Chapter 12

12.1 (a) T; (b) T.

12.2 (a) T; (b) F.

12.3 The contribution of sucrose to the vapor pressure can be neglected.

P = PA = aA PA* . Since the solution is reasonably dilute, we can take aA xA
and P = xA PA* . In 100 g of solution, there are (98.00 g)/(18.015 g/mol) = 5.440
mol of water and (2.00 g)/(342.3 g/mol) = 0.00584 mol of sucrose. Then xA = Con formato: Alemn (Alemania)

0.99893 and PA = 0.99893(1074.6 torr) = 1073.4 torr.

12.4 (a) T; (b) F; (c) F; (d) T; (e) T; (f) T; (g) T.

12.5 nC 5 H12 = (0.226 g)(1 mol/72.15 g) = 0.003132 mol. mC 5 H12 = (0.003132 mol)/
(0.01645 kg) = 0.1904 mol/kg. kf = MA RT *f 2 / fus H m,A =
(84.16 g/mol)(8.3145 J/mol-K)(279.62 K)2/(31.3 J/g)(84.16 g/mol) =
2.08 104 K g/mol = 20.8 K kg/mol. Tf = k f m = (20.8 K kg/mol)
(0.1904 mol/kg) = 3.96 K. Tf = 6.47C 3.96C = 2.51C. We assumed an
ideally dilute solution and that only pure cyclohexane freezes out.

12.6 m = Tf / kf = (0.112 K)/(1.860 K kg/mol) = 0.0602 mol/kg = ni/wA =

ni/(0.0980 kg), so ni = 0.00590 mol of maltose. Mi = wi/ni =
(2.00 g)/(0.00590 mol) = 339 g/mol and Mr,i = 339.

12.7 (a) Tf = kf mB = kf nB/wA = kf wB/MBwA and MB = kf w B/Tf wA.

(b) For 100 g of solution, the 3% solution has wB = 3.00 g and wA =
97.00 g; MB = (1.86 K kg/mol)(3.00 g)/(0.169 K)(97.0 g) =
0.3404 kg/mol = 340.4 g/mol. For the 6, 9, 12, and 15% solutions, we find
MB = 337.3, 334.5, 331.6, and 328.2 g/mol. Plotting MB vs. wt. % maltose,
we get a nearly linear graph that extrapolates to MB = 343 g/mol at 0 wt.
%.

175
 y = -1.0033x + 343.43
344
342
MB
340
338
336
334
332
330
328
0 2 4 6 8 10 12 14 16

Wt. % maltose

12.8 (a) murea = [(1.00 g)/(60.06 g/mol)]/(0.200 kg) = 0.0833 mol/kg;

kf = Tf / murea = (0.250 K)/(0.0833 mol/kg) = 3.00 K kg/mol.
mY = Tf /kf = (0.200 K)/(3.00 K kg/mol) = 0.06667 mol/kg =
nY/(0.125 kg) and nY = 0.00833 mol. MY = wY/nY =
(1.50 g)/(0.00833 mol) = 180 g/mol. Mr,Y = 180.
(b) fusHm,A = MA RT *f 2/k f = (200 g/mol)(1.987 cal/mol-K)(285 K)2/
(3000 g K/mol) = 10.8 kcal/mol = 45.0 kJ/mol.

12.9 Let U denote CO(NH2)2. Tf (A + Z) = kf mz; Tf (A + U) = kf mU; so 1.65

= Tf (A + Z)/Tf (A + U) = mz/mU = (nZ/wA)/(nU/wA) = nZ/nU and nZ = 1.65nU
= 1.65(0.679 g)/(60.05 g/mol) = 0.01866 mol. MZ = (0.542 g)/(0.01866 mol) =
29.0 g/mol; Mr,Z = 29.0.

12.10 1/ T*f T f = (1/ T*f )[1/( T*f + Tf)] = (1/ T*f )(1/ T*f )[1/(1 + Tf / T*f )] =
(1/ T*f )2[1 Tf / T*f + (Tf / T*f )2 + ].

12.11 kb = MA RT *b 2/ vapH m,A = (18.0153 g/mol)(8.3145 J/mol-K)

(373.15 K)2/(40660 J/mol) = 512.95 K g/mol = 0.51295 K kg/mol.

12.12 We have 0.003136 mol of C10H8 and mB = (0.003136 mol)/(26.6 g) =

1.18 104 mol/g. Hence kb = (0.455 K)/(1.18 104 mol/g) = 3860 K g/mol.
Equation (12.19) gives vapHm = (119.4 g/mol)(8.314 J/mol-K)
(334.8 K)2/(3860 K g/mol) = 28.8 kJ/mol = 6.89 kcal/mol.

176
12.13 (a) We have AxA = aA and Tf = [R (T *f ) 2 /fusHm,A] ln aA =
(kf /MA)( M A m i) = kf m i.
(b) In 96.0 g of water we have 4.00 g (or 0.02295 mol) of K2SO4. Hence
mi = (0.02295 mol)/(0.0960 kg) = 0.239 mol/kg. Then = Tf /kf m i =
(0.950 K)/(1.86 K kg/mol)3(0.239 mol/kg) = 0.712.

