Chapter 6 Solutions

Engineering and Chemical Thermodynamics

Wyatt Tenhaeff
Milo Koretsky
Department of Chemical Engineering
Oregon State University
[email protected]

6.1
(a)
The Clausius-Clapeyron equation:

vap
dPisat hi dT

Pisat
RT 2

or

so

h vap 1
1
Pisat 101 kPaexp i

R T 373[K]

(b) and (c)

Using

we obtain the following table

T [K]

Eqn 6.24
[kPa]

273.156
278.15
283.15
288.15
293.15
298.15
303.15
308.15
313.15
318.15
323.15
328.15
333.15
338.15
343.15
348.15
353.15
358.15
363.15
368.15
373.15

0.84
1.16
1.58
2.13
2.84
3.76
4.93
6.40
8.24
10.54
13.36
16.82
21.04
26.13
32.26
39.58
48.28
58.56
70.67
84.84
101.35

Steam Tables
%
[kPa]
Difference
0.6113
0.87
1.23
1.71
2.34
3.17
4.25
5.63
7.38
9.59
12.35
15.76
19.94
25.03
31.19
38.58
47.39
57.84
70.14
84.55
101.35

37.30%
33.02%
28.30%
24.51%
21.51%
18.62%
15.94%
13.68%
11.71%
9.86%
8.19%
6.75%
5.50%
4.40%
3.42%
2.58%
1.87%
1.25%
0.75%
0.34%
0.00%

The logarithmic trend is well-represented. However, at lower temperatures the ClausiusClapeyron equation is up to 37% off. The actual heat of vaporization changes from
kJ

kg

2501.3

kJ

at 0.01 oC to 2257.0 kg at 100 oC, a difference of around 10%.

Pressure [kPa]

100.00

10.00

Eqn 6.23
Tables
1.00

0.10
273

283

293

303

313

323

333

343

353

363

373

Temperature [K]

(d)
For 100 C to 200 C, we obtain the following table:
T [K]

Eqn 6.24
[kPa]

Steam Tables
[kPa]

%
Difference

373.15
378.15
383.15
388.15
393.15
398.15
403.15
408.15
413.15
418.15
423.15
428.15
433.15
438.15
443.15
448.15
453.15
458.15
463.15
468.15
473.15

101.35
120.51
142.64
168.11
197.30
230.63
268.55
311.54
360.11
414.82
476.24
545.00
621.74
707.16
801.99
906.98
1022.93
1150.68
1291.10
1445.10
1613.62

101.35
120.82
143.28
169.06
198.53
232.1
270.1
313
361.3
415.5
475.9
543.1
617.8
700.5
791.7
892
1002.2
1122.7
1254.4
1397.8
1553.8

0.00%
0.26%
0.44%
0.56%
0.62%
0.63%
0.57%
0.47%
0.33%
0.16%
0.07%
0.35%
0.64%
0.95%
1.30%
1.68%
2.07%
2.49%
2.93%
3.38%
3.85%

Pressure [kPa]

10000.00

Eqn 6.23

1000.00

Tables

100.00
373

383

393

403

413

423

433

443

453

463

473

Temperature [K]

Over this range the Clausius-Clapeyron equation represents the data well and is no more than 4
% off. The actual heat of vaporization changes from 2257.0 kJ/kg at 100 oC to
1940.7 kJ/kg at 200 oC, a difference of around 15%.
(e)
The heat of vaporization can be corrected for temperature as follows
hvap T

Tb

Tb

l
c P dT hvap Tb

c P dT

We can acquire heat capacity data from Appendix A.2, but to simplify the analysis, we will use
an average heat capacity for the vapor.
hvap T 75.4 373.15 T 40626 34.13 T 373.15
hvap T 56026 41.27T

Substitute this expression into the Clausius-Clapeyron equation

dPisat
Pi

sat

56026 41.27T dT
RT 2

Integrate:
1
1
T
1

56026

41.27 ln

T 373.15
373.15
R

Pisat 101.35 kPa exp

Now plot the data as before from 0.01 C to 200 C.

7

T [K]

Eqn 6.24
[kPa]

Steam Tables
[kPa]

%
Difference

273.16
278.15
283.15
288.15
293.15
298.15
303.15
308.15
313.15
318.15
323.15
328.15
333.15
338.15
343.15
348.15
353.15
358.15
363.15
368.15
373.15
378.15
383.15
388.15
393.15
398.15
403.15
408.15
413.15
418.15
423.15
428.15
433.15
438.15
443.15
448.15
453.15
458.15
463.15
468.15
473.15

0.64
0.91
1.28
1.78
2.43
3.29
4.39
5.81
7.60
9.86
12.66
16.12
20.35
25.49
31.68
39.10
47.91
58.32
70.54
84.80
101.35
120.46
142.40
167.48
196.00
228.29
264.70
305.56
351.26
402.16
458.64
521.10
589.92
665.51
748.27
838.59
936.89
1043.55
1158.98
1283.56
1417.67

0.6113
0.87
1.23
1.71
2.34
3.17
4.25
5.63
7.38
9.59
12.35
15.76
19.94
25.03
31.19
38.58
47.39
57.84
70.14
84.55
101.35
120.82
143.28
169.06
198.53
232.1
270.1
313
361.3
415.5
475.9
543.1
617.8
700.5
791.7
892
1002.2
1122.7
1254.4
1397.8
1553.8

4.95
4.96
4.24
3.88
3.86
3.65
3.35
3.17
3.03
2.78
2.51
2.28
2.06
1.84
1.58
1.34
1.09
0.82
0.57
0.29
0.00
0.30
0.61
0.94
1.28
1.64
2.00
2.38
2.78
3.21
3.63
4.05
4.51
4.99
5.49
5.99
6.52
7.05
7.61
8.17
8.76

The agreement between the two values at lower temperatures improves significantly at lower
temperatures, but actually worsens at higher temperatures. The agreement could potentially be
improved by not averaging the heat capacity.

6.2
We can find the required pressure by applying the Clapeyron equation:
dP
hl h s

dT
vl v s T

We can find the molar volume of water ice from any number of reference books. At 0 C and 1
bar:
kg

l 1000

s 917

m3

mol

v l 1.80 10 5

m3
kg
v s 1.97 10 5
3
m

m3

mol

Also at 0 C and 1 bar,

J
mol

h l h s 6010

If we assume that h l h s and v l v s are independent of temperature and pressure, we can

separate variables in the Clapeyron equation and integrate.
P2 P1

hl h s

P2 1 10 5 Pa

so

T2
T1

ln

1.80 10

6010 J/mol
1.97 10

P2 66.1 bar

10

/ mol

268.15 K

273.15 K

ln

6.3
(a)
At 1 bar, the gas will act as an ideal gas.

