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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

ln

P

2

P

1

H



H

sublimation

, use the vapor pressures of the solid phase

H

m

sublimation

1

1

 

R

R ln

P

2

T

2

T

1

8.314 J mol

-1

K

-1

ln

100

Torr

P

1

   

400

Torr

1

1

 

1

1

T

1

T

2

 

1048 + 273.15

K

1108 + 273.15

K

sublimation

m

= 231.7 kJ mol

-1

To estimate

H

vaporization , use the vapor pressures of the liquid phase

m

vaporization H

H

H

m

vaporization

m

fusion

m



R ln

P

2

P

1

1

T

1

1

T

2

8.314 J mol

-1

K

-1

ln

760

400

1

1221 + 273.15

1

1281 + 273.15

206.5 kJ mol

-1

H

sublimation

m



H

vaporization

m

231.7 kJ mol

-1

20 6.5 kJ mol

-1

-1

25.2 [kJ mol ]

At the triple point, the solid and liquid have the same vapor pressure.

ln


P

solid

H

sublimation

m

1

 

1

ln

 

P

solid ref

,

P

liquid

H

R

T

solid ref

,

vaporization

m

1

 

T

1

H

P

liquid ref

,

sublimation

m

1

R

1

T

liquid ref

,

ln

P

T

 

R

T

solid ref

,

T

solid ref

,

 

1

H

vaporiza tion

1

 

 

m

R

T

 

liquid ref

,

1

1

T

H

sublimation



H

sublimation

 

m m

 

for

T

H

m

,

ln

P

liquid ref

,

H

sublimation

vaporization

T

solid ref

m

T

liquid ref

,

R

ln

P

solid ref

,

P

solid ref

,

100 Torr ,

P

liquid ref

,

400 Torr

T

solid ref

,

1381 K

,

T

liquid ref

,

1 1

T

tp

232

207

10

3

J mol

-1

1494 K

232

10

3

J mol

-1

1381 K

8.314 J mol

-1

K

-1

ln

100.

T orr

400.

Torr

7.16

10

4

K

-1

T

tp

1398 [K]

207

10

3

J mol

-1

1494 K

R

ln

P

liquid ref

,

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

P

solid

P

tp

T

P

solid ref

,

exp

 

H

sublimation

m

R

1

1

T

solid ref

,

T

 

 

100. Torr

exp

232

 

10

3

J mol

-1

8.314 J mol

-1

K

-1

1

1381 K

P tp

128 [Torr]

1

1398 K



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

a) Which phase has the higher density, the fcc or the bcc phase? Explain your answer.

According to LeChatelier’s 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 C 2 N 2 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

T

solid ref

,

221.4 K

P

solid ref

,

100. Torr

T

liquid ref

,

240.2 K

P

liquid ref

,

1 1

T

tp

32.6

26.9

10

3

+ 8.314 J mol

-1

J mol

K

-1

-1

ln

400. Torr


32.6

10

3

J mol

-1

221.4 K

100. Torr

400. Torr

1

T tp

P

tp

-1

0.00416 K ,

100. Torr

exp

T

tp

240. K

32.6

10

3

J mol

-1

8.314 J mol

-1

K

-1

1

221.4 K

26.9

10

3

J mol

-1

240.2 K

1

240.3 K



403 [Torr]

P8.23) Calculate the vapor pressure of ethanol droplets of radius 1.00 10 8 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.

ln

P

T

Pa

P

5.07

A

10



1

A

2

T

K

A

3

4

[Pa]

23.58

3.6745 10

3

335

46.702

10.8345

We next calculate the pressure difference across the interface using Equation 8.29.