12.14 Equation (12.17) gives iA mi = (2.37 K)/(14.1 K kg/mol) = 0.168 mol/kg; in

100 g of bromoform, we have 0.0168 total moles of solutes. Let P and P2 be

phenol and its dimer. Then 2P P2. The 2.58 g is 0.0274 mol of phenol. Let
2z mol of phenol react. At equilibrium, nP/mol = 0.0274 2z, nP2 = z, and ntot =
0.0274 z. Then 0.0168 = 0.0274 z and z = 0.0106. So nP = 0.0062 mol and
nP2 = 0.0106 mol. The molalities are mP = (0.0062 mol)/(0.100 kg) = 0.062
mol/kg and mP2 = 0.106 mol/kg. Thus Km = (0.106 mol/kg)/(0.062 mol/kg)2 =
27.6 kg/mol.

12.15 iA mi = Tf /kf = (0.70 K)/(5.1 K kg/mol) = 0.137 mol/kg = (nnap + nan)/

(0.300 kg); so nnap + nan = 0.0412 mol. We have 6.0 g = nnap(128.2 g/mol) +
nan(178.2 g/mol) = nnap(128.2 g/mol) + (0.0412 mol nnap)(178.2 g/mol). We
get nnap = 0.027 mol and nan = 0.014 mol.

12.16 (a) In 100 g of solution, nB = (8.00 g)/(342.3 g/mol) = 0.02337 mol and
mB = (0.02337 mol)/(0.092 kg) = 0.254 mol/kg.
Tf = (1.860 K kg/mol)(0.254 mol/kg) = 0.4725 K.
(b) ln aA = (fusHm,A/R)(1/ T*f 1/Tf) =
[(6007 J/mol)/(8.3145 J/mol-K)](1/273.15 1/272.665)/K = 0.00470
and aA = 0.99531. 100 g of solution has nA = (92.00 g)/(18.0153 g/mol)
= 5.1068 mol of H2O, so xA = 5.1068/(5.1068 + 0.02337) = 0.99544 and
A = aA/xA = 0.99531/0.99544 = 0.99987.
(c) = (ln aA)/MAmi = 0.00470/(0.018015 kg/mol)(0.254 mol/kg) = 1.027.

12.17 False.

12.18 (a) cRT = (0.282 mol/L)(1 L/103 cm3)(82.06 cm3-atm/mol-K)(293.1 K)

= 6.78 atm.

177
 (b) * H 2 O = (18.015 g/mol)/(0.998 g/cm3) = 18.05 cm3/mol.
V m,
ln aH 2 O = Vm,
* A /RT = [(7.61 atm)(18.05 cm3/mol)]/
(82.06 cm3-atm/mol-K)(293.1 K)] = 0.00571; aH 2 O = 0.99431. xH 2 O =
55.508/(55.508 + 0.300) = 0.99462. H 2 O = 0.99431/0.99462 = 0.99969.

12.19 cB = /RT = (6.1/760)atm/(82.06 cm3-atm/mol-K)(273 K) =

3.58 107 mol/cm3. One cm3 of solution contains 3.58 107 mol of the
protein and contains 0.0200 g of protein; so MB = (0.0200 g)/(3.58 107 mol)
= 56000 g/mol; Mr,B = 56000. This is approximate because the solution is not
actually ideally dilute.

12.20 We have 5.55 moles of water and 0.00292 moles of sucrose. Equation (12.26)
gives = [(82.06 cm3-atm/mol-K)(298.1 K)/(18.07 cm3/mol)]
[(0.00292 mol)/(5.55 mol)] = 0.712 atm. We have = gh and h = / g =
0.712 atm 8.314 J
7.36 m 736 cm
(1.00 103 kg/cm3 )(9.807 m/s2 ) 82.06 cm3 atm

12.21 = gh. In the infinite-dilution limit, of the solution goes to of water, and
we shall use of water in the following calculations. For the first solution,
= (0.996 g/cm3)(980.7 cm/s2)(2.18 cm) = 2129 erg/cm3 and /B =
(2129 erg/cm3)/(0.00371 g/cm3) = 5.74 105 erg/g. The other solutions give
/ B values of 6.29 105, 7.18 105, and 8.10 105 erg/g. A plot of / B
vs. B is nearly linear and extrapolates to 4.54 105 erg/g at B = 0. This
intercept equals RT/MB and MB = (8.314 107 erg/mol-K)(303.1 K)/(4.54 105
erg/g) = 5.55 104 g/mol; the number average molecular weight is 55500.
y = 31924x + 453459
8.50E+05
/ B 8.00E+05
erg/g 7.50E+05
7.00E+05
6.50E+05
6.00E+05
5.50E+05
5.00E+05
4.50E+05
0 2 4 6 8 10 12 B/(g/L)

178
12.22 / B RT/MB + A2RT B + A3 RT B2 = RT/MB + A2RT B + A22 M B RT B2 /4 =
[(RT/MB)1/2 + A2(MBRT)1/2 B /2]2 and taking the square root of both sides gives
the desired result.

12.23 (a) iA ci /RT = (7 atm)/(82.06 cm3-atm/mol-K)(310 K) =

0.000275 mol/cm3 = 0.275 mol/dm3 cNa cCl . Therefore cNa
0.138 mol/dm3 as compared with 0.15 mol/dm3.
(b) We shall approximate the concentration by the molalities. Then
iA ci [2(0.460) + 3(0.034) + 2(0.019) + 2(0.009)] mol/dm3 =
1.078 mol/dm3 = 0.001078 mol/cm3. Then
(82.06 cm3-atm/mol-K)(293 K)(0.001078 mol/cm3) = 26 atm.