J
300 K
m3
mol K

0
.
0249

1 10 5 Pa
mol

8.314

RT

The number of moles of vapor are found as follows (neglect molar volume of liquid)
V

nv

0.001 m 3
m3
0.0249

mol

n v 0.0402 mol

(b)
At 21 bar, the gas will not behave ideally. Since we are assuming that the molar volume of liquid
is negligible and the heat of vaporization is independent of temperature, the Clapeyron
equation becomes
dP h vap
v
dT
vT

The molar volume using pressure expansion of the virial equation is

vv

RT 1 B ' P
1

RT
B'
P
P

Substituting this expression into the Clapeyron equation yields

dP

dT

h vap
1

R
B' T 2
P

Separation of variables yields

P2 21 10 5 Par

P1 1 10 5 Pa

h vap
1
'
B dP

R
P

T2

dT
2
T1 300 K T

and integration results in

11

 P2
P1

ln

B ' P2 P1

h vap
R

1 1

T2 T1

We can substitute values for given quantities and constants to solve for T2.
T2 523.3 K

(c)
Using the virial equation,

J
1

B ' 8.314
P

mol K

v v RT

3
1
7 m

10

5
J
21 10 Pa

523.3 K

mol

v v 0.00164

We can assume the volume occupied by the liquid is negligible. Therefore,

nv

vv

0.001 m 3
m3
0.00164

mol

n v 0.61 mol

12

6.4
We can use the following computational path to solve for pressure at which graphite and
diamond are in equilibrium at 25 oC.
graphite

diamond

P = 1 [atm]
J
mol

g 2866

g1

v graphdP

g 3

v diam dP

P
diamond

g 2 0

graphite

Summing together the three steps we get:

J
g1 g 2 g 3
mol

g 1[atm] 2866

To find the change in Gibbs energy with pressure, we apply the fundamental property relation,
Equation 5.9. At constant temperature:
0
dgi v idP sidT
If the solid is assumed incompressible, we can integrate to get

vi dP vi P

g i

Thus the sum of Gibbs energy becomes

J
v graph dP 0 v diam dP v graph v diam P 1
mol
1
P

g 1[atm] 2866

Solving

J
mol

2866

1
1

2.26 3.51

cm 3

g
12
mol

or
P = 1,514 [MPa] = 15,143 [bar]

13

1 m3

10 6 cm 3

P 1.01 10 5 Pa

6.5
From the Clausius-Clapeyron equation:
(I)
T

where h fus is the enthalpy of fusion at temperature T. We can get the molar volumes from the
densities:
kg

MW
mol 1.17 10 5
v lAl

kg
l
2,300

m3

m3

mol

kg

mol 1.00 10 5
s
v Al

kg
s
2,700

m3

m3

mol

0.027

and

MW

0.027

so
m3
v lAl v sAl 1.7 10 6

mol

We can use the following path to calculate for h Tfus .

solid

liquid

h Tfus
933

933

cPs dT

cPl dT

T = 933 [K]
solid

J
h fus 10,711
mol

liquid

14

h Tfus

933.45
T
J
s
l
cP
dT 10,711
cP
dT

mol
T
933.45

s
l
Using c P 20.608 0.0138T mol K and c P 31.748 mol K , we get:

2
h T
fus 5,819.9 11 .68T 0.0069T

Back into Equation (I) gives:

5,819.9 11.68T 0.0069T 2

1.7 10 6 T

dP

dT

Integrating:
100 [bar]

933.45 [K]

dP

5,819.9 11.68T 0.0069T 2

1.7 10 6 T

dT

or

100 1 105 1.7 10 6 5819.9 ln

T
2
2
11.68 T 993.45 0.00345 T 993.45
933.45

solving for T gives

T = 934.91 [K]

15

6.6
We can assume that silver acts as an ideal gas at 1500 K. We can also assume the molar volume
of the vapor is much greater than the molar volume of liquid. Therefore, we can use Equation
6.22
dP sat
P sat

h vap dT

RT 2

This can be rearranged to show

dP sat h vap P sat

dT
RT 2

This relation assumes

1.
vv>>vl
2.
Silver acts as an ideal gas
We can differentiate the expression for pressure in the problem statement to obtain
dP sat
dT
dP sat
dT

14260 0.458
14260

0.458 ln T 12.23
exp
2
T
T
T

14260 0.458 sat

P
2
T
T

Therefore,
h vap
14260 0.458

2
T
RT 2
T

Therefore,
h vap R 14260 0.458T

At 1500 K,

h vap 8.314
mol K

kJ
h vap 112 .8
mol

14260 0.4581500 K

16

6.7
For a single component system:
Gi g i g

From the fundamental property relation given by Equation 5.9:

dg sdT vdP

We can identify a phase transition from the vertical line of the g vs. T plot, as indicated below.
Since this transition is vertical, i.e., the temperature is constant, the pressure must also be
constant. Thus, we can differentiate the Gibbs energy with respect to temperature at constant
pressure to get:
g

s
P

Hence the slope of a plot of g (or ) vs. T at any temperature must be the negative of the value of
entropy on the plot for s vs. T. The resulting curve is sketched below.

phase transition;
vertical line indicates
P = const

Thick line denotes

lowest value of

Slope = the negative

value of s at the same
T on the curve above

T*

17

6.8
The ferrite phase has stronger bonds. At room temperature, iron is in the ferrite phase. The
heating to 912 C has the effect of increasing the entropy contribution to the Gibbs energy. At a
high enough temperature, the austenite phase becomes stable, so that its entropy must be greater
than the ferrite phase. If the entropy of the austenite phase is greater, the enthalpy of the ferrite
phase must be greater or else the austenite phase would be stable over the entire temperature
range. Hence, the ferrite phase has stronger bonds.

18

6.9
Since the pressures are low, we can assume ideal gas behavior. We can also assume that the
molar volume of the vapor is much greater than the molar volume of liquid and the heat of
vaporization is independent of temperature. Therefore, we can rearrange Equation 6.24 to obtain

h vap

h vap

J 760 torr

8.314
ln

mol K 400 torr

1
1

353.25
K
333
.
75
K

kJ

32.3

mol

This value is 7.7% smaller than the reported value.

19

6.10
(a)
The freezing point occurs where there is a discontinuity in the g vs. T plot, as indicated below.
The liquid is at a temperature higher than the freezing point and the solid at lower temperature.
These are demarked below. The melting temperature is 250 K, which occurs at a value g = 3,000
[J/mol]
Purespecies"a"

Gibb'sEnergy,g(J/mol)

6000

1unit
up
NewFreezing
point

4,000
solid
Freezing
point

2,000

liquid

100

200

1.2
units
up

300

Temperature,T(K)
(b)
At constant pressure, the entropy can be found from Equation 5.14. For the solid we have:
g
s

g 1,000
J

10

T
10
mol K

And for the liquid, we get:

g
s

g
2,000
J

40
T
50
mol
K

(c)
As we change pressure, we can see how the Gibbs energy changes at any given temperature by
Equation 5.14:

20

v
T

Assuming the molar volumes of the liquid and vapor stay constant over the temperature range
around the melting point, we see that the Gibbs energy of the liquid increases by 1.2 times the
Gibbs energy of the solid, since the molar volume of the liquid is 20% larger. The Gibbs energy
of the new freezing point at higher pressure is schematically drawn on the plot above. For
convenience, we choose the solid to increase by 1 unit on the plot. Thus, the liquid increases by
1.2 units. As the sketch shows, the freezing point, where the two lines intersect, will shift to
higher temperature.

