M.Sc.

S E M – I (2019 – 2021)

C H A P T E R - STATISTICAL THERMODYNAMICS

By - Dr. Rabindra Kumar, Associate Professor, University Dept. of Chemistry, T.M.B.U.,

Bhagalpur.

Application of Partition Function for mono atomic gases

(a) Calculation of Entropy ( Sackur – Tetrode Equation ) :

In monoatomic gases , rotational and vibrational motions and hence energies are
absent. The only contributions towards partition function of a monoatomic molecules are
translation and electronic only i.e.

𝑄 = 𝑄𝑒 × 𝑄𝑡 ------------------------------------(1)

But we know that -

3
( 2 𝜋 𝑚 𝑘 𝑇)2 . 𝑉
𝑄𝑡 =
ℎ3
3
( 2 𝜋 𝑚 𝑘 𝑇)2 . 𝑉
∴ 𝑄 = 𝑄𝑡 = 𝑄𝑒 . 3 ---------------------- (2)
ℎ

Assuming 𝑄𝑒 to be independent of temperature, as is true for most molecules , and hence at

not too high temperature, the equation (2) can be written as -
3
( 2 𝜋 𝑚 𝑘 𝑇)2 . 𝑉 3/2
𝑄 = [𝑄𝑒 . 3 ].𝑇
ℎ

Now let us assume the quantity within the bracket is constant and let it be equal to C. Then -

𝑄 = 𝐶 . 𝑇 3/2

Taking log on both sides, we get -

3
ln 𝑄 = ln 𝐶 + 2 ln 𝑇

Now differentiating the above equation w. r. t T at constant volume, we have -

𝑑 ln 𝑄 𝑑 ln 𝐶 3
( )𝑉 = ( )𝑉 +
𝑑𝑇 𝑑𝑇 2𝑇
 (2)

𝑑 ln 𝑄 3 𝑑 ln 𝐶
or, ( )𝑉 = 0 + [∵ ( )𝑉 = 0 ]
𝑑𝑇 2𝑇 𝑑𝑇

Again multiplying the above equation by R on both sides, we have -

𝑑 ln 𝑄
𝑅( )𝑉 = 3𝑅/2𝑇
𝑑𝑇

𝑑 ln 𝑄 3
or, RT( )𝑉 = . 𝑅 --------------------------------- ( 3 )
𝑑𝑇 2

But we know that molar entropy is given by the following expression ( relation of entropy and
partition function) -
𝑄 𝑑 ln 𝑄
𝑆 = 𝑅 ln (𝑁) + 𝑅𝑇 ( )𝑉 + 𝑅 ---------------------- (4)
𝑑𝑇

Hence combining equation (2) , (3) and (4), we get -

3
𝑄𝑒 ( 2 𝜋 𝑚 𝑘 𝑇)2 . 𝑉 3
𝑆 = 𝑅 ln [ ] + 𝑅 +𝑅 ------------------ (5)
𝑁 ℎ3 2

For one mole of an ideal gas, V = R T / P ,

3
𝑄𝑒 ( 2 𝜋 𝑚 𝑘 𝑇)2 . 𝑅 𝑇 5
𝑆 = 𝑅 ln [ ] + 𝑅 ---------------------------- (6)
𝑁 ℎ3 𝑃 2

Equation (50 and (6) are the two alternative forms of well known Sackur – Tetrode Equation.

****************