Molecular Thermodynamics (CH3141)

First application of Canonical Probability Distribution

The Ideal Gas

N.A.M. (Klaas) Besseling

1

The Ideal Gas I (monoatomic, not-too-high T )

Sandler Ch3

Independent degrees of freedom (Divide and Rule)

Single-particle translational partition function
Total partition function of the monoatomic ideal gas
Thermodynamic properties of the monoatomic ideal gas

Review of the Boltzmann distribution law:

The probability that a system
is in (quantum) state i is

pi =

exp ( Ei kT )
Q

where Ei is the energy of state i, and

the normalisation factor is
Q = exp ( Ei kT )
i
the (canonical) partition function
The canonical partition function
is related to the Helmholtz energy

A = kT lnQ

the mean mechanical energy

E = Ei Pi =
i

Ei exp ( Ei kT )
Q

is identified with
the thermodynamic
internal energy: E = U
3

First example of Molecular Thermodynamics applied.

Demonstration of the machinery of Molecular Thermodynamics:
Formulation of expression for the partition function,
based on the quantum mechanics of the molecules.
Derivation of expressions for thermodynamic properties from
these molecular properties.
Ideal gas:
molecules do not interact (molecules are point masses)
does not exist in reality (but ideal-gas behaviour is observed at
low densities, when intermolecular encounters are rare)
molecules do have intramolecular degrees of freedom (e.g.
vibrations)
4

For this first example: simplest possible system:

monoatomic ideal gas at not-too-high temperature.
For an ideal gas (independent molecules) the total partition
function can be factorised into
single-molecule partition functions.

Divide and Rule

Intermezzo: independent subsystems, modes / degrees of freedom

independent subsystems e.g.
molecules in an ideal gas
binding sites
they do not interact => energy is sum of the energies of subsystems
independent modes / degrees of freedom e.g.
molecular translations and vibrations
energy contributions of separate modes can be added up to
obtain the total energy

afmaken

Sandler 2.3

According to quantum mechanics

a molecule has discrete (quantum) states
these quantum states are numbered: by quantum numbers (e.g. n)

n is the energy level of quantum state n

The single-molecule partition function:

q = exp n
kT
n

generally, molecular quantum states involve

- molecular translations (in three independent directions)
- molecular vibrations (depending on the molecular structure)
- molecular rotations (in maximal three independent directions)
- molecular electronic states
- nuclear states

First examine the simplest case: mono-atomic ideal gas

- For mono-atomic molecules, e.g. Argon,
there are no vibrations and no rotations.
- at moderate temperatures
electronic and nuclear states are not thermally active;
(only ground states populated because >> kT )
8

only translational degrees of freedom are relevant:

l
q = qtrans = exp trans
kT
ltrans

Sandler 1.3, 3.1 ,

sum over all translational states

A molecule has
three translational degrees of freedom.
These are independent.

Lz
Ly
Lx

- ltrans = (lx , ly , lz ) specifies the translational quantum states

of a particle in a 3D rectangular container of size V = Lx Ly Lz
Quantum number lx specifies the quantum states
(with energy level lx ) for a particle in a 1D box of size Lx.
lx = 1, 2, 3, ...
- The energy levels for the 3D box are ltrans = lx + ly + lz

Energies of quantum states follow from the Schrdinger equation:

For a particle in a 1D box of size Lx the energy levels are

lx =

h 2lx2
8mL2x

(lx = 1, 2, 3, . . . )

h = Plancks constant (= 6.627 10 34 Js)

m = the mass of the particle

hlx
mvx
2Lx
pl2x
p2
lx =
x = 12 mvx2
2m
2m
!
classical limit

The momentum levels are plx =

ideal gas:
no potential energy
10

 ltrans = lx + ly + lz

l + ly + lz

l
qtrans = exp trans = exp x

kT
kT lx ly lz

ltrans

l
l
l

ea+b = eae b
= exp x exp y exp z
kT
kT
kT
l x l y lz

hence

qtrans

l
l
l
= exp x exp y exp z
kT ly
kT
kT lz
lx
l
= q x q y qz
with qx = exp x etc.
kT
lx