12.24 We have Vi = niRT/P, so Vi is proportional to ni and to xi. Then Mn =

i xiMi and Mn,r = (0.78)(28.01) + 0.21(32.00) + 0.01(39.95) = 29.0.

12.25 = (RT/ V m, * A )(MAmi) = (RT/ V m,

* A ) ln aA = (RT/ V m, * A )MAni/nAMA =
RTni/nA V m,
* A.

12.26 (a) A,1 = A,2. Assuming ideally dilute solutions, we have A* (P1, T) +
RT ln xA,1 = A* (P1 + , T) + RT ln xA,2 and A* (P1 + , T) A* (P1, T)
= RT ln xA,1 RT ln xA,2 RTxB,1 + RTxB,2, where (12.11) was used.
From (12.22), A* (P1 + , T) A* (P1, T) = V m,A
* , where the pressure
dependence of V m,A * = RT(xB,2 xB,1).
* is neglected. Hence V m,A
(b) xB,2 = 0.100/(0.100 + 55.51) = 0.00180 and
xB,1 = 0.0200/(0.0200 + 55.51) = 0.000360. =
(82.06 cm3-atm/mol-K)(298.1 K)(0.00144)/(18.07 cm3/mol) = 1.95 atm.

12.27 At equilibrium, the equality sign holds in (4.12) and P dV P dV =

dA + dA = P dV + i i dni P dV + i i dni , so i i dni +
i i dni = 0. Let dn moles of substance j move from phase to phase .
Then dnj = dn and dn j = dn; we have j dn + j dn = 0 and j = j .

179
12.28 f = cind p + 2 = 2 p + 2 = 4 p and p = 4 f. The minimum f is 0, so the
maximum p is 4 in a binary system.

12.29 (a) Yes. The horizontal tie line at T1 intersects the boundaries of the two-
phase region at x Bl = 0.23 (point L) and at x B = 0.68 (point Q).
(b) No. The overall mole fraction is different for different points on the tie
line.

12.30 As noted in Sec. 12.6, the upper curve is the P-vs.- x Bl curve and the lower
curve is the P-vs.- x B curve. We take B as acetone. Table 10.1 gives P and the
x Bl and x B values that correspond to each P value. Plotting these points, we get
a phase diagram with a minimum in P at xacetone = 0.4.

12.31 The width between the vertical axes is 60 mm and xB = 0.3 lies at 18 mm.
We draw a vertical line at 18 mm, and then a horizontal line that goes from the
liquid line at 18 mm to the vapor line; the intersection with the vapor line is at
45 mm (corresponding to xB = 0.75) and gives the result of the first
distillation step; drawing a horizontal line from the liquid line at 45 mm, we
find it intersects the vapor line at 58 mm, corresponding to xB = 0.97.

12.32 (a) The width of the figure is 60 mm and x = 0.72 corresponds to 43.2 mm.
Drawing a vertical line at 43 mm and then a horizontal line from the
intersection of this vertical line with the liquid line, we find the
horizontal line intersects the vapor line at 52 mm, which corresponds to
x B = 52/60 = 0.875.
(b) x Bl is given by point D as (36 mm)/(60 mm) = 0.60. Point G gives
x B = (48 mm)/(60 mm) = 0.81.

12.33 The point giving the systems state lies on the horizontal line at T1 and cannot
lie to the left of point Q, since all points to the left of Q have some liquid
present. Point Q corresponds to xB = (41 mm)/(60 mm) = 0.68, so xB =
nB/(nB + nC) 0.68; nB 0.68nB + 0.68nC; nC 0.47nB = 0.47(2.00 mol) =
0.94 mol. nC 0.94 mol.

180
12.34 xB,overall = 4.00/7.00 = 0.571. Point L gives x Bl = (14 mm)/(60 mm) = 0.23.
Point Q gives x B = (41 mm)/(60 mm) = 0.68. The lever rule gives
nl(0.571 0.23) = n(0.68 0.571) and n = 3.1n = 3.1(7.00 mol n) and
n = 5.3 mol; nl = 7.00 mol 5.3 mol = 1.7 mol. n Bl = 0.23(1.7 mol) = 0.39
mol; nCl = (1.7 0.39) mol = 1.3 mol. n B = 0.68(5.3 mol) = 3.6 mol;
nC = 1.7 mol.

12.35 P = Pben + Ptol = xben P*ben + x tol P*tol = xben P*ben + (1 xben ) P*tol =
P*tol + (P*ben P*tol )xben. The graph is linear, so we need only two points to plot
it: P = P*tol = 22.3 torr at xben = 0 and P = P*ben = 74.7 torr at xben = 1.

12.36 (a) As found in the Prob. 12.31 solution, the first vapor has x B = 0.75.
(b) A horizontal line starting from x B = 0.30 intersects the liquid line at
x Bl = 0.03.
(c) When nl = n, the horizontal tie line is bisected by the vertical line at xB =
0.30. By trial and error, we find that the tie line with equal halves is the
one that joins x Bl = 0.11 with x B = 0.50.

