Heat And Thermodynamics

UNIT – 2
The thermodynamic state of a substance is specified by some of its
properties like pressure, volume, temperature, internal energy and entropy.
These properties undergo a change when the system passes from one state to
another. These variables are known as thermodynamic variables or co-ordinates.
These are called macroscopic co-ordinates.
➢ Thermodynamic Potentials: -
The state of a system can be completely described by any two of the
five state variables P, V, T, S, V. The internal energy is determined by using the
remaining four
According to first law of thermodynamics,
𝛿𝑄 = 𝛿𝑈 + 𝛿𝑊

𝛿𝑄 = 𝛿𝑈 + 𝑃𝑑𝑉 (Eq. - 1)

From the second law of thermodynamics,

𝛿𝑄 = 𝑇𝑑𝑆 (Eq. - 2)
Substituting for dQ, we get
𝑑𝑈 + 𝑃𝑑𝑉 = 𝑇𝑑𝑆

𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉
Thus, V can be eliminated and we are left with four state variables PVTS
only. Taking two of the four state variables at a time there are six possible
pairs.
(P, V); (P, T); (P, S); (V, T); (V, S); (T, S)
The pair (P, V) is connected with composite and in exact differential
quantity 𝛿𝑊 as 𝛿𝑊 = 𝑃𝑑𝑉 and pair (T, S) with 𝛿𝑄 as 𝛿𝑄 = 𝑇𝑑𝑆. Hence these
two pairs can be eliminated. Thus, we are left with four pairs of
thermodynamical variables (P, T); (P, S); (V, T); (V, S) corresponding to each
pair we can write a thermodynamical relation. These four thermodynamical
relations are known as Maxwell’s thermodynamical relations.
 These are four thermodynamical potentials,
1. Internal energy U
2. Helmholtz free energy F = U – TS
3. Enthalpy, H = U + PV
4. Gibbs function G = U+PV -TS
Each of Maxwell’s four thermodynamical relations can be derived from
one of these thermodynamic potentials U, F, H and G. Hence, only four
thermodynamic potentials are defined.
1. Internal Energy (U): -
The internal energy is the total energy of a system according to
the first law of thermodynamics,
𝑑𝑄 = 𝑑𝑈 + 𝑑𝑊 = 𝑑𝑈 + 𝑃𝑑𝑉

𝑑𝑈 = 𝑑𝑄 − 𝑃𝑑𝑉
From second law of thermodynamics, dQ = TdS
Substituting for dQ, we get
𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉
Internal energy is called first thermodynamical potential,
a) For an adiabatic process: -
𝑑𝑄 = 0
𝑑𝑈 = −𝑃𝑑𝑉
i.e., the work done by the system in an adiabatic process is at the
expense of its internal energy.
b) For an isochoric adiabatic process: -
𝑑𝑈 = 0 𝑎𝑛𝑑 𝑑𝑄 = 0
𝑑𝑈 = 0 𝑜𝑟 𝑈 = 𝑎 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
i.e., the internal energy of system remains constant in an
isochoric adiabatic process
2. Helmholtz free energy (F): -
𝐹 = 𝑈 − 𝑇𝑆
According to first and second law of thermodynamics,
𝑑𝑈 = 𝑇𝑑𝑆 − 𝑑𝑊
If the system is maintained at a constant temperature by
exchanging heat continuously with the surroundings. Then,
𝑇𝑑𝑆 = 𝑑(𝑇𝑆)
𝑑𝑈 = 𝑑(𝑇𝑆) − 𝑑𝑊
𝑑(𝑈 − 𝑇𝑆) = −𝑑𝑊
 𝑑𝐹 = −𝑑𝑊
Where F =(U – TS) is known as Helmholtz free energy.
𝑑𝐹 = 𝑑(𝑈 − 𝑇𝑆)
𝑑𝐹 = 𝑑𝑈 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇
𝑑𝐹 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇
𝑑𝐹 = −𝑃𝑑𝑉 − 𝑆𝑑𝑇
a) For reversible isothermal process: -
𝑑𝑇 = 0
𝑑𝐹 = −𝑃𝑑𝑉 𝑜𝑟 𝑃𝑑𝑉 = −𝑑𝐹
Thus, the work done in a reversible isothermal process is equal
to the decrease in Helmholtz free energy.
b) For isothermal isochoric process: -
𝑑𝑇 = 0 𝑎𝑛𝑑 𝑑𝑉 = 0
𝑑𝐹 = 0 𝑜𝑟 𝐹 = 𝑎 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
i.e., The Helmholtz free energy remains constant during
isothermal isochoric process.
3. Enthalpy (H): -
This is known as the total heat and given by,
𝐻 = 𝑈 + 𝑃𝑉
Change in enthalpy,
𝑑𝐻 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃
𝑑𝐻 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃
𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃
a) For reversible isobaric process: -
𝑑𝑃 = 0
𝑑𝐻 = 𝑇𝑑𝑆 = 𝑑𝑄
i.e., for an isobaric process, the change in enthalpy is equal to
the heat absorbed.
b) For an isobaric adiabatic process: -
𝑑𝑃 = 0 𝑎𝑛𝑑 𝑑𝑄 = 0
𝑑𝐻 = 0 𝑜𝑟 𝐻 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
i.e., enthalpy remains constant in a reversible isobaric adiabatic
process.
4. Gibbs free Energy: -
𝐺 = 𝑈 − 𝑇𝑆 + 𝑃𝑉
𝐺 = 𝐹 + 𝑃𝑉 𝑊ℎ𝑒𝑟𝑒 {𝑈 − 𝑇𝑆 = 𝐹}
This is the relation between Gibbs function and Helmholtz function
 Enthalpy 𝐻 = 𝑈 + 𝑃𝑉 therefore 𝐺 = 𝐻 − 𝑇𝑆
𝐻 = 𝐺 + 𝑇𝑆

a) For an isothermal Process: -

𝑇𝑑𝑆 = 𝑑(𝑇𝑆)

b) For an isobaric process: -

𝑑𝑃 = 0
Hence, if the process is isothermal and isobaric then,
𝑑𝐻 = 𝑑(𝑇𝑆)
𝑑(𝐻 − 𝑇𝑆) = 0
𝑑𝐺 = 0 𝑜𝑟 𝐺 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
Thus, Gibbs free energy remains constant in an isothermal
isobaric process.

