Chapter 9

9.1 (a) mol/m3; (b) mol/kg; (c) no units.

9.2 c i ; c i. Con formato: Espaol (Costa Rica)

9.3 (a) ni = ciV = (0.800 mol/L)(0.145 L) = 0.116 mol.

(b) (145 g) 10.0% = 14.5 g; 0.398 mol.
(c) mi = ni/wA = ni/(w wi) = ni/(w niMi), where w is the mass of the
solution, wi is the mass of the HCl, ni is the number of moles of HCl, and
Mi is the HCl molar mass. Solving for ni, we get ni = miw/(1 + miMi) =
(4.85 mol/kg)(0.145 kg)/[1 + (4.85 mol/kg)(0.03646 kg/mol)] = 0.598
mol HCl. Alternatively, a solution with 1000 g of solvent has 4.85 mol
HCl, which is 176.83 g of HCl. The weight percent of HCl is
[176.83/(1000 + 176.83)]100% = 15.03%. 15.03% of 145 g is 21.79 g of
HCl, which is 0.598 mol HCl.

9.4 (a) All quantities involved are intensive, so we can use any convenient
amount of solution. Let us take 1 dm3 of solution. This amount of
solution has 8.911 mol of CH3OH, which is 285.5 g of CH3OH. Since the
solution is 30% CH3OH, the solutions mass is (100/30)(285.5 g) = 951.8
g. Its density is (951.8 g)/(1 dm3) = 0.9518 g/cm3.
Con formato: Espaol (Costa Rica)
(b) mi = ni/wA = (8.911 mol)/(951.8 g 285.5 g) = 0.01337 mol/g =
13.37 mol/kg.
(c) CH OH mCH OH /V (285.5 g)/(1 dm3) = 285.5 g/L.
3 3

9.5 Let us take 1000 g of solution. This contains (0.800 %)(1000 g) =

8.00 g of NH3 and 1000 g 8 g = 992 g of water. This is 0.4697 mol of
NH3 and 55.06 mol of water. Then mi = ni/wA = (0.4697 mol)/(992 g) =
0.000474 mol/g = 0.474 mol/kg. Also, xi = 0.4697/(0.4697 + 55.06) = 0.00846.

9.6 The solutions mass is m = V = (1.2885 g/cm3)(1000 cm3) = 1288.5 g. The

CsCl mass is (2.296 mol) (168.358 g/mol) = 386.6 g. The solvent mass is

123
 1288.5 g 386.6 g = 901.9 g. The molality is (2.296 mol)/(0.9019 kg) =
2.546 mol/kg.

9.7 All quantities involved are intensive, so we can take any amount of solution.
Take an amount of solution that contains one kg of water and hence contains
1.506 mol of KI. The solutions mass is 1000 g + (1.506 mol)(166.00 g/mol) =
1250.0 g. The solutions volume is V = m/ = (1250.0 g)/(1.1659 g/cm3) =
1072.1 cm3. The molarity is (1.506 mol)/(1.0721 L) = 1.405 mol/L.

9.8 ci = n i / V = n i / (w/) = n i /w, where w is the solutions mass. Because the

solution is very dilute, we have w = wi + wA wA = nAMA, where A is the
solvent. Then ci = n i /nAMA. Also, xi = ni/(nA + ni) ni/nA, so ci Con formato: Espaol (Costa Rica)

xi/MA. For the molality, we have mi = ni/wA = ni/nAMA xi/MA. From Con formato: Espaol (Costa Rica)

ci x i /MA and mi xi/MA, we get ci m i. Con formato: Espaol (Costa Rica)

Con formato: Espaol (Costa Rica)
Con formato: Espaol (Costa Rica)
9.9 As noted after Eq. (1.4), MA = Mr,A 1 g/mol, so mB = nB/nAMA =
nB/(nAMr,A g/mol) = nB/(nAMr,A103 kg/mol) = (1000 nB/nAMr,A) mol/kg.

Con formato: Alemn (Alemania)

9.10 (a) F (b) F; (c) F; (d) T; (e) T; (f) F; (g) F; (h) T; (i) T.

Con formato: Espaol (Costa Rica)

9.11 V = n1V1 + n2V2 =
Cdigo de campo cambiado
(0.500 mol)(18.63 cm3/mol) + (55.51 mol)(18.062 cm3/mol) = 1011.9 cm3.
Con formato: Espaol (Costa Rica)
Cdigo de campo cambiado

9.12 CP = n1CP1 + n2CP 2 . An amount of 0.1000-mol/kg solution that contains Con formato: Espaol (Costa Rica)

1000 g of solvent has 0.1000 mol (which is 5.844 g) of NaCl and has an NaCl
weight percentage of [5.844/(5.844 + 1000)]100% = 0.581%. Taking 0.581%
of 1000 g gives 5.81 g of NaCl in the 1000 g of solution, which is 0.0994 mol
of NaCl. The percent water is 100 0.581 = 99.419%. The H2O mass is 994.19
g, which is 55.186 mol H2O. So CP = (55.186 mol)(17.992 cal/mol-K) +
(0.0994 mol)(17.00 cal/mol-K) = 991.22 cal/K.

9.13 V = n1V1 + n2V2 = 307.09 cm3 = [(72.061/18.0153) mol](16.488 cm3/mol) +

[(192.252/32.0422) mol] VCH 3OH and VCH 3OH = 40.19 cm3/mol.

