Physical Chemistry II Chem 402 Spring 2012

Chapter 8 (4, 6, 11, 23, 28, 34, 39)

P8.4) Use the vapor pressures for PbS given in the following table to estimate the temperature
and pressure of the triple point and also the enthalpies of fusion, vaporization, and sublimation.

Phase T (C) P (Torr)

Solid 1048 40.0
Solid 1108 100.
Liquid 1221 400.
Liquid 1281 760.
To estimate H msublimation , use the vapor pressures of the solid phase

P2 H sublimation 1 1
ln
P1 R T2 T1
P 100 Torr
R ln 2 8.314 J mol-1 K -1 ln
H msublimation
P1
400 Torr
1 1 1 1
1048 + 273.15 K 1108 + 273.15 K
T1 T2
= 231.7 kJ mol-1

To estimate H mvaporization , use the vapor pressures of the liquid phase

P2 760
R ln 8.314 J mol-1 K -1 ln
H mvaporization
P1
400
1 1 1

1

T1 T2 1221 + 273.15 1281 + 273.15
H mvaporization 206.5 kJ mol-1
H mfusion H msublimation H mvaporization
231.7 kJ mol-1 206.5 kJ mol-1
25.2 [kJ mol-1 ]
 At the triple point, the solid and liquid have the same vapor pressure.

P H msublimation 1 1
ln solid
P

solid ,ref R Tsolid ,ref T
Pliquid H mvaporization 1 1
ln
P

liquid ,ref R Tliquid ,ref T
H msublimation 1 1
ln Psolid ,ref
R
Tsolid ,ref T
H mvaporization 1 1
ln Pliquid ,ref
R
Tliquid ,ref T
1 1 H msublimation H mvaporization
R ln Psolid ,ref R ln Pliquid ,ref
T H msublimation H msublimation Tsolid ,ref Tliquid ,ref

for
Psolid ,ref 100 Torr , Pliquid ,ref 400 Torr
Tsolid ,ref 1381 K , Tliquid ,ref 1494 K
1 1 232 103 J mol-1 207 103 J mol-1

Ttp 232 207 103 J mol-1 1381 K 1494 K
100. Torr
8.314 J mol-1 K -1 ln
400. Torr
7.16 104 K -1
Ttp 1398 [K]

The pressure at the triple point can be obtained from either the equation for vapor pressure of
the solid or the solid phases.

H sublimation 1 1
Psolid T Psolid ,ref exp m


R Tsolid ,ref T
232 103 J mol-1 1 1
Ptp 100. Torr exp
8.314 J mol K 1381 K 1398 K
-1 -1

Ptp 128 [Torr]

P8.6) A PT phase diagram for potassium is shown below

a) Which phase has the higher density, the fcc or the bcc phase? Explain your answer.
According to LeChateliers principle, for a given temperature, the phase with the higher density
will be found at higher pressure. Therefore the fcc phase is more dense
b) Indicate the range of P and T in the phase diagram for which fcc and liquid potassium are in
equilibrium. Does fcc potassium float on or sink in liquid potassium? Explain your answer.
fcc and liquid potassium are in equilibrium on the liquidsolid coexistence line existing upward
from the triple point. The fcc phase will sink in the liquid because the slope of the two phase
liquidsolid coexistence line is positive.
c) Extend P and T on this diagram and indicate where you might expect to find the vapor phase.
Explain how you chose the slope of your liquidvapor coexistence line.
The vapor phase is found at much lower pressures and higher temperatures. The slope of the
vaporliquid coexistence line is always positive because the vapor pressure increases rather than
decreases with increasing temperature.

P8.11) Use the vapor pressures for C2N2 given in the following table to estimate the temperature
and pressure of the triple point and also the enthalpies of fusion, vaporization, and sublimation.
Phase T (C) P (Torr)
Solid 62.7 40.0
Solid 51.8 100.
Liquid 33.0 400.
Liquid 21.0 760.

to calculate the triple point temperature, take

Tsolid ,ref 221.4 K Psolid ,ref 100. Torr

Tliquid ,ref 240.2 K Pliquid ,ref 400. Torr

1 1 32.6 103 J mol-1 26.9 103 J mol-1

Ttp 32.6 26.9 103 J mol-1 221.4 K 240.2 K
100. Torr
+ 8.314 J mol-1 K -1 ln
400. Torr
1
0.00416 K -1 , Ttp 240. K
Ttp
32.6 103 J mol-1 1 1
Ptp 100. Torr exp 403 [Torr]
8.314 J mol K 221.4 K 240.3 K
-1 -1

P8.23) Calculate the vapor pressure of ethanol droplets of radius 1.00 108 m at 335 K in
equilibrium with ethanol vapor. Use the tabulated value of the density and the surface tension
at 298 K from Appendix B for this problem. (Hint: You need to calculate the vapor pressure of
ethanol at this temperature.)
We first calculate the vapor pressure of ethanol at 298 K using Table 8.3.

