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THERMODYNAMIC RELATIONS

Legendre differential Transformations: -

Let us consider 𝑓 = 𝑓(𝑥, 𝑦) is

The Legendre transformation changes a function of two or more variables 𝑓(𝑥, 𝑦) into a
function 𝑔(𝑝, 𝑦) where one variable is the same, while other 𝑥, is replaced by its conjugate
under 𝑓 defined as,
𝜕𝑓
𝑝=( )
𝜕𝑥 𝑦
is given by,
𝑔(𝑝, 𝑦) = 𝑓(𝑥, 𝑦) − 𝑥𝑝

It can be noted that,

𝜕𝑓 𝜕𝑓
𝑑𝑓 = ( ) 𝑑𝑥 + ( ) 𝑑𝑦
𝜕𝑥 𝑦 𝜕𝑦 𝑥
= 𝑝 𝑑𝑥 + 𝑞 𝑑𝑦
𝑑𝑔 = 𝑑𝑓 − 𝑝 𝑑𝑥 − 𝑥𝑑𝑝
= 𝑝 𝑑𝑥 + 𝑞 𝑑𝑦 − 𝑝 𝑑𝑥 − 𝑥𝑑𝑝
= 𝑞 𝑑𝑦 − 𝑥𝑑𝑝
Hence,
𝜕𝑔 𝜕𝑔
𝑞=( ) ; 𝑥 = −( )
𝜕𝑦 𝑝 𝜕𝑝 𝑦

We can construct another function, from the expression,

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𝜕𝑓 𝜕𝑓
𝑑𝑓 = ( ) 𝑑𝑥 + ( ) 𝑑𝑦
𝜕𝑥 𝑦 𝜕𝑦 𝑥
= 𝑝 𝑑𝑥 + 𝑞 𝑑𝑦 = 𝑞 𝑑𝑦 + 𝑝 𝑑𝑥
We can get another function considering the conjugate (q,y) as,
ℎ(𝑞, 𝑥) = 𝑓(𝑥, 𝑦) − 𝑞𝑦

Derivation of thermodynamic potentials:-

From 1 𝑠𝑡 law of thermodynamics,

𝑑𝑄 = 𝑑𝑈 + 𝑃𝑑𝑉
Using 2nd law,
𝑇 𝑑𝑆 = 𝑑𝑈 + 𝑃𝑑𝑉
𝑜𝑟, 𝑑𝑈 = 𝑇 𝑑𝑆 − 𝑃 𝑑𝑉 … … (1)

(i) Internal Energy:-

From (1) we have 𝑈 = 𝑈(𝑆, 𝑉), 𝑈 is internal energy.

Here
𝜕𝑈 𝜕𝑈
𝑇=( ) 𝑎𝑛𝑑 𝑃 = − ( )
𝜕𝑆 𝑉 𝜕𝑉 𝑆
T, S and V, P(𝑏𝑒𝑡𝑡𝑒𝑟 𝑡𝑜 𝑠𝑎𝑦 − 𝑃) are the conjugate variables under internal energy.

(ii) Helmholtz free energy:-

Using Legendre transformation, we get a new function 𝐹(𝑇, 𝑉) as
𝐹(𝑇, 𝑉) = 𝑈(𝑆, 𝑉) − 𝑇𝑆
𝐹 is called Helmholtz free energy.
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Differentiating
𝑑𝐹 = 𝑑𝑈 − 𝑑(𝑇𝑆)
= 𝑇𝑑𝑆 − 𝑃𝑑𝑉 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇
𝑑𝐹 = −𝑃𝑑𝑉 − 𝑆𝑑𝑇 … . . (2)
Here,
𝜕𝐹 𝜕𝑈
𝑃 = −( ) 𝑎𝑛𝑑 𝑆 = − ( )
𝜕𝑉 𝑇 𝜕𝑇 𝑉

T, S and V, P are the conjugate variables under Helmholtz free energy.

(iii) Enthalpy: -
Taking internal energy as,
𝑈 = 𝑈(𝑉, 𝑆)
Using Legendre transformation we get a new function,
𝐻(𝑃, 𝑆) = 𝑈(𝑆, 𝑉) − (−𝑃𝑉)
𝐻 = 𝑈 + 𝑃𝑉
This is called Enthalpy.
∴ 𝑑𝐻 = 𝑑𝑈 + 𝑑(𝑃𝑉)
= 𝑇𝑑𝑆 − 𝑃𝑑𝑉 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃
∴ 𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃 … … (3)
Here,
𝜕𝐻 𝜕𝐻
𝑇=( ) 𝑎𝑛𝑑 𝑉 = ( )
𝜕𝑆 𝑃 𝜕𝑃 𝑆

(iv) Gibbs free energy:-

Using Legendre differential transformation from,
𝐻 = 𝐻(𝑆, 𝑃)
𝐺(𝑇, 𝑃) = 𝐻(𝑆, 𝑃) − 𝑇𝑆
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∴ 𝐺 = 𝑈 + 𝑃𝑉 − 𝑇𝑆
Differentiating,
𝑑𝐺 = 𝑑𝐻 − 𝑑(𝑇𝑆)
= 𝑇𝑑𝑆 + 𝑉𝑑𝑃 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇
𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇

