Chemistry 431

Problem Set 9
Fall 2018
Solutions
1. A certain gas obeys the equation of state
RT a
P = − 4
Vm − b Vm
where a and b are numerical constants. Derive an expression for the critical volume of
the gas in terms of b.
Answer: !
∂P RT 4a
=− +
∂Vm T (Vm − b)2 Vm5
∂ 2P
!
2RT 20a
= − 6
∂Vm2 T
(Vm − b)3 Vm
At the critical point both the first and second derivatives vanish
RTc 4a
2
= 5
(Vc − b) Vc
or
(Vc − b)2
! !
4a
Tc = .
Vc5 R
(Vc − b)2
! !
2R 4a 20a
=
(Vc − b)3 Vc5 R Vc6
8 20
=
Vc − b Vc
12Vc = 20b
5
Vc = b
3
2. Derive expressions for the critical pressure, temperature, volume and compression fac-
tor for the Berthelot equation of state given by

nRT an2
P = −
V − nb T V 2

1
Answer:
RT a
P = −
V − b TV 2
!
∂P RT 2a
=− + (1)
∂V T
(V − b)2 T V 3
∂ 2P
!
2RT 6a
= − (2)
∂V 2 T
(V − b)3 TV 4
From Eq.(1)
2a RT
3
=
TV (V − b)2
and
2a(V − b)2
T2 = (3)
RV 3
From Eq.(2)
2RT 6a
3
=
(V − b) TV 4
or
3a(V − b)3
T2 = (4)
RV 4
Equating Eqs.(3) and (4)
2a(V − b)2 3a(V − b)3
=
RV 3 RV 4
3(V − b)
2=
V
or
Vc = 3b (5)
From Eqs.(3) and (5)
2a(3b − b)2
Tc2 =
R(3b)3
1/2
8a

=
27Rb
1/2
2 2a

= (6)
3 3Rb
Using the equation of state
1/2 !1/2
R 2 2a a 3 3Rb

Pc = − 2
2b 3 3Rb 9b 2 2a

2
 1/2
1 2Ra

= (7)
12 3b3
Then
Pc V c (1/12)(2Ra/3b3 )1/2 3b 3
zc = = 1/2
= = 0.375
RTc R(2a/3Rb) (2/3) 8
3. Use the result of problem 2 to find the reduced equation of state for a Berthelot gas.
Answer:
RT a
P = −
V − b TV 2
P = Pr Pc V = Vr Vc T = Tr Tc
1/2 !1/2
1 2aR RTr (2/3)(2a/3Rb)1/2 a 3 3Rb 1

Pr = − 2 2
12 3b3 3bVr − b 9b Vr 2 2a Tr
Then !1/2
1/2
Tt 2R 2a 3b3

Pr = 12
b(3Vr − 1) 3 3Rb 2aR
!1/2 !1/2
1 3 3Rb a 3b3
− 12
T Vr2 2 2a 9b2 2aR
8Tr 3
= −
3Vr − 1 Tr Vr2
4. A certain gas obeys the equation of state
RT a
P = −
Vm − b (Vm + b)2
where a and b are numerical constants. Derive an expression for the critial volume of
the gas in terms of b.
Answer: !
∂P RT 2a
=− 2
+
∂Vm T (Vm − b) (Vm + b)3
(Vc − b)2
! !
2a
=0 at Tc =
(Vc + b)3 R
∂ 2P
!
2RT 6a
= −
∂Vm2 T
(Vm − b)3 (Vm + b)4
(Vc − b)2
! ! !
2R 2a 6a
=0 at =
(Vc − b)3 (Vc + b)3 R (Vc + b)4
2 3
=
Vc − b Vc + b
Vc = 5b

3
5. Derive an expression for the critical volume of a gas that obeys the equation of state
RT a
P = − 6
Vm − b Vm

where a and b are constants.

Answer: !
∂P RT 6a
=− 2
+ 7
∂Vm T
(Vm − b) Vm
∂ 2P
!
2RT 42a
= − 8
∂Vm2 T
(Vm − b)3 Vm
(∂P/∂Vm )T = 0 at
RTc 6a 6a (Vc − b)2
= or Tc =
(Vc − b)2 Vc7 Vc7 R
(∂ 2 P/∂Vm2 )T = 0 at
2RTc 42a
=
(Vc − b)3 Vc8
Then
2R 6a (Vc − b)2 42a
3 7
= 8
(Vc − b) Vc R Vc
12 42 7
= or Vc = b
Vc − b Vc 5
6. Expand the van der Waals equation of state as a virial expansion in powers of 1/V
using the geometric series
1
= 1 + x + x2 + x3 + . . .
1−x
for |x| < 1. You may terminate the series after the third virial coefficient.
Answer:
RT a
P = − 2
V −b V
" #
RT 1 a
= −
V 1 − b/V V2
 !2 
b b a
P V = RT 1 + + + . . . −
V V V
 !2 
b − a/RT b
= RT 1 + + . . .
V V

