TRAPP: CHAP05 2006/3/8 17:05 PAGE 94 #1

5
Simple mixtures
Answers to discussion questions
D5.1 At equilibrium, the chemical potentials of any component in both the liquid and vapor phases must be
equal. This is justied by the requirement that, for systems at equilibriumunder constant temperature and
pressure conditions, with no additional work, G = 0 [see Section 3.5(e) and the answer to Discussion
question 3.3]. Here G =
i
(v)
i
(1), for all components, i, of the solution; hence their chemical
potentials must be equal in the liquid and vapor phases.
D5.3 All of the colligative properties are a function of the concentration of the solute, which implies that the
concentration can be determined by a measurement of these properties. See eqns 5.33, 5.34, 5.36, 5.37,
and 5.40. Knowing the mass of the solute in solution then allows for a calculation of its molar mass. For
example, the mole fraction of the solute is related to its mass as follows:
x
B
=
m
B
/M
B
m
B
/M
B
+ m
A
/M
A
.
The only unknown in this expression is M
B
which is easily solved for. See Example 5.4 for the details
of how molar mass is determined from osmotic pressure.
D5.5 A regular solution has excess entropy of zero, but an excess enthalpy that is non-zero and dependent on
composition, perhaps in the manner of eqn 5.30. We can think of a regular solution as one in which the
different molecules of the solution are distributed randomly, as in an ideal solution, but have different
energies of interaction with each other.
Solutions to exercises
E5.1(a) Let A denote acetone and C chloroform. The total volume of the solution is
V = n
A
V
A
+ n
C
V
C
.
V
A
and V
c
are given; hence we need to determine n
A
and n
C
in 1.000 kg of the solution with the stated
mole fraction. The total mass of the sample is m = n
A
M
A
+ n
C
M
C
(a). We also know that
x
A
=
n
A
n
A
+ n
C
implies that (x
A
1)n
A
+ x
A
n
C
= 0
TRAPP: CHAP05 2006/3/8 17:05 PAGE 95 #2
SIMPLE MIXTURES 95
and hence that
x
C
n
A
+ x
A
n
C
= 0. (b)
On solving (a) and (b), we nd
n
A
=
_
x
A
x
C
_
n
C
, n
C
=
mx
C
x
A
M
A
+ x
C
M
C
.
Since x
C
= 0.4693, x
A
= 1 x
C
= 0.5307,
n
C
=
(0.4693) (1000 g)
[(0.5307) (58.08) + (0.4693) (119.37)] g mol
1
= 5.404 mol,
n
A
=
_
0.5307
0.4693
_
(5.404) mol = 6.111 mol.
The total volume, V = n
A
V
A
+ n
B
V
B
, is therefore
V = (6.111 mol) (74.166 cm
3
mol
1
) + (5.404 mol) (80.235 cm
3
mol
1
)
= 886.8 cm
3
.
E5.2(a) Let A denote water and B ethanol. The total volume of the solution is V = n
A
V
A
+ n
B
V
B
We are given V
A
, we need to determine n
A
and n
B
in order to solve for V
B
.
Assume we have 100 cm
3
of solution; then the mass of solution is
m = d V = (0.914 g cm
3
) (100 cm
3
) = 91.4 g
of which 45.7 g is water and 45.7 g ethanol.
100 cm
3
=
_
45.7 g
18.02 g mol
1
_
(17.4 cm
3
mol
1
) +
_
45.7g
46.07 g mol
1
_
V
B
= 44.13 cm
3
+ 0.9920 mol V
B
,
V
B
=
55.87 cm
3
0.9920 mol
= 56.3 cm
3
mol
1
.
E5.3(a) Check whether
p
B
x
B
is equal to a constant (K
B
)
x 0.005 0.012 0.019
p/x 6.4 10
3
6.4 10
3
6.4 10
3
kPa
Hence, K
B
6.4 10
3
kPa .
TRAPP: CHAP05 2006/3/8 17:05 PAGE 96 #3
96 SOLUTIONS MANUAL
E5.4(a) In Exercise 5.3(a), the Henrys law constant was determined for concentrations expressed in mole
fractions. Thus the concentration in molality must be converted to mole fraction.
m(GeCl
4
) = 1000 g, corresponding to
n(GeCl
4
) =
1000 g
214.39 g mol
1
= 4.664 mol, n(HCl) = 0.10 mol.
Therefore, x =
0.10 mol
(0.10 mol) + (4.664 mol)
= 0.0210.
From K
B
= 6.4 10
3
kPa (Exercise 5.3(a)), p = (0.0210 6.4 10
3
kPa) = 1.3 10
2
kPa .
E5.5(a) We assume that the solvent, benzene, is ideal and obeys Raoults law.
Let B denote benzene and A the solute; then
p
B
= x
B
p

B
and x
B
=
n
B
n
A
+ n
B
.
Hence p
B
=
n
B
p

B
n
A
+ n
B
, which solves to
n
A
=
n
B
(p

B
p
B
)
p
B
.
Then, since n
A
=
m
A
M
A
, where m
A
is the mass of A present,
M
A
=
m
A
p
B
n
B
(p

