Chemistry 2300

Problem Set 4 Answers Professor: C. E. Loader

1. At –5.0 ºC, the vapor pressure of ice is 3.013 mm and that of liquid water is
3.163 mm. Calculate ∆G for the change of one mole of liquid water at –5.0 ºC to
solid at –5.0 ºC.

ANS:
The system will not be in equilibrium, so ∆G is not zero. We have to find a series of
steps between the initial and final states. For ∆S, we raised the temperture to 0 º but
won't do that now because of the difficulty of calculating ∆G for a change in T. The
clue to the solution is given by the inclusion of vapor pressures in the problem. We
can calculate ∆G for a change in pressure at constant temperature. The alternative
path for the process has three steps, all at –5 º;

Step 1: Liquid water at 3.163 mm → vapor at 3.163 mm.

Step 2: Vapor at 3.163 mm → vapor at 3.013 mm.
Step 3: Vapor at 3.013 mm → solid water at 3.013 mm.

Steps (1) and (3) are equilibrium processes (∆G = 0), so the total ∆G is the ∆G of step
(2).
P
∆G = nRT ln P 21 = 1(8.314)(268.2) ln 3.013
3.163 = –108.3 J

2. Calculate the pressure at which the conversion of graphite to diamond would

become thermodynamically possible.
(a) At 298.15 K.
(b) At 1000 K.

The densities of diamond and graphite are 3.513 g mL–1 and 2.260 g mL–1
V V
respectively, D r H = +1.895 kJ mol–1 and D r S = –3.255 J mol–1K–1. All of these
values may be considered to be independent of temperature
C (graphite) C (diamond)
ANS:
(a) At constant temperature
dG = VdP
or d(D r G) = (D r V)dp equation (i)
V 0
where D r G V
298.15 K = DH − TD r S
= 1895 J/mol – (298.15 K)(–3.255 J/mol)
= 2865.48 J mol–1

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 Chemistry 2300

and DrV = V(diamond) − V(graphite)

12.011 g mol −1 12.011 g mol −1
= 3.513 g mL −1 − 2.260 g mL −1
= –1.89559 mL mol–1
= –1.89559 x 10–3 L mol–1

So, from equation (i), integrating with D r V taken as constant (since densities are
constant)
2 2 2
°d(D r G) = °(D r V)dP = (D r V) ° dP
1 1 1
∴ D r G2 – D r G2 = D r V(P2–P1) equation (ii)

Set P1 = 1 bar, Then D r G1 = D r G 0 = 2865.48 J mol–1

P2 will be the pressure required for D r G2 = 0 (thermodynamic possibility)

∴ 0 – 2854.48 J/mol = –1.89559 x 10–3 L/mol (P2 –100 kPa)

∴ P2 = 1.512 x 106 kPa or 1.512 x 104 bar

(b) at 1000 K,
DrGV 1000 K = D r H V − TD r S 0
= 1895 J/mol – (1000 K)(–3.255 J/mol·K)
= 5150 J mol–1
Again using equation (ii),
0 – 5150 J/mol = –1.89559 x 10–3 L/mol (P2 –100 kPa)
∴ P2 = 2.717 x 106 kPa or 2.717 x 104 bar
∴ A higher pressure is required at higher temperature. So, why do you think high
temperatures are used to make artificial diamonds?

3. Calculate the freezing point of benzene at a pressure of 2000 atm. The normal
freezing point is 5.533 ºC and the densities of liquid and solid benzene are
0.8780 g cm–3 and 0.900 g cm–3, respectively. DH FUS = 10.58 kJ mol–1.
ANS:
Using the Clapeyron equation.
dP DH FUS DP DH FUS
dT = T M DV FUS
or DT = T M DV FUS
.
78.11 g mol −1 78.11 g mol −1
where DV FUS = V(l) - V(s) = 0.8787 g cm −3
- 0.9000 g cm−3
DV FUS = 2.11 cm3 mol–1 = 2.11 x 10–6 m3 mol–1
DP 10.58 x 10 3 J K -1 mol −1
∴ DT = 2.11 x 10−6 m 3 mol −1 x 278.68 K
= 1.799 x 107 Pa K–1

Now DP= 2000 − 1 atm = 2.025 x 108 Pa

8
∴ ∆T = 1.799
2.025 x 10 Pa
x 10 7 Pa K −1
= 11.26 K
∴ TM (2000 atm) = (278.68 + 11.26) K = 289.94 K

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 Chemistry 2300

4. Using the data provided for benzene, calculate the vapor pressure of solid
benzene at –20 ºC.
Benzene: Boiling point = 80.10 ºC
Melting point = 5.53 ºC
DH VAP = 30.76 kJ mol–1
DH FUS = 10.59 kJ mol–1
ANS:
We assume that the triple point occurs at
the same temperature as the normal 1 atm
melting point. Then we can apply the
Clausius-Clapeyron equation to the TRIPLE
vaporization curve to find the vapour POINT
VAPORIZATION
pressure of liquid benzene at the triple CURVE
point (taken as 5.53 ºC). Remember that Pressure SUBLIMATION
the vapour pressure at the normal boiling CURVE
point is 1 atm. 5.53 ºC 80.10 ºC
–20 ºC Temperature
Then
Pt 30.76 x 10 3 J$ mol −1
ln 1 atm = 8.314 J$ mol −1 $ K −1
1
( 278.68 K -
1
353.25 K
)
Hence Pt = 6.07 x 10–2 atm. (vapour pressure at triple point)