21

6.11
For a single component system the fundamental property relation, Equation 5.9, gives:
dg sdT vdP

We can identify a phase transition from the vertical line of the g vs. P plot, as indicated below.
Since this transition is vertical, i.e., the pressure is constant, the temperature must also be
constant. Thus, we can differentiate the Gibbs energy with respect to pressure at constant
temperature to get:
g

v
T

Hence the slope of a plot of g vs. P must have a slope that matches the plot for v vs. T. Since the
molar volume of phase is about twice the value of phase , its slope should be twice as big.
The resulting curve is sketched below.
v

phase transition;
vertical line indicates
T = const

v
v

Slope of top line is

Straight line since

v is constant

Thick line denotes

lowest value of g

P*

22

about twice as big as

the slope of bottom
line

6.12
The saturation pressure can be found using the Clausius-Clapeyron equation with the assumption
that the heat of vaporization is independent of temperature. First, we need to use the given data
for the 63.5 C and 78.4 C to find the heat of vaporization.

h vap

P sat
R ln 2
P sat
1

1
1

T2 T1
kJ
h vap 42.39
mol

J 760 torr

8.314
ln

mol K 400 torr

1
1

351.55 K 336.65 K

Now we can calculate the vapor pressure at 100 C.

h vap
sat
sat
P3 P2 exp

P3sat

kJ

42.39

1
1
1
1

mol
760 torr exp

kJ 373.15 K 351.55 K
T3 T2
0.008314
mol K

1760 torr 2.32 atm

In comparison, ThermoSolver gives a value of 2.23 atm, using the Antoine equation.

23

6.13
We can show using the Chain Rule that

gi
T

T

Tg i g i T

T2

1 g i

T T

gi
T2

Using fundamental property relations, Equation 5.14 states

g i

si
T P

Therefore,

gi
T
T

Ts i g i
T

Ts i hi Ts i
T

hi
T2

24

6.14
Let T1 922 K, T2 1,300 K
g 2 h2 T2 s 2
dh c P dT
1,300 K

h2 h1

c P dT

922 K

J
mol

h2 h1 c P T2 T1 39,116

c
ds P dT
T
T2
J
85.10
mol K
T1

s2 s1 c P ln

J
mol

g 2 h2 T2 s2 71,500

Alternative solution using the result from Problem 6.13:

dg
T hT h1 c P T T1

dT
T2
T2

We must leave h as a function of T

h1 c P T T1

dT
T2

922 K

1300 K

g

T

d
1

1 1
T
J
g
g

c P ln 2 55.01
h1 c PT1
T 2 T1
mol K
T2 T1
T1

mol

g 2 71,500

25

6.15
A possible hypothetical solution path is presented below:
monoclinic

orthorhombic
T = 298 [K]

g1

g3

T = 368.3 [K]
monoclinic

g2=0

orthorhombic

From the diagram, we see that the Gibbs energy for steps one and three can be calculated as
follows:
g m
T
298 K

368 K

g1

dT

and
g o
T
368 K

298 K

g 3

dT

respectively. We can apply Equation 5.14 from the thermodynamic web

g
s

T P

At 368 K, sulfur undergoes a phase transition, so

o
g 3m68
K 0

Using these above relationships, the expression for

mo
g 298
K

368 K
m

dT 0

298 K

m o
g 298
K

becomes

298 K
o

368 K

298 K

368 K

298 K

368 K

s dT

13.8 0.066T dT 11 0.071T dT

mo
g 298
K 79.5

J
mol

Therefore, the transition from the monoclinic to orthorhombic state occurs spontaneously. The
orthorhombic state is more stable.

26

6.16
At the phase transition, the following is true
g
g


T Sr ( s ) T Sr (l )

Using the thermodynamic web, the following can be shown (see Problem 6.13)
h
g / T

2
T P T

The enthalpies can be written as follows

T

h l T 49179

35.146 dT

35.146T 3540

37.656 dT

37.656T 16305.4

1500 K
T

h s T 20285

900 K

g
can also be calculated at 900 K for solid Sr and 1500 K for liquid Sr.
T
gl

gs

mol K

83.85

ref

mol K

68.68

ref

g
at any temperature using the differential equation as follows
T

We can find

g

T

g / T
T

dT

h
T2

dT

Substituting our expressions, we get

g l /T

83.85

g

T

1500 K

35.146T 3540

T2

dT

gl

35.146 ln(T ) 3540 176.04

T
T

g s /T

68.68

g

T

900 K

37.656T 16305.4

dT

T2

27

 gs
T

37.646 ln(T ) 16305.4 205.5

Set

gl

l
g
T

and solve for T:

T melt 1059.8 K

The enthalpy of melting is defined as

h fus h s T melt h l T melt

Using the expressions developed above

kJ
kJ
kJ
33.71
7.41

mol
mol
mol

h fus 26.30

28

6.17
At the phase transition, the temperature and Gibbs energy of both phases must be equal.
Mathematically, this is equivalent to
g
g


T SiO2 ( s ) T SiO 2 (l )

Using the thermodynamic web, the following can be shown (see Problem 6.13)
h
g / T

2
T P T

Using the definition of enthalpy, we can write the following

h T

h ref

T ref

dh

cP

dT

h T href

c P dT

Tref

The enthalpies can be written as follows

h l T 738440
h s T 856840

85.772 dT

2500 K
T

53.466 0.02706T 1.27 10

T 2 2.19 10 9 T 3 dT

1100 K

g
can also be calculated at 1100 K for solid SiO2 and 2500 K for liquid SiO2.
T
gl

ref

mol K

487.3

ref

mol K

903.5

We can substitute our expressions for

g
and h T into the above differential equation and
T

separate variables to obtain

29


g l /T

487.3

738440

85.772 dT

2500 K

g s /T

903 .5

53.466 0.02706T

1100 K

856840

dT

T2

2500 K

1100 K

1.27 10 5 T 2 2.19 10 9 T 3 dT

dT

Integration provides
gl
9.5268 10 9 85.772 ln(T ) 1052.4T

487.5
T
T
gs
1.82 10 10 T 4 2.12 10 6 T 3 0.01353T 2 927190.9 53.466T ln(T ) 1230T

903.5
T
T

If we plot

gl g s

T T

vs. T, we obtain the following:

There are three solutions, but only the solution between 1100 K and 2500 K is physically
meaningful. If we magnify the plot near the middle solution, we find
T 1983 K

The enthalpy of fusion is defined as

h fus h s T melt h l T melt

Using the expressions developed above

30

 kJ
kJ
kJ
782.78
9.72

mol
mol
mol

h fus 792.5

31

6.18
From the Clausius-Clapeyron equation
sat
dPCS

dT

h vap

T vv vl

Assuming:
v v v l

we get
sat
dPCS

h vap

dT

(I)

Tv v

The saturation pressure is given by:

sat
ln PCS
62.7839
2

4.7063 10 3
6.7794 ln T 8.0194 10 3 T (II)
T

sat
5
At T = 373 K, PCS 2 4.48 10 Pa. Taking the derivative of Equation II
sat
d ln PCS

dT

sat
dPCS

sat
PCS
2

dT

4.7063 10 3
T

6.7794
8.0194 10 3
T

(III)

Plugging Equation III into Equation I,

4.7063 10 3

T2

sat
6.7794
h vap
8.0194 10 3 PCS

2
T
Tv v

kJ
gives:
mol

vap
Solving for vv using hCS 24.050
2

h vap 4.7063 10 3 6.7794

8.0194 10 3

sat
T
TPCS
T2

Pv
B
0.878 1
RT
v

or
m3
cm 3
740

mol
mol

B 7.4 10 4

32

m3

mol

6.08 10 3

This value is about 50% higher than the reported value.