➢ Maxwell’s Thermodynamical Reactions: -

From the first and second law of thermodynamics, Maxwell was able
to derive six fundamental thermodynamical relations. From the first law
of thermodynamics.
𝛿𝑄 = 𝑑𝑉 + 𝛿𝑊
𝛿𝑄 = 𝑑𝑉 + 𝑃𝑑𝑉
𝑑𝑉 = 𝑑𝑄 − 𝑃𝑑𝑉
For the second law of thermodynamics,
𝛿𝑄
𝑑𝑆 =
𝑇
𝛿𝑄 = 𝑇𝑑𝑆
Substituting this value of 𝛿𝑄 we get,
𝛿𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 (Eq. - 1)
Considering V S and V to be function of two independent variables x
and y.
𝜕𝑈 𝜕𝑈
𝑑𝑈 = ( ) 𝑑𝑥 + ( ) 𝑑𝑦
𝜕𝑥 𝑦 𝜕𝑦 𝑥
𝜕𝑆 𝜕𝑆
𝑑𝑆 = ( ) 𝑑𝑥 + ( ) 𝑑𝑦
𝜕𝑥 𝑦 𝜕𝑦 𝑥
𝜕𝑉 𝜕𝑉
𝑑𝑉 = ( ) 𝑑𝑥 + ( ) 𝑑𝑦
𝜕𝑥 𝑦 𝜕𝑦 𝑥
 Substituting these values in eq. (1)

𝜕𝑈 𝜕𝑈 𝜕𝑆 𝜕𝑆 𝜕𝑉 𝜕𝑉
( ) 𝑑𝑥 + ( ) 𝑑𝑦 = 𝑇 [( ) 𝑑𝑥 + ( ) 𝑑𝑦] − 𝑃 [( ) 𝑑𝑥 + ( ) 𝑑𝑦]
𝜕𝑥 𝑦 𝜕𝑦 𝑥 𝜕𝑥 𝑦 𝜕𝑥 𝑦 𝜕𝑥 𝑦 𝜕𝑦 𝑥

𝜕𝑆 𝜕𝑉 𝜕𝑆 𝜕𝑉
= [𝑇 ( ) − 𝑃 ( ) ] 𝑑𝑥 + [𝑇 ( ) − 𝑃 ( ) ] 𝑑𝑦
𝜕𝑥 𝑦 𝜕𝑥 𝑦 𝜕𝑦 𝑥 𝜕𝑦 𝑥

Comparing the coefficients of dx and dy we get,

𝜕𝑈 𝜕𝑆 𝜕𝑉
( ) = 𝑇( ) −𝑃( ) … … … … … … … … . (2)
𝜕𝑥 𝑦 𝜕𝑥 𝑦 𝜕𝑥 𝑦

𝜕𝑉 𝜕𝑆 𝜕𝑉
( ) = 𝑇( ) −𝑃( ) … … … … … … … … (3)
𝜕𝑥 𝑦 𝜕𝑦 𝑥 𝜕𝑦 𝑥

Differentiating equation (2) with respect to y.

𝜕2𝑈 𝜕𝑇 𝜕𝑆 𝜕𝑃 𝜕𝑉 𝜕2𝑠 𝜕2𝑉

=( ) ( ) −( ) ( ) +𝑇 −𝑃
𝜕𝑦 𝜕𝑥 𝜕𝑦 𝑥 𝜕𝑥 𝑦 𝜕𝑦 𝑥 𝜕𝑥 𝑦 𝜕𝑦𝜕𝐼 𝜕𝑦𝜕𝑥

Differentiating equation (1) with respect to x.

𝜕2𝑈 𝜕𝑇 𝜕𝑆 𝜕2𝑠 𝜕𝑃 𝜕𝑉 𝜕2𝑉

=( ) ( ) + 𝑇 −( ) ( ) −𝑃
𝜕𝑥𝜕𝑦 𝜕𝑥 𝑦 𝜕𝑦 𝑥 𝜕𝑥𝜕𝑦 𝜕𝑥 𝑦 𝜕𝑦 𝑥 𝜕𝑥𝜕𝑦

The change in internal energy brought about by changing V and T,

whether V is changed by dV first and T by dT later or vice versa is the same. It
means dV is a perfect differential.

𝜕2𝑈 𝜕2𝑈
=
𝜕𝑦𝜕𝑥 𝜕𝑥𝜕𝑦

𝜕𝑇 𝜕𝑆 𝜕𝑃 𝜕𝑉 𝜕2𝑠 𝜕2𝑉
( ) ( ) −( ) ( ) +𝑇 −𝑃
𝜕𝑦 𝑥 𝜕𝑥 𝑦 𝜕𝑦 𝑥 𝜕𝑥 𝑦 𝜕𝑦𝜕𝐼 𝜕𝑦𝜕𝑥
𝜕𝑇 𝜕𝑆 𝜕2𝑠 𝜕𝑃 𝜕𝑉 𝜕2𝑉
=( ) ( ) + 𝑇 −( ) ( ) −𝑃 … … … (4)
𝜕𝑥 𝑦 𝜕𝑦 𝑥 𝜕𝑥𝜕𝑦 𝜕𝑥 𝑦 𝜕𝑦 𝑥 𝜕𝑥𝜕𝑦
Since dS and dV are also perfect differentials, we have

𝜕2𝑠 𝜕2𝑠
=
𝜕𝑥𝜕𝑦 𝜕𝑦𝜕𝑥

𝜕2𝑣 𝜕2𝑣
=
𝜕𝑥𝜕𝑦 𝜕𝑦𝜕𝑥

𝜕𝑇 𝜕𝑠 𝜕𝑃 𝜕𝑉 𝜕𝑇 𝜕𝑠 𝜕𝑃 𝜕𝑉
( ) ( ) − ( ) ( ) = ( ) ( ) − ( ) ( ) … … … (5)
𝜕𝑦 𝑥 𝜕𝑥 𝑦 𝜕𝑦 𝑥 𝜕𝑥 𝑦 𝜕𝑥 𝑦 𝜕𝑦 𝑥 𝜕𝑥 𝑦 𝜕𝑦 𝑥

This is the general expression for Maxwell’s thermodynamical relation. In place

of the independent variables x and y, any two of the four variables S, T, P and V
can be substituted o that there may one mechanical variables (P or V) and one
thermal variables (S or T).