124
9.14 Take solutions that each contain 1000 g of H2O (constant nH 2O ). Let w be the
solution mass. For the 12% solution: (1000 g)/w = 0.88000 and w = 1136.36 g;
this solution contains 136.36 g of CH3OH, which is 4.2557 mol of CH3OH; the
solution has V = (1136.36 g)/(0.97942 g/cm3) = 1160.24 cm3. For the 13%
solution: (1000 g)/w = 0.87000 and w = 1149.43 g; this solution has 149.43 g
of CH3OH, which is 4.6636 mol of CH3OH; the solutions volume is V =
(1149.43 g)/(0.97799 g/cm3) = 1175.30 cm3. We have VCH 3OH
(V/nCH 3OH )T , P, nH O = (15.06 cm3)/(0.4079 mol) = 36.92 cm3/mol. To find
2

VH 2O , we now take solutions with 100 g of CH3OH (constant nCH 3OH ) and do
the calculations the same way as for the constant nH 2O solutions. For the 12%
solution, we find nH 2O = 40.706 mol and V = 850.84 cm3. For the 13%
solution, we find nH 2O = 37.148 mol and V = 786.54 cm3. Hence VH 2O
(V/ nH2O )T , P,nCH OH = (64.30 cm3)/(3.558 mol) = 18.07 cm3/mol.
3

9.15 (a) V of MgSO4 at a given composition equals the slope of Fig. 9.3 at that
composition. The slope is zero at the minimum, which occurs at nMgSO 4 =
0.07 moles in 1000 g of water, which is a molality of 0.07 mol/kg.
(b) Infinite dilution corresponds to nMgSO 4 0. Drawing the tangent line to
the curve at nMgSO 4 = 0, one finds its slope to be 3.5 cm3/mol, which is

V of MgSO4.
(c) Drawing the tangent line to the curve at nMgSO 4 = 0.05 mol, one finds its
slope to be 0.54 cm3/mol = VMgSO 4 . V = nH2OVH2O + nMgSO 4 VMgSO 4 =
1001.697 cm3 = (55.509 mol) VH 2O + (0.05 mol)(0.54 cm3/mol) and
VH 2O = 18.046 cm3/mol.

9.16 VNaCl = V (Na ) + V (Cl ) , VKNO

3
= V (K ) + V (NO3 ) , and


VNaNO3
= V (Na ) + V (NO3 ) . Then VKCl

= V (K ) + V (Cl ) =

VKNO3
+ VNaCl VNaNO3
= (38.0 + 16.6 27.8) cm3/mol = 26.8 cm3/mol.

9.17 Substitution of G = i nii into G U + PV TS gives the desired result.

125
9.18 Ai (A/ni )T , P,n j i , where A is the Helmholtz energy of the solution, ni is the
number of moles of i in the solution, T and P are temperature and pressure, and
n j i indicates that all mole numbers except i are held fixed.

9.19 H U + PV. Partial differentiation gives

(H/ni )T , P,n j i (U/ni )T , P,n j i P(V/ni )T , P,n j i , so Hi Ui PVi .

9.20 (a) G = i nii = i ni [ i + RT ln (Pi/P)]. Taking P1 = P and P2 = Pi in

(4.65), we have for ni moles of pure gas i: G*i (T , Pi , ni ) G*i (T, P, ni)
= niRT PPi P1dP = niRT ln (Pi/P). So G*i (T, Pi, ni) = G*i (T, P, ni) +
niRT ln (Pi/P) = ni G*m,i (T, P) + niRT ln (Pi/P) = ni [ i + RT ln (Pi/P)],
since G*m,i = i for a pure substance. Hence the above sum for G of the
mixture becomes G = i G*i (T, Pi, ni).
(b) S = (/T ) P, ni G i [(G*i / T ) P, ni ] i S *i (T , Pi , ni ), where (4.51)
was used.
(c) H = G + TS = i G*i + T i S*i = i (G*i + TS*i ) = i H*i (T, ni), where
Pi is absent since H is independent of P for an ideal gas.
(d) CP = (H/T ) P, ni = (/T ) P, ni i H*i = i (H *i /T ) ni = i C*P, i (T, ni).
U = H PV = i H*i P(i niRT/P) = i ( H*i niRT) = i ( H*i PiV) =
i U*i (T, ni).
(e) Assuming the mixture is ideal, we have CP = i C*P,i (T , ni )
C*P, O 2 C*P, CO 2 nO 2 C*P, m, O 2 nCO 2 C*P, m, CO 2 =
(0.100 mol)(29.355 J/mol-K) + (0.300 mol)(37.11 J/mol-K) = 14.07 J/K.

9.21 Taking /T of (9.32), we get ( mixG/T ) P,ni (/T ) P, ni i ni (Gi G*m,i ) =

i ni [(Gi /T ) P, ni (G*m,i /T ) P, ni ] = i ni (S i S *m,i ) = i ni S *m,i i ni S i =
S* S = mixS, where (9.30) was used.

9.22 n(H2O) = 1.110 mol and n(C2H5OH) = 0.977 mol. x(C2H5OH) =

0.977/2.087 = 0.468. For this composition, Fig. 9.9 gives V (H 2O) =

126
 16.8 cm3/mol, V (C 2 H 5 OH) = 57.0 cm3/mol. V = V1n1 V2 n2 =
(16.8 cm3/mol)(1.11 mol) + (57.0 cm3/mol)(0.977 mol) = 74.3 cm3.

