHAP03 2006/3/8 17:27 PAGE 55 #3
THE SECOND LAW 55
Integrating, we obtain
S
m
(500 K) = S
m
(298 K) +C
V,m
ln
T
f
T
i
= (146.22 J K
1
mol
1
) +(12.472 J K
1
mol
1
) ln
_
500 K
298 K
_
= (146.22 +6.45) J K
1
mol
1
= 152.67 J k
1
mol
1
.
E3.3(a) Since entropy is a state function, S may be calculated from the most convenient path, which in this
case corresponds to constant-pressure heating followed by constant-temperature compression.
S = nC
p,m
ln
_
T
f
T
i
_
[3.19, at p
i
] +nR ln
_
V
f
V
i
_
[3.13, at T
f
].
Since pressure and volume are inversely related (Boyles law),
V
f
V
i
=
p
i
p
f
.
Hence,
S = nC
p,m
ln
_
T
f
T
i
_
nRln
_
p
f
p
i
_
= (3.00 mol)
5
2
(8.314 J K
1
mol
1
) ln
_
398 K
298 K
_
(3.00 mol) (8.314 J K
1
mol
1
) ln
_
5.00 atm
1.00 atm
_
= (18.0

4 40.1

4) J K
1
= 22.1 J K
1
.
Though S (system) is negative, the process can still occur spontaneously if S (total) is positive.
E3.4(a) For an adiabatic reversible process, q = q
rev
= 0 .
S =
_
f
i
dq
rev
T
= 0 .
U = nC
V,m
T [2.16b] = (3.00 mol) (27.5 J K
1
mol
1
) (50 K) = 4.1 10
3
J
= +4.1 kJ .
w = U [First Law with q = 0].
H = nC
p,m
T [2.23b].
C
p,m
= C
V,m
+R [2.26] = (27.5 +8.3) J K
1
mol
1
= 35.8 J K
1
mol
1
.
H = (3.00 mol) (35.8 J K
1
mol
1
) (50 K) = 5.4 10
3
J = +5.4 kJ .
COMMENT. Neither initial nor nal pressures and volumes are needed for the solution to this exercise.
E3.5(a) Since the container is isolated, the heat ow is zero and therefore H = 0 ; since the masses of the
blocks are equal, the nal temperature must be their mean temperature, 50

C. Specic heat capacities

are heat capacities per gram and are related to the molar heat capacities by
C
s
=
C
m
M
[C
p,m
C
V,m
= C
m
].
TRAPP: CHAP03 2006/3/8 17:27 PAGE 56 #4
56 SOLUTIONS MANUAL
So nC
m
= mC
s
[nM = m].
H(individual) = mC
s
T = 1.00 10
4
g 0.385 J K
1
g
1
(50 K)
= 1.9 10
2
kJ.
These two enthalpy changes add up to zero: H
tot
= 0 .
S = mC
s
ln
_
T
f
T
i
_
[3.19].
S
1
= (10.0 10
3
g) (0.385 J K
1
g
1
) ln
_
323 K
273 K
_
= 5.541 10
2
J K
1
,
S
2
= (10.0 10
3
g) (0.385 J K
1
g
1
) ln
_
323 K
273 K
_
= 6.475 10
2
J K
1
,
S
tot
= S
1
+S
2
= +93.4 J K
1
.
COMMENT. The positive value of S
tot
corresponds to a spontaneous process.
E3.6(a) (a) q = 0 [adiabatic].
(b) w = p
ex
V [2.8] = (1.01 10
5
Pa) (20 cm) (10 cm
2
)
_
10
6
m
3
cm
3
_
= 20 J .
(c) U = q +w = 0 20 J = 20 J .
(d) U = nC
V,m
T[2.16b],
T =
20 J
(2.0 mol) (28.8 J K
1
mol
1
)
= 0.34

7 K .
(e) Entropy is a state function, so we can compute it by any convenient path. Although the specied trans-
formation is adiabatic, a more convenient path is constant-volume cooling followed by isothermal
expansion. The entropy change is the sum of the entropy changes of these two steps:
S = S
1
+S
2
= nC
V,m
ln
_
T
f
T
i
_
+nRln
_
V
f
V
i
_
[3.19 & 3.13].
T
f
= T
i
0.34

7 K = (298.15 K) (0.34

7 K) = 297.80

3 K.
V
i
=
nRT
p
i
=
(2.0 mol) (0.08206 dm
3
atmK
1
mol
1
) (298.15 K)
10 atm
= 4.893 dm
3
.
V
f
= V
i
+V = (4.893 +0.20) dm
3
= 5.093 dm
3
.
Substituting these values into the expression for S above gives
S = (2.0 mol) (28.8 J K
1
mol
1
) ln
_
297.80

3 K
298.15 K
_
+(2.0 mol) (8.314 J K
1
mol
1
) ln
_
5.093 dm
3
4.893 dm
3
_
= (0.067

1 +0.66

6) J K
1
= +0.60 J K
1
.
TRAPP: CHAP03 2006/3/8 17:27 PAGE 57 #5
THE SECOND LAW 57
E3.7(a) (a)
vap
S =

vap
H
T
b
=
29.4 10
3
J mol
1
334.88 K
= +87.8 J K
1
mol
1
.
(b) If the vaporization occurs reversibly, S
tot
= 0, so S
surr
= 87.8 J K
1
mol
1
.
E3.8(a) In each case
r
S

Products
S

Reactants
S

m
[3.21]
with S

m
values obtained from Tables 2.5 and 2.6.
(a)

r
S

= 2S

m
(CH
3
COOH, l) 2S

m
(CH
3
CHO, g) S

m
(O
2
, g)
= [(2 159.8) (2 250.3) 205.14] J K
1
mol
1
= 386.1 J K
1
mol
1
.
(b)

r
S

= 2S

m
(AgBr, s) +S

m
(Cl
2
, g) 2S

m
(AgCl, s) S

m
(Br
2
, l)
= [(2 107.1) +(223.07) (2 96.2) (152.23)] J K
1
mol
1
= +92.6 J K
1
mol
1
.
(c)

r
S

= S

m
(HgCl
2
, s) S

m
(Hg, l) S

m
(Cl
2
, g)
= [146.0 76.02 223.07] J K
1
mol
1
= 153.1 J K
1
mol
1
.
E3.9(a) In each case we use

r
G

=
r
H

T
r
S

[3.39]
along with

r
H

Products

f
H

Reactants

f
H

[2.32].
(a)

r
H

= 2
f
H

(CH
3
COOH, l) 2
f
H

(CH
3
CHO, g)
= [2 (484.5) 2 (166.19)] kJ mol
1
= 636.6

2 kJ mol
1
.

r
G

= 636.6

2 kJ mol
1
(298.15 K) (386.1 J K
1
mol
1
) = 521.5 kJ mol
1
.
(b)

r
H

= 2
f
H

(AgBr, s) 2
f
H

(AgCl, s)
= [2 (100.37) 2 (127.07)] kJ mol
1
= +53.40 kJ mol
1
.

r
G

= +53.40 kJ mol
1
(298.15 K) (+92.6) J K
1
mol
1
= +25.8 kJ mol
1
.
(c)

r
H

=
f
H

(HgCl
2
, s) = 224.3 kJ mol
1
.

r
G

= 224.3 kJ mol
1
(298.15 K) (153.1 J K
1
mol
1
) = 178.7 kJ mol
1
.
TRAPP: CHAP03 2006/3/8 17:27 PAGE 58 #6
58 SOLUTIONS MANUAL
E3.10(a) In each case
r
G

=

Products

f
G

Reactants

f
G

[3.40]
with
f
G

(J) values from Table 2.6.