➢ First Relation: -
Put x = sand y = v in equation (5) so that,
𝜕𝑠 𝜕𝑉
= 1, =1
𝜕𝑥 𝜕𝑦
𝜕𝑠 𝜕𝑣
= 0, =0
𝜕𝑦 𝜕𝑥
𝜕𝑇 𝜕𝑃
( ) = −( )
𝜕𝑦 𝑥 𝜕𝑥 𝑦
𝜕𝑇 𝜕𝑃
( ) = −( )
𝜕𝑉 𝑠 𝜕𝑠 𝑉
This is Maxwell’s first thermodynamical relation.

➢ Second Relation: -
Put x = T, y = V in equation (5)
𝜕𝑇 𝜕𝑉
= 1, =1
𝜕𝑥 𝜕𝑦
𝜕𝑇 𝜕𝑉
= 0, =0
𝜕𝑦 𝜕𝑥
 𝜕𝑠 𝜕𝑃
( ) =( )
𝜕𝑉 𝑇 𝜕𝑇 𝑉
This is Maxwell’s second thermodynamical relation.

➢ Third Relation: -
Put 𝑥 = 𝑆 and𝑦 = 𝑃 in equation (5) gives.

𝜕𝑆 𝜕𝑆 𝜕𝑃 𝜕𝑃
= 1; = 0; = 0; =1
𝜕𝑥 𝜕𝑦 𝜕𝑥 𝜕𝑦

𝜕𝑇 𝜕𝑉
( ) =( )
𝜕𝑃 𝑆 𝜕𝑆 𝑃

This is maxwell’s third thermodynamical relation.

➢ Fourth Relation: -
Put 𝑥 = 𝑇 and 𝑦 = 𝑃 in equation (5) gives.

𝜕𝑇 𝜕𝑃 𝜕𝑇 𝜕𝑃
= 1; = 1; = 0; =0
𝜕𝑥 𝜕𝑦 𝜕𝑦 𝜕𝑥

𝜕𝑆 𝑑𝑉
( ) = −( )
𝜕𝑃 𝑇 𝜕𝑇 𝑃
This is maxwell’s fourth thermodynamical relation.
➢ Fifth Relation: -
Put 𝑥 = 𝑃 and 𝑦 = 𝑉 in equation (5) gives.

𝜕𝑃 𝜕𝑉 𝜕𝑃 𝜕𝑉
= 1; = 1; = 0; =0
𝜕𝑥 𝜕𝑦 𝜕𝑦 𝜕𝑥

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

This is maxwell’s fifth thermodynamical relation.

➢ Sixth Relation: -
Put 𝑥 = 𝑇 and 𝑦 = 𝑆 in equation (5) gives.
𝜕𝑇 𝜕𝑆 𝜕𝑇 𝜕𝑆
= 1; = 1; = 0; =0
𝜕𝑥 𝜕𝑦 𝜕𝑦 𝜕𝑥

𝜕𝑃 𝜕𝑉 𝜕𝑃 𝜕𝑉
( ) ( ) −( ) ( ) =1
𝜕𝑇 𝑠 𝜕𝑆 𝑇 𝜕𝑆 𝑇 𝜕𝑇 𝑠

This maxwell’s sixth thermodynamical relation.

➢ Application of Maxwell’s Thermodynamic Relations: -

Clausius-Clapeyron’s Equation (First latent heat equation)
ⅆ𝑃 𝐿
The 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 = was First derived by Clapeyron using
ⅆ𝑇 𝑇(𝑉2 −𝑉1 )
Carnot’s reversible cycle Therefore it is sometimes called Clapeyron’s
equation.
Derivation: -
From second thermodynamical relation
𝜕𝑆 𝜕𝑃
( ) =( )
𝜕𝑉 𝑇 𝜕𝑇 𝑉
Multiplying both sides by T, we have
𝜕𝑆 𝑑𝑃
𝑇( ) = 𝑇( )
𝜕𝑉 𝑇 𝑑𝑇 𝑉

𝜕𝑄 𝜕𝑃
( ) = 𝑇 ( ) [𝑇𝜕𝑆 = 𝜕𝑄]
𝜕𝑉 𝑇 𝜕𝑇 𝑣
𝜕𝑄
The quantity ( ) represents the quantity of heat absorbed or liberated
𝜕𝑉 𝑇
per unit charge in volume at constant temperature. As there is a change
in volume due to the heat absorbed at constant temp. the heat represents
the latent heat used when a substance changes from solid to the change
of state.
IF L is the quantity of heat required to charge the state of a unit
mass of the substance V2 and V1 the corresponding specific volumes they.
𝜕𝑄 = 𝐿
 𝜕𝑉 = 𝑉2 − 𝑉1
𝜕𝑄 𝐿 𝐿 𝜕𝑃
Hence ( ) = therefore, = 𝑇( )
𝜕𝑉 𝑉 −𝑉
𝑇 2 1 𝑉 −𝑉 2 𝜕𝑇 1 𝑉

𝑑𝑃 𝐿
=
𝑑𝑇 𝑇(𝑉2 − 𝑉1 )
This is Clausius Clapeyron latent heat equation.

➢ Effect Of Pressure on Boiling Point of Liquid: -

When a liquid converts into vapor state, there is on increase in
𝜕𝑃
volume Hence V2 > V1 T and L being Positive quantities( ) is positive.
𝜕𝑇 𝑉
This shows that the boiling point of the liquid is raised by increasing the
pressure This known as elevation of boiling point.

