Chemistry 5350

Advanced Physical Chemistry

Fall Semester 2013

The Properties of Gases-Chapter 7

Problems on Thermochemistry October 3, 2013

1. One mole of Ar, initially at 298 K, undergoes an adiabatic expansion against a pressure of Pexternal = 0
from an intial volume at 20.0 L to a final volume at 65.0 L.
Calculate the final temperature using the ideal gas and van der Waals equations of state.
The Pexternal = 0 and w = 0. It is an adiabatic expansion, and q = 0.

∆U = q + w = 0

Z   Z  
∂U ∂U
∆U = 0 = dT + dV
T ∂T V V ∂V T
and Z   Z  
∂U ∂U
dT = − dV
T ∂T V V ∂V T

Ideal Gas
Z 
∂U✘✘✘✘ ✘0
✿ Z 
CV dT = − ✘✘✘ dV = 0
T ✘✘V ∂V T
∂U



∂V T
= 0 for an ideal gas, and ∂U
∂T V
= CV .

CV (T2 − T1 ) = 0 and T2 = T1

∆T = 0, because ∆U is a function of T only.

van der Waals Gas
Z Z  
∂U
CV dT = − dV
T V ∂V T
RT a
P = − 2
Vm − b Vm
   
∂U ∂P a
=T −P = 2
∂V T ∂T V Vm
 
1 1
CV,m ∆T = a −
Vm,f V
| {z m,i }
∆UT,m

 
5 −2 105 Pa 1 x 10−6 m3 1 1
∆UT,m = 1.355 dm bar mol × × × −
1 bar dm6 65.0 x 10−3 x m2 x mol−1 20.0 x 10−3 x m2 x mol−1

∆UT,m = -4.69 J mol−1

UT,m -4.69 J mol−1
∆T = Tf − 298 K = = = -0.376 K Tf = 297.6 K
CV,m 12.5 J K−1 mol−1
2. One mole of Ar undergoes an isothermal reversible expansion from an initial volume of 1.00 L to a
final volume of 65.0 L at 298 K.
Calculate the work done in this process using the ideal gas and van der Waals equations of state.

Ideal Gas
Vf 65.0 L
w = −nRT ln = - 1 mol x 8.314 J mol−1 K−1 x 298 K × ln = -10.34 kJ
Vi 1.00 L

van der Waals Gas

ZVf     Vf
nRT n2 a n2 a
w=− − 2 dV = − nRT ln(V − nb) +
V − nb V V Vi
Vi
 0.065 m3
−1 −1 −5 3 0.1355 Pa m6
w = - 1 mol x 8.314 J mol K x 298 K × ln(V − 3.20 x 10 m )+
V 0.001 m3
w = -10.41 kJ
What percentage of the work done by the van der Waals gas arises from the attractive potential?
133 J
100 × = 1.3%
10.41 x 103 J
3. Another equation of state used for the description of gases is the Berthlot equation:
RT a
Vm = +b−
P RT 2
Derive expressions for    
1 ∂V 1 ∂V
β= and κ=−
V ∂T P V ∂P T
for the Berthelot equation in terms of V, T and P .
     
1 ∂V 1 nR 2na 1 R 2a
β= = + = +
V ∂T P V P RT 3 Vm P RT 3
   
1 ∂V 1 nRT nRT RT
κ=− =− − 2 = 2 = 2
V ∂P T V P P V P Vm
Find an expression of the Boyle temperature in terms of a, b and R.
For many purposes, it is convenient to use P as the independent variable, and write the virial equation
as
P Vm
z= = 1 + B′P + C ′P 2 + · · ·
RT

P Vm Pb Pa
z= =1+ + 2 3
RT RT R T
∂z


At the Boyle temperature (T = TB ), ∂P T
= 0, and therefore,
 
∂z b a
= − 2 3 =0
∂P T RT R T

which yields r
a
TB =
Rb
4. Show that the second virial coefficient for a van der Waals equation is given by
a
B(T ) = b −
RT

The van der Waals equation is given by

RT a
P = − 2
Vm − b Vm
Vm
Multiplying the above equation by RT
,

P Vm Vm a
= −
RT Vm − b RT Vm
and
P Vm 1 a
= b
−
RT 1 − Vm RT Vm
b 1 1
Since Vm
<< V , the term 1− Vb
can be expanded in a series of Vm
, and the above equation becomes
m

 
P Vm b b2 a 1
=1+ + 2 + ··· −
RT Vm Vm RT Vm

P Vm  a  1 b2
=1+ b− × + 2 + ···
RT RT Vm Vm
1
Comparing the Vm
term with the virial expansion, we see that
a
B(T ) = b −
RT