(a)

r
G

= 2
f
G

(CH
3
COOH, l) 2
f
G

(CH
3
CHO, g)
= [2 (389.9) 2 (128.86)] kJ mol
1
= 522.1 kJ mol
1
.
(b)

r
G

= 2
f
G

(AgBr, s) 2
f
G

(AgCl, s) = [2 (96.90) 2 (109.79)] kJ mol

1
= +25.78 kJ mol
1
.
(c)

r
G

=
f
G

(HgCl
2
, s) = 178.6 kJ mol
1
.
COMMENT. In each case these values of
r
G

agree closely with the calculated values in Exercise 3.9(a).

E3.11(a)
r
G

=
r
H

T
r
S

[3.39],
r
H

Products

f
H

Reactants

f
H

[2.32],

r
S

Products
S

Reactants
S

m
[3.21].

r
H

= 2
f
H

(H
2
O, l) 4
f
H

(HCl, g) = {2 (285.83) 4 (92.31)} kJ mol

1
= 202.42 kJ mol
1
.

r
S = 2S

m
(Cl
2
, g) +2S

m
(H
2
O, l) 4S

m
(HCl,g) S

m
(O
2
, g)
= [(2 69.91) +(2 223.07) (4 186.91) (205.14)] J K
1
mol
1
= 366.82 J K
1
mol
1
= 0.36682 kJ K
1
mol
1
.

r
G

= 202.42 kJ mol
1
(298.15 K) (0.36682 kJ K
1
mol
1
) = 93.05 kJ mol
1
.
Question. Repeat the calculation based on
f
G data of Table 2.6. What difference, if any, is there
from the value above?
E3.12(a) The formation reaction for phenol is
6C(s) +3H
2
(g) +
1
2
O
2
(g) C
6
H
5
OH(s),

f
G

=
f
H

T
f
S

[3.39].

f
H

is to be obtained from
c
H

for phenol and data from Tables 2.5 and 2.6. Thus
C
6
H
5
OH(s) +7O
2
(g) 6CO
2
(g) +3H
2
O(l),

c
H

= 6
f
H

(CO
2
, g) +3
f
H

(H
2
O, l)
f
H

(C
6
H
5
OH, s),

f
H

(C
6
H
5
OH, s) = 6
f
H

(CO
2
, g) +3
f
H

(H
2
O, l)
c
H

= [6 (393.51) +3 (285.83) (3054)] kJ mol

1
= 164.55 kJ mol
1
.
TRAPP: CHAP03 2006/3/8 17:27 PAGE 59 #7
THE SECOND LAW 59

r
S

Products
S

Reactants
S

m
[3.21].

f
S

= S

m
(C
6
H
5
OH, s) 6S

m
(C, s) 3S

m
(H
2
, g)
1
2
S

m
(O
2
,g)
=
_
144.0 (6 5.740) (3 130.68)
_
1
2
205.14
__
J K
1
mol
1
= 385.0

5 J K
1
mol
1
.
Hence

r
G

= 164.55 kJ mol
1
(298.15 K) (385.05 J K
1
mol
1
) = 50 kJ mol
1
.
E3.13(a) (a) S(gas) = nRln
V
f
V
i
[3.13] =
_
14 g
28.02 g mol
1
_
(8.314 J K
1
mol
1
) (ln 2)
= +2.9 J K
1
.
S(surroundings) = 2.9 J K
1
[overall zero entropy production].
S (total) = 0 [reversible process].
(b) S (gas) = +2.9 J K
1
[S a state function].
S (surroundings) = 0 [surroundings do not change].
S (total) = +2.9 J K
1
.
(c) S (gas) = 0 [q
rev
= 0].
S (surroundings) = 0 [no heat transferred to surroundings].
S (total) = 0 .
E3.14(a) CH
4
(g) +2O
2
(g) CO
2
(g) +2H
2
O(l).

r
G

Products

f
G

Reactants

f
G

[3.40],

r
G

=
f
G

(CO
2
, g) +2
f
G

(H
2
O, l)
f
G

(CH
4
, g)
= {394.36 +(2 237.13) (50.72)} kJ mol
1
= 817.90 kJ mol
1
.
Therefore, the maximum non-expansion work is 817.90 kJ mol
1
since |w
add
| = |G|.
E3.15(a)
rev
= 1
T
c
T
h
[3.10].
(a) = 1
333 K
373 K
= 0.11 (11 per cent efciency for the old steam engine).
(b) = 1
353 K
573 K
= 0.38 (38 per cent efciency for the modern turbine).
TRAPP: CHAP03 2006/3/8 17:27 PAGE 60 #8
60 SOLUTIONS MANUAL
E3.16(a) G = nRT ln
_
p
f
p
i
_
[3.56] = nRT ln
_
V
i
V
f
_
[Boyles law].
G = (3.0 10
3
mol) (8.314 J K
1
mol
1
) (300 K) ln
_
36
60
_
= 3.8 J .
E3.17(a)
_
G
T
_
p
= S [3.50]; hence
_
G
f
T
_
p
= S
f
, and
_
G
i
T
_
p
= S
i
.
S = S
f
S
i
=
_
G
f
T
_
p
+
_
G
i
T
_
p
=
_
(G
f
G
i
)
T
_
p
=
_
G
T
_
p
=

T
_
85.40 J +36.5 J
T
K
_
= 36.5 J K
1
.
E3.18(a) dG = S dT +V dp[3.49]; at constant T, dG = V dp ; therefore
G =
_
p
f
p
i
V dp.
The change in volume of a condensed phase under isothermal compression is given by the isothermal
compressibility (eqn 2.44).