12.37 Regina is correct. Going horizontally in the two-phase region varies the overall
mole fraction (whose value depends on the sizes of the two phases present),
but does not change the mole fractions in either of the phases present.

12.38 A horizontal line at 80C in Fig. 12.17b intersects the curve at wnic values of
0.076 for phase and 0.69 for phase . We have 10 g = 0.076m +
0.69(20 g m) and m = 6.2 g; then m = 20 g 6.2 g = 13.8 g. (Alternatively,
the lever rule could be used.) The phase therefore has 0.076(6.2 g) = 0.5 g of
nicotine and 5.7 g of water. The phase has 0.69(13.8 g) = 9.5 g of nicotine
and 4.3 g of water.

12.39 Drawing a horizontal tie line at 80C, we find it intersects the water-poor
portion of the curve at wnic = 0.69. Drawing the vertical line at weight fraction
wnic = 0.5 and using the lever rule (12.41), we find

181
 (20 g)(17 12 mm) = mwp(7 34 mm) and the mass of the water-poor phase is
mwp = 45 g. The mass of nicotine in the water-poor phase is 0.69(45 g) = 31 g
and the mass of water in this phase is 45 g 31 g = 14 g.

12.40 (a) Let be the water-poor phase and the water-rich phase.
(0.400 0.375)m = (0.89 0.40)m = (0.89 0.40)(10.0 g m);
0.025m = 4.90 g 0.49m and m = 9.51g, m = 0.49 g. Then mH 2 O =

0.375(9.51 g) = 3.6 g, mphenol = (9.5 3.6) g = 5.9 g; mH 2 O = 0.89(0.49 g)

= 0.44 g; mphenol = 0.05 g.
(b) 0.375 = mH 2 O /m , 0.89 = mH 2 O /m = (4.00 g mH 2 O )/(10.0 g m).
The first equation gives mH 2 O = 0.375m and substitution in the second
equation gives 0.89 = (4.00 g 0.375m)/(10.00 g m). Solving, we get
m = 9.5 g, and the problem is completed as in (a).

12.41 Let be the octanol-rich phase. We assume the small amount of DDT does not
affect the water (w) and octanol (oc) mole fractions in the phases. We use the
mole fractions given on p. 372 of the text. We have a total of 4.44 mol of water
and 0.0768 mol of octanol (C8H17OH, molecular weight 130.2), for a total
number of moles of 4.518 mol. The total moles of water equals the sum of the
water moles in each phase, so 4.44 mol = (1 0.793)n + 0.993(4.518 n) and
n = 0.0577 mol. So n = 4.46 mol. Then nw 0.207(0.0577 mol) = 0.0119
mol, and mw = 0.215 g. We are assuming no volume change on mixing, so we
shall take the volume of each phase as the sum of the volumes of the water
and octanol that went into that phase (neglecting the small contribution of
DDT). The contribution of water (density 1.00 g/cm3) to the volume of is

thus 0.22 cm3. We have noc = (0.793)(0.0577 mol) = 0.0458 mol, and moc =
5.96 g; from the density, the volume of this octanol is 7.18 cm3. The volume of
phase is then V = (0.22 + 7.18) cm3 = 7.4 cm3. For phase , nw
(0.993)(4.46 mol) = 4.43 mol; mw = 79.8 g; Vw = 79.8 cm3. Also, noc



(0.007)(4.46 mol) = 0.031 mol; moc = 4.06 g; Voc = 4.9 cm3. Then V = 84.7
cm3. The 0.100 g of DDT is 0.000282 mol. We have Kow,DDT = 8.1 106 =

182

cDDT nDDT / V (0.000282 nDDT

) /( 7.4 cm 3 )


and nDDT = 4.0 1010 mol,
cDDT nDDT /V
nDDT /(84.7 cm 3 )

which is 1.4 107 g. nDDT = 0.000282 mol, which is 100 mg.

12.42 We have Kow,napth = 2.0 103. In Eq. (12.45), corresponds to the octanol-rich
phase. The quantity in parentheses in the equation preceding (12.45) is the
desired G. If we make the approximation that the activity coefficient ratio is
approximately equal to 1 (which may not be accurate), we have
Gc RT ln Kow,napth = (8.314 J/mol-K)(298 K)3.30 = 8.2 kJ/mol.

12.43 The diagram should bear some resemblance to Fig. 12.19. The phases present
in each area are given in Fig. 12.19. On the horizontal line, three phases are
present: pure solid B, pure solid C, and liquid solution. On this line, f is zero.
In the two-phase areas, f is 1 (the temperature). In the one-phase liquid-
solution area, f is 2.

12.44 Let B = benzene and A = cyclohexane. Equation (12.46) becomes

1
T T */
B [1 RT*B (fusHm,B) ln xB] = (278.6 K)/(1 0.233 ln xB) and
Tr (279.7 K)/(1 0.884 ln xA), where T and Tr are the left- and right-hand
curves in Fig. 12.19. We get

xA 0 0.1 0.2 0.3 0.4 0.5 0.6

T 278.6 271.9 264.8 257.2 249.0 239.9 229.6
Tr 192.7

xA 0.7 0.8 0.9 1

T 217.6 202.6 181.3
Tr 212.7 233.6 255.9 279.7

Plotting the curves, we find they intersect at 71 mole percent cyclohexane

and 58C.

