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 justified by the requirement that, for systems at equilibrium under 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 = µi (v) − µi (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:

mB /MB
xB = .
mB /MB + mA /MA

The only unknown in this expression is MB 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 VC .

VA and Vc are given; hence we need to determine nA and nC in 1.000 kg of the solution with the stated
mole fraction. The total mass of the sample is m = nA MA + nC MC (a). We also know that
nA
xA = implies that (xA − 1)nA + xA nC = 0
nA + n C

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 SIMPLE MIXTURES 95

and hence that

−xC nA + xA nC = 0. (b)

On solving (a) and (b), we find


xA mxC
nA = × nC , nC = .
xC xA MA + x C MC

Since xC = 0.4693, xA = 1 − xC = 0.5307,

(0.4693) × (1000 g)
nC = = 5.404 mol,
[(0.5307) × (58.08) + (0.4693) × (119.37)] g mol−1


0.5307
nA = × (5.404) mol = 6.111 mol.
0.4693

The total volume, V = nA VA + nB VB , is therefore

V = (6.111 mol) × (74.166 cm3 mol−1 ) + (5.404 mol) × (80.235 cm3 mol−1 )

= 886.8 cm3 .

E5.2(a) Let A denote water and B ethanol. The total volume of the solution is V = nA VA + nB VB
We are given VA , we need to determine nA and nB in order to solve for VB .
Assume we have 100 cm3 of solution; then the mass of solution is

m = d × V = (0.914 g cm−3 ) × (100 cm3 ) = 91.4 g

of which 45.7 g is water and 45.7 g ethanol.



45.7 g 45.7g
100 cm3 = × (17.4 cm3 mol−1 ) + × VB
18.02 g mol−1 46.07 g mol−1
= 44.13 cm3 + 0.9920 mol × VB ,

55.87 cm3
VB = = 56.3 cm3 mol−1 .
0.9920 mol
pB
E5.3(a) Check whether is equal to a constant (KB )
xB

x 0.005 0.012 0.019

p/x 6.4 × 103 6.4 × 103 6.4 × 103 kPa

Hence, KB ≈ 6.4 × 103 kPa .

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 96 SOLUTIONS MANUAL

E5.4(a) In Exercise 5.3(a), the Henry’s law constant was determined for concentrations expressed in mole
fractions. Thus the concentration in molality must be converted to mole fraction.

m(GeCl4 ) = 1000 g, corresponding to

1000 g
n(GeCl4 ) = = 4.664 mol, n(HCl) = 0.10 mol.
214.39 g mol−1

0.10 mol
Therefore, x = = 0.0210.
(0.10 mol) + (4.664 mol)

From KB = 6.4 × 103 kPa (Exercise 5.3(a)), p = (0.0210 × 6.4 × 103 kPa) = 1.3 × 102 kPa .

E5.5(a) We assume that the solvent, benzene, is ideal and obeys Raoult’s law.
Let B denote benzene and A the solute; then

nB
pB = xB p∗B and xB = .
nA + n B

nB p∗B
Hence pB = , which solves to
nA + n B

nB (p∗B − pB )
nA = .
pB

mA
Then, since nA = , where mA is the mass of A present,
MA

mA pB m A MB pB
MA = = .
nB (p∗B − pB ) mB (p∗B − pB )

From the data

(19.0 g) × (78.11 g mol−1 ) × (51.5 kPa)

MA = = 82 g mol−1
(500 g) × (53.3 − 51.5) kPa

mass of B
E5.6(a) MB = [B = compound].
hB

nB = mass of CCl4 × bB [bB = molality of B].

T
bB = [5.37]; thus
Kf
mass of B × Kf
MB = Kf = 30 K/(mol kg−1 )[Table 5.2],
mass of CCl4 ×
T
(100 g) × (30 K kg mol−1 )
MB = = 381 g mol−1 .
(0.750 kg) × (10.5 K)

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 SIMPLE MIXTURES 97

nB nB
E5.7(a)
T = Kf bB [5.37], bB = ≈ [dilute solution].
mass of water Vρ

ρ ≈ 103 kg m−3 [density of solution ≈ density of water].