T
=
1
V
_
V
p
_
T
= 76.8 10
6
atm
1
[Table 2.8]
This small isothermal compressibility (typical of condensed phases) tells us that we can expect a small
change in volume from even a large increase in pressure. So we can make the following approximations
to obtain a simple expression for the volume as a function of the pressure

T

1
V
_
V V
i
p p
i
_

1
V
i
_
V V
i
p
_
so V = V
i
(1
T
p),
where V
i
is the volume at 1 atm, namely the sample mass over the density, m/.
G =
_
3000 atm
1 atm
m

(1
T
p) dp
=
m

_
_
3000 atm
1 atm
dp
T
_
3000 atm
1 atm
p dp
_
=
m

_
p

3000 atm
1 atm

T
p
2

3000 atm
1 atm
_
=
35g
0.789 g cm
3
_
2999 atm (76.8 10
6
atm
1
) (9.00 10
6
atm
2
)
_
= 44.4 cm
3

_
1 m
100 cm
_
3
2308 atm(1.013 10
5
Pa atm
1
)
= 1.0

4 10
4
J = 10 kJ .
TRAPP: CHAP03 2006/3/8 17:27 PAGE 61 #9
THE SECOND LAW 61
E3.19(a) G
m
= G
m,f
G
m,i
= RT ln
_
p
f
p
i
_
[3.56] = (8.314 J K
1
mol
1
) (313 K) ln
_
29.5
1.8
_
= +7.3 kJ mol
1
E3.20(a) For an ideal gas, G
O
m
= G

m
+RT ln
_
p
p

_
[3.56 with G
m
= G
O
m
].
But for a real gas, G
m
= G

m
+RT ln
_
f
p

_
[3.58].
So G
m
G
O
m
= RT ln
f
p
[3.58 minus 3.56];
f
p
=
= RT ln = (8.314 J K
1
mol
1
) (200 K) (ln 0.72) = 0.55 kJ mol
1
.
E3.21(a)
G = nV
m
p [3.55] = Vp.
G = (1.0 dm
3
)
_
1m
3
10
3
dm
3
_
(99 atm) (1.013 10
5
Pa) = 10 kPa m
3
= +10 kJ .
E3.22(a) G
m
= RT ln
p
f
p
i
[3.56] = (8.314 J K
1
mol
1
) (298 K) ln
_
100.0
1.0
_
= +11 kJ mol
1
.
Solutions to problems
Solutions to numerical problems
P3.1 (a) Because entropy is a state function
trs
S(l s, 5

C) may be determined indirectly from the

following cycle
H
2
O(1, 0

C)

trs
S(ls,0

C)
H
2
O(s, 0

C)
S
1
S
s
H
2
O(1, 5

C)

trs
S(ls,5

C)
H
2
O(s, 5

C).
Thus
trs
S(l s, 5

C) = S
l
+
trs
S(l s, 0

C) +S
s
,
where S
l
= C
p,m
(l) ln
T
f
T
[3.19;
f
= 0

C, = 5

C]
and S
s
= C
p,m
(s) ln
T
T
f
.
S
l
+S
s
= C
p
ln
T
T
f
with C
p
= C
p,m
(l) C
p,m
(s) = +37.3 J K
1
mol
1
.

trs
S(l s, T
f
) =

fus
H
T
f
[3.16].
TRAPP: CHAP03 2006/3/8 17:27 PAGE 62 #10
62 SOLUTIONS MANUAL
Thus,
trs
S(l s, T) =

fus
H
T
f
C
p
ln
T
T
f
.

trs
S(l s, 5

C) =
6.01 10
3
J mol
1
273K
(37.3 J K
1
mol
1
) ln
268
273
= 21.3 J K
1
mol
1
.
S
sur
=

fus
H(T)
T
.

fus
H(T) = H
l
+
fus
H(T
f
) H
s
.
H
l
+H
s
= C
p,m
(l)(T
f
T) +C
p,m
(s)(T T
f
) = C
p
(T
f
T).

fus
H(T) =
fus
H(T
f
) C
p
(T
f
T).
Thus, S
sur
=

fus
H(T)
T
=

fus
H(T
f
)
T
+C
p
(T T
f
)
T
,
S
sur
=
6.01 kJ mol
1
268 K
+(37.3 J K
1
mol
1
)
_
268 273
268
_
= +21.7 J K
1
mol
1
.
S
total
= S
sur
+S = (21.7 21.3) J K
1
mol
1
= +0.4 J K
1
mol
1
.
Since S
total
> 0, the transition l s is spontaneous at 5

C.
(b) A similar cycle and analysis can be set up for the transition liquid vapor at 95

C. However,
since the transformation here is to the high temperature state (vapor) from the low temperature state
(liquid), which is the opposite of part (a), we can expect that the analogous equations will occur
with a change of sign.

trs
S(1 g, T) =
trs
S(1 g, T
b
) +C
p
ln
T
T
b
=

vap
H
T
b
+C
p
ln
T
T
b
, C
p
= 41.9 J K
1
mol
1
.

trs
S(1 g, T) =
40.7 kJ mol
1
373 K
(41.9 J K
1
mol
1
) ln
_
368
373
_
= +109.7 J K
1
mol
1
.
S
sur
=

vap
H(T)
T
=

vap
H(T
b
)
T

C
p
(T T
b
)
T
=
_
40.7 kJ mol
1
368 K
_
(41.9 J K
1
mol
1
)
_
368 373
368
_
= 111.2 J K
1
mol
1
.
S
total
= (109.7 111.2) J K
1
mol
1
= 1.5 J K
1
mol
1
.
Since S
total
< 0, the reverse transition, g l, is spontaneous at 95

C.
TRAPP: CHAP03 2006/3/8 17:27 PAGE 63 #11
THE SECOND LAW 63
P3.3 (a)
q(total) = q(H
2
O) +q(Cu) = 0; hence q(H
2
O) = q(Cu).
q(H
2
O) = n(
vap
H) +nC
p,m
(H
2
O, l) ( 100

C)
where is the nal temperature of the water and copper.
q(Cu) = mC
s
( 0) = mC
s
, C
s
= 0.385 J K
1
g
1
.
Setting q(H
2
O) = q(Cu) allows us to solve for .
n(
vap
H) nC
p,m
(H
2
O, l) ( 100

C) = mC
s

Solving for yields:

=
n{
vap
H +C
p,m
(H
2
O, l) 100

C}
mC
s
+nC
p,m
(H
2
O, l)
=
(1.00 mol) (40.656 10
3
J mol
1
+75.3 J

C
1
mol
1
100

C)
2.00 10
3
g 0.385 J

C
1
g
1
+1.00 mol 75.3 J

C
1
mol
1
= 57.0

C = 330.2 K.
q(Cu) = (2.00 10
3
g) (0.385 J K
1
g
1
) (57.0 K) = 4.39 10
4
J = 43.9 kJ .
q(H
2
O) = 43.9 kJ .
S(total) = S(H
2
O) +S(Cu).
S(H
2
O) =
n
vap
H
T
b
[3.16] +nC
p,m
ln
_
T
f
T
i
_
[3.19]
=
(1.00 mol) (40.656 10
3
J mol
1
)
373.2 K
+(1.00 mol) (75.3 J K
1
mol
1
) ln
_
330.2 K
373.2 K
_
= 108.9 J K
1
9.22 J K
1
= 118.

