Statistical Thermodynamics

(The link between individual molecular properties

and bulk thermodynamic properties)

The Statistical Entropy

1
 To derive S = k lnW
(a) When a system is heated, the energy levels are
unchanged but their populations are changed. (b)
When work is done on a system, the energy levels
themselves are changed. The levels in this case
are the one-dimensional particle-in-a-box energy
levels: they depend on the size of the container
and move apart as its length is decreased

In the absence of all changes other than heating,

𝒅𝑼 = σ𝒊 𝜺𝒊 𝒅𝒏𝒊
 The Statistical Entropy

The Boltzmann formula for the entropy 𝑺 = 𝒌 𝒍𝒏𝑾

W is the weight of the most probable configuration of the

system

When S → 0 as T → 0, which is compatible with the

Third Law of thermodynamics, that the entropies of
all perfect crystals approach the same value as T → 0
 Statistical Definition
H Cl H Cl H Cl H Cl
S = k ln W
H Cl H Cl H Cl H Cl
Large electronegativity
difference between H and Cl
H Cl H Cl H Cl H Cl

at T = 0 K ; W = 1;
H Cl H Cl H Cl H Cl

S = k ln 1 = 0
Perfectly ordered system
4
C O O C C O C O

Molecular dipole moment of CO

is very small
O C C O O C C O
Either of two orientations possible
with virtually the same energy
at T =0 K
C O O C C O C O

O C C O C O O C

W = 2 ; Hence S = k ln W = k ln 2 = NK ln 2 = nR ln 2
N N

−1 −1 −1 −1
S = 1.0 mol  8.3145 J K mol  ln 2 = 5.76 J K mol (at T = 0 K)
5
 𝑺 = 𝒌 𝒍𝒏𝑾
• Statistical entropy behaves in exactly the same way as the
thermodynamic entropy

• As the temperature is lowered, the value of W, and hence of S, decreases

as lesser

• Configurations are compatible with total energy

• In the limit T → 0, W = 1, ln W = 0, because only one configuration is

compatible with E = 0

• Thus S → 0, as T → 0, which is compatible with Third Law of

thermodynamics

• The entropies of all perfect crystals approach the same value as T → 0

Relating Boltzmann formula for entropy to partition function

𝑼 − 𝑼(𝟎)
𝑺= + 𝑵𝒌 𝒍𝒏𝒒
𝑻
Calculate the entropy of a collection of N independent harmonic
oscillators, and evaluate it using vibrational data for I2 vapour at
25°C

𝛽𝜀
𝑆 = 𝑁𝑘 𝛽𝜀 − 𝑙𝑛 1 − 𝑒 −𝛽𝜀
𝑒 −1
 𝛽𝜀
𝑆 = 𝑁𝑘 𝛽𝜀 − 𝑙𝑛 1 − 𝑒 −𝛽𝜀
𝑒 −1

For I2 at 25oC:

 = 1.036

Sm = 8.38 J K-1 mol-1

The entropy approaches

zero as T → 0, and increases
without limit as T → ∞.
Calculate constant-volume heat capacity of a monatomic gas
𝝏𝑼
𝑪𝑽 =
𝝏𝑻 𝑽
𝟑𝑵 𝟑𝒌𝑻𝒏𝑵𝑨 𝟑
𝑼=𝑼 𝟎 + =𝑼 𝟎 + = 𝑼 𝒐 + 𝒏𝑹𝑻
𝟐𝜷 𝟐 𝟐
𝟑 𝟑
𝑪𝑽 = 𝒏𝑹 = × 𝟏 × 𝟖. 𝟑𝟏𝟒𝟓 = 𝟏𝟐. 𝟓 𝑱 𝑲−𝟏 𝒎𝒐𝒍−𝟏
𝟐 𝟐

• This value agrees almost exactly with experimental data on monatomic

gases at normal pressures

• For more complex molecules, other modes of motion contribute

To show that heat capacity of N two-level systems, heat capacity CV is given by
𝟐 𝒆𝜷𝜺 / 𝜷𝜺 𝟐
𝑪𝑽 = 𝑵𝒌 𝜷𝜺 𝟏 +𝒆

 𝒅
=
𝒅𝜷
×
𝒅 𝟏 𝒅
=− 𝟐
𝒅𝑻 𝒅𝑻 𝒅𝜷 𝒌𝑻 𝒅𝜷

0
To show that heat capacity of N two-level systems, heat capacity CV is given by
𝟐 𝒆𝜷𝜺 / 𝜷𝜺 𝟐
𝑪𝑽 = 𝑵𝒌 𝜷𝜺 𝟏 +𝒆
Evaluate the molar entropy of N two-level systems plot the
resulting expression. What is the entropy when two state are
equally thermally accessible?

𝑼 − 𝑼(𝟎)
𝑺= + 𝑵𝒌 𝒍𝒏𝒒
𝑻
 The temperature variation of
the entropy of a two-level
system (expressed as a
multiple of Nk). As T → ∞, the
two states become equally
populated and S approaches
Nk ln 2.

𝑺 𝜷𝜺 −𝜷𝜺
= + 𝒍𝒏 𝟏 + 𝒆
𝑵𝑲 𝟏 + 𝒆𝜷𝜺
 Evaluate the molar entropy of N two-level
systems plot the resulting expression. What is
the entropy when two state are equally
thermally accessible?

The temperature variation of

the entropy of a two-level
system (expressed as a
multiple of Nk). As T → ∞, the
two states become equally
populated and S approaches
Nk ln 2.

𝑺 𝜷𝜺 −𝜷𝜺
= + 𝒍𝒏 𝟏 + 𝒆
𝑵𝑲 𝟏 + 𝒆𝜷𝜺
Consider a system which has doubly degenerate ground state, non-
degenerate first excited state at 1 and a doubly degenerate second
excited state at 2. Derive expressions for its internal energy and
entropy
 𝑺 𝜷 𝜺𝟏 𝒆−𝜷𝜺𝟏 + 𝟐𝜺𝟐 𝒆−𝜷𝜺𝟐 −𝜷𝜺𝟏 + 𝟐𝒆−𝜷𝜺𝟐 )
= + 𝐥𝐧(𝟐 + 𝒆
𝑵𝑲 𝟐 + 𝒆−𝜷𝜺𝟏 + 𝟐𝒆−𝜷𝜺𝟐
 𝑺 𝜷 𝜺𝟏 𝒆−𝜷𝜺𝟏 + 𝟐𝜺𝟐 𝒆−𝜷𝜺𝟐 −𝜷𝜺𝟏 −𝜷𝜺𝟐
= −𝜷𝜺 −𝜷𝜺
+ 𝐥𝐧(𝟐 + 𝒆 + 𝟐𝒆 )
𝑵𝑲 𝟐 + 𝒆 𝟏 + 𝟐𝒆 𝟐
Statistical Thermodynamics
(The link between individual molecular properties
and bulk thermodynamic properties)

The Canonical Partition Function

19
The Canonical Ensemble
 The Canonical Ensemble
• The crucial new concept we need when treating systems
of interacting particles is the ‘ensemble’

• Like so many scientific terms, the term has basically its

normal meaning of ‘collection’, but it has been
sharpened and refined into a precise significance

• To set up an ensemble, we take a closed system of

specified volume, composition, and temperature, and
think of it as replicated Ñ times

• All the identical closed systems are regarded as being in

thermal contact with one another, so they can exchange
energy
• The total energy of all the systems is L and, because they
are in thermal equilibrium with one another, they all have
the same temperature, T

• This imaginary collection of replications of the actual

system with a common temperature is called the
canonical ensemble

• The word ‘canon’ means ‘according to a rule’

• All the identical closed systems are regarded as being

in thermal contact with one another, so they can exchange
energy
 Microcanonical ensemble: N, V, E common
Canonical ensemble: N, V, T common
Grand canonical ensemble: , V, T common

• In the microcanonical ensemble the condition of constant temperature is

replaced by the requirement that all the systems should have exactly the
same energy: each system is individually isolated.

• In the grand canonical ensemble the volume and temperature of each

system is the same, but they are open, which means that matter can be
imagined as able to pass between the systems; the composition of each
one may fluctuate, but now the chemical potential is the same in each
system
• The important point about an ensemble is that
it is a collection of imaginary replications of
the system, so we are free to let the number of
members be as large as we like; when
appropriate, we can let Ñ become infinite

• The number of members of the ensemble in a

state with energy Ei is denoted ñi, and we can
speak of the configuration of the ensemble and
its weight, Ŵ

• Note that Ñ is unrelated to N, the number of

molecules in the actual system; Ñ is the
number of imaginary replications of that
system
 Dominating configurations
It is very unlikely that the whole of the total energy, Ĕ, will accumulate in one
system

Some of the configurations of the ensemble will be very much more probable
than others

We can anticipate that there will be a dominating configuration, and that we

can evaluate the thermodynamic properties by taking the average over the
ensemble using that single, most probable, configuration

In the thermodynamic limit of Ñ → ∞, this dominating configuration is

overwhelmingly the most probable, and it dominates the properties of the
system virtually completely
The weight of a configuration {ñ0,ñ1, . . . } is

Ñ!
Ŵ=
ñ𝟎 ! ñ𝟏 ! ñ𝟐 ! … … … … .