V 
nB ≈ [5.40],
T ≈ Kf ×
RT RT ρ

with Kf = 1.86 K/(mol kg−1 ) [Table 5.2].

(1.86 K kg mol−1 ) × (120 × 103 Pa)

T ≈ = 0.089 K.
(8.314 J K −1 mol−1 ) × (300 K) × (103 kg m−3 )

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.

pV
E5.8(a)
mix G = nRT {xA ln xA + xB ln xB }[5.18], xA = xB = 0.5, n= .
RT
Therefore,


1 1 1 1

mix G = (pV ) × ln + ln = −pV ln 2
2 2 2 2
= (−1.0) × (1.013 × 105 Pa) × (5.0 × 10−3 m3 ) × (ln 2)

= −3.5 × 102 J = −0.35 kJ .

−
mix G −0.35 kJ

mix S = −nR{xA ln xA + xB ln xB } = [5.19] = = +1.2 J K−1 .
T 298 K

E5.9(a)
mix S = −nR xJ ln xJ [5.19].
J

Therefore, for molar amounts,



mix S = −R xJ ln xJ
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(xA ln xA + xB ln xB )[5.19].

We need to differentiate eqn 5.19 with respect to xA and look for the value of xA at which the derivative
is zero. Since xB = 1 − xA , we need to differentiate

mix S = −nR{xA ln xA + (1 − xA ) ln(1 − xA )}.

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 98 SOLUTIONS MANUAL


d ln x 1
This gives using =
dx x

d
mix S xA
= −nR{ln xA + 1 − ln(1 − xA ) − 1} = −nR ln
dxA 1 − xA
1
which is zero when xA = . Hence, the maximum entropy of mixing occurs for the preparation of a
2
mixture that contains equal mole fractions of the two components.


m(Hex)
n(Hex) M(Hex)
(a) =1=
.
n(Hep) m(Hep)
M(Hep)
m(Hex) M(Hex) 86.17 g mol−1
(b) = = = 0.8600 .
m(Hep) M(Hep) 100.20 g mol−1

E5.11(a) With concentrations expressed in molalities, Henry’s law [5.26] becomes pB = bB K.

pB
Solving for b, the solubility, we have bB = .
K
(a) pB = 0.10 atm = 10.1 kPa.

10.1 kPa
b= = 3.4 mmol kg−1 .
3.01 × 103 kPa kg mol−1

(b) pB = 1.00 atm = 101.3 kPa.

101.3 kPa
b= = 34 mmol kg−1 .
3.01 × 103 kPa kg mol−1

E5.12(a) As in Exercise 5.11(a), we have

pB 5.0 × 101.3 kPa

bB = = = 0.17 mol kg−1 .
K 3.01 × 103 kPa kg mol−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.



fus H 1 1
ln xB = × − [5.39; B, the solute, is anthracene]
R T∗ T
 

28.8 × 103 J mol−1 1 1
= × − = −4.55.
8.314 J K −1 mol−1 490.15 K 298.15 K

Therefore, xB = e−4.55 = 0.0106.

n(anthracene)
Since xB  1, x(anthracene) ≈ .
n(benzene)

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 SIMPLE MIXTURES 99

Therefore, in 1 kg of benzene,


1000 g
n(anthr.) ≈ x(anthr.) × ≈ (0.0106) × (12.80 mol) = 0.136 mol.
78.11 g mol−1

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.

mRT cRT m
ΠV = nB RT [5.40], so π== , c= .
MV M V


RT
 = ρgh [hydrostatic pressure], so h = c.
ρgM

dm–3 Figure 5.1

RT
Hence, plot h against c and identify the slope as . Figure 5.1 shows the plot of the data.
ρgM
The slope of the line is 0.29 cm/(g dm−3 ), so

RT 0.29 cm
= = 0.29 cm dm3 g−1 = 0.29 × 10−2 m4 kg−1 .
ρgM g dm−3

Therefore,

RT
M=
(ρg) × (0.29 × 10−2 m4 kg−1 )
(8.314 J K −1 mol−1 ) × (298.15 K)
= = 87 kg mol−1 .
(1.004 × 103 kg m−3 ) × (9.81 m s−2 ) × (0.29 × 10−2 m4 kg−1 )