9.23 We draw the tangent line at xethanol = 0.4. This line intersects the xethanol =
0 axis at 1.1 cm3/mol = VH 2O V * 3
m,H 2 O = VH 2O 18.05 cm /mol, and

VH 2O = 16.95 cm3/mol. The tangent line intersects the xethanol = 1 axis at

1.15 cm3/mol = Vethanol V *
m, ethanol Vethanol 58.4 cm /mol, and
3

Vethanol = 57.3 cm3/mol.

9.24 * , H 2 O = M/ = (18.015 g/mol)/(0.99705 g/cm3)

The pure molar volumes are V m
= 18.07 cm3/mol; V m*, CH 3OH = 40.71 cm3/mol. We plot mixV/n vs. xH 2O
(similar to Fig. 9.7).
(a) Drawing the tangent line at xH 2O = 0, we find it intersects the xH 2O = 1
line at 3.6 cm3/mol. (With a reasonable choice of scale, the intersection
occurs off the paper and can be calculated by extrapolation.) Hence, at
* , H 2 O = 3.6 cm3/mol = VH 2O 18.1 cm3/mol and
xH 2O = 0, VH 2O V m
VH 2 O = 14.5 cm3/mol. Of course, VCH OH = V m*, CH 3OH = 40.7 cm3/mol at
3

xH 2O = 0.

mixV/n

(b) The tangent line at xH 2O = 0.4 intersects the xH 2O = 0 line at

0.5 cm3/mol and intersects xH 2O = 1 at 1.6 cm3/mol, so

127
 VCH 3OH V m*, CH 3OH = 0.5 cm3/mol and VCH 3OH = 40.2 cm3/mol; also,
VH 2O = 16.5 cm3/mol.
(c) VCH 3OH V m*, CH 3OH = 1.45 cm3/mol and VCH 3OH = 39.25 cm3/mol;
* , H 2 O = 0.7 cm3/mol and VH 2O = 17.4 cm3/mol.
VH 2 O V m

9.25 (a) VB = (V/nB )T , P, n A = b + (3/2)cnB1/2 + 2knB for nAMA = 1 kg.

(b) For mB = 1 mol/kg, we have nB = 1 mol in a solution with nAMA = 1 kg.
VB = 16.6253 cm3/mol + 1.5(1.7738 cm3/mol3/2)(1.0000 mol)1/2 + Con formato: Espaol (Costa Rica)

2(0.1194 cm3/mol2)(1.0000 mol) = 19.5248 cm3/mol.

(c) V nAVA nBVB and nAVA V nBVB a + bnB + cn B3/ 2 + knB2 nBb
1.5 cn B3/2 2 knB2 = a 12 cn B3/2 knB2 . Since nA = (1 kg)/MA, we get VA =
(MA/1000 g)(a 1
2 cn B3/ 2 knB2 ) for nAMA = 1 kg.
(d) mB = nB/nAMA = nB/(1 kg) = nB/kg and nB = mB kg. Substitution in the
results of (a) and (c) gives the desired equations.
(e) VH 2O = (18.0152 g/mol)[1002.96 cm3 1
2 (1.7738 cm3/mol3/2)
(1 mol/kg)3/2 kg3/2 (0.1194 cm3/mol2)(1 mol/kg)2 kg2]/(1000 g) =
18.050 cm3/mol.
(f) In the infinite-dilution limit, mB goes to zero and V B in (d) becomes
VB = b = 16.6253 cm3/mol.

9.26 (a) z mixV/n = (V V*)/(nA + nB), so V V* = (nA + nB)z and

* nBV m,B
V = (nA + nB)z + V* = (nA + nB)z + nAV m,A * .
(b) Taking (/n A ) nB , T , P of the result of (a) gives (V/n A ) nB , T , P VA for
the left side and z + (nA + nB) (z/nA )nB + V m,
* A for the right side. (Note
that V m,A
* is constant at fixed T and P and is independent of nA.)
Equating these expressions, we get VA = z + n (z/nA )nB + V m,A
*. .
(c) Equation (1.35) gives (z/nA )nB = (dz/dxB )(xB /nA )nB . Since xB =
nB/(nA + nB), we have (xB /nA )nB = nB/(nA + nB)2 = xB/(nA + nB) =
xB/n. The result of (b) gives (z/nA )nB (VA V*m,A z ) / n.
Substitution of these expressions for xB /nA and z/nA into

128
 z/nA = (dz/dxB)(xB/nA) gives dz/dxB = ( V m,
* A V A + z)/xB. The nB
subscript can be omitted from (z/x B ) nB because z (V V*)/n is an
intensive quantity and so is a function of xB only and is independent of
the size of the system and hence of nB.
(d) The plotted quantity mixV/n is symmetric in A and B. Since the intercept
at xB = 0 is V A Vm,A
* , the A-B symmetry means that the intercept at
xA = 0 is V B V m,B
* . But xA = 0 is xB = 1.

9.27 The tangent to the mixH/n versus x H 2SO 4 curve at x H 2SO 4 = 0.4 intersects
x H 2SO 4 = 0 at 13.0 kJ/mol = H diff, H2O and intersects x H 2SO 4 = 1 at 16.4
kJ/mol = H diff,H2SO4 . Drawing the tangent at x H 2SO 4 = 0.333, we find
H diff,H2O = 9.5 kJ/mol and H diff,H2SO4 = 22.6 kJ/mol.