➢ Effect Of Pressure on Melting point of solid: -

When a solid melts, there may be increase in volume. As in case of
wax or there may be decrease in volume, as in ease of ice. In melting of
wax.
(𝑉2 − 𝑉1 ) = +𝑣𝑒

𝑑𝑃
= +𝑣𝑒
𝑑𝑇
Hence the melting point is raised by increase of pressure. In case of
ice (𝑣2 − 𝑣1 ) = −𝑣𝑒 hence melting point is lowered by increase of
pressure. This is known as depression in melting point. In general
substances which expands on melting, have their melting points raised by
increase of pressure and the substance which contract on melting have
their melting points lowered by increase of pressure.
➢ Specific Heat Equation: -
The specific heat at constant pressure is given as,
𝜕𝑄 𝜕𝑆
𝐶𝑃 = ( ) = 𝑇 ( )
𝜕𝑇 𝑃 𝜕𝑇 𝑃

And the specific heat at constant volume is

𝜕𝑄 𝜕𝑆
𝐶𝑣 = ( ) = 𝑇 ( )
𝜕𝑇 𝑣 𝜕𝑇 𝑣
Now, if the entropy S is regarded as a function of Tend V and since dS is a
perfect differential,
𝜕𝑆 𝜕𝑆
𝑑𝑆 = ( ) 𝑑𝑇 + ( ) 𝑑𝑣
𝜕𝑇 𝑉 𝜕𝑉 𝑇

𝜕𝑆 𝜕𝑆 𝜕𝑇 𝜕𝑆 𝜕𝑉
( ) =( ) ( ) +( ) ( )
𝜕𝑇 𝑃 𝜕𝑇 𝑣 𝜕𝑇 𝑣 𝜕𝑉 𝑇 𝜕𝑇 𝑃

𝜕𝑆 𝜕𝑆 𝜕𝑆 𝜕𝑉
𝑇( ) = 𝑇( ) +𝑇( ) ( )
𝜕𝑇 𝑃 𝜕𝑇 𝑉 𝜕𝑣 𝑇 𝜕𝑇 𝑃

𝜕𝑆 𝜕𝑃
𝐵𝑈𝑇 ( ) = ( ) , 𝑓𝑟𝑜𝑚 𝑀𝑎𝑥𝑤𝑒𝑙𝑙 ′ 𝑠𝑠𝑒𝑐𝑜𝑛𝑑 𝑟𝑒𝑙𝑎𝑡𝑖𝑜𝑛
𝜕𝑉 𝑇 𝜕𝑇 𝑉
𝜕𝑆 𝜕𝑆 𝜕𝑃 𝜕𝑉
𝑇( ) −𝑇( ) = 𝑇( ) ( )
𝜕𝑇 𝑃 𝜕𝑇 𝑉 𝜕𝑇 𝑉 𝜕𝑇 𝑃

𝜕𝑃 𝜕𝑉
𝐶𝑝 − 𝐶𝑣 = 𝑇 ( ) ( ) − − − − − −(𝐸𝑞. 1)
𝜕𝑇 𝑉 𝜕𝑇 𝑃

a) For a perfect gas: -

The equation of state is PV = RT
𝜕𝑃 𝑅 𝜕𝑉 𝑅
( ) = , 𝑎𝑛𝑑 ( ) =
𝜕𝑇 𝑉 𝑉 𝜕𝑇 𝑃 𝑃
Hence equation (1) becomes
𝑅 𝑅 𝑅2 𝑇 𝑅2 𝑇
𝐶𝑃 − 𝐶𝑉 = 𝑇 ( ) ( ) = =
𝑉 𝑃 𝑃𝑉 𝑅𝑇
𝐶𝑃 − 𝐶𝑉 = 𝑅
 b) Vander Waals: -
𝑎
The equation of state is (𝑃 +
𝑉2
) (𝑉 − 𝑏) = 𝑅𝑇 where a and b
are constants.
𝑎 𝑅𝑇
(𝑃 + ) =
𝑉2 (𝑉 − 𝑏)
Differentiating with respect to T at constant volume we get

𝜕𝑃 𝑅
( ) =
𝜕𝑇 𝑉 (𝑉 − 𝑏)
And differentiating with respect to T at constant pressure we get
𝜕𝑃 𝑅
( ) =
𝜕𝑇 𝑉 (𝑉 − 𝑏)
And differentiating with respect to T at constant volume, we get
𝜕𝑃 𝑅
( ) =
𝜕𝑇 𝑉 (𝑣 − 𝑏)
And differentiating with respect to T at constant pressure we get
2𝑎 𝜕𝑉 𝑅𝑇 𝜕𝑉 𝑅
0− 3( ) = ( ) +
𝑉 𝜕𝑇 𝑃 (𝑉 − 𝑏)2 𝜕𝑇 𝑃 (𝑉 − 𝑏)

𝜕𝑣 𝑅𝑇 2𝑎 𝑅
𝑜𝑟 ( ) [ − ] =
𝜕𝑇 𝑃 (𝑉 − 𝑏)2 𝑉 3 (𝑉 − 𝑏)

𝑅
𝜕𝑉 [ ]
(𝑉 − 𝑏)
𝑜𝑟 ( ) =
𝜕𝑇 𝑃 𝑅𝑇 2𝑎
[ ̅̅̅̅̅̅̅ 2 ̅̅̅̅3 ]
(𝑉 − 𝑏) 𝑉

𝜕𝑃 𝜕𝑉
𝑠𝑢𝑏𝑠𝑡𝑖𝑡𝑢𝑡𝑖𝑛𝑔 𝑡ℎ𝑒𝑠𝑒 𝑣𝑎𝑙𝑢𝑒𝑠 𝑜𝑓 ( ) 𝑎𝑛𝑑 ( ) 𝑖𝑛 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 (1)𝑤𝑒 𝑔𝑒𝑡
𝜕𝑇 𝑉 𝜕𝑇 𝑃

𝑅 𝑅
−𝑇 ( )( )
𝐶𝑃 − 𝐶𝑉 = 𝑉 − 𝑏 𝑉 − 𝑏
𝑅𝑇 2𝑎
[ ̅̅̅̅̅̅̅ 2 ̅̅̅̅3 ]
(𝑉 − 𝑏) 𝑉

𝑅
𝐶𝑃 − 𝐶𝑉 =
2𝑎 (𝑉 − 𝑏)2
1− 3⋅(
𝑉 𝑅𝑇 )
 Neglecting b in comparison to V
𝑅
𝐶𝑃 − 𝐶𝑉 =
2𝑎 2
1 − 3 ⋅ 𝑉 ⁄𝑅𝑇
𝑉

𝑅
𝐶𝑃 − 𝐶𝑉 =
2𝑎
1−
𝑉𝑅𝑇

2𝑎 −1
𝐶𝑃 − 𝐶𝑉 = 𝑅 (1 − )
𝑉𝑅𝑇
Expanding binomially and neglecting a in higher powers as a is also
small as compared to V, we have,

2𝑎
𝐶𝑃 − 𝐶𝑉 = 𝑅 (1 + )
𝑉𝑅𝑇

➢ Joule – Thomson Porous Plug Experiment: -

The experiment setup consists of the following main parts.