1 J K
1
.
S(Cu) = mC
s
ln
T
f
T
i
= (2.00 10
3
g) (0.385 J K
1
g
1
) ln
_
330.2 K
273.2 K
_
= 145.

9 J K
1
.
S(total) = 118.1 J K
1
+145.9 J K
1
= 28 J K
1
.
This process is spontaneous since S(surroundings) is zero and, hence, S(universe) =
S(total) > 0.
(b) The volume of the container may be calculated from the perfect gas law.
V =
nRT
p
=
(1.00 mol) (0.08206 dm
3
atmK
1
mol
1
) (373.2 K)
1.00 atm
= 30.6 dm
3
TRAPP: CHAP03 2006/3/8 17:27 PAGE 64 #12
64 SOLUTIONS MANUAL
At 57

C the vapor pressure of water is 130 Torr (Handbook of Chemistry and Physics). The amount
of water vapor present at equilibrium is then
n =
pV
RT
=
(130 Torr)
_
1 atm
760 Torr
_
(30.6 dm
3
)
(0.08206 dm
3
atmK
1
mol
1
) (330.2 K)
= 0.193 mol.
This is a substantial fraction of the original amount of water and cannot be ignored. Consequently the
calculation needs to be redone taking into account the fact that only a part, n
l
, of the vapor condenses
into a liquid while the remainder (1.00 mol n
l
) remains gaseous. The heat ow involving water,
then, becomes
q(H
2
O) =n
1

vap
H +n
1
C
p,m
(H
2
O, l)T(H
2
O)
+(1.00 mol n
1
)C
p,m
(H
2
O, g)T(H
2
O).
Because n
l
depends on the equilibrium temperature through n
1
= 1.00 mol
pV
RT
, where p is the
vapor pressure of water, we will have two unknowns (p and T) in the equation q(H
2
O) = q(Cu).
There are two ways out of this dilemma: (1) p may be expressed as a function of T by use of the
Clapeyron equation (Chapter 4), or (2) by use of successive approximations. Redoing the calculation
yields:
=
n
l

vap
H +n
l
C
p,m
(H
2
O, l) 100

C +(1.00 n
l
)C
p,m
(H
2
O, g) 100

C
mC
s
+nC
p,m
(H
2
O, l) +(1.00 n
l
)C
p,m
(H
2
O, g)
.
With
n
1
= (1.00 mol) (0.193 mol) = 0.80

7 mol
(noting that C
p,m
(H
2
O, g) = 33.6 J mol
1
K
1
[Table 2.6]), = 47.2

C. At this temperature, the

vapor pressure of water is 80.41 Torr, corresponding to
n
1
= (1.00 mol) (0.123 mol) = 0.87

7 mol.
This leads to = 50.8

C. The successive approximations eventually converge to yield a value of

= 49.9

C = 323.1 K for the nal temperature. (At this temperature, the vapor pressure is 0.123
bar.) Using this value of the nal temperature, the heat transferred and the various entropies are
calculated as in part (a).
q(Cu) = (2.00 10
3
g) (0.385 J K
1
g
1
) (49.9 K) = 38.4 kJ = q(H
2
O).
S(H
2
O) =
n
vap
H
T
b
+nC
p,m
ln
_
T
f
T
i
_
= 119.8 J K
1
.
S(Cu) = mC
s
ln
T
f
T
i
= 129.2 J K
1
.
S(total) = 119.8 J K
1
+129.2 J K
1
= 9 J K
1
.
TRAPP: CHAP03 2006/3/8 17:27 PAGE 65 #13
THE SECOND LAW 65
P3.5
Step 1 Step 2 Step 3 Step 4 Cycle
q +11.5 kJ 0 5.74 kJ 0 5.8 kJ
w 11.5 kJ 3.74 kJ +5.74 kJ +3.74 kJ 5.8 kJ
U 0 3.74 kJ 0 +3.74 kJ 0
H 0 6.23 kJ 0 +6.23 kJ 0
S +19.1 J K
1
0 19.1 J K
1
0 0
S
tot
0 0 0 0 0
G 11.5 kJ mol
1
? +11.5 kJ mol
1
? 0
Step 1
U = H = 0 [isothermal].
w = nRT ln
_
V
f
V
i
_
= nRT ln
_
p
f
p
i
_
[2.11, and Boyles law]
= (1.00 mol) (8.314 J K
1
mol
1
) (600 K) ln
_
1.00 atm
10.0 atm
_
= 11.5 kJ .
q = w = 11.5 kJ .
S = nRln
_
V
f
V
i
_
[3.15] = nRln
_
p
f
p
i
_
[Boyles law]
= (1.00 mol) (8.314 J K
1
mol
1
) ln
_
1.00 atm
10.0 atm
_
= +19.1 J K
1
.
S(sur) = S(system) [reversible process] = 19.1J K
1
.
S
tot
= S(system) +S(sur) = 0 .
G = H TS = 0 (600K) (19.1 J K
1
) = 11.5 kJ mol
1
.
Step 2
q = 0 [adiabatic] .
U = nC
V,m
T [2.16b]
= (1.00 mol)
_
3
2
_
(8.314 J K
1
mol
1
) (300 K 600 K) = 3.74 kJ .
w = U = 3.74 kJ .
H = U +(pV) = U +nRT
= (3.74 kJ) +(1.00 mol) (8.314 J K
1
mol
1
) (300 K)
= 6.23 kJ .
S = S(sur) = 0 [reversible adiabatic process].
TRAPP: CHAP03 2006/3/8 17:27 PAGE 66 #14
66 SOLUTIONS MANUAL
S
tot
= 0 .
G = (H TS) = H ST [no change in entropy].
Although the change in entropy is known to be zero, the entropy itself is not known, so G is
indeterminate .
Step 3
These quantities may be calculated in the same manner as for Step 1 or more easily as follows.
U = H = 0 [isothermal].

