Maxwell’s Thermodynamic Relation

Maxwell derived the relation by combining 1st & 2nd law of thermodynamics for a PVT
system undergoing an infinitesimal reversible process.
We have from 1st law of thermodynamics,

dQ =dU +dW

 dQ =dU + pdV
dU =dQ −pdV ---------- (i)
From second law of thermodynamics,
dQ
dS=
T

 dQ =TdS
dU =TdS−pdV ---------- (ii)
Considering U, S & V are function of two independent variables x∧ y .

dU =( ∂∂Ux ) dx +( ∂∂Uy ) dy
y x

dS=( ) dx+ (
∂ y)
∂S ∂S
dy
∂x y x

dV =(
∂x )
dx +(
∂y)
∂V ∂V
dy
y x

Substituting their value in eq. (ii) we have-

( ∂∂Ux ) dx +( ∂∂Uy ) dy =T {( ∂∂ Sx ) dx+( ∂∂ Sy ) dy }− p {( ∂V∂x ) dx+( ∂V∂y ) dy }

y x y x y x

{ ( ) ( )} { ( ) ( )}
¿ T
∂S
∂x y
−P
∂V
∂x y
dx + T
∂S
∂y y
−P
∂V
∂y x
dy ---(iii)

Comparing the coefficient of dx∧dy from equation (iii) we have-

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 ( ) ( ) ( )
∂U
∂x y
=T
∂S
∂x y
−P
∂V
∂x y
----------- (iv)

( ∂∂Uy ) =T ( ∂∂ Sy ) −P ( ∂V∂y )
x y x
----------- (v)

Differentiating equation (iv) & (v) with respect to y∧x we have-

∂2 U
=
∂T
( )( )
∙
∂S
∂ y∙∂ x ∂ y x ∂ x y
+T ∙
∂2 S
−
∂p
∙
∂U
∂ y∙∂ x ∂ y x ∂ x x
−p ( )( ) (
∂2 V
∂ y ∙∂x )
− p(
∂x ∙∂ y ( ∂x ) (∂ y ) ∂ x∙∂ y ( ∂x ) ( ∂ y ) ∂ y ∙∂x )
2 2 2
∂U ∂T ∂S ∂ S ∂p ∂U ∂V
= ∙ +T − ∙
y x y x

2 2
∂U ∂ U
Since dU is a perfect differential, above two expressions are equal = and
∂ y∙∂ x ∂ x∙∂ y
single dS & dV are perfect differential.
After simplifying we can write,

( ∂∂ Ty ) ∙( ∂∂ Sx ) −( ∂∂ py ) ∙( ∂∂Ux ) =( ∂∂Tx ) ∙( ∂∂ Sy ) −( ∂∂ px ) ∙( ∂∂ Uy )
x y x x y x y x
------ (vi)

Equation (vi) is the general equation for Maxwell’s thermodynamic Relation.

1st Relation:
Putting x=T , y =V and taking T ∧V as independent variables.
∂T ∂V ∂T ∂V
=1 , =1 , =0 , =0
∂x ∂y ∂y ∂x

∂S
( ) ( )
∂P
(vi)  ∂ V = ∂ T
T V
[ But , dS=
dQ
T ]
∴(
∂V ) (∂T )
∂Q ∂P
=
T V

For a thermodynamic system, the increase of entropy per unit increase of volume at
constant temperature is equal to the increase of temperature in a isochoric process.
2nd Relation:
Taking T & P are independent variables. i.e. x=T & y=P
We get from (vi)

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 ∂T ∂ P 1∧∂ T ∂P
=1 , = =0 , =0
∂x ∂y ∂y ∂x

( ∂∂ Sp ) =−( ∂∂ VT )
T p

( ∂∂ Qp ) =−( ∂∂ VT )
T p

The decrease of entropy per unit increase of pressure in a isothermal process is equal to
the increase of volume per unit increase of temperature for a isobaric process.
3rd Relation:
Taking entropy & volume as independent variables. i.e. x=S & y=V
We get,
∂S ∂ V 1∧∂ S ∂V
=1, = =0 , =0
∂x ∂y ∂y ∂x

From equation (vi) we can write,

( ∂∂ Tx ) =−( ∂∂Ps )
s v

( ∂ x ) =−T ( ∂ Q )
∂T ∂P
s v

The increase of temperature per unit increase of volume in a reversible adiabatic

process is equal to the decrease of pressure per unit increase of entropy in a isochoric
process.
4th Relation:
Taking entropy & Pressure as independent variable. i.e. x=S & y=P
We have,
∂S ∂ P 1∧∂ S ∂P
=1, = =0 , =0
∂x ∂y ∂y ∂x