The translational partition function for a particle in a 3D box

can be written as a product of 3 partition functions for the
three independent translational degrees of freedom.
11

On the previous slide we saw

ny
nz
nx
exp

exp

exp

kT kT kT =
n x n y nz

n
n
n
= exp x exp y exp z
kT ny
kT
kT nz
nx

If you dont see this right away, write out for yourself:
2

[ FnGm ] and
n=1 m=1

2 2

Fn Gm
n=1 m=1

to see that they are equal

Compare with the above equation

12

Divide and Rule

Generally:
When a system has independent degrees of freedom
(also called independent modes),
meaning that the energy contributions of the modes are additive,
then the partition function can be written as a product of the
partition functions for each of the degrees of freedom

(as illustrated above, for the three translational degrees of

freedom of a particle in a 3D box: qtrans = qx qy qz )
13

Single-particle translational partition function

l
h 2lx2
>> kT
Terms of qx = exp x for which lx =
8mL2x
kT
lx
that is for which

lx
h 2lx2
=
>> 1
kT 8mL2x kT

that is for which lx >> 8mkT Lx h lmax

contribute little to the partition function qx.
- lmax indicates the state for which = kT

l 2
l
- exp x = exp x decreases rapidly for lx lmax > 1
kT
lmax
- states with lx > lmax (that is > kT ) are relatively sparsely occupied
14

Typical value of lmax???

For example when
- size of the 1D box Lx = 1 cm = 0.01 m
- particle mass m = 1.67 10 27 M kg
mass of proton or neutron

relative atomic mass (e.g. 40 for 40Ar)

- h = 6.627 10 34 J.s
- k = 1.38 10 23 J K

21
kT = 4.14 10 J
- room temperature T = 300 K
then lmax =

8mkT Lx
10 9 M
h

number of easily accessible states in a macroscopic system is huge!!!

15

the relative decrease of exp l kT = exp l x lmax

x
upon increase of lx by 1

exp lx +1 kT exp lx kT
1

(lx +1) lx
exp lx kT
l
l
1
d
d

exp x =
lnexp x =
dlx
kT
kT
exp lx kT dlx

d lx
d lx
2l
=
=
= 2x

dlx kT dlx lmax

lmax

lx +1

lx kT

the energy difference between adjacent states /kT

16

For all relevant translational energy levels

(energy levels for which not l x >> lmax x >> kT )

the relative decrease of exp lx kT

upon increase of lx by 1 is extremely small

2lx
2
lmax

It increases with lx, but even for lx = lmax

it is only

2
lmax

1
10

17

l 2
l
x
" l x = O(1)#### ##exp = exp x exp0 = 1
kT
lmax
effectively constant
l
" lx = O(lmax ) relative decrease of exp x is O(1 lmax )
kT
(previous slide)

l
" relative decrease of exp x becomes significant when
kT
l
2
l x lmax
but then the value of exp x 0
kT

18

We see that

the number of thermally accessible translational states is huge

energy levels very close (for adjacent levels: << kT )
exp ( kT ) varies smoothly with lx
lx

So we may treat lx, lx and exp lx kT as continuous variables.