• Derivation of Maxwell’s relation from

Thermodynamic potentials: -

If a relation exists among 𝑥 & 𝑦 as,

𝑓(𝑥, 𝑦) = 0
Then,
𝜕𝑓 𝜕𝑓
𝑑𝑓 = ( ) 𝑑𝑦 + ( ) 𝑑𝑦
𝜕𝑥 𝑦 𝜕𝑦 𝑥
= 𝑀𝑑𝑥 + 𝑁𝑑𝑦
𝜕𝑓 𝜕𝑓
𝑊ℎ𝑒𝑟𝑒 𝑀 = ( ) ;𝑁 = ( )
𝜕𝑥 𝑦 𝜕𝑦 𝑥
If 𝑀, 𝑁 are differentiable, we get by partial differentiating w.r.t. 𝑥 𝑎𝑛𝑑 𝑦
𝜕𝑀 𝜕2𝑓 𝜕 𝜕2𝑓
= & =
𝜕𝑦 𝜕𝑦𝜕𝑥 𝜕𝑥 𝜕𝑥𝜕𝑦
Now if 𝑓(𝑥, 𝑦) is a state function or 𝑑𝑓 is exact differential.
𝜕2𝑓 𝜕2𝑓
=
𝜕𝑥𝜕𝑦 𝜕𝑦𝜕𝑥
𝜕𝑀 𝜕𝑁
𝑖. 𝑒. , ( ) = ( ) … … (𝐴)
𝜕𝑦 𝑥 𝜕𝑥 𝑦

(𝑖)For state function 𝑈, 𝑑𝑈 is exact differential. From 1st law,

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𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉
By the condition (A) we have,
𝜕𝑇 𝜕𝑃
( ) = − ( ) … … . (1)
𝜕𝑉 𝑆 𝜕𝑆 𝑉
(𝑖𝑖)For state function 𝐻, 𝑑𝐻 is exact differential. Now,
𝐻 = 𝑈 + 𝑃𝑉
∴ 𝑑𝐻 = 𝑑𝑈 + 𝑑(𝑃𝑉)
= 𝑇𝑑𝑆 − 𝑃𝑑𝑉 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃
= 𝑇𝑑𝑆 + 𝑉𝑑𝑃
By the condition (A) we have,
𝜕𝑇 𝜕𝑉
( ) = ( ) … … . (2)
𝜕𝑃 𝑆 𝜕𝑆 𝑃
(𝑖𝑖𝑖)For state function 𝐹, 𝑑𝐹 is exact differential. Now
𝐹 = 𝑈 − 𝑇𝑆
∴ 𝑑𝐹 = 𝑑𝑈 − 𝑑(𝑇𝑆)
= 𝑇 𝑑𝑆 − 𝑃𝑑𝑉 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇
= −𝑆𝑑𝑇 − 𝑃𝑑𝑉
By condition (A)
𝜕𝑆 𝜕𝑃
( ) = ( ) … . . (3)
𝜕𝑉 𝑇 𝜕𝑇 𝑉
(𝑖𝑣)For state function 𝐺, 𝑑𝐺 is exact differential. Now,
𝐺 = 𝐻 − 𝑇𝑆
∴ 𝑑𝐺 = 𝑑𝐻 − 𝑑(𝑇𝑆)
= 𝑇𝑑𝑆 + 𝑉𝑑𝑃 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇
= −𝑆𝑑𝑇 + 𝑉𝑑𝑃
∴By condition (A)
𝜕𝑆 𝜕𝑉
( ) = ( ) − ⋯ . (4)
𝜕𝑃 𝑇 𝜕𝑇 𝑃
Equations (1), (2), (3), (4) are called Maxwell’s relation.
Thermodynamic relations with heat capacities:-
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𝑪𝑷 − 𝑪𝒗 𝒓𝒆𝒍𝒂𝒕𝒊𝒐𝒏𝒔: −

There are 4 such relations;

𝜕𝑈 𝜕𝑉
1. 𝐶𝑃 − 𝐶𝑣 = [𝑃 + ( ) ] ( )
𝜕𝑉 𝜕𝑇 𝑇 𝑃

𝜕𝑃 𝜕𝑉
2. 𝐶𝑃 − 𝐶𝑉 = 𝑇 ( ) ( )
𝜕𝑇 𝜕𝑇
𝑉 𝑃
𝜕𝑃 𝜕𝑉 2
3. 𝐶𝑃 − 𝐶𝑉 = −𝑇 ( ) + ( )
𝜕𝑉 𝜕𝑇
𝑇 𝑃
𝜕𝑉 𝜕𝑃 2
4. 𝐶𝑃 − 𝐶𝑉 = −𝑇 ( ) ( )
𝜕𝑃 𝜕𝑇 𝑇 𝑉

𝝏𝑼 𝝏𝑽
𝟏. 𝑪𝑷 − 𝑪𝒗 = [𝑷 + ( ) ]( )
𝝏𝑽 𝑻 𝝏𝑻 𝑷

From 1st law , 𝑑𝑄 = 𝑇𝑑𝑆 = 𝑑𝑈 + 𝑃𝑑𝑉 … . . (𝑖)