E5.15(a) For A (Raoult’s law basis; concentration in mole fraction)

pA 250 Torr aA 0.833

aA = ∗ [5.43] = = 0.833 ; γA = = = 0.93 .
pA 300 Torr xA 0.90

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 100 SOLUTIONS MANUAL

For B (Henry’s law basis; concentration in mole fraction)

pB 25 Torr aB 0.125
aB = [5.50] = = 0.125 ; γB = = = 1.25 .
KB 200 Torr xB 0.10

For B (Henry’s law basis; concentration in molality)

pB
An equation analogous to eqn 5.50 is used, aB = with a modified Henry’s law constant KB that
KB
corresponds to the pressure of B in the limit of very low molalities,

bB
pB =  × KB ,
b

xB
is analogous to pB = xB KB . Since xB and bB are related as bB = , K and KB are related as
MA xA B
KB = xA MA b KB .
We also need MA ,

xB 0.10
MA = = = 0.050 kg mol−1 .
xA bB (0.90) × (2.22 mol kg−1 )

Then, KB = (0.90) × (0.050 kg mol−1 ) × (1 mol kg−1 ) × (200 Torr) = 9.0 Torr
25 Torr aB 2.8
and aB = = 2.8 , γB =
 = = 1.25 .
9.0 Torr bB 2.22
b
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 µ† and µ are different.

Question. What are the activity and activity coefficient of B in the Raoult’s law basis?

E5.16(a) In an ideal dilute solution the solvent (CCl4 ) obeys Raoult’s law and the solute (Br2 ) obeys Henry’s law;
hence

p(CCl4 ) = x(CCl4 )p∗ (CCl4 )[5.24] = (0.950) × (33.85Torr) = 32.2 Torr ,

p(Br2 ) = x(Br2 )K(Br2 )[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

p(CCl4 ) 32.2 Torr

y(CCl4 ) = = = 0.841 ,
p(Total) 38.3 Torr
p(Br2 ) 6.1 Torr
y(Br2 ) = = = 0.16 .
p(Total) 38.3 Torr

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 SIMPLE MIXTURES 101

E5.17(a) Let A = acetone and M = methanol.

pA pA
yA = [Dalton’s law] = = 0.516.
pA + p M 101.3 kPa
pA = 52.3 kPa, pM = 49.0 kPa.
pA 52.3 kPa pM 49.0 kPa
pA = [5.43] = = 0.499 , aM = = = 0.668 .
p∗A 105 kPa p∗M 73.5 kPa
aA 0.499 aM 0.668
γA = = = 1.25 , γM = = = 1.11 .
xA 0.400 xM 0.600

1
E5.18(a) I= (bi /b )zi2 [5.70]
2
and for an M p Xq salt, (b+ /b ) = p(b/b ), (b− /b ) = q(b/b ), so


1 2 b
I= (pz+ + qz−
2
)  .
2 b



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



1 b b
I(CuSO4 ) = (1 × 22 + 1 × 22 )  = 4  .
2 b b



b b
I = I(KCL) + I(CuSO4 ) = (KCL) + 4  (CuSO4 )
b b
= (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,
1 bi 2
by summing the product zi for each individual ion as in the definition of I [5.71].
2 b


b
E5.19(a) I = I(KNO3 ) = (KNO3 ) = 0.150.
b
Therefore, the ionic strengths of the added salts must be 0.100.



1 b b
(a) I(Ca(NO3 )2 ) = (22 + 2)  = 3  .
2 b b
1
Therefore, the solution should be made × 0.100 mol kg−1 = 0.0333 mol kg−1 in Ca(NO3 )2 . The
3
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
(b) I(NaC1) = ; therefore, with b = 0.100 mol kg−1 ,
b

(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.)

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 102 SOLUTIONS MANUAL

E5.20(a) These concentrations are sufficiently dilute for the Debye–Hückel limiting law to give a good approximate
value for the mean ionic activity coefficient. Hence

log γ± = −|z+ z− |AI 1/2 [5.69].