The configuration of greatest weight, subject to the

constraints that the total energy of the ensemble is
constant at Ĕ and that the total number of members is
fixed at Ñ, is given by the canonical distribution:

ñ𝒊 𝒆−𝜷𝑬𝑖
=
Ñ 𝑸

𝑸 = ෍ 𝒆−𝜷𝑬𝒊
𝒊
Statistical Thermodynamics
(The link between individual molecular properties
and bulk thermodynamic properties)

Relating Canonical Partition Function

Internal Energy and Entropy

27
 𝑪𝒂𝒏𝒐𝒏𝒊𝒄𝒂𝒍 𝑷𝒂𝒓𝒕𝒊𝒕𝒊𝒐𝒏 𝑭𝒖𝒏𝒄𝒕𝒊𝒐𝒏: 𝑸 = ෍ 𝒆−𝜷𝑬𝒊
𝒊

• Like the molecular partition function, the canonical partition

function carries all the thermodynamic information about a
system

• However, Q is more general than q because it does not assume that

the molecules are independent

• We can therefore use Q to discuss the properties of condensed

phases and real gases where molecular interactions are
important
If the total energy of the ensemble is Ĕ, and there are Ñ members,
the average energy of a member is

Ĕ
𝑬=
Ñ

Ĕ
𝑰𝒏𝒕𝒆𝒓𝒏𝒂𝒍 𝒆𝒏𝒆𝒓𝒈𝒚: 𝑼 = 𝑼 𝟎 +
Ñ
If the total energy of the ensemble is Ĕ, and there are Ñ members,
the average energy of a member is

Ĕ
𝑬=
Ñ

Ĕ
𝑰𝒏𝒕𝒆𝒓𝒏𝒂𝒍 𝒆𝒏𝒆𝒓𝒈𝒚: 𝑼 = 𝑼 𝟎 +
Ñ
The fraction of members of the ensemble in a state i
with energy Ei is given by
 Ĕ
𝑰𝒏𝒕𝒆𝒓𝒏𝒂𝒍 𝒆𝒏𝒆𝒓𝒈𝒚: 𝑼 = 𝑼 𝟎 +
Ñ
 The Internal Energy:
𝟏 𝝏𝑸 𝝏𝒍𝒏𝑸
𝑼=𝑼 𝟎 − =𝑼 𝟎 −
𝑸 𝝏𝜷 𝑽 𝝏𝜷 𝑽
 The entropy
The total weight, Ŵ , of a configuration of the
ensemble is the product of the average weight W of
each member of the ensemble, Ŵ = WÑ
 The entropy
The total weight, Ŵ , of a configuration of the
ensemble is the product of the average weight W of
each member of the ensemble, Ŵ = WÑ

𝟏
𝒌
𝑺 = 𝒌 𝒍𝒏𝑾 = 𝒌 𝒍𝒏ŴÑ = 𝐥𝐧Ŵ
Ñ

𝑼 − 𝑼(𝟎)
𝑺= + 𝒌 𝒍𝒏𝑸
𝑻
Statistical Thermodynamics
(The link between individual molecular properties
and bulk thermodynamic properties)

Recovering molecular partition function q

from canonical partition function Q

35
 Recovering molecular partition function q from
canonical partition function Q

• Recovering the molecular partition function from the more general

canonical partition function when the molecules are independent

• The total energy of a collection of N independent molecules is the sum

of the energies of the molecules

• Therefore, we can write the total energy of a state i of the system is

𝑬𝒊 = 𝜺𝒊 𝟏 + 𝜺𝒊 𝟐 + 𝜺𝒊 𝟑 + ⋯ … … …

• In this expression, εi(1) is the energy of molecule 1 when the system is

in the state i, εi(2) the energy of molecule 2 when the system is in the
same state i, and so on.
 Recovering molecular partition function q from
canonical partition function Q
• The total energy of a state i of the system is

𝑬𝒊 = 𝜺𝒊 𝟏 + 𝜺𝒊 𝟐 + 𝜺𝒊 𝟑 + ⋯ + 𝜺𝒊 (𝑵)
 Recovering molecular partition function q from canonical
partition function Q (Independent molecules)
• The total energy of a state i of the system is

𝑬𝒊 = 𝜺𝒊 𝟏 + 𝜺𝒊 𝟐 + 𝜺𝒊 𝟑 + ⋯ + 𝜺𝒊 (𝑵)

𝑸 = ෍ 𝒆−𝜷𝜺𝒊 𝟏 −𝜷𝜺𝒊 𝟐 −⋯𝜷𝜺𝒊 (𝑵)

𝒊
The sum over the states of the system can be reproduced by letting each molecule enter
all its own individual states. Therefore, instead of summing over the states i of the
system, we can sum over all the individual states i of molecule 1, all the states i of
molecule 2, and so on.

𝑸= ෍ 𝒆−𝜷𝜺𝒊 ෍ 𝒆−𝜷𝜺𝒊 … … . ෍ 𝒆−𝜷𝜺𝒊 = 𝒒𝑵

𝒊 𝒊 𝒊
 Distinguishable and indistinguishable molecules

If all the molecules are identical and free to move through space,
we cannot distinguish them and the relation Q = qN is not valid

• Suppose that molecules 1 is in some state a, molecule 2

is in b, and molecule 3 is in c, then one member of the
ensemble has energy 𝑬 = 𝜺𝒂 + 𝜺𝒃 + 𝜺𝒄

• This member is indistinguishable from one molecule 1

in state b, molecule 2 in state c, and molecule 3 in state
a or some other permutation
 Distinguishable and indistinguishable molecules

If all the molecules are identical and free to move through space,
we cannot distinguish them and the relation Q = qN is not valid
 Distinguishable and indistinguishable molecules

If all the molecules are identical and free to move through space,
we cannot distinguish them and the relation Q = qN is not valid

• For distinguishable independent molecules: 𝑸 = 𝒒𝑵

𝑸𝑵
• For indistinguishable independent molecules: 𝑸 =
𝑵!
 • For distinguishable independent molecules: 𝑸 = 𝒒𝑵
𝑸𝑵
• For indistinguishable independent molecules: 𝑸 =
𝑵!
• For molecules to be indistinguishable, they must be of the same kind

• An Ar atom is never indistinguishable from a Ne atom

• Each identical molecule in a crystal lattice, for instance, can be ‘named’

with a set of coordinates

• Identical molecules in a lattice can therefore be treated as

distinguishable because their sites are distinguishable

• Identical molecules in a gas are free to move to different locations, and

there is no way of keeping track of the identity of a given molecule
Identify systems for which it is essential to include a factor of 1/N! on
going from Q to q:
(a)A sample of helium gas
(b)A sample of carbon monoxide gas
(c)A solid sample of carbon monoxide
(d)Water vapour
(e)ice
 The Internal Energy

𝟏 𝝏𝑸 𝝏𝒍𝒏𝑸
𝑼=𝑼 𝟎 − =−
𝑸 𝝏𝜷 𝑽
𝝏𝜷 𝑽
 The Internal Energy

𝟏 𝝏𝑸 𝝏𝒍𝒏𝑸
𝑼=𝑼 𝟎 − =−
𝑸 𝝏𝜷 𝑽
𝝏𝜷 𝑽
 The Internal Energy

𝑵 𝝏𝒒 𝝏𝒍𝒏𝒒
𝑼=𝑼 𝟎 − = −𝑵
𝒒 𝝏𝜷 𝑽
𝝏𝜷 𝑽

Same expression for distinguishable (𝑸 = 𝒒𝑵 ) or

𝒒𝑵
indistinguishable 𝑸 = molecules
𝑵!
Statistical Thermodynamics
(The link between individual molecular properties
and bulk thermodynamic properties)

Entropy of a monatomic gas

47
 The Internal Energy

𝟏 𝝏𝑸 𝝏𝒍𝒏𝑸
𝑼=𝑼 𝟎 − =−
𝑸 𝝏𝜷 𝑽
𝝏𝜷 𝑽
 The Internal Energy

𝑵 𝝏𝒒 𝝏𝒍𝒏𝒒
𝑼=𝑼 𝟎 − = −𝑵
𝒒 𝝏𝜷 𝑽
𝝏𝜷 𝑽

Same expression for distinguishable (𝑸 = 𝒒𝑵 ) or

𝒒𝑵
indistinguishable 𝑸 = molecules
𝑵!
Entropy of a monatomic gas

𝑼 − 𝑼(𝟎)
𝑺= + 𝒌 𝒍𝒏𝑸
𝑻

50
 Entropy of a monatomic gas

𝑼 − 𝑼(𝟎)
𝑺= + 𝒌 𝒍𝒏𝑸
𝑻

𝒆𝟓/𝟐 𝑽
Sackur-Tetrode Equation 𝑺 = 𝒏𝑹 𝒍𝒏
𝒏𝑵𝑨 Ʌ𝟑

𝟏/𝟐
𝜷𝒉𝟐 𝒉
Ʌ= =
𝟐𝝅𝒎 𝟐𝝅𝒎𝒌𝑻
51
 Entropy of a monatomic gas

𝒆𝟓/𝟐 𝑽 𝒆𝟓/𝟐 𝒌𝑻
𝑺 = 𝒏𝑹 𝒍𝒏 𝑺 = 𝒏𝑹 𝒍𝒏
𝒏𝑵𝑨 Ʌ𝟑 𝒑Ʌ𝟑
𝟏/𝟐
𝜷𝒉𝟐 𝒉
Ʌ= =
𝟐𝝅𝒎 𝟐𝝅𝒎𝒌𝑻

Sackur-Tetrode equation implies that the molar entropy of

a perfect gas of high molar mass is greater than one of low
molar mass under the same conditions (because the former
has more thermally accessible translational states)
52
Statistical Thermodynamics
(The link between individual molecular properties
and bulk thermodynamic properties)

Further discussion on entropy of a

monatomic gas

53
 Entropy of a monatomic gas

𝒆𝟓/𝟐 𝑽 𝒆𝟓/𝟐 𝒌𝑻
𝑺 = 𝒏𝑹 𝒍𝒏 𝑺 = 𝒏𝑹 𝒍𝒏
𝒏𝑵𝑨 Ʌ𝟑 𝒑Ʌ𝟑
𝟏/𝟐
𝜷𝒉𝟐 𝒉
Ʌ= =
𝟐𝝅𝒎 𝟐𝝅𝒎𝒌𝑻

Sackur-Tetrode equation implies that the molar entropy of

a perfect gas of high molar mass is greater than one of low
molar mass under the same conditions (because the former
has more thermally accessible translational states)
54
Calculate standard molar entropy of gaseous argon at 25oC
(Mass of an Ar atom = 39.95 u)
Standard state: Substance should be pure, temperature can be any,
but pressure should be 1 bar

𝟓/𝟐 𝟏/𝟐
𝒆 𝒌𝑻 𝜷𝒉 𝟐
𝒉
𝑺𝒐𝒎 = 𝒏𝑹 𝒍𝒏 Ʌ= = = 𝟏𝟔. 𝟎 𝐩𝐦
𝒑𝒐 Ʌ 𝟑 𝟐𝝅𝒎 𝟐𝝅𝒎𝒌𝑻

𝟓/𝟐 −𝟐𝟑 −𝟏
𝒐
𝒆 × 𝟏. 𝟑𝟖𝟏 × 𝟏𝟎 𝑱 𝑲 × 𝟐𝟗𝟖. 𝟏𝟓 𝑲 −𝟏 𝒎𝒐𝒍−𝟏
𝑺𝒎 = 𝑹 𝒍𝒏 = 𝟏𝟖. 𝟔 𝐑 = 𝟏𝟓𝟓 𝐉 𝑲
𝟏𝟎𝟓 𝑵 𝒎−𝟐 × 𝟏. 𝟔𝟎 × 𝟏𝟎−𝟏𝟏 𝒎 𝟑
55
Calculate standard molar entropy of gaseous argon at 25oC
(Mass of an Ar atom = 39.95 u)