rev
= 1
T
c
T
h
[3.10] = 1
300 K
600 K
= 0.500 = 1 +
q
c
q
h
[3.9].
q
c
= 0.500 q
h
= (0.500) (11.5 kJ) = 5.74 kJ.
q
c
= 5.74 kJ , w = q
c
= 5.74 kJ .
S =
q
rev
T
[isothermal] =
5.74 10
3
J
300 K
= 19.1 J K
1
.
S(sur) = S(system) = +19.1 J K
1
.
S
tot
= 0 .
G = H TS = 0 (300 K) (19.1 J K
1
) = +11.5 kJ mol
1
.
Step 4
U and H are the negative of their values in Step 2. (Initial and nal temperatures reversed.)
U = +3.74 kJ , H = +6.23 kJ , q = 0 [adiabatic].
w = U = +3.74 kJ .
S = S(sur) = 0 [reversible adiabatic process].
S
tot
= 0 .
Again G = (H TS) = H ST [no change in entropy]
but S is not known, so G is indeterminate .
Cycle
U = H = S = G = 0 [(state function) = 0 for any cycle].
S(sur) = 0 [all reversible processes].
S
tot
= 0 .
q(cycle) = (11.5 5.74) kJ = 5.8 kJ , w(cycle) = q(cycle) = 5.8 kJ .
TRAPP: CHAP03 2006/3/8 17:27 PAGE 67 #15
THE SECOND LAW 67
P3.7 S

m
(T) = S

m
(298 K) +S.
S =
_
T
2
T
1
C
p,m
dT
T
=
_
T
2
T
1
_
a
T
+b +
c
T
3
_
dT = a ln
T
2
T
1
+b(T
2
T
1
)
1
2
c
_
1
T
2
2

1
T
2
1
_
.
(a)
S

m
(373 K) = (192.45 J K
1
mol
1
) +(29.75 J K
1
mol
1
) ln
_
373
298
_
+(25.10 10
3
J K
2
mol
1
) (75.0 K)
+
_
1
2
_
(1.55 10
5
J K
1
mol
1
)
_
1
(373.15)
2

1
(298.15)
2
_
= 200.7 J K
1
mol
1
.
(b)
S

m
(773 K) = (192.45 J K
1
mol
1
) +(29.75 J K
1
mol
1
) ln
_
773
298
_
+(25.10 10
3
J K
2
mol
1
) (475K)
+
_
1
2
_
(1.55 10
5
J K
1
mol
1
)
_
1
773
2

1
298
2
_
= 232.0 J K
1
mol
1
.
P3.9 S = nC
p,m
ln
T
f
T
h
+nC
p,m
ln
T
f
T
c
[3.19]
_
T
f
is the nal temperature, T
f
=
1
2
(T
h
+T
c
)
_
.
In the present case, T
f
=
1
2
(500 K +250 K) = 375 K.
S = nC
p,m
ln
T
2
f
T
h
T
c
= nC
p,m
ln
(T
h
+T
c
)
2
4T
h
T
c
=
_
500 g
63.54 g cm
3
_
(24.4 J K
1
mol
1
)
ln
_
375
2
500 250
_
= +22.6 J K
1
.
P3.11 S
m
(T) = S
m
(0) +
_
T
0
C
p,m
dT
T
[3.18].
From the data, draw up the following table.
T/ K 10 15 20 25 30 50
C
p,m
T
/(J K
2
mol
1
) 0.28 0.47 0.540 0.564 0.550 0.428
T/ K 70 100 150 200 250 298
C
p,m
T
/(J K
2
mol
1
) 0.333 0.245 0.169 0.129 0.105 0.089
Plot C
p,m
/T against T (Fig. 3.1). This has been done on two scales. The region 0 to 10 K has been
constructed using C
p,m
= aT
3
, tted to the point at T = 10 K, at which C
p,m
= 2.8 J K
1
mol
1
,
so a = 2.8 10
3
J K
4
mol
1
. The area can be determined (primitively) by counting squares.
Area A = 38.28 J K
1
mol
1
.
TRAPP: CHAP03 2006/3/8 17:27 PAGE 68 #16
68 SOLUTIONS MANUAL
Figure 3.1
Area B up to 0

C = 25.60 J K
1
mol
1
; area B up to 25

C = 27.80 J K
1
mol
1
. Hence
(a) S
m
(273 K) = S
m
(0) + 63.88 J K
1
mol
1
,
(b) S
m
(298 K) = S
m
(0) + 66.08 J K
1
mol
1
.
P3.13 S
m
(T) = S
m
(0) +
_
T
0
C
p,m
dT
T
[3.18].
Perform a graphical integration by plotting C
p,m
/T against T and determining the area under the curve.
Draw up the following table. (The last two columns come from determining areas under the curves
described below.)
T/K
C
p,m
J K
1
mol
1
C
p,m
/T
J K
2
mol
1
S

m
S

m
(0)
J K
1
mol
1
H

m
H

m
(0)
kJ mol
1
0.00 0.00 0.00 0.00 0.00
10.00 2.09 0.21 0.80 0.01
20.00 14.43 0.72 5.61 0.09
30.00 36.44 1.21 15.60 0.34
40.00 62.55 1.56 29.83 0.85
50.00 87.03 1.74 46.56 1.61
60.00 111.00 1.85 64.62 2.62
70.00 131.40 1.88 83.29 3.84
80.00 149.40 1.87 102.07 5.26
90.00 165.30 1.84 120.60 6.84
100.00 179.60 1.80 138.72 8.57
110.00 192.80 1.75 156.42 10.44
150.00 237.60 1.58 222.91 19.09
160.00 247.30 1.55 238.54 21.52
170.00 256.50 1.51 253.79 24.05
180.00 265.10 1.47 268.68 26.66
190.00 273.00 1.44 283.21 29.35
200.00 280.30 1.40 297.38 32.13
TRAPP: CHAP03 2006/3/8 17:27 PAGE 69 #17
THE SECOND LAW 69
Plot C
p,m
/T against T (Fig. 3.2(a)). Extrapolate to T = 0 using C
p,m
= aT
3
tted to the point at T =
10 K, which gives a = 2.09 mJ K
2
mol
1
. Determine the area under the graph up to each T and plot
S
m
against T (Fig. 3.2(b)).
(
(
C
p
,
m
/
T
)
/
(
J

K

2

m
o
l

1
)
)
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0 (a)
0 50 100 150 200
T/K
Figure 3.2(a)
(b)
50
100
150
200
250
0 50 100 150 200
T/K
0
300
(
S
m
(
T
)

S
m
(
0
)
)
/
(
J

K

1

m
o
l

1
)
Figure 3.2(b)
The molar enthalpy is determined in a similar manner from a plot of C
p,m
against T by determining the
area under the curve (Fig. 3.3)
H

m
(200 K) H

m
(0) =
_
200 K
0
C
p,m
dT = 32.1 kJ mol
1
.
TRAPP: CHAP03 2006/3/8 17:27 PAGE 70 #18
70 SOLUTIONS MANUAL
0 50 100 150 200
50
100
150
200
250
(
C
p
,
m
/
(
J