#This implies we could have started just as well from

classical mechanics rather than from quantum mechanics.
Hence this is called the classical limit. This applies if

1
lmax

h
0
8mkT Lx

h
=
0
Lx
2 mkT Lx

or
~ equivalently

see next slide

mass m is large, temperature T is high, system size Lx is large

19

Classical limit: replace the sum over states by an integral:

l 2
l 2
x
exp x dl x =
qx = exp
= exp

kT lx =1
lmax 1
lmax
l x =1
l
(using the substitution rule, x = x (see next slide))
lmax

= lmax

1 lmax

qx = lmax

1
2

exp x dx lmax exp x 2 dx = lmax 12

2

2 mkT Lx Lx
=
h

where =

h
2 mkT

Thermal Wavelength
( the De Broglie wavelength of a particle with kinetic energy kT )
20

10

( )

x t2

t2

f ( x (t )) x (t )dt = f ( x )dx!

substitution rule:

( )
x (t ) = dx dt so x (t )dt = dx

t1

(
special case:

x t1

()

x t = Ct,"""""x'(t) = C

t2

x( t 2 )

t1

x( t1 )

f ( x(t ))Cdt = f ( x )dx

x( t )
1
f x(t ) dt =
f ( x )dx
C x(t )

t2

(
t1

x=

Hence, with

lx
lmax

C=

1
lmax

2
x

exp

dl
=
l
l x max exp x dx
1
1 lmax
max

(as on the previous slide)

21

For the 3D box

qtrans = qx qy qz =

L x L y Lz V
=
3

In the classical limit the shape of the box does not matter,
only the volume.
(If not in classical limit then the shape of the box matters,
because the values for the energy levels depend on the shape)
As said before,
for an ideal monoatomic gas at not-too-high T
this is essentially the complete molecular partition function.
q = qtrans
22

11

Rough intuitive meaning of lmax and

number of accessible quantum states of a
8mkT Lx
particle in 1D box of size Lx at temperature T
lmax =
h
Lx (as you probably expected)

qx =

lmax =

1
2

qtrans =
=

Lx
2 mkT Lx
=

V
3

idem

the number of accessible quantum states of a

particle in 3D box of size V at temperature T

h
2 mkT

thermal wavelength ~ the de Broglie wavelength

of a particle with kinetic energy kT
length element in a 1D box that corresponds to
1 accessible quantum state

3 volume element in a 3D box corresponding to 1 accessible

quantum state

The multiparticle partition function

23

Sandler 2.4

(for a one-atomic ideal gas at not-too-high temperatures)

If there are N independent, distinguishable particles in the box:
microstate of the whole system defined by the states of all particles:

i = l1 ,l2 ,l3 ,...lN

and the energy of a state of the total system is

sum of all single-particle energies

Ei = l + l + l + . . . + l
1

i indicates the state of the total system

lm indicates the state of particle nr. m
24

12

Since Ei = l1 + l2 + l3 + . . . + lN

l + l2 + . . . + lN
E
Q = exp i = ... exp 1

kT l1 l2 lN
kT

i
Q = q1q2 q3...qN (check this, similar procedure as with qtrans = qx qy qz)

For distinguishable independent particles, the total partition

function can be written as a product of single-particle partition
functions (Divide and Rule)

25

Distinguishability and Indistinguishability

What if the particles are indistinguishable
(all atoms of the same kind e.g. 40Ar)
then
# the single-particle states nm
# the single-particle energy levels n
# the single particle partition functions qm
m

are all the same for each particle m

Can we then just write Q = q1q2 q3...qN = q N

?
26

13

Distinguishability and Indistinguishability

examine e.g. the following two different states i = I and i = II
for the whole system containing N distinguishable particles:
i=I:
i = II:

l1= iv l2 = iii
l1= iii l2 = iv

l3 = ii . . . . . . . . . . . lN = vi
l3 = ii . . . . . . . . . . . lN = vi

(2 permutations for particle 1 and 2)

if particle 1 and 2 are indistinguishable then
I and II are not different states of the total system
I and II do not deserve two terms in the partition function!

27

How many permutation are there for N distinguishable particles

that are each in a different state?
formulated differently:

How many ways are there to distribute N distinguishable

particles over N different states?
Distribute N particles over N states:
N
possible states for the first particle,
( N 1) for the second,
( N 2) for the third,
and so on)
= N!

28

14

The previous slide asked: How many permutation are there

for N distinguishable particles that are each in a different state?