1  2 bi 1
I= zi [5.71] = [(4 × 0.010) + (1 × 0.020) + (1 × 0.030) + (1 × 0.30)
2 b 2
i

= 0.060 .

log γ± = −2 × 1 × 0.509 × (0.060)1/2 = −0.2494; γ± = 0.563 = 0.56 .

A|z+ z− |I 1/2
E5.21(a) log γ± = − [5.72].
1 + BI 1/2
Solving for B,


1 A|z+ z− |
B=− + .
I 1/2 log γ±


b
For HBr, I = and |z+ z+ | = 1; so
b


b 0.509
B=− + .
(b/b )1/2 log γ±

Hence, draw up the following table.

(b/b ) 5.0 × 10−3 10.0 × 10−3 120.0 × 10−3

γ± 0.930 0.907 0.879

B 2.01 2.01 2.02

The constancy of B indicates that the mean ionic activity coefficient of HBr obeys the extended Debye–
Hückel law very well.

Solutions to problems

Solutions to numerical problems

pA = yA p and pB = yB p (Dalton’s law). Hence, draw up the following table.

P5.1 pA /kPa 0 1.399 3.566 5.044 6.996 7.940 9.211 10.105 11.287 12.295
xA 0 0.0898 0.2476 0.3577 0.5194 0.6036 0.7188 0.8019 0.9105 1
yA 0 0.0410 0.1154 0.1762 0.2772 0.3393 0.4450 0.5435 0.7284 1

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 SIMPLE MIXTURES 103

pB /kPa 0 4.209 8.487 11.487 15.462 18.243 23.582 27.334 32.722 36.066

xB 0 0.0895 0.1981 0.2812 0.3964 0.4806 0.6423 0.7524 0.9102 1

yB 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 Henry’s law will hold. The Henry’s
law constants are then given by
pA
KA = = 15.58 kPa from the point at xA = 0.0898.
xA

pB
KB = = 47.03 kPa from the point at xB = 0.0895.
xB


∂V
P5.3 Vsalt = mol−1 [Problem 5.2]
∂b H2 O
= 69.38(b − 0.070)cm3 mol−1 with b ≡ b/(mol kg−1 ).

Therefore, at b = 0.050 mol kg−1 , Vsalt = −1.4 cm3 mol−1 .

The total volume at this molality is

V = (1001.21) + (34.69) × (0.02)2 cm3 = 1001.22 cm3 .

Hence, as in Problem 5.2,

(1001.22 cm3 ) − (0.050 mol) × (−1.4 cm3 mol−1 )

V (H2 O) = = 18.04 cm2 mol−1 .
55.49 mol

Question. What meaning can be ascribed to a negative partial molar volume?

P5.5 Let E denote ethanol and W denote water; then

V = nE VE + nW VW [5.3].

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104 SOLUTIONS MANUAL

For a 50 per cent mixture by mass, mE = mW , implying that

nE ME
nE ME = nW MW , or nW = .
MW
nE ME VW
Hence, V = nE VE +
MW
V ME V
which solves to nE = ,n = .
ME VW W VE M W + M E V W
VE +
MW
nE 1
Furthermore, xE = = .
nE + n W ME
1+
MW
ME
Since ME = 46.07 g mol−1 and MW = 18.02 g mol−1 , = 2.557. Therefore
MW

xE = 0.2811, xW = 1 − xE = 0.7189.

At this composition

VE = 56.0 cm3 mol−1 , VW = 17.5 cm3 mol−1 [Fig.5.1 of the text].

100 cm3
Therefore, nE = −1
= 0.993 mol,
(56.0 cm3 mol ) + (2.557) × (17.5 cm3 mol−1 )

nW = (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:

mE = nE ME = (0.993 mol) × (46.07 g mol−1 ) = 45.7 g ethanol,

mW = nW MW = (2.54 mol) × (18.02 g mol−1 ) = 45.7 g water.

