Solutions to Unit 1 Homework No.

1
1. (a) Z

RT R RT

A plot of Z versus :

The two partial derivatives are:

, and

K
dT

K
2
3
2

2. The total differential of P is:

P
P
P
dV
dT
dn

n,T

n,V
n V ,T

dP

We can determine each partial derivative. The total differential is then:

dP

nRT
V

nRT
V

dV

nR
RT
dT
dn , which can then be approximated as:
V
V

nR
RT
T
n
V
V

1.0000mol 8.3144 JK 1mol 1 298.15 K 0.200 10 3 m 3

0.020000m
1.0000mol 8.3144 JK mol 298.15K 0.85K

0.020000m
1.0000mol 8.3144 JK mol 298.15K 0.0015mol

0.020000m
3 2

1.779 10 3 Nm 2

We have used the fact that 1 J = 1 Nm.

3. We need to solve each second derivative. For the ideal gas equation:
2P

VT

nR
nR

V2
n V V T , n

2 P
nRT
nR

TV
V V ,n
V2
T
n

For the van der Waals equation:

nR
2 P

VT

n V V b

T, n

3

2 P
nRT 2a

2
TV

V 3

n T V b

nR
2

V, n

nR

V 2 b 2

4. Book problems.
H-3. For an ideal gas PV nRT
nRT
P
nRT
V
P
V

, and

2
2
V
P
V n,T
P n,T
V
P

For the equation of state P

nRT
V nb , the partial derivative of P with respect to V is:

nRT
P
P

V
V

nb

n, T
V nb

The partial derivative of V with respect to P is:

nRT
V nb
V

2
P
P n,T
P

H-5. The total differential of P is:

P
P
dT
dV

V
V T

dP

For a Redlich-Kwong gas: T

And, V

RT

V B

A
T

12

R
A

3
2
V B 2T V V B

V B

T 1 2V V B
RT

RT

V B

A 2V B

A 2V B

2
T 1 2V 2 V B

dV
dT
Then, dP V B 3 2
V B 2 T 1 2V 2 V B 2
2T V V B

H-8

H-11

Because these derivatives are equal, dx/T is an exact differential.

H-13. We begin with:

an 2
nRT
V b RT , which can be written as: P

2
2

V nb
V
V

Solving for pressure gives: P

nRT
an 2

V nb V 2

RT

Also in terms of molar volume, this equation is: P V b 2

V
RT
2a
P
P

,
and
2
3
V T
V
V b V

nRT

V nb

RT

2n 2 a
V

RT

nV b

2a
nV

1 P

n V T

5. Using the van der Waals equation of state P V b 2 , where V = 0.05 dm3 mol-1.
V
P

0.083145dm bar mol K 273.15K 3.6551dm bar mol

0.05dm mol 0.042816dm mol 0.05dm mol
1

Ideal gas: P

1 2

1699bar

RT
454.22bar
V
RT

Redlich-Kwong: P V B 1 / 2
T V V B
With A = 64.597 dm6 bar mol-2 K1/2, and B = 0.029677 dm3 mol-1, P = 136.38 bar
6. We use the Newton-Raphson method.
The cubic form of the van der Waals equation is:
RT 2 a
ab

V 3 b
0
V V
P
P
P

For ethane

a = 5.5088 dm6 atm mol-2

b = 0.065144 dm3 mol-1

Putting these values into the above cubic equation yields the following:
V 3 0.189 V 2 0.027 V 0.00175 0

Vn 1 Vn

0.189V 2 0.027V 0.00175

3V 2 0.378V 0.027

We can get an initial guess for the molar volume using the ideal gas equation.
Vo

RT
0.0820579dm 3atm K 1mol 1 310 K

0.124 L mol 1
P
205 atm

V1 0.124

0.0019 0.0029 0.0033 0.00175

0.103L mol 1
0.046 0.047 0.027

Continuing the iterations will lead to the molar volume converging to V 0.096 Lmol 1
7.

8. V
H

2RT
B,
P

2R B

P
T

2R B
2RT
B T

P
P T

B T