CHM 346 Physical Chemistry II, Spring 2008

Problem Set 6 Solutions

Problems from Chapter 3 of Engel and Reid:


P3.3) This problem will give you practice in using the cyclic rule. Use the ideal gas law
to obtain the three functions ( ) ( ) , , ( , ), and , . P f V T V g P T T h P V = = = Show
that the cyclic rule 1
T P V
P V T
V T P


=



is obeyed.

2
2
; ;
; ;
1
T P V
T P V
nRT nRT PV
P V T
V P nR
P nRT V nR T V
V V T P P nR
P V T nRT nR V nRT
V T P V P nR PV
= = =


= = =





= = =








P3.7) Because V is a state function, .
P T
T P
V V
P T T P

=




Using this
relationship, show that the isothermal compressibility and isobaric expansion
coefficient are related by .
T P
P T

=





[ ] [ ]
1 1
Because and
or
P T
T P
P T
T P
T P
V V
P T T P
V V
V T V P
V V
P T P T





=






= =





= =















P3.9) The molar heat capacity C
P,m
of SO
2
(g) is described by the following equation
over the range 300 K < 1700 K.

2 3
, 3 7 9
2 3
3.093 6.967 10 45.81 10 1.035 10
K K K
P m
C
T T T
R

= + +
In this equation, T is the absolute temperature in Kelvin. The ratios
K
n
n
T
ensure
that C
P,m
has the correct dimension. Assuming ideal gas behavior, calculate q, w,
U, and H if 1 mol of SO
2
(g) is heated from 75 to 1350C at a constant
pressure of 1 bar. Explain the sign of w.

2
3 7
1623.15
2
1 1
,
3
9 348.15
3
1623
2 3 4
1 6 10
2 3 4
348.15
3.093 6.967 10 45.81 10
K K
8.314 J mol K
K
1.035 10
K
1 mol 8.314 J mol 3.093 0.0034835 1.527 10 2.5875 10
K K K K
f
i
T
P m
T
T T
T
H q n C dT d
T
T T T T

+

= = =

+



= + +



.15
4 1 4 1 4 1
4 1 1
4
1 mol 3.279 10 J mol 7.279 10 J mol 5.375 10 J mol
1.490 10 J mol K
6.67 10 J


+
=


+

=

( )
( )
4 1 1
4
6.67310 J 1 mol 8.314J mol K 1623.15 K 348.15 K
= 5.6110 J
U H PV H nR T

= =
=
4 4 4
5.613 10 J 6.673 10 J 1.06 10 J w U q = = =

Because the gas is heated, it expands. Therefore V > 0 and w < 0.


(3.10 on next page)
P3.13) Equation (3.38),
2
P V
C C TV

= + , links C
P
and C
V
with and . Use this
equation to evaluate C
P
C
V
for an ideal gas.

2
2
2 2 2
2
1 1 1 1
;
1
P T
P V
V nR V nRT
V T V P V P VP P
nR n R
C C TV TV P TV nR
V P V P

= = = = =




= = = =







P3.10) Starting with the van der Waals equation of state, find an expression for the total
differential dP in terms of dV and dT. By calculating the mixed partial derivatives
V
and ,
T V
T
P P
T V V T





determine if dP is an exact differential.

( )
( )
( )
( )
2 2 3
2
2 3
2
2
m m m
m T
m m m
V
m m
m
RT a a RT
V V b V V
V b
RT a R
T V b V V b
a RT R
dP dV dT
V V b
V b

=






=





= +

( ) ( )
( )
( )
2 2 3
V
V
2
2
=

T m
m m
V m
T m
T
P a RT R
T V T V
V b V b
P R R
V T V V b
V b



=








= =








Therefore, dP is an exact differential.




P3.15) An 80.0-g piece of gold at 650 K is dropped into 100.0 g of H
2
O(l) at 298 K in an
insulated container at 1 bar pressure. Calculate the temperature of the system
once equilibrium has been reached. Assume that C
P,m
for Au and H
2
O is constant
at their values for 298 K throughout the temperature range of interest.

( ) ( )
2 2
2
2 2
2
2
2
, ,
, ,
, ,
1 1 1 1
2
1 1
2
0
80.0 g Au 100.0 g H O
25.42 J K mol 650 K 75.291 J K mol 298 K
196.97 g Au mol 18.02 g H Omol
80.0 g Au
196.9
H O H O Au Au
Au P m f i H O P m f i
H O H O Au Au
Au P m i H O P m i
f H O Au
Au P m H O P m
n C T T n C T T
n C T n C T
T
n C n C


+ =
+
=
+
+
=
1 1 1 1 2
1 1
2
100.0 g H O
25.42 J K mol 75.291 J K mol
7 g Au mol 18.02 g H Omol
306 K
f
T


+
=





P3.18) Calculate w, q, H, and U for the process in which 1 mol of water undergoes the
transition H
2
O(l, 373 K) H
2
O(g, 460 K) at 1 bar pressure. The volume of liquid
water at 373 K is 1.89 10
5
m
3
mol
1
and the volume of steam at 373 and 460 K
is 3.03 and 3.74 10
2
m
3
mol
1
, respectively. For steam, C
P,m
can be considered
constant over the temperature interval of interest at 33.58 J mol
1
K
1
.

( )
( ) ( )
,
1 1 4
5 2 3 5 3 5 2 3 2 3
3
40656 J 1mol 33.58 J mol K 460 K 373 K 4.35 10 J
10 Pa 3.03 10 m 1.89 10 m 10 Pa 3.74 10 m 3.03 10 m
3028 J 710 J 3.74 10 J
steam
vaporization P m
external
q H n H nC T
w P V


= = +
= + =
= =
= =

4 4
4.35 10 J 3738 J 3.98 10 J U w q = + = =

P3.19) Because ,
P J T
T
H
C
P



=

the change in enthalpy of a gas expanded at constant
temperature can be calculated. In order to do so, the functional dependence of
J T

on P must be known. Treating Ar as a van der Waals gas, calculate H when
1 mol of Ar is expanded from 400 bar to 1.00 bar at 300 K. Assume that
J T

is
independent of pressure and is given by
2
J T
a
b
RT

=


/C
P,m
= 5/2R for Ar.
What value would H have if the gas exhibited ideal gas behavior?

( )
( )
, ,
6 2
3 3 1 5 5
, 1 1
,
3
1 2 0.1355 m Pa mol
0.03201 10 m mol 1.00 10 Pa 400 10 Pa
8.314 J mol K 300 K
3.06 10 J
f
i
P
m P m J T P m J T f i
P
P m
P m
H C dP C P P
C x
C

=

=

For an ideal gas, H

m
= 0 because
J T

is zero for an ideal gas.

P3.21) The Joule coefficient is defined as
1
U V V
T P
P T
V C T


=




. Calculate the
Joule coefficient for an ideal gas and for a van der Waals gas.

For an ideal gas

( )
, ,
2 2
, ,
1 1
0
For a van der Waals gas
1 1 1
U V V m V m
U V m m m V m m V m
V
T nRT nRT
P T P
V C T V C V
T RT a RT a
P T P
V C T V b V C V b C V


= = =








= = =