Taking 𝑈 = 𝑈(𝑇, 𝑉)
𝜕𝑈 𝜕𝑈
∴ 𝑑𝑈 = ( ) 𝑑𝑇 + ( ) 𝑑𝑉 … . . (𝑖𝑖)
𝜕𝑇 𝑉 𝜕𝑉 𝑇
From (i)
𝜕𝑈 𝜕𝑈
𝑑𝑄 = 𝑇𝑑𝑆 = ( ) 𝑑𝑇 + ( ) 𝑑𝑉 + 𝑃𝑑𝑉 … … (𝑖𝑖𝑖)
𝜕𝑇 𝑉 𝜕𝑉 𝑇
By definition,
𝑑𝑄 𝜕𝑉
𝐶𝑉 = ( ) = ( ) [𝐹𝑟𝑜𝑚 (𝑖𝑖𝑖)]
𝑑𝑇 𝑉 𝜕𝑇 𝑉
∴From (𝑖𝑖𝑖)
𝑑𝑄 𝜕𝑈 𝜕𝑈 𝜕𝑉
𝐶𝑃 = ( ) = ( ) + {𝑃 + ( ) } ( )
𝑑𝑇 𝑃 𝜕𝑇 𝑉 𝜕𝑉 𝑇 𝜕𝑇 𝑃
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𝜕𝑈 𝜕𝑉
∴ 𝐶𝑃 − 𝐶𝑉 = [𝑃 + ( ) ]( )
𝜕𝑉 𝑇 𝜕𝑇 𝑃

𝝏𝑷 𝝏𝑽
𝟐. 𝑪𝑷 − 𝑪𝒗 = 𝑻 ( ) ( )
𝝏𝑻 𝑽 𝝏𝑻 𝑷
We have, 𝑆 = 𝑆(𝑇, 𝑉)
𝜕𝑆 𝜕𝑆
𝑜𝑟, 𝑑𝑆 = ( ) 𝑑𝑇 + ( ) 𝑑𝑉
𝜕𝑇 𝑉 𝜕𝑉 𝑇
Differentiating with respect to 𝑇 at constant P,
𝜕𝑆 𝜕𝑆 𝜕𝑆 𝜕𝑉
( ) =( ) +( ) ( )
𝜕𝑇 𝑃 𝜕𝑇 𝑉 𝜕𝑉 𝑇 𝜕𝑇 𝑃
Multiplying by 𝑇 we get,
𝜕𝑆 𝜕𝑉
𝐶𝑃 = 𝐶𝑣 + 𝑇 ( ) ( )
𝜕𝑉 𝑇 𝜕𝑇 𝑃
𝜕𝑆 𝜕𝑉
∴ 𝐶𝑝 − 𝐶𝑉 = 𝑇 ( ) ( )
𝜕𝑉 𝑇 𝜕𝑇 𝑃
Now, using Maxwell’s relation
𝜕𝑆 𝜕𝑃
( ) =( )
𝜕𝑉 𝑇 𝜕𝑇 𝑣
We can write
𝜕𝑃 𝜕𝑉
𝐶𝑃 − 𝐶𝑣 = 𝑇 ( ) ( )
𝜕𝑇 𝑉 𝜕𝑇 𝑃

𝝏𝑷 𝝏𝑽 𝟐
𝟑. 𝑪𝑷 − 𝑪𝒗 = −𝑻 ( ) ( )
𝝏𝑽 𝑻 𝝏𝑻 𝑷
We know,

𝜕𝑃 𝜕𝑉 𝜕𝑇
( ) ( ) ( ) = −1
𝜕𝑉 𝑇 𝜕𝑇 𝑃 𝜕𝑃 𝑣

And
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𝜕𝑃 1
( ) =
𝜕𝑉 𝑇 𝜕𝑉
( )
𝜕𝑃 𝑇
And so on. Now,
𝜕𝑃 𝜕𝑉
𝐶𝑃 − 𝐶𝑉 = 𝑇 ( ) ( ) … … . (1)
𝜕𝑇 𝑉 𝜕𝑇 𝑃
Replacing,
𝜕𝑃 1 𝜕𝑃 𝜕𝑉
( ) = = −( ) ( )
𝜕𝑇 𝑉 𝜕𝑇 𝜕𝑉 𝑇 𝜕𝑇 𝑃
( )
𝜕𝑃 𝑣
We get,
𝜕𝑃 𝜕𝑉 2
𝐶𝑃 − 𝐶𝑉 = −𝑇 ( ) ( )
𝜕𝑉 𝑇 𝜕𝑇 𝑃
𝝏𝑽 𝝏𝑷 𝟐
𝟒. 𝑪𝑷 − 𝑪𝒗 = −𝑻 ( ) ( )
𝝏𝑷 𝑻 𝝏𝑻 𝑽
Again replacing,
𝜕𝑉 1
( ) =−
𝜕𝑇 𝑃 𝜕𝑃 𝜕𝑇
( ) ( )
𝜕𝑉 𝑇 𝜕𝑃 𝑣
𝜕𝑉 𝜕𝑃
= −( ) ( )
𝜕𝑃 𝑇 𝜕𝑇 𝑣
In equation (𝑖) we get,
𝜕𝑉 𝜕𝑃 2
𝐶𝑃 − 𝐶𝑉 = −𝑇 ( ) ( )
𝜕𝑃 𝑇 𝜕𝑇 𝑉