B
p
B
)
=
m
A
M
B
p
B
m
B
(p

B
p
B
)
.
From the data
M
A
=
(19.0 g) (78.11 g mol
1
) (51.5 kPa)
(500 g) (53.3 51.5) kPa
= 82 g mol
1
E5.6(a) M
B
=
mass of B
h
B
[B = compound].
n
B
= mass of CCl
4
b
B
[b
B
= molality of B].
b
B
=
T
K
f
[5.37]; thus
M
B
=
mass of B K
f
mass of CCl
4
T
K
f
= 30 K/(mol kg
1
)[Table 5.2],
M
B
=
(100 g) (30 Kkg mol
1
)
(0.750 kg) (10.5 K)
= 381 g mol
1
.
TRAPP: CHAP05 2006/3/8 17:05 PAGE 97 #4
SIMPLE MIXTURES 97
E5.7(a) T = K
f
b
B
[5.37], b
B
=
n
B
mass of water

n
B
V
[dilute solution].
10
3
kg m
3
[density of solution density of water].
n
B

V
RT
[5.40], T K
f


RT
with K
f
= 1.86 K/(mol kg
1
) [Table 5.2].
T
(1.86 Kkg mol
1
) (120 10
3
Pa)
(8.314 J K
1
mol
1
) (300 K) (10
3
kg m
3
)
= 0.089 K.
Therefore, the solution will freeze at about 0.09

C .
COMMENT. Osmotic pressures are inherently large. Even dilute solutions with small freezing point
depressions have large osmotic pressures.
E5.8(a)
mix
G = nRT{x
A
ln x
A
+ x
B
ln x
B
}[5.18], x
A
= x
B
= 0.5, n =
pV
RT
.
Therefore,

mix
G = (pV)
_
1
2
ln
1
2
+
1
2
ln
1
2
_
= pV ln 2
= (1.0) (1.013 10
5
Pa) (5.0 10
3
m
3
) (ln 2)
= 3.5 10
2
J = 0.35 kJ .

mix
S = nR{x
A
ln x
A
+ x
B
ln x
B
} =

mix
G
T
[5.19] =
0.35 kJ
298 K
= +1.2 J K
1
.
E5.9(a)
mix
S = nR

J
x
J
ln x
J
[5.19].
Therefore, for molar amounts,

mix
S = R

J
x
J
ln x
J
= R[(0.782 ln 0.782) + (0.209 ln 0.209) + (0.009 ln 0.009) + (0.0003 ln 0.0003)]
= 0.564R = +4.7 J K
1
mol
1
.
E5.10(a) Hexane and heptane form nearly ideal solutions; therefore eqn 5.19 applies.

mix
S = nR(x
A
ln x
A
+ x
B
ln x
B
)[5.19].
We need to differentiate eqn 5.19 with respect to x
A
and look for the value of x
A
at which the derivative
is zero. Since x
B
= 1 x
A
, we need to differentiate

mix
S = nR{x
A
ln x
A
+ (1 x
A
) ln(1 x
A
)}.
TRAPP: CHAP05 2006/3/8 17:05 PAGE 98 #5
98 SOLUTIONS MANUAL
This gives
_
using
d ln x
dx
=
1
x
_
d
mix
S
dx
A
= nR{ln x
A
+ 1 ln(1 x
A
) 1} = nRln
x
A
1 x
A
which is zero when x
A
=
1
2
. Hence, the maximum entropy of mixing occurs for the preparation of a
mixture that contains equal mole fractions of the two components.
(a)
n(Hex)
n(Hep)
= 1 =
_
m(Hex)
M(Hex)
_
_
m(Hep)
M(Hep)
_.
(b)
m(Hex)
m(Hep)
=
M(Hex)
M(Hep)
=
86.17 g mol
1
100.20 g mol
1
= 0.8600 .
E5.11(a) With concentrations expressed in molalities, Henrys law [5.26] becomes p
B
= b
B
K.
Solving for b, the solubility, we have b
B
=
p
B
K
.
(a) p
B
= 0.10 atm = 10.1 kPa.
b =
10.1 kPa
3.01 10
3
kPa kg mol
1
= 3.4 mmol kg
1
.
(b) p
B
= 1.00 atm = 101.3 kPa.
b =
101.3 kPa
3.01 10
3
kPa kg mol
1
= 34 mmol kg
1
.
E5.12(a) As in Exercise 5.11(a), we have
b
B
=
p
B
K
=
5.0 101.3 kPa
3.01 10
3
kPa kg mol
1
= 0.17 mol kg
1
.
Hence, the molality of the solution is about 0.17 mol kg
1
and, since molalities and molar con-
centrations for dilute aqueous solutions are approximately equal, the molar concentration is about
0.17 mol dm
3
.
E5.13(a) The solubility in grams of anthracene per kg of benzene can be obtained from its mole fraction with use
of the equation.
ln x
B
=

