2023 FTE2011 Chemical Energetics

Statistical Thermodynamics
Tutorial exercises
𝑉 𝑉!
The Binomial Coefficient: ( ) = =𝑊
𝑀 𝑀! (𝑉 − 𝑀)!

(1). Determine 𝑊 for 𝑉 = 6 sites and 𝑀 = 4 particles

(2). Determine 𝑊 for 𝑉 = 12 sites and 𝑀 = 4 particles

(3). Determine 𝑊 for 𝑉 = 12 sites and 𝑀 = 6 particles

Boltzmann’s Entropy, 𝑺

𝑆 = 𝑘𝐵 ln 𝑊

𝑘𝐵 is Boltzmann’s constant, 𝑘𝐵 = 1.380 649 × 10−23 J K −1 .

1.3 Equilibrium for a model chemical process

Consider the conversion of 𝐴 into 𝐵, for the very specific case where 𝐴 and 𝐵 have the
same energy:

𝐴⇋𝐵

We have 𝑁 total particles and 𝑁 = 𝑁𝐴 + 𝑁𝐵 . Now the binomial coefficient looks like:

𝑁 𝑁! 𝑁!
The Binomial Coefficient: ( ) = = =𝑊
𝑁𝐴 𝑁𝐴 ! (𝑁 − 𝑁𝐴 )! 𝑁𝐴 ! 𝑁𝐵 !

For 𝑁 = 𝑁𝐴 + 𝑁𝐵 = 10:

(3). Calculate, 𝑊, for 𝑁𝐴 = 2 and 𝑁𝐵 = 8.

(4). Calculate, 𝑊, for 𝑁𝐴 = 4 and 𝑁𝐵 = 6.

(5). Calculate, 𝑊, for 𝑁𝐴 = 5 and 𝑁𝐵 = 5.

(6). What are the values of (𝑁𝐴 , 𝑁𝐵 ) that give maximum entropy?

(7). In general, what is the relationship between 𝑁𝐴 and 𝑁𝐵 that gives the maximum
entropy?

(8). What is the relationship between 𝑁𝐴 and 𝑁𝐵 at equilibrium?

1.4 Fluctuations and Stability

Repeat this exercise for:

(9). 𝑁𝐵 = 60, 𝑁𝐴 = 40; compare with and 𝑁𝐴 = 𝑁𝐵 = 50

(10). 𝑁𝐵 = 600, 𝑁𝐴 = 400; compare with and 𝑁𝐴 = 𝑁𝐵 = 500

In both cases, calculate the ratio

𝑊max (𝑁)
𝑊(𝑁, 𝑁𝐴 )

Noting that 𝑊max (𝑁) is obtained for 𝑁𝐴 = 𝑁𝐵

Stirling’s approximation can be used to calculate ln 𝑊 for really large values of 𝑁:

Stirling’s Approximation for Factorials: ln 𝑛! ≈ 𝑛 ln 𝑛 − 𝑛

Properties of logs:

log(𝑎𝑏) = log(𝑎) + log(𝑏)

𝑎
log ( ) = log(𝑎) − log(𝑏)
𝑏
log(𝑥 𝑎 ) = 𝑎 log(𝑥)
ln(𝑥) ≡ log 𝑒 (𝑥) = log 𝑒 (10) × log10 (𝑥)

Calculate 𝑊 = 𝑒 [ln 𝑊] .
1000!
ln 𝑊(1000,400) = ln ( ) = ln 1000! − ln 600! − ln 400!
400! 600!

ln 1000! = 1000 × ln 1000 − 1000 = 5907.76

ln 600! = 600 × ln 600 − 600 = 3238.16

ln 400! = 400 × ln 400 − 400 = 1996.56

ln 𝑊(1000,400) = 673.04

𝑊(1000,400) = 𝑒 ln 𝑊 = 𝑒 673.04 = 1.984 × 10292

(11). Calculate 𝑊 and 𝑆 if 𝑁𝐴 = 1 × 1020 and 𝑁𝐵 = 5 × 1023 .
Use the properties of logs given above and Stirling’s approximation to simplify the
factorials.