Variation of 𝑪𝑷 with pressure: -

𝜕𝐶𝑝 𝜕2𝑉
( ) = −𝑇 ( 2 )
𝜕𝑃 𝑇 𝜕𝑇 𝑃

From Maxwell’s relation

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𝜕𝑆 𝜕𝑉
( ) = −( )
𝜕𝑃 𝑇 𝜕𝑇 𝑃
Differentiating with respect to 𝑇 at constant pressure,
𝜕 𝜕𝑆 𝜕2𝑉
{ ( ) } = − ( 2)
𝜕𝑡 𝜕𝑃 𝑇 𝑃 𝜕𝑇 𝑃
𝜕 𝜕𝑆 𝜕2𝑉
𝑜𝑟, { ( ) } = − ( 2 )
𝜕𝑃 𝜕𝑇 𝑃 𝑇 𝜕𝑇 𝑃

Multiplying by 𝑇 we get,
𝜕 𝜕𝑆 𝜕2𝑉
𝑜𝑟, { 𝑇 ( ) } = −𝑇 ( 2 )
𝜕𝑝 𝜕𝑇 𝑃 𝑇 𝜕𝑇 𝑃
𝜕𝐶𝑃 𝜕2𝑉
𝑜𝑟, ( ) = −𝑇 ( 2 )
𝜕𝑃 𝑇 𝜕𝑇 𝑃

• Variation of 𝑪𝒗 with 𝑽:-

Maxwell’s relation
𝜕𝑆 𝜕𝑃
( ) =( )
𝜕𝑉 𝑇 𝜕𝑇 𝑣
Differentiating with respect to 𝑇 at constant volume.

𝜕 𝜕𝑆 𝜕2𝑃
{ ( ) } = ( 2)
𝜕𝑡 𝜕𝑉 𝑇 𝑉 𝜕𝑇 𝑉
𝜕 𝜕𝑆 𝜕2𝑃
⟹ { ( ) } = 𝑇 ( 2)
𝜕𝑉 𝜕𝑇 𝑣 𝑇 𝜕𝑇 𝑣
𝜕𝐶𝑣 𝜕2𝑃
⟹( ) = 𝑇 ( 2)
𝜕𝑉 𝑇 𝜕𝑇 𝑣

• Tds Equation:-
There are there 𝑇𝑑𝑠 equations depending up on the choice of independent variables.
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𝟏𝒔𝒕 𝒓𝒆𝒍𝒂𝒕𝒊𝒐𝒏: − Here we take, 𝑆 = 𝑆(𝑇, 𝑉)
𝜕𝑆 𝜕𝑆
∴ 𝑑𝑆 = ( ) 𝑑𝑇 + ( ) 𝑑𝑉
𝜕𝑇 𝑉 𝜕𝑉 𝑇
𝜕𝑆 𝜕𝑆
∴ 𝑇 𝑑𝑆 = 𝑇 ( ) 𝑑𝑇 + 𝑇 ( ) 𝑑𝑉
𝜕𝑇 𝑉 𝜕𝑉 𝑇
𝜕𝑃
= 𝐶𝑣 𝑑𝑇 + 𝑇 ( ) 𝑑𝑉 [𝑀𝑎𝑥𝑤𝑒𝑙𝑙 ′ 𝑠 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛]
𝜕𝑇 𝑣

[𝐻. 𝑤. 𝑠ℎ𝑜𝑤𝑡ℎ𝑎𝑡 𝑇𝑑𝑆 = 𝐶𝑣 𝑑𝑇 + 𝑇 ∝ 𝐸𝑇 𝑑𝑉]

𝟐𝒏𝒅 𝑹𝒆𝒍𝒂𝒕𝒊𝒐𝒏: −
Here we consider, 𝑆 = 𝑆(𝑇, 𝑃)

𝜕𝑆 𝜕𝑆
∴ 𝑑𝑆 = ( ) 𝑑𝑇 + ( ) 𝑑𝑃
𝜕𝑇 𝑝 𝜕𝑃 𝑇

𝑑𝑉 𝜕𝑆 𝑑𝑉
∴ 𝑇 𝑑𝑆 = 𝐶𝑝 𝑑𝑇 − 𝑇 ( ) 𝑑𝑃 [ 𝐹𝑟𝑜𝑚 𝑀𝑎𝑥𝑤𝑒𝑙𝑙 ′ 𝑠 𝑟𝑒𝑙𝑎𝑡𝑖𝑜𝑛 ( ) = − ( ) ]
𝑑𝑇 𝑃 𝜕𝑃 𝑇 𝑑𝑇 𝑃
𝜕𝑉
∴ 𝑇 𝑑𝑆 = 𝐶𝑝 𝑑𝑇 − 𝑇 ( ) 𝑑𝑃
𝜕𝑇 𝑃

[𝐻. 𝑤. 𝑆ℎ𝑜𝑤 𝑡ℎ𝑎𝑡 𝑇 𝑑𝑆 = 𝐶𝑃 𝑑𝑇 − 𝑇𝑉 ∝ 𝑑𝑃]