fus
H
R

_
1
T

1
T
_
[5.39; B, the solute, is anthracene]
=
_
28.8 10
3
J mol
1
8.314 J K
1
mol
1
_

_
1
490.15 K

1
298.15 K
_
= 4.55.
Therefore, x
B
= e
4.55
= 0.0106.
Since x
B
1, x(anthracene)
n(anthracene)
n(benzene)
.
TRAPP: CHAP05 2006/3/8 17:05 PAGE 99 #6
SIMPLE MIXTURES 99
Therefore, in 1 kg of benzene,
n(anthr.) x(anthr.)
_
1000 g
78.11 g mol
1
_
(0.0106) (12.80 mol) = 0.136 mol.
The molality of the solution is therefore 0.136 mol kg
1
. Since M = 178 g mol
1
, 0.136 mol corresponds
to 24 g anthracene in 1 kg of benzene.
E5.14(a) The best value of the molar mass is obtained from values of the data extrapolated to zero concentration,
since it is under this condition that eqn 5.40 applies.
V = n
B
RT[5.40], so =
mRT
MV
=
cRT
M
, c =
m
V
.
= gh [hydrostatic pressure], so h =
_
RT
gM
_
c.
dm
3
Figure 5.1
Hence, plot h against c and identify the slope as
RT
gM
. Figure 5.1 shows the plot of the data.
The slope of the line is 0.29 cm/(g dm
3
), so
RT
gM
=
0.29 cm
g dm
3
= 0.29 cmdm
3
g
1
= 0.29 10
2
m
4
kg
1
.
Therefore,
M =
RT
(g) (0.29 10
2
m
4
kg
1
)
=
(8.314 J K
1
mol
1
) (298.15 K)
(1.004 10
3
kg m
3
) (9.81 ms
2
) (0.29 10
2
m
4
kg
1
)
= 87 kg mol
1
.
E5.15(a) For A (Raoults law basis; concentration in mole fraction)
a
A
=
p
A
p

A
[5.43] =
250 Torr
300 Torr
= 0.833 ;
A
=
a
A
x
A
=
0.833
0.90
= 0.93 .
TRAPP: CHAP05 2006/3/8 17:05 PAGE 100 #7
100 SOLUTIONS MANUAL
For B (Henrys law basis; concentration in mole fraction)
a
B
=
p
B
K
B
[5.50] =
25 Torr
200 Torr
= 0.125 ;
B
=
a
B
x
B
=
0.125
0.10
= 1.25 .
For B (Henrys law basis; concentration in molality)
An equation analogous to eqn 5.50 is used, a
B
=
p
B
K

B
with a modied Henrys law constant K

B
that
corresponds to the pressure of B in the limit of very low molalities,
p
B
=
b
B
b

B
,
is analogous to p
B
= x
B
K
B
. Since x
B
and b
B
are related as b
B
=
x
B
M
A
x
A
, K

B
and K
B
are related as
K

B
= x
A
M
A
b

K
B
.
We also need M
A
,
M
A
=
x
B
x
A
b
B
=
0.10
(0.90) (2.22 mol kg
1
)
= 0.050 kg mol
1
.
Then, K

B
= (0.90) (0.050 kg mol
1
) (1 mol kg
1
) (200 Torr) = 9.0 Torr
and a
B
=
25 Torr
9.0 Torr
= 2.8 ,
B
=
a
B
_
b
B
b

_ =
2.8
2.22
= 1.25 .
COMMENT. The two methods for the solute B give different values for the activities. This is reasonable
since the chemical potentials in the reference states

and

are different.
Question. What are the activity and activity coefcient of B in the Raoults law basis?
E5.16(a) In an ideal dilute solution the solvent (CCl
4
) obeys Raoults law and the solute (Br
2
) obeys Henrys law;
hence
p(CCl
4
) = x(CCl
4
)p

(CCl
4
)[5.24] = (0.950) (33.85Torr) = 32.2 Torr ,
p(Br
2
) = x(Br
2
)K(Br
2
)[5.26] = (0.050) (122.36Torr) = 6.1 Torr ,
p(Total) = (32.2 + 6.1)Torr = 38.3 Torr .
The composition of the vapor in equilibrium with the liquid is
y(CCl
4
) =
p(CCl
4
)
p(Total)
=
32.2 Torr
38.3 Torr
= 0.841 ,
y(Br
2
) =
p(Br
2
)
p(Total)
=
6.1 Torr
38.3 Torr
= 0.16 .
TRAPP: CHAP05 2006/3/8 17:05 PAGE 101 #8
SIMPLE MIXTURES 101
E5.17(a) Let A = acetone and M = methanol.
y
A
=
p
A
p
A
+ p
M
[Daltons law] =
p
A
101.3 kPa
= 0.516.
p
A
= 52.3 kPa, p
M
= 49.0 kPa.
p
A
=
p
A
p

A
[5.43] =
52.3 kPa
105 kPa
= 0.499 , a
M
=
p
M
p

M
=
49.0 kPa
73.5 kPa
= 0.668 .

A
=
a
A
x
A
=
0.499
0.400
= 1.25 ,
M
=
a
M
x
M
=
0.668
0.600
= 1.11 .
E5.18(a) I =
1
2

(b
i
/b

)z
2
i
[5.70]
and for an M
p
X
q
salt, (b
+
/b

) = p(b/b

), (b

/b

) = q(b/b

), so
I =
1
2
(pz
2
+
+ qz
2

)
_
b
b

_
.
I(KCl) =
1
2
(1 1 + 1 1)
_
b
b

_
=
_
b
b

_
.
I(CuSO
4
) =
1
2
(1 2
2
+ 1 2
2
)
_
b
b

_
= 4
_
b
b

_
.
I = I(KCL) + I(CuSO
4
) =
_
b
b

_
(KCL) + 4
_
b
b

_
(CuSO
4
)
= (0.10) + (4) (0.20) = 0.90 .
COMMENT. Note that the strength of a solution of more than one electrolyte may be calculated by summing
the ionic strengths of each electrolyte considered as a separate solution, as in the solution to this exercise,
by summing the product
1
2
_
b
i
b

