Chemistry 231

Tutorial Session # 5
G. Marangoni

Date: December 2, 2011.

The following questions will be answered on the tutorial session.

1. The experimental critical constants of NH3 are Tc = 405.4 K and Pc = 113.53 bar. The
experimentally determined value of Vc is 0.0725 L/mol. Use the values of Pc and Tc to
calculate Vc, Zc for an ideal gas and the van der Waals and obtain the van der Waals
constants for NH3 (g).
2. The vapor pressures of ClF3 are given below. Plot the vapour pressures of ClF3 to calculate
the enthalpy of vaporization and estimate the boiling temperature of ClF3.
T(C)
P(Torr)
46.97
29.06
41.51
42.81
33.14
74.31
30.75
86.43
35.59
63.59
27.17
107.66

3. The vapour pressure above 1-pentanol is found to fit the equation

(

Calculate the enthalpy of vapourization and the standard boiling point of 1-pentanol.
4. The stability of a phase depends on its chemical potential variation as a function of
temperature and pressure.
a) Calculate the difference in the chemical potential of supercooled water versus that of ice
at 3.50C and standard pressure?
b) Calculate the difference in the chemical potential of steam and superheated water at 1 bar
pressure. (note S H 2O , s = 48.0 J mol1 K1, S H 2O ,l = 70.0 J mol1 K1, and S H 2O , g = 188.8
J mol1 K1).
5. Calculate the vapor pressure above ethanol droplets of radius 1.00 108 m at 19.0C,
25.0C, and 62.0C (note: use EtOH = 22.6, 22.0, and 18.5 mN/m at the three temperatures,
EtOH = 0.7893, 0.7767, and 0.756 g/cm3, and vap H 38.56 kJ mol 1 , pEtOH = 41.0 and 58.7
mm Hg at 292 K and 295 K).

Please answer the following questions. Answers will be posted on the website.
6. Calculate the van der Waals parameters of methane from the values of the critical constants.

7. Plot the vapour pressures of ice listed in the table below to calculate the enthalpy of
sublimation using the Clausius Clapeyron Equation.
T(C)
P(Torr)
28.00
0.3510
29.00
0.3169
30.00
0.2859
31.00
0.2575
32.00
0.2318
8. Autoclaves that are used to sterilize surgical tools require a temperature
of 134C to kill some bacteria. If water is used for this purpose, at what pressure must the
autoclave operate? The normal boiling point of water is 373.15 K, and
vap H 40.650 kJ mol 1 at the normal boiling point.
9. It has been suggested that the surface melting of ice plays a role in enabling speed skaters to
achieve peak performance. Given the following data, Tfus = 273.2 K, =
= 6010 J mol
1
, 920 kg m3, and the density of liquid water is 997 kg m3, calculate the following.
a) What pressure is required to lower the melting temperature by 5.0C?
b) Assume that the width of the skate in contact with the ice is 25 103 cm, and that the
length of the contact area is 15 cm. If a skater of mass 85 kg is balanced on one skate,
what pressure is exerted at the interface of the skate and the ice?
c) What is the melting point of ice under this pressure?
d) If the temperature of the ice is 5.0C, do you expect melting of the ice at the iceskate
interface to occur?

Answers
1. Using the ideal gas equation.

Vc

RTc 8.314 10-2 Lbar mol -1 K -1 405.4 K

0.297 L mol -1
Pc
113.53 bar

Hence, NH3 is not really effectively modeled as an ideal gas near the critical point.
PV
For a van der Waals gas, Z c c c 0.375
RTc
From the experimentally determined critical molar volume

Zc

Vc Pc
113.53 bar 0.0725L mol 1

0.244
RTc 0.08314 Lbar K -1 mol -1 405.4 K

Hence, NH3 is not really effectively modeled as a van der Waals gas in his region, although the
agreement is better for the vdw than for the ideal gas.
Calculate a and b

2
8.314 10-2 L bar K -1mol -1 405.4 K

27 RTc
L2bar
a

0.156
64 Pc
64 113.53 bar
mol 2
2

RTc 8.314 10-2 Lbar K -1mol -1 405.4 K

L

0.0372
8Pc
113.53 bar
mol

2. Plot the ln (vapour pressure) versus 1 /T (K) according to

(

Clausius-Clapeyron Plot for Question 2

5.00

Ln (P/Torr)

4.50
4.00
3.50
3.00
y = -3,677.89x + 19.63
R = 1.00

2.50
2.00
4.00E-03

4.10E-03

4.20E-03

4.30E-03

4.40E-03

4.50E-03

1/T ( K-1)

The equation of the line has a slope

From the intercept,

= 3678 K; hence,

30579 J mol-1 = 30.6 kJ mol-1

(

= 19.632

(
Tb = 283 K

3. This expression is the Clausius-Clapeyron equation for the liquid in the form of
( )

)
)

Hence,

Two ways to calculate the Tb. First, use P = 1.00 x 105 in the above equation and solve for T.