1. The apparatus consists of a porous plug having two perforated brass
disc D, D.
2. The space between D, D is packed with cotton wool or silk fibers.
3. The porous plug is fitted in a cylindrical box -wood W which is
surrounded by a vessel containing cotton wool. This is done to avoid
loss or gain of heat from the surroundings.
 4. T 1 and T 2 are two sensitive platinum resistance thermometers and
they measure the temperature of the incoming and outcoming gas.
5. The gas is compressed to a high pressure with the help of piston P
and it is passed through a spiral tube immersed in water bath
maintained at a constant temperature. If there is any heating of the
gas due to compression, this heat is absorbed by the circulating water
in the water-bath.
➢ Experimental Procedure: -
By means of the compression pump P, the experimental gas is
passed slowly and uniformly through the porous plug keeping the high-
pressure constant, read by pressure gauge. During its passage through the
porous plug, the gas is throttled, i.e. the separation between the
molecules increases on passing through the porous plug, the volume of
the gas increases against the atmospheric pressure.
As there is no loss or gain of heat during the whole process the
expansion of the gas takes place adiabatically. The initial and final
temperature are noted by mems of the platinum resistance thermometers
T1 and T2.
➢ Experimental Result: -
• Inversion Temperature
1. At sufficiently low temperature all gases show a cooling effect.
2. At ordinary temperature, all gases except hydrogen and helium show
cooling effect. Hydrogen and Helium show heating instead of cooling
at room temperature.
3. The tall in temperature for a given difference of a pressure decreases
with rise in the initial temperature of the gas. It was found that the
cooling effect decreased with the increase of initial temperature and
become zero at a certain temperature and at a temperature higher
than this temperature, instead of cooling, heating was observed.
This particular temperature at which the Joule – Thomson effect
changes sign is called the temperature of inversion.
4. The fall in temperature is directly proportional to the difference in
pressure on the two side of the porous plug.
 • Definition
The temperature at which Joule – Thomson effect is zero and
changes sign is known as the temperature of inversion (Ti)
2𝑎
=𝑏
𝑅𝑇𝑖
2𝑎
𝑇𝑖 =
𝑅𝑏
𝑇 < 𝑇𝑖 (𝑐𝑜𝑜𝑙𝑖𝑛𝑔)
𝑇 > 𝑇𝑖 (ℎ𝑒𝑎𝑖𝑛𝑔)

➢ Theory: -
The gas is allowed to pass through the porous plug from the high-
pressure side to the low-pressure side. Consider one gram molecule of the
porous plug. Let 𝑃1, 𝑉1 and 𝑃2, 𝑉2 represents the pressure and volume
on the two sides of the porous plug.

When the piston A is moved through a certain distance 𝑑𝑥, the

piston B also moves through the same distance 𝑑𝑥. The work done on the
gas by the piston 𝐴 = 𝑃2𝐴2𝑑𝑥 = 𝑃1 𝑉1. The work done by the gas on
the piston 𝐵 = 𝑃2𝐴2𝑑𝑥 = 𝑃2 𝑉2. Thus, the net external work f=done
by the gas is 𝑃2𝑉2 – 𝑃1𝑉1.If 𝑊 is the work done by the gas in separating
the molecules against their intermolecular attraction, the total amount of
work done by the gas,
𝑊 = 𝑃2 𝑉2 − 𝑅𝑉1 + 𝜔
Assuming that the Vander walls equation is obeyed, the attractive
𝑎
force between the molecules is equivalent to an internal pressure 2,
𝑉
when the gas expands from 𝑉1 to 𝑉2 , the work done in overcoming
intermolecular attraction,
 𝑉2

𝜔 = ∫ 𝑃 ⋅ 𝑑𝑉
𝑉1

𝑉2
𝑎
𝜔= ∫ ⋅ 𝑑𝑉
𝑉2
𝑉1

𝑎 𝑉2
𝜔 = [− ]
𝑉 𝑉1

𝑎 𝑎
𝜔=− +
𝑉2 𝑉1
If 𝑉1 and 𝑉2 represents the gram molecular volumes on the high and
the low-pressure sides respectively, the external work done by the gas is,
(𝑃2 𝑉2 − 𝑃1 𝑉1 )
Hence the total work done by the gas is

𝑤 = (𝑃2 𝑉2 − 𝑃1 𝑉1 ) + 𝜔

𝑎 𝑎
𝑊 = (𝑃2 𝑉2 − 𝑃1 𝑉1 ) − +
𝑉2 𝑉1

Vander walls equation of state for a gas is

𝑎
(𝑃 + ) (𝑉 − 𝑏) = 𝑅𝑇
𝑉2

𝑎 𝑎𝑏
𝑃𝑉 + − 𝑏𝑃 − 2 = 𝑅𝑇
𝑉 𝑉

𝑎
𝑃𝑉 = 𝑅𝑇 + 𝑏𝑃 −
𝑉

𝑎 𝑎 𝑎 𝑎
𝐻𝑒𝑛𝑐𝑒, 𝑊 = [𝑅𝑇 + 𝑏𝑃2 − ] − [𝑅𝑇 + 𝑏𝑃1 − ] − +
𝑉2 𝑉1 𝑉2 𝑉1

2𝑎 2𝑎
𝑊 = 𝑏(𝑃2 − 𝑃1 ) − +
𝑉2 𝑉1
 1 1
𝑊 = 𝑏(𝑃2 − 𝑃1 ) + 2𝑎 ( − )
𝑉1 𝑉2

1 1
𝑊 = −𝑏(𝑃1 − 𝑃2 ) + 2𝑎 ( − )
𝑉1 𝑉2

𝑅𝑇 𝑅𝑇
𝑏𝑢𝑡 𝑉1 = ; 𝑉2 =
𝑃1 𝑃2

𝑃1 𝑃2
𝑊 = −𝑏(𝑃1 − 𝑃2 ) + 2𝑎 ( − )
𝑅𝑇 𝑅𝑇

2𝑎
𝑊 = −𝑏(𝑃1 − 𝑃2 ) + (𝑃 − 𝑃2 )
𝑅𝑇 1

2𝑎
𝑊 = (𝑃1 − 𝑃2 ) ( − 𝑏)
𝑅𝑇

Suppose the fall in temperature is 𝛿𝑇

𝑊 = 𝐽𝐻 = 𝐽(𝑀𝐶𝑝 𝛿𝑇)