Alternative solution:
Following similar development as Problem 6.3:
sat
dPCS

dT

h vap

1
RT 2 sat B '
PCS 2

1
h vap
'
sat
sat B dPCS
2 dT
2
RT
PCS2

We must be careful about the limits of integration. We need to pick a value of T close so
enthalpy of vaporization is not too different, but far enough away to avoid round off error. If we
sat
5
choose T = 378 K, Equation I gives PCS 2 5.04 10 Pa. Integrating:
4.4810 5 Pa

373
1
h vap
'
sat
sat B dPCS
2 dT
2
P
RT
5

378
5.0410 Pa CS2

4.48 105
h vap 1
1
'
5
5
ln

B
4.48
10

5.04

10

5
R 373 378
5.04 10

Solving for B gives:

B' 2.55 107 Pa
or
m 3
B B ' RT 7.9 104

mol

33

6.19
Calculate vA, vB, v, VA, VB, and V from the ideal gas law:
RT
0.05 m 3 / mol
P
RT
vB
0.05 m 3 / mol
P
RT
v
0.05 m 3 / mol
P
vA

V A n A v A 0.1 m 3
V B n B v B 0.15 m 3
V

ntot v 0.25 m 3

We calculate the partial molar volumes as follows

V
V A
n A
V
V B
n B

T , P, n B

T , P, n A

n A n B RT RT 0.05 m 3 / mol

n A
P
P

n A n B RT RT 0.05 m 3 / mol
n B
P
P

To find the remaining quantities, we can apply Equations 6.44 and 6.46
Vmix n A V A v A n B V B v B
Vmix 2 0.05 0.05 3 0.05 0.05 0
v mix x A V A v A x B V B v B
v mix 0

34

6.20
(a)
For a pure species property
v a v y a 1

Substitution yields
cm 3

mol

v a 1001 80 0 2.51 0 100

(b)
From Equation 6.29
V
Va
na

n b ,T , P

We can find V by multiplying the given expression for molar volume by the total number of
moles.

y y
n n
V na nb 100 ya 80 yb 2.5 a b 100na 80nb 2.5 a b
y a yb
na nb

Differentiating with respect to na we get,

Va

na

100na 80nb 2.5

na nb
nb
na nb

100 2.5
2.5
na nb n
na nb
na nb 2
b

so
Va 100 2.5 yb 1 y a 100 2.5 yb2

To find the molar volume at infinite dilution, we can use the following relation
Va lim Va
y a 0

cm 3

mol

Va 102.5

(c)
Since species A contributes more to a mixture than to a pure species,

35

v mix 0

Note: The Gibbs-Duhem equation says that species B also contributes more.

36

6.21
Calculate mole fractions:
n1
1 mol

0 .2
ntot 5 mol

y1

y 2 0.4

y3 0.4

Calculate v.
Obtain an expression for v:
v

RT
P

B
2 A
1 P RT y1 y 2 RT

Substitute values:

82.06 cm atm

mol K
v
50 atm

500 K

1 50 9.0 10
2

0.2 0.4 3.0 10 5

cm 3

mol

v 919.0

Calculate V.
V ntot v

cm 3
V 5 mol 919.0

mol

V 4595 cm 3

Calculate v1.
The value of v1 can be found by substituting y1=1 into the expression for v1.

82.06 cm atm

mol K
v1
50 atm

500 K

1 50 9.0 10
2

cm 3

mol

v1 698

Calculate v2.

37

1 0 3.0 10 5

82.06 cm atm

mol K

v2

500 K

50 atm

1 50 9.0 10
2

0 1 3.0 10 5

cm 3

mol

v2 1067

Calculate v3.

82.06 cm atm

mol K

v3

500 K

50 atm

1 50 3.0 10
2

cm 3
v3 882

mol

Calculate V1 .
From Equation 6.29:
V
nv

V1

n1 n 2 , n3 ,T , P n1 n 2 , n3 ,T , P

We can substitute the expression for V into this derivative and use the fact that ntot n1 n2 n3
to obtain
V1

RT

n1 n2 n3 P 2 A n1 n2 B n1 n2 n3

n1 P
RT
RT

n 2 , n 3 ,T , P

Differentiating we get
RT
P

V1

B
2 A
1 P RT RT

Substitute values:

82.06 cm atm

mol K
V1
50 atm

500 K

1 50 9 10
2

cm 3

mol

V1 697.5

38

3 10 5

6.22
(a)
By definition:
H
H a
na

T , P , nb , n c

n na nb nc
H nh 5,000na 3,000nb 2,200nc 500

na nbnc

na nb nc 2

H
nbn c
2na nbnc

5,000 500

2
3
na T ,P,n ,n
n

n
n

a
b
c
a
b
c

b c
H

Ha
5,000 500xb x c 1 2xa J/mol
na T ,P,n ,n
b c
(b)
xa xb xc

1
3

Ha 5,018.5J/mol
(c)
xa 1 , xb xc 0

Ha 5,000J/mol
(d)
xb 1 , xa xc 0

Hb hb 3,000J/mol

39

6.23
Let the subscript 1 designate CO2, and 2 designate propane. To calculate the partial molar
volumes, the following formulas will be used:
V1 v y 2

dv
dy 2

v y1V1 y 2V2

Expressions cant be obtained for the molar volume with the van der Waals EOS; therefore, the
problem will be solved graphically. First, obtain an expression for the pressure that contains the
mole fractions of CO2 and propane:
a mix y12 a1 2 y1 y 2 a1a 2 y 22 a 2

bmix y1b1 y 2 b2

y 2 a 2 y1 y 2 a1a2 y 22 a 2
RT
1 1
v y1b1 y 2 b2
v2

Solve for a and b using data from the appendices.

J m3

a1 0.366

mol

b1 4.29 10 5

m3

mol
J m3
a 2 0.941

mol 2

mol

b2 9.06 10 5

m3

Now we can create a spreadsheet with the following headings:

y1

y2

amix

bmix

The last column contains the molar volumes obtained by solving the van der Waals equation with
the spreadsheets solver function. After the table is completed, we create the following graph.