𝒆 𝟓/𝟐 × 𝟏. 𝟑𝟖𝟏 × 𝟏𝟎−𝟐𝟑 𝑱 𝑲−𝟏 × 𝟐𝟗𝟖. 𝟏𝟓 𝑲

𝑺𝒐𝒎 = 𝑹 𝒍𝒏 = 𝟏𝟖. 𝟔 𝐑 = 𝟏𝟓𝟓 𝐉 𝑲−𝟏 𝒎𝒐𝒍−𝟏
𝟏𝟎𝟓 𝑵 𝒎−𝟐 × 𝟏. 𝟔𝟎 × 𝟏𝟎−𝟏𝟏 𝒎 𝟑

𝟏/𝟐
𝜷𝒉𝟐 𝒉
Ʌ= = = 𝟏𝟔. 𝟎 𝐩𝐦
𝟐𝝅𝒎 𝟐𝝅𝒎𝒌𝑻
• Neon (m = 20.18 u), a lighter molecule has higher thermal wavelength

• Hence standard molar entropy of Ne is smaller than Ar and is 146.3 J K-1 mol-1

• The translational contribution to the standard molar entropy of H2 at 25oC

is 118 J K-1 mol-1 56
 𝒆𝟓/𝟐 𝑽
Sackur-Tetrode Equation 𝑺 = 𝒏𝑹 𝒍𝒏
𝒏𝑵𝑨 Ʌ𝟑
𝟏/𝟐
𝜷𝒉𝟐 𝒉
Ʌ= =
𝟐𝝅𝒎 𝟐𝝅𝒎𝒌𝑻

At constant temperature: 𝑺 = 𝒏𝑹 𝐥𝐧(𝒂𝑽)

57
 𝒆𝟓/𝟐 𝑽
Sackur-Tetrode Equation 𝑺 = 𝒏𝑹 𝒍𝒏
𝒏𝑵𝑨 Ʌ𝟑

𝟏/𝟐
𝜷𝒉𝟐 𝒉
Ʌ= =
𝟐𝝅𝒎 𝟐𝝅𝒎𝒌𝑻

At constant temperature: 𝑺 = 𝒏𝑹 𝐥𝐧(𝒂𝑽)

𝑽𝒇
∆𝑺 = 𝒏𝑹 𝐥𝐧 𝒂𝑽𝒇 − 𝒏𝑹 𝒍𝒏 𝒂𝑽𝒊 = 𝒏𝑹 𝒍𝒏
𝑽𝒊
58
Derivation based on concepts of classical thermodynamics:

𝑽𝒇
∆𝑺 = 𝒏𝑹 𝐥𝐧 𝒂𝑽𝒇 − 𝒏𝑹 𝒍𝒏 𝒂𝑽𝒊 = 𝒏𝑹 𝒍𝒏
𝑽𝒊
𝑽𝒇
∆𝑺 = 𝒏𝑹 𝒍𝒏 Constant temperature
𝑽𝒊

𝒅𝒒𝒓𝒆𝒗
From classical thermodynamics: 𝒅𝑺 =
𝑻

59
 Derivation based on concepts of classical thermodynamics:

𝑽𝒇
∆𝑺 = 𝒏𝑹 𝐥𝐧 𝒂𝑽𝒇 − 𝒏𝑹 𝒍𝒏 𝒂𝑽𝒊 = 𝒏𝑹 𝒍𝒏
𝑽𝒊

𝑽𝒇
∆𝑺 = 𝒏𝑹 𝒍𝒏 Constant temperature
𝑽𝒊

• This is exactly the expression we obtained by using both classical

thermodynamics and statistical thermodynamics

• The classical expression is in fact a consequence of the increase in the

number of accessible translational states when the volume of the container
is increased 60
 𝑽𝒇
∆𝑺 = 𝒏𝑹 𝒍𝒏 Constant temperature
𝑽𝒊

As the width of a container is

increased (going from (a) to (b)),
the energy levels become closer
together (as 1/L2 ), and as a result
more are thermally accessible at a
given temperature. Consequently,
the entropy of the system rises as
the container expands.
61
Statistical Thermodynamics
(The link between individual molecular properties
and bulk thermodynamic properties)

Further discussion on entropy of a

monatomic gas

62
Calculate the change in entropy when one mol of a perfect gas
expands from 10 L to 100 L under isothermal conditions

𝑽𝒇
∆𝑺 = 𝒏𝑹 𝒍𝒏 Constant temperature
𝑽𝒊

∆𝑺 = 𝟏. 𝟎 × 𝟖. 𝟑𝟏𝟒𝟓 × 𝒍𝒏𝟏𝟎 = 𝟏𝟗. 𝟏 𝑱 𝑲−𝟏 𝒎𝒐𝒍−𝟏

63
Calculate the change in entropy when one mol of a perfect gas
expands from 10 L to 100 L under constant pressure conditions

𝒆𝟓/𝟐 𝒌𝑻
𝑺 = 𝒏𝑹 𝒍𝒏
𝒑Ʌ𝟑

𝟓 𝑻𝒇 𝟓 𝑽𝒇
∆𝑺 = 𝒏𝑹 𝒍𝒏 = 𝒏𝑹 𝒍𝒏 = 𝟐. 𝟓 𝑹 𝒍𝒏𝟏𝟎 = 𝟒𝟕. 𝟗 𝑱 𝑲−𝟏 𝒎𝒐𝒍−𝟏
𝟐 𝑻𝒊 𝟐 𝑽𝒊 64
By using classical thermodynamics:

65
Consider a system A consisting of subsystems A1 and A2, for which W1 = 1 ×
1020 and W2 = 2 × 1020. What is the number of configurations available to
the combined system? Also, compute the entropies S, S1, and S2. What is the
significance of this result?

Number of configurations of combined system, W = W1W2

W = (1020) x (2 x 1020) = 2 X 1040

S = k ln W; S1 = k InWI ; S2 = k lnW2
S = k In (2 x 1040) = k{ln 2 + 40 In 10) = 92.8 x (1.381 x 10-23 J K-1) = 1.282 x 10- 21 J K- I
S1 = k In(1020) = k{20 In 10) = 46.7 k = 46.1 x (1.381 x 10- 23 J K-1 ) = 0.637 X 10-21 J K-1

S2 = k ln(2 x 1020) = k{ln 2 + 20 In 10) = 46.7 x (1.381 x 10- 23 J K-1) = 0.645 X 10-21 J K-1
These results are significant in that they show that the statistical mechanical entropy is an
additive property consistent with the thermodynamic result

That is, S = S1 + S2 = (0.637 X 10-21 + 0.645 x 10-21) J K-1 = 1.282 X 10- 21 J K-1
66
By what factor does the number of available configurations increase
when 100 J of energy is added to a system containing 1.00 mol of
particles at constant volume at 298 K?

67
By what factor does the number of available configurations increase
when 100 J of energy is added to a system containing 1.00 mol of
particles at constant volume at 298 K?

∆𝑾 ∆𝑼 𝟏𝟎𝟎 × 𝟏𝟎−𝟑 𝑱 𝟐𝟓
≈ = = 𝟐. 𝟒 × 𝟏𝟎
𝑾 𝒌𝑻 𝟏. 𝟑𝟖𝟏 × 𝟏𝟎−𝟐𝟑 𝑱 𝑲−𝟏 × 𝟐𝟗𝟖 𝑲
68
Statistical Thermodynamics
(The link between individual molecular properties
and bulk thermodynamic properties)

The Thermodynamic Functions

(Pressure)

69
 Fundamental Relations

𝟏 𝝏𝑸 𝝏𝒍𝒏𝑸
The Internal Energy 𝑼=𝑼 𝟎 − =−
𝑸 𝝏𝜷 𝑽
𝝏𝜷 𝑽

Entropy of a 𝑼 − 𝑼(𝟎)
𝑺= + 𝒌 𝒍𝒏𝑸
monatomic gas 𝑻

Decide relationship between Q and q

70
The Helmholtz Energy (A)

𝑨 = 𝑼 − 𝑻𝑺

𝐴 − 𝐴 0 = −𝑘𝑇 𝑙𝑛𝑄 71
The Helmholtz Energy (A)

𝑨 = 𝑼 − 𝑻𝑺

𝐴 − 𝐴 0 = −𝑘𝑇 𝑙𝑛𝑄 72
The pressure

𝝏𝑨
𝒑=−
𝝏𝑽 𝑻
73
 𝝏𝑨
The pressure 𝒑=−
𝝏𝑽 𝑻

𝐴 − 𝐴 0 = −𝑘𝑇 𝑙𝑛𝑄

This is an entirely general relation is entirely general

𝝏𝒍𝒏𝑸
𝒑 = 𝒌𝑻 relation which may be used for any type of substance,
𝝏𝑽 𝑻 including perfect gases, real gases, and liquids 74
 𝝏𝒍𝒏𝑸
𝒑 = 𝒌𝑻 𝑺𝒉𝒐𝒘 𝒕𝒉𝒂𝒕 𝒇𝒐𝒓 𝒂𝒏 𝒊𝒅𝒆𝒂𝒍 𝒈𝒂𝒔 𝒑𝑽 = 𝒏𝑹𝑻
𝝏𝑽 𝑻

75
Statistical Thermodynamics
(The link between individual molecular properties
and bulk thermodynamic properties)

The Thermodynamic Functions

(Enthalpy)

76
 Fundamental Relations
𝟏 𝝏𝑸 𝝏𝒍𝒏𝑸
The Internal Energy 𝑼=𝑼 𝟎 − =−
𝑸 𝝏𝜷 𝑽
𝝏𝜷 𝑽

𝝏𝒍𝒏𝑸
Pressure 𝒑 = 𝒌𝑻
𝝏𝑽 𝑻

The Enthalpy 𝑯 = 𝑼 + 𝒑𝑽

77
 Fundamental Relations
𝟏 𝝏𝑸 𝝏𝒍𝒏𝑸
The Internal Energy 𝑼=𝑼 𝟎 −
𝑸 𝝏𝜷
=−
𝝏𝜷
𝑽 𝑽

𝝏𝒍𝒏𝑸
Pressure 𝒑 = 𝒌𝑻
𝝏𝑽 𝑻

The Enthalpy 𝑯 = 𝑼 + 𝒑𝑽

𝝏𝒍𝒏𝑸 𝝏𝒍𝒏𝑸
𝑯−𝑯 𝟎 =− + 𝒌𝑻𝑽
𝝏𝜷 𝑽
𝝏𝑽 𝑻
78
Calculate the enthalpy of a perfect monatomic gas at temperature T
𝟑
By equipartition theorem: 𝑼 − 𝑼 𝟎 = 𝒏𝑹𝑻
𝟐

𝟓
𝑯 − 𝑯 𝟎 = 𝒏𝑹𝑻
𝟐 79
Calculate the enthalpy of a perfect monatomic gas at temperature T

𝝏𝒍𝒏𝑸 𝝏𝒍𝒏𝑸
𝑯−𝑯 𝟎 =− + 𝒌𝑻𝑽
𝝏𝜷 𝑽
𝝏𝑽 𝑻

80
Statistical Thermodynamics
(The link between individual molecular properties
and bulk thermodynamic properties)

The Thermodynamic Functions

(The Gibbs Energy)

