CHM 421 Assignment 1

August 16, 2015

Due on 24th August, 2014.

1. For a particular gaseous system it has been determined that the energy
is given by U = 2.5pV + constant. Consider the 3 states A (p = 0.2
MPa, V = 0.01 m3 ), B (p = 0.2 MPa, V = 0.03 m3 ) and C(p = 0.5
MPa, V = 0.01 m3 ). The system is taken through the cycle of the three
processes (A B, B C and C A). Calculate Q and W for each
of the three processes. Calculate Q and W for a process from A to B
along the parabola P = 105 + 109 (V 0.02)2 .
2. The energy of a particular system, of one mole, is given by U = Ap2 V
where A is a positive constant of dimensions [p]1 . Find the equation
of the adiabats in the p V plane.
3. Two moles of a particular single-component system are found to have
a dependence of internal energy U on pressure and volume given by
U = ApV 2 (for N = 2). Remembering that while U, V, N are extensive
p is intensive and A is a positive constant of dimensions [p]1 , write the
complete dependence of U on p, V and N for arbitrary mole number.
4. The fundamental equations of system A is
1

S = k (N V U ) 3
and similarly for system B (k is a constant). The two systems are
separated by a rigid, impermeable, adiabatic wall. System A has a
volume 9 106 m3 and mole number of 3 moles. System B has a
1

volume of 4 106 m3 and a mole number of 2 moles. The total energy

of the composite system is 80 J. Plot the entropy as a function of
UA /(UA + UB ). If the internal wall is now made diathermal and the
system is allowed to come to equilibrium, what are the internal energies
of each of the individual systems?
5. Two systems with equations of state given by:
1
T (1)

3 N (1)
= R (1)
2 U

5 N (2)
=
R
T (2)
2 U (2)
are separated by a diathermal wall. The respective mole numbers are
N (1) = 2 and N (2) = 3. The inital temperatures are T (1) = 250K and
T (2) = 350K. What are the values of U (1) and U (2) after equilibrium
has been established? What is the equilibrium temperatures?
1

6. Find the three equations of state (intensive variables for a system with
the fundamental equation
U =k

S3
NV

7. Show that the equations of state are homogenous zero order and hence
that T , P and are intensive parameters.
8. Show that if a single-component system is such that pV k is constant
in an adiabatic process (k is a positive constant) the energy is
U=

1
pV + N f (P V k /N k )
k1

where f is an arbitrary function.

9. A particular system obeys the two equations of state
T =

3As2
, thermal equation of state
v

As3
, mechanical equation of state
v2
where A is a constant.
p=

(a) Find the chemical equation of state (for ) and then find the
fundamental equation (for s).
(b) Find the fundamental equation of this system by direct integration
of the molar form of the equation.
10. Show that j , the electrochemical potential of the j th component in a
multicomponent simple idea gas, satisfies


Nj v0
+ g(T )
j = RT ln
V
and find the explicit form of the g(T ). Show that j can be expressed
in terms of the partial pressure and the temperature.
11. An impermeable, diathermal, and rigid partition divides a container
into two subvolumes, each of volume V . The subvolumes contain, respectively, 1 mole of H2 and 3 moles of Ne. The system is maintained
at constant temperature T . The partition is suddenly made permeable
to H2 but not Ne and equilibrium is allowed to reestablish. Find the
final mole numbers and the pressures.