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1. The internal energy of a perfect monotomic gas relative to its value at T = 0 is 23 nRT .
and U
for the gas.
Calculate H
P T
P T
3
U=
nRT ;
2
U
P
=0
by direct differentiation
5
3
nRT + nRT =
nRT
H = U + PV =
2
2
H
P
=0
T
by direct differentiation
CP
p
2. Express
Because
Thus,
H
P T
Cp
P
=
P
H
T
P
=
T
H
P
H
P T
T
CP
P
=0
T
d ln V = T dP + dT
T
P
1
=
CP
H
P
1
=
CP
V
T
+V
T P
b
CP
T
P H
< 0.
This equation indicates that when the pressure drops during the Joule-Thomson expansion,
P = P2 P1 < 0
the temperature must increase
T
P
and
T =
b
CP
b
P > 0
CP
5. At low pressure and 298 K, the experimental value of N2 for the Joule-Thomson coefficient, JT =
(T /P )H = 0.222K atm1 .
a. Derive the expression for the Joule-Thomson coefficient for a gas which obeys the van der Waals
equation of state
a
RT
2
P =
Vm b Vm
can be shown to be
JT =
2a
b
RT
1
Cp,m
ab
V2
a
ab
+ bP + 2
V
V
a
PV
is replaced by
a
,
RT
RT
a
+b
P
RT
a
R
V
= +
T P
P
RT 2
V =
from above
then
JT
R
V b
a
=
+
P
T
RT 2
V
2a
T
b
V =
T P
RT
V
2a
1
1
T
b
=
+V =
CP
T P
CP RT
then
b. At what temperature does the Joule-Thomson coefficient for N2 vanish? For N2 , a = 1.35
106 atm cm6 mol2 , b = 38.6 cm3 mol1 , and Cp,m = 29.125J mol1 K1
Set JT = 0 to find the inversion temperature:
T =
2a
2 1.35 106 atm cm6 mol2
= 852 K
=
Rb
(82.0578cm3 atm K1 mol1 ) (36cm3 mol1 )
JT > 0 below the inversion temperature, and JT < 0 above the inversion temperature.
c. Can N2 gas be cooled by a Joule-Thomson expansion if the temperature is higher than the
temperature calculated above? Explain in terms of the value given for JT .
In an expansion of a gas, the change in pressure is negative, P = P2 P1 < 0, because P2 is
less than P1 .
Using the equation for the Joule-Thomson expansion, the change in temperature is given by
T = P JT
If the temperature of the gas is less than the inversion temperature, (Tinversion < 852K, JT >
0), the temperature of the gas decreases during the expansion.
If the temperature of the gas is greater than the inversion temperature, (Tinversion > 852K, JT <
0), the temperature of the gas increases during the expansion.
Thus, for temperatures greater than 852 K, it is not possible to cool the N2 gas by a JouleThomson expansion
6. 2.00 moles of Kr gas at 300 K expands isothermally and reversibly from 20.0 L to 50.0 L. Calculate
q, w, U , and H. Assume ideal gas behavior.
U = 0 and H = 0 for an ideal gas
q = w
For this reversible process Pext = P , giving
Z
Z V2
P dV =
w=
V1
V2
V1
nRT
V2
dV = nRT ln
V
V1
V2
= 2.00 8.314 J mol1 K1 (300 K) ln
w = nRT ln
V1
50.0 L
20.0 L
= -4.57 kJ
q = w = 4.57 kJ
7. 2.00 moles of Kr gas at 20 L and 300 K expands adiabatically and reversibly to a final volume
of 80.0 L. Calculate q, w, U , and H. Assume ideal gas behavior.
First determine the final temperature using CV = 32 R:
CV
CV
T2 R V2 = T1 R V1
CV
T2 R (80.0 L) = (300 K)
3
CV
R
(20.0 L)
T2 = 119 K
q=0
U = w =
w = 2.00 mol
H =
119K
nCV dT = nCV T
300K
3
8.314 J mol1 K1 (119 K - 300 K) = -4.51 kJ
2
1299K
nCP dT = nCP T = 2
300K
5
8.314 J mol1 K1 (119 K - 300 K) = -7.52 kJ
2
nRT
.
V nb
a. Give the total differential for the equation of state of this gas with respect to volume.
V
V
dT +
dP
dV =
T P
P T
nRT
nR
dT
dP
dV =
P
P2
b. Solve for the change in volume as a function of state variables at constant pressure.
For constant pressure, dP = 0 and the second term in the exact differential vanishes.
Z T2
Z V2
nR
dV =
dT
P
T1
V1
(V2 V1 ) =
nR
(T2 T1 )
P
c. Obtain an expression from Part b for one mole of gas under the following conditions: P = 2.00
atm, T = 273 K, b = 0.115 L/mol.
Using this data, one can obtain a value of V1
V1 =
nRT
+ b = 11.2 L
P
Equation e
40
V
30
Equation c
20
10
0
273
373
473
T
573
U
T
dT + Pext +
V
U
V
dV
at constant pressure
dqP = CV dT + Pext +
U
V
dV
dqP
dT
= CP , we obtaine
V
U
CP CV = P +
V T
T P
The above equation takes on a simple form for an ideal gas because
Then
CP CV = nR
U
V T
= 0 and
V
T
nR
.
P