Under what condition will particles, all be in a different state?

formulated differently:

Under what condition is it very unlikely that some particles will

be in the same state?

the number of accessible states >> number of particles

lmax >> N

29

If the particles are indistinguishable

all those N! permutations correspond to
only one quantum state of the system
- so the sum

l + l + '.'.'.' + l
N
N
= q1q2q3 ...qN = q
... exp 1 2 kT

l1 l2
lN

includes many terms that should not be included when particles are
indistinguishable!
- each term in the correct partition function Q, occurs N! times in
the above sum
1 N
Q=
q
- the above sum should be divided by N!
N!
30

15

Conclusion:
the canonical partition function of a one-component ideal gas is

Q=

1 N
q
N!

This is called
Maxwell-Boltzmann statistics

division by N! correct if
the nr. of accessible states >> nr. of particles
lmax >> N
or, equivalently
typical distance between the particles >> thermal wavelength
or, equivalently
volume per particle >> (thermal wavelength) cubed
1 V
= >> 3
N

31

Why is this Boltzmann statistics not exact?

l + l + '.'.'.' + l
N
N
...
exp
=q
1 2 kT

l1 l2
lN

also includes terms for which not all N particles are in a different state.
e.g.

l1= iii l2 = iii l3 = ii . . . . . . . . . . . lN = vi

Hence, division by N! (the number of ways to distribute

N distinguishable particles over N different states)
not exact.
(as indicated before the number of such terms is relatively very small
when the nr. of accessible states >> nr. of particles)
32

16

For most cases Boltzmann statistics works fine

because for most cases
nr. of accessible
single-particle states
>> the nr. of particles
lmax >> N

lmax states

the typical distance between the particles >> thermal wavelength

N
1
<< 3
V

(check this)
33

Simple illustration / example:

system consisting of two independent distinguishable particles N = 2
particle 1
particle 2
each particle
3 states
states l1 energies
states l2 energies
same energies
3
3
3
3
2
2
2
2
1

l



q1 = exp 1 = exp 1 + exp 2 + exp 3
kT
kT
kT
l1
kT
l



q2 = exp 2 = exp 1 + exp 2 + exp 3
kT
kT
kT
l2
kT
34

17

Simple illustration / example:

system consisting of two independent distinguishable particles N = 2
whole system (of 2 particles)
l1 / l2
1
2
3
1
1:11 2:12 3:13
2
4:21 5:22 6:23
3
7:31 8:32 9:33

system states i
i = 1: l1 = 1, l2 = 1, E1 = 1 + 1
i = 2: l1 = 1, l2 = 2, E1 = 1 + 2
etc.

i:l1l2

l + l
E
2
Q = exp i = xp 1

kT
kT

l1 l2

i
+
1 + 1
1 + 2
= exp
+ exp
+ exp 1 3

kT
kT
kT

2 + 3
2 + 1
2 + 2
+ exp
+ exp
+ exp
kT
kT
kT

+
+
+
+ exp 3 1 + exp 3 2 + exp 3 3
kT
kT
kT

= q1q2 = q 2

Maxwell-Boltzmann
Statistics
when particle 1, 2
indistinguishable
then divide by N! = 2!
35

Maxwell-Boltzmann statistics applies when

typical distance between particles >> thermal wavelength 1 3 >>
Else
Bose-Einstein statistics should be used for Bosons
Fermi-Dirac statistics should be used for Fermions
Fermions (particles consisting of odd nr. of spin- particles)
are subject to the Pauli exclusion principle:
not more than 1 particle can be in the same quantum state.
Bosons (spinless particles and particles consisting of even nr.
of spin- particles)
more than 1 particle allowed to be in the same state
(This will not be discussed further in this course.)
36

18

Sandler 3.3, 3.4

Harvest time
We have now all the ingredients to find expressions for
the thermodynamic properties
of the ideal monoatomic gas at not-too-high T.