K

1

m
o
l

1
)
0
300
T/K
Figure 3.3
P3.15 The entropy at 200 K is calculated from
S

m
(200K) = S

m
(100 K) +
_
200 K
100 K
C
p,m
dT
T
.
The integrand may be evaluated at each of the data points; the transformed data appear below. The
numerical integration can be carried out by a standard procedure such as the trapezoid rule (taking the
integral within any interval as the mean value of the integrand times the length of the interval). Programs
for performing this integration are readily available for personal computers. Many graphing calculators
will also perform this numerical integration.
T/K 100 120 140 150 160 180 200
C
p,m
/(J K
1
mol
1
) 23.00 23.74 24.25 24.44 24.61 24.89 25.11
C
p,m
T
/(J K
2
mol
1
) 0.230 0.1978 0.1732 0.1629 0.1538 0.1383 0.1256
Integration by the trapezoid rule yields
S

m
(200 K) = (29.79 +16.81) J K
1
mol
1
= 46.60 J K
1
mol
1
.
Taking C
p,m
constant yields
S

m
(200 K) = S

m
(100 K) +C
p,m
ln (200 K/100 K)
= [29.79 +24.44 ln (200/100 K)] J K
1
mol
1
= 46.60 J K
1
mol
1
.
The difference is slight.
P3.17 The GibbsHelmholtz equation [3.52] may be recast into an analogous equation involving G and H,
since
_
G
T
_
p
=
_
G
f
T
_
p

_
G
i
T
_
p
TRAPP: CHAP03 2006/3/8 17:27 PAGE 71 #19
THE SECOND LAW 71
and H = H
f
H
i
.
Thus,
_

T

r
G

T
_
p
=

r
H

T
2
,
d
_

r
G

T
_
=
_

T

r
G

T
_
p
dT[constant pressure] =

r
H

T
2
dT,

r
G

T
_
=
_
T
T
c

r
H

dT
T
2

r
H

_
T
T
c
dT
T
2
=
r
H

_
1
T

1
T
c
_
[
r
H

assumed constant].
Therefore,

r
G

(T)
T


r
G

(T
c
)
T
c

r
H

_
1
T

1
T
c
_
and so

r
G

(T) =
T
T
c

r
G

(T
c
) +
_
1
T
T
c
_

r
H

(T
c
)
=
r
G

(T
c
) +(1 )
r
H

(T
c
) where =
T
T
c
.
For the reaction
N
2
(g) +3H
2
(g) 2NH
3
(g),
r
G

= 2
f
G

(NH
3
, g).
(a) At 500 K, =
500
298
= 1.67

8,
so
r
G

(500 K) = {(1.678) 2 (16.45) +(1 1.678) 2 (46.11)} kJ mol

1
= 7 kJ mol
1
.
(b) At 1000 K, =
1000
298
= 3.356,
so
r
G

(1000 K) = {(3.356) 2 (16.45) +(1 3.356) 2 (46.11)} kJ mol

1
= +107 kJ mol
1
.
Solutions to theoretical problems
P3.19 The isotherms correspond to T = constant, and the reversibly traversed adiabats correspond to S =
constant. Thus we can represent the cycle as in Fig. 3.4.
In this gure, paths 1, 2, 3, and 4 correspond to the four stages of the Carnot cycle listed in the text
following eqn 3.6. The area within the rectangle is
Area =
_
TdS = (T
h
T
c
) (S
2
S
1
) = (T
h
T
c
)S = (T
h
T
c
)n Rln
V
B
V
A
(isothermal expansion from V
A
to V
B
, stage 1).
TRAPP: CHAP03 2006/3/8 17:27 PAGE 72 #20
72 SOLUTIONS MANUAL
4
1
2
3
T
e
m
p
e
r
a
t
u
r
e
Entropy
Figure 3.4
But, w(cycle) = q
h
=
_
T
h
T
c
T
h
_
n RT
h
ln
V
B
V
A
[text Fig. 3.6] = n R(T
h
T
c
) ln
V
B
V
A
.
Therefore, the area is equal to the net work done in the cycle.
P3.21 The thermodynamic temperature scale denes a temperature T
a
(where the superscript a is used to
distinguish this absolute thermodynamic temperature from the perfect gas temperature) in terms of
the reversible heat ows of a heat engine operating between it and an arbitrary xed temperature T
a
h
(eqn 3.11)
T
a
= (1
rev
)T
a
h
where the efciency of a heat engine is given in terms of work and heat ows:
=
|w|
q
h
[3.8] = 1 +
q
c
q
h
[3.9].
The problem asks us to show that the thermodynamic and perfect gas temperatures differ by at most a
constant numerical factor. That amounts to showing that
T
a
c
T
a
h
=
T
g
c
T
g
h
where the superscipt g indicates the perfect gas temperature dened by the perfect gas law. The subscripts
c and h represent two reservoirs between which one might run a heat engine and whose temperat-
ures one might characterize using either temperature scale. Justication 3.1 relates the ratio of two
perfect-gas temperatures to reversible isothermal heat ows in a Carnot cycle run between the two
temperatures.
q
h
q
c
=
T
g
h
T
g
c
[3.7, Justication 3.1] so
T
g
c
T
g
h
=
q
c
q
h
.
TRAPP: CHAP03 2006/3/8 17:27 PAGE 73 #21
THE SECOND LAW 73
The corresponding ratio of thermodynamic temperatures is:
T
a
c
T
a
h
= 1
rev
= 1
_
1
|w|
q
h
_
rev
=
_
q
c
q
h
_
rev
.
As Section 3.2(b) shows, the efciency of any reversible heat engine (including one that uses a perfect
gas as a working uid) is the same, and therefore the ratio of heat ows to the two reservoirs is the
same. That is, the ratio
q
c
q
h
is the same in the expression for the perfect-gas temperature ratio and the
thermodynamic ratio; since the two ratios are equal to the same heat ratio, they are equal to each other.
The constant numerical factor becomes 1 if T
h
and T
a
h
are both assigned the same value, say 273.16 at
the triple point of water.
P3.23
_
S
V
_
T
=
_
p
T
_
V
[Table 3.5].
(a) For a van der Waals gas
p =
nRT
V nb