40

From the line of best fit, we find

v 8 10 5 y 22 8 10 5 y 2 0.00147

Therefore,
dv
1.6 10 4 y 2 8 10 5
dy 2

and

V1 v y 2 1.6 10 4 y 2 8 10 5

We can find the partial molar volume of propane from the following relationship
v y1V1 y 2V2

V2

v y1V1
y2

Tabulate the values of the partial molar volumes in the spreadsheet and create the following
graph

41

42

6.24
(a)
ga 40

kJ
mol

Ga g x b

dg
dx b

dg
40 60 RT ln xa 1 ln x b 1 5x a 5xb
dx b
Ga 40xa 60x b RT xa ln x a x b ln xb 5xa x b

x b40 60 RT ln xa 1 ln x b 1 5x a 5xb

Ga 40xa xb RT xa xb ln x a 5xb2
Ga 40 RT ln x a 5xb2
Ga 40

8.314(300)
kJ
kJ
ln 0.2 5(0.64)
40.8
1000
mol
mol

Ga
Gmix ng x a ga xb gb
g xa ga x bgb RT x a ln xa xb ln x b 5x a xb
Gmix nT RT x a ln xa xb ln x b 5xa x b 2.2kJ
(b)
gmix hmix Tsmix
Assume the entropy of mixing is ideal:
hmix 5x a xb 0
so

so

h hmix hsensibleheat 0

hsensibleheat 0 and T goes down

43

6.25
To find V1 and V2 , we can read values directly from the graphs. Calculate mole fractions
x1

1
0.2
5

At x1 0.2 ,
cm 3

mol

V1 46.5

cm 3

mol

V2 69.8

The following relationships are employed to calculate the molar volumes of pure species
v1 lim V1
x1 1

v 2 lim V2 lim V2
x 2 1

x1 0

From the graph

cm 3

mol

v1 50

cm 3

mol

v2 70

Therefore,

V1 50 cm 3

V2 280 cm 3

To calculate the total volume, we can use

V n1V1 n 2V2

Substituting the values, we find

V 1 46.5 4 69.8 325.7 cm 3

Therefore

44

V
325.7

ntot
1 4
cm 3

mol

v 65.14

Using Equation 6.43 we can calculate the change in volume.

Vmix V V1 V2 325.7 50 280

Vmix 4.3 cm 3

45

6.26
(a)
Expression for hmix :
hmix X i H i X i hi X Cd H Cd X Sn H Sn X Cd hCd X Sn hSn

Multiply both sides by the total number of moles

H mix nCd H Cd n Sn H Sn nCd hCd n Sn hSn

Therefore,

H mix Cd

H mix

H Cd hCd
nCd n Sn ,T , P

(b)
We can show by repeating Part (a) for Sn that

H mix Sn H Sn hSn
Equation 6.65:

H mix Cd hmix X Sn dhmix

dX Sn
H mix Sn hmix X Cd dhmix
dX Cd

Since,

hmix 13000 X Cd X Sn

We get,
dhmix
d
13000 X Cd X Sn 13000 X Cd X Sn

dX Sn
dX Sn
dhmix
d
13000 X Cd X Sn 13000 X Sn X Cd

dX Cd
dX Cd

Therefore, for 3 moles of cadmium and 2 moles of tin at 500 C:

46

2
H Cd hCd H mix Cd 13000 X Cd X Sn X Sn13000 X Cd X Sn 13000 X Sn

mol

H Cd hCd H mix Cd 2080

and

J
mol

2
H Sn hSn H mix Sn 13000 X Cd
4680

(c)
Equation 6.37:
nCd d H mix Cd n Sn d H mix Sn 0

Differentiate with respect to XCd:

d H mix Cd

nCd

dxCd

n Sn

d H mix Sn
dxCd

where
d H mix Cd
dX Cd

d H mix Sn
dX Sn

26000 X Sn 26000 26000 X Cd

26000 X Cd

Therefore,

nCd

d H mix Cd
dxCd

nSn

d H mix Sn
dxCd

xCd ntot 26000 26000 xCd 1 xCd ntot 26000 xCd

Inspection of the above expression reveals that

nCd

d H mix Cd
dxCd

n Sn

d H mix Sn
dxCd

(d)
A graphical solution can be found using the tangent-slope method discussed on pages 285-287:
A plot of a line tangent to the enthalpy of mixing curve at XCd = 0.6, is given below:

47

Heatofmixin gincadmium(Cd )Tin (Sn)s ystem

6000
5400

hmix
mol

4800
4200
3600

data

3000
2400
1800
1200
600
0
0

0 .2

fitto:
J
hmix 13, 000 xCd x Sn
mol

0.4

0.6

0.8

xCd

The intercepts give the respective partial molar quantities as follows:

J
mol
J
4800
mol

H Cd hCd 2050
H Sn hSn

The values using the graphical method are reasonably close to the analytical method.

48

6.27
The following can be shown with the Gibbs-Duhem equation
0 x1V1 x 2V2

Differentiation with respect to x1:

0 x1

dV1
dV 2
x2
dx1
dx1

If the partial molar volume of species 1 is constant, the Gibbs-Duhem equation simplifies to
0

dV 2
dx1

Therefore, the partial molar volume of species 2 is also constant.

Note that in this case, since the partial molar volume of species 1 is constant:
V1 v1

and similarly for species 2:

`

V2 v2

Hence, the molar volume can be written:

v x1V1 x2V2 x1v1 x2v2

This is known as Amagats law.

49

6.28
(a)
Let species 1 represent HCl and species 2 represent H2O. An expression for the enthalpy of the
solution is
h x1h1 x 2 h2 hmix

which can be written

~
h x1h1 x2 h2 x1hs

Therefore,
~
H n1h1 n2 h2 n1hs

To use the heat of solution data in Table 6.1, we need to determine the values of n1 and n2
consistent with the convention used in the table. As seen in Example 6.6,

x1

n1
1

n1 n2 1 n

For this problem

x1 0.2

Therefore,
n1 1
n2 n 4

Now we can find expressions for the partial molar enthalpies.

H
H H 2 O H 2
n2

n1 ,T , P

~
dhs
H H 2 O H 2 h2 n1
dn2

H H 2 O hH 2 O H 2 h2 n1

~
dhs
dn2

Using the data in Table 6.1 for n 4 ,

50

hs 61,204

mol
solute

J
J

64049
56852
~
~
~

dhs hs n 5 hs n 3
mol solute
mol solute

dn2
5 mol 3 mol
5 mol 3 mol

~
dhs
J

3598.5
dn2
mol mol solute

Therefore,

H H 2 O hH 2 O 1 mol solute 3598.5

mol mol solute

J
mol

3599

We can calculate H HCl hHCl using Equation 6.46

~
hmix x H 2 O H H 2 O hH 2 O x HCl hs x H 2 O H H 2 O hH 2 O
H HCl hHCl

x HCl
x HCl

H HCl hHCl

J
0.2 61204
mol

J
0.8 3599
mol

0 .2

(b)
For n1 2 and n2 80 ,
n n
82
n 1 2 1 1 40
n1
2

The new values for the number of moles consistent with Table 6.1
n1 1 mol

n2 40 mol

Using the data in the table for n 40 ,

~
~
~
dhs hs n 50 hs n 30

50 mol 30 mol
dn2

Interpolating the data in Table 6.1

51

46808

J
mol

hs n 30 72428

mol
solute

Therefore,

J
J

73729
72428
~

dhs
J
and
mol solute
mol solute 65.05

50 mol H 2O 30 mol H 2 O
dn2
mol mol solute

H H 2 O hH 2 O 1 mol solute 65.05

mol

mol
solute

52

mol H 2 O

65.05

6.29
First perform an energy balance on the mixing process.
hmix q

We can calculate hmix using data from Table 6.1. Referring to Equation E6.7A, we find
~
hmix x HCl hs

