Heat &Thermodynamics

Dr. Mostak Hossain

Professor, Dept. of Physics, BUET.
 Maxwell’s Relations
Thermodynamic Variables:
1) Entropy, S
2) Pressure, P

k
3) Temperature, T
4) Volume, V

s
Thermodynamic Functions:t a
1)
o
Internal Energy, E

M
E=Q-W

.
2) Helmholtz Free Energy, F F = E – TS
3)
4)
Enthalpy, H

Dr
Gibb’s Free Energy, G
H = E + PV
G = H - TS
These functions together with the entropy S are called the
thermodynamic potentials.
Helmholtz Free Energy F is called the thermodynamic potential at
constant volume.

k
Gibb’s Free Energy G is called the thermodynamic potential at
a
constant pressure.

s t
o
Change of thermodynamic Functions:
1) dE = dQ – dW = TdS – PdV

. M
2) dF = dE – TdS – SdT = -PdV - SdT

Dr
3) dH = dE + PdV + VdP =TdS + VdP
4) dG = dH - TdS – SdT = VdP - SdT
Maxwell’s 1st relation:
We know Internal Energy Change dE = TdS – PdV (1)
Now differentiating the above expression partially

!"
!# 𝑉
t a
=𝑇 k (2)
!"
o
= −𝑃 s
M 𝑆 (3)
!'

r.
Now from (2) again differentiating vice versa
! !"
!' !#
D = 𝑉 𝑆
!+
!' S
(4)
and from (3) again differentiating vice versa
! !" !,
=− (5)
!# !' 𝑆 𝑉 !# V

ta k
Since thermodynamic functions are perfect differential. So for perfect
differential condition, left side of equations (4) and (5) are equal.

o s
=M
!+ !,
−
.
Hence

Dr
!' S !# V

This is Maxwell’s 1st thermodynamic relation.

Maxwell’s 2nd relation:
We know Helmholtz Free Energy Change dF = - PdV - SdT (1)
Now differentiating the above expression partially

!-
t a k
= −𝑃 (2)
!' 𝑇
!-
o s
r.
!+ M
= −𝑆
𝑉 (3)

D
Now from (2) again differentiating vice versa
! !-
=−
!,
(4)
!+ !' 𝑇 𝑉 !+ V
and from (3) again differentiating vice versa
! !- !#
𝑉 𝑇 =− (5)
!' !+ !' T

a k
Since thermodynamic functions are perfect differential. So for perfect

t
differential condition, left side of equations (4) and (5) are equal.
s
!#
=M
o !,

.
Hence
!' T !+ V

Dr
This is Maxwell’s 2nd thermodynamic relation.
Maxwell’s 3rd relation:
We know Enthalpy Change dH = TdS + VdP (1)
Now differentiating the above expression partially

!/
=𝑇 t a k
s
(2)
!# 𝑃
=o
!/

.r
!, M 𝑉 𝑆
Now from (2) again differentiating vice versa
(3)

!,
D =
! !/
!# 𝑃 𝑆
!+
!, S
(4)
and from (3) again differentiating vice versa
! !/ !'
= (5)
!# !, 𝑆 𝑃 !# P

k
Since thermodynamic functions are perfect differential. So for perfect

a
differential condition, left side of equations (4) and (5) are equal.

st
= o
!+ !'
Hence

r. M
!, S !# P

D
This is Maxwell’s 3rd thermodynamic relation.
Maxwell’s 4th relation:
We know Gibb’s Free Energy Change dG = VdP - SdT (1)
Now differentiating the above expression partially

=t𝑉a
!0
k
o s !, 𝑇
(2)

r. M!0
=
!+
−𝑆 𝑃 (3)

D
Now from (2) again differentiating vice versa
! !0
=
!'
(4)
!+ !, 𝑇 𝑃 !+ P
and from (3) again differentiating vice versa
! !0 !#
𝑃 𝑇 =− (5)
!, !+ !, T

ta k
Since thermodynamic functions are perfect differential. So for perfect
differential condition, left side of equations (4) and (5) are equal.

o s
M
!# !'
= -
.
Hence

Dr!, T !+ P

This is Maxwell’s 4th thermodynamic relation.

•Thanks