_
z
2
i
for each individual ion as in the denition of I [5.71].
E5.19(a) I = I(KNO
3
) =
_
b
b

_
(KNO
3
) = 0.150.
Therefore, the ionic strengths of the added salts must be 0.100.
(a) I(Ca(NO
3
)
2
) =
1
2
(2
2
+ 2)
_
b
b

_
= 3
_
b
b

_
.
Therefore, the solution should be made
1
3
0.100 mol kg
1
= 0.0333 mol kg
1
in Ca(NO
3
)
2
. The
mass that should be added to 500 g of the solution is therefore (0.500 kg) (0.0333 mol kg
1
)
(164 g mol
1
) = 2.73 g .
(b) I(NaC1) =
_
b
b

_
; therefore, with b = 0.100 mol kg
1
,
(0.500 kg) (0.100 mol kg
1
) (58.4 g mol
1
) = 2.92 g .
(We are neglecting the fact that the mass of solution is slightly different from the mass of solvent.)
TRAPP: CHAP05 2006/3/8 17:05 PAGE 102 #9
102 SOLUTIONS MANUAL
E5.20(a) These concentrations are sufcientlydilute for the DebyeHckel limitinglawtogive a goodapproximate
value for the mean ionic activity coefcient. Hence
log

= |z
+
z

|AI
1/2
[5.69].
I =
1
2

i
z
2
i
_
b
i
b

_
[5.71] =
1
2
[(4 0.010) + (1 0.020) + (1 0.030) + (1 0.30)
= 0.060 .
log

= 2 1 0.509 (0.060)
1/2
= 0.2494;

= 0.563 = 0.56 .
E5.21(a) log

=
A|z
+
z

|I
1/2
1 + BI
1/2
[5.72].
Solving for B,
B =
_
1
I
1/2
+
A|z
+
z

|
log

_
.
For HBr, I =
_
b
b

_
and |z
+
z
+
| = 1; so
B =
_
b
(b/b

)
1/2
+
0.509
log

_
.
Hence, draw up the following table.
(b/b

) 5.0 10
3
10.0 10
3
120.0 10
3

0.930 0.907 0.879

B 2.01 2.01 2.02
The constancy of B indicates that the mean ionic activity coefcient of HBr obeys the extended Debye
Hckel law very well.
Solutions to problems
Solutions to numerical problems
P5.1
p
A
= y
A
p and p
B
= y
B
p (Daltons law). Hence, draw up the following table.
p
A
/kPa 0 1.399 3.566 5.044 6.996 7.940 9.211 10.105 11.287 12.295
x
A
0 0.0898 0.2476 0.3577 0.5194 0.6036 0.7188 0.8019 0.9105 1
y
A
0 0.0410 0.1154 0.1762 0.2772 0.3393 0.4450 0.5435 0.7284 1
TRAPP: CHAP05 2006/3/8 17:05 PAGE 103 #10
SIMPLE MIXTURES 103
p
B
/kPa 0 4.209 8.487 11.487 15.462 18.243 23.582 27.334 32.722 36.066
x
B
0 0.0895 0.1981 0.2812 0.3964 0.4806 0.6423 0.7524 0.9102 1
y
B
0 0.2716 0.4565 0.5550 0.6607 0.7228 0.8238 0.8846 0.9590 1
The data are plotted in Fig. 5.2.
Figure 5.2
We can assume, at the lowest concentrations of both A and B, that Henrys law will hold. The Henrys
law constants are then given by
K
A
=
p
A
x
A
= 15.58 kPa from the point at x
A
= 0.0898.
K
B
=
p
B
x
B
= 47.03 kPa from the point at x
B
= 0.0895.
P5.3 V
salt
=
_
V
b
_
H
2
O
mol
1
[Problem 5.2]
= 69.38(b 0.070)cm
3
mol
1
with b b/(mol kg
1
).
Therefore, at b = 0.050 mol kg
1
, V
salt
= 1.4 cm
3
mol
1
.
The total volume at this molality is
V = (1001.21) + (34.69) (0.02)
2
cm
3
= 1001.22 cm
3
.
Hence, as in Problem 5.2,
V(H
2
O) =
(1001.22 cm
3
) (0.050 mol) (1.4 cm
3
mol
1
)
55.49 mol
= 18.04 cm
2
mol
1
.
Question. What meaning can be ascribed to a negative partial molar volume?
P5.5 Let E denote ethanol and W denote water; then
V = n
E
V
E
+ n
W
V
W
[5.3].
TRAPP: CHAP05 2006/3/8 17:05 PAGE 104 #11
104 SOLUTIONS MANUAL
For a 50 per cent mixture by mass, m
E
= m
W
, implying that
n
E
M
E
= n
W
M
W
, or n
W
=
n
E
M
E
M
W
.
Hence, V = n
E
V
E
+
n
E
M
E
V
W
M
W
which solves to n
E
=
V
V
E
+
M
E
V
W
M
W
, n
W
=
M
E
V
V
E
M
W
+ M
E
V
W
.
Furthermore, x
E
=
n
E
n
E
+ n
W
=
1
1 +
M
E
M
W
.
Since M
E
= 46.07 g mol
1
and M
W
= 18.02 g mol
1
,
M
E
M
W
= 2.557. Therefore
x
E
= 0.2811, x
W
= 1 x
E
= 0.7189.
At this composition
V
E
= 56.0 cm
3
mol
1
, V
W
= 17.5 cm
3
mol
1
[Fig.5.1 of the text].
Therefore, n
E
=
100 cm
3
(56.0 cm
3
mol
1
) + (2.557) (17.5 cm
3
mol
1
)
= 0.993 mol,
n
W
= (2.557) (0.993 mol) = 2.54 mol.
The fact that these amounts correspond to a mixture containing 50 per cent by mass of both components
is easily checked as follows:
m
E
= n
E
M
E
= (0.993 mol) (46.07 g mol
1
) = 45.7 g ethanol,
m
W
= n
W
M
W
= (2.54 mol) (18.02 g mol
1
) = 45.7 g water.
At 20