9.28 mixH = H H*. ( mix H/nB )T , P,nA = (H/nB )T , P, nA (H */nB )T , P, n A .

But by definition, H B = (H/nB )T , P, nA . Also, H* = nA H m*, A (T, P) +
* B (T , P), so (H */nB )T , P, nA = H m*, B . Therefore ( mix H/nB )T , P,nA =
nB Hm,
H B Hm*, B = Hdiff,B, where (9.38) was used.

9.29 Subtraction of f H NaCl(s)

from the apparent f H values give the following
integral heats of solution per mole of NaCl vs. xNaCl:
Hint,NaCl/(kJ/mol) 1.874 2.347 3.016 3.711 Con formato: Alemn (Alemania)

xNaCl 0.1 0.0625 0.03846 0.019608

The Hint,NaCl values are mixH/nNaCl [Eq. (9.37)]. Hence multiplication of
Hint,NaCl = mixH/nNaCl by nNaCl/n = xNaCl gives the following mixH/n values:
(mixH/n)/(J/mol) 187.4 146.7 116.0 72.77 0
xNaCl 0.1 0.0625 0.03846 0.019608 0
We plot mixH/n vs. xNaCl and draw the tangent at xNaCl = 0.05. The tangent line
intersects xNaCl = 0 at 69 J/mol = H H 2 O Hm*, H 2 O and intersects xNaCl = 0.1 at
198 J/mol. Extrapolation gives the intersection at xNaCl = 1 as
[69 + 10(198 69)]J/mol = 1.36 kJ/mol = H NaCl Hm*, NaCl .

129
 mixH/n

9.30 The NBS tables give f H 298

= 92.307 kJ/mol for HCl(g) and f H 298

=
121.55 kJ/mol for HCl in 1 mol of H2O. Thus Hint,HCl = 29.24 kJ/mol for a
solution with xHCl = 0.500. From (9.37), mixH = nHCl Hint,HCl and mixH/ntot =
xHCl Hint,HCl = 14.62 kJ/mol at xHCl = 0.5. Use of further data gives (values in
kJ/mol)
xHCl 0.500 0.400 0.333 0.286 0.250 0.200
Hint, HCl 29.24 40.36 48.65 53.17 56.18 60.61
mixH/ntot 14.62 16.15 16.22 15.19 14.05 12.12
We plot mixH/ntot vs. xHCl and draw the tangent line at xHCl = 0.30. The
intercepts at xHCl = 0 and xHCl = 1 give H diff,H2O = 8.3 kJ/mol and
H diff,HCl = 32.6 kJ/mol.

mixH/n

130
9.31 Use of (9.38) in (9.36) gives the desired result.

9.32 (a) F; (b) T; (c) T; (d) F;

9.33 No. Models show that the A-B intermolecular forces differ from the A-A and
B-B intermolecular forces.

Con formato: Alemn (Alemania)

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

9.35 The vapor is ideal and the pressure dependence of of the liquid can be
neglected.

9.36 nben = 1.280 mol and ntol = 1.085 mol. xben = 0.5412 and xtol = 0.4588.
Equation (9.44) gives mixG = (8.314 J/mol-K)(293.1 K)
[(1.280 mol) ln 0.5412 + (1.085 mol) ln 0.4588] = 3976 J = 950 cal.
mixV = 0, mixH = 0. mixG = mixH T mixS,
so mixS = (3976 J)/(293.1 K) = 13.56 J/K = 3.24 cal/K.

9.37 (a) nben = (100.0 g)/(78.11 g/mol) = 1.280 mol. ntol = 1.085 mol.
xben = 1.280/(1.280 + 1.085) = 0.5412. xtol = 0.4588.
Pben = 0.5412(74.7 torr) = 40.4 torr. Ptol = 0.4588(22.3 torr) = 10.2 torr.
(b) Ptot = (40.4 + 10.2) torr = 50.6 torr. Use of Pi = xi P gives

x ben = (40.4 torr)/(50.6 torr) = 0.798. x tol = 0.202.

Con formato: Espaol (Costa Rica)

9.38 * (1 xhex, )Poct
P = Phex + Poct = xhex, P hex * . xhex, ( P Poct * P oct
* )/(P hex *)
Con formato: Espaol (Costa Rica)
(666 torr 354 torr)/(1836 torr 354 torr) = 0.211. xoct, = 1 0.211 = 0.789. Cdigo de campo cambiado
Phex = x hex, P*hex = 0.211(1836 torr) = 387 torr. xhex, = Phex/P = Cdigo de campo cambiado
(387 torr)/(666 torr) = 0.581; xoct, = 0.419. Con formato: Espaol (Costa Rica)
Con formato: Espaol (Costa Rica)
Con formato: Espaol (Costa Rica)
9.39 Pi = xi P = xil P*i . 0.555(95.0 torr) = 0.305P*hex and P*hex = 173 torr.
Cdigo de campo cambiado
1 x2 P*
x1l P* l
P= 2 = 95.0 torr = 0.305P*hex + 0.695P*hept = Con formato: Espaol (Costa Rica)

131
 0.305(173 torr) + 0.695P*hept and P*hept = 60.8 torr. We assumed an ideal
solution, ideal vapor, and the pressure independence of * .