𝟑𝒓𝒅 𝑹𝒆𝒍𝒂𝒕𝒊𝒐𝒏: −
Here we take,

𝑆 = 𝑆(𝑃, 𝑉)
𝜕𝑆 𝜕𝑆
∴ 𝑑𝑆 = ( ) 𝑑𝑃 + ( ) 𝑑𝑉
𝜕𝑃 𝑉 𝜕𝑉 𝑃
𝜕𝑆 𝜕𝑇 𝜕𝑆 𝜕𝑇
= ( ) ( ) 𝑑𝑃 + ( ) ( ) 𝑑𝑉
𝜕𝑇 𝑣 𝜕𝑃 𝑐 𝜕𝑇 𝑃 𝜕𝑉 𝑃
𝜕𝑇 𝜕𝑇
∴ 𝑇 𝑑𝑆 = 𝐶𝑉 ( ) 𝑑𝑃 + 𝐶𝑃 ( ) 𝑑𝑉
𝜕𝑃 𝑣 𝜕𝑉 𝑃
The importance of 𝑇 𝑑𝑆 relation is that they relate the entropy of a substance with directly
measurable quantities.
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𝑻𝒉𝒆 𝒆𝒏𝒆𝒓𝒈𝒚 𝑬𝒒𝒖𝒂𝒕𝒊𝒐𝒏𝒔: −
The dependence of internal energy on volume and pressure is given by following two
equations.

𝟏𝒔𝒕 𝑬𝒏𝒆𝒓𝒈𝒚 𝑬𝒒𝒖𝒂𝒕𝒊𝒐𝒏: −

From 1st law of thermodynamics for a 𝑃, 𝑉, 𝑇 system, 𝑑𝑄 = 𝑇𝑑𝑆 = 𝑑𝑈 + 𝑃𝐷𝑉

𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉
𝜕𝑈 𝜕𝑆
∴ ( ) = 𝑇( ) −𝑃
𝜕𝑉 𝑇 𝜕𝑉 𝑇
𝜕𝑃
= 𝑇( ) −𝑃
𝜕𝑇 𝑉

This is the first equation of energy.

Again taking
𝑈 = 𝑈(𝑉, 𝑇)
𝜕𝑈 𝜕𝑈
𝑑𝑉 = ( ) 𝑑𝑉 + ( ) 𝑑𝑇
𝜕𝑉 𝑇 𝜕𝑇 𝑣
𝜕𝑃
= 𝐶𝑣 𝑑𝑇 + [𝑇 ( ) − 𝑃] 𝑑𝑉
𝜕𝑇 𝑉

∴Integrating we can get change of internal for a pure substance.

𝜕𝑃
𝑖. 𝑒. , ∆𝑈 = ∫ 𝐶𝑣 𝑑𝑇 + ∫ [𝑇 ( ) − 𝑃] 𝑑𝑉
𝜕𝑇 𝑉

• Change of 𝑼 with volume for real gas:-

For van Dar Waals gas,
𝑎
(𝑃 + ) (𝑉 − 𝑏) = 𝑅𝑇
𝑉2
𝑅𝑇 𝑎
𝑜𝑟, 𝑃 = − 2
𝑉−𝑏 𝑉
𝜕𝑃 𝑅
∴( ) =
𝜕𝑇 𝑉 𝑉 − 𝑏

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Now,
𝜕𝑈 𝜕𝑃
( ) = 𝑇 ( ) − 𝑃[𝐹𝑟𝑜𝑚 1𝑠𝑡 𝑒𝑛𝑒𝑟𝑔𝑦 𝑟𝑒𝑙𝑎𝑡𝑖𝑜𝑛]
𝜕𝑉 𝑇 𝜕𝑇 𝑉
𝑅𝑇 𝑎
= −𝑃 = 2
𝑉−𝑏 𝑉
This actually represent co-pressure originated from intermolecular interaction.

Here,
𝑇2 𝑉2
𝑎
∆𝑈 = ∫ 𝐶𝑉 𝑑𝑇 + ∫ 𝑑𝑉
𝑉2
𝑇1 𝑉1
𝑇2
1 1
= ∫ 𝐶𝑉 𝑑𝑇 − 𝑎 ( − )
𝑉2 𝑉1
𝑇1

∴Change of internal energy for a real gas also depends on change in volume.

𝟐𝒏𝒅 𝑬𝒏𝒆𝒓𝒈𝒚 𝑬𝒒𝒖𝒂𝒕𝒊𝒐𝒏: −

Here we consider 𝑈 = 𝑈(𝑇, 𝑃)