C the densities of ethanol and water are,

E
= 0.789 g cm
3
,
W
= 0.997 g cm
3
. Hence,
V
E
=
m
E

E
=
45.7 g
0.789 g cm
3
= 57.9 cm
3
of ethanol,
V
W
=
m
W

W
=
45.7 g
0.997 g cm
3
= 45.8 cm
3
of water.
The change in volume upon adding a small amount of ethanol can be approximated by
V =
_
dV
_
V
E
dn
E
V
E
n
E
where we have assumed that both V
E
and V
W
are constant over this small range of n
E
. Hence
V (56.0 cm
3
mol
1
)
_
(1.00 cm
3
) (0.789 g cm
3
)
(46.07 g mol
1
)
_
= +0.96 cm
3
.
TRAPP: CHAP05 2006/3/8 17:05 PAGE 105 #12
SIMPLE MIXTURES 105
P5.7
b
B
=
T
K
f
=
0.0703 K
1.86 K/(mol kg
1
)
= 0.0378 mol kg
1
.
Since the solution molality is nominally 0.0096 mol kg
1
in Th(NO
3
)
4
, each formula unit supplies
0.0378
0.0096
4 ions . (More careful data, as described in the original reference gives 5 to 6.)
P5.9 The data are plotted in Figure 5.3. The regions where the vapor pressure curves showapproximate straight
lines are denoted R for Raoult and H for Henry. A and B denote acetic acid and benzene respectively.
H
A
R
H
R
B
40.0
26.7
13.3
k
P
a
0
0 0.2 0.4 0.6
x
A
0.8 1.0
Henry
Henry
Raoult
Raoult
Extrapolate
for K
B
Figure 5.3
As in Problem5.8, we need to form
A
=
p
A
x
A
p

A
and
B
=
p
B
x
B
p

B
for the Raoults lawactivity coefcients
and
B
=
p
B
x
B
K
for the activity coefcient of benzene on a Henrys law basis, with K determined by
extrapolation. We use p

A
= 7.3 kPa, p

B
= 35.2 kPa, and K

B
= 80.0 kPa to draw up the following
table.
x
A
0 0.2 0.4 0.6 0.8 1.0
p
A
/kPa 0 2.7 4.0 5.1 6.7 7.3
p
B
/kPa 35.2 30.4 25.3 20.0 12.4 0
a
A
(R) 0 0.36 0.55 0.69 0.91 1.00[p
A
/p

A
]
a
B
(R) 1.00 0.86 0.72 0.57 0.35 0[p
B
/p

B
]

A
(R) 1.82 1.36 1.15 1.14 1.00[p
A
/x
A
p

A
]

B
(R) 1.00 1.08 1.20 1.42 1.76 [p
B
/x
B
p

B
]
a
B
(H) 0.44 0.38 0.32 0.25 0.16 0[p
B
/K
B
]

B
(H) 0.44 0.48 0.53 0.63 0.78 1.00[p
B
/x
B
K
B
]
TRAPP: CHAP05 2006/3/8 17:05 PAGE 106 #13
106 SOLUTIONS MANUAL
G
E
is dened as [Section 5.4]
G
E
=
mix
G(actual)
mix
G(ideal) = nRT(x
A
ln a
A
+ x
B
ln a
B
) nRT(x
A
ln x
A
+ x
B
ln x
B
)
and, with a = x,
G
E
= nRT(x
A
ln
A
+ x
A
ln
B
).
For n = 1, we can draw up the following table from the information above and RT = 2.69 kJ mol
1
.
x
A
0 0.2 0.4 0.6 0.8 1.0
x
A
ln
A
0 0.12 0.12 0.08 0.10 0
x
B
ln
B
0 0.06 0.11 0.14 0.11 0
G
E
/(kJ mol
1
) 0 0.48 0.62 0.59 0.56 0
P5.11 (a) The volume of an ideal mixture is
V
ideal
= n
1
V
m,1
+ n
2
V
m,2
so the volume of a real mixture is
V = V
ideal
+ V
E
.
We have an expression for excess molar volume in terms of mole fractions. To compute partial molar
volumes, we need an expression for the actual excess volume as a function of moles.
V
E
= (n
1
+ n
2
)V
E
m
=
n
1
n
2
n
1
+ n
2
_
a
0
+
a
1
(n
1
n
2
)
n
1
+ n
2
_
so V = n
1
V
m,1
+ n
2
V
m,2
+
n
1
n
2
n
1
+ n
2
_
a
0
+
a
1
(n
1
n
2
)
n
1
+ n
2
_
.
The partial molar volume of propionic acid is
V
1
=
_
V
n
1
_
p,T,n
2
= V
m,1
+
a
0
n
2
2
(n
1
+ n
2
)
2
+
a
1
(3n
1
n
2
)n
2
2
(n
1
+ n
2
)
3
,
V
1
= V
m,1
+ a
0
x
2
2
+ a
1
(3x
1
x
2
)x
2
2
.
That of oxane is
V
2
= V
m,2
+ a
0
x
2
1
+ a
1
(x
1
3x
2
)x
2
1
.
(b) We need the molar volumes of the pure liquids,
V
m,1
=
M
1