Where M is the gram molecular weight of the gas

2𝑎
𝐽(𝑀𝐶𝑝 𝛿𝑇) = (𝑃1 − 𝑃2 ) ( − 𝑏)
𝑅𝑇

(𝑃1 − 𝑃2 ) 2𝑎
𝛿𝑇 = × ( − 𝑏)
𝐽𝑀𝐶𝑝 𝑅𝑇

i. Since𝑃1 > 𝑃2 ; 𝑃1 − 𝑃2 𝑖𝑠 𝑝𝑜𝑠𝑖𝑡𝑖𝑣𝑒. 𝛿𝑇 will be positive if

2𝑎 2𝑎 2𝑎
[( ) − 𝑏] is positive i.e., > 𝑏 ; >𝑇
𝑅𝑇 𝑅𝑇 𝑅𝑏
Therefore, cooling will take place if the temperature of the gas is
2𝑎
less than .
𝑅𝑏

2𝑎−𝑏 2𝑎
ii. For 𝛿𝑇 to be zero =0; 𝑇 = .
𝑅𝑇 𝑅𝑏
 This temperature is called the temperature of inversion and is
represented by 𝑇𝑖
2𝑎
𝑇𝑖 =
𝑅𝑏

2𝑎
iii. 𝛿𝑇 will be negative if, − 𝑏 is positive
𝑅𝑇
2𝑎 2𝑎
𝑏> ; 𝑇> ; 𝑇 > 𝑇𝑖
𝑅𝑇 𝑅𝑏

Therefore, heating will take place if the temperature of the gas is

more than the temperature of inversion.

➢ Result: -
1. If the gas at a temperature lower than the temperature of
inversion, cooling will take place when it is passed through the
porous plug. This is called regenerative cooling or Joule-kelvin
cooling.
2. If the gas is at the temperature of inversion, then no cooling or
heating is observed when it is passed through the porous plug.
3. If the gas is at a temperature higher than the temperature of
inversion, instead of cooling heating is observed when the gas is
passed through the porous plug.

➢ The (𝑇 ∙ 𝑑𝑆) equations: -

First Equation:
The entropy S of a pure substance can be taken as a function of
temperature and volume.
𝑆 = 𝑆(𝑇, 𝑉)

𝜕𝑆 𝜕𝑆
𝑑𝑆 = ( ) 𝑑𝑇 + ( ) 𝑑𝑉
𝜕𝑇 𝑉 𝜕𝑉 𝑇

Multiplying both sides by T

𝜕𝑆 𝜕𝑆
𝑇 ⋅ 𝑑𝑆 = 𝑇 ( ) 𝑑𝑇 + 𝑇 ( ) 𝑑𝑉
𝜕𝑇 𝑉 𝜕𝑉 𝑇
 𝜕𝑆
𝐵𝑢𝑡𝑇 ( ) = 𝐶𝑉 𝑎𝑛𝑑 𝑓𝑟𝑜𝑚 𝑀𝑎𝑥𝑤𝑒𝑙𝑙 ′ 𝑠 𝑟𝑒𝑙𝑎𝑡𝑖𝑜𝑛𝑠.
𝜕𝑇 𝑉
𝜕𝑆 𝜕𝑃
( ) =( )
𝜕𝑉 𝑇 𝜕𝑇 𝑉

𝜕𝑃
𝑇 ⋅ 𝑑𝑆 = 𝐶𝑉 𝑑𝑇 + 𝑇 ( ) 𝑑𝑉
𝜕𝑇 𝑉

This called the first 𝑇 ⋅ 𝑑𝑆 equation

Second Equation:
The entropy of a pure substance can be regarded as a function
of temperature and pressure 𝑆 = 𝑆(𝑇, 𝑃)

𝜕𝑆 𝜕𝑆
𝑑𝑆 = ( ) 𝑑𝑇 + ( ) 𝑑𝑃
𝜕𝑇 𝑃 𝜕𝑃 𝑇

Multiplying both sides by 𝑇

𝜕𝑆 𝜕𝑆
𝑇 ⋅ 𝑑𝑆 = 𝑇 ( ) 𝑑𝑇 + 𝑇 ( ) 𝑑𝑃
𝜕𝑇 𝑃 𝜕𝑃 𝑇

𝜕𝑆
𝐵𝑢𝑡𝐶𝑃 = 𝑇 ( ) 𝑎𝑛𝑑 𝑓𝑟𝑜𝑚 𝑀𝑎𝑥𝑤𝑒𝑙𝑙 ′ 𝑠 𝑟𝑒𝑙𝑎𝑡𝑖𝑜𝑛
𝜕𝑇 𝑃

𝜕𝑆 𝜕𝑉
( ) = −( )
𝜕𝑃 𝑇 𝜕𝑇 𝑃

This is called the second𝑇 ⋅ 𝑑𝑆 equation

➢ Joule – Kelvin Coefficient: -

The joule-kelvin coefficient is defined as the slope of the
enthalpic curve at any point on the temperature pressure curve.