Now, 1st law says,

𝑇𝑑𝑆 = 𝑑𝑈 + 𝑃𝑑𝑉
𝜕𝑈 𝜕𝑆 𝜕𝑉
⟹ ( ) = 𝑇( ) −𝑃( )
𝜕𝑃 𝑇 𝜕𝑃 𝑇 𝜕𝑃 𝑇
𝜕𝑉 𝜕𝑉
= −𝑇 ( ) − 𝑃 ( )
𝜕𝑇 𝑃 𝜕𝑃 𝑇

This gives 2nd energy relation. Now change in internal energy,

𝜕𝑈 𝜕𝑉
∆𝑈 = ( ) 𝑑𝑃 − ( ) 𝑑𝑃
𝜕𝑇 𝑃 𝜕𝑃 𝑇
𝜕𝑉 𝜕𝑉 𝜕𝑉
= ( ) 𝑑𝑇 − {𝑇 ( ) + 𝑃 ( ) } 𝑑𝑃
𝜕𝑇 𝑃 𝜕𝑇 𝑃 𝜕𝑃 𝑇

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• 𝑨𝒑𝒑𝒍𝒊𝒄𝒂𝒕𝒊𝒐𝒏𝒔: −

1. Ratio of the adiabatic to isothermal elasticity is 𝜸.

We have adiabatic elasticity
𝜕𝑃
𝐸𝑆 = −𝑉 ( )
𝜕𝑉 𝑆

Isothermal elasticity
𝜕𝑃
𝐸𝑇 = −𝑉 ( )
𝜕𝑉 𝑇
𝜕𝑃
𝐸𝑆 (𝜕𝑉 )𝑆
∴ =
𝐸𝑇 𝜕𝑃
( )
𝜕𝑉 𝑇
𝜕𝑃 𝜕𝑇
( ) ( )
𝜕𝑇 𝑆 𝜕𝑉 𝑆
=
𝜕𝑃 𝜕𝑆
( ) ( )
𝜕𝑆 𝑇 𝜕𝑉 𝑇
𝜕𝑆 𝜕𝑇
( ) ( ) 𝜕𝑥 1
𝜕𝑃 𝑇 𝜕𝑉 𝑆
= [∵ ( ) = ]
𝜕𝑇 𝜕𝑆 𝜕𝑦 𝑧 𝜕𝑦
( ) ( ) ( )
𝜕𝑃 𝑆 𝜕𝑉 𝑇 𝜕𝑥 𝑧
𝜕𝑉 𝜕𝑃
( ) ( )
𝜕𝑇 𝑃 𝜕𝑆 𝑣
= [𝑀𝑎𝑥𝑤𝑒𝑙𝑙 ′ 𝑠 𝑟𝑒𝑙𝑎𝑡𝑖𝑜𝑛]
𝜕𝑉 𝜕𝑃
( ) ( )
𝜕𝑆 𝑃 𝜕𝑇 𝑉

𝜕𝑆 1
=( ) ×[ ]
𝜕𝑇 𝑃 𝜕𝑆
( )
𝜕𝑇 𝑉

Now, multiplying by 𝑇, we get

𝐶𝑝
=𝛾
𝐶𝑣
𝐾𝑇 𝐸𝑆
[𝑁𝑜𝑡𝑒, = = 𝛾]
𝐾𝑆 𝐸𝑇

For isoentropic process show that-

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𝜕𝑉 𝐶𝑣 𝜕𝑉
(𝑖) ( ) =− ( )
𝜕𝑇 𝑆 𝐶𝑃 − 𝐶𝑉 𝜕𝑇 𝑃
𝜕𝑃 𝐶𝑃 𝜕𝑃
(𝑖𝑖) ( ) = ( )
𝜕𝑇 𝑆 𝐶𝑝 − 𝐶𝑣 𝜕𝑇 𝑉

𝜕𝑃 𝜕𝑉
[𝑅𝑒𝑚𝑒𝑚𝑏𝑒𝑟, 𝐶𝑃 − 𝐶𝑣 = 𝑇 ( ) ( ) ]
𝜕𝑇 𝑉 𝜕𝑇 𝑃

From 1st 𝑇𝑑𝑆 relation,

𝜕𝑃
𝑇𝑑𝑆 = 𝐶𝑣 𝑑𝑇 + 𝑇 ( ) 𝑑𝑉
𝜕𝑇 𝑣

For iso entropic process 𝑑𝑆 = 0

𝜕𝑃 𝜕𝑉
∴ 𝐶𝑣 = −𝑇 ( ) ( )
𝜕𝑇 𝑣 𝜕𝑇 𝑆

Similarly from 2nd relation of 𝑇𝑑𝑆

𝜕𝑉
𝑇𝑑𝑆 = 𝐶𝑃 𝑑𝑇 − 𝑇 ( ) 𝑑𝑃
𝜕𝑇 𝑃

Hence for iso entropic process,

𝜕𝑉 𝜕𝑃
𝐶𝑃 = 𝑇 ( ) ( )
𝜕𝑇 𝑃 𝜕𝑇 𝑆
𝜕𝑃 𝜕𝑉
𝐶𝑣 −𝑇 ( ) ( )
𝜕𝑇 𝑣 𝜕𝑇 𝑆
∴ =
𝐶𝑃 − 𝐶𝑣 𝜕𝑃 𝜕𝑉
𝑇( ) ( )
𝜕𝑇 𝑣 𝜕𝑇 𝑃
𝜕𝑉 𝜕𝑉
= − ( ) ⁄( )
𝜕𝑇 𝑠 𝜕𝑇 𝑃
𝜕𝑉 𝐶𝑣 𝜕𝑉
∴( ) =− ( ) [𝑃𝑟𝑜𝑣𝑒𝑑]
𝜕𝑇 𝑆 𝐶𝑃 − 𝑐𝑣 𝜕𝑇 𝑃