Calculate x HCl :

x HCl

wHCl
0.30
MW HCl
36.46

0.175
wH 2 O
0.30
0.70
wHCl

MW HCl MW H 2O 36.46 18.0148

Heats of data are tabulated for a solution containing one mole of the solute for various amounts
of water. Thus, we need to calculate how many moles of water must be added to HCl to obtain
the above mole fraction.
x HCl

1 mol HCl
; where n is the number of moles of H2O
1 mol HCl n

n 4.71 mol H 2 O

By interpolation of data from Table 6.1, we get

~

hs 63224

J
mol

(for n 4.71 )

Therefore,

J
hmix 0.175 63224
mol

J
mol

11064

and

J
mol

q hmix 11064

53

6.30
To calculate the enthalpy of mixing from Table 6.1, we must use the following expression
~
hmix x H 2 SO 4 hs

The mole fraction of sulfuric acid is

x H 2 SO 4

1
1 n

where n is the number of moles of water.

Equation 6.47 states

hmix 74.4 x H 2 SO 4 x H 2 O 1 0.561x H 2 SO

For n 1 , x H

SO 4 0.5 and x H 2 O 0.5

Table 6.1:

hs 31087

J
mol

J
J
hmix 0.5 31087
15543.5

mol
mol

Equation 6.47: hmix 74.4 0.5 0.5 1 0.561 0.5

J
mol

hmix 13383

The following table was made

n [mol H2O]

x H 2 SO 4

1
2
3
4
5
10
20
50
100

0.5
0.333333
0.25
0.2
0.166667
0.090909
0.047619
0.019608
0.009901

hmix [ kJ/mol]

hmix [kJ/mol]

(Table 6.1)

(Eq. 6.47)

-15543.5
-14978.7
-13001.8
-11414
-10174.2
-6367.27
-3548.43
-1497.22
-762.238

-13382.7
-13441.6
-11993.5
-10568.4
-9367.17
-5835.17
-3284.01
-1414.49
-725.289

% Difference
14.94
10.82
8.07
7.69
8.26
8.72
7.74
5.68
4.97

As you can see, the percent difference between the two methods decreases as the mole fraction of
sulfuric acid decreases. Although Equation 6.47 fit data at 21 C, while the Table 6.1 tabulates

54

data taken at 25 C, we do not expect the temperature dependence to account for all the observed
difference. The table and equation come from different experimental data sets, and also
represent measurement uncertainty. Nevertheless, the agreement is reasonable.

55

6.31
To calculate the enthalpy of mixing from Table 6.1, we must use the following expression
~
hmix x HCl hs

The mole fraction of HCl is

x HCl

1
1 n

where n is the number of moles of water. The following table was made using these two
equations.
n [mol H2O]

x1

~
J

hs

mol
HCl

J
hmix
mol

1
2
3
4
5
10
20
50
100

0.5
0.333
0.25
0.2
0.167
0.091
0.048
0.020
0.0099

-26225
-48819
-56852
-61204
-64049
-69488
-71777
-73729
-73848

-13112.5
-16273
-14213
-12240.8
-10674.8
-6317.09
-3417.95
-1445.67
-731.168

56

6.32
A schematic for the process is given below. The inlet streams are labeled 1 and 2 and the
exit stream 3.
q

50wt%NaOH

10wt%NaOH

50wt%H2O

90wt%H2O

Stream1

Stream3

H2O

Stream2

The energy balance for this process reduces to

Q H 3 H 2 H1

We first convert from weight percentage to mole fraction. For stream 1,

x NaOH ,1

wNaOH
0.50
MW NaOH
40

0.311
wH 2 O
0.50
0.50
wNaOH

MW NaOH MW H 2O 40 18.0148

and for stream 3,

x NaOH ,3

wNaOH
0.10
MW NaOH
40

0.048
wH 2 O
0.10
0.90
wNaOH

MW NaOH MW H 2O 40 18.0148

We now calculate the moles of water per mole of NaOH so that we can use Table 6.1:
x NaOH

1
1 nH 2O

Therefore, for every mole of NaOH

n H 2 O,1 2.21
57

n H 2 O ,3 19.8

Since enthalpy is a state function, we can choose any hypothetical path to calculate the change in
enthalpy. One such path is shown below. The box in our original schematic is depicted with
dashed lines below. We pick a basis of 1 mole NaOH. In step A, the inlet stream is separated
into its pure components. In step B, 17.6 additional moles of water are added to the pure water
stream. Finally the H2O and NaOH streams are remixed

StepA

1molNaOH

StepC

1molNaOH

2.2molH2O

19.8molH2O

StepB

2.2molH2O

hmix =0

1molNaOH

19.8molH2O

17.6molH2O

The enthalpy change is found by adding each step

H 3 H 2 H 1 H A H B H C

Since H B represents the mixing of water with water, H B 0 .

The enthalpies of mixing for steps A and C can be related to enthalpy of solution data from Table
6.1:
~

hs ,1 23906

hs ,3 42858

mol NaOH
J

mol NaOH

Note: The enthalpy of solution for Stream 1 is calculated by extrapolation. Generally,

extrapolation should be avoided, but it is necessary to complete this problem, and we are
not extrapolating very far.
For step A, we need the negative value of the heat of solution of stream 1. Thus for a basis of 1
mole NaOH:
H A 23906 J

while for step C:

58

H C 42858 J

Now adding the enthalpies of each step per 1 mole of NaOH:

H 23906 0 42858 18952 J

To get the total heat that must be removed per mole of product solution, we divide by the number
of moles of product per mol of NaOH:
q

H
J
910
n NaOH
mol

59

6.33
The partial molar property can be written as follows:
nT K
n1

K1

T , P , n2 , n3

Applying the chain rule to the above relationship:

nT
K1 k
n1

T , P , n2 , n3

k
n1

K 1 k nT

n1

nT

(1)
T , P , n2 , n3

Now focus on nT n

T , P , n2 , n3

. At constant T and P, we can write,

T , P , n2 , n3

k
k
k

dk
dx1
dx2
dx3
x1 T , P , x2 , x3
x2 T , P, x1 , x3
x3 T , P , x1 , x2

Therefore,
k

n1

T , P , n2 , n3

x1

T , P , x2 , x3

k

x3

x1

n1

T , P , x1 , x2

T , P , n2 , n3

x3

n1

k
x 2

T , P , x1 , x3

x 2

n1

T , P , n2 , n3

T , P , n2 , n3

but,
x1

n1
n1 n2 n3

so
x1

n1

T , P , n2 , n3

n1
1
1
1 x1

2
n1 n2 n3 n1 n2 n3
nT

(3)

