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CHM 346 Physical Chemistry II, Spring 2008

Problem Set 5 Solutions



Problems from Chapter 2 of Engel and Reid:

P2.2) 3.00 moles of a gas are compressed isothermally from 60.0 L to 20.0 L using a
constant external pressure of 5.00 atm. Calculate q, w, U, and H.

( )
5 3 3 4
4
5 1.013 10 Pa 60 10 L 20 10 L 2.03 10 J
0 and 0 because 0
2.03 10 J
external
w P V
U H T
q w

=
= =
= = =
= =



P2.3) A system consisting of 57.5 g of liquid water at 298 K is heated using an
immersion heater at a constant pressure of 1.00 bar. If a current of 1.50 A passes
through the 10.0 Ohm resistor for 150 s, what is the final temperature of the
water? The heat capacity for H
2
O can be found in the Data Tables in App. A.

( )
( )
2
, 2
,
,
2
-1 -1
-1
-1 -1
-1
;
57.5g
1.50A 10.0 Ohm 150 s + 75.291 J mol K 298 K
18.02 gmol
312 K
57.5 g
75.291 J mol K
18.02 gmol
P m i
P m f i f
P m
f
I Rt nC T
q I Rt nC T T T
nC
T
+
= = =

= =



P2.6) Calculate H and U for the transformation of one mole of an ideal gas from
27.0C and 1.00 atm to 327C and 17.0 atm if
-1 -1
,
20.9 0.042 in units of J K mol
K
P m
T
C = + .

( )
,
600
300
600 K
2
300K
3 3
3
20.9 0.42
K
20.9 600 K 300 K J 0.21 J
6.27 10 J 56.7 10 J
63.0 10 J
f
i
T
P m
T
K
K
H n C dT
T
dT
T
=


= +


= +

= +
=



( )
3 -1 1
3
63.0 10 J 8.314 J K mol 300 K
60.5 10 J
U H PV H nR T

= =
=
=

Errors in solution
0.021T
2

11.9 kJ
P2.8) In the adiabatic expansion of one mole of an ideal gas from an initial temperature
of 25C, the work done on the surroundings is 1200 J . If C
V,m
=3/2R, calculate q,
w, U, and H.

( )
,
,
,
-1 1
-1 -1
0 because the process is adiabatic
1200 J
1200 J 7.5 8.314 J mol K 298 K

1.5 8.314 J mol K
202 K
V m f i
V m i
f
V m
q
U w
U nC T T
U nC T
T
nC

=
= =
=
+
=
+
=

=

( ) ( ) ( )
( )
, ,
-1 1
3
2.5 8.314 J mol K 202 K 298 K
2.00 10 J
P m f i V m f i
H nC T T n C R T T

= = +
=
=



P2.11) 3.50 moles of an ideal gas is expanded from 450 K and an initial pressure of 5.00
bar to a final pressure of 1.00 bar. C
P,m
=5/2R. Calculate w for the following two
cases.
a) The expansion is isothermal and reversible.
b) The expansion is adiabatic and reversible.

Without resorting to equations, explain why the result to part b) is greater than (or
less than) the result to part a).

a)
-1 -1 3
ln ln
5.00 bar
3.50 mol 8.314J mol K 450 Kln 21.1 10J
1.00 bar
f
i
i f
V
P
w nRT nRT
V P
= =
= =


b) Because q =0, w =U. In order to calculate U, we first calculate T
f
.
1
1 1
1 1
5
1
3
5
3
; ;
5.00 bar
0.525
1.00 bar
0.525450 K 236 K
f f f f f
i i i
i i i f i f i f
f
i
f
T V T T T
P P P
T V T P T P T P
T
T
T



= = = =






= =


= =

( )
-1 -1
3
,
3 8.314 J mol K
3.50 mol 236 K 450 K 9.3410J
2
V m
w U nC T

= = = =
Less work is done on the surroundings in part b) because in the adiabatic expansion, the
temperature falls and therefore the final volume is less than that in part a).
P2.17) One mole of an ideal gas, for which C
V,m
=3/2 R , initially at 20.0C and 1.00 x
10
6
Pa undergoes a two stage transformation. For each of the stages described
below, calculate the final pressure, as well as q, w, U and H. Also calculate q,
w, U and H for the complete process.

a) The gas is expanded isothermally and reversibly until the volume doubles.
b) Beginning at the end of the first stage, the temperature is raised to 80.0C at
constant volume.