n
2
a
V
2
=
RT
V
m
b

a
V
2
m
.
Hence,
_
S
V
_
T
=
_
p
T
_
V
=
R
V
m
b
.
(b) For a Dieterici gas
p =
RTe
a/RTV
m
V
m
b
,
_
S
V
_
T
=
_
p
T
_
V
=
R
_
1 +
a
RV
m
T
_
e
a/RV
m
T
V
m
b
.
For an isothermal expansion, S =
_
V
f
V
i
dS =
_
V
f
V
i
_
S
V
_
T
dV,
so we can simply compare
_
S
V
_
T
expressions for the three gases. For a perfect gas,
p =
nRT
V
=
RT
V
m
so
_
S
V
_
T
=
_
p
T
_
V
=
R
V
m
.
_
S
V
_
T
is certainly greater for a van der Waals gas than for a perfect gas, for the denominator is smaller
for the van der Waals gas. To compare the van der Waals gas to the Dieterici gas, we assume that both
have the same parameter b. (That is reasonable, for b is an excluded volume in both equations of state.)
In that case,
_
S
V
_
T,Die
=
R
_
1 +
a
RV
m
T
_
e
a/RV
m
T
V
m
b
=
_
S
V
_
T,vdW
_
1 +
a
RV
m
T
_
e
a/RV
m
T
.
TRAPP: CHAP03 2006/3/8 17:27 PAGE 74 #22
74 SOLUTIONS MANUAL
Now notice that the additional factor in
_
S
V
_
T,Die
has the form (1 +x)e
x
, where x > 0. This factor
is always less than 1. Clearly (1 + x)e
x
< 1 for large x, for then the exponential dominates. But
(1+x)e
x
< 1 even for small x, as can be seen by using the power series expansion for the exponential:
(1 + x)(1 x + x
2
/2 + ) = 1 x
2
/2 + So
_
S
V
_
T,Die
<
_
S
V
_
T,vdW
. To summarize, for
isothermal expansions:
S
vd
w > S
Die
and S
vd
w > S
perfect
.
The comparison between a perfect gas and a Dieterici gas depends on particular values of the constants
a and b and on the physical conditions.
P3.25 H U +pV.
dH = dU +p dV +V dp = T dS p dV [3.43] +p dV +V dp = T dS +V dp.
Since H is a state function, dH is exact, and it follows that
_
H
S
_
p
= T and
_
V
S
_
p
=
_
T
p
_
S
.
Similarly, A U TS.
dA = dU T dS SdT = T dS p dV [3.43] T dS SdT = p dV S dT.
Since dA is exact,
_
S
V
_
T
=
_
p
T
_
V
.
P3.27
_
S
V
_
T
=
_
p
T
_
V
[Maxwell relation];
_
p
T
_
V
=
_

T
_
nRT
V
__
V
=
nR
V
.
dS =
_
S
V
_
T
dV [constant temperature] = nR
dV
V
= nRd ln V.
S =
_
dS =
_
nRd ln V.
S = nRln V +constant or S Rln V.
P3.29

T
= T
_
p
T
_
V
p[3.48].
TRAPP: CHAP03 2006/3/8 17:27 PAGE 75 #23
THE SECOND LAW 75
p =
RT
V
m
+
BRT
V
2
m
[rst two terms of the virial expansion, 1.19].
_
p
T
_
V
=
R
V
m
+
BR
V
2
m
+
RT
V
2
m
_
B
T
_
V
=
p
T
+
RT
V
2
m
_
B
T
_
V
.
Hence,
T
=
RT
2
V
2
m
_
B
T
_
V

RT
2
B
V
2
m
T
.
Since
T
represents a (usually) small deviation from perfect gas behaviour, we may approximate V
m
.
V
m

RT
p

T

p
2
R

B
T
.
From the data B = {(15.6) (28.0)} cm
3
mol
1
= +12.4 cm
3
mol
1
Hence,
(a)
T
=
(1.0 atm)
2

_
12.4 10
3
dm
3
mol
1
_
_
8.206 10
2
dm
3
atmK
1
mol
1
_
(50 K)
= 3.0 10
3
atm .
(b)
T
p
2
; so at p = 10.0 atm,
T
= 0.30 atm .
COMMENT. In (a)
T
is 0.3 per cent of p; in (b) it is 3 per cent. Hence at these pressures the approximation
for V
m
is justied. At 100 atm it would not be.
Question. How would you obtain a reliable estimate of
T
for argon at 100 atm?
P3.31

T
= T
_
p
T
_
V
p [3.48].
p =
nRT
V nb
e
an/RTV
[Table 1.7].
T
_
p
T
_
V
=
nRT
V nb
e
an/RTV
+
na
RTV

nRT
V nb
e
an/RTV
= p +
nap
RTV
.
Hence,
T
=
nap
RTV
.

T
0 as p 0, V , a 0, and T . The fact that
T
> 0 ( because a > 0) is consistent
with a representing attractive contributions, since it implies that
_
U
V
_
T
> 0 and the internal energy
rises as the gas expands (so decreasing the average attractive interactions).
TRAPP: CHAP03 2006/3/8 17:27 PAGE 76 #24
76 SOLUTIONS MANUAL
P3.33 If S = S(T, p)
then dS =
_
S
T
_
p
dT +
_
S
p
_
T
dp,
TdS = T
_
S
T
_
p
dT +T
_
S
p
_
T
dp.
Use
_
S
T
_
p
=
_
S
H
_
p
_
H
T
_
p
=
1
T
C
p
_
_
H
S
_
p
= T, Problem 3.25
_
,
_
S
p
_
T
=
_
V
T
_
p
[Maxwell relation].
Hence, TdS = C
p
dT T
_
V
T
_
p
dp = C
p
dT TVdp .
For reversible, isothermal compression, TdS = dq
rev
and dT = 0; hence
dq
rev
= TVdp.
q
rev
=
_
p
f
p
i
TV dp = TV p [ and Vassumed constant].
For mercury
q
rev
=
_
1.82 10
4
K
1
_
(273 K) (1.00 10
4
m
3
) (1.0 10
8
Pa) = 0.50 kJ .
P3.35 ln =
_
p
0
_
Z 1
p
_
dp [3.60],
Z = 1 +
B
V
m
+
C
V
2
m
= 1 +B

p +C

p
2
+
with B

=
B
RT
, C

=
C B
2
R
2
T
2
[Problem 1.18].
Z 1
p
= B

+C

p + .
Therefore, ln =
_
p
0
B

dp +
_
p
0
C

p dp + = B

p +
1
2
C

p
2
+ =
Bp
RT
+
(C B
2
)p
2
2R
2
T
2
+ .
For argon,
Bp
RT
=
(21.13 10
3
dm
3
mol
1
) (1.00 atm)
(8.206 10
2
dm
3
atmK
1
mol
1
) (273 K)
= 9.43 10
4
,
(C B
2
)p
2
2R
2
T
2
=
{(1.054 10
3
dm
6
mol
2
) (21.13 10
3
dm
3
mol
1
)
2
} (1.00 atm)
2
(2) {(8.206 10
2
dm
3
atmK
1
mol
1
) (273 K)}
2
= 6.05 10
7
.
TRAPP: CHAP03 2006/3/8 17:27 PAGE 77 #25
THE SECOND LAW 77
Therefore, ln = (9.43 10
4
) +(6.05 10
7
) = 9.42 10
4
; = 0.9991.
Hence, f = (1.00 atm) (0.9991) = 0.9991 atm .
Solutions to applications
P3.37 w
add, max
=
r
G [3.38].

