Practice Problems 1

Thermodynamics & Statistical mechanics

1. Starting with the first law of thermodynamics and the definitions of Cp and Cv ,
(a) show that
h
 U  i V 
Cp Cv = P +
V T T P
where CP and Cv are specific heat capacities per mole at constant pressure and volume, respectively, and U and
V are energy and volume of one mole.
(b) Use above result to find Cp Cv for a van der Waals gas

a 
P + 2 (V b) = RT
V
Use that result to show that as V , at constant P , you obtain the ideal gas result for Cp Cv .
2. One mole of gas obeys Van der Waals equation of state. If its molar internal energy is given by u = cT a/V (in which
V is the molar volume, a is the one of the constant in the equation of state, and c is a constant), calculate molar heat
capacities Cv and Cp .
3. Two system with heat capacities C1 and C2 , respectively, interact thermally and come to a common temperature Tf .
If the initial temperature of the system 1 was T1 , what was the initial temperature of the system 2 ?. You may assume
that the total energy of the combined systems remains constant.
4. An ideal monoatomic gas, for which = 5/3 undergoes a quasi static expansion to one third of the initial pressure.
Find the ratio of the final volume to the initial volume if the process is (a) isothermal; (b) adiabatic.
5. Show that Cp Cv = T V
tively.

2
,

where and are coefficient of volume expansion and isothermal compressibility respec-

6. The equation of state of an ideal gas is P V = nRT , where n and R are constants.
(a) Show that the volume expansivity is equal to 1/T .
(b) Show that the isothermal compressibility is equal to 1/P .
7. What is the temperature on the Fahrenheit scale of the normal boiling point of H2 O, if this temperature is 99.974 C ?
8. Calculate the work done upon expansion of 1 mole of gas quasi-statically and isothermally from volume vi to a volume
vf , when the equation of state is

a
p + 2 (v b) = RT
v
where a and b are the van der Waals constants.
9. (a) Show that for an elastic hard sphere gas, obeying the equation of state P (V b) = nRT , undergoing a transition
from state 1 to 2 at constant temperature
q = w = nRT ln

(V2 b)
(V1 b)

(b) Show that for an elastic hard-sphere gas

Cp Cv = nR
10. An ideal gas is changed from a state (P1 , V1 , T1 ) to a state (P2 , V2 , T2 ) by a quasi-static adiabatic process. Show that, if
the heat equivalent of the work done by the gas in this process is added to the gas in the final state while maintaining
the volume constant, the temperature will return to T1 .
Answers:
1. (b). Cp Cv =

R
12a(1b/V )2 /V RT

2. Cv = c, Cp = c +
3. T2 =

C1
C2 (Tf

R
1

2a(V b)2
RT V 3

T1 ) + Tf

4. (a) = 3, (b) = 1.9

5. 6. 7. 211.95
8. RT ln[(V2 b)/(V1 b)] a(1/V2 1/V1 )