37

As derived before:
for mono-atomic ideal gas at not-too-high T
the single-particle
partition function

q = qtrans

V 2 mkT
= 3 =

h2

32

assuming Maxwell-Boltzmann statistics

1
1 VN
1 2 mkT
Q(N,V ,T) = qN =
=
3N
N!
N!
N! h2

3N 2

VN

(taking electronic and nuclear partition functions to be 1)

generalise this for a two-components ideal-gas mixture

Q(NA ,NB ,V ,T) = Q(NA ,V ,T)Q(NB ,V ,T) =

1
N N
qA A qB B
NA !NB !

?
38

19

The Helmholtz energy

A = kT lnQ
1 VN
= kT ln
3N
N!
1
V
= kT ln + N ln 3
N!

using the Stirling approximation for large N:

ln N! N ln N N + ln 2N N ln N N

( ( ) )

A = kTN ln 3 e = kTN ln 3 1

with =

check this (see next slide)

N
V
39

Check

(( ) )

1 VN
3
A
= kT ln
=
Nln
= N ln 3 1

3N
kT
N!
e

hint: use Stirling approximation lnN! NlnN N

1
A
V
3
= ln + N ln 3 = lnN !+ N ln
kT
V
N!

3

3
= N lnN N + N ln
= N lnN 1+ ln
V
V

= N ln 3 1 = N ln
e

( ( ) )

40

20

The pressure

A
from thermodynamics p =
V T ,N

( ( ) )

The only V-dependent term in A = kTN ln 3 1 is kTN lnV

A
lnV
Hence p = = kTN

V T ,N
V T ,N
p = kTN V = kT
p = RT n V = RTc

Tada!!!
the ideal gas law

41

We have now managed to derive the equation of state of a gas,

starting from the quantum mechanical description of the atoms
as particles in a box!!!

The ideal gas law holds just as well for poly-atomic molecules
because molecular vibrations and rotations are independent of V,
and hence do not introduce extra V-dependent contributions in the
partition function.
The ideal gas law also holds for a mixed ideal gas with
N = N1 + N 2 + N 3 + ...
(in an ideal gas mixture pressures are simply additive)

42

21

The energy
from thermodynamics
(Gibbs-Helmholtz relation)
For the mono-atomic ideal gas:

A T
U =

1 T V ,N

A
= kN ln 3 e
T

h
2mkT

The only T-dependent term is kN lnT 3 2 = 23 kN ln1 T

ln1 T
U = 23 kTN
Hence
U = 23 kN

1 T V ,N
The average kinetic energy per molecule is 23 kT ( 23 RT per mol)
( 21 kT per degree of freedom, 12 RT per mol of degrees of freedom)
NB for polyatomic molecules extra terms are added
43

The heat capacity

The constant-volume heat capacity
for the monoatomic gas at not-too-high T is

U
CV =
T V ,N

with U = 23 kTN

hence

CV = 23 Nk

3
2

k per atom

3
2

R per mole of atoms

1
2

k per degree of freedom

1
2

R per mole of degrees

of freedom

These are just the translational contributions.

For polyatomic molecules there are additional contributions
44

22

The chemical potential

N3
A

= = kTN ln

N T ,V N T ,V
Ve

( )

= kT ln 3

check this

45

or

http://www.aps.org/publications/apsnews/200908/physicshistory.cfm

A
S =
T N ,V

S = (U A) T

e5 2
e5 2 kT
S = kN ln 3 = kN ln 3

p
ideal gas law
Sackur-Tetrode equation (1912)

The absolute value of the entropy of a monoatomic ideal gas!

what is the limiting behaviour for T $ 0 according to this equation?
why does this go wrong?

(http://nl.wikisage.org/wiki/Hugo_Martin_Tetrode)

The entropy

Check that for an ideal gas the entropy change upon a volume change is
V
S = S(N ,V2 ,T ) S(N ,V1 ,T ) = kN lnV2 lnV1 = kN ln 2
V

46

23