r
G

(37

C) =
r
G

(T
c
) +(1 )
r
H

(T
c
)
_
Problem 3.17, =
T
T
c
_
=
_
310 K
298.15 K
_
(6333 kJ mol
1
) +
_
1
310 K
298.15 K
_
(5797 kJ mol
1
)
= 6354 kJ mol
1
.
The difference is

r
G

(37

C)
r
G

(T
c
) = {6354 (6333)} kJ mol
1
= 21 kJ mol
1
. Therefore an
additional 21 kJ mol
1
of non-expansion work may be done at the higher temperature.
COMMENT. As shown by Problem 3.16, increasing the temperature does not necessarily increase the
maximum non-expansion work. The relative magnitude of
r
G

and
r
H

is the determining factor.

P3.39 The relative increase in water vapor in the atmosphere at constant relative humidity is the same as the
relative increase in the equilibrium vapor pressure of water. Examination of the molar Gibbs function
will help us estimate this increase. At equilibrium, the vapor and liquid have the same molar Gibbs
function. So at the current temperature
G
m,liq
(T
0
) = G
m,vap
(T
0
) so G

m,liq
(T
0
) = G

m,vap
(T
0
) +RT
0
ln p
0
,
where the subscript 0 refers to the current equilibrium and p is the pressure divided by the standard
pressure. The Gibbs function changes with temperature as follows
(G/T) = S so G

m,liq
(T
1
) = G

m,liq
(T
0
) (T)S

liq
and similarly for the vapor. Thus, at the higher temperature
G

m,liq
(T
0
) (T)S

liq
= G

m,vap
(T
0
) (T)S

vap
+R(T
0
+T) ln p.
Solving both of these expressions for G

m,liq
(T
0
) G

m,liq
(T
0
) and equating them leads to
(T)(S

liq
S

vap
) +R(T
0
+T) ln p = RT
0
ln p
0
.
Isolating p leads to
ln p =
(T)(S

vap
S

liq
)
R(T
0
+T)
+
T
0
ln p
0
T
0
+T
,
p = exp
_
(T)(S

vap
S

liq
)
R(T
0
+T)
_
P
(T
0
/(T
0
+T))
0
.
TRAPP: CHAP03 2006/3/8 17:27 PAGE 78 #26
78 SOLUTIONS MANUAL
So p = exp
_
(2.0 K) (188.83 69.91) J mol
1
K
1
(8.3145 J mol
1
K
1
) (290 +2.0 K)
_
(0.0189)
(290K/(290+2.0)K)
,
p = 0.0214 which represents a 13 per cent increase.
P3.41 The change in the Helmholtz energy equals the maximum work associated with stretching the polymer.
Then
dw
max
= dA = f dl.
For stretching at constant T
f =
_
A
l
_
T
=
_
U
l
_
T
+T
_
S
l
_
T
.
Assuming that (U/U)
T
= 0 (valid for rubbers)
f = T
_
S
l
_
T
= T
_

l
_
T
_

3k
B
l
2
2Na
2
+C
_
= T
_

3k
B
l
Na
2
_
=
_
3k
B
T
Na
2
_
l.
This tensile force has the Hookes law form f = k
H
l with k
H
= 3k
B
T/Na
2
.
P3.43 The Otto cycle is represented in Fig. 3.5. Assume one mole of air.
Figure 3.5
=
|w|
cycle
|q
2
|
[3.8].
w
cycle
= w
1
+w
3
= U
1
+U
3
[q
1
= q
3
= 0] = C
V
(T
B
T
A
) +C
V
(T
D
T
C
) [2.27].
q
2
= U
2
= C
V
(T
C
T
B
).
=
|T
B
T
A
+T
D
T
C
|
|T
C
T
B
|
= 1
_
T
D
T
A
T
C
T
B
_
.
TRAPP: CHAP03 2006/3/8 17:27 PAGE 79 #27
THE SECOND LAW 79
We know that
T
A
T
B
=
_
V
B
V
A
_
1/c
and
T
D
T
C
=
_
V
C
V
D
_
1/c
[2.28a].
Since V
B
= V
C
and V
A
= V
D
,
T
A
T
B
=
T
D
T
C
, or T
D
=
T
A
T
C
T
B
.
Then = 1
T
A
T
C
T
B
T
A
T
C
T
B
= 1
T
A
T
B
or = 1
_
V
B
V
A
_
1/c
.
Given that C
p,m
=
7
2
R, we have C
V,m
=
5
2
R [2.26] and c =
2
5
.
For
V
A
V
B
= 10, = 1
_
1
10
_
2/5
= 0.47 .
S
1
= S
3
= S
sur,1
= S
sur,3
= 0 [adiabatic reversible steps].
S
2
= C
V,m
ln
_
T
C
T
B
_
.
At constant volume
_
T
C
T
B
_
=
_
p
C
p
B
_
= 5.0.
S
2
=
_
5
2
_
(8.314 J K
1
mol
1
) (ln 5.0) = +33 J K
1
.
S
sur,2
= S
2
= 33 J K
1
.
S
4
= S
2
_
T
C
T
D
=
T
B
T
A
_
= 33 J K
1
.
S
sur,4
= S
4
= +33 J K
1
.
P3.45 In case (a), the electric heater converts 1.00 kJ of electrical energy into heat, providing 1.00 kJ of
energy as heat to the room. (The Second Law places no restriction on the complete conversion of
work to heatonly on the reverse process.) In case (b), we want to nd the heat deposited in the
room |q
h
|:
|q
h
| = |q
c
| +|w| where
|q
c
|
|w|
= c =
T
c
T
h
T
c
[Impact I3.1]
so |q
c
| =
|w|T
c
T
h
T
c
=
1.00 kJ 260 K
(295 260)K
= 7.4 kJ.
TRAPP: CHAP03 2006/3/8 17:27 PAGE 80 #28
80 SOLUTIONS MANUAL
The heat transferred to the room is |q
h
| = |q
c
| +|w| = 7.4 kJ +1.00 kJ = 8.4 kJ . Most of the thermal
energy the heat pump deposits into the room comes from outdoors. Difcult as it is to believe on a cold
winter day, the intensity of thermal energy (that is, the absolute temperature) outdoors is a substantial
fraction of that indoors. The work put into the heat pump is not simply converted to heat, but is leveraged
to transfer additional heat from outdoors.