6 1 1 1
2
2
-1 -1 3 2
1
3
a) 0.500 10 Pa
2
ln 8.314 J mol K ln2 1.69 10 J
0 and 0 because 0
1.69 10 J
PV P
P
V
V
w nRT
V
U H T
q w
= = =
= = =
= = =
= =


( )
( )
6
5 1 2 2 1
2
1 2 1
-1 1
,
-1
, ,
353 K 0.500 10 Pa
b) ; 6.02 10 Pa
293 K
1.5 8.314 J mol K 353 K 293 K 748 J
0 because 0
748 J
3
8.314 J mol K
2
V m
P m V m
T T T P
P
P P T
U nC T
w V
q U
H nC T n C R T

= = = =
= = =
= =
= =
= = + = ( )
1
3
353 K 293 K
1.25 10 J


=


For the overall process,

3 3
3 3
3 3
1.69 10 J 748 J 2.44 10 J
1.69 10 J 0 1.69 10 J
0 748 J 748 J
0 1.25 10 J 1.25 10 J
q
w
U
H
= + =
= + =
= + =
= + =












P2.24) The heat capacity of solid lead oxide is given by
3 -1 -1
,
44.35 1.47 10 in units of J K mol
P m
T
C
K

= + .
Calculate the change in enthalpy of 1 mol of PbO(s) if it is cooled from 500 K to
300 K at constant pressure.

( )
,
300
3
500
300 K
2
3
500 K
3
44.35 1.47 10
K K
=44.35 300 K 500 K
1.47 10

2 K
8870 J 117 J
8.99 10 J
f
i
T
p m
T
H n C dT
T T
d
T

=

= +




+





=
=





P2.27) Calculate q, w, U and H if 1.00 mole of an ideal gas with C
V,m
=3/2R
undergoes a reversible adiabatic expansion from an initial volume V
i
=5.25 m
3
to
a final volume V
f
=25.5 m
3
. The initial temperature is 300 K.

q =0 because the process is adiabatic.

1
5
1
3
25.5
0.349
5.25
0.349300 K 105 K
f f
i i
f
i
f
T V
T V
T
L
T L
T


=



= =


= =


( )
( )
-1 -1
3
,
3 -1 -1
3
3 8.314 J mol K
1.00 mol 105 K 300 K 2.43 10J
2
2.4310 J +1.00 mol 8.314 J mol K 105 K 300 K
4.05 10 J
V n
U w nC T
H U nR T
H

= = = =
= + =
=









2. A sample consisting of 2.0 moles of an ideal gas, for which C
V,m
= R
2
5
, has an initial
pressure and temperature of 1.095 atm and 277 K, respectively. The sample is heated
in a reversible manner to 356 K at constant volume. Calculate the final pressure, U,
q, and w for the heating process.

Using the combined gas law, with V
1
=V
2
, we first find P
2
:

( )( )
( )
atm 1.407
K 277
K 356 atm 1.095
1
2 1
2
= = =
T
T P
P

The work equals 0 since there is no volume change.

The heat is found from C
V,m
:

( )( )( ) J T C dT C q
v v
10 3.28 K 79 mol 2.0 8.314 2.5
3
K mol
J
= = =



Finally, the change in internal energy is found:

J w q U 10 28 . 3
3
= + =




3. A sample of argon gas of mass 6.56 g occupies 18.5 L at 305 K.
a) Calculate the work done when the gas expands isothermally against a constant
external pressure of 57.8 torr until its volume has increased by 2.5 L.
b) Calculate the work that would be done if the same expansion occurred reversibly.
(This is similar to Problem 2.11)

a) For the isothermal expansion (units are converted to SI to give joules):

( ) J
J
V P w
ext
19
L atm 1
101.3
L 2.5
torr 760
atm 1
torr 57.8 =

= =

b) For the reversible expansion process:

( )( ) J ln
V
V
ln nRT w
K mol
J
i
f
2.8 5
L 18.5
L 21.0
K 305 314 . 8
39.95
Ar g 6.56
mol
g
=

=




4. Calculate the final pressure of a sample of water vapor that expands reversibly and
adiabatically from 87.3 torr and 500 mL to a final volume of 3.00 L. Take =1.3.


For the reversible adiabatic expansion:

( ) torr 8.50
L 3.00
L 0.500
torr 87.3
1.3
=

= =


f
i
i f i i f f
V
V
P P V P V P

5. A sample consisting of 1.50 mol of an ideal gas with C
p,m
=20.8
K mol
J

is initially at
2.27 atm and 315 K. It undergoes a reversible adiabatic expansion until its pressure
reaches 1.68 atm. Calculate the final volume and temperature of the sample and the
work done during the expansion.

For an ideal gas:

67 . 1
5 . 12
8 . 20
5 . 12
,
,
, , , ,
= = =
= = + =

K mol
J
K mol
J
m v
m p
K mol
J
m p m v m v m p
C
C
R C C R C C



First, we need to find the initial volume using the ideal gas law:

( )( )( )
( )
L 30 17
atm 7 2 . 2
K 5 31 314 . 8 mol 0 5 . 1
= = =
K mol
J
i
i
i
P
nRT
V

The final volume is found next:

( ) L 2070
atm 1.68
atm 2.27
L 1730
67 . 1
1
1
=

= =


f
i
i f i i f f
P
P
V V V P V P

The final temperature is also found from the ideal gas law:

( )( )
( )( )
K 9 27
8.314 mol 1.50
L 2070 atm 1.68
K mol
J
= = =

nR
V P
T
f f
f


Now the work done during the adiabatic expansion is found:

( )( ) J T C w
K mol
J
v
675 K 36 mol 1.50 5 . 12 = = =