Capitulo 3:

3.31 Evaluate

for a Dieterici gas (Table 1.7). Justify physically the form of

the expression obtained.

Resolution :

=T(

P
T
V

an

For a Dieterici gas P=

T(

P
T
V

Hence
t=

nRT RTV
e
V nb

an
nRT
RTV
V nb . e

=( P +

nRT
na
V nb . RTV .

an
RTV

=P+

na
RTV .P

na
RTV .P ) P

na
RTV .P

t 0 as p0 , V , a0 and T . The fact that

T >0

(because a>0) is consistent with a representing attractive contributions,

since it implies that

U
V )t>0 and the internal energy rises as the gas

expands ( so decreasing the average attractive interactions )

, is defined like (eqn 2.43) but at

constant entropy. Show that for a perfect gas p 1 (where
is the ratio of
3.32 The adiabatic compressibility,

heat capacities).

Resolution:

S is defined as

S=

1
V

.(

V
p
S

p
V

V
1

=-

The only constant-entropy changes of state for a perfect gas are reversible
adiabatic changes, for which :

PV =const .

Then

Therefore

=S

p k s

Hence

const .
)
V
V

= -

1
P
V(
)
V

=+

p
V

+1

.(constant)

P
V

1
p

= +1

3.33 Suppose that S is regarded as a function of p and T. Show that

TdS CpdT

TVdp. Hence, show that the energy transferred as heat when

the pressure on an incompressible liquid or solid is increased by

to

TV

p is equal

p. Evaluate q when the pressure acting on 100 cm of mercury at

0C is increased by 1.0 kbar. (

1.82

Resolution:
If S(T,p) = S

Then

S
S

T
dS = (
( P dp
T
p dT +

S
S
T
TdS = T(
( P dp
T
p dT +T

104

1/K.)

S
Use ( T
P

S
H
= ( H . ( T
P
P

1
T

Cp

S
V

P
Using the Maxwell relation (
= - ( T
T
p

Hence TdS = T .

1
T

C p dT T

V
( T dp =
p

For reversible isothermal compression

dq rev = -

TdS =

C p dT

dq rev

TV dp

and dT = 0

TV dp

pf

q rev= TV dp
pi

TV ( P) ( V assumed constant

=-

For mercury

q rev

= (-

1.82

104

1/K). (273 K). (1,00.

m3 ).(1,0. 108 Pa

104 .

= -0.50

KJ

3.34 Suppose that (a) the attractive interactions between gas particles can be

neglected, (b) the attractive interaction is dominant in a van der Waals gas, and
the pressure is low enough to make the approximation 4ap/(RT)2 1. Find
expressions for the fugacity of a van der Waals gas in terms of the pressure
and estimate its value for ammonia at 10.00 atm and 298.15 K in each case.

Resolution:
p

The starting point for the calculation is ln =

Z1
p
0

dp

To evaluate the integral we need an analytical expression for Z, which can be

obtained from equation state
a) We saw in section 1,4 that the Van der Waals coefficient a represents the
attractions between molecules, so it may be set ecual to zero in this
calculation. When we neglect a in the Van der Waals equation,that equation
becomes:
P=

RT
V mb

after several calculations

The integral we require is therefore

Z=1+

bp
RT

Z1
dp =
p
0

ln =

b
RT
0

dp =

Consecuently, from this equation and

bp
RT
=

f
p

when f is the fugacity at

the pressure p is

f=p e

bp
RT

,.
2

For ammonia b= 3,71. 10

dm/mol and so

bp
RT

2
= 1,516. 10 ,

giving

f = (10,00 atm).

e 0.01516 = 10.2 atm

b) When we neglect b in the Van der Waals we have

P=

RT
Vm

a
V m

And hence Z= 1-

a
V m RT
p

Then substituting in this equation we get ln

Z1
p
0

dp =

pVaRT
0

dp

In order to perform this integration we must eliminate the variable

Vm

by

solving fot it in term of p. Rewriting the expression for p in the form of a

quadratic we have

V m

RT
P

a
P

Vm +

=0

The solution is

Vm =

1
2

RT
P

1
( RT )24 ap

1
( RT )2 ) =

Applying the aproximation

( RT )2 >> 4 ap
Vm =

1
2

RT
P

1
2

RT
P

RT
P

Choosing the + sign we get

Vm

RT
P

which is the perfect-gas volume

Then
p

ln =

a
RT
RT
p dp = p

ap
( RT )

For ammonia a = 4.169 atm dm/mol

ap
(RT )

=-

ln

ln(

f
p

4.169 atm

dm
.(10.00 atm)
2
mol

d m3 atm
( 0.08206
.298.15 K )
K mol

= - 0.06965

) = - 0.06965

0.06965
f = (10.00 atm) e

f = 9.327 atm

3.35 Find an expression for the fugacity coefficient of a gas that obeys the

equation of state

pVm RT(1 B/Vm C/Vm). Use the resulting expression to

estimate the fugacity of argon at 1.00 atm and 100 K using B 21.13

mol
Resolution:
p

Z1
p

ln =

Z= 1 +

B
Vm

With B =

Z1
p

+
B
RT

dp

C
V m

= 1 + BP + CP +

and C =

B + Cp +

CB
( RT )

cm /mol

and C 1054

cm /

B
( '+C p+)

Therefore ln =

dp =

Bp +

C p
+=
2

B
RT p +

CB
( RT )

p
2

For argn
BP
RT =

CB
p
.
2
( RT )

6.05.

103 d m3
.(1.00 atm)
mol

)
( 8.206. 10mold m ) .(273 K)

21,13.

4
= -9.43 . 10

103 d m 6
103 d m3
(2
1.13
.
)
mol
mol 2

1.054 .

102 d m 3
2. 8.206.
(273 K )
mol

. (1.00 atm)

10

Therefore ln

= (-9.43

. 10

) + (6.05. 10

) = -9,42.

Hence f = (1,00 atm). (0.9991) = 0.9991 atm

Capitulo 5:

5.31 The osmotic coefficient is defined as

(xA/xB) ln aA. By writing r xB/xA,

and using the GibbsDuhem equation, show that we can calculate the activity
of B from the activities of A over a composition range by using the formula

aB
r )=

(0)

1
r
() dr
r

Resolution:

10

0.9991

ln (