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Application of Partition Fuction (C)

This document discusses the calculation of internal energy and entropy for the translational, rotational, and vibrational modes of diatomic molecules using partition functions. It shows that: 1) The rotational energy (Er) of diatomic molecules is equal to RT and the rotational entropy (Sr) can be calculated using Er and the rotational partition function. 2) The vibrational energy (Ev) can be calculated using the vibrational partition function and Ev is equal to RT[hν0/(e^hν0/kT -1)]. 3) The vibrational entropy (Sv) can be calculated using Ev and the vibrational partition function.

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NITISH KUMAR
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162 views2 pages

Application of Partition Fuction (C)

This document discusses the calculation of internal energy and entropy for the translational, rotational, and vibrational modes of diatomic molecules using partition functions. It shows that: 1) The rotational energy (Er) of diatomic molecules is equal to RT and the rotational entropy (Sr) can be calculated using Er and the rotational partition function. 2) The vibrational energy (Ev) can be calculated using the vibrational partition function and Ev is equal to RT[hν0/(e^hν0/kT -1)]. 3) The vibrational entropy (Sv) can be calculated using Ev and the vibrational partition function.

Uploaded by

NITISH KUMAR
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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M.Sc.

S E M – I (2019 – 2021)

C H A P T E R - STATISTICAL THERMODYNAMICS

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

Application of Partition Function for Diatomic molecules :


The diatomic molecules possess all the four ( i.e. translational, rotational, vibrational
and electronic energies). Hence ,
𝐸 = 𝐸𝑡 + 𝐸𝑟 + 𝐸𝑣 + 𝐸𝑒

or, 𝐸 = 𝐸𝑡 + 𝐸𝑟 + 𝐸𝑣 ( 𝐸𝑒 = 𝑣𝑒𝑟𝑦 − 𝑣𝑒𝑟𝑦 𝑠𝑚𝑎𝑙𝑙)

(a) Translation Internal energy and Entropy : These quantities for diatomic molecule are same
as those for monoatomic molecules.
(b) Rotational Internal energy and Entropy :
The internal energy of one mole of substance is given by -
𝑑 ln 𝑄
𝐸 = 𝑅𝑇 2 ( )𝑉
𝑑𝑇
Therefore rotational energy will be -
𝑑 ln 𝑄𝑟
𝐸𝑟 = 𝑅𝑇 2 ( )𝑉 ------------------------------------ (1)
𝑑𝑇
But we know that -
8 𝜋2 𝐼 𝐾 𝑇
𝑄𝑟 =
𝜎 ℎ2
Taking log on both sides, we have -
8 𝜋2 𝐼 𝐾
𝑙𝑛𝑄𝑟 = ln ( ) + 𝑙𝑛𝑇
𝜎 ℎ2
Differentiating this equation with respect to T at constant volume V, we have -
𝑑𝑙𝑛𝑄𝑟
( )𝑉 = 0 + 1/𝑇 [𝐴𝑠𝑠𝑢𝑚𝑖𝑛𝑔 𝜋, 𝑘, 𝜎, ℎ 𝑎𝑛𝑑 𝐼 𝑎𝑟𝑒 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡]
𝑑𝑇
or,
𝑑𝑙𝑛𝑄𝑟
( )𝑉 = 1/𝑇 --------------------------------------- (2)
𝑑𝑇
Hence from equation (1) and (2), we have -
𝐸𝑟 = 𝑅 𝑇 2 × 1/𝑇
or, 𝐸𝑟 = 𝑅 𝑇 ------------------------------------------------- (3)
From third law of thermodynamics in terms of partition function , we know tat -
𝐸
𝑆 = + 𝑅 𝑙𝑛𝑄
𝑇
𝐸𝑟
or, 𝑆𝑟 = + 𝑅 𝑙𝑛𝑄𝑟 ( for rotational entropy )
𝑇
(2)
Now putting the value of 𝐸𝑟 𝑎𝑛𝑑 𝑄𝑟 in the above equation, we get -
𝑅𝑇 8 𝜋2 𝐼 𝐾 𝑇
𝑆𝑟 = 𝑇
+ 𝑅 ln ( 2 )
𝜎ℎ
8 𝜋2 𝐼 𝐾 𝑇
or, 𝑆𝑟 = 𝑅 + 𝑅 ln ( )
𝜎 ℎ2
8 𝜋2 𝐼 𝐾 𝑇
or, 𝑆𝑟 = 𝑅 [1 + ln( 2 ] ------------------------------ (4)
𝜎ℎ
Again on expansion of the above equation, we have -
𝑆𝑟 = 𝑅 [1 + ln 8 + 2 ln 𝜋 + ln 𝐼 + ln 𝑘 + ln 𝑇 − ln 𝜎 − 2 ln ℎ]
Now putting the value of 𝜋, 𝑘, ℎ 𝑎𝑛𝑑 𝑅 in the above equation , we get

𝑆𝑟 = 4.576(𝐿𝑜𝑔 𝐼 + 𝐿𝑜𝑔 𝑇 − 𝐿𝑜𝑔 𝜎 + 38.82)

(c) Vibrational Energy and Entropy :


We know that -
𝑑 ln 𝑄
𝐸 = 𝑅𝑇 2 ( )𝑉
𝑑𝑇
𝑑 ln 𝑄𝑣
∴ 𝐸𝑉 = 𝑅𝑇 2 ( )𝑉
𝑑𝑇
But we know that -
𝑄𝑉 = ( 1 − 𝑒 − ℎ𝜈0/𝐾𝑇 )−1
𝑑 ln ( 1−𝑒 − ℎ 𝜈0 /𝐾𝑇 )−1
∴ 𝐸𝑉 = 𝑅 𝑇 2 [ ]𝑉
𝑑𝑇

Taking log and on differentiation, we get -


ℎ 𝜈0 /𝐾𝑇
𝐸𝑉 = 𝑅 𝑇 [ ] ----------------------------------- (1)
(𝑒 0 /𝐾𝑇 −1)
ℎ𝜈

Again we know that -


𝐸
𝑆 = + 𝑅 𝑙𝑛𝑄
𝑇
𝐸𝑉
∴ 𝑆𝑉 = + 𝑅 𝑙𝑛𝑄𝑉
𝑇

Now putting the value of 𝐸𝑣 𝑎𝑛𝑑 𝑄𝑣 , we get -


ℎ 𝜈0 /𝐾𝑇
𝑆𝑉 = 𝑅 [ ℎ𝜈0/𝐾𝑇 ] + 𝑅 𝑙𝑛( 1 − 𝑒 − ℎ𝜈0/𝐾𝑇 )−1
(𝑒 −1)
ℎ 𝜈0 /𝐾𝑇
or, 𝑆𝑉 = 𝑅 [ ℎ𝜈0 /𝐾𝑇 + 𝑙𝑛( 1 − 𝑒 − ℎ𝜈0/𝐾𝑇 )−1 ] ------------------------- (2)
(𝑒 −1)

**********

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