ln 𝑊 is now too large even for WolframAlpha or Excel to calculate 𝑊. The best we
can do is to write the value as
20
𝑊 = 𝑒 9.52×10
or using some further properties of logs:
ln 𝑊 ≡ log e 𝑊 = log e 10 × log10 𝑊 = ln 10 × log 𝑊 = 2.303 × log 𝑊
9.52 × 1020
log 𝑊 = = 4.132 × 1020
2.303
20
𝑊 = 104.132×10
Now, let’s repeat the calculation of the ratio
𝑊max (𝑁)
𝑊(𝑁𝐴 , 𝑁𝐵 )

for 𝑁𝐴 = 0.6 × 1023 and 𝑁𝐵 = 0.4 × 1023

ln 𝑊(1.0 × 1023 , 0.4 × 1023 ) = 6.7301 × 1022

ln 𝑊max (1.0 × 1023 , 0.5 × 1023 ) = 6.9315 × 1022

𝑊max
ln ( ) = ln 𝑊max − ln 𝑊 = 2.0136 × 1021
𝑊

𝑊max 21 20
= 𝑒 2.0136×10 = 108.7432×10
𝑊

Let’s think about what these numbers mean:

• 𝑊max is the maximum number of arrangements for the system; this occurs for 𝑁𝐴 =
𝑁𝐵 .
• 𝑊 is the number of arrangements for the system with a 10% change (or
fluctuation) away from the most likely arrangement.
 20
So the most likely configuration is a mind-boggling 108.7432×10 times more likely to
occur than the configuration that corresponds to a 10% fluctuation away from the most
likely configuration if we have numbers of particles on the order of a mole.

𝑊max
(12). Find the ratio 𝑊
for a one part per thousand fluctuation. Use the following values:

𝑁𝐴 = 1.001 × 1023 and 𝑁𝐵 = 1.000 × 1023 .

𝑁 = 𝑁𝐴 + 𝑁𝐵 = 2.001 × 1023

𝑁 𝑁
Note that 𝑊max = 𝑊 ( 2 , 2 ).

ANSWER:
𝑊max 𝑊max
ln = 2.499 × 1016 ⇒ = exp(2.499 × 1016 )
𝑊 𝑊
(13). Repeat (12) for a one part per million fluctuation.
Gibbs Entropy
Every distribution has an associated entropy, which can be calculated from the probability
of occupying each state:

𝑆 = −𝑘𝐵 ∑ 𝑝𝑖 ln 𝑝𝑖 (𝑠𝑢𝑚 𝑜𝑣𝑒𝑟 𝑠𝑡𝑎𝑡𝑒𝑠)

𝑖

EXCEL

(14). Calculating entropy for distributions

For the distribution below:

𝑗 1 2 3 4 5 6

𝑝𝑗 0.0312 0.156 0.312 0.312 0.156 0.0312

(i). Calculate the average value of 𝑗. (〈𝑗〉 = 3.5)

(ii). Calculate the entropy for this distribution. (𝑆 = 1.524)

(15). Calculating entropy for distributions

For the distribution below:

𝑗 1 2 3 4 5 6

𝑝𝑗 0.328 0.410 0.205 0.0512 0.0064 0.0003

(i). Calculate the average value of 𝑗. (〈𝑗〉 = 2.0)

(ii). Calculate the entropy for this distribution. (𝑆 = 1.243)