Similarly,
x 2

n1

T , P ,n2 , n3

n2
x
2
2
nT
n1 n2 n3

(4)

and
60

(2)

 x3

n1

T , P ,n2 , n3

n3
x
3
2
nT
n1 n2 n3

(5)

Substituting Equations 2, 3, 4, and 5 into the expression 1 for K1 and simplifying:

K1 k
1 x1 k
x2 k
x3
x1 T , P, x 2 , x 3
x2 T , P , x1 , x 3
x3 T , P , x1 , x 2

Utilize the fact that x1 x 2 x3 1

k
k

K1 k x 2

x1 T , P, x , x
x 2
2
3

x3 k

1 T , P, x 2 , x 3
T , P , x1 , x 3

x3 T , P, x1 , x 2

(6)

When we hold species 3 constant:

k
k

dk
dx1

x
1 T , P , x2 , x3

x 2

x 2

x1

T , P , x3

T , P , x2 , x3

T , P, x1 , x3

dx1

dx 2

dx 2

k

x2

T , P , x1 , x3

dx 2

dx 2

Thus,
k

x2

T , P , x3

x1

T , P , x2 , x3

k
x2

(7)
T , P , x1 , x3

When we hold species 2 constant, a similar analysis shows:

k

x3

T , P , x2

x1

T , P , x2 , x3

k
x3

(8)
T , P , x1 , x2

Substituting Equations 7 and 8 into Equation 6 gives

k
x 2

K1 k x2

T , P , x3

k
x3

x3

T , P , x2

Furthermore, the above analysis can be extended to m components. In general,

k
xm

K i k xm
mi

T , P , x j i ,m

61

62

6.34
The expression can be found by employing the Gibbs-Duhem equation:
0 n1V1 n 2V2

Differentiate with respect to x1 and then divide by the total number of moles:
0 x1

dV1
dV2
dV
dV
x2
x1 1 1 x1 2
dx1
dx1
dx1
dx1

Differentiate the expression given in the problem statement.

dV1
5.28 5.28 x1
dx1

Substitution of this result into the Gibbs-Duhem equation and rearrangement yields
dV2
5.28 x12 5.28 x1

5.28 x1
dx1
x1 1

Integrate:
cm 3

mol

V2 2.64 x12 C

To determine C, we can use the density information given in the problem statement.
V2 x 2 1 V2 x1 0 C v 2

where
C v2

1
2
MW2

0.768 g/cm 3

84.16 g/mol

cm 3

mol

109.58

Therefore,
cm 3

mol

V2 2.64 x12 109.58

63

6.35
An expression for the enthalpy of the solution is
h x1h1 x 2 h2 hmix

which is equivalent to
~
h x1h1 x 2 h2 x1hs

Multiplication by the total number of moles yields

~
H n1h1 n2 h2 n1hs

To use the heat of solution data in Table 6.1, we need to determine the values of n1 and n2
consistent with the convention used in the table. As seen in Example 6.6,

x1

n1
1

n1 n2 1 n

For this problem

x1 0.33

Therefore,
n1 1
n2 n 2

Now we can find expressions for the partial molar enthalpies.

H
n2

H H 2 O H 2

n1 ,T , P

~
dhs
H H 2 O H 2 h2 n1
dn2

~
dhs
H H 2 O hH 2 O H 2 h2 n1
dn2

Using the data in Table 6.1 for n 2 ,

64

J
J

2,787
812
~
~
~

dhs hs n 3 hs n 1
mol solute
mol solute

3 mol 1 mol
3 mol H 2O 1 mol H 2O
dn2

~
dhs
J

987.5
dn2
mol mol solute

Therefore,

H H 2 O hH 2 O 1 mol solute 987.5

mol mol solute

Calculate the partial molar enthalpy:

J
mol

H H 2 O hH 2 O 987.5

From the saturated steam tables at 25 C:

kJ
hH 2 O 104.87

kg
kJ
hH 2 O 1.89
mol

Now we can find the partial molar enthalpy

kJ
J
J
0.988
0.90

mol H 2 O
mol H 2 O
mol H 2 O

H H 2 O 1.89

65

J
mol

987.5

6.36
(a)
Calculate the mole fraction of sulfuric acid

x1

w1
MW 1
w1
w2

MW 1 MW 2

0.20
98.078

0.044
0.20
0.80

98.078 18.0148

Calculate n to use in Table 6.1:

x1

1
0.044
1 n

n 21.7 mol H 2 O
Interpolating from Table 6.1
~

hs 74621

J
mol

Now calculate the heat transfer

~

J
q hmix x1hs 0.044 74621

mol

J
mol

q 3283

(b)
Calculate the mole fraction of pure sulfuric acid. Consider a mixture of 20 kg of 18 M sulfuric
acid and 80 kg of water. Find the mass of sulfuric acid present.
VH 2 SO4

mH 2 SO4

H 2 SO4

20 kg
10.9 L
1.84 kg/L

nH 2 SO4 VM 10.9 L 18 mol/L 196.2 mol

m H 2 SO4 n H 2 SO 4 MW H 2 SO4 196.2 mol 0.098 kg/mol 19.2 kg

Since both the initial (i) and final (f) states contain mixtures, to get the enthalpy of mixing, we
need to calculate the relative differences follows:
~
~
q hmix x1, f hs , f x1, i hs ,i

66

calculate the mole fraction in the final state

w1
MW 1

0.192
98.078
x1, f

0.042
w1
w2
0.192
0.808

MW 1 MW 2 98.078 18.0148
Calculate n to use in Table 6.1:
x1, f

1
0.042
1 n

n 22.8 mol H 2 O
Interpolating from Table 6.1
~

hs, f 74689

J
mol

For the initial 18 M sulfuric acid:

w1
MW 1

0.192
98.078
x1,i

0.81
w1
w2
0.192
0.008

MW 1 MW 2 98.078 18.0148
Calculate n to use in Table 6.1:
x1,i

1
0.81
1 n

n 0.23 mol H 2 O
We must extrapolate from Table 6.1. To do this we wish to extend the trend at low water
concentration. A plot of the data in Table 6.1 is useful. A semi-log plot follows:

67

3200 [J /mol]

en th alp o f so lu tio n [J /m o l so lu te]

-10000
-20000
-30000
-40000
-50000
-60000
-70000
-80000
-90000
0.1

10

100

hs,i 3200

mol

Now calculate the heat transfer

~
~

J
J
q hmix x1, f hs, f x1, i hs, i 0.042 74689
0.81 3200

mol
mol

J
mol

q 710

(c)
Calculate the mole fraction of sodium hydroxide

x1

w1
MW 1
w1
w2

MW 1 MW 2

0.20
40

0.101
0.20
0.80

40 18.0148

Calculate the n value to use in Table 6.1:

x1

1
0.101
1 n

n 8.9 mol H 2 O
Interpolating from Table 6.1
~

hs 41458

J
mol

68

Now calculate the heat transfer

~

J
q hmix x1hs 0.101 41458
mol

mol

q 4187

(d)
Calculate the mole fraction of ammonia

x1

w1
MW 1
w1
w2

MW 1 MW 2

0.20
17.03

0.209
0.20
0.80

17.03 18.0148

Calculate the n value to use in Table 6.1:

x1

1
0.209
1 n

n 3.78 mol H 2 O
Interpolating from Table 6.1
~

hs 33153

J
mol

Now calculate the heat transfer

~

J
q hmix x1hs 0.209 33153
mol

J
mol

q 6929

69

6.37
Let species 1 designate ethanol and species 2 designate water. We need to obtain an expression
for the molar volume, so first, convert the given the mass fractions and densities to mole
fractions and molar volumes.

w1
MW 1

Mole fractions:

x1

Specific molar volumes:

v v MW mixture

w1
w2

MW 1 MW 2

where MW mixture x1 MW 1 x 2 MW 2

Using this set of equations, the following table was made.