9.40 (a) PB = x B P = xBl P B*, so x B = xBl P B* /P. Also, P = PB + PC =

xBl P B* + xCl PC* = xBl P B* + (1 x Bl ) P*
C , so x B =

xBl P B* /( xBl P B* + PC* xBl P C* ) = ( xBl P *B /P *C )/ ( xBl P *B /P *C + 1 x Bl ).

(b) If B is benzene, then P B*/P *C = 74.7/22.3 = 3.35 and the equation in (a)
gives xB = 3.35 x Bl /(1 + 2.35 x Bl ). We get
x B 0 0.456 0.691 0.834 0.931 1
x Bl 0 0.2 0.4 0.6 0.8 1
The plot resembles the upper curve in Fig. 9.18b. For toluene (t), we find
xt = 0.299 xtl /(1 0.701 xtl ) and
xt 0 0.070 0.166 0.310 0.545 1
xtl 0 0.2 0.4 0.6 0.8 1

9.41 * 2 = n1M1/ *1 + n2M2/ *2 =

For an ideal solution, V = V* = n1V *m1 + n2V m
m1/ *1 + m2 / *2 = (33.33 g)/(0.8790 g/cm ) + (33.33 g)/(0.8668 g/cm3) =
3

76.37 cm3. Then = m/V = (66.66 g)/(76.37 cm3) = 0.8729 g/cm3.

9.42 (a) mixCP = CP C*P = (H/T ) P, ni (H */T ) P, ni = (/T ) P, ni (H H*) =

( mix H/T ) P,ni = 0, since mixH = 0 for an ideal solution.
(b) CP = C*P = n1C*P, m,1 + n2C*P, m,2 = [(100/78.11) mol](136 J/mol-K) +
(100/92.14)mol(156 J/mol-K) = 343 J/mol-K.

9.43 At xB = 0.50, the tangent is horizontal and intersects the xB = 0 and xB = 1 axes
at 0.415 kcal/mol = A A* = B *B ; the calculated result is
i *i = RT ln 0.5 = (1.987 cal/mol-K)(298.1 K) ln 0.5 = 0.411 kcal/mol.
At xB = 0.25, the tangent lines intercept at xB = 0 is 0.180 kcal/mol =
A A* and that at xB = 1 is 0.815 kcal/mol = B *B ; the calculated values
are A A* = RT ln 0.75 = 0.170 kcal/mol and B *B = RT ln 0.25 =
0.821 kcal/mol.

132
9.44 From (9.30), (9.31), (9.42), and (9.28):
S i = ( i /T ) P, n j = (*i /T ) P, n j R ln xi = S *
m ,i R ln xi.

Vi = ( i /P)T , n j = (*i /P)T = V m,

*i.
H i = i + TSi = *i + RT ln xi + TS*m,i RT ln xi = H *
m , i (since *
i = G*
m,i ).

9.45 i = i + RT ln (Pi/P) = i + RT ln (xiP/P) = i + RT ln (P/P) + RT ln xi.

For xi = 1, this equation becomes *i = i + RT ln (P/P), so
i = *i + RT ln xi.

9.46 Substitution of Equation (9.42) into the phase-equilibrium condition 1 = 1

gives *1 + RT ln x1 = *1 + RT ln x1 , so x1 = x1 . Similarly, x 2 = x 2 .

9.47 (a) The use of G = nii + nAA for the solution gives G of the final state in
the dilution process as G2 = nii,2 + nA,2A,2. For the initial state of the
dilution process, G1 = nii,1 + nA,1A,1 + (nA,2 nA,1) A* . G of the
dilution process is G2 G1 and use of these expressions for G2 and G1
gives the desired result.
(b) Equating the right sides of (9.66) and (9.67) and using (9.68), we get
(9.70).

9.48 (a) The solvent A is ethanol and Raoults law gives PA = xAl PA* =
Peth = 0.9900(172.76 torr) = 171.03 torr. Pchl = P Peth =
(177.95 171.03) torr = 6.92 torr.

(b) In a gas mixture, Pi = xiP, so xeth = 171.03/177.95 = 0.96111 and
Con formato: Alemn (Alemania)
xchl = 6.92/177.95 = 0.03889.
Cdigo de campo cambiado
l
(c) Pi = Ki xil , so Kchl = Pchl/ xchl = (6.92 torr)/0.0100 = 692 torr. Con formato: Alemn (Alemania)
Cdigo de campo cambiado
(d) PA = xAl PA* = Peth = 0.9800(172.76 torr) = 169.30 torr; Pchl = Kchl xchl
l =
Con formato: Alemn (Alemania)
(692 torr)(0.0200) = 13.84 torr. P = (169.30 + 13.84) torr = 183.14 torr. Con formato: Espaol (Costa Rica)

xeth = Peth/P = 169.30/183.14 = 0.9244 and xchl = Pchl/P = 13.84/183.14 Con formato: Espaol (Costa Rica)

= 0.0756. Cdigo de campo cambiado

Con formato: Espaol (Costa Rica)
Cdigo de campo cambiado

133

9.49 (a) Pchl = xchl P = 0.9794(438.59 torr) = 429.56 torr; Peth =
(1 0.9794)(438.59 torr) = 9.03 torr.
l
(b) Raoults law for the solvent chloroform gives Pchl = xchl P*chl and
P*chl = (429.56 torr)/0.9900 = 433.90 torr.
l
(c) Peth = Keth xeth and Keth = (9.03 torr)/0.0100 = 903 torr.

l
9.50 (a) At xCS 2
= 1 in Fig. 9.21b, P = 424 torr.
l
(b) At xchl = 0.40 in Fig. 9.21a, the curves give P = 266 torr and Pchl =

82 torr, so xchl = Pchl/P = 0.31.

