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1. One mole of nitrogen gas is allowed to expand from 0.5 to 10 L (reversible and isothermal process at 300 K). Calculate the change in
molar entropy using (a) the ideal gas law and (b) the van der Waals
equation with a = 1.408 atm L2 mol2 , b = 0.03913 L mol1 .
Solution:
a) Use the following equation from the lecture notes:
S = nR ln
V2
V1
= 8.314 J K1 mol1 ln
10 L
0.5 L
= 24.91 J K1 mol1
b) Start with the following equation (see lecture notes):
S
V
=
T
P
T
S
V
nR
S =
=
V nb
ZV2
P
T
=
V
nR
V nb
nR
dV = nR ln
V nb
V2 nb
V1 nb
V1
or S = R ln
V2 b
V1 b
S = 8.314 J K1 mol1
2. Derive the relation for CP CV for a gas that follows the van der Waals
equation.
Solution:
Based on the lecture notes we have:
1
T V 2
with =
CP CV =
V
1 V
and =
T P
V P T
And the van der Waals equation can be written in the following forms:
RT
a
1
P =
2 or T =
R
V b V
ab
a
P V P b + 2
V
V
Next and must be calculated. Since the van der Waals equation of
state cannot be written for the molar volume easily, one must use the
reciprocal identity:
V
1
=
T P
T / V P
= V
T
V
= V
P
a
2ab
P
2 + 3
R RV
RV
a
2ab
P V
+ 2
R
RV
RV
2a
2a
V T
2ab
V T
+ 2 =
2 V b
1 =
V b RV
V b RV
RV
1
= V T
2a 2 V b
V b
Next we calculate :
RV
= V
P
V
V RT
2a
2 2
V
V b
R
2
2a (V b)
RT
V 3
S
P
=
T
V
T
= V S V P
P
78.11 g mol1 2
1.237 103 K1 999 105 Pa
10 m cm1
3
0.879 g cm
= 10.99 J K1 mol1
4. Derive the expression for (U/V )T (the internal pressure) for a gas
following the virial equation with Z = 1 + B/V . Consider only P V work and a reversible process. Note that B = B(T ) (i.e. it depends on
temperature).
Solution:
Recall the first law of thermodynamics: dU = dq + dw. For P V work dw = P dV and by the second law: dq = T dS. Thus: dU =
T dS P dV and dividing both sides by dV and imposing constant
temperature:
U
V
=T
T
S
V
P =T
T
P
T
P
T
R BR
= + 2 +
V
V
B
T
RT
V 2
U
V
=T
T
R BR
+ 2 +
V
V
B
T
RT
RT 2
RT BRT
B
T V V 2
V 2
V
V 2
T
T
ZT2
T1
H
dT =
T2
G
Z2 /T2
d (G/T )
G1 /T1
1
1
= G2 /T2 G1 /T1
T2 T1
T2 T2
+ G1 T2 /T1
G2 = H
T2 T1
d (G/T ) =
T1
G1 /T1
G2 G1
= H1
T2
T1
ZT2
H1
dT CP
T2
ZT2
T T1
dT
T2
T1
T2
1
1
1
1
CP ln
CP T1
T2 T1
T1
T2 T1
G1 T2
T2
T2
G2 =
CP T2 ln
+ T1 T2
+H1 1
T1
T1
T1
G2 = RT ln
P2
P1
= (8.314 J K
0.1 bar
1 bar
= 5.708 kJ mol1
b) Gibbs energy is a state function and depends only on the endpoints. Thus the answer is the same as in a).
w = RT ln
P2
P1
= (8.314 J K
mol )(373.15 K) ln
1
10 bar
2 bar
10 bar
2 bar
P2
P1
= (8.314 J K
mol )(373.15 K) ln
1
= 4993 J mol1
6
9. Toluene (molecular weight 92.13 g mol1 ) is vaporized at constant external pressure and its boiling point, 111 C (constant temperature).
The heat of vaporization at this temperature is 361.9 J g1 . For the
vaporization of toluene, calculate (a) w per mole, (b) q per mole, (c)
(d) U , (e) G,
and (f) S.
In part (a) assume that the volume
H,
of the liquid is negligible and that toluene vapor behaves according to
the ideal gas law (this assumption is not needed elsewhere). Note also
that evaporation at the boiling point is a reversible process.
Solution:
a) w = P V = P (Vf in Vinit ) = (RT 0) = (8.314 J K1 mol1 )
(384 K) = 3193 J mol1 . The final volume was obtained from
the ideal gas law (P V = nRT ).
= (361.9 J g1 )
b) and c) For vaporization process we have q = H
(92.13 g mol1 ) = 33.340 kJ mol1 .
d) U = q+w = (33340 J mol1 )+(3193 J mol1 ) = 30.147 kJ mol1 .
Note that if ideal gas behavior was assumed here, U would have
been zero as it would depend only on temperature.
e) and f) G = U + P V T S and hence G = U + V P + P V T S
ST . At constant temperature and pressure P = T = 0
and therefore G = U + P V T S. From part a) P V =
3193 J mol1 and we need to calculate S. S = qrev /T =
(33.340 kJ mol1 )/(384 K) = 86.8 J K1 mol1 . And finally G =
0 by combining all the required terms.
10. Calculate mix G and mix S for the formation of a quantity of air
containing 1 mol of gas by mixing nitrogen and oxygen at 298.15 K.
Air may be taken to be 80% nitrogen and 20% oxygen (in mol %).
Assume ideal gas behavior.
Solution:
In the lecture notes, the following realtions were given:
mix G = RT (n1 ln(y1 ) + n2 ln(y2 ))
mix S = R (n1 ln(y1 ) + n2 ln(y2 ))
mix H = mix V = 0
n1 = 0.80 mol of N2 (y1 = 0.80) and n2 = 0.20 mol of O2 (y2 = 0.20).
By inserting the values in above equations, we get: mix G = 1239 J
mol1 and mix S = 4.159 J K1 mol1 .