1
=
74.08 g mol
1
0.97174 g cm
3
= 76.23 cm
3
mol
1
and V
m,2
=
86.13 g mol
1
0.86398 g cm
3
= 99.69 cm
3
mol
1
.
TRAPP: CHAP05 2006/3/8 17:05 PAGE 107 #14
SIMPLE MIXTURES 107
In an equimolar mixture, the partial molar volume of propionic acid is
V
1
= 76.23 + (2.4697) (0.500)
2
+ (0.0608) [3(0.5) 0.5] (0.5)
2
cm
3
mol
1
= 75.63 cm
3
mol
1
and that of oxane is
V
2
= 99.69 + (2.4697) (0.500)
2
+ (0.0608) [0.5 3(0.5)] (0.5)
2
cm
3
mol
1
= 99.06 cm
3
mol
1
.
P5.13 Henrys law constant is the slope of a plot of p
B
versus x
B
in the limit of zero x
B
(Fig. 5.4). The partial
pressures of CO
2
are almost but not quite equal to the total pressures reported above.
p
CO
2
= py
CO
2
= p(1 y
cyc
).
Linear regression of the low-pressure points gives K
H
= 371 bar .
0.0 0.1 0.2 0.3
0
20
40
60
80
Figure 5.4
The activity of a solute is
a
B
=
p
B
K
H
= x
B

B
so the activity coefcient is

B
=
p
B
x
B
K
H
=
y
B
p
x
B
K
H
where the last equality applies Daltons lawof partial pressures to the vapor phase. Aspreadsheet applied
this equation to the above data to yield
TRAPP: CHAP05 2006/3/8 17:05 PAGE 108 #15
108 SOLUTIONS MANUAL
p/bar y
cyc
x
cyc

CO
2
10.0 0.0267 0.9741 1.01
20.0 0.0149 0.9464 0.99
30.0 0.0112 0.9204 1.00
40.0 0.00947 0.892 0.99
60.0 0.00835 0.836 0.98
80.0 0.00921 0.773 0.94
P5.15 G
E
= RTx(1 x){0.4857 0.1077(2x 1) + 0.0191(2x 1)
2
}
with x = 0.25 gives G
E
= 0.1021RT. Therefore, since

mix
G(actual) =
mix
G(ideal) + nG
E
,

mix
G = nRT(x
A
ln x
A
+ x
B
ln x
B
) + nG
E
= nRT(0.25 ln 0.25 + 0.75 ln 0.75) + nG
E
= 0.562nRT + 0.1021nRT = 0.460nRT.
Since n = 4 mol and RT = (8.314 J K
1
mol
1
) (303.15 K) = 2.52 kJ mol
1
,

mix
G = (0.460) (4 mol) (2.52 kJ mol
1
) = 4.6 kJ .
Solutions to theoretical problems
P5.17
A
=
_
G
n
A
_
n
B
[5.4] =
o
A
+
_

n
A
(nG
E
)
_
n
B
[
o
A
is ideal value =

A
+ RT ln x
A
],
_
nG
E
n
A
_
n
B
= G
E
+ n
_
G
E
n
A
_
n
B
= G
E
+ n
_
x
A
n
A
_
B
_
G
E
x
A
_
B
= G
E
+ n
x
B
n

_
G
E
x
A
_
B
[x
A
/n
A
= x
B
/n]
= gRTx
A
(1 x
A
) + (1 x
A
)gRT(1 2x
A
)
= gRT(1 x
A
)
2
= gRTx
2
B
.
Therefore,
A
=

A
+ RT ln x
A
+ gRTx
2
B
.
P5.19 n
A
dV
A
+ n
B
dV
B
= 0 [Example 5.1].
Hence
n
A
n
B
dV
A
= dV
B
.
Therefore, by integration,
V
B
(x
A
) V
B
(0) =
_
V
A
(x
A
)
V
A
(0)
n
A
n
B
dV
A
=
_
V
A
(x
A
)
V
A
(0)
x
A
dV
A
1 x
A
[n
A
= x
A
n, n
B
= x
B
n].
Therefore, V
B
(x
A
, x
B
) = V
B
(0, 1)
_
V
A
(x
A
)
V
A
(0)
x
A
dV
A
1 x
A
.
TRAPP: CHAP05 2006/3/8 17:05 PAGE 109 #16
SIMPLE MIXTURES 109
We should now plot x
A
/(1 x
A
) against V
A
and estimate the integral. For the present purpose we
integrate up to V
A
(0.5, 0.5) = 74.06 cm
3
mol
1
[Fig. 5.5], and use the data to construct the following
table.
V
A
(cm
3
mol
1
) 74.11 73.96 73.50 72.74
x
A
0.60 0.40 0.20 0
x
A
/(1 x
A
) 1.50 0.67 0.25 0
The points are plotted in Fig. 5.5, and the area required is 0.30. Hence,
1.5
1.0
0.5
0
72 73 74 75
x
A
/
(
1

x
A
)
V
A,m
/cm
3
mol
1
( )
Figure 5.5
V(CHCl
3
; 0.5, 0.5) = 80.66 cm
3
mol
1
0.30 cm
3
mol
1
= 80.36 cm
3
mol
1
.
P5.21
=
ln a
A
r
.
Therefore, d =
1
r
d ln a
A
+
1
r
2
ln a
A
dr,
d ln a
A
=
1
r
ln a
A
dr rd.
From the GibbsDuhem equation, x
A
d
A
= x
B
d
B
= 0, which implies that (since =