9.51 We have Ki = Pi/ xil for very dilute solutions of i. For CS2 as solute, we draw
l
the line tangent to the P(CS2) curve at the point xCS 2
= 0. Since Pi = Ki xil , the
slope of this tangent line equals K CS 2 ; the slope equals the intercept of the
l
tangent line with the xCS 2
= 1 line. We find K CS 2 = 1.25 103 torr in acetone as
l
solvent. Drawing the tangent line to the P(ac) curve at the point xCS 2
= 1 and
l
finding its intercept with xCS 2
= 0, we get Kac = 2.0 103 torr in the solvent
CS2.

9.52 From (9.62), i i , = RT ln (Ki/P) = (8.314 J/mol-K)(308 K) ln (145/750)

= 4.21 kJ/mol.

9.53 (a) nH 2 = 8.14 105 mol, nH 2O = 5.55 mol; x Hl 2 = 1.47 105.

K H 2 = PH 2 / x Hl 2 = (1.00 atm)/(1.47 105) = 6.82 104 atm.

(b) x Hl 2 = PH 2 / K H 2 = (10.00 atm)/(68200 atm) = 1.47 104.

nH 2 = 8.14 104 mol and mH 2 = 1.64 mg.

9.54 x Nl 2 = PN 2 /K N 2 = (0.780 760 torr)/(5.75 107 torr) = 1.03 105,

xO 2 = (0.210 760 torr)/(2.95 107 torr) = 5.41 106. nO2 and n N 2 are
negligible compared to nH 2O = 5.55 mol, so n N 2 = (1.03 105)(5.55 mol) =

134
 5.72 105 mol and nO2 = (5.41 106)(5.55 mol) = 3.00 105 mol.
m N 2 = 1.60 mg and mO 2 = 0.960 mg.

9.55 For the solvent in an ideally dilute solution, A obeys the same equation as the
chemical potential (9.42) and (9.43) for the chemical potential of a component
of an ideal solution, so the solvents partial molar properties in an ideally dilute
solution obey the equations in Prob. 9.44 for an ideal-solution component.

9.56 (a) Vi ( i / P)T ,n j ( / P)T ,n j ( i RT ln xi ) ( i / P)T ,n j . But

(9.31) shows that ( i / P)T ,n j Vi , so Vi Vi . Since i for an
ideally dilute solution is a function of T and P only, its derivative
( i / P)T ,n j is a function of T and P only, and ( i / P)T ,n j and Vi
(which equals ( i / P)T ,n j ) are independent of concentration for
concentrations in the ideally dilute range. Therefore Vi (which equals
Vi ) equals its limiting infinite-dilution value Vi .
(b) Using the intercept method of Fig. 9.7, we draw the tangent line to the
curve at xethanol = 1. The tangent line intersects the xethanol = 0 vertical axis
at 4.7 cm3/mol = VH2O Vm, *H2O . Since Vm,*H 2O = 18.0 cm3/mol at 20C,
we get VH2O = 13.3 cm3/mol in ethanol, in rough agreement with Fig.
9.9.

9.57 Equations (9.30), (9.28), and (9.58) give: S i = (i /T ) P,n j =

(/T ) P, n j ( i + RT ln xi) = S i R ln xi. [The infinite-dilution limit of this
equation gives Si = ( S i + R ln xi).] We have H i = G i + T S i =

i + RT ln xi + T S i RT ln xi = H i . The infinite-dilution limit of this

equation gives H i = H i .

9.58 Equation (9.17) and equations in Probs. 9.55 and 9.56 give mixV =
iA ni( Vi V m, * ) = iA ni( Vi V m,
* i ) + nA( VA V m,A * i ). Equations in Probs.

135
 9.55 and 9.57 give
mixH = iA ni( H i H *m, i ) + nA( HA H m,A
* ) = iA ni( H i H *m, i ).

9.59 0 = i i i i i (i RT ln xi ,eq ) i i i RT i ln( xi ,eq ) i

G + RT ln i ( xi ,eq ) i G RT ln K x , and G RT ln K x , where
(1.70) and (1.69) were used.

9.60 (a) xi = Pi/Ki, so as Ki increases, xi decreases. The solubility of O2 in water

decreases as T increases.
Con formato: Alemn (Alemania)
(b) ( H i, H i, l )/RT 2 = ( ln Ki/T)P ( ln Ki/T)P.
Con formato: Alemn (Alemania)
ln Ki = ln (3.52 107) ln (2.95 107) = 0.177. Cdigo de campo cambiado
H i, l H i, (8.314 J/mol-K)(298 K)20.177/(10 K) = 13.1 kJ/mol. Con formato: Alemn (Alemania)
, l , Cdigo de campo cambiado
(c) The log of (9.62) gives RT ln Ki/bar = i , l i , = Gi Gi and we
Con formato: Alemn (Alemania)
, l ,
have G i G i (8.314 J/mol-K)(298 K) ln (44100 bar/1 bar) = Con formato: Alemn (Alemania)

26.5 kJ/mol. Con formato: Alemn (Alemania)

