Monatomic Gases

John W Daily
 Monatomic Gases
• For monatomic gases we will need the
translational and electronic partition
functions, as those are the two modes of
energy storage available.
 The Translational Partition
Function
To evaluate qtr we need the energy:
2 2 2
2 (
h *" n x % " ny % " nz % ,*
ε tr = )$ ' + $ ' + $ ' -
8m *# lx & # ly & # lz & *
+ .

If the motions in the three coordinate directions are

independent, then
2
β h 2 nx 2 β h 2 ny β h 2 nz
2
− − −
8 m lx 2 8 m ly 2 8 m lz 2
qtr = qx qy qz = ∑ e ∑e ∑e
nx ny nz
The Continuum Approximation
Because we are dealing with such large quantum numbers
we can approximate the sum in the partition function with
an integral:
β h 2 nx 2 ∞ β h 2 nx 2
− −
8 m lx 2 8 m lx 2
qx = ∑ e ≅ ∫e dnx
nx 0

1/2
If we let " βh % 2
nx
x=$
# 8m '& lx

1/2 ∞
# 8m & − x2
Then qx ≅ % 2 ( lx ∫ e dx
$ βh ' 0
 The definite integral has the value π /2

So that
3/2
" 2π mkT %
qtr = $ V
# h 2 '&

where V = lx lylz

This will be the only place where the volume appears

and is due to the dependency of translational quantum
states on the volume.
 Translational Degeneracy
Recall that the translational states are degenerate.
Therefore, if we are interested in energy rather, than state,
we need to account for the degeneracy.

If we define f (ε )dε as the fraction of particles in the

interval e to e + de , and dg as the degeneracy for the
energy increment de, then

e− βε k
f (ε )dε = − βε k
dg
∑e
k
 To relate de to dg first consider that

2
h 2
ε= n
8mV 2 / 3

where n is the total translational quantum number equal to

n = nx2 + ny2 + nz2

Therefore, n is the radius of a one-eighth sphere in the
positive octant of translational quantum number space.
All states on the surface of the sphere have the same
energy. Therefore, each state with energy between e +
de occupies the one-eighth spherical shell between n
and n + dn. The volume of this shell is

2
4π n dn
dg =
8
Differentiating e with respect to n and substituting we get:
 2ε 1/2 − ε / kT
f (ε ) = 1/2 e
π (kT )3/2

mc 2
Since ε = dε = mcdc
2
(where c is the molecular translational speed)

And we must have f (ε )dε = f (c)dc

1/2 3/2
" 2% " m% 2 − mc 2 /2 kT
f (c) = $ ' $# '& ce
#π& kT

Maxwellian Speed Distribution

 Speed Distribution
0.001
4
9.856 .10

F(c) 4
f( c ) 5 .10

0 0
0 200 400 600 800 1000
0 c 3
1 .10

∞ 1/2
$ 8kT '
Average speed c = ∫ cf (c)dc = & )(
0
% π m
The Electronic Partition Function
• Electronic motion is degenerate, thus the
partition function becomes:
− βε k
qe = ∑ gk e
k

• Sum is over energy states rather than

quantum states
 The Boltzmann Ratio
Recall that N k = e− γ e− βε k

and since N = e− γ ∑ e− βε k
k

the probability of finding a particle in a given state is thus

Nk e− βε k
=
N ∑ e− βε k
k

This is called the Boltzmann ratio.

 Population of Electronic States
• For Nitrogen, e1 = 19,227 cm-1, and g0 and
g1 = 4 and 10 respectively. If the
temperature is 300 K, then
19227hc
−
N1 g1e− ε1 / kT 10e kT
= = 1.67x10 −40
N 0 g0 e− ε 0 / kT 4

This is a pretty small number!

• Thus we can ignore electronic energies
above the ground state, then

qe = ge

• Otherwise we just have to perform the sum.

• Thus the fundamental relation becomes (ignoring excited electronic
states:

µ 3/2
" 1 −µ % − ) 2π mkT ,
S$ , ' = ke kT
+* . Vge
#T T & h2 -

• Recall
" 1 −µ % 1 P µ
dS $ , ' = −Ud + dV + Nd
#T T & T T T

• And the Euler relation:

r
1 P µi
S = U + V − ∑ Ni
T T i =1 T
Equations of State
# 1 −µ &
−∂S % ,
$ T T (' 3 # 1 − µ & 3 3
U= = TS % , ( = PV = NkT
1 2 $ T T ' 2 2
∂
T

# 1 −µ &
∂S % ,
P $ T T (' 1 # 1 − µ & P
= = S% , ( =
T ∂V V $T T ' T

# 1 −µ &
∂S % ,
$ T T (' 1 # 1 − µ & PV
N= = S% , ( =
−µ k $ T T ' kT
∂
T
• The average energy per atom is:
U 3
u = = kT
N 2

• The entropy is
" 1 −µ % 1 µ ( 1 µ+ (5 µ +
S = S$ , ' + U − N = k )N + U − N , = k ) − ,
# T T & T T * T T - * 2 kT -

• Specific heat
∂u " 3
cv = $# = k
∂T V 2
 Useful Energy Units
• Electron volt - Energy to move an electron
through a potential of one volt
– 1 ev = 1.602 x 10-19 J
• Inverse centimeter - Energy of photon
– E = hv = hc/l, l’ = 1/l, l’ =E/hc
– 1 ev = 8066 cm-1
• Temperature - kT
– 1 ev = 11,600 K

1 ev = 8066 cm-1 = 11,600 K = 1.602 x 10-19 J

Recall the Maxwell-Boltzmann
Limit
Must have

3/2
" 2π mkT % kT
$# 2 '& ge >> 1
h P

For H2 at 300 K and 1 atmosphere, the left hand side

has a value of 40,747, clearly satisfying the
inequality.