Similarly,

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𝜕𝑉 𝜕𝑃
𝐶𝑃 𝑇( ) ( )
𝜕𝑇 𝑃 𝜕𝑇 𝑆
=
𝐶𝑃 − 𝐶𝑣 𝑇 𝜕𝑃 𝜕𝑉
( ) ( )
𝜕𝑇 𝑣 𝜕𝑇 𝑃
𝜕𝑃 𝜕𝑃
= ( ) ⁄( )
𝜕𝑇 𝑆 𝜕𝑇 𝑣
𝜕𝑃 𝐶𝑝 𝜕𝑃
∴( ) = ( )
𝜕𝑇 𝑣 𝐶𝑝 − 𝐶𝑣 𝜕𝑇 𝑆

𝑇𝑉𝛼 2
• Show, 𝐶𝑃 − 𝐶𝑣 =
𝐾𝑇
𝜕𝑃 𝜕𝑉
𝐶𝑃 − 𝐶𝑉 = 𝑇 ( ) ( )
𝜕𝑇 𝑣 𝜕𝑇 𝑃
𝜕𝑃 𝜕𝑉 2
= −𝑇 ( ) ( ) [𝑃𝑟𝑜𝑣𝑒𝑑 𝑒𝑎𝑟𝑙𝑖𝑒𝑟]
𝜕𝑉 𝑇 𝜕𝑇 𝑃
1 𝜕𝑉 1 𝜕𝑉
𝑁𝑜𝑤, 𝛼 = ( ) 𝑎𝑛𝑑 𝐾𝑇 = ( )
𝑣 𝜕𝑇 𝑃 𝑣 𝜕𝑃 𝑇
2
𝑇𝑉𝛼
∴ 𝐶𝑝 − 𝐶𝑣 = [𝑃𝑟𝑜𝑣𝑒𝑑]
𝐾𝑇

𝑃𝑉 𝐵 (𝑇 )
A gas obeying equation 𝑅𝑇 = 1 + . Then prove that
𝑣
𝑅𝑇 𝑑 2 [𝐵𝑇]
𝐶𝑃 − 𝐶𝑣0 =−
𝑉 𝑑𝑇 2
From thermodynamic relation,

𝜕𝐶𝑣 𝜕2𝑃
= 𝑇 ( 2)
𝜕𝑉 𝜕𝑇 𝑣

From given equation,

𝑅𝑇 𝐵(𝑇)
𝑃= (1 + )
𝑣 𝑣

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𝑅 𝐵𝑇
= (𝑇 + )
𝑣 𝑣
2
𝜕 𝑃 𝑅 𝜕 2 (𝐵𝑇)
∴ ( 2) = 2 [ ]
𝜕𝑇 𝑣 𝑣 𝜕𝑇 2 𝑣
𝜕𝐶𝑣 𝜕2𝑃 𝑅𝑇 𝑑 2 (𝐵𝑇)
∴( ) = 𝑇 ( 2) = 2
𝜕𝑉 𝑇 𝜕𝑇 𝑣 𝑣 𝑑𝑇 2

Integrating we get,

𝑅𝑇 𝑑 2 (𝐵𝑇)
𝐶𝑣 = − + 𝐾[𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡]
𝑉 𝑑𝑇 2
𝑎𝑡 𝑇 = 𝑇0 , 𝑘 = 𝐶𝑉0
𝑅𝑇 𝑑 2 (𝐵𝑇)
∴ 𝐶𝑉 − 𝐶𝑣𝑜 = − [𝑃𝑟𝑜𝑣𝑒𝑑]
𝑉 𝑑𝑇 2

𝑎
𝑅𝑇 −
For a gas obeying the equation 𝑃 = 𝑉−𝑏 𝑒 𝑅𝑇𝑉 . Show that
𝜕𝑈 𝑎𝑃
( ) =
𝜕𝑉 𝑇 𝑅𝑇𝑉

From 1st and 2nd law

𝑇𝑑𝑆 = 𝑑𝑈 + 𝑃𝑑𝑉
⟹ 𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉
𝜕𝑈 𝜕𝑆 𝜕𝑃
∴ ( ) = 𝑇( ) −𝑃 = 𝑇( ) −𝑃
𝜕𝑉 𝑇 𝜕𝑉 𝑇 𝜕𝑇 𝑉
𝜕𝑆 𝜕𝑃
[𝑈𝑠𝑖𝑛𝑔 𝑀𝑎𝑥𝑤𝑒𝑙𝑙 ′ 𝑠𝑟𝑒𝑙𝑎𝑡𝑖𝑜𝑛 ( ) = ( ) ]
𝜕𝑉 𝑇 𝜕𝑇 𝑉
𝑅𝑇 − 𝑎
𝑁𝑜𝑤, 𝑃 = 𝑒 𝑅𝑇𝑉
𝑉−𝑏
𝜕𝑃 𝑅 −
𝑎 𝑅𝑇 − 𝑎 𝑎
( ) = 𝑒 𝑅𝑇𝑉 + 𝑒 𝑅𝑇𝑉 ( 2 )
𝜕𝑇 𝑉 𝑉 − 𝑏 𝑉−𝑏 𝑅𝑇 𝑉
𝜕𝑃 𝑅𝑇 − 𝑎 𝑅𝑇 − 𝑎 𝑎
∴ 𝑇( ) = 𝑒 𝑅𝑇𝑉 + 𝑒 𝑅𝑇𝑉 ( )
𝜕𝑇 𝑉 𝑉 − 𝑏 𝑉−𝑏 𝑅𝑇𝑉
𝑎𝑃
=𝑃+
𝑅𝑇𝑉