At 20◦ C the densities of ethanol and water are,

ρE = 0.789 g cm−3 , ρW = 0.997 g cm−3 . Hence,

mE 45.7 g
VE = = = 57.9 cm3 of ethanol,
ρE 0.789 g cm−3
mW 45.7 g
VW = = = 45.8 cm3 of water.
ρW 0.997 g cm−3
The change in volume upon adding a small amount of ethanol can be approximated by
 

V = dV ≈ VE dnE ≈ VE
nE

where we have assumed that both VE and VW are constant over this small range of nE . Hence


(1.00 cm3 ) × (0.789 g cm−3 )

V ≈ (56.0 cm3 mol−1 ) × = +0.96 cm3 .
(46.07 g mol−1 )

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 SIMPLE MIXTURES 105

T 0.0703 K
P5.7 bB = = = 0.0378 mol kg−1 .
Kf 1.86 K/(mol kg−1 )

Since the solution molality is nominally 0.0096 mol kg−1 in Th(NO3 )4 , each formula unit supplies
0.0378
≈ 4 ions . (More careful data, as described in the original reference gives ν ≈ 5 to 6.)
0.0096

P5.9 The data are plotted in Figure 5.3. The regions where the vapor pressure curves show approximate straight
lines are denoted R for Raoult and H for Henry. A and B denote acetic acid and benzene respectively.

40.0
Extrapolate
for KB

R
Henry
26.7
B

Raoult
kPa

13.3
Henry

A
H
Raoult
R H
0
0 0.2 0.4 0.6 0.8 1.0
xA Figure 5.3

pA pB
As in Problem 5.8, we need to form γA = and γB = for the Raoult’s law activity coefficients
xA p∗A xB p∗B
pB
and γB = for the activity coefficient of benzene on a Henry’s law basis, with K determined by
xB K
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.

xA 0 0.2 0.4 0.6 0.8 1.0

pA /kPa 0 2.7 4.0 5.1 6.7 7.3

pB /kPa 35.2 30.4 25.3 20.0 12.4 0
aA (R) 0 0.36 0.55 0.69 0.91 1.00[pA /p∗A ]
aB (R) 1.00 0.86 0.72 0.57 0.35 0[pB /p∗B ]
γA (R) — 1.82 1.36 1.15 1.14 1.00[pA /xA p∗A ]
γB (R) 1.00 1.08 1.20 1.42 1.76 —[pB /xB p∗B ]
aB (H) 0.44 0.38 0.32 0.25 0.16 0[pB /KB ]
γB (H) 0.44 0.48 0.53 0.63 0.78 1.00[pB /xB KB ]

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 106 SOLUTIONS MANUAL

GE is defined as [Section 5.4]

GE =
mix G(actual) −
mix G(ideal) = nRT (xA ln aA + xB ln aB ) − nRT (xA ln xA + xB ln xB )

and, with a = γ x,

GE = nRT (xA ln γA + xA ln γB ).

For n = 1, we can draw up the following table from the information above and RT = 2.69 kJ mol−1 .

xA 0 0.2 0.4 0.6 0.8 1.0

xA ln γA 0 0.12 0.12 0.08 0.10 0

xB ln γB 0 0.06 0.11 0.14 0.11 0
GE /(kJ mol−1 ) 0 0.48 0.62 0.59 0.56 0

P5.11 (a) The volume of an ideal mixture is

Videal = n1 Vm,1 + n2 Vm,2

so the volume of a real mixture is

V = Videal + 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.


n 1 n2 a1 (n1 − n2 )
V E = (n1 + n2 )VmE = a0 +
n1 + n 2 n1 + n 2


n1 n2 a1 (n1 − n2 )
so V = n1 Vm,1 + n2 Vm,2 + a0 + .
n1 + n 2 n1 + n 2
The partial molar volume of propionic acid is


∂V a0 n22 a1 (3n1 − n2 )n22
V1 = = Vm,1 + + ,
∂n1 p,T ,n2 (n1 + n2 ) 2 (n1 + n2 )3

V1 = Vm,1 + a0 x22 + a1 (3x1 − x2 )x22 .

That of oxane is

V2 = Vm,2 + a0 x12 + a1 (x1 − 3x2 )x12 .