(vi) ( ) ( )
∂T ∂v
 ∂ p = ∂S
s p

( ∂ p ) =T ( ∂ Q )
∂T ∂v
s p

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The increase of temperature per unit increase pressure in a reversible adiabatic process
is equal to the increase of volume per unit increase of entropy in a isobaric process.
5th Relation:
Taking p & v as independent variable. i.e. x=p & y=v
We get,
∂p ∂ v 1∧∂ p ∂v
=1, = =0 , =0
∂x ∂y ∂y ∂x

(vi) ( )( ) ( )( )
∂T ∂S ∂T ∂S
 ∂ p ∙ ∂ v − ∂ v ∙ ∂ p =1
v v p v

6th Relation:
Taking T & S as independent variable. i.e. x=T & y=S
We get,
∂T ∂ S 1∧∂ T ∂S
=1 , = =0 , =0
∂x ∂y ∂y ∂x

(vi) ( )( ) ( )( )
∂p ∂v ∂p ∂v
 ∂ T ∙ ∂ S − ∂ S ∙ ∂T =1
S T T S

Clausius – Clapeyron equation (1st latent heat equation)

From Maxwell’s 1st relation we can write

( ∂∂ Sv ) =( ∂∂Pt )
T v

T ( ∂ v ) =T ( ∂ T )
∂S ∂P
[ ∵ dQ=TdS ]
T v

( ∂ v ) =T ( ∂T )
∂Q ∂P
------------ (i)
T v

Here, ( ∂ v ) represents the quantity of heat absorbed per unit increase in volume at
∂Q
T

constant temperature. This quantity of heat absorbed at constant temperature is the

latent heat (L),
Thus dQ=L∧dV =V 2−V 1

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 ∴
( L
V 2−V 1 T ) ( )
=T
dp
dT V

dp
( ) L
 dT = T V −V which is the 1st latent heat equation.
( 2 1)

Specific heat of constant volume Cv:

The amount of heat required to raise the temperature of unit mass of a gas through 1C
when its volume keep constant, it is represented by C v = ∆ T ( ∆Q) v

Specific heat of constant Pressure Cp: The amount of heat required to raise the
temperature of unit mass of a gas through 1C when its pressure keep constant, it is
represented by C p= ∆ T ( ∆Q ) p

Show that C p−C v =R

If V ∧T are chosen as the independent variables U =f (V , T ) ------------- (i)

Differentiating (i)

dU = ( ∂∂TU ) dT +( ∂U
V ∂V )
dV
T
-------------(ii)

According to the 1st law of thermodynamics-

dQ =dU +dW

¿ dU + pdV

¿ ( ∂∂TU ) dT +( ∂U
V ∂V )
dV + pdV ----------------(iii)
T

Dividing both side by dT

dQ ∂ U
dT
=
∂T ( ) + {p+( ∂U
V ∂ V ) } dT
dV
------------------ (iv)
T

If the gas is heated at constant volume-

( ) ( ∂∂TQ ) =( ∂∂UT ) =C
∂Q C ∧dV
= V =0 V --------------------- (v)
∂T V dT V V

When the gas is heated at constant pressure,

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 dQ
=C p
dT

∴ C p= ( ∂∂ UT ) +{ p+( ∂∂UV ) }( ∂∂VT )

V T p

∴ C p=CV + p+ { ( ) }( )
∂U
∂V T
∂V
∂T p

∂U
( )
But ∂V =0
T

For ideal gas equation we can write

P V =RT

( )
∂V
 P ∂ T =R
p

∴ C p−CV =P∙ ( ∂∂ VT ) +( ∂∂ UV ) ∙( ∂∂TV )

p T ¿

 C p−C V =R (Shown)

Maxwell's law of Equipartition energy:

According to kinetic theory of gas we can write,

1 2 3
m c = kT
2 2

But, c 2=u 2+ v 2+ w2 as x , y , z are all equivalent. Mean square velocities along three axes
are equal.
2 2 2
u =v =w

Hence,
1
u2=v 2=w2= c 2
3
1 1 1
∴ mu2= m v 2= m w2
2 2 2

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 1 1
2 ( 1
2 )(1
2 )( 3
∴ mc 2=3 mu2 = mv 2 = mw 2 = kT
2 2 )
( )
1 2 3
 3 2 m u = 2 kT
1 2 1
or, 2 mu = 2 kT

 3 ( 2 m v )= 2 kT
1 2 3 1 2 1
or, 2 m v = 2 kT

 3 ( 2 m w )= 2 kT
1 2 3 1 2 1
or, 2 m w = 2 kT

1
Thus, the average K.E. associated with each degree of freedom ¿ 2 kT

7 Composed by: KN, ARB