12.45 The halt at 84.3 wt. % Zn must correspond to a compound with melting point
595C. (It could not be a eutectic halt since its temperature is too high for this.)
The compounds empirical formula is found as follows: (84.3 g)/(65.38 g/mol)

183
 = 1.289 mol Zn; (15.7 g)/(24.305 g/mol) = 0.646 mol Mg. The Zn:Mg mole
ratio is 2:1 and the compounds empirical formula is MgZn2. The phase
diagram is of the type shown in Fig. 12.25. The eutectic temperatures are
345C and 368C. One eutectic composition is 97 wt. % Zn (corresponding to
368C). It is difficult to tell which curve the reading at 50% belongs to, so all
that can be said is that the second eutectic composition is close to 50 wt. % Zn.

12.46 (a) The phase diagram is the same type as Fig. 12.26c with line PM lying at
0.1C. The Liquid () is a solution of salt in water, B is H2O, the
compound is NaCl 2H2O, and A is NaCl. Since the diagram goes up to
only 100C, the right-hand melting-point curve (which is almost vertical
below 100C) does not reach the NaCl axis. The compound lies at 62 wt.
% NaCl.
(b) 20C lies above the peritectic temperature of 0.1C. As the solution
evaporates, we move horizontally to the right on the diagram, eventually
reaching the + A (solution + solid NaCl) region; eventually, pure NaCl
is obtained.
(c) This system lies initially in the + A (solution + solid NaCl) region.
When the peritectic temperature of 0.1C is reached, solid NaCl 2H2O
begins to form. The 80 wt. % composition lies to the right of MN in Fig.
12.26c, and the system stays at 0.1C until all the liquid disappears,
leaving a mixture of the two solids NaCl and NaCl 2H2O. Then this
mixture is cooled to 10C. No solid H2O (ice) is present at 10C.

12.47 A cooling curve that corresponds to l.s. l.s. + + shows three

breaks. A cooling curve that corresponds to l.s. l.s. + l.s. + +
+ shows a break followed by a eutectic halt. A cooling curve at the eutectic
composition shows no break and one halt. Similarly for curves to the right of
the eutectic composition.

12.48 For + B B + A2B + B + A2B, a break followed by a (eutectic)

halt. For cooling a liquid with the eutectic composition, a halt. For +
A2B + B + A2B B + A2B, a break and then a halt. For + A
+ A + A2B + A2B + B + A2B B + A2B, break, halt, halt. For
+ A + A2B + A A2B, break, halt. For + A + A +
A2B A + A2B, break, halt.

184
12.49 Just as Fig. 12.25 resembles two Fig. 12.19 diagrams placed side by side, the
Bi-Te diagram resembles two Fig. 12.22 diagrams placed side by side:

is a solid solution of Bi2Te3 in Bi. is a solid solution of Bi in Bi2Te3. is a

solid solution of Te in Bi2Te3. is a solid solution of Bi2Te3 in Te.

12.50 The intersection of the miscibility gap with the phase transition loop does not
include the composition corresponding to the minimum, so we get a

185
 combination of Figs. 12.24 and 12.21. Phase is a solution of Au in Fe. Phase
is a solution of Fe in Au.

12.51 Let A = HNO3 3H2O and B = HNO3 H2O.

12.52 (a) Equation (12.46) gives ln xB = [(147 J/g)(128.2 g/mol)/

(8.314 J/mol-K)][1/(353 K) 1/(298 K)] = 1.185 and xB = 0.306.
(b) The same as (a); xB = 0.306.
(c) ln xB = [(162 J/g)(178.2 g/mol)/(8.314 J/mol-K)][1/(489 K) 1/(333 K)]
= 3.326 and xB = 0.036.

12.53 (1000 g)(1 mol/78.1 g) = 12.8 mol. The 52C point on the solubility curve
CE is at xben = 0.47 = (12.8 mol)/(12.8 mol + nnaph). We get nnaph = 14 mol.

186
12.54

12.55 We change the formula in cell H1, choose a temperature and initial guesses for
cells D2 and D3, and run the Solver. Repeating at several temperatures, one
finds that at each temperature, the two phases have equal mole fractions,
indicating complete miscibility at all temperatures.

12.56 We change the formula in cell H1, choose a temperature and initial guesses for
cells D2 and D3, and run the Solver. Repeating at several temperatures, one
finds that there is partial miscibility at 240 K and at temperatures below 240 K,
and there is complete miscibility at 260 K. Trying various temperatures
between 240 K and 260 K, we get the critical solution temperature as 254 K.

12.57 (a) We get a lower critical solution temperature of about 200 K. (Note that as
T decreases, W becomes more negative, favoring miscibility (Prob.
12.55).
(b) We get a lower critical solution temperature of about 265 K.

12.58 The relation is quite simple. In (b), we get a lower critical solution temperature
of about 174 K, and this satisfies the relation.

12.59 When (12.48) and the three other similar equations for the other three chemical
potentials are substituted into (12.47), the terms that involve *D and E* are

187
 nD*D nE*E nD *
D nE*

E = (nD nD )*

D (nE nE )*
E , and the total number
of moles of D and of E in the system are constant.