But at the triple point, solid is in equilibrium with the vapour at this same vapour
pressure. We can now apply the Clausius-Clapeyron equation to the sublimation curve
to determine the vapour pressure (p) at –20 ºC. For the sublimation curve we need

∆HSUB = ∆HFUS + ∆HVAP = 41.35 x 103 J·mol–1

Then
−41350 J$ mol −1
ln P
6.07 x 10 −2
= 8.314 J$ mol −1 $ K −1
1
( 253.15 K -
1
278.68 K
)

Hence p = 1.00 x 10–2 atm

(Vapour pressure of solid benzene at –20 ºC)

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5. The normal melting point of naphthalene (molar mass = 128.2 g mol–1) is 80.2 ºC
and it rises by 2.32 ºC when the pressure increases by 100 atmospheres. It boils
at 217.9 ºC and it's molar enthalpy of vaporization is 40.5 kJ mol–1. The density of
solid naphthalene is 1.15 g mL–1 and that of the liquid is 10% less. Calculate.
(a) The molar enthalpy of fusion of naphthalene.
ANS:
128.2 g$ mol−1
V(s) = 1.15 g$ mL−1
∴ V(s) = 111.5 mL·mol–1

128.2 g$ mol−1
V(l) = 1.035 g$ mL−1
∴ V(l) = 123.9 mL·mol–1

∴ DV FUS = 123.9 - 111.5

∴ DV FUS = 12.4 mL·mol
= 0.0124 L·mol

dT T mp DV FUS
dP =
DH FUS

(353.35 K)(.0124 L/mol)

∴ 2.32 K
100 x 101.3 kPa = DH FUS

∴ DH FUS = 19.13 kJ·mol–1

(b) The vapor pressure of liquid naphthalene at the triple point (you may
assume that this is the same temperature as the normal melting point).
ANS:
Apply the Clausius-Clapeyron equation to the vaporization curve, assuming that the
triple point temperature is the same as the melting point,
DH
− T1bpt
P 1
ln( 1 atm ) = – RVAP T mpt

−40500 J$ mol −1
∴ ln(P) = 8.314 J$ mol −1 $ K −1
1
( 353.35 K −
1
491.05 K
)

∴ ln(P) = –3.8659
∴ P = 2.09 x 10–2 atm = 2.12 kPa (vapour pressure at the triple point)

(c) The vapor pressure of solid naphthalene at 75.0 ºC.

ANS:
DH SUB = DH FUS + DH VAP
= 19.13 kJ·mol–1 + 40.5 kJ·mol–1

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∴ DH SUB = 59.63 kJ·mol–1

The vapor pressure of solid naphthalene and liquid naphthalene are the same at the
triple point. Apply the Clausius-Clapeyron equation to the sublimitation curve

DH SUB
∴ ln P
2.12 kPa = – R
1
( 348.15 K −
1
353.35 K
)

−59630 J$ mol −1
∴ ln P
2.12 kPa = 8.314 J$ mol −1 $ K −1
(.0028723 – .0028301)

∴ ln P
2.12 kPa = –0.303

P
2.12 kPa = 0.738

∴ P = 1.56 kPa (vapor pressure of solid at 75 ºC)

(d) The free energy change when 1.00 mol of supercooled liquid naphthalene
solidifies at 75.0 ºC.
ANS:
We already have the vapour pressure of solid naphthalene at 75 ºC. Use the
extrapolated liquid vaporization curve to find the vapour pressure of supercooled liquid
naphthalene at 75 ºC:

DH VAP
K −
P 1 1
ln 2.12 kPa = R
( 348.15 353.35 K
)

∴ ln P
2.12 kPa = –0.206

∴ P
2.12 kPa = 0.814

∴ P = 1.73 kPa (vapor pressure of (l) at 75 ºC)

At 75 ºC (l ) ∆G = ? (s)

∆G1 = O ∆G3 = O

(g), 1.73 kPa (g), 1.56 kPa

∆G2

∆G = ∆G2
P
= nRTln P 12
= 1 x 8.314 x 348.15 x ln( 1.56
1.73
)
∴ ∆G = –293 J·mol –1

(spontaneous of course)

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NOTE: That (l) naphthalene is in equilibrium with vapour at 1.73 kPa at 75 ºC (see
above), so ∆G1 = zero. Likewise, solid naphthalene is equilibrium with vapour at
1.56 kPa at 75 ºC (part (c) above) and ∴ ∆G3 = zero. This part of the problem is the
same as problem #1 in this problem set.