81
𝑮 = 𝑯 − 𝑻𝑺 = 𝑨 + 𝒑𝑽

82
 𝑮 − 𝑮 𝟎 = 𝑨 − 𝑨 𝟎 − 𝒑𝑽

𝑨 − 𝑨 𝟎 = −𝒌𝑻 𝒍𝒏𝑸

𝝏𝒍𝒏𝑸
𝒑 = 𝒌𝑻
𝝏𝑽 𝑻

𝝏𝒍𝒏𝑸
𝑮 − 𝑮 𝟎 = −𝒌𝑻𝒍𝒏𝑸 + 𝒌𝑻𝑽
𝝏𝑽 𝑻
83
 𝑮 − 𝑮 𝟎 = 𝑨 − 𝑨 𝟎 + 𝒑𝑽

𝑨 − 𝑨 𝟎 = −𝒌𝑻 𝒍𝒏𝑸

𝑮 − 𝑮 𝟎 = −𝒌𝑻𝒍𝒏𝑸 + 𝒏𝑹𝑻

84
 𝒒
𝑮 − 𝑮 𝟎 = −𝒏𝑹𝑻𝒍𝒏
𝑵

𝒒𝒎
𝑮 − 𝑮 𝟎 = −𝒏𝑹𝑻𝒍𝒏
𝑵𝑨 85
 𝒒𝒎
𝑮 − 𝑮 𝟎 = −𝒏𝑹𝑻𝒍𝒏
𝑵𝑨

𝒒𝒐𝒎
𝑮𝒐𝒎 − 𝑮𝒐𝒎 𝟎 = −𝑹𝑻𝒍𝒏
𝑵𝑨 86
 𝝏𝒍𝒏𝑸
𝑮 − 𝑮 𝟎 = −𝒌𝑻𝒍𝒏𝑸 + 𝒌𝑻𝑽
𝝏𝑽 𝑻

87
Statistical Thermodynamics
(The link between individual molecular properties
and bulk thermodynamic properties)

The Thermodynamic Functions

(The Molecular Partition Function)

88
Different modes of motion make contributions to the
energy of a molecule as follows
𝑻 𝑹 𝑽 𝑬
𝜺𝒋 = 𝜺𝒋 + 𝜺𝒋 + 𝜺𝑱 + 𝜺𝒋

𝒒 = ෍ 𝒆−𝜷𝜺𝒋
𝒋

89
 𝒒 = 𝒒𝑻 𝒒𝑹 𝒒𝑽 𝒒𝑬

• Monatomic

• Diatomic

• Triatomic

• Multiatomic 90
The translational partition function 0f a particle that is free
to move in one-dimensional container of length X is qX

1/2
2𝜋𝑚
𝑞𝑋 = 𝑋
ℎ2 𝛽

• 𝒎 𝒊𝒔 𝒎𝒂𝒔𝒔 𝒐𝒇 𝒐𝒏𝒆 𝒑𝒂𝒓𝒕𝒊𝒄𝒍𝒆

• h is Planck constant
𝟏
• 𝜷 = ; 𝒌 𝒊𝒔 𝑩𝒐𝒍𝒕𝒛𝒎𝒂𝒏𝒏 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕
𝒌𝑻
91
 The translational partition function of a particle that is free
to move in one-dimensional container of length X is qX

1/2 • 𝒎 𝒊𝒔 𝒎𝒂𝒔𝒔 𝒐𝒇 𝒐𝒏𝒆 𝒑𝒂𝒓𝒕𝒊𝒄𝒍𝒆

2𝜋𝑚 𝑋 • h is Planck constant
𝑞𝑋 = 𝑋=
ℎ2 𝛽 Λ 𝟏
• 𝜷 = ; 𝒌 𝒊𝒔 𝑩𝒐𝒍𝒕𝒛𝒎𝒂𝒏𝒏 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕
𝒌𝑻

𝟏/𝟐 𝟐 𝟏/𝟐
𝜷 𝜷𝒉 𝒉
𝑻𝒉𝒆𝒓𝒎𝒂𝒍 𝒘𝒂𝒗𝒆𝒍𝒆𝒏𝒈𝒕𝒉: 𝜦 = 𝒉 = =
𝟐𝝅𝒎 𝟐𝝅𝒎 𝟐𝝅𝒎𝒌𝑻

(𝚲 𝒉𝒂𝒔 𝒅𝒊𝒎𝒆𝒏𝒔𝒊𝒐𝒏𝒔 𝒐𝒇 𝒍𝒆𝒏𝒈𝒕𝒉) 92

 The translational partition function of a particle that is free
to move in two-dimensional container of lengths X,Y is qX

1/2 • 𝒎 𝒊𝒔 𝒎𝒂𝒔𝒔 𝒐𝒇 𝒐𝒏𝒆 𝒑𝒂𝒓𝒕𝒊𝒄𝒍𝒆

2𝜋𝑚 𝑋𝑌 • h is Planck constant
𝑞𝑋 = 𝑋= 2
ℎ2 𝛽 Λ 𝟏
• 𝜷 = ; 𝒌 𝒊𝒔 𝑩𝒐𝒍𝒕𝒛𝒎𝒂𝒏𝒏 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕
𝒌𝑻

𝟏/𝟐 𝟐 𝟏/𝟐
𝜷 𝜷𝒉 𝒉
𝑻𝒉𝒆𝒓𝒎𝒂𝒍 𝒘𝒂𝒗𝒆𝒍𝒆𝒏𝒈𝒕𝒉: 𝜦 = 𝒉 = =
𝟐𝝅𝒎 𝟐𝝅𝒎 𝟐𝝅𝒎𝒌𝑻

(𝚲 𝒉𝒂𝒔 𝒅𝒊𝒎𝒆𝒏𝒔𝒊𝒐𝒏𝒔 𝒐𝒇 𝒍𝒆𝒏𝒈𝒕𝒉) 93

 The translational partition function of a particle that is free
to move in two-dimensional container of sides X,Y is qX

1/2 • 𝒎 𝒊𝒔 𝒎𝒂𝒔𝒔 𝒐𝒇 𝒐𝒏𝒆 𝒑𝒂𝒓𝒕𝒊𝒄𝒍𝒆

2𝜋𝑚 𝑋𝑌 𝐴(𝐴𝑟𝑒𝑎) • h is Planck constant
𝑞𝑋 = 𝑋= 2 = •
𝟏
𝜷 = ; 𝒌 𝒊𝒔 𝑩𝒐𝒍𝒕𝒛𝒎𝒂𝒏𝒏 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕
ℎ2 𝛽 Λ Λ2 𝒌𝑻

𝟏/𝟐 𝟐 𝟏/𝟐
𝜷 𝜷𝒉 𝒉
𝑻𝒉𝒆𝒓𝒎𝒂𝒍 𝒘𝒂𝒗𝒆𝒍𝒆𝒏𝒈𝒕𝒉: 𝜦 = 𝒉 = =
𝟐𝝅𝒎 𝟐𝝅𝒎 𝟐𝝅𝒎𝒌𝑻

(𝚲 𝒉𝒂𝒔 𝒅𝒊𝒎𝒆𝒏𝒔𝒊𝒐𝒏𝒔 𝒐𝒇 𝒍𝒆𝒏𝒈𝒕𝒉) 94

 The translational partition function of a particle that is free
to move in three-dimensional container of edges X,Y,Z is qX

1/2
2𝜋𝑚 𝑋𝑌𝑍 𝑉(𝑉𝑜𝑙𝑢𝑚𝑒) • 𝒎 𝒊𝒔 𝒎𝒂𝒔𝒔 𝒐𝒇 𝒐𝒏𝒆 𝒑𝒂
𝑞𝑋 = 𝑋= 3 = • h is Planck constant
ℎ2 𝛽 Λ Λ3 •
𝟏
𝜷 = 𝒌𝑻 ; 𝒌 𝒊𝒔 𝑩𝒐𝒍𝒕𝒛𝒎𝒂

𝟏/𝟐 𝟐 𝟏/𝟐
𝜷 𝜷𝒉 𝒉
𝑻𝒉𝒆𝒓𝒎𝒂𝒍 𝒘𝒂𝒗𝒆𝒍𝒆𝒏𝒈𝒕𝒉: 𝜦 = 𝒉 = =
𝟐𝝅𝒎 𝟐𝝅𝒎 𝟐𝝅𝒎𝒌𝑻

(𝚲 𝒉𝒂𝒔 𝒅𝒊𝒎𝒆𝒏𝒔𝒊𝒐𝒏𝒔 𝒐𝒇 𝒍𝒆𝒏𝒈𝒕𝒉) 95

Statistical Thermodynamics
(The link between individual molecular properties
and bulk thermodynamic properties)

The Rotational Contribution to

Molecular Partition Function
(Linear Rotor)
96
 The partition function of a
nonsymmetrical linear rotor of type AB

The energy levels of a linear rotor are 𝜺𝑱 = 𝒉𝒄𝑩𝑱(𝑱 + 𝟏) with J = 0, 1, 2, …….

The state of lowest energy has zero energy, so no adjustment needed

Each level consists of 𝟐𝑱 + 𝟏 degenerate states
 𝑞 𝑅 = ෍ 2𝐽 + 1 𝑒 −𝛽ℎ𝑐B𝐽 𝐽+1

𝐽
The direct method of calculating qR is to substitute experimental values of
rotational energy levels into this equation and to sum the series numerically
 𝑞 𝑅 = ෍ 2𝐽 + 1 𝑒 −𝛽ℎ𝑐B𝐽 𝐽+1

𝑘𝑇
At room temperature = 200 𝑐𝑚−1
ℎ𝑐

𝑪𝑶𝟐 𝑰𝟐 𝑯𝑰 𝑯𝑪𝒍
𝐵/𝑐𝑚−1 0.39 0.037 6.5 10.6

H2, a very light molecule is an exception for which B = 60.9 cm-1

At normal temperature, many rotational levels are significantly populated

 𝑞 𝑅 = ෍ 2𝐽 + 1 𝑒 −𝛽ℎ𝑐B𝐽 𝐽+1

∞
𝑞𝑅 = න 2𝐽 + 1 𝑒 −𝛽ℎ𝑐B𝐽 𝐽+1 𝑑𝐽
0

100
 𝟏
𝒒𝑹 =
𝜷𝒉𝒄𝑩
101
 𝑹
𝟏
𝒒 =
𝜷𝒉𝒄𝑩

Above what temperature this approximation is valid?