These examples do indeed have smaller entropy than the uniform distribution.
NA and NB are fixed. We assume low densities, i.e. N/M << 1.
The volume is free to change between the A and B subsystems. Equilibrium will be
reached when entropy, and therefore the number of arrangements, 𝑊, is a maximum.
First, we will find a relationship between 𝑊 and the volume of the system.
Then we will use the idea from calculus that the maximum value for 𝑊 will occur when
the derivative of 𝑊 with respect to volume is zero.
i). Find an expression for 𝑊 = 𝑊𝐴 𝑊𝐵 . For low densities, we can use the following
approximation for factorial functions:
𝑀!
≈ 𝑀𝑁
(𝑀 − 𝑁)!
ii). Find the value of 𝑀𝐴 that maximises the entropy. Because 𝑆 = 𝑘 ln 𝑊 this value
of 𝑀𝐴 will also maximise ln 𝑊. This is a calculus problem; the maximum value of a
function occurs when the derivative is equal to zero. So we need the derivative of 𝑆
with respect to 𝑀𝐴 . This part can be broken down into three steps:
(1). Find a simplified expression for ln 𝑊 (using properties of logs)

(2). Determine the derivative, 𝑑 ln 𝑊 /𝑑𝑀𝐴 .

(3). Solve
𝑑 ln 𝑊
=0
𝑑𝑀𝐴
iii). Use the ideal gas law
𝑝𝑉 = 𝑁𝑅𝑇
to show that the condition for maximum 𝑊 is equivalent to the pressures being equal
for A and B (for constant temperature).
2). Show that the entropy change for a change in volume of an ideal gas from 𝑽𝑩 to 𝑽𝑨 is
𝑽𝑩
𝚫𝑺 = 𝑵𝒌 ln ( )
𝑽𝑨

ANSWER:
The entropy change in terms of the number of arrangements is
𝑊𝐵
Δ𝑆 = 𝑆𝐵 − 𝑆𝐴 = 𝑘 ln 𝑊𝐵 − 𝑘 ln 𝑊𝐴 = 𝑘 ln ( )
𝑊𝐴
Using the model from (a) above but using 𝑉 for the number of sites rather than 𝑀,
and noting that the number of molecules is 𝑁 in both 𝐴 and 𝐵 states:
𝑉𝐴 ! 1 1
𝑊𝐴 = ≅ × 𝑉𝐴𝑁 𝑊𝐴 ≅ × 𝑉𝐵𝑁
𝑁! (𝑉𝐴 − 𝑁)! 𝑁! 𝑁!
So
1
𝑁! × 𝑉𝐵𝑁 𝑉𝐵 𝑁 𝑉𝐵
Δ𝑆 = 𝑘 ln ( ) = 𝑘 ln ( ) = 𝑁𝑘 ln ( )
1 𝑁 𝑉𝐴 𝑉𝐴
𝑁! × 𝑉𝐴
3). 2015 Final exam

Consider the model above for mechanical equilibrium in two-dimensions. A lattice site
occupies an area, 𝑎0 , so the area for subsystem 1 is 𝐴1 = 𝑀1 × 𝑎0 . The barrier between
Subsystem 1 and Subsystem 2 is allowed to move, subject to the constraint, 𝐴𝑡𝑜𝑡𝑎𝑙 = 𝐴1 +
𝐴2 . Equilibrium will be established when entropy is maximised. Then

𝑑𝑆 𝑑𝑆 𝑑𝑀1 𝑘 𝑑 ln 𝑊
=( )∙( )= ( )=0
𝑑𝐴1 𝑑𝑀1 𝑑𝐴1 𝑎0 𝑑𝑀1
(a) Give an expression for the total multiplicity of the combined system as a
function of 𝑀1 .

(b) Use the approximation, 𝑀!⁄(𝑀 − 𝑁)! ≈ 𝑀𝑁 (for 𝑁 ≪ 𝑀) to show that

1
ln 𝑊 ≈ ln + 𝑁1 ln 𝑀1 + 𝑁2 ln(𝑀 − 𝑀1 )
𝑁1 ! 𝑁2 !
(c) Use the condition of maximum entropy and 𝜋𝐴 = 𝑁𝑅𝑇 to show that the condition
for mechanical equilibrium is
𝜋1 𝜋2
=
𝑇1 𝑇2