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 (
