CENTRAL UNIVERSITY

OF KASHMIR
DEPARTMENT OF PHYSICS

PRESENTATION ON: THERMODYNAMIC

POTENTIALS
COURSE: THERMAL PHYSICS
SEMESTER : SECOND

SUBMITTED TO: DR FAROOQ AHMAD

PREPARED BY : SHARIEKA SHARIEF
  CONTENTS INSIDE

THERMODYNAMIC
POTENTIALS

HELMHOLTZ
INTERNAL ENERGY ENTHALPY GIBB’S FUNCTION
FUNCTION
  THERMODYNAMIC POTENTIALS
 In order to describe the behaviour of a thermodynamic
system , it is more convenient to use certain energy terms
rather than the basic coordinates P, T ,V and S .
 These energy terms which are mathematically formed by
combining the basic coordinates P, T, V and S in various
ways are called Thermodynamic potentials or
thermodynamic functions.
 They are called so because their difference in two states
gives the work done from one state to another.
 INTERNAL ENERGY
 The internal energy is the energy of a system which is not
subject to the action of external forces and is in a state of
macroscopic rest.
 The internal energy is defined by using first and second law of
thermodynamics , which provide us two relations;
𝜕𝑄 = 𝑑𝑈 + 𝑃𝑑𝑉
and 𝜕𝑄 = 𝑇𝑑𝑆
 Combining equations (i) and (ii), we have
𝑇𝑑𝑆 = 𝑑𝑈 + 𝑃𝑑𝑉
𝒅𝑼 = 𝑻𝒅𝑺 − 𝑷𝒅𝑽 (iii)
This expresses the change in internal energy of the system in
terms of four thermodynamic variables and is called as the first
thermodynamic potential.
HELMHOLTZ FUNCTION
 The Helmholtz function is defined by the equation ;
F=U-TS
For an infinitesimal process:
𝑑𝐹 = 𝑑𝑈 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇
From equation (iii)
𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉
𝑑𝐹 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇

𝒅𝑭 = −𝑷𝒅𝑽 − 𝑺𝒅𝑻 (v)

 From equation (v) , it follows:
(a) For a reversible isothermal process (i.e dT=0)
𝑑𝐹 = −𝑃𝑑𝑉
Hence the change of the Helmholtz function during a reversible
isothermal process equals the work done on the system.
(b) For a reversible isothermal and isochoric process (i.e dT=
dV=0)
dF=0
and F= constant
 Hence Helmholtz function is a physical quantity in energy units
which does not change during an isothermal-isochoric
process.
  THE ENTHALPY H

 Enthalpy is the function of the state of a thermodynamic system

that is equal to sum of its internal energy and the product of the
pressure of the system by its volume .
𝐻 = 𝑈 + 𝑃𝑉

 Consider the change in enthalpy that takes place when a system

undergoes an infinitesimal process from an initial equilibrium state
to a final equilibrium state. We have ,
𝑑𝐻 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃
𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉

𝒅𝑯 = 𝑻𝒅𝑺 + 𝑽𝒅𝑷 (iv)

THE GIBB’S POTENTIAL
 The Gibb’s function is defined by:
𝐺 = 𝐻 − 𝑇𝑆
The Change in Gibbs function for an infinitesimal reversible
process,
𝑑𝐺 = 𝑑𝐻 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 (v)
We know from equation (iv),
𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃 (vi)
Combining equations (v) and (vi) , we get

𝒅𝑮 = 𝑽𝒅𝑷 − 𝑺𝒅𝑻
 In case of a reversible isothermal and isobaric process:
𝑑𝑇 = 𝑑𝑃 = 0
𝑑𝐺 = 0
or G= Constant.
 This is particularly important result in connection with process
involving change of phase like Sublimation, fusion and
vaporization. In such processes , the Gibb’s function of the
system remains constant.
THANK YOU