(b) We need the molar volumes of the pure liquids,

M1 74.08 g mol−1
Vm,1 = = = 76.23 cm3 mol−1
ρ1 0.97174 g cm−3
86.13 g mol−1
and Vm,2 = = 99.69 cm3 mol−1 .
0.86398 g cm−3

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 SIMPLE MIXTURES 107

In an equimolar mixture, the partial molar volume of propionic acid is

V1 = 76.23 + (−2.4697) × (0.500)2 + (0.0608) × [3(0.5) − 0.5] × (0.5)2 cm3 mol−1

= 75.63 cm3 mol−1

and that of oxane is

V2 = 99.69 + (−2.4697) × (0.500)2 + (0.0608) × [0.5 − 3(0.5)] × (0.5)2 cm3 mol−1

= 99.06 cm3 mol−1 .

P5.13 Henry’s law constant is the slope of a plot of pB versus xB in the limit of zero xB (Fig. 5.4). The partial
pressures of CO2 are almost but not quite equal to the total pressures reported above.

pCO2 = pyCO2 = p(1 − ycyc ).

Linear regression of the low-pressure points gives KH = 371 bar .

80

60

40

20

0
0.0 0.1 0.2 0.3
Figure 5.4

The activity of a solute is

pB
aB = = xB γ B
KH

so the activity coefficient is

pB yB p
γB = =
xB KH xB K H

where the last equality applies Dalton’s law of partial pressures to the vapor phase. A spreadsheet applied
this equation to the above data to yield

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 108 SOLUTIONS MANUAL

p/bar ycyc xcyc γCO2

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 GE = RTx(1 − x){0.4857 − 0.1077(2x − 1) + 0.0191(2x − 1)2 }

with x = 0.25 gives GE = 0.1021RT . Therefore, since

mix G(actual) =
mix G(ideal) + nGE ,

mix G = nRT (xA ln xA + xB ln xB ) + nGE = nRT (0.25 ln 0.25 + 0.75 ln 0.75) + nGE
= −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



∂G ∂
P5.17 µA = [5.4] = µoA + (nGE ) [µoA is ideal value = µ∗A + RT ln xA ],
∂nA nB ∂nA nB


 
E

∂nGE ∂GE ∂xA ∂G
=G +nE
=G +n E
∂nA nB ∂nA nB ∂n A B ∂xA B

E
xB ∂G
= GE + n × × [∂xA /∂nA = xB /n]
n ∂xA B
= gRTxA (1 − xA ) + (1 − xA )gRT (1 − 2xA )
= gRT (1 − xA )2 = gRTxB2 .

Therefore, µA = µ∗A + RT ln xA + gRTxB2 .

P5.19 nA dVA + nB dVB = 0 [Example 5.1].

nA
Hence dVA = −dVB .
nB
Therefore, by integration,
 VA (xA )  VA (xA )
nA xA dVA
VB (xA ) − VB (0) = − dVA = − [nA = xA n, nB = xB n].
VA (0) nB VA (0) 1 − xA

 VA (xA ) xA dVA
Therefore, VB (xA , xB ) = VB (0, 1) − VA (0) 1 − x .
A

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 SIMPLE MIXTURES 109

We should now plot xA /(1 − xA ) against VA and estimate the integral. For the present purpose we
integrate up to VA (0.5, 0.5) = 74.06 cm3 mol−1 [Fig. 5.5], and use the data to construct the following
table.

VA (cm3 mol−1 ) 74.11 73.96 73.50 72.74

xA 0.60 0.40 0.20 0

xA /(1 − xA ) 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 ( )
xA/(1–xA)

0.5

0
72 73 74 75
VA,m /cm3 mol–1 Figure 5.5

V(CHCl3 ; 0.5, 0.5) = 80.66 cm3 mol−1 − 0.30 cm3 mol−1

= 80.36 cm3 mol−1 .

P5.21 ln aA
φ=− .
r

1 1
Therefore, dφ = − d ln aA + 2 ln aA dr,
r r

1
d ln aA = ln aA dr − rdφ.
r

From the Gibbs–Duhem equation, xA dµA = xB dµB = 0, which implies that (since µ = µ +
RT ln a, dµA = RT d ln aA , dµB = RT d ln aB )

xA d ln aA
d ln aB = − d ln aA = −
xB r
1 1
= − 2 ln aA dr = dφ[from(b)] = φdr = dr = dφ[from(a)]
r r
= φd ln r + dφ.