𝒌𝜽𝑹 = 𝒉𝒄𝑩
𝜽𝑹 𝒊𝒔 𝐫𝐨𝐚𝐭𝐢𝐨𝐧𝐚𝐥 𝐭𝐞𝐦𝐩𝐞𝐫𝐚𝐭𝐮𝐫𝐞
High temperature means 𝑻 ≫ 𝜽𝑹
𝑰𝟐 𝑪𝑶𝟐 𝑯𝑰 𝑯𝑪𝒍 𝑪𝑯𝟒 𝑯𝟐
𝑩/𝒄𝒎−𝟏 0.053 0.56 7.5 9.4 15 88
102
 𝑰𝟐 𝑪𝑶𝟐 𝑯𝑰 𝑯𝑪𝒍 𝑪𝑯𝟒 𝑯𝟐
𝑩/𝒄𝒎−𝟏 0.053 0.56 7.5 9.4 15 88

𝑹
𝟏
𝒒 = 𝒌𝜽𝑹 = 𝒉𝒄𝑩
𝜷𝒉𝒄𝑩

• The molecules which have large moments of inertia have small rotational
constants and hence low rotational temperatures

• Such molecules have large rotational partition functions

• Large values of 𝒒𝑹 reflect closeness in energy of rotational energy levels (for

heavy molecules) and large number are populated at normal temperatures
103
 Caution: Do not include too many rotational states in the sum
• For a homonuclear diatomic molecule (symmetrical linear molecule):
𝑪𝑶𝟐 𝒐𝒓 𝑯𝑪 ≡ 𝑪𝑯 , rotation through 180 degree results in an
indistinguishable state of the molecule

• Therefore, the number of thermally accessible states is only half of the

number that can be occupied by a heteronuclear diatomic molecule in
which rotation through 180 degree results in distinguishable state

𝑹 𝒌𝑻
• For symmetrical linear molecule 𝒒 =
𝟐𝒉𝒄𝑩
104
Rotational contribution to q in the high temperature limit (linear rotors)

𝑹 𝒌𝑻
In general: 𝒒 =
𝝈𝒉𝑪𝑩
𝒌𝜽𝑹 = 𝒉𝒄𝑩
𝒌𝑻 𝑻
𝒒𝑹 = =
𝛔𝐡𝐜𝑩 𝝈𝜽𝑹

𝝈: 𝑺𝒚𝒎𝒎𝒆𝒕𝒓𝒚 𝒏𝒖𝒎𝒃𝒆𝒓

For heteronuclear diatomic molecules, 𝝈 = 𝟏

For homonuclear diatomic molecules, 𝝈 = 𝟐 105

Statistical Thermodynamics
(The link between individual molecular properties
and bulk thermodynamic properties)

The Rotational Contribution to

Molecular Partition Function
(Nonlinear Rotor)
106
Rotational contribution to q in the high temperature limit (linear rotors)

𝑹 𝒌𝑻
In general: 𝒒 =
𝝈𝒉𝑪𝑩
𝒌𝜽𝑹 = 𝒉𝒄𝑩
𝒌𝑻 𝑻
𝒒𝑹 = =
𝛔𝐡𝐜𝑩 𝝈𝜽𝑹

𝝈: 𝑺𝒚𝒎𝒎𝒆𝒕𝒓𝒚 𝒏𝒖𝒎𝒃𝒆𝒓

For heteronuclear diatomic molecules, 𝝈 = 𝟏

For homonuclear diatomic molecules, 𝝈 = 𝟐 107

Evaluate the rotational partition function of 1H35Cl at 25°C, given that
B= 10.591 cm−1 .
𝑘𝑇 ℎ𝑐𝐵
= 207.22 cm−1 = 0.051
ℎ𝑐 kT
ℎ𝑐𝐵
− 𝑘𝑇 𝐽(𝐽+1)
𝑞𝑅 = ෍ 2𝐽 + 1 𝑒 −𝛽ℎ𝑐B𝐽 𝐽+1 = ෍(2𝐽 + 1)𝑒
𝐽 𝐽

J 0 1 2 3 4 10
ℎ𝑐𝐵 1 2.71 3.68 3.79 3.24 0.08
− 𝑘𝑇 𝐽(𝐽+1)
(2𝐽 + 1)𝑒

By this sum, 𝒒𝑹 = 𝟏𝟗. 𝟗

Taking J up to 50, 𝒒𝑹 = 𝟏𝟗. 𝟗𝟎𝟐

Evaluate the rotational partition function of 1H35Cl at 25°C, given that
B= 10.591 cm−1 .
𝑘𝑇 ℎ𝑐𝐵෨
= 207.22 cm−1 = 0.051 11
ℎ𝑐 kT

• Contributions to the rotational partition function of an HCl

molecule at 25°C.

෩ 𝐉+𝟏
• The vertical axis is the value of 𝟐𝐉 + 𝟏 𝐞−𝛃𝐡𝐜𝐁𝐉

• Successive terms (which are proportional to the populations

of the levels) pass through a maximum because the
population of individual states decreases exponentially, but
the degeneracy of the levels increases with J
 Rotational contribution to q in the high temperature limit
(nonlinear molecules)
3/2 1/2
𝑅
1 𝑘𝑇 𝜋
𝑞 = Typical values of symmetry number
𝜎 ℎ𝑐 𝐴𝐵𝐶 𝑯𝟐 𝑶 𝑵𝑯𝟑 𝑪𝑯𝟒 𝑪𝟔 𝑯𝟔
𝝈 2 3 12 12
𝑨, 𝑩, 𝒂𝒏𝒅 𝑪 𝒂𝒓𝒆
𝒓𝒐𝒕𝒂𝒕𝒊𝒐𝒏𝒂𝒍 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕𝒔
• 𝝈 𝑯𝟐 𝑶 = 𝟐: 𝟏𝟖𝟎𝒐 𝒓𝒐𝒕𝒂𝒕𝒊𝒐𝒏 𝒂𝒃𝒐𝒖𝒕 𝒊𝒕𝒔 𝑪𝟐 𝒂𝒙𝒊𝒔 𝒊𝒏𝒕𝒆𝒓𝒄𝒉𝒂𝒏𝒈𝒆𝒔 𝒕𝒘𝒐𝒊Indistinguishable stoms

• 𝝈 𝑵𝑯𝟑 = 𝟑: 𝒕𝒉𝒓𝒆𝒆 𝒊𝒏𝒅𝒊𝒔𝒕𝒊𝒏𝒈𝒖𝒊𝒔𝒉𝒂𝒃𝒍𝒆 𝒐𝒓𝒊𝒆𝒏𝒕𝒂𝒕𝒊𝒐𝒏𝒔 𝒂𝒓𝒐𝒖𝒏𝒅 𝒊𝒕𝒔 𝑪𝟑 𝒂𝒙𝒊𝒔

• 𝝈 𝑪𝑯𝟒 = 𝟏𝟐: 𝒂𝒏𝒚 𝒐𝒇 𝒕𝒉𝒓𝒆𝒆 𝟏𝟐𝟎𝒐 𝒓𝒐𝒕𝒂𝒕𝒊𝒐𝒏 𝒂𝒃𝒐𝒖𝒕 𝒂𝒏𝒚 𝒐𝒇 𝒊𝒕 𝐟our C-H bonds leaves the moleculas
in an indistinguishable state, hence symmetry number is 𝟑 × 𝟒 = 𝟏𝟐

• 𝝈 𝑪𝟔 𝑯𝟔 = 𝟏𝟐: 𝒂𝒏𝒚 𝒐𝒇 𝒔𝒊𝒙 𝒐𝒓𝒊𝒆𝒏𝒕𝒂𝒕𝒊𝒐𝒏𝒔 𝒂𝒓𝒐𝒖𝒏𝒅 𝒊𝒕𝒔 𝒔𝒊𝒙 𝑪𝟔 𝒂𝒙𝒊𝒔 𝒍𝒆𝒂𝒗𝒆𝒔 𝒊𝒕 𝒖𝒏𝒄𝒉𝒂𝒏𝒈𝒆𝒅, and
rotation of 𝟏𝟖𝟎𝒐 𝒂𝒓𝒐𝒖𝒏𝒅 𝒂𝒏𝒚 𝒐𝒇 𝒊𝒕𝒔 𝒔𝒊𝒙 𝑪𝟐 𝒂𝒙𝒆𝒔 𝒊𝒏 𝒕𝒉𝒆 𝒑𝒍𝒂𝒏𝒆 𝒐𝒇 𝒎𝒐𝒍𝒆𝒄𝒖𝒍𝒆
Statistical Thermodynamics
(The link between individual molecular properties
and bulk thermodynamic properties)

The Rotational Contribution to

Molecular Partition Function
(Linear and Nonlinear Rotor)
111
Rotational contribution to q in the high temperature limit (linear rotors)

𝑹 𝒌𝑻
In general: 𝒒 =
𝝈𝒉𝑪𝑩
𝒌𝜽𝑹 = 𝒉𝒄𝑩
𝒌𝑻 𝑻
𝒒𝑹 = =
𝛔𝐡𝐜𝑩 𝝈𝜽𝑹

𝝈: 𝑺𝒚𝒎𝒎𝒆𝒕𝒓𝒚 𝒏𝒖𝒎𝒃𝒆𝒓

For heteronuclear diatomic molecules, 𝝈 = 𝟏

For homonuclear diatomic molecules, 𝝈 = 𝟐 112

The bond length of O2 is 120.75 pm. Use the high temperature
approximation to calculate the rotational partition of the molecule at
300 K.

𝒌𝑻 𝑻 𝟖𝝅 𝟐 𝒌𝑻𝝁𝑹𝟐
𝒒𝑹 = = =
𝛔𝐡𝐜𝑩 𝝈𝜽𝑹 𝝈𝒉𝟐

113
 𝑹
𝒒 = 𝟕𝟏. 𝟐
114
 Rotational contribution to q in the high temperature limit
(nonlinear molecules)
3/2 1/2
𝑅
1 𝑘𝑇 𝜋
𝑞 = Typical values of symmetry number
𝜎 ℎ𝑐 𝐴𝐵𝐶 𝑯𝟐 𝑶 𝑵𝑯𝟑 𝑪𝑯𝟒 𝑪𝟔 𝑯𝟔
𝝈 2 3 12 12
𝑨, 𝑩, 𝒂𝒏𝒅 𝑪 𝒂𝒓𝒆
𝒓𝒐𝒕𝒂𝒕𝒊𝒐𝒏𝒂𝒍 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕𝒔
• 𝝈 𝑯𝟐 𝑶 = 𝟐: 𝟏𝟖𝟎𝒐 𝒓𝒐𝒕𝒂𝒕𝒊𝒐𝒏 𝒂𝒃𝒐𝒖𝒕 𝒊𝒕𝒔 𝑪𝟐 𝒂𝒙𝒊𝒔 𝒊𝒏𝒕𝒆𝒓𝒄𝒉𝒂𝒏𝒈𝒆𝒔 𝒕𝒘𝒐𝒊Indistinguishable stoms