+
RT ln a, d
A
= RTd ln a
A
, d
B
= RTd ln a
B
)
d ln a
B
=
x
A
x
B
d ln a
A
=
d ln a
A
r
=
1
r
2
ln a
A
dr = d[from(b)] =
1
r
dr = dr = d[from(a)]
= d ln r + d.
TRAPP: CHAP05 2006/3/8 17:05 PAGE 110 #17
110 SOLUTIONS MANUAL
Subtract d ln r from both sides, to obtain
d ln
a
B
r
= ( 1) d ln r + d =
( 1)
r
dr + d.
Then, by integration and noting that ln
_
a
B
r
_
r=0
= ln
_

B
x
B
r
_
r=0
= ln (
B
)
r=0
= ln 1 = 0,
ln
a
B
r
= (0) =
_
r
0
_
1
r
_
dr .
P5.23 A(s) A(l).

A
(s) =

A
(l) + RT ln a
A
and
fus
G =

A
(l)

A
(s) = RT ln a
A
.
Hence, ln a
A
=

fus
G
RT
.
d ln a
A
dT
=
1
R
d
dT
_

fus
G
T
_
=

fus
H
RT
2
[GibbsHelmholtz eqn].
For T = T

f
T, dT = dT and
d ln a
A
dT
=

fus
H
RT
2


fus
H
RT
2
f
.
But K
f
=
RT
2
f
M
A

fus
H
.
Therefore,
d ln a
A
dT
=
M
A
K
f
and d ln a
A
=
M
A
dT
K
f
.
According to the GibbsDuhem equation
n
A
d
A
+ n
B
d
B
= 0
which implies that
n
A
d ln a
A
+ n
B
d ln a
B
= 0[ =

+ RT ln a]
and hence that d ln a
A
=
n
B
n
A
d ln a
B
.
Hence,
d ln a
B
dT
=
n
A
M
A
n
B
K
f
=
1
b
B
K
f
[for n
A
M
A
= 1kg]
We know from the GibbsDuhem equation that
x
A
d ln a
A
+ x
B
d ln a
B
= 0
TRAPP: CHAP05 2006/3/8 17:05 PAGE 111 #18
SIMPLE MIXTURES 111
and hence that
_
d ln a
A
=
_
x
B
x
A
d ln a
B
.
Therefore ln a
A
=
_
x
B
x
A
d ln a
B
The osmotic coefcient was dened in Problem 5.21 as
=
1
r
ln a
A
=
x
A
x
B
ln a
A
.
Therefore,
=
x
A
x
B
_
x
B
x
A
d ln a
B
=
1
b
_
b
0
b d ln a
B
=
1
b
_
b
0
b d ln b =
1
b
_
b
0
b d ln b +
1
b
_
b
0
b d ln
= 1 +
1
b
_
b
0
b d ln .
From the DebyeHckel limiting law,
ln = A

b
1/2
[A

= 2.303A].
Hence, d ln =
1
2
A

b
1/2
db and so
= 1 +
1
b
_

1
2
A

_ _
b
0
b
1/2
db = 1
1
2
_
A

b
_

2
3
b
3/2
= 1
1
3
A
1/2
.
COMMENT. For the depression of the freezing point in a 1,1-electrolyte
ln a
A
=

fus
G
RT
+

fus
G
RT

and hence r =

fus
H
R
_
1
T

1
T

_
.
Therefore, =

fus
H
x
A
R
x
B
_
1
T

1
T

_
=

fus
H
x
A
R
x
B
_
T

T
TT

_


fus
H
x
A
T
R
x
B
T
2

fus
HT
Rb
B
T
2
M
A
where = 2. Therefore, since K
f
=
MRT
2

fus
H
,
=
T
2b
B
K
f
.
Solutions to applications
P5.25 In this case it is convenient to rewrite the Henrys law expression as
mass of N
2
= p
N
2
mass of H
2
O K
N
2
.
TRAPP: CHAP05 2006/3/8 17:05 PAGE 112 #19
112 SOLUTIONS MANUAL
(1) At p
N
2
= 0.78 4.0 atm = 3.1 atm,
mass of N
2
= 3.1 atm 100 g H
2
O 0.18 g N
2
/(g H
2
Oatm) = 56 g N
2
.
(2) At p
N
2
= 0.78 atm, mass of N
2
= 14 g N
2
.
(3) In fatty tissue the increase in N
2
concentration from 1 atm to 4 atm is
4 (56 14) g N
2
= 1.7 10
2
g N
2
.
P5.27 (a) i = 1 only, N
1
= 4, K
1
= 1.0 10
7
dm
3
mol
1
,

[A]
=
4 10 dm
3
mol
1
1 + 10 dm
3
mol
1
[A]
.
The plot is shown in Fig. 5.6(a).
Figure 5.6(a)
(b)
i = 1; N
1
= 4, N
2
= 2; K
1
= 1.0 10
5
dm
3
mol
1
= 0.10 dm
3
mol
1
,
K
2
= 2.0 10
6
dm
3
mol
1
= 2.0 dm
3
mol
1
.