4
 Then
a
B(T ) = b −
RT
C(T ) = b2
..
.

7. A gas obeys the Berthelot equation of state

RT a
P = −
Vm − b T Vm2

where a and b are numerical constants. By expanding the equation of state in virial
form using powers of 1/Vm , determine an expression for the second virial coefficient of
the Berthelot gas.
Answer:
RT a
P = !−
b T Vm2
Vm 1 −
Vm
 !2 
RT  b b a
= 1+ + + . . . −
Vm Vm Vm T Vm2
 !2 
RT  b b a 
= 1+ + + ... −
Vm Vm Vm RT 2 Vm
 !2 
RT  b − a/RT 2 b
= 1+ + + . . .
Vm Vm Vm
so that the second virial coefficient is
a
B(T ) = b − .
RT 2

8. The Boyle temperature of a gas is defined to be the temperature at which the second
virial coefficient in the inverse volume expansion vanishes. A certain gas obeys the
equation of state
RT a
P = − 2 2
Vm − b T Vm
where a and b are numerical constants. Expand the equation of state in virial form,
and determine the Boyle temperature of the gas in terms of a, b and R.
Answer:
RT 1 a
P = − 2 2
Vm b T Vm
1−
Vm

5
  !2 
b b a
P Vm = RT 1 + + + . . . −
Vm Vm T 2 Vm
 !2 
1 a b
 
= RT 1 + b− 3
+ + . . .
Vm RT Vm
Then the second virial coefficient is given by
a
B(T ) = b − =0
RT 3
when 1/3
a

T =
Rb
9. A certain gas obeys the equation of state
RT a
P = −
Vm − b (Vm + b)2

where a and b are numerical constants. Given the critical volume of the gas is Vc = 5b,
derive an expression for the compression factor at the critical point.
Answer: !
∂P RT 2a
=− 2
+
∂Vm T (Vm − b) (Vm + b)3
= 0 at
2a (Vm − b)2 2a (4b)2 4a
Tc = 3
= 3
=
(Vm + b) R (6b) R 27Rb
RTc a R 4a a a
Pc = − 2
= − 2
=
Vc − b (Vc + b) 4b 27Rb 36b 4(27)b2
Pc Vc a 5b(27Rb) 5
zc = = =
RTc 4(27)b2 R(4a) 16
10. A certain gas obeys the equation of state
RT A B
P = − 2+ 3
V V V
where A and B are positive constants. The critical volume is found to be Vc = 3B/A.
Derive an expression for the compression factor zc at the critical point thereby showing
zc to be independent of A and B.
Answer !
∂P RT 2A 3B
=− 2 + 3 − 4 =0
∂V T V V V

6
 at the critical point. Then
2A 3B
RTc = − 2
Vc Vc
or
A2 2 A2 A2
!
1
Tc = − =
R B 3B 3RB
RTc A B RA2 A A3 A3 A3
Pc = − 2+ 3 = − + =
Vc Vc Vc 3RB 3B 9B 2 27B 2 27B 2
Pc Vc A3 3B 3RB 1
zc = = 2 2
=
RTc 27B AR A 3
11. A certain gas obeys the equation of state
P Vm αP
=1+
RT 1 + αP
where α is a function of temperature only. Determine the fugacity of the gas as a
function of pressure.
Answer: (Z )
P z(P, T ) − 1
f = P exp dP
0 P
Now
αP
z(P, T ) = 1 +
1 + αP
Let Z P
z(P, T ) − 1 Z P
αP 1
I= dP = dP
0 P 0 1 + αP P
Z P
dP
=α
0 1 + αP

Let
1
y = 1 + αP dP = dy
α
Then Z (1+αP )
dy
I= = ln(1 + αP )
1 y
Then
f = P exp{ln(1 + αP )} = P (1 + αP ) = P + αP 2

12. Derive an expression for the fugacity of a gas that obeys the equation of state

P Vm (1 − bP ) = RT

7
 where b is a numerical constant. Determine the behavior of the fugacity as b → 0 and
as P → 0.
Answer: !
Z P
z−1
f = P exp dP
0 P
P Vm P Vm
z= (1 − bP ) = z(1 − bP ) = 1
RT RT
1 1 1 − 1 + bp bP
z= z−1= −1= =
1 − bP 1 − bP 1 − bP 1 − bP
Z P
z−1 Z P
dP
dP = b
0 P 0 1 − bP

dy
y = 1 − bP dy = −bdP dP = −
b
Z P
z−1 Z 1−bP
dy 1
dP = − = − ln(1 − bP ) = ln
0 P 1 y 1 − bP
P
f=
1 − bP
f
lim f = P lim =1
b→0 P →0 P

13. Use the virial expansion

P Vm = RT [1 + b(T )P + c(T )P 2 + d(T )P 3 + . . .]

to derive an expression for the fugacity coefficient γ of a gas in terms of the virial
coefficients. Use the result to find the value of γ in the limit that P → 0.
Answer:
P Vm
z= = 1 + b(T )P + c(T )P 2 + d(T )P 3 . . .
RT
Z P
z−1 Z P
dP = [b(T ) + c(T )P + d(T )P 2 + . . .]
0 P 0

c(T )P 2 d(T ) 3
= b(T )P + + P + ...
2 3
(Z )
P z −1
γ = exp dP
0 P
c(T )P 2 d(T ) 3
( )
= exp b(T )P + + P + ...
2 3
lim γ = e0 = 1
P →0