12.60 (a) Higher acetone concentrations correspond to tie lines that are closer to
point K in Fig. 12.33. Consider moving from the tie line below FH to the
FH tie line. In doing so, the left end (water-rich phase) of the tie line
moves up a smaller amount than the right end (ether-rich phase) does, so
there is a greater enrichment of acetone in the ether-rich phase than in the
water-rich phase as the acetone concentration increases. Hence Kew,ac
ether- rich
increases, since cac is in the numerator of Kew,ac.
(b) The right end of each tie line is higher than the left end, meaning a
greater concentration of acetone in the ether-rich phase, so Kew,ac > 1.

12.61 Pure water (wat) lies at the point xwat = 1, xeth = 0; pure ether (eth) lies at
xwat = 0, xeth = 1; pure acetone (ac) lies at xwat = 0, xeth = 0. States with xac = 0
correspond to the line xwat + xeth = 1 or xeth = 1 xwat. This line has intercept 1
and slope 1; the two-phase region is bounded on one side by part of this line.
The plait point K is richer in water than in ether. The phase diagram is

188
12.62 Draw DA, DB, and DC in Fig. 12.32a. Let Ar(ABC) be the area of triangle
1
ABC and let h be the altitude of this triangle. We have 2 hBC = Ar(ABC) =
Ar(ABD) + Ar(BDC) + Ar(CDA) = 12 ( AB DG) + 12 ( BC DE ) +
1
2 (CA DF ) = 1
2 BC ( DG DE DF ). Hence h = DG DE DF.

12.63 (a) We drop perpendiculars from point F to each of the three sides of the
triangle and take the ratio of each perpendicular distance to the triangles
height. We get for phase F: xac = 0.06, xwat = 0.92, xeth = 0.02. Dropping
perpendiculars from point H, we get the phase-H composition as:
xac = 0.23, xwat = 0.05, xeth = 0.72.
(b) FG = 30 mm and GH = 22 mm. The lever rule gives 30 nF =
22 nH = 22 (40 mol nF); then nF = 17 mol and nH = 23 mol. Phase F
has 0.06(17 mol) = 1.0 mol of acetone, 0.92(17 mol) = 15.6 mol of water,
and 0.02(17 mol) = 0.34 mol of ether. Phase H has 5.3 mol of acetone, 1.2
mol of water, and 16.6 mol of ether.

12.64 (a) The diagram resembles Fig. 12.33 with ether replaced by ethyl acetate.
(b) The overall composition is xac = 0.20, xethyl = 0.40, xwat = 0.40. This point
lies in the two-phase region and is just a bit below one of the tie lines
graphed in (a). Drawing in a tie line through this point, we find it
intersects the binodal curve at points corresponding to the following

compositions. Phase : xwat = 0.915, xac = 0.062, xethy l = 0.023.

Phase : xwat = 0.260, xac = 0.238, xethy l = 0.502. We have

0.915n + 0.260(0.50 mol n) = 0.20 mol; so n = 0.107 mol and

n = 0.393 mol. (Alternatively, the lever rule could be used.) Then nwat

=

0.915(0.107 mol) = 0.098 mol, nac = 0.0066 mol, nethy l = 0.0025 mol;

nwat = 0.102 mol, nac = 0.0935 mol, nethy l = 0.197 mol. Multiplication

by the molar masses gives mwat = 1.76 g, mac = 0.38 g, methy l = 0.22 g;

mwat = 1.84 g, mac = 5.43 g, methy l = 17.4 g.

12.65 The overall composition of the system is given by point G, so the overall mole
fraction xA of A equals the distance GS to the side opposite vertex A. Points F

189
 and H give the compositions of the two phases F and H in equilibrium, and
x AF = FR , x AH = HT . Equation (12.49) with = F, = H becomes
n F (GS FR ) = n H ( HT GS ) and n F /n H HK/GM . The figure gives sin
= HK/GH = GM/ FG . So HK/GM = GH/ FG and the boxed equation
becomes nF/nH = GH/ FG or FGn F = GHn H .

12.66 (a) Since the solution in beaker B has a lower vapor pressure than that in A,
the evaporation rate from the A solution exceeds that from the B solution
and the equilibrium state will have beaker A empty, its liquid having
vaporized from A and condensed in B. The vapor pressure in the box will
be that of the diluted salt solution in B.
(b) The vapor pressure of the B solution is lower than that of the A solution.
Liquid will evaporate from A and condense in B until the sucrose
molalities are equalized. Let a mass z of H2O vaporize from A. Equating
molalities, we have (0.01 mol)/(100 g z) = (0.03 mol)/(100 g + z) and z
= 50 g. Beaker A ends up with 50 g of water and 0.01 mol of sucrose;
beaker B ends up with 150 g of water and 0.03 mol of sucrose.

12.67 The diagram has the same appearance as Fig. 12.22. With xA going from 0 to 1
on the horizontal axis, the areas are relabeled as follows: l.s. becomes vapor,
l.s. + becomes vapor + (where is a dilute solution of liquid A in the
solvent liquid B), l.s. + becomes vapor + (where is a dilute solution of
liquid B in liquid A). The horizontal line is a mixture of phase , vapor, and
phase . The region + is a mixture of the two immiscible liquids and .