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 110 SOLUTIONS MANUAL

Subtract d ln r from both sides, to obtain

aB (φ − 1)
d ln = (φ − 1) d ln r + dφ = dr + dφ.
r r
a
γ x

B B B
Then, by integration and noting that ln = ln = ln (γB )r=0 = ln 1 = 0,
r r=0 r r=0


aB r φ−1
ln = φ − φ(0) = 0 dr .
r r

P5.23 A(s)
A(l).

µ∗A (s) = µ∗A (l) + RT ln aA

and
fus G = µ∗A (l) − µ∗A (s) = −RT ln aA .

−
fus G
Hence, ln aA = .
RT


d ln aA 1 d
fus G
fus H
=− = [Gibbs–Helmholtz eqn].
dT R dT T RT 2

For
T = Tf∗ − T , d
T = −dT and

d ln aA −
fus H −
fus H
= ≈ .
d
T RT 2 RTf2

RTf2 MA
But Kf = .

fus H
Therefore,

d ln aA −MA −MA d
T

= and d ln aA = .
d
T Kf Kf

According to the Gibbs–Duhem equation

nA dµA + nB dµB = 0

which implies that

nA d ln aA + nB d ln aB = 0[µ = µ + RT ln a]

nB
and hence that d ln aA = − d ln aB .
nA
d ln aB nA M A 1
Hence, = = [for nA MA = 1kg]
d
T nB Kf bB Kf
We know from the Gibbs–Duhem equation that

xA d ln aA + xB d ln aB = 0

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 SIMPLE MIXTURES 111

  xB
and hence that d ln aA = − d ln aB .
xA
 xB
Therefore ln aA = − d ln aB
xA
The osmotic coefficient was defined in Problem 5.21 as
1 xA
φ=− ln aA = − ln aA .
r xB
Therefore,
  b  b  b  b
xA xB 1 1 1 1
φ= d ln aB = b d ln aB = b d ln γ b = b d ln b + b d ln γ
xB xA b 0 b 0 b 0 b 0

1 b
=1+ b d ln γ .
b 0
From the Debye–Hückel limiting law,

ln γ = −A b1/2 [A = 2.303A].

1
Hence, d ln γ = − A b−1/2 db and so
2

 b

1 1 1 A 2 1
φ =1+ − A b1/2 db = 1 − × b3/2 = 1 − A 1/2 .
b 2 0 2 b 3 3

COMMENT. For the depression of the freezing point in a 1,1-electrolyte

−
fus G
fus G
ln aA = +
RT RT ∗


−
fus H 1 1
and hence −rφ = − ∗ .
R T T




fus HxA 1 1
fus HxA T∗ − T
fus HxA
T
Therefore, φ = − ∗ = ≈
RxB T T RxB TT ∗ RxB T ∗2

fus H
T
≈
νRbB T ∗2 MA

MRT ∗2
where ν = 2. Therefore, since Kf = ,

fus H

T
φ= .
2bB Kf

Solutions to applications

P5.25 In this case it is convenient to rewrite the Henry’s law expression as

mass of N2 = pN2 × mass of H2 O × KN2 .

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 112 SOLUTIONS MANUAL

(1) At pN2 = 0.78 × 4.0 atm = 3.1 atm,

mass of N2 = 3.1 atm × 100 g H2 O × 0.18 µg N2 /(g H2 O atm) = 56 µg N2 .

(2) At pN2 = 0.78 atm, mass of N2 = 14 µg N2 .

(3) In fatty tissue the increase in N2 concentration from 1 atm to 4 atm is

4 × (56 − 14) µg N2 = 1.7 × 102 µg N2 .

P5.27 (a) i = 1 only, N1 = 4, K1 = 1.0 × 107 dm3 mol−1 ,

ν 4 × 10 dm3 µmol−1
= .
[A] 1 + 10 dm3 µmol−1 × [A]
The plot is shown in Fig. 5.6(a).