[A]
=
4 0.10 dm
3
mol
1
1 + 0.10 dm
3
mol
1
[A]
+
2 2.0 dm
3
mol
1
1 + 2.0 dm
3
mol
1
[A]
.
The plot is shown in Fig. 5.6(b).
P5.28 By the vant Hoff equation [5.40],
= [B]RT =
cRT
M
.
Division by the standard acceleration of free fall, g, gives

8
=
c(R/g)T
M
.
TRAPP: CHAP05 2006/3/8 17:05 PAGE 113 #20
SIMPLE MIXTURES 113
Figure 5.6(b)
(a) This expression may be written in the form

=
cR

T
M
,
which has the same form as the vant Hoff equation, but the unit of osmotic pressure (

) is now
force/area
length/time
2
=
(mass length)/(area time
2
)
length/time
2
=
mass
area
.
This ratio can be specied in g cm
2
. Likewise, the constant of proportionality (R

) would have the

units of R/g,
energy K
1
mol
1
length/time
2
=
(mass length
2
/time
2
) K
1
mol
1
length/time
2
= mass length K
1
mol
1
.
This result may be specied in g cm K
1
mol
1
.
R

=
R
g
=
8.314 47 J K
1
mol
1
9.806 65 ms
2
= 0.847 840 kg mK
1
mol
1
_
10
3
g
kg
_

_
10
2
cm
m
_
R

= 84784.0 g cm K
1
mol
1
.
In the following we will drop the primes giving
=
cRT
M
and use the units of g cm
2
and the R units g cmK
1
mol
1
.
TRAPP: CHAP05 2006/3/8 17:05 PAGE 114 #21
114 SOLUTIONS MANUAL
(b) By extrapolating the low concentration plot of /c versus c (Fig. 5.7 (a)) to c = 0 we nd the
intercept 230 g cm
2
/g cm
3
. In this limit vant Hoff equation is valid so
RT
M
= intercept or M =
RT
intercept
,
M =
(84 784.0 g cmK
1
mol
1
) (298.15 K)
(230 g cm
2
)/(g cm
3
)
,
M = 1.1 10
5
g mol
1
.
500
450
400
350
300
250
200
0.000 0.010 0.020 0.030 0.040
Figure 5.7(a)
(c) The plot of /c versus c for the full concentration range (Fig. 5.7(b)) is very nonlinear. We may
conclude that the solvent is good. This may be due to the nonpolar nature of both solvent and solute.
(d) /c = (RT/M)(1 + B

c + C

c
2
).
Since RT/M has been determined in part (b) by extrapolation to c = 0, it is best to determine the
second and third virial coefcients with the linear regression t
(/c)/(RT/M) 1
c
= B

+ C

c,
R = 0.9791.
B

= 21.4 cm
3
g
1
,
C

= 211cm
6
g
2
,
standard deviation = 2.4 cm
3
g
1
.
standard deviation = 15 cm
6
g
2
.
TRAPP: CHAP05 2006/3/8 17:05 PAGE 115 #22
SIMPLE MIXTURES 115
7000
6000
5000
4000
3000
2000
1000
0
0.300 0.250 0.200 0.150 0.100 0.050 0.00
Figure 5.7(b)
(e) Using 1/4 for g and neglecting terms beyond the second power, we may write
_

c
_
1/2
=
_
RT
M
_
1/2
(1 +
1
2
B

c).
We can solve for B

; then g(B

)
2
= C

,
_
_
_
_
_
_
_

c
1/2
_
_
RT
M
_
1/2
_

_
1 =
1
2
B

c.
RT/M has been determined above as 230 g cm
2
/g cm
3
. We may analytically solve for B

from
one of the data points, say, /c = 430 g cm
2
/g cm
3
at c = 0.033 g cm
3
.
_
430 g cm
2
/g cm
3
230 g cm
2
/g cm
3
_
1/2
1 =
1
2
B

(0.033 g cm
3
).
TRAPP: CHAP05 2006/3/8 17:05 PAGE 116 #23
116 SOLUTIONS MANUAL
B

=
2 (1.367 1)
0.033 g cm
3
= 22.

2 cm
3
g
1
.
C

= g(B

)
2
= 0.25 (22.

2 cm
3
g
1
)
2
= 12

3 cm
6
g
2
.
Better values of B

and C

can be obtained by plotting

_

c
_
1/2
/
_
RT
M
_
1/2
against c. This plot is
shown in Fig. 5.7(c). The slope is 14.03 cm
3
g
1
. B

= 2 slope = 28.0 cm
3
g
1
. C

is then
196 cm
6
g
2
. The intercept of this plot should theoretically be 1.00, but it is in fact 0.916 with a
standard deviation of 0.066. The overall consistency of the values of the parameters conrms that g
is roughly 1/4 as assumed.
6.0
5.0
4.0
3.0
2.0
1.0
0.0
0.00 0.05 0.10 0.15 0.20 0.25 0.30
n
Figure 5.7(c)