Statistical Molecular

Thermodynamics
Christopher J. Cramer
Video 3.4
Ideal Gas Equation of State Redux

Monatomic Ideal Gas Heat Capacity

The molar heat capacity of a substance expresses the energy
required to raise the temperature of 1 mole of that substance
by 1 K.

Thus, multiplication of the molar heat capacity by a measured

temperature rise will provide the amount of energy that was
supplied to the system to induce that temperature increase.

Monatomic Ideal Gas Heat Capacity

The change in energy associated with a change in temperature
(the molar heat capacity) can be expressed as a derivative; in
particular, at constant volume,

U
C V =
T V
From our prior work, however, we have

U E ( 3 RT)
3
2

=
=
= R

T V T T V 2
V
Statistical thermodynamics can be used to understand where
the energy goes when a system is heated (and why the
capacity to store energy is different for different substances).

Further Manipulation of Q
Q( N,V,) = e

More differential calculus:

lnQ 1
=
Q
Q
So,

E j ( N ,V )

E j ( N,V ) E ( N ,V )
Q
=
e j
V N ,
V

E j ( N,V )
lnQ
E j ( N,V ) E j ( N ,V )
=
=

e
p j ( N,V,)

V N ,
Q j V
V

j
or:

E j ( N,V )
lnQ
V p j (N,V,) = kBT V

N ,
j

Pressure As an Ensemble Average

E j
lnQ
V p j (N,V,) = kBT V
N ,
j

E
P =
V N

Later, we will prove:

If pressure is like energy, i.e., an average over weighted

ensembles, then,

P = P j ( N,V ) p j ( N,V,)
j

E j
lnQ
=

p j ( N,V,) = k BT
V N ,
V N
j

Pressure of a Monatomic Ideal Gas

lnQ
P = kBT

V N ,
Again,

And,

q(V,)]
[
Q(N,V,) =
N!

2m 2
q(V,) = 2 V
h

lnQ = N lnq ln N!
3

= N (ln2m ln h 2
ln) + N lnV ln N!
2
lnQ
N
kBT
= k BT = P
V N ,
V
observed

When N = NA,

RT
=P
V

The Ideal Gas

Equation of State!

The Big Picture, So far

The par((on func(on encompasses all possible states of an
ensemble
Thermodynamic func(ons can be computed from the par((on
func(on (the central one is internal energy)
For simple par((on func(ons, the relevant calcula(ons are
straigh>orward and give results that agree with, and ra(onalize,
both classical thermodynamics and experiment
We have yet to derive the ideal monatomic gas par((on func(on,
but the one presented is consistent with the ideal gas equa(on of
state