𝜕𝑇
𝜇=( )
𝜕𝑃 𝐻

From the definition of enthalpy

 𝐻 = 𝑈 + 𝑃𝑉

𝑑𝐻 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃

𝐴𝑙𝑠𝑜, 𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 ; 𝑑𝑈 + 𝑃𝑑𝑉 = 𝑇𝑑𝑆

𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃 − − − − − −(𝐸𝑞. 1)

𝐴𝑙𝑠𝑜, 𝑆 = 𝑆(𝑇, 𝑃)

𝜕𝑆 𝜕𝑆
𝑑𝑆 = ( ) 𝑑𝑇 + ( ) 𝑑𝑃 − − − − − (𝐸𝑞. 2)
𝜕𝑇 𝑃 𝜕𝑃 𝑇

Let put equation (2) in (1)

𝜕𝑆 𝜕𝑆
𝑑𝐻 = 𝑇 ( ) 𝑑𝑇 + [𝑇 ( ) + 𝑉] 𝑑𝑃 − − − − − (𝐸𝑞. 3)
𝜕𝑇 𝑃 𝜕𝑃 𝑇

𝜕𝑆
But 𝑇 ( ) = 𝐶𝑃
𝜕𝑇 𝑃

The volume coefficient ∝ is given by

1 𝜕𝑉
𝛼= ( )
𝑉 𝜕𝑇 𝑃

𝜕𝑉 𝜕𝑆
𝑏𝑢𝑡 ( ) = − ( ) = 𝛼𝑉 = −𝛼𝑉
𝜕𝑇 𝑃 𝜕𝑃 𝑇

Substituting these values in equation (3)

𝜕𝑉
𝑑𝐻 = 𝐶𝑃 𝑑𝑇 + [𝑉 − 𝑇 ( ) ] 𝑑𝑃
𝜕𝑇 𝑃

1 1 𝜕𝑉
𝑑𝑇 = 𝑑𝐻 + [𝑇 ( ) − 𝑉] 𝑑𝑃 − − − − − (𝐸𝑞. 4)
𝐶𝑃 𝐶𝑃 𝜕𝑇 𝑃

But𝑇 = 𝑇(𝐻, 𝑃)
 𝜕𝑇 𝜕𝑇
𝑑𝑇 = ( ) 𝑑𝐻 + ( ) 𝑑𝑃 − − − − − (𝐸𝑞. 5)
𝜕𝐻 𝑃 𝜕𝑃 𝐻

comparing the coefficients of eq. (4) and eq. (5)

𝜕𝑇 𝜕𝑉 𝜕𝑇
( ) = 1⁄𝐶 [𝑇 ( ) − 𝑉] 𝑏𝑢𝑡 𝜇 = ( )
𝜕𝑃 𝐻 𝑃 𝜕𝑇 𝑃 𝜕𝑃 𝐻

1 𝜕𝑉
𝜇= [𝑇 ( ) − 𝑉]
𝐶𝑃 𝜕𝑇 𝑃

1 1 𝜕𝑉
𝜇= 𝑉 [𝑇 ( ) − 1] − − − − − (𝐸𝑞. 6)
𝐶𝑃 𝑉 𝜕𝑇 𝑃

1 𝜕𝑉
𝐵𝑢𝑡 ( ) =𝛼
𝑉 𝜕𝑇 𝑃

𝑉
𝜇= [𝑇𝛼 − 1] − − − − − (𝐸𝑞. 7)
𝐶𝑃

For a Vander Waals gas

𝑎
(𝑃 + ) (𝑉 − 𝑏) = 𝑅𝑇
𝑉2

𝑎 𝑎𝑏
𝑃𝑉 − 𝑃𝑏 + − = 𝑅𝑇
𝑉 𝑉2

Differentiating keeping P constant,

𝑎 𝑑𝑉 2𝑎𝑏 𝑑𝑉
𝑃 𝑑𝑉 − − = 𝑅 𝑑𝑇
𝑉2 𝑉3

𝑑𝑉 12
=
𝑑𝑇 𝑃 − 𝑎 + 2𝑎𝑏
𝑉2 𝑉3

𝜕𝑉 𝑅
( ) =
𝜕𝑇 𝑃 𝑅𝑇 𝑞 𝑎 2𝑎𝑏
− 2− 2+ 3
𝑉−𝑏 𝑉 𝑉 𝑉
 𝜕𝑉 𝑅𝑉 3 (𝑉 − 𝑏)
( ) =
𝜕𝑇 𝑃 𝑅𝑇𝑉 3 − 2𝑎(𝑉 − 𝑏)2

Substituting this value in eq. (6)

𝑉 𝑅𝑇𝑉 2 (𝑉 − 𝑏)
𝜇= [ − 1]
𝑐𝑃 𝑅𝑇𝑉 3 − 2𝑎(𝑉 − 𝑏)2

𝑉 𝑅𝑇𝑉 2 (𝑉 − 𝑏) − 𝑅𝑇𝑉 3 + 2𝑎(𝑉 − 𝑏)2

𝜇= [ ]
𝑐𝑃 𝑅𝑇𝑉 3 − 2𝑎(𝑉 − 𝑏)2

𝑉 2𝑎(𝑉 − 𝑏)2 − 𝑅𝑇𝑉 2 𝑏

𝜇= [ ] − − − − − (𝐸𝑞. 8)
𝑐𝑃 𝑅𝑇𝑉 3 − 2𝑎(𝑉 − 𝑏)2

From eq. (7) as V and CP are always positive. The value of 𝜇vand
hence the temperature of a Vander Waals gas passing through a porous
plug will depend on the value of 𝛼𝑇 − 1.
1. If 𝛼𝑇 > 1, temperature of the gas will Increase.
2. If 𝛼𝑇 > 1, temperature of the gas will Increase.
3. If 𝛼𝑇 = 1, temperature of the gas will not change.
This temperature at which the inversion takes place is called the
temperature of inversion Ti in this case from eq. (2).
𝜇 = 0 𝑎𝑛𝑑 𝑓𝑟𝑜𝑚 𝑒𝑞. 8

2𝑎(𝑉 − 𝑏)2 = 𝑅𝑇𝑖 𝑉 2 𝑏

2𝑎(𝑉 − 𝑏)2
𝑇𝑖 =
𝑅𝑉 2 𝑏

2𝑎
𝐼𝑓 𝑉 ≫ 𝑏 ; 𝑇𝑖 =
𝑅𝑏

𝜕 𝑉
𝜇𝐶𝑃 = 𝑇 2 [ ( ) ]
𝜕𝑇 𝑇 𝑃

𝑇2 𝜕 𝑉
𝜇= [ ( ) ]
𝑐𝑃 𝜕𝑇 𝑇 𝑃
 𝑉 𝑅
For an ideal gas: - =
𝑇 𝑃
𝑇2 𝜕 𝑅
𝜇= ⋅ ( ) =0
𝐶𝑃 𝜕𝑇 𝑃 𝑃
Thus, the joule-Kelvin coefficient for an ideal gas is zero and the
ideal gas passing through the porous gas doesn’t show any change in
temperature.