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𝜕𝑃 𝑎𝑃
∴ 𝑇( ) −P=
𝜕𝑇 𝑉 𝑅𝑇𝑉
𝜕𝑈 𝑎𝑃
⟹( ) = [𝑃𝑟𝑜𝑣𝑒𝑑]
𝜕𝑉 𝑇 𝑅𝑇𝑉

𝑃𝑉
• A gas obeying the equation of state = 1 + 𝑃𝐵 (𝑇); 𝐵 is a function of
𝑅𝑇
temperature. Show ,

𝑑2 (𝐵𝑇)
𝐶𝑃 − 𝐶𝑃 0 = −𝑅𝑇𝑃
𝑑𝑇 2
Where 𝐶𝑝0 is the value of 𝐶𝑝 at same reference temperature.

⟹ We know,

𝜕 𝜕2𝑉
(𝐶 ) = −𝑇 ( 2 ) … . . (1)
𝜕𝑃 𝑝 𝜕𝑇 𝑃

From the equation of state,

𝑃𝑉
= 1 + 𝑃𝐵(𝑇)
𝑅𝑇
1
𝑉 = 𝑅𝑇 [ + 𝐵(𝑇)]
𝑃
𝜕𝑉 𝑅 𝑑
𝑜𝑟, ( ) = + 𝑅 (𝑇𝐵)
𝜕𝑇 𝑃 𝑃 𝑑𝑡

∴Differentiating again,

𝜕2𝑉 𝑑2
( 2 ) = 𝑅 2 (𝑇𝐵)
𝜕𝑇 𝑃 𝑑𝑇

From (1),

𝜕 𝑑2
(𝐶 ) = −𝑅𝑇 2 (𝑇𝐵)
𝜕𝑃 𝑃 𝑑𝑇
From (1)

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𝜕 𝑑2
(𝐶 ) = −𝑅𝑇 2 (𝑇𝐵)
𝜕𝑃 𝑃 𝑑𝑇
Integrating,

𝑑2
𝐶𝑃 = − ∫ 𝑅𝑇 2 (𝑇𝐵) 𝑑𝑃
𝑑𝑇
𝑑2
= −𝑃𝑅𝑇 2 (𝑇𝐵) + 𝐾[𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡]
𝑑𝑇
𝑎𝑡 𝑇 = 0, 𝐶𝑝 = 𝐶𝑝0 𝑖. 𝑒. , 𝐾 = 𝐶𝑝0
𝑑2
∴ 𝐶𝑝 − 𝐶𝑃0 = −𝑅𝑇𝑃 2 (𝑇𝐵) [𝑃𝑟𝑜𝑣𝑒𝑑]
𝑑𝑇

Derivation of one thermodynamic potential from other

A. Calculation of F from U
𝐹 = 𝑈 − 𝑇𝑆
𝑈 = 𝐹 + 𝑇𝑆
𝜕𝐹
= 𝐹 −𝑇( )
𝜕𝑇 𝑉
𝜕 𝐹
= −𝑇 2 { ( ) }
𝜕𝑇 𝑇 𝑉

Hence
𝐹 𝑈
= − ∫ 2 𝑑𝑇 + 𝐶1 (𝑉)
𝑇 𝑇

B. Calculation of G from F
𝐹 = 𝑈 − 𝑇𝑆 = 𝑈 + 𝑃𝑉 − 𝑇𝑆 + 𝑃𝑉
𝐹 = 𝐺 + 𝑃𝑉
𝜕𝐺
= 𝐺 −𝑃( ) 𝑑𝐺 = 𝑆𝑑𝑇 − 𝑉𝑑𝑃
𝜕𝑃 𝑇

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𝜕 𝐺
= −𝑃2 { ( ) }
𝜕𝑃 𝑃 𝑇

Hence
𝐺 𝐹
= − ∫ 2 𝑑𝑃 + 𝐶2 (𝑉)
𝑃 𝑃

C. Calculation of H from G
𝐺 = 𝐻 − 𝑇𝑆
𝜕𝐻
= 𝐻 −𝑆( ) 𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃
𝜕𝑆 𝑃
𝜕 𝐻
= −𝑆 2 { ( ) }
𝜕𝑆 𝑆 𝑇

Hence
𝐻 𝐺
= − ∫ 2 𝑑𝑆 + 𝐶3 (𝑇)
𝑆 𝑆

D. Calculation of H from U
𝑈 = 𝐻 + 𝑃𝑉
𝜕𝐻
= 𝐻+𝑃( ) 𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃
𝜕𝑃 𝑆
𝜕 𝐻
= −𝑃2 { ( ) }
𝜕𝑃 𝑃 𝑆

Hence
𝐻 𝑈
= − ∫ 2 𝑑𝑃 + 𝐶4 (𝑆)
𝑃 𝑃

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