Statistical
Thermodynamics
Dr Cristina Trujillo
Session 3
1
An Ideal Gas of Diatomic
Molecules
Statistical Mechanics of an ideal gas
Aims
• Derive an expression for the vibrational partition function of a harmonic
oscillator
• Evaluate the electronic partition function, given the energies and
degeneracies of the electronic energy levels
3
Vibrational Partition Function
The harmonic oscillator
A diatomic molecule possess just one vibration frequency normal mode for the
stretching bond:
1 𝑘 𝜔 frequency
𝜔= 𝑘 force constant of the bond
2𝜋 𝜇
𝜇 Reduced mass
1
𝑢!" = 𝑛+ ℎ𝜔
2
Harmonic
oscillator
approximation 𝑛 = 0, 1,2 …
vibrational quantum number
4
Vibrational Partition Function
1 Unit used here is cm-1,
&
1 𝑛 + ℎ𝜔
2 to use s-1 or Hz it is
𝑢!" = 𝑛 + ℎ𝜔 𝑞 # = ; exp − necessary to multiply by the
2 !$%
𝑘' 𝑇
speed of light, c
Unlike the other forms of energy, the spacing of the vibrational energy levels is
almost always large compared to 𝑘! 𝑇. Therefore, it must be treated as a sum and
not as an integral.
We can group together a number of terms that have the units of kelvin to a quantity
known as the vibrational temperature, 𝜃" :
& 1
ℎ𝜔 𝑛+ 𝜃
𝑞 # = ; exp − 2 "
𝜃" =
𝑘' 𝑇
!$%
5
Vibrational Partition Function
Because the vibrational frequency and temperature are always positive, the terms in the
exponent are less than 1, therefore the sum will be convergent, so we can eliminate the
explicit summation.
Unit used here is cm-1,
exp − ℎ𝜔02𝑘 𝑇 1 to use s-1 or Hz it is
𝑞# = ! 𝑞B =
1 − exp − ℎ𝜔0𝑘 𝑇 1 − eC DE/G% H necessary to multiply by the
! speed of light, c
For a polyatomic molecule with m normal modes of vibration each with a harmonic frequency:
$
Is the product of the values exp − ℎ𝜔 02𝑘 𝑇
!
for each mode 𝑞# = 2 $
ℎ𝜔 0
$ 1 − exp − 𝑘! 𝑇
6
Vibrational Partition Function
To calculate the vibrational partition function The wavenumbers of the three normal modes of H2O are
of I2 molecule at 298.15 K, that their 3656.7 cm−1, 1594.8 cm−1, and 3755.8 cm−1.
vibrational wavenumber is 214.6 cm-1 Evaluate the vibrational partition function at 1500 K.
1 7
𝑞# = exp − ℎ𝜔 Z2𝑘 𝑇
1 − e( )*/,! -
𝑞# = Y '
7
ℎ𝜔 Z
7 1 − exp −
−
𝜔 = 214.6𝑐𝑚 1 𝑋 2.9979𝑋102% 𝑐𝑚/𝑠 = 𝑘' 𝑇
6.41654X1012 s−1
...0.12%!"# 1I.KLIMKNLO12
𝑞 B = 𝑞 B 1 ×𝑞 B 2 ×𝑞 B 3 … . .
ℎ𝜔/𝑘' 𝑇 = = 1.035
2.34%.12%!$" 1 054.26
L The overall vibrational partition function is therefore
𝑞B = = 1.55 qV = 1.031x 1.276 x 1.028 = 1.352
LCX& '.)*+
If the vibrational partition function for a The three normal modes of H2O are at such high
single mode is very close to 1, implies wavenumbers that even at 1500 K most of the
that only the zero-point level is molecules are in their vibrational ground state.
significantly occupied.
7
Total Rotational and Vibrational Partition Function
Total rotational partition function
For a system of N independent diatomic molecules:
𝑇 N
𝑄= 𝑞[ 𝑁 =
𝜎𝜃\
Total vibrational partition function
For a system of N independent vibrating diatomic molecules:
−𝜃]1
exp 2𝑇 N
𝑄= 𝑞] 𝑁 =
−𝜃]1
1 − exp 𝑇
8
Thermodynamic Properties of the Harmonic Oscillator
Expression of the total vibrational partition function
−𝜃]1
exp 2𝑇
𝑄 = 𝑞] 𝑁 =
−𝜃]1
1 − exp 𝑇
We can substitute this into the expression for the energy
!"#$ #$% (!
𝑈= k𝐵𝑇2 𝑈= + 𝑁𝑘' "!
!% & & )*+ ,# -.
9
Electronic Partition Function
It is impossible to write down a simple expression for the electronic energy levels.
These must be obtained by solving the electronic Schrödinger equation,
and then used in the general expression for the partition function
011 230342
𝑢-, 𝑔8 degeneracies
𝑞, = 3 𝑔- −
𝑘! 𝑇
-./
The separation between the electronic states is larger than the thermal energies,
and therefore, often only the ground state is important in the calculation if the
partition function.
Hence the electronic partition function is usually just equal to the degeneracy of
the electronic ground state.
