Chem 467

Fall 2012

Problem Set #12 key

1. Problem 1.12 1 H2O (l) [5 C, 4.108 mbar] 1 H2O (s) [5 C, 3.912 mbar] Since both the liquid and the solid must be in equilibrium with the vapor, we can treat everything in terms of the response of the vapor. When the phase transition takes place, the vapor pressure will drop from 4.108 mbar to 3.912 mbar. This process is 1 H2O (g) [5 C, 4.108 mbar] 1 H2O (g) [5 C, 3.912 mbar] We write the differential for the Gibbs energy We are at constant temperature, and treating the gas as ideal Gm = R T p
p2
1

d G m=S m dT V m dp RT d G m=V m dp= dp p p 1 dp = R T ln 2 p p1

Integrating this expression gives us

Gm = 109 J mol-1 Since G < 0, this process is spontaneous. 2. Problem 1.17 a) We start with the Clapeyron equation dp S = dT V RT . p H S= T dp p H = 2 dT RT 1 dp = p dT d ln p H = dT RT2

We assume the gas is ideal, and that V g , m V l ,m , or that V V g ,m = We also have, for a reversible phase transition

Putting it all together, gives us

Rearranging gives us

b) To change the form of the Clausius-Claperyron equation, we need to look at the temperature 1 dT d = 2 derivative. Let's start with the derivative of the reciprocal of T T T 2 Rearranging gives us dT =T d 1 / T

Substituting this in gives us

H d ln p = 2 T d 1 / T R T 2

Or

d ln p H = R d 1 /T

c) At the normal boiling point, the vapor pressure is 1 atm. At a lower temperature, the vapor pressure will be lower. To determine the vapor pressure at the lower temperature, we integrate the ClausiusClapeyron equation. Again, this assumes we can treat the vapor as an ideal gas.

p
ln

p1
0

d ln p =T

T1
0

H 1 d R T

= 2.1948 or p0 = 0.1114 atm

p 1 H 1 1 = p0 R T1 T0

p1 = 8.978 p0 3. Problem 1.21 Clearly state any assumptions a) The change is

70 g liquid (l) [T, 1 bar] 70 g liquid (l) [T, 30 bar]

dG =S dT V dp dG =V dp

b) Starting with the Gibbs energy We are at constant T, so we have

Since we are working with a liquid, we can reasonably assume that V is constant. That gives us

G= V p
The density is c) For a gas, we have d = 0.845 g cm-3

V=

G 240 J = =8.28105 m3=82.8 cm3 5 p 2910 Pa

70 g ideal gas (g) [300 K, 1 bar] 70 g ideal gas (g) [300 K, 30 bar]

d) Now, we can no longer assume the volume is constant. T is constant, though, so n RT dG =V dp= dp p p 70 g 30 bar G= n R T p d ln p = 8.3145 J mol 1 K 1 300 K ln 1 1 bar 40 g mol
2 1

G = 14850 J 4. Problem 1.24 [For part a), derive general expressions, then the specific results for an ideal gas. For part b), describe the types of interactions that occur with a van der Waals gas. Note that the a and b parameters are always positive quantities.]

d U =T d S p d V a) We start with the Gibbs equation for internal energy Now we take the derivative with respect to volume at constant temperature

U V =T
T

S V

V V

=T

S V

We use the Maxwell relation

For an ideal gas, Therefore,

S p = V T T
Vm

to have

Um p =T Vm T T

p R = T V Vm

Um RT = p =0 Vm T V m

For the enthalpy

d H =T d S V dp gives

The Maxwell relation gives

For an ideal gas, we already have Substituting in gives us

Hm p =T V m T T

H V =T
T

S V

p V

Vm

V m

p V m

p R = , so we just need T V Vm

Hm RT R T = V m =0 V m T V m V2 m

U V

p R T = 2 . Vm T Vm

Both these results agree with the definition of an ideal gas that the internal energy (enthalpy) only depends on the temperature. b) We start with our general expression We write the van der Waals equation as The pressure derivative is then

=T

p p T V T RT a p= 2 V m b V m p R = T V V m b
m

Substituting these in gives us

Um a = 2 Vm T Vm Because this is always a positive quantity, this describes attractive interactions, which is exactly what van der Waals meant to accomplish.