We also recognize that from the intercept, we can calculate the Tb as follows.

4. Note - from the dependence of the Gibbs energies on conditions.

Gm S m T at constant P

a) Gm S H 2O ,l S H 2O ,s

T 70.0 J K

-1

mol-1 48.0 J K -1mol-1 3.50 C

77.0 J mol-1

b)

Gm S H 2O ,l S H 2O , g

T 70.0 J K

-1

mol-1 188.8 J K -1mol-1 3.50 C

416 J mol-1

5. We will show you the calculation first at 291 and 298 K, and then at 335 K using the
appropriate values of the surface tension and the density of ethanol. For the calculations at
291 and 298 K, we use the vapour pressures listed in the question. For the calculation at 335
K, we have to use either the vp of ethanol at 291 K or 298 K to calculate the vp at 335 K
using the C-C or the Antoine equation.

At 292 K
Calculate the pressure difference across the ethanol/air interface using the Laplace equation.

2 2 22.6 10-3 N m-1

P

4.52 106 Pa
-8
r
1.00 10 m
We calculate the increase in the vapor pressure using the Kelvin equation
M

P'
ln
RT
P0

46.07 10-3 kg mol -1

4.52 106 Pa
-3
789.3 kg m

0.1094
8.314 J mol -1 K -1 292.15 K

P'
e0.1094 1.116
P*
P ' 1.1016 P* 1.109 5466 Pa 6062 Pa

At 298 K
Calculate the pressure difference across the ethanol/air interface using the Laplace equation.

2 2 22.0 10-3 N m-1

4.40 106 Pa
-8
r
1.00 10 m

We calculate the increase in the vapor pressure using the Kelvin equation
46.07 10-3 kg mol -1
4.40 106 Pa
P
-3
P'
776.7 kg m
ln

0.1053
RT
8.314 J mol -1 K -1 298 K
P0
P'
e0.1034 1.111
P*
P ' 1.109 P* 1.111 7826 Pa 8695 Pa
M

At 335 K
To do the calculation at 335 K, we must first estimate the vapour pressure of ethanol at 335
K using either the Clausius-Clapeyron equation (Table 8.2) or the Antoine equation (Table
8.3)
Using the C-C equation

ln

ln

P335
P298

vap H
P2

P298
R

T2 298.15K
38560 J mol 1 1
1

1
1
8.314 JK mol
335K 298.15K

ln

P335
4638K 1 2.9851103 K 1 3.3540 103 K 1
P298
1.711

P335
e1.711 5.578
P298
P335 43660 Pa

Again, calculate the pressure difference across the ethanol/air interface using the Laplace
equation (8.29) and the surface tension for ethanol at 335 K.

2 2 18.5 10-3 N m-1

3.70 106 Pa
-8
r
1.00 10 m
Using the Kelvin equation (8.25).

46.07 10-3 kg mol -1

3.70 106 Pa
756 kg m -3

0.08097
8.314 J mol -1 K -1 335 K

P'
ln
RT
P0
P ' 1.084 P0 1.084 43660 Pa 4.73 104 Pa

6. Critical constants are found in Table 7.2 Appendix A, page 550 of the Thermodynamics book
(the short version); Table 7.2 Appendix B, page 1010 of the Physical Chemistry book (the
full text).

7. Plot the vapour pressures according to the Clausius-Clapeyron equation. In this case, since
we are dealing with the solid-vapour equilibrium, the slope will be proportional to the
enthalpy of sublimation.
(

Clausius-Clapeyron Plot for Question 4

4.06E-03
-0.80

4.08E-03

4.10E-03

4.12E-03

4.14E-03

4.16E-03

-0.90

Ln (P/Torr)

-1.00
y = -6,132.93x + 23.97
R = 1.00

-1.10
-1.20
-1.30
-1.40
-1.50

1/T ( K-1)

The equation of the line has a slope

= 6133 K; hence,

50990 J mol-1 = 51.0 kJ mol-1

8. Use the Clausius-Claypeyron equation

vap H
P
ln 2
P1
R

1 1

T2 T1
P
40.656 103 J mol -1
1
1

ln 2

1.09349
-1 -1
P1
8.314 J mol K
407.15 K 373.15 K
P2
2.99; P2 2.99 atm
P1

9. A) Use the Clapeyron equation to estimate the pressure increase required.

(

The pressure must be increased by 720 bar to lower the melting point by 5.0C.
B) To calculate the pressure the person exerts on the blade, we will assume that the pressure is
exerted on one edge of the blade.

C) Calculate the melting point difference at this applied pressure.

(

)
Tm = 1.5C

d) Note that because the lowering of the melting temperature is less than the temperature of the
ice, we do not expect that the ice will melt at this pressure. This means that frictional heating
between the ice and the blade will also make a contribution to the melting.