➢ First Order Phase Transitions: -

The changes of phase which take place at constant temperature
and pressure and in which heat is either absorbed or evolved during
change of phase are called first order phase transitions. In first order phase
transitions, the entropy and density change phase; while its derivative
with respect to temperature and pressure is discontinuous at transition
point.
Consider an enclosure containing a liquid and its saturated
vapor in equilibrium. If this system undergoes an isothermal, isobaric
change then.

𝑔1 = 𝑔2 − − − − − (𝐸𝑞. 1)

Let the temperature of the system be increased from 𝑇 to 𝑇 + 𝑑𝑇, for

equilibrium
𝑔1 + 𝑑𝑔1 = 𝑔2 + 𝑑𝑔2

𝑑𝑔1 = 𝑑𝑔2

If the condition of saturation is satisfied,

𝑑𝑔1 𝑑𝑔2
( ) =( ) − − − − − (𝐸𝑞. 2)
𝑑𝑇 𝑠𝑎𝑡 𝑑𝑇 𝑠𝑎𝑡

The pressure also changes from 𝑃 to 𝑃 + 𝑑𝑃

𝜕𝑔1 𝜕𝑔1
𝑑𝑔1 = ( ) 𝑑𝑇 + ( ) 𝑑𝑃 − − − − − (𝐸𝑞. 3)
𝜕𝑇 𝑃 𝜕𝑃 𝑇

𝐺 = 𝐻 – 𝑇𝑆
 𝐺 = 𝑑(𝑉 + 𝑃𝑉) − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇

𝑑𝑔 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇

𝜕𝑔 𝜕𝑔
( ) = 𝑉 ; ( ) = −𝑆
𝜕𝑃 𝑇 𝜕𝑇 𝑃

Substituting these values in eq. (4)

𝜕𝑔1 𝜕𝑃 𝜕𝑔2 𝜕𝑃
( ) = −𝑆1 + 𝑉1 ( ) ;( ) = −𝑆2 + 𝑉2 ( )
𝜕𝑇 𝑠𝑎𝑡. 𝜕𝑇 𝑠𝑎𝑡. 𝜕𝑇 𝑠𝑎𝑡. 𝜕𝑇 𝑠𝑎𝑡.

Substituting these values in eq. (2)

𝑑𝑃 𝑑𝑃
−𝑆1 + 𝑉1 ( ) = −𝑆2 + 𝑉2 ( )
𝑑𝑇 𝑑𝑇

𝑑𝑃 𝑆2 − 𝑆1
( ) =
𝑑𝑇 𝑠𝑎𝑡 𝑉2 − 𝑉1

𝛿𝑄 𝐿
𝐵𝑢𝑡, 𝑆2 − 𝑆1 = =
𝑇 𝑇

𝐿 = 𝑙𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑣𝑎𝑝𝑜𝑟𝑖𝑧𝑎𝑡𝑖𝑜𝑛

𝑑𝑃 𝐿
( )=
𝑑𝑇 𝑇(𝑉2 − 𝑉1 )

This is Clauses-Clapeyron latent heat equation.

When heat is given to water at 100℃ and 1𝑎𝑡𝑚 pressure, it
𝑘𝑔
changes from liquid to vapor state. The density of water is 1000 ⁄ 3 .
𝑚
𝑘𝑔⁄
While that of vapor is 0.6 . Therefore, the transformation of water
𝑚3
into vapor at constant temperature and volume is first order phase
transitions similarly the transformation of the ice into water at 0℃ and
1𝑎𝑡𝑚 pressure is an example of first order phase transition.
➢ Cooling by adiabatic De-magnetization: -
Debye Giang and MacDougall were able to produce
temperatures below 1 K with the help of gadolinium sulphate. Hans and
Karmen used the magnetic balance for a number of paramagnetic
substances. They found that potassium and chromium alum give a much
lower temperature.
❖ Method: -
The apparatus used is shown in figure. The paramagnetic salt is
suspended in vessel A, which is surrounded by liquid helium. Liquid helium
taken in Delver flask D, is boiled meter reduced pressure. It is surrounded
by mother Delver flask D2 containing liquid hydrogen. The salt I s in contact
with the helium gas. A magnetic field of the order of 30,000 Gauss is
applied.
❖ Theory: -
When a paramagnetic material is placed in a magnetizing field.
H, its elementary magnetic dipoles get aligned parallel to the direction of
the field. The magnetic moment per unit volume thus produced is called
the intensity of magnetization (I).
According to curie’s law, this intensity of magnetization is directly
proportional to the magnetizing field H and inversely proportional to
temperature. T of the paramagnetic substance.

𝐻
𝐼𝛼
𝑇

𝐻
𝐼 =𝐶( )
𝑇
𝑊ℎ𝑒𝑟𝑒 𝐶 𝑖𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 = 𝑐𝑢𝑟𝑖𝑒 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
If V is the volume of 1 mole, the intensity of magnetization of 1 mole of
paramagnetic substance.
𝑀 = 𝐼𝑉

𝐻
𝑀 = 𝐶𝑉 ( ) − − − − − (𝐸𝑞. 1)
𝑇
In the thermodynamic system an increase in pressure P results in decrease
in volume v analogously in our case My increase in H results in om increase
in M. Hence replacing P by-H and V by M in Maxwell’s third
thermodynamic relation.
𝜕𝑇 𝜕𝑉
( ) =( )
𝜕𝑃 𝑆 𝜕𝑆 𝑃

𝜕𝑇 𝜕𝑀
( ) = −( )
𝜕𝐻 𝑠 𝜕𝑆 𝐻

𝜕𝑀
−( )
𝜕𝑇 𝐻
=
𝜕𝑆
( )
𝜕𝑇 𝐻

𝜕𝑀
𝜕𝑇 −𝑇 ( )
𝜕𝑇 𝐻
( ) =
𝜕𝐻 𝑆