Mole Frac. EtOH
0.000
0.042
0.089
0.144
0.207
0.281
0.370
0.477
0.610
0.779
1.000

Mole Frac. H2O v (ml/mol)

1.000
18.05
0.958
19.54
0.911
21.18
0.856
23.11
0.793
25.47
0.719
28.34
0.630
31.85
0.523
36.19
0.390
41.65
0.221
48.73
0.000
58.36

The following graph plots the data. The trendline relates v to x1.
60.00

v (ml/mol)

50.00
40.00
v = 4.5491x12 + 35.918x1 + 17.957

30.00

R2 = 1

20.00
10.00
0.00
0.000

0.200

0.400

0.600

Mole Fraction EtOH (x 1)

70

0.800

1.000

Now, we can calculate V1 .

V
nv

V1

n1 n 2 , n3 ,T , P n1 n 2 , n3 ,T , P

We can substitute the trendline for V into this derivative and use the fact that ntot n1 n2 to
obtain
V1

n12

4.5491
35.918n1 17.957 n1 n2

n1 n2
n1

n 2 ,T , P

Differentiating we get
2n n n n 2
2
1 53.875 ml
V1 4.5491 1 1

mol
n1 n2 2

ml
mol

V1 4.5491 2 x1 x12 53.875

Calculate V2 :
V2

n2

4.5491

n12
35.918n1 17.957 n1 n2

n1 n2

Differentiating we get

n12
ml
V2 4.5491
17.957
2
mol
n1 n2
ml
mol

V2 4.5491x12 17.957

Plotting V1 and V2 vs. x1 we obtain

71

n1 , T , P

60
59
58
57
56
55
54
53
52

20
19
18
17
16
15
14
13
12
0

0.2

0.4

0.6

0.8

H2O Partial Molar

Volume (ml/mol)

EtOH Partial Molar

Volume (ml/mol)

Partial Molar Volumes vs. EtOH Mole Fractions

EtOH
H2O

Mole Fraction EtOH (x1)

(b)

v mix can be calculated using Equation 6.46

v mix x H 2 O V H 2 O v H 2 O x EtOH V EtOH v EtOH

From the data table in Part (a),

ml
mol
ml
v H 2 O v x1 0 18.05
mol
v EtOH v x1 1 58.36

Using the expressions for partial molar volumes

ml
mol

V1 4.5491 2 0.5 0.5 2 53.875 57.29

ml

mol

V 2 4.5491 0.5 2 17.957 16.82

Therefore,

ml
ml
v mix 0.5 16.82 18.05
0.5 57.29 58.36

mol
mol

ml
vmix 1.15

mol

6.38
72

We can use the density data given in the problem statement to determine the pure species
properties. For pure ethanol x1 1 :
MW1

v1

46 g/mol

0.7857 g/cm 3

cm 3

mol

58.55

cm 3
3
V1 n1v1 3 mol 58.55
175.7 cm

mol

For pure formamide x1 0 :

cm 3
MW2
45 g/mol

39.77

2
1.1314 g/cm 3
mol

cm 3
3
V2 n 2 v 2 1 mol 39.77
39.77 cm

mol

v2

To calculate V and v, interpolate in the data table to obtain the density of the mixture when
x1 0.75 :

0.8550 g/cm 3

Therefore,
v

where

MW

MW 0.75 46 g/mol 0.25 45 g/mol 45.75 g/mol

Substitute numerical values:

v

45.75 g/mol

0.8550 g/cm

53.51 cm 3 /mol

cm 3
3
V nv 4 mol 53.51
214.0 cm

mol

Now, we can calculate the volume change of mixing by using Equation 6.43:

Vmix V V1 V2 214 cm 3 175.7 cm 3 39.77 cm 3

Vmix 1.47 cm

The intensive volume change of mixing:

73

v mix

Vmix 1.47 cm 3

0.368 cm 3 / mol
n
4

We can use Equation 6.65 to determine the partial molar volume of formamide:
V2 v x1

dv
v
v x1
dx1
x1

From the provided data table

45.8
45.7

v
0.8401 0.8701 19.50 cm 3 / mol
x1
0.8009 0.6986

Therefore,

V2 53.51 cm 3 / mol 0.75 19.5 cm 3 / mol 38.89 cm 3 / mol

Now calculate the partial molar volume of ethanol:

V n1V1 n 2V2
V1

214.0 cm 3 1 mol 38.89 cm 3 /mol

58.37 cm 3 / mol
3 mol

74

6.39
Using the definition of G, the Gibbs energy of mixing of an ideal gas can be rewritten in terms of
the enthalpy of mixing and the entropy of mixing:
ideal gas
ideal gas
ideal gas
g mix
hmix
Tsmix

Since an ideal gas exerts no intermolecular interactions,

ideal gas
hmix
0

From Equation 6.48:

ideal gas
smix
R xa ln xa xb ln xb

so
ideal gas
g mix
RT xa ln xa xb ln xb

To find the partial molar Gibbs energy of mixing of species a, we apply Equation 6.29:

Gmix a nng mix

T , P , nb

Applying the expression above

na
nb
RT na ln na nb ln nb na nb ln na nb
ng mix RT na ln
nb ln
n

n
n

n
a
b
a
b

where the mathematical relation of logarithms was used. Thus,

Gmix a nng mix

n
n n
RT ln na a 0 ln na nb a b RT ln xa
na
na nb
T , P , nb

at infinite dilution xa goes to zero, and the ln term blows up,

Gmix a a g a
As chemical engineers, we are often interested in the limiting case of infinite dilution. We see
that even for ideal gas mixtures the chemical potential in this limit is not mathematically
well-.behaved, In Chapter 7, we will develop a different function, the fugacity, which behaves
better.

75

6.40
At equilibrium
l
v
H
H
O
O
2
2

or
l
v
GH
GH
O
O
2
2

Since the water in the liquid phase is pure

GHl 2O g Hl 2O hHl 2O Ts Hl 2O
The enthalpy and entropy of liquids are not sensitive to pressure changes. We can use data from
the saturated steam tables at 25 C to determine the Gibbs energy.
l
g H
104.87 kJ/kg 298.15 K 0.3673 kJ/kg K
2O
l
g H
4.640 kJ/kg
2O

l
l
gH
MWH 2 O g H
0.0180148 kg/mol 4.640 kJ/kg 0.0836 kJ/mol
2O
2O

Therefore,
v
H

2O

g lH O 83.6 J/mol
2

76