, l , Con formato: Alemn (Alemania)

(d) S = (H G)/T, so S i Si [(13100 26500)/298] J/mol-K = Con formato: Alemn (Alemania)
133 J/mol-K. Con formato: Alemn (Alemania)
Cdigo de campo cambiado

9.61 The log of Eq. (9.62) reads ln Ki = ln P + i , )/RT. Partial

( i , l Con formato: Alemn (Alemania)
Cdigo de campo cambiado
differentiation with respect to T gives ( ln Ki/T)P = ( i , l i , )/RT 2 + Con formato: Alemn (Alemania)
, , l , l ,
[( i , l /T)P d i , /dT]/RT = ( G i G i )/RT 2 + ( S i + S i )/RT = Con formato: Alemn (Alemania)

, , , l , l
( Gi + T Si Gi T S i )/RT 2 = ( H i, H i, l )/RT 2. Partial
differentiation of ln Ki with respect to P gives ( ln Ki/P)T = ( i , l /P)T =
, l , l
V i /RT = V i /RT (since i , depends only on T).

9.62 Troutons rule is vapHm,nbp/Tb 21 cal/mol-K. We find vapHm,nbp,ben

7420 cal/mol; vapHm,nbp,tol 8060 cal/mol. Equation (7.21) gives for the vapor
pressure of pure benzene at 120C: ln [ P*ben /(1 atm)] =
(7420 cal/mol)(1/353.2 K 1/393.1 K)/(1.987 cal/mol-K) = 1.073 and

P*ben = 2.92 atm. Similarly, we find P*tol = 1.29 atm. Pben = xben P*ben =

136
 0.68(2.92 atm) = 1.99 atm. Ptol = 0.32(1.29 atm) = 0.41 atm. P = 2.40 atm.

x ben = Pben/P = (1.99 atm)/(2.40 atm) = 0.83. We assumed the accuracy of
Troutons rule, the T independence of H of vaporization, ideal gases, an ideal
solution, and the pressure independence of *.

9.63 mixG = G G* = G nA *A nB *B . Then A = (G/n A )T , P, nB =

(/n A )T , P, nB (nA *A + nB *B + mixG) = *A + RT ln xA +
nART(ln xA/nA) nB + nB RT( ln xB/nA) nB = *A + RT ln xA +
nART[1/nA 1/(nA + nB)] + nBRT[1/(nA + nB)] = *A + RT ln xA +
RT xART xBRT = *A + RT ln xA, since xA + xB = 1. (The partial derivatives
of the logs are found as in Prob. 9.66b.)

* *
9.64 (a) Use of (G/P)T = V gives G1 = PPA V *A dP + PPB V *B dP. We have
G2 = 0 for this constant-T-and-P equilibrium process. G3 = H3
T S3 = T S3 = nART ln ( P*A /PA) nBRT ln ( P*
B /PB), where (3.30) and
Boyles law were used. G4 = 0 (see the end of Sec. 6.1). G5 = 0
(constant-T-and-P equilibrium process). G6 = PPA PB VA+B dP.
(b) They are small because G of a liquid varies only slowly with P.
(c) With G1 and G6 neglected,
G mixG G3 = nART ln (PA/ P*
A ) + nBRT ln ( PB /P*
B) .

(d) Use (9.51).

9.65 Eq. (9.74) becomes mixG/(nA + nB) = RT[xA ln ( x A P/ P*

A ) + xB ln ( x B P/ P*
B )].
At xeth = 0.200, mixG/(nA + nB) = (8.314 J/mol-K)(318 K)
{0.200 ln [(0.1552)454.53/172.76] + 0.800 ln [(1 0.1552)454.53/433.54]} =
731 J/mol. At xeth = 0.400, 0.600, 0.800, we get mixG/ntot = 1034 J/mol,
1554 J/mol, 997 J/mol, respectively. At xeth = 0 and 1, mixG/ntot = 0.

9.66 (a) From (9.35), mixS = ( mixG/T ) P,n j = nA R ln xA nB R ln xB

(nA + nB)xAxB(W/T)P. From (9.33), Hmix = mixG + T mixS =
(nA + nB)xAxB[W T(W/T)P]. From (9.34), mixV = ( mixG/P ) T , n j =
(nA + nB)xAxB(W/P)T.

137
 (b) mixG = G G*, so G = G* + mixG = nA A* (T, P) + nB *B (T, P) + mixG.
Then A = (G/n A )T , P, nB = A* + ( mixG/n A )T , P,nB . We have ln xA =
ln nA ln (nA + nB) and ln xB = ln nB ln (nA + nB), so ln xA/nA =
1/nA 1/(nA + nB) and ln xB/nA = 1/(nA + nB). Also, xA xB(nA + nB) =
nAnB/(nA + nB). Using these equations, we find A = A* + RT ln xA +
nART [1/nA 1/(nA + nB)] nBRT/(nA + nB) +
W(T, P)[nB/(nA + nB) nAnB/(nA + nB)2] = A* + RT ln xA + W(T, P) x B2 .
Since mixG is symmetric in A and B, by analogy to A we have
B = *B + RT ln xB + W(T, P) x A2 .
(c) Equating A in the solution to A in the vapor above the solution, we get
A* + RT ln xA + W x B2 = A, gas + RT ln (PA/P). Also, for pure liquid A
in equilibrium with its vapor at T: A* = A, gas + RT ln ( P*
A /P).