10
Electronic Partition Function
011 230342
𝑢-,
𝑞, = 3 𝑔- 𝑒𝑥𝑝 −
𝑘! 𝑇
-./
Consider the oxygen atom with the following low-lying electronic states:
& )*+.-./ 001.)./
g=1 𝑞% = 5 𝑒𝑥𝑝 − ' + 3 𝑒𝑥𝑝 − + 𝑒𝑥𝑝 −
226.1 cm-1 9( '9 ( '9 (
g=3
c cm s-1
157.4 cm-1 h 𝑞% = 5 𝑒𝑥𝑝 0 + 3 𝑒𝑥𝑝 −0.0075 + 𝑒𝑥𝑝 −0.0108 = 8.97
g=5 T 300K
11
Summary of Key Points
1. The vibrational partition function
The vibrational partition function for a diatomic molecule with a single frequency, 𝜔
exp − ℎ𝜔02𝑘 𝑇
!
𝑞# =
1 − exp − ℎ𝜔0𝑘 𝑇
!
2. The vibrational temperature
For the vibration, the partition function can be expressed in terms of constants with units of
temperature. ℎ𝜔
𝜃" =
𝑘'
2. The electronic partition function
011 230342
𝑢-,
𝑞, = 3 𝑔- −
𝑘! 𝑇
-./
12
Statistical Mechanics and
Equilibrium
Statistical Mechanics and equilibrium
Aims
• State orders of magnitude for the partition functions of different types of
energy
• Express the Gibbs free energy in terms of the partition function
• Calculate the equilibrium constant for a gas phase reaction based on the
partition function
14
Summary of the partition functions for an ideal gas
Energy Degrees of Partition function Order of magnitude
freedom
Translational 3 2𝜋𝑚𝑘𝐵𝑇 3/2 1031-1032 x V
𝑉
ℎ2
Rotational linear 2 8π0 𝐼𝑘' 𝑇 10-102
𝜎ℎ0
1/2
Rotational non-linear 3 𝐼: 𝐼' 𝐼; 8π0 𝐼𝑘' 𝑇 2/3
102-103
𝜎 ℎ0
Vibrational 1 exp − ℎ𝜔Z2𝑘 𝑇 1 - 10
'
𝑞# =
1 − exp − ℎ𝜔Z𝑘 𝑇
'
15
The Gibbs Free Energy
Relationship between the Gibbs and Helmholtz free energy:
𝐺 = 𝐴 + 𝑝𝑉 𝐺 = 𝐴 + 𝑛𝑅𝑇
The Helmholtz free energy can be expressed in terms of the total partition function:
We have replaced 𝐴% by 𝐺%
𝐺 − 𝐺O = −𝑘i 𝑇ln𝑄 + 𝑛𝑅𝑇 since at absolute zero both
terms are the same
𝑞j In terms of the molecular
𝐺 − 𝐺O = −𝑘i 𝑇ln + 𝑛𝑅𝑇 partition function
𝑁!
For a gas of independent molecules In terms of molar partition fraction and the
Avogadro constant
𝑞 𝑞𝑚
𝐺 − 𝐺O = −𝑛𝑅𝑇ln 𝐺 − 𝐺O = −𝑛𝑅𝑇ln
𝑁 𝑁𝐴
16
The Standard Gibbs Free Energy
The standard molar Gibbs function for a substance 𝐽 is defined at the standard pressure, 𝑝< = 1 𝑏𝑎𝑟 , as:
s
𝑞r
𝐺rs − 𝐺rs (0) = −𝑅𝑇ln
𝑁t
Where 𝑞=< is the partition function for one molecule of 𝐽 in a volume 𝑅𝑇/ 𝑝<
Gibbs energy 𝐺 = 𝐻 − 𝑇𝑆 𝐺 = 𝑈 + 𝑛𝑅𝑇 − 𝑇𝑆
Enthalpy 𝐻 = 𝑈 + 𝑝𝑉 T=0, G=U
17
The Standard Gibbs Free Energy
𝑞 s T=0, G=U 𝑞 s
r r
𝐺rs − 𝐺rs (0) = −𝑅𝑇ln 𝐺rs = 𝑈rs (0) − 𝑅𝑇ln
𝑁t 𝑁t
𝑈=< 0 is now the molar internal energy of the
substance 𝐽 at absolute zero. This is the intrinsic
energy in the atom or molecule
Generalise equation to any reaction with multiple reactants and products
𝑣𝑗
is the number of
𝑞rs
𝑣𝑗
moles associated with
∆𝑟𝐺 s = ∆𝑟𝑈 s (0) − 𝑅𝑇ln J each species in the
𝑁t reaction
w
18
The Equilibrium Constant, 𝐾!
s 𝑣𝑗
𝑞r
∆\ 𝐺 s = −𝑅𝑇𝑙𝑛𝐾x ∆𝑟𝐺 s = ∆𝑟𝑈 s (0) − 𝑅𝑇ln J
𝑁t
w
Combining and dividing by RT
𝑣𝑗
∆%7> (&) <?>
𝑙𝑛𝐾5 = + ln ∏;
:( =@
𝑣𝑗
<?> ∆%7> (&)
𝐴 = ln(exp 𝐴 ) 𝐾5 = ∏; =@
𝑥 exp − :(
19
Summary of Key Points
1. The Gibbs free energy
Through calculating the partition functions for 1 mole of reactants and products under
standard conditions, as well as knowing the intrinsic internal energy difference at absolute
zero temperature, the standard Gibbs free energy of reaction can be determined in the gas
phase.
𝑞56
𝐺56 − 𝐺56 (0) = −𝑅𝑇ln
𝑁7
2. The equilibrium constant
From knowing the standard Gibbs free energy of reaction, the equilibrium constant can also
be determined in the gas phase via statistical mechanics.
<?> ∆%7> (&)
𝐾5 = ∏; =@
𝑥 exp − :(
20