BITS Pilani

Pilani Campus

CHEM F312 : Physical Chemistry IV

Semester I: AY 2022-23
Lecture-02, 7 Sep 2022, Wednesday

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Review of Last class:

• Discussion of Handout and course flow.

• Introduction to Statistical Thermodynamics.

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Statistical Statistical Mechanics

Macrostate: Thermodynamic state of the system.

Enough parameters to characterize the system,
Composition, Temp, Pressure/Volume etc.

Example: 18.0g of water, 54o C, 17.2 cm3 etc.

Microstate: For a macrostate many microstates are

possible. Also known as quantum state.
Consider 18.0 g of water: The wavefunction has to
include 6.02x 1023 x (10 electrons + 3 nuclei) spin,
spatial coordinates. Impossible to solve or use.

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Statistical Statistical Mechanics

Assuming no interactions (inter/intra) we can also

define molecular states.
Consider monoatomic ideal gas:
No Rotation, vibration
Macrostate: (T, P, n) or (T, V, n)
Quantum state: Translational states
(nx =1, ny = 1, nz =1) , (nx =1, ny = 1, nz =2), (nx =1, ny = 2,
nz =1) ,…, etc.

To relate the macrostate to the quantum state we have

to make certain definitions.

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Statistical Mechanics

The Canonical Ensemble

Ensemble: Hypothetical collection of infinite number of

non-interacting systems each of which is in the same
macrostate as the system of interest.

Canon: standard, basic, authoritative (Canons of the religion)

Micro canonical, Grand canonical ensembles are also

defined.

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Statistical Mechanics

The Canonical Ensemble

Time averaging is impossible.

Consider Kinetic theory of the gases:

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Statistical Mechanics

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Statistical Mechanics

Kinetic Theory: Time averaging of the impact of the

molecules  Pressure.
1017 impacts /cm2 / 10-6 sec.  x Pascal

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Statistical Mechanics

Maxwell – Boltzmann Distribution

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Statistical Mechanics

Helium – Costliest gases; Rare ; Why?

Escape velocity.

Source: Petroleum, mining industries (monazite rocks,

sand)

Applications:
Superconductivity; diving etc. many applications

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Statistical Mechanics

Macrostate

Microstate-1 Microstate-2 Microstate-3 …………

Microstates are also called quantum states;

Macrostates are defined by thermodynamic parameters and mass;

Microstates are defined by quantum numbers of individual particles.

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Statistical Mechanics

The Canonical Ensemble

Macrostate wise all ensemble members are same.
But they are different in microstate (quantum
state).

Postulate I: The measured time average of a

macroscopic property in the system of interest is
equal to the average value of that property in that
ensemble.

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Statistical Mechanics

Canonical Ensemble entities: Same macrostate, rigid,

impermeable, thermally conducting walls.
Rigid  fixed volume
Impermeable  fixed composition
Thermally conducting  same temp. (const. temp. bath)
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Statistical Mechanics

e.g, 1.00 m mol H2 (273 K, 2.00 L)

Microstates:
Let the jth microstate is connected to wavefunction ψj and
energy Ej, so that,

ℋ ψj = Ejψj

Now Ej depends on composition (inter molecular and

intramolecular forces depend on N)
Ej depends on Volume (Remember particle in a box the
volume appears in the denominator).
Ej does not depend on Temp.
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Statistical Mechanics
Microstates:
Therefore let
Ej = Ej (V, NB, Nc, ……)

Multiple species B,C,…. Etc.

NA is reserved for Avogadro Number
One Phase is assumed, but applicable to multi-phases
also.

Macroscopic property
Ensemble Averages : Example internal energy

U = <Ej> = Σj pj Ej
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Statistical Mechanics

Internal Energy
U = <Ej> = Σj pj Ej
pj

One way
pj = the probability that the system in the ensemble has
energy Ej

Alternatively,
pj = the probability that the system is in the microstate j.

We will go with the second definition.

Σj = sum over all quantum states
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 Statistical Mechanics
Σj = sum over all quantum states
Note: sum over states not levels.
L3 s5
Energy L2 s2 s3 s4
L1 s1
Degeneracy has to be taken into account.
How to get pj and Ej ???
Postulate II
For a thermodynamic system of fixed volume
composition and temperature, all quantum states
that have equal energy have equal probability of
occurring.
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Statistical Mechanics
Consider a set of constant temp. baths each having
two systems I II
separated by rigid, impenetrable, adiabatic walls.

……

I and II (black and white) are two different systems

All I are macroscopically identical and
All II are macroscopically identical.
I and II differ in volume, composition
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Statistical Mechanics

Let 𝒑𝑰,𝒋 = 𝒇 𝑬𝑰,𝒋 𝒂𝒏𝒅 𝒑𝑰𝑰,𝒌 = 𝒈 𝑬𝑰𝑰,𝒌 where f

and g are unknown functions.

If I and II are combined, then 𝒑𝑰+𝑰𝑰,𝒊 = 𝒉 𝑬𝑰+𝑰𝑰,𝒊

The subsystems I and II are independent of each other.