Subtraction of this equation from the preceding one gives RT ln xA +

W x B2 = RT ln (PA/ P*
A ), so ln (PA/ P*
2
A ) = ln xA + W x B /RT; so PA/ P*
A =
exp(ln xA)exp(W x B2 /RT), and PA = xA P* 2
A exp(W x B /RT). By symmetry,

PB = xB P*B exp(W x A2 /RT).

9.67 vapG involves isothermal conversion of liquid at 1 bar to vapor at 1 bar. We

use this isothermal path:
1 2 3
liq(P) liq(Pi) vap(Pi) vap(P)
G1 0, since moderate pressure changes have little effect on liquid
thermodynamic properties. G2 = 0, since this is an equilibrium process at
constant T and P. Assuming ideal vapor, we have G3 = H3 T S3 = T S3
= nRT ln (Pi/P), where (3.30) and Boyles law were used. Therefore vapG
= Gm,1 + Gm,2 + Gm,3 = RT ln (Pi/P) and Pi = P exp(vapG/RT).

9.68 (a) All; (b) ideal; (c) ideal and ideally dilute; (d) all; (e) ideal;
(f) ideal; (g) ideal.

9.69 (a) Neither; neither.

(b) CCl4 Raoults law; CH3OH Henrys law.
(c) CH3OH Raoults law; CCl4 Henrys law.
(d) Both Raoults law.

138
9.70 (a) True, since the equilibrium condition at constant T and P is minimization
of G. (b) False; see Fig. 9.5. (c) False. In a liquid solution,
intermolecular interactions are large. (d) T. (e) F. (f) T.

R9.1 (a) f c p 2 r a 1 3 2 0.
(b) f 1 2 2 1.
(c) f 1 1 2 2.

R9.2 From dGm Sm dT Vm dP, we have (Gm / P)T Vm RT / P B(T ). So

2
Gm 1
( RT / P B) dP RT ln( P2 / P1 ) B(T )( P2 P1 ).

R9.3 Integration of d ln P / dT H m / RT 2 with H m assumed constant, gives

ln( P2 / P1 ) (H m / R)(T11 T21 ). So
ln(0.74/0.57) [H m /(8.314 J/mol-K)][(105.0 K)1 (108.0 K)1 ] and
H m 8200 J/mol. The other approximations are neglecting the volume of
the liquid compared with the vapor and treating the vapor as an ideal gas.

R9.4 (a) F. (b) T. (c) F (see Fig. 9.5). (d) T. (e) T. (f) T. We have
P PB PC xBl PB* (1 xBl ) PB* PB*, as is obvious from Fig. 9.18a with
PB* PC* . Then PB xB P xBl PB*, and setting P PB* , we get xB xBl .

R9.5 (a) See p. 262. (b) See p. 264. (c) See p. 268. (d) See p. 269.

R9.6 PB xB P xBl PB*, so PB* xB P / xBl 0.650(139 torr)/0.400 = 226 torr.

PC* xC P / xCl 0.350(139 torr)/0.600 = 81.1 torr.

R9.7 (a) Since the molecules do not closely resemble each other and since the
solution is not dilute neither component obeys Raoults law or Henrys
law.
(b) The solution is very dilute, so water approximately obeys Henrys law
and acetone approximately obeys Raoults law.

139
 (c) The two components have very similar molecules, so each component
approximately obeys Raoults law.

R9.8 (a) See the derivation of (9.28).

(b) See the lines preceding (9.31).

R9.9 See Example 9.4.

R9.10 (a) f c p 2 r a 2 2 2 2. T and xbenzene

l
.
(b) f 3 1 2 1 1 2, where the additional restriction is that
xH2 3xNH3 . T and P.
(c) With the ionization of water included, we have 5 chemical species, 2
reactions, and the electroneutrality condition, so f = 5 1 + 2 2 1 = 3.
T, P, and xHF .

R9.11 Integration of d ln P / dT H m / RT 2 with H m assumed constant, gives

ln( P2 / P1 ) (H m / R)(T11 T21 ). We have ln[ P2 /(760 torr)]
[(2256.7 J/g)(18.015 g/mol)/(8.3145 J/mol-K)][(373.15 K)1 (363.15 K)1 ] =
0.3608; so P2 /(760 torr) = 0.697 and P2 = 530 torr. Figure 14.17 shows that T
is not constant as the altitude changes, so there is some uncertainty as to what
value of T to use. A reasonable choice might be 270 K. Then 530 torr =
(760 torr) exp[(0.0290 kg/mol)(9.81 m/s2 ) z /(8.314 J/mol-K)(270 K)] and
0.697 exp(0.0001267 z/m) . We get z = 2850 m = 2.85 km.

R9.12 The equation given is for fixed T, P, and nA, so we have

VB (V /nB )T , P,nA b 2cnB 3enB2 . Also, V nAVA nBVB , so
VA (V nBVB )/nA (V bnB 2cnB2 3enB3 )/nA .

R9.13 Integration of dP/dT H /(T V ) with H and V assumed constant gives

P2 P1 (H /V )ln(T2 /T1 )
333.6 J 82.06 cm3 atm 272.35
ln = 107 atm
(1 g)[(1.000 g/cm3 )1 (0.917 g/cm3 )1 ] 8.3145 J 273.15

140
and P2 = 108 atm. The same answer is found by assuming S and V
constant.

141