12.68 Yes. For example, an endothermic chemical reaction might occur. Another
example is adding a salt to a mixture of water and ice at 0C (see Sec. 12.10).

190
12.69 (a) c = 2, p = 1; f = c p + 2 r a = 2 1 + 2 0 0 = 3, but since P is
held fixed, there are two degrees of freedom (temperature and xA).
(b) c = 2, p = 2; f = 2 2 + 2 0 0 = 2, but since P is held fixed, there is
one degree of freedom. Once T is fixed, the mole-fraction composition of
each phase is fixed.
(c) c = 2, p = 3; f = 2 3 + 2 0 0 = 1, but since P is held fixed, there are
no degrees of freedom. All intensive variables (T, P, mole fractions) are
fixed.

12.70 Assuming ideal vapor, we have Pi xi,vapP = I , i xi P*i . But for an azeotrope,
xi = xil , so xil P = I ,i xil P*i and I,i = P/P*i . I,ethanol = (760 torr)/(581 torr) =
1.31 and I,ethyl acetate = (760 torr)/(631 torr) = 1.20.

12.71 (a) For each substance, i = i and *i + RT ln I , i xi = *i +

RT ln I , i xi , so I , i xi = I , i xi . For phase , xw is very close to 1 and
I , w 1. Hence (1) xw = I , w xw and I , w = xw /xw = 0.999595/0.00300 =
333. For phase , I , ben 1 and I , ben xben

= (1) xben , so I , ben =

xben /xben = 0.99700/0.000405 = 2460.
(b) This solution is phase . With ideal vapor assumed, Pi = I , i xi P*i , so
Pben = 1(0.997)(95.2 torr) = 94.9 torr and Pw = 333(0.00300)(23.8 torr) =
23.8 torr. P = Pben + Pw = 118.7 torr.
(c) This solution is phase . Pben = 2460(0.000405)(95.2 torr) = 94.8 torr;
Pw = 1(0.999595)(23.8 torr) = 23.8 torr. P = 118.6 torr.

12.72 Let b stand for benzene and and be the two liquid phases. b = b and
*b + RT ln I , b xb = *b + RT ln I , b xb , so I , b xb = I , b xb . Above solution
, Pb = I ,b xb P*b . Above solution , Pb = I , b xb P*b . Use of I , b xb = I , b xb
gives Pb = Pb .

12.73 Assuming an ideally dilute solution, we have 0.64C kf mB and mB

(0.64 K)/(1.86 K kg/mol) = 0.344 mol/kg.

191
 (a) Tb kbmb = (0.513 K kg/mol)(0.344 mol/kg) = 0.176 K. The normal
boiling point of water is 99.974C (Sec. 1.5 and Fig. 7.1), so Tb
100.15C.
(b) P = PA xA PA* . We have mB = nB/wA = nB/nAMA xB/MA since the
solution is dilute. Then xB mBMA = (0.344 mol/kg)(0.01801 kg/mol) =
0.0062. So P 0.9938(23.76 torr) = 23.61 torr.
(c) xBRT/ V m,A
* = 0.0062(82.06 cm3 atm/mol-K)(293 K)/(18.0 cm3/mol)
= 8.3 atm.

12.74 (a) Same. (b) Same. (c) Same. (d) Same. (e) Different. (f) Different.

12.75 (a) False. See Fig. 12.20.

(b) True. See Fig. 12.2.
(c) False. See line FHK in Fig. 12.19.
(d) False. The eutectic solution in Fig. 12.19 freezes entirely at one
temperature.
(e) True as xB increases in the solution, B in the solution must increase
[Eq. (4.90)]. So B in the vapor in equilibrium with the solution must
increase. Since B = B, (T ) + RT ln (PB/P), if B increases at constant
T, then PB must increase.
(f) True. (g) False. (h) True. (i) False. (j) True. (k) False.

Reminder: Use this manual to check your work, and not to

avoid working the problems.

R12.1 I m 1
2 zm
i
2
i i
1
2 [2 (0.040) (1)2 (0.080) 0.060 0.060] mol/kg 0.18 mol/kg .
2

(0.18)1/ 2
log 0.51(2)(1) 0.30(0.18) 0.124 , 0.751.
1 (0.18)
1/ 2

192
R12.2 The standard state for species in liquid solutions was chosen to be at the
pressure of the solution; consequently, G and the equilibrium constant for
such reactions depend on P. Therefore the equilibrium constants for (d) and (e)
depend on pressure.

R12.3 (a) If the system is treated as an ideal-gas reaction, there is no shift when P is
changed because there is no change in total number of moles of gas. If
nonideality is allowed for, the change in P will change the intermolecular
interactions and will change the fugacity coefficients, and so the
equilibrium composition will change with pressure.
(b) The total moles of product gases differs from the total moles of reactant
gases and the equilibrium composition changes when P changes.
(c) Suppose we consider the gas as ideal and neglect the change in activity of
the solids with change in P. Then Eq. (11.25) gives K PCO2 /P If we
isothermally increase the pressure by decreasing the volume, then, since
K depends on T only and T is constant, the equilibrium will shift to the
left to reduce PCO2 to its previous value. Hence the numbers of moles
change when P is changed.
(d) As discussed in Prob. R12.2, the equilibrium constant depends on P and a
change in P changes the equilibrium composition. This change is small
unless the change in P is large.
(e) Same as (d).