Um p =T Vm T T

p=

Vm

RT RT a 2 V m b V m b V m

5. Problem 1.25 [The density change should be 0.16%, not 1.6%.] a) Start with the definition of the isothermal compressibility 1 d V m=d ln V m Vm V V0 = 1 V m Vm p

We now write

dp =

Integrating gives us

p p 0 =ln

We know the density increases by 0.16%, so the volume is 99.84% of the initial volume p p0= ln 0.9984 = 2180 atm Solving for p - p0 b) Assuming we can treat the volume as constant, and given that T is constant Gm =V m p = 1570 J mol-1 6. Given the following data for the compression factor of oxygen at 200 K: p/atm 1.0000 Z 0.9971 4.0000 0.98796 7.0000 0.97880 10.000 0.96956 40.00 0.8734 70.00 0.7764 100.0 0.6871

a) Evaluate the fugacity and fugacity coefficient at each pressure. To determine the fugacity, we need to evaluate the integral pressure. The results are tabulated below.
p 1 4 7 10 40 70 100 Z 0.9971 0.98796 0.9788 0.96956 0.8734 0.7764 0.6871 Z-1 / p area trap area sum f/p f -0.0029 -0.00145 -0.00145 0.998551051 -0.00301 -0.008865 -0.010315 0.989738017 -0.0030285 -0.009057857 -0.0193728 0.980813591 -0.003044 -0.009108857 -0.0284817 0.971920066 -0.003165 -0.093135 -0.1216167 0.885487698 -0.0031942 -0.095389286 -0.217006 0.80492514 -0.003129 -0.094849286 -0.3118552 0.732087464 1.0 4.0 6.9 9.7 35.4 56.3 73.2

ln =ln

p Z 1 f =0 dp at each p p

b) Determine the Gibbs energy change associated with an isothermal pressure change at 200 K from 10 atm to 100 atm and compare to the Gibbs energy change for an ideal gas. To evaluate the change in Gibbs energy, we need to evaluate the Gibbs energy at the initial and final pressures. ff fi G f =Go RT ln o Gi =Go RT ln o so p p

 G = RT ln

f f 73.2 atm 1 1 = 8.3145 J mol K 200 K ln fi 9.7 atm

G = 3.36 kJ mol-1. If the gases were ideal, we would use the pressures and not the fugacities p 100 atm Gideal = RT ln f = 8.3145 J mol 1 K1 200 K ln pi 10 atm Gideal = 3.83 kJ mol-1. The nonideal behavior results in about a 12% change in the Gibbs energy. c) The Berthelot equation of state is given by V m= RT 9 R T c 54 R T c p 128 p c 128 p c T 2
3

Derive an expression for the fugacity coefficient of a Berthelot gas. (Note the difference between the critical and absolute temperatures and pressures in the EOS.) We need to evaluate Z for this equation of state pVm 9 pTc 54 p T 3 c Z= =1 RT 128 T p c 128 p c T 3 9Tc 54 T 3 Z 1 c = p 128 T pc 128 p c T 3 ln
p 9Tc 54 T c 9Tc 54 T c f =0 dp= p 3 p 128 T p c 128 pc T 128 T p c 128 p c T 3

9Tc 54 T 3 f c = =exp p p 128 T pc 128 p c T 3

d) The critical temperature and pressure of oxygen are 154.8 K and 50.14 atm, respectively. Calculate the fugacity coefficient for each pressure in part a) and plot the calculated and experimental values. Comment on how well, and over what pressure range, the Berthelot equation accurately describes the behavior of oxygen gas.

The results of the calculations are summarized in the table.

p 1 4 7 10 40 70 100 experimental Berthelot 0.999 0.997 0.990 0.989 0.981 0.980 0.972 0.972 0.885 0.893 0.805 0.821 0.732 0.755

The Berthelot equation works quite well up to 10 atm, but by 40 atm there are significant deviations. The deviations get worse as the pressure increases. Writing Prompt The Gibbs energy is one of the most useful quantities we use in thermodynamics. Briefly describe why this quantity is so important, including some discussion of how it relates to spontaneity.