6. 0.810 g of hydrocarbon of the type; H(CH2)nH, is dissolved in 190 g of ethylene

bromide. The freezing point of the solution is 0.53 K lower than the pure solvent
(KF = 12.4 K m–1). Calculate the value of n in the formula of the hydrocarbon.
What assumption is it necessary to make about the hydrocarbon?
ANS:
Assume that the hydrocarbon is non-volatile.

Then ∆TF = KFm

DT
∴ m = K FF = 0.53 K
12.4 K (molal) -1
= 0.04274 molal

∴ 1000 g ethylene bromide contains 0.04274 mol hydrocarbon

190 x 0.042 74
∴ 190 g ethylene bromide contains 1000 mol hydrocarbon
= 0.008121 mol hydrocarbon

But, from question, this hydrocarbon has a mass of 0.810 g

0.810 g
∴ Molar mass of the hydrocarbon = 0.0081 21 mol
= 100 g mol–1

For H(CH2)nH, the molar mass = 14n + 2

∴ 14n + 2 = 100
∴ 14n = 98
∴ n = 98
14 = 7

∴ The formula is H(CH2)nH.

7. Bovine serum albumin (BSA) has a molar mass of 65000 g mol–1. Calculate the
osmotic pressure of a solution of 2.0 g BSA in 0.100 L of water at 25.0 ºC.
ANS:
Assume VSOLN = 0.100 L
2g
M2 65000 g mol −1
C2 = V = 0.100 L = 3.077 x 10–4 mol L–1

π = C2RT where C2 in mol L–1, R in L atm, π in atm

∴π = 3.077 x 10–4 mol L–1 x 0.08206 L atm K–1 mol–1 x 298 K
= 7.5 x 10–3 atm
8. The normal boiling point of nitrobenzene is 210.9 ºC. If the vapor pressure at
180 ºC is 353.2 mm Hg, what is the vapor pressure at 200 ºC?

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ANS:
This problem has two steps. Since DH, isn't given, you must calculate it. Remember
that the normal boiling point is at 1 atm. You have two pressures with corresponding
temperatures, and, using the Clausius-Clapeyron equation

760 484.1(453.2)
DH V = 8.314 (ln 353.2
) 484.1 − 453.2 = 45.23 kJ mol–1

In order to obtain the vapor pressure at a given temperature, use the

Clausius-Clapeyron equation again and solve for the desired quantity.

DH V T 2 −T 1
ln P2 = ln P1 + R T 2T 1
Choosing 353.2 mm as P1,
45.23 x 103 473.2 − 453.2
ln P2 = ln(353.2) + 8.314 473.2( 453.2) = 5.8670 + 0.5074

P2 = 586.6 mm Hg

9. When 4.07 g of a new water soluble polymer was dissolved in 82.4 mL of water
the measured osmotic pressure was 6.23 kPa at 22.0 ºC.
(a) Calculate the molar mass of the polymer.
ANS:
π = C2RT so C2 = 6.23 Pa
8.314 J K −1 mol −1 x 295.15 K = 2.53 x 10--3 mol L-1

∴ molar mass = 4.07 g

2.53 x 10 −3 mol L −1 x 82.4 x 10 −3 L = 1.95 x 104 g mol-1

(b) Calculate the freezing point of the solution.

ANS:
Assuming the density of the water is 1.0 g ml-1, the molality is
4.07 g
1.95 x 10 4 g mol −1
m = 82.4 % 10−3 kg = 0.0253 m

DT = K f m
∴ DT=1.86 K m−1 % 0.0253 m = 0.047 K.

So the freezing point of the solution is still 22.0 ºC to 3 significant digits - the
change in fp is barely measurable.
10. Phenol (C6H5OH) is partially dimerized in the solvent bromoform. When 2.58 g of
phenol is dissolved in 100 g of bromoform, the bromoform freezing point is
lowered by 2.37 ºC. Pure bromoform has a molal freezing-point-depression

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constant of 14.1 ºC kg mol–1 and freezes at 8.3 ºC. Calculate the equilibrium
constant, Km. for the dimerization reaction of phenol in bromoform at 6 ºC,
assuming an ideally dilute solution.
2 C6H5OH (C6H5OH)2
ANS:
∆T = Kf ma
2.37 = 14.1 ma
∴ ma = 0.1681 mol kg–1 (i)

where ma is the apparent molality of the phenol. (i.e. based on actual # mole present at
equilibrium)

2.58 g
Also mp = 94.11 g mol −1
/0.100 kg

∴ mp = 0.2741 mol kg–1 (ii)

where mp is the molality of the phenol if it it were all present as monomer (i.e. no
dimerization).
So, in molalities,

2 C6H5OH (C6H5OH)2
I (all monomer) 0.2741 0 (from (ii))
C –2x +x
E (0.2741 – 2x) x

∴ At equilibrium, actual # mole of solute per kilogram of solvent = (0.2741 – 2x) + x

= 0.2741 – x
But from (i) above, this # of mole also = 0.1681
∴ 0.2741 – x = 0.1681
∴ x = 0.1060 mol
Finally,
(m P ) eq
2 x
Km = (m p ) 2eq
= (0.2741 − 2x) 2

0.1060
= (0.2741 − 2(0.1060)) 2

= 27.5

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