P T A 2 3.6745 103
ln A 1 23.58 10.8345
Pa T
A 3 335 46.702
K
P 5.07 104 [Pa]
 We next calculate the pressure difference across the interface using Equation 8.29.

2 2 21.97 10-3 N m -1
P = 4.39 106 Pa
r 1.00 10-8 m
Pinside Pvapor P 5.07 10 4 Pa + 4.39 10 6 Pa = 4.44 10 6 Pa

We calculate the increase in the vapor pressure using Equation (8.25).

46.07 10-3 kg mol-1

4.44 106 5.07 104 Pa
M
P
P P0 -3
789.3 kg m
ln = 9.2083 10-2
P0 RT 8.314 J mol K 335 K
-1 -1

P 1.096 P0 5.56 104 [Pa]

P8.28) Use the vapor pressures of Cl2(l) given in the following table to calculate the enthalpy of
vaporization using a graphical method or a least squares fitting routine.

T (K) P (atm) T (K) P (atm)

227.6 0.585 283.15 4.934
238.7 0.982 294.3 6.807
249.8 1.566 305.4 9.173
260.9 2.388 316.5 12.105
272.0 3.483 327.6 15.676
A least squares fit of ln P versus 1/T gives the result H mvaporization = 20.32 kJ mol-1.

P8.34) Carbon tetrachloride melts at 250. K. The vapor pressure of the liquid is 10,539 Pa at 290.
K and 74,518 Pa at 340. K. The vapor pressure of the solid is 270. Pa at 232 K and 1092 Pa at
250. K.
a. Calculate H mvaporization and H msublimation .

b. Calculate H mfusion .

c. Calculate the normal boiling point and Smvaporization at the boiling point.
d. Calculate the triple point pressure and temperature.
a)

Pf H mvaporization 1 1
ln
Pi R T f Ti
P
R ln f
Pi
H mvaporization
1 1

T f Ti
74518 Pa
8.314 J mol-1K -1 ln
H mvaporization 10539 Pa = 32.1103[J mol-1 ]
1 1

340 K 290 K
 Pf H msublimation 1 1
ln
Pi R T f Ti
P
R ln f
Pi
H msublimation
1 1

T f Ti
1092 Pa
8.314 J mol-1K -1 ln
H msublimation 270 Pa = 37.4 103[J mol-1 ]
1 1

250 K 232 K
b)

H mfusion H msublimation H mvaporization = 37.4 103 J mol-1 32.1 103 J mol-1

= 5.3 103 [J mol-1].

c)

Pf H mvaporization 1 1
ln
Pi R T f Ti
H mvaporization
Tf
H mvaporization P
R ln f
RTi Pi
At the normal boiling point, P = 101325 Pa.
32.1103 J mol-1
Tb ,normal 350. [K]
-1 32.1103 J mol-1 101325 Pa
8.314 J mol K
-1
ln
8.314 J mol K 340 K
-1 -1
74518 Pa
H mvaporization 32.1103 J mol-1
S mvaporization = 91.8 [J mol-1K -1 ]
Tvaporization 349.5 K
 d)
From Example Problem 8.2,

Ttp
H vaporization
m H msublimation
P liquid P solid H msublimation H mvaporization
R ln i ln i
P P RTi solid RTi liquid

Ttp
32.110 3
J mol-1 37.4 103 J mol-1
264 K
10539 Pa 270 Pa 37.4 103 J mol-1
ln ln
5
10 Pa 10 Pa 8.314 J K mol 232 K
5 -1 -1

8.314 J K -1 mol-1
32.1103 J mol-1
+
8.314 J K mol 290. K
-1 -1

Ptp H mvaporization 1 1
ln
Pi R Ttp Ti
Ptp 32.1103 J mol-1 1 1
ln 1.3112
264 K 290. K
-1 -1
10539 Pa 8.314 J K mol
Ptp
0.269
10539 Pa
Ptp 2.84 103 [Pa]

P8.39) At 298.15 K, G f (H2O,g) = 228.6 kJ mol-1 and G f (H2O,l)= 237.1 kJ mol-1.

Calculate the vapor pressure of water at this temperature.

G G f H 2O, g G f H 2O, l 228.6 kJ mol1 237.1 kJ mol1
8.5 kJ mol1
P G 8.5 kJ mol1
ln 3.429
P RT 8.314 J mol1 K 1 298.15 K
P 3.24 103 [Pa]