Figure 5.6(a)

(b) i = 1; N1 = 4, N2 = 2; K1 = 1.0 × 105 dm3 mol−1 = 0.10 dm3 µmol−1 ,

K2 = 2.0 × 106 dm3 mol−1 = 2.0 dm3 µmol−1 .

ν 4 × 0.10 dm3 µmol−1 2 × 2.0 dm3 µmol−1

= + .
[A] 1 + 0.10 dm3 µmol−1 × [A] 1 + 2.0 dm3 µmol−1 × [A]
The plot is shown in Fig. 5.6(b).

P5.28 By the van’t Hoff equation [5.40],

cRT
Π = [B]RT = .
M
Division by the standard acceleration of free fall, g, gives
Π c(R/g)T
= .
8 M

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 SIMPLE MIXTURES 113

Figure 5.6(b)

(a) This expression may be written in the form

cR T
Π = ,
M

which has the same form as the van’t Hoff equation, but the unit of osmotic pressure ( ) is now

force/area (mass length)/(area time2 ) mass

2
= 2
= .
length/time length/time area

This ratio can be specified in g cm−2 . Likewise, the constant of proportionality (R ) would have the
units of R/g,

energy K −1 mol−1 (mass length2 /time2 ) K −1 mol−1

= = mass length K −1 mol−1 .
length/time2 length/time2

This result may be specified in g cm K−1 mol−1 .

R 8.314 47 J K−1 mol−1

R = =
g 9.806 65 m s−2



103 g 102 cm
= 0.847 840 kg m K−1 mol−1 ×
kg m

R = 84784.0 g cm K−1 mol−1 .

In the following we will drop the primes giving

cRT
Π=
M

and use the  units of g cm−2 and the R units g cm K−1 mol−1 .

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114 SOLUTIONS MANUAL

(b) By extrapolating the low concentration plot of /c versus c (Fig. 5.7 (a)) to c = 0 we find the
intercept 230 g cm−2 /g cm−3 . In this limit van’t Hoff equation is valid so

RT RT
= intercept or M = ,
M intercept
(84 784.0 g cm K−1 mol−1 ) × (298.15 K)
M= ,
(230 g cm−2 )/(g cm−3 )

M = 1.1 × 105 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 Π/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) Π/c = (RT /M)(1 + B c + C c2 ).
Since RT /M has been determined in part (b) by extrapolation to c = 0, it is best to determine the
second and third virial coefficients with the linear regression fit

(Π/c)/(RT /M) − 1
= B + C c,
c
R = 0.9791.

B = 21.4 cm3 g−1 , standard deviation = 2.4 cm3 g−1 .

C = 211cm6 g−2 , standard deviation = 15 cm6 g−2 .

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 SIMPLE MIXTURES 115

7000

6000

5000

4000

3000

2000

1000

0
0.00 0.050 0.100 0.150 0.200 0.250 0.300
Figure 5.7(b)

(e) Using 1/4 for g and neglecting terms beyond the second power, we may write

1/2
1/2
Π RT 1
= (1 + B c).
c M 2

We can solve for B ; then g(B )2 = C ,

 
Π 1/2
 c 
  1

1/2 
  − 1 = 2 B c.
 RT 
M

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, Π/c = 430 g cm−2 /g cm−3 at c = 0.033 g cm−3 .

1/2
430 g cm−2 /g cm−3 1
−1= B × (0.033 g cm−3 ).
230 g cm−2 /g cm−3 2

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116 SOLUTIONS MANUAL

2 × (1.367 − 1)
B = = 22.2̄ cm3 g−1 .
0.033 g cm−3

C = g(B )2 = 0.25 × (22.2̄ cm3 g−1 )2 = 123̄ cm6 g−2 .

1/2

Π RT 1/2
Better values of B and C can be obtained by plotting / against c. This plot is
c M
shown in Fig. 5.7(c). The slope is 14.03 cm3 g−1 . B = 2 × slope = 28.0 cm3 g−1 . C is then
196 cm6 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 confirms that g
is roughly 1/4 as assumed.

6.0

5.0

4.0
n

3.0

2.0

1.0

0.0
0.00 0.05 0.10 0.15 0.20 0.25 0.30
Figure 5.7(c)

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