• 𝝈 𝑵𝑯𝟑 = 𝟑: 𝒕𝒉𝒓𝒆𝒆 𝒊𝒏𝒅𝒊𝒔𝒕𝒊𝒏𝒈𝒖𝒊𝒔𝒉𝒂𝒃𝒍𝒆 𝒐𝒓𝒊𝒆𝒏𝒕𝒂𝒕𝒊𝒐𝒏𝒔 𝒂𝒓𝒐𝒖𝒏𝒅 𝒊𝒕𝒔 𝑪𝟑 𝒂𝒙𝒊𝒔

• 𝝈 𝑪𝑯𝟒 = 𝟏𝟐: 𝒂𝒏𝒚 𝒐𝒇 𝒕𝒉𝒓𝒆𝒆 𝟏𝟐𝟎𝒐 𝒓𝒐𝒕𝒂𝒕𝒊𝒐𝒏 𝒂𝒃𝒐𝒖𝒕 𝒂𝒏𝒚 𝒐𝒇 𝒊𝒕 𝐟our C-H bonds leaves the moleculas
in an indistinguishable state, hence symmetry number is 𝟑 × 𝟒 = 𝟏𝟐

• 𝝈 𝑪𝟔 𝑯𝟔 = 𝟏𝟐: 𝒂𝒏𝒚 𝒐𝒇 𝒔𝒊𝒙 𝒐𝒓𝒊𝒆𝒏𝒕𝒂𝒕𝒊𝒐𝒏𝒔 𝒂𝒓𝒐𝒖𝒏𝒅 𝒊𝒕𝒔 𝒔𝒊𝒙 𝑪𝟔 𝒂𝒙𝒊𝒔 𝒍𝒆𝒂𝒗𝒆𝒔 𝒊𝒕 𝒖𝒏𝒄𝒉𝒂𝒏𝒈𝒆𝒅, and
rotation of 𝟏𝟖𝟎𝒐 𝒂𝒓𝒐𝒖𝒏𝒅 𝒂𝒏𝒚 𝒐𝒇 𝒊𝒕𝒔 𝒔𝒊𝒙 𝑪𝟐 𝒂𝒙𝒆𝒔 𝒊𝒏 𝒕𝒉𝒆 𝒑𝒍𝒂𝒏𝒆 𝒐𝒇 𝒎𝒐𝒍𝒆𝒄𝒖𝒍𝒆 115
Statistical Thermodynamics
(The link between individual molecular properties
and bulk thermodynamic properties)

Rotational Partition Function

(Nonlinear Rotor and some numerical
problems)
116
 Rotational contribution to q in the high temperature limit
(nonlinear molecules)
3/2 1/2
𝑅
1 𝑘𝑇 𝜋
𝑞 = Typical values of symmetry number
𝜎 ℎ𝑐 𝐴𝐵𝐶 𝑯𝟐 𝑶 𝑵𝑯𝟑 𝑪𝑯𝟒 𝑪𝟔 𝑯𝟔
𝝈 2 3 12 12
𝑨, 𝑩, 𝒂𝒏𝒅 𝑪 𝒂𝒓𝒆
𝒓𝒐𝒕𝒂𝒕𝒊𝒐𝒏𝒂𝒍 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕𝒔
• 𝝈 𝑯𝟐 𝑶 = 𝟐: 𝟏𝟖𝟎𝒐 𝒓𝒐𝒕𝒂𝒕𝒊𝒐𝒏 𝒂𝒃𝒐𝒖𝒕 𝒊𝒕𝒔 𝑪𝟐 𝒂𝒙𝒊𝒔 𝒊𝒏𝒕𝒆𝒓𝒄𝒉𝒂𝒏𝒈𝒆𝒔 𝒕𝒘𝒐𝒊Indistinguishable stoms

• 𝝈 𝑵𝑯𝟑 = 𝟑: 𝒕𝒉𝒓𝒆𝒆 𝒊𝒏𝒅𝒊𝒔𝒕𝒊𝒏𝒈𝒖𝒊𝒔𝒉𝒂𝒃𝒍𝒆 𝒐𝒓𝒊𝒆𝒏𝒕𝒂𝒕𝒊𝒐𝒏𝒔 𝒂𝒓𝒐𝒖𝒏𝒅 𝒊𝒕𝒔 𝑪𝟑 𝒂𝒙𝒊𝒔

• 𝝈 𝑪𝑯𝟒 = 𝟏𝟐: 𝒂𝒏𝒚 𝒐𝒇 𝒕𝒉𝒓𝒆𝒆 𝟏𝟐𝟎𝒐 𝒓𝒐𝒕𝒂𝒕𝒊𝒐𝒏 𝒂𝒃𝒐𝒖𝒕 𝒂𝒏𝒚 𝒐𝒇 𝒊𝒕 𝐟our C-H bonds leaves the moleculas
in an indistinguishable state, hence symmetry number is 𝟑 × 𝟒 = 𝟏𝟐

• 𝝈 𝑪𝟔 𝑯𝟔 = 𝟏𝟐: 𝒂𝒏𝒚 𝒐𝒇 𝒔𝒊𝒙 𝒐𝒓𝒊𝒆𝒏𝒕𝒂𝒕𝒊𝒐𝒏𝒔 𝒂𝒓𝒐𝒖𝒏𝒅 𝒊𝒕𝒔 𝒔𝒊𝒙 𝑪𝟔 𝒂𝒙𝒊𝒔 𝒍𝒆𝒂𝒗𝒆𝒔 𝒊𝒕 𝒖𝒏𝒄𝒉𝒂𝒏𝒈𝒆𝒅, and
rotation of 𝟏𝟖𝟎𝒐 𝒂𝒓𝒐𝒖𝒏𝒅 𝒂𝒏𝒚 𝒐𝒇 𝒊𝒕𝒔 𝒔𝒊𝒙 𝑪𝟐 𝒂𝒙𝒆𝒔 𝒊𝒏 𝒕𝒉𝒆 𝒑𝒍𝒂𝒏𝒆 𝒐𝒇 𝒎𝒐𝒍𝒆𝒄𝒖𝒍𝒆 117
The NOF molecule is an asymmetric rotor with rotational constants
3.1752 cm-1, 0.3951 cm-1 and 0.3505 cm-1. Calculate the rotational
partition function of the molecule at 100oC
𝟑/𝟐
𝑹
𝟏 𝒌𝑻 𝝅 𝟏/𝟐 𝟏. 𝟎𝟐𝟕𝟎 𝑻/𝑲 𝟑/𝟐
𝒒 = = ×
𝝈 𝒉𝒄 𝑨𝑩𝑪 𝝈 𝑨𝑩𝑪/𝒄𝒎−𝟑 𝟏/𝟐

𝒒𝑹 = 𝟏. 𝟏𝟐 × 𝟏𝟎𝟒 118
Calculate the equation of state associated with the partition function
𝟑𝑵
𝟏 𝟐𝝅𝒎 𝟐 𝜷𝒂𝑵𝟐
𝑸 𝑵, 𝑽, 𝜷 = 𝑽 − 𝒏𝒃 𝑵𝒆 𝑽
𝑵! 𝒉𝟐 𝜷
Where a and b are constants

𝝏𝒍𝒏𝑸
𝒑 = 𝒌𝑻
𝝏𝑽 𝑻

119
 𝒂𝑵𝟐
𝒑+ 𝟐 𝑽 − 𝒏𝒃 = 𝑵𝒌𝑻
𝑽
120
Derive an equation for the <E> for simple system of a (bare) proton in
a magnetic field BZ
𝟏
The energy is given by 𝑬±𝟏/𝟐 = ∓ ℏ𝜸𝑩𝒁
𝟐

𝑴𝒂𝒈𝒏𝒆𝒕𝒐𝒈𝒚𝒓𝒊𝒄 𝒓𝒂𝒕𝒊𝒐 𝜸 = 𝒏𝒖𝒄𝒍𝒆𝒂𝒓 𝒇𝒂𝒄𝒕𝒐𝒓 𝒈𝑵 × 𝒏𝒖𝒄𝒍𝒆𝒂𝒓𝒎𝒂𝒈𝒏𝒆𝒕𝒐𝒏 (𝜷𝑵 )

𝜷ℏ𝜸𝑩𝒁 𝜷ℏ𝜸𝑩𝒁
−
𝑸= 𝒆 𝟐 +𝒆 𝟐

𝝏𝒍𝒏𝑸 𝟏 𝝏𝑸
𝑼−𝑼 𝟎 =− =−
𝝏𝜷 𝑩𝒁
𝑸 𝝏𝜷 𝑩𝒁

𝜷ℏ𝜸𝑩𝒁 𝜷ℏ𝜸𝑩𝒁
−
ℏ𝜸𝑩𝒁 𝒆 𝟐 −𝒆 𝟐
𝑬 =− 𝜷ℏ𝜸𝑩𝒁 𝜷ℏ𝜸𝑩
𝟐 − 𝟐 𝒁
𝒆 𝟐 +𝒆 121
Statistical Thermodynamics
(The link between individual molecular properties
and bulk thermodynamic properties)

Vibrational Partition Function - I

122
 Vibrational contribution to partition function 𝒒𝑽

A nonlinear molecule that consists of N atoms, there are 3N − 6

independent modes of vibration

If the molecule is linear, there are 3N − 5 independent

vibrational modes

• In a polyatomic molecule, each normal mode has its own partition function
(as long as anharmonicities are very small)

𝒒𝑽 = 𝒒𝑽 𝟏 𝒒𝑽 𝟐 … … … … .