 

P

P

inside

2

r

2

21.97 10

-3

N m

-1

 

1.00 10

-8

m

= 4.39 10

6

Pa

P

vapor

 

P

5.07

10

466

Pa + 4.39 10

Pa = 4.44 10

Pa

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

ln

P

P

 

P

0

1.096

M

P

P

0

RT

P

0

5.56 10

46.07

10

-3

kg mol

-1

4.44

10

6

5.07

10

4

Pa

789.3 kg m

-3

 
 

8.314 J mol

-1

K

-1

335 K

 

4 [Pa]

= 9.2083 10

-2

P8.28) Use the vapor pressures of Cl 2 (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

A least squares fit of ln P versus 1/ T gives the result

H

vaporization

m

= 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

Calculate

H

H

vaporization

m

fusion

m

.

and

H

sublimation

m

.

b.

c. Calculate the normal boiling point and

d. Calculate the triple point pressure and temperature.

S

vaporization

m

at the boiling point.

a)

P

f



H

vaporization

m


1

1

P

i

 

R

R ln

 

T

f

P

f

 

T

i

 

vaporization

 

P

i

H

m

 

1

T

f

1

T

i

74518

Pa

 

-1

8.314 J mol K

-1

ln

 
 

H

vaporization



 

10539

Pa

m

 

1

340 K

1

290 K

 

ln

3

= 32.1 10 [J mol

-1

]

ln

P

f



H

sublimation

m

1

1

P

i

 

R

R ln

T

f

P

f

T

i

 

sublimation

 

P

i

H

m

 

1

T

f

1

T

i

1092 Pa

 

-1

8.314 J mol K

-1

ln

 

H

sublimation



270 Pa

= 37.4

3

10 [J mol

-1

]

m

1

 

1

   

 

b)

250 K

 

232 K

H

fusion H

m

m sublimation

H

m vaporization

= 37.410 3 J mol -1 32.110 3 J mol -1

= 5.310 3 [J mol -1 ].

c)

ln

T

f

P

f

P

i



H

vaporization

m

1

1

R

T

f

T

i

H

vaporization

m

R

H

vaporization

m

RT

i

ln

P

f

P

i

At the normal boiling point,

P = 101325 Pa.

T

b normal

,

32.1

10

3

J mol

-1

8.314 J mol

-1

K

-1

32.1

10

3

J mol

-1

8.314 J mol

- 1

K

-1

340 K

ln

101325 Pa

74518 Pa

S

vaporization

m

H

vaporization

m

32.1

10

3

J mol

-1

T

vaporization

349.5

K

-1

= 91.8 [J mol K

-1

]

350. [K]

d)

From Example Problem 8.2,

T

tp

T

tp

ln

ln

vaporization sublimation   H  H  m m liquid solid sublimation vaporization 
vaporization
sublimation
H

H
m
m
liquid
solid
sublimation
vaporization
P
P
H
H
i
i
m
m
R
ln
ln
solid
liquid
P
P
RT
RT
i
i
3
-1
3
32.1
10
J mol
37.4 10

J mol

-1

8.314 J K

-1

mol

-1

ln

10539 Pa

5

10 Pa

ln

270 Pa

5

10 Pa

37.4 10

3

J mol

-1

8.314 J K

-1

mol

-1

232 K

+

32.1

10

3

J mol

-1

8.314 J K

-1

mol

-1

290. K

P

tp

P

i



H

vaporization

m

1

1

R

T

tp

T

i

P

tp

10539

Pa



32.1

10

3

J mol

-1

8.314 J K

-1

mol

-1

1

264 K

1

290. K



1 .3112

P

tp

10539 Pa

0.269

P tp

2.84 10

3

[Pa]

264 K

P8.39) At 298.15 K,

G

(H 2 O, g ) = ─ 228.6 kJ mol - 1 and 2 O,g ) = 228.6 kJ mol -1 and

f

K,  G (H 2 O, g ) = ─ 228.6 kJ mol - 1 and

G

f

(H 2 O, l )= 237.1 kJ mol -1 .

Calculate the vapor pressure of water at this temperature.

G

 G  H O, g   G  H O, l  f

G
H O,
g

G
H O,
l
f
2
f
2



228.6 kJ mol

1

237.1 kJ mol

8.5 kJ mol

1

ln

 G   RT
 G


RT

P

P

8.5 kJ mol

1

1

K

1

298.15 K

8.314 J mol

P

3.24

10

3

[Pa]



3.429

1