R12.4 (a) See Eq. (6.4) with Pi = xi P.

(b) See Eq. (10.97) with fi i xi P.
(c) See Eq. (9.42).
(d) See Eqs. (9.58) and (9.59).
(e) See Eq. (10.6).

R12.5 (a) The negative term is eliminated when xR 0.40, and tmax 63C (the
critical solution temperature). At the maximum, the slope is zero and
dt/dx 0 1440( xR 0.40) and xR 0.40.

193
 (b) 25 63 720( xR 0.40)2 ; xR 0.40 (38/720)1/ 2 0.23 ;
xR 0.63 and 0.17.
(c) ntot 5.08 mol. nR nR nR and
2.30 mol = 0.63n 0.17(5.08 mol n ) ; n 3.12 mol;
n 1.96 mol. nR 0.63n 1.97 ; nR 0.17n 0.33 ;
nS 0.37n 1.15 ; nS 0.83n 1.63 .
(d) To produce a one-phase system, we must increase the overall mole
fraction of S to make it equal to 1 0.17 = 0.83. If z is the number of
moles of S to add, then 0.83 = (2.78 mol + z)/(5.08 mol + z) and z = 8.45
mol.

R12.6 (a) With activity coefficients neglected, 6.8 104 = x2/(0.15 x) and x =
0.0098 (mol/kg). The initial estimate of the ionic strength is 0.0098
mol/kg and the Davies equation gives log 0.0444 and 0.903 .
Then 6.8 104 = (0.903)2x2/(0.15 x) and x = 0.0108. For an ionic
strength of 0.0108 mol/kg, the Davies equation gives log 0.0464
and 0.899 . Then 6.8 104 = (0.899)2x2/(0.15 x) and x = 0.0108.
The H+ molality is 0.0108 mol/kg. From Prob. 11.21,
c(H+ ) m(H+ ) H2O (0.0108 mol/kg)(0.997 kg/L) = 0.0108 mol/L.
(b) The initial estimate of the ionic strength is 0.20 mol/kg from the KCl.
The Davies equation gives log 0.127 and 0.746 . Then
6.8 104 = (0.746)2x2/(0.15 x) and x = 0.0129. The improved estimate
of the ionic strength is 0.213, and the Davies equation gives
log 0.1285 ; 0.744 . Then 6.8 104 = (0.744)2x2/(0.15 x)
and x = 0.0130. The H+ molality is 0.0130 mol/kg. Then
c(H+ ) m(H+ ) H2O (0.0130 mol/kg)(0.997 kg/L) = 0.0130 mol/L.

R12.7 3 2 .

R12.8 If the vapor is assumed ideal, then Pi xi P I,i xil Pi* . Then
0.194(286 torr) = I,chl (0.291)(293 torr) and I,chl = 0.651.
(1 0.194)(286 torr) = I,ac (1 0.291)(344 torr) and I,ac = 0.945.

194
R12.9 (a) am,i i mi /m .
(b) ac,i i ci /c .
(c) aII,i II,i xi .

R12.10 See Fig. 12.19 and the accompanying discussion.

R12.11 k f M A R(T f *)2 /fus H m,A

(0.06207 kg/mol)(8.314 J/mol-K)(260.6 K)2/(9960 J/mol) = 3.519 K kg/mol
(258.8 K 260.6 K) = (3.519 K kg/mol)mY and mY = 0.512 mol/kg.
nY = (0.512 mol/kg)(0.0864 kg) = 0.0442 mol. MY = (4.25 g)/(0.0442 mol) =
96 g/mol and the approximate molecular weight is 96.

R12.12 The mole fractions in the two phases in equilibrium in the miscibility gap
region are xB 0.125/(1 0.125) 0.111 and xB 3.00/4.00 0.750.
The system has xB,overall 0.556 and so lies in the two-phase region. The
total moles of B is the sum of the B moles in each phase, so 2.50 mol =
0.111n 0.750(4.50 mol n ) so n 1.37 mol and n = 3.13 mol.
Then nB 0.111(1.37 mol) = 0.152 mol and nB = 2.50 mol 0.15 mol
= 2.35 mol. Also, nC = (1 0.111)(1.37 mol) = 1.22 mol and nC =
0.250(3.13 mol) = 0.78 mol.

R12.13 (a) Hypothetical, since the standard state is the ideal gas at 1 bar.
(b) Real, since it is the pure solvent at the T and P of the solution.
(c) Hypothetical; see Sec. 10.4.

R12.14 For AgCl(s) Ag+(aq) + Cl(aq), G
298 /(kJ/mol) =

77.09 131.23 + 109.79 = 55.65, so

55650 J/mol = (8.3145 J/mol-K)(298.15 K) ln K and
K = 1.78 1010 at 25C. Integration of the vant Hoff equation with
H assumed constant gives ln( K2/K1) (H /R)(T11 T21 ) .
/(kJ/mol) = 105.56 167.16 + 127.07 = 65.47.
H 298

195
 /(1.78 1010 )] = [(65470 J/mol)/(8.3145 J/mol-K)]K1
ln[ K323
(298.11 323.11) and K323 = 1.37 109.

196