Therefore,
𝑬𝑰+𝑰𝑰,𝒊 = 𝑬𝑰,𝒋 + 𝑬𝑰𝑰,𝒌

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Statistical Mechanics
Therefore, the probability of the combined state energy
is the product of the probabilities of two independent
events to occur simultaneously.
𝒑𝑰+𝑰𝑰,𝒊 = 𝒑𝑰,𝒋 . 𝒑𝑰𝑰,𝒌
𝒉 𝑬𝑰,𝒋 + 𝑬𝑰𝑰,𝒌 = 𝒇 𝑬𝑰,𝒋 . 𝒈(𝑬𝑰𝑰,𝒌 )

Let 𝒙 = 𝑬𝑰,𝒋 , 𝒚 = 𝑬𝑰𝑰,𝒌 𝒂𝒏𝒅 𝒛 = 𝒙 + 𝒚

𝒉 𝒙 + 𝒚 = 𝒇 𝒙 .𝒈 𝒚
𝒉(𝒛) = 𝒇 𝒙 . 𝒈 𝒚

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Statistical Mechanics

𝝏𝒉 𝒛 𝒅𝒇 𝒙
= 𝒈 𝒚
𝛛𝒙 𝒚
𝒅𝒙

𝒅𝒉 𝒛 𝝏𝒛
= 𝒇′ 𝒙 .𝒈 𝒚 =
𝒅𝒛 𝝏𝒙 𝒚

𝛛𝒛 𝛛(𝒙 + 𝒚)
𝑵𝒐𝒘 = =𝟏
𝛛𝒙 𝒚
𝛛𝒙 𝒚

𝒅𝒉
Therefore, = 𝒇′ 𝒙 . 𝒈 𝒚
𝒅𝒛

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Statistical Mechanics

Similarly, by partial differentiation w.r.t. y

we get
𝒅𝒉
= 𝒇 𝒙 . 𝒈′ 𝒚
𝒅𝒛
Therefore,
𝒇′ 𝒙 . 𝒈 𝒚 = 𝒇 𝒙 . 𝒈′ 𝒚
𝒇′ (𝒙) 𝒈′ (𝒚)
= ≡ −𝜷
𝒇(𝒙) 𝒈(𝒚)

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Statistical Mechanics

𝒇′ (𝒙) 𝒈′ (𝒚)
= ≡ −𝜷
𝒇(𝒙) 𝒈(𝒚)
𝒇′ (𝒙)
First part of the equation is independent of y
𝒇(𝒙)
𝒈′ (𝒚)
and the second part is independent of x
𝒈(𝒚)
And therefore 𝜷 is independent of both x and y.

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Statistical Mechanics

𝒅𝒇(𝒙) 𝟏
. = −𝜷
𝒅𝒙 𝒇(𝒙)
𝒅𝒇(𝒙)
න = −𝜷 න 𝒅𝒙
𝒇(𝒙)
𝒍𝒏𝒇(𝒙) = −𝜷𝒙 + 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕
𝒇 𝒙 = 𝒆−𝜷𝒙 . 𝒆𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕 = 𝒂𝒆−𝜷𝒙
𝒇 𝒙 = 𝒂𝒆−𝜷𝒙

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Statistical Mechanics

Similarly, we can get

𝒈 𝒚 = 𝒄𝒆−𝜷𝒚
𝒇 𝒙 . 𝒈 𝒚 = 𝒂. 𝒄. 𝒆−𝜷(𝒙+𝒚)
Also
𝒑𝑰,𝒋 = 𝒇 𝑬𝑰,𝒋 = 𝒂𝒆−𝜷𝑬𝑰,𝒋
And
𝒑𝑰𝑰,𝒌 = 𝒇 𝑬𝑰𝑰,𝒌 = 𝒄𝒆−𝜷𝑬𝑰𝑰,𝒌

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Statistical Mechanics

What are these constants a, c, and 𝜷 ?

These are constants for particular T, V.
May be dependent on T, V.
But definitely independent of microstate energies.

𝜷 is same for I and II (Same Temperature). In

general 𝜷 = 𝝓 𝑻 .

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Statistical Mechanics

𝒑𝒋 = 𝒂𝒆−𝜷𝑬𝒋

෍ 𝒑𝒋 = 𝟏 = 𝒂 ෍ 𝒆−𝜷𝑬𝒋
𝒋 𝒋
𝟏
𝒂=
σ𝒋 𝒆−𝜷𝑬𝒋
𝒆−𝜷𝑬𝒋 𝒆−𝜷𝑬𝒋
𝒑𝒋 = −𝜷𝑬
=
σ𝒋 𝒆 𝒋 𝒁
𝒁 = 𝑪𝒂𝒏𝒐𝒏𝒊𝒄𝒂𝒍 𝑷𝒂𝒓𝒕𝒊𝒕𝒊𝒐𝒏 𝑭𝒖𝒏𝒄𝒕𝒊𝒐𝒏
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