• Here 𝒒𝑽 (𝑲) is the partition function for the kth normal mode
Given that a typical value of the vibrational partition of one normal mode is about
1.1, estimate the overall vibrational partitional function of non-linear molecule
containing 10 atoms

𝒒𝑽 ≈ 𝟏. 𝟏 𝟐𝟒 = 𝟗. 𝟗
 Vibrational Contribution

If the vibrational excitation is not too large, harmonic oscillator

approximation may be made

Vibrational energy levels:

𝟏
𝑬𝒗 = 𝒗 + 𝒉𝒄෥
𝒗 𝒗 = 𝟎, 𝟏, 𝟐 … .
𝟐

Measuring energies from zero-point level, then

𝜺𝒗 = 𝒗𝒉𝒄෥
𝒗
 Vibrational Contribution

If the vibrational excitation is not too large, harmonic oscillator

approximation may be made

Vibrational energy levels:

1
𝐸𝑣 = 𝑣 + ℎ𝑐 𝑣෤ 𝑣 = 0,1,2 … .
2

Measuring energies from zero-point level, then

𝜀𝑣 = 𝑣ℎ𝑐 𝑣෤
Statistical Thermodynamics
(The link between individual molecular properties
and bulk thermodynamic properties)

Vibrational Partition Function-II

127
 Vibrational Contribution

If the vibrational excitation is not too large, harmonic oscillator

approximation may be made

Vibrational energy levels:

1
𝐸𝑣 = 𝑣 + ℎ𝑐 𝑣෤ 𝑣 = 0,1,2 … .
2

Measuring energies from zero-point level, then

𝜀𝑣 = 𝑣ℎ𝑐 𝑣෤
 ෤ 𝑣
𝑞𝑉 = ෍ 𝑒 −𝛽𝑣ℎ𝑐𝑣෤ =෍ 𝑒 −𝛽ℎ𝑐 𝑣

𝑣 𝑣
 ෤ 𝑣
𝑞𝑉 = ෍ 𝑒 −𝛽𝑣ℎ𝑐𝑣෤ =෍ 𝑒 −𝛽ℎ𝑐 𝑣

𝑣 𝑣
 ෤ 𝑣
𝑞𝑉 = ෍ 𝑒 −𝛽𝑣ℎ𝑐𝑣෤ =෍ 𝑒 −𝛽ℎ𝑐 𝑣

𝑣 𝑣

𝑉
1
𝑞 =
1 − 𝑒 −𝛽𝑣ℎ𝑐𝑣෤
 𝑉
1
𝑞 =
1 − 𝑒 −𝛽ℎ𝑐𝑣෤

For very high vibrational wavenumbers 𝜷𝒗𝒉𝒄෥

𝒗 >> 𝟏

𝒒𝑽 ≈ 𝟏

Example:

For 𝑪𝑯𝟒 the lowest vibrational wavenumbers in cm-1 is

1306

𝒗 = 6 at room temperature in this case

𝜷𝒗𝒉𝒄෥

𝒆−𝟔 = 𝟎. 𝟎𝟎𝟐
 𝑉
1
𝑞 =
1 − 𝑒 −𝛽ℎ𝑐𝑣෤

For weak bonds 𝜷𝒉𝒄෥

𝒗 ≪ 𝟏; 𝐨𝐫 𝐤𝐓 ≫ 𝒉𝒄෥
𝒗

1
𝑞𝑉 =
1 − (1 − 𝛽ℎ𝑐𝑉෨ + ⋯ )

1 𝑘𝑇
𝑞𝑉 = =
𝛽ℎ𝑐 𝑉 ℎ𝑐𝑉෨
෨
The vibrational partition function
of a molecule in the harmonic
approximation. Note that the
partition function is linearly
proportional to the temperature
when the temperature is high (T >>
θV)
 For weak bonds 𝜷𝒗𝒉𝒄෥
𝒗 ≪ 𝟏; 𝐨𝐫 𝐤𝐓 ≫ 𝜷𝒉𝒄෥
𝒗
𝑉
1 𝑘𝑇
𝑞 = =
𝛽ℎ𝑐 𝑣෤ ℎ𝑐𝑣෤

The temperatures where this expansion approximation is valid can be

expressed in terms of Vibrational Temperature 𝜽𝑽

𝒌𝜽𝑽 = 𝒉𝒄෥
𝒗

1 𝑘𝑇 𝑇
𝑞𝑉 = = =
𝛽ℎ𝑐 𝑣෤ ℎ𝑐 𝑣෤ 𝜃𝑉
Statistical Thermodynamics
(The link between individual molecular properties
and bulk thermodynamic properties)

Vibrational Partition Function-

Applications
136
 𝑉
1 𝑯𝒊𝒈𝒉 𝒕𝒆𝒎𝒑𝒆𝒓𝒂𝒕𝒖𝒓𝒆 𝒓𝒆𝒔𝒖𝒍𝒕:
𝑮𝒆𝒏𝒆𝒓𝒂𝒍: 𝑞 = 1 𝑘𝑇 𝑇
1 − 𝑒 −𝛽ℎ𝑐𝑣෤ 𝑉
𝑞 = = =
𝛽ℎ𝑐 𝑣෤ ℎ𝑐 𝑣෤ 𝜃𝑉

The temperatures where this expansion approximation is valid can be

expressed in terms of Vibrational Temperature 𝜽𝑽

𝒌𝜽𝑽 = 𝒉𝒄෥
𝒗
In terms of vibrational temperature, “high temperature” means 𝑻 ≫ 𝜽𝑽

𝑰𝟐 𝑭𝟐 𝑯𝑪𝒍 𝑯𝟐
෥/𝒄𝒎−𝟏
𝒗 215 892 2990 4400
𝜽𝑽 /K 309 1280 4300 6330 137
The wavenumbers of the three normal modes of H2O are 3656.7 cm−1,
1594.8 cm−1, and 3755.8 cm−1. Evaluate the vibrational partition function
at 1500 K.

𝒉 = 𝟔. 𝟔𝟐𝟑 × 𝟏𝟎−𝟑𝟒 𝑱 𝒔; 𝒌 = 𝟏. 𝟑𝟖𝟏 × 𝟏𝟎−𝟐𝟑 𝑱 𝑲−𝟏 ; 𝒄 = 𝟑. 𝟎 × 𝟏𝟎𝟏𝟎 𝒄𝒎 𝒔−𝟏

138
The wavenumbers of the three normal modes of H2O are 3656.7 cm−1,
1594.8 cm−1, and 3755.8 cm−1. Evaluate the vibrational partition function
at 1500 K.

Mode 1 2 3
෥/𝒄𝒎−𝟏
𝒗 3656.7 1594.8 3755.8
𝒗/kT
hc෥ 3.508 1.530 3.603
𝒒𝑽 1.031 1.276 1.028

The overall vibrtational partition function: 𝒒𝑽 = 𝟏. 𝟎𝟑𝟏 × 𝟏. 𝟐𝟕𝟔 × 𝟏. 𝟎𝟐𝟖 = 𝟏. 𝟑𝟓𝟑

The vibrations of 𝑯𝟐 𝑶 are at such high wavenumber that even at 1500 K,

most of the molecules are in their vibrational ground state 139
Calculate the value of the molecular partition function for 𝑵𝟑 (𝒈) at 298 K.
For 𝑵𝟑 𝒈 ; 𝒗
෥(1) = 1800 cm-1; 𝒗
෥(2) = 500 cm-1; 𝒈𝟐 = 𝟐; 𝒗
෥(3) 1200 cm-1

𝑉
1
𝑮𝒆𝒏𝒆𝒓𝒂𝒍: 𝑞 =
1 − 𝑒 −𝛽ℎ𝑐𝑣෤

𝒌𝜽𝑽 = 𝒉𝒄෥
𝒗

𝜽𝑽 𝟏 = 𝟐𝟓𝟖𝟖. 𝟒 𝑲; 𝜽𝑽 𝟐 = 𝟕𝟏𝟗 𝑲; 𝜽𝑽 𝟑 = 𝟏𝟕𝟐𝟓. 𝟔 𝑲

140
 𝑉
1
𝑮𝒆𝒏𝒆𝒓𝒂𝒍: 𝑞 = ෤
1 − 𝑒 −ℎ𝑐𝑣/𝑘𝑇

𝒒𝑽 𝟏 = 𝟏. 𝟎𝟎𝟎𝟏𝟗

𝒒𝑽 𝟐 = 𝟏. 𝟎𝟗𝟖𝟑𝟎; 𝒈𝒐 = 𝟐

𝒒𝑽 𝟑 = 𝟏. 𝟎𝟎𝟑𝟎𝟔

𝒒𝑽 = 𝒒𝑽 (𝟏) × [𝒒𝑽 (𝟐) × 𝒒𝑽 (𝟐)] × 𝒒𝑽 (𝟑) = 𝟏. 𝟎𝟎𝟎𝟏𝟕 × 𝟏. 𝟎𝟗𝟖𝟑𝟎 𝟐 × 𝟏. 𝟎𝟎𝟑𝟎𝟔 = 𝟏. 𝟐𝟏𝟎

141
Statistical Thermodynamics
(The link between individual molecular properties
and bulk thermodynamic properties)

Electronic Partition Function

142
 Electronic Contribution

Electronic energy separations from ground state are usually very large

𝒒𝑬 = ෍ 𝒈𝒋 𝒆−𝜷𝜺𝒋
𝒆𝒏𝒆𝒓𝒈𝒚 𝒍𝒆𝒗𝒆𝒍𝒔

Usually 𝒒𝑬 = 𝟏 𝒆𝒙𝒄𝒆𝒑𝒕 𝒊𝒏 𝒄𝒂𝒔𝒆 𝒐𝒇 𝒂𝒕𝒐𝒎𝒔 𝒐𝒓 𝒎𝒐𝒍𝒆𝒄𝒖𝒍𝒆𝒔 𝒉𝒂𝒗𝒊𝒏𝒈

𝒆𝒍𝒆𝒄𝒕𝒓𝒐𝒏𝒊𝒄𝒂𝒍𝒍𝒚 𝒅𝒆𝒈𝒆𝒏𝒆𝒓𝒂𝒕𝒆 𝒈𝒓𝒐𝒖𝒏𝒅 𝒔𝒕𝒂𝒕𝒆 143
Some atoms and molecules have low-lying electronically excited states

Example: NO with configuration …….𝝅𝟏

𝑵𝟐 NO 144
 Electronic Contribution
• The orbital angular momentum may take two
orientations with respect to the molecular axis
(corresponding to circulation clockwise or counter-clockwise around the axis)

• The spin angular momentum may also take two

• Thus there are four states in all

• The energy of the two states in which the orbital

and spin momenta are parallel [ 𝟐𝜫𝟑/𝟐 ]

• The other [ 𝟐𝜫𝟏/𝟐 ] with antiparallel momenta is

lower in energy

• At normal temperature, all four states are accessible 145

 Electronic Contribution

𝑞𝐸 = ෍ 𝑔𝑗 𝑒 −𝛽𝜀𝑗 = 2 + 2𝑒 −𝛽𝜀
𝑒𝑛𝑒𝑟𝑔𝑦 𝑙𝑒𝑣𝑒𝑙𝑠

The doubly degenerate ground electronic level of NO

(with the spin and orbital angular momentum around
the axis in opposite directions) and the doubly
degenerate first excited level (with the spin and orbital
momenta parallel). The upper level is thermally
accessible at room temperature.
146
 𝑞𝐸 = ෍ 𝑔𝑗 𝑒 −𝛽𝜀𝑗 = 2 + 2𝑒 −𝛽𝜀
𝑒𝑛𝑒𝑟𝑔𝑦 𝑙𝑒𝑣𝑒𝑙𝑠

At T = 0, 𝒒𝑬 = 𝟐

As T is very large, 𝒒𝑬 approaches a value of 4

At 𝟐𝟓𝒐 𝑪, 𝒒𝑬 = 𝟐. 𝟖

147
Statistical Thermodynamics
(The link between individual molecular properties
and bulk thermodynamic properties)

Mean Energies

148
 The overall partition function
For a diatomic molecule with no low-lying electronically excited states:

𝑽 𝒌𝑻 𝟏
𝒒= 𝒈𝑬 × 𝟑× ×
Ʌ 𝝈𝒉𝒄𝜷 𝟏 − 𝒆−𝜷𝒉𝒄ῡ

𝑽 𝑬
𝑻 𝟏
𝒒=𝒈 × 𝟑× × 𝑻
Ʌ 𝝈𝜽𝑹 −𝜽
𝟏 −𝒆 𝑽

Overall partition functions obtained in this way are approximate because

they assume that the rotational levels are very close and that the vibrational
levels are harmonic

These approximations are avoided by using the energy levels identified

spectroscopically and evaluating the sums explicitly.
 Mean Energies

𝑵 𝝏𝒒
𝑼−𝑼 𝟎 =−
𝒒 𝝏𝜷 𝑽
 Mean Energies

𝑵 𝝏𝒒
𝑼−𝑼 𝟎 =−
𝒒 𝝏𝜷 𝑽
 The Mean Translational Energy
𝑴
𝟏 𝝏𝒒
𝜺 =− 𝑴 𝑴 = 𝑻, 𝑹, 𝑽, 𝑬
𝒒 𝝏𝜷 𝑽

𝟏
For one-dimensional system of length X: < 𝜺 > =
𝑻
𝒌𝑻
𝟐
• For a molecule free to move in three dimensions: < 𝜺𝑻 > =
𝟑
𝒌𝑻
𝟐

• Both conclusions are in agreement with the classical

equipartition theorem

• Furthermore, the fact that the mean energy is independent

of the size of the container is consistent with the
thermodynamic result that the internal energy of a perfect
gas is independent of its volume
The Mean Rotational Energy

𝒒𝑹 = 𝟏 + 𝟑𝒆−𝟐𝜷𝒉𝒄𝑩 + 𝟓𝒆−𝟔𝜷𝒉𝒄𝑩 + ⋯
 𝒉𝒄𝑩 𝟔𝒆−𝟐𝜷𝒉𝒄𝑩 + 𝟑𝟎𝒆−𝟔𝜷𝒉𝒄𝑩 + ⋯
𝜺𝑹 =
𝟏 + 𝟑𝒆−𝟐𝜷𝒉𝒄𝑩 + 𝟓𝒆−𝟔𝜷𝒉𝒄𝑩 + ⋯ .
 𝒉𝒄𝑩 𝟔𝒆−𝟐𝜷𝒉𝒄𝑩 + 𝟑𝟎𝒆−𝟔𝜷𝒉𝒄𝑩 + ⋯
𝜺𝑹 =
𝟏 + 𝟑𝒆−𝟐𝜷𝒉𝒄𝑩 + 𝟓𝒆−𝟔𝜷𝒉𝒄𝑩 + ⋯ .
At high temperatures 𝑻 ≫ 𝜽𝑹

𝜺𝑹 = 𝒌𝑻
qR is independent of V, so the partial derivatives can
been replaced by complete derivatives

It follows from equipartition theorem that the mean

rotational energy for linear rotor is kT

The results are in agreement

Statistical Thermodynamics
(The link between individual molecular properties
and bulk thermodynamic properties)

Mean Energies

159
 The overall partition function
For a diatomic molecule with no low-lying electronically excited states:

𝑽 𝒌𝑻 𝟏
𝒒= 𝒈𝑬 × 𝟑× ×
Ʌ 𝝈𝒉𝒄𝜷 𝟏 − 𝒆−𝜷𝒉𝒄ῡ

𝑽 𝑬
𝑻 𝟏
𝒒=𝒈 × 𝟑× × 𝑻
Ʌ 𝝈𝜽𝑹 −𝜽
𝟏 −𝒆 𝑽

Overall partition functions obtained in this way are approximate because

they assume that the rotational levels are very close and that the vibrational
levels are harmonic

These approximations are avoided by using the energy levels identified

spectroscopically and evaluating the sums explicitly.
 Mean Energies

𝑵 𝝏𝒒
𝑼−𝑼 𝟎 =−
𝒒 𝝏𝜷 𝑽
 Mean Energies

𝑵 𝝏𝒒
𝑼−𝑼 𝟎 =−
𝒒 𝝏𝜷 𝑽
 The Mean Translational Energy
𝑴
𝟏 𝝏𝒒
𝜺 =− 𝑴 𝑴 = 𝑻, 𝑹, 𝑽, 𝑬
𝒒 𝝏𝜷 𝑽

𝟏
For one-dimensional system of length X: < 𝜺 > =
𝑻
𝒌𝑻
𝟐
• For a molecule free to move in three dimensions: < 𝜺𝑻 > =
𝟑
𝒌𝑻
𝟐

• Both conclusions are in agreement with the classical

equipartition theorem

• Furthermore, the fact that the mean energy is independent

of the size of the container is consistent with the
thermodynamic result that the internal energy of a perfect
gas is independent of its volume
The Mean Rotational Energy

𝒒𝑹 = 𝟏 + 𝟑𝒆−𝟐𝜷𝒉𝒄𝑩 + 𝟓𝒆−𝟔𝜷𝒉𝒄𝑩 + ⋯
 𝒉𝒄𝑩 𝟔𝒆−𝟐𝜷𝒉𝒄𝑩 + 𝟑𝟎𝒆−𝟔𝜷𝒉𝒄𝑩 + ⋯
𝜺𝑹 =
𝟏 + 𝟑𝒆−𝟐𝜷𝒉𝒄𝑩 + 𝟓𝒆−𝟔𝜷𝒉𝒄𝑩 + ⋯ .
 𝒉𝒄𝑩 𝟔𝒆−𝟐𝜷𝒉𝒄𝑩 + 𝟑𝟎𝒆−𝟔𝜷𝒉𝒄𝑩 + ⋯
𝜺𝑹 =
𝟏 + 𝟑𝒆−𝟐𝜷𝒉𝒄𝑩 + 𝟓𝒆−𝟔𝜷𝒉𝒄𝑩 + ⋯ .
At high temperatures 𝑻 ≫ 𝜽𝑹

𝜺𝑹 = 𝒌𝑻
qR is independent of V, so the partial derivatives can
been replaced by complete derivatives

It follows from equipartition theorem that the mean

rotational energy for linear rotor is kT

The results are in agreement

Statistical Thermodynamics
(The link between individual molecular properties
and bulk thermodynamic properties)

Mean Energies (continued)

170
The Mean Energy

𝟏 𝝏𝒒
𝜺𝑴 =− 𝑴 𝑴 = 𝑻, 𝑹, 𝑽, 𝑬
𝒒 𝝏𝜷 𝑽
 𝒉𝒄𝑩 𝟔𝒆−𝟐𝜷𝒉𝒄𝑩 + 𝟑𝟎𝒆−𝟔𝜷𝒉𝒄𝑩 + ⋯
𝜺𝑹 =
𝟏 + 𝟑𝒆−𝟐𝜷𝒉𝒄𝑩 + 𝟓𝒆−𝟔𝜷𝒉𝒄𝑩 + ⋯ .

𝜺𝑹 = 𝒌𝑻 High temperature
qR is independent of V, so the partial derivatives can
been replaced by complete derivatives

It follows from equipartition theorem that the mean

rotational energy for linear rotor is kT

The results are in agreement

 The mean vibrational energy

𝑉
ℎ𝑐 𝑣෤
𝜀 = 𝛽ℎ𝑐 ෤
𝑣
𝑒 −1
ℎ𝑐 𝑣෤ 1 Mean vibrational energy
𝜀𝑉 = ≈ = 𝑘𝑇 (High temperature limit)
1 + −𝛽ℎ𝑐 𝑣෤ + … … . − 1 𝛽
 The mean vibrational energy

𝑉
ℎ𝑐 𝑣෤
𝜀 =
𝑒𝛽ℎ𝑐𝑣෤ − 1

ℎ𝑐 𝑣෤ 1 Mean vibrational energy

𝜀𝑉 = ≈ = 𝑘𝑇 (High temperature limit)
1 + 𝛽ℎ𝑐 𝑣෤ + … … . − 1 𝛽
Statistical Thermodynamics
(The link between individual molecular properties
and bulk thermodynamic properties)

Heat Capacity

176
 𝝏𝑼
Constant volume heat capacity 𝑪𝑽 =
𝝏𝑻 𝑽

𝟐
𝝏𝑼
𝑪𝑽 = −𝒌𝜷
𝝏𝜷 𝑽
 𝟐
𝝏𝑼
𝑪𝑽 = −𝒌𝜷
𝝏𝜷 𝑽

𝑴
𝑴 𝝏 𝜺 𝝏 𝜺𝑴
𝑪𝑽 = 𝑵 = −𝑵𝒌𝜷𝟐
𝝏𝑻 𝑽
𝝏𝜷 𝑽
 𝑴
𝝏 𝜺 𝝏 𝜺𝑴
𝑪𝑴
𝑽 =𝑵 = −𝑵𝒌𝜷𝟐
𝝏𝑻 𝑽
𝝏𝜷 𝑽

𝑴 𝝏 𝜺𝑴 𝝏 𝜺𝑴
𝑪𝑽 = 𝒏𝑵𝑨 = −𝒏𝑵𝑨 𝒌𝜷𝟐
𝝏𝑻 𝑽
𝝏𝜷 𝑽

𝝏 𝜺𝑴 𝝏 𝜺𝑴
𝑪𝑴
𝑽,𝒎 = 𝑵𝑨 = −𝑵𝑨 𝒌𝜷𝟐
𝝏𝑻 𝑽
𝝏𝜷 𝑽
 Individual contributions

The temperature is always high enough (provided the gas is above its
condensation temperature) for the mean translational energy to be
𝟑
𝒌𝑻, the equipartition value.
𝟐

𝟑
𝑪𝑻𝑽,𝒎 = 𝑹
𝟐
 𝑪𝒑 𝟓
𝜸= =
𝑪𝑽 𝟑
When the temperature is high enough for the rotations of the molecules
to be highly excited (when T >> θR), we can use the equipartition value kT
for the mean rotational energy (for a linear rotor) or derived formula to
obtain CV,m = R.

𝟑
For nonlinear molecules, the mean rotational energy rises to kT, so the
𝟐
𝟑
molar rotational heat capacity rises to 𝑹 when T >> θR.
𝟐
When the temperature is not very high

𝝏 𝜺𝑹
𝑪𝑹
𝑽,𝒎 = 𝑵𝑨
𝝏𝑻 𝑽

𝒉𝒄𝑩 𝟔𝒆−𝟐𝜷𝒉𝒄𝑩 + 𝟑𝟎𝒆−𝟔𝜷𝒉𝒄𝑩 + ⋯

𝜺𝑹 =
𝟏 + 𝟑𝒆−𝟐𝜷𝒉𝒄𝑩 + 𝟓𝒆−𝟔𝜷𝒉𝒄𝑩 + ⋯ .