Chemistry 5350

Advanced Physical Chemistry

Fall Semester 2013
Take Home Quiz 2
Due: September 26, 2013

First Law and State Functions

1. The internal energy of a perfect monotomic gas relative to its value at T = 0 is 23 nRT .




and U
for the gas.
Calculate H
P T
P T
 
3
U=
nRT ;
2

U
P

=0

by direct differentiation
 
 
5
3
nRT + nRT =
nRT
H = U + PV =
2
2


H
P

=0
T

by direct differentiation

CP
p

as a second derivative of H, and find its relation to

T


P
From this relation show that C
= 0 for a perfect gas.
P T

2. Express


Because
Thus,

H
P T

Cp
P

=
P

H
T

 
P

=
T

H
P

H
P T

 
T

= 0 for a perfect gas, the temperature derivative also equals zero.



CP
P

=0
T

3. Write an expression for dV given that V is a function of P and T .

Deduce an expression for d ln V in terms of the expansion coefficient and isothermal compressibility
V = V (P, T )
Hence,



V
V
dV =
dP +
dT
P T
T P
 


 
1
V
V
dV
1
=
dP +
dT
d ln V =
V
V
P T
V
T P


 
 
V
V
1
1
T =
=
V
T p
V
P T


d ln V = T dP + dT

4. A gas obeying the following equation of state

P (V nb) = nRT
is subjected to a Joule-Thomson expansion.
Will the temperature increase, decrease, or remain the same?
JT =

T
P

1
=
CP

H
P

1
=
CP





V
T
+V
T P

For a gas which obeys the above equation of state

JT =

b
CP

Since b > 0 and CP > 0, then for this gas JT < 0 or

T
P H

< 0.

This equation indicates that when the pressure drops during the Joule-Thomson expansion,
P = P2 P1 < 0
the temperature must increase


T
P

and
T =

b
CP

b
P > 0
CP

5. At low pressure and 298 K, the experimental value of N2 for the Joule-Thomson coefficient, JT =
(T /P )H = 0.222K atm1 .
a. Derive the expression for the Joule-Thomson coefficient for a gas which obeys the van der Waals
equation of state
a
RT
2
P =
Vm b Vm
can be shown to be
JT =

2a
b
RT

1
Cp,m

The van der Waals equation of state can be written as:

P V = RT
If the very small term

ab
V2

a
ab
+ bP + 2
V
V

is neglected and the term

a
PV

is replaced by

a
,
RT

RT
a

+b
P
RT


a
R
V
= +
T P
P
RT 2
V =

from above
then

JT

R
V b
a
=
+
P
T
RT 2


V
2a
T
b
V =
T P
RT






V
2a
1
1
T
b
=
+V =
CP
T P
CP RT

then

b. At what temperature does the Joule-Thomson coefficient for N2 vanish? For N2 , a = 1.35
106 atm cm6 mol2 , b = 38.6 cm3 mol1 , and Cp,m = 29.125J mol1 K1
Set JT = 0 to find the inversion temperature:
T =

2a
2 1.35 106 atm cm6 mol2
= 852 K
=
Rb
(82.0578cm3 atm K1 mol1 ) (36cm3 mol1 )

JT > 0 below the inversion temperature, and JT < 0 above the inversion temperature.
c. Can N2 gas be cooled by a Joule-Thomson expansion if the temperature is higher than the
temperature calculated above? Explain in terms of the value given for JT .
In an expansion of a gas, the change in pressure is negative, P = P2 P1 < 0, because P2 is
less than P1 .
Using the equation for the Joule-Thomson expansion, the change in temperature is given by
T = P JT
If the temperature of the gas is less than the inversion temperature, (Tinversion < 852K, JT >
0), the temperature of the gas decreases during the expansion.
If the temperature of the gas is greater than the inversion temperature, (Tinversion > 852K, JT <
0), the temperature of the gas increases during the expansion.
Thus, for temperatures greater than 852 K, it is not possible to cool the N2 gas by a JouleThomson expansion

6. 2.00 moles of Kr gas at 300 K expands isothermally and reversibly from 20.0 L to 50.0 L. Calculate
q, w, U , and H. Assume ideal gas behavior.
U = 0 and H = 0 for an ideal gas

q = w
For this reversible process Pext = P , giving
Z
Z V2
P dV =
w=
V1

V2
V1

nRT
V2
dV = nRT ln
V
V1

V2
= 2.00 8.314 J mol1 K1 (300 K) ln
w = nRT ln
V1

50.0 L
20.0 L

= -4.57 kJ

q = w = 4.57 kJ

7. 2.00 moles of Kr gas at 20 L and 300 K expands adiabatically and reversibly to a final volume
of 80.0 L. Calculate q, w, U , and H. Assume ideal gas behavior.
First determine the final temperature using CV = 32 R:
CV

CV

T2 R V2 = T1 R V1
CV

T2 R (80.0 L) = (300 K)
3

T22 = 300 2 K (0.25);

CV
R

(20.0 L)

T2 = 119 K

q=0
U = w =
w = 2.00 mol
H =

119K

nCV dT = nCV T
300K

3
8.314 J mol1 K1 (119 K - 300 K) = -4.51 kJ
2

1299K

nCP dT = nCP T = 2
300K

5
8.314 J mol1 K1 (119 K - 300 K) = -7.52 kJ
2

8. An equation of state of a gas is given by P =

nRT
.
V nb

a. Give the total differential for the equation of state of this gas with respect to volume.




V
V
dT +
dP
dV =
T P
P T




nRT
nR
dT
dP
dV =
P
P2
b. Solve for the change in volume as a function of state variables at constant pressure.
For constant pressure, dP = 0 and the second term in the exact differential vanishes.
Z T2
Z V2
nR
dV =
dT
P
T1
V1
(V2 V1 ) =

nR
(T2 T1 )
P

c. Obtain an expression from Part b for one mole of gas under the following conditions: P = 2.00
atm, T = 273 K, b = 0.115 L/mol.
Using this data, one can obtain a value of V1
V1 =

nRT
+ b = 11.2 L
P

The equation now becomes

V2 = 11.2 L + 0.0410L K1 (T2 273 K)
d. Plot the expression from part c on a graph of volume versus temperature for this gas:
e. Add to the graph in part d the plot of similar function for P = 1.000 atm.
V2 = 22.4L + 0.0820L K1 (T2 273 K)
Label the two functions c and e.
50

Equation e

40
V

30

Equation c

20
10
0
273

373

473
T

573

9. Derive a general relation between CV and CP





U
U
dU =
dT +
dV = dq Pext dV
T V
V T
then
dq =

U
T

dT + Pext +
V

U
V

 

dV

at constant pressure


dqP = CV dT + Pext +

U
V

 

dV

dqP
dT

= CP , we obtaine
 



V
U
CP CV = P +
V T
T P

Dividing through by dT and setting

The above equation takes on a simple form for an ideal gas because
Then
CP CV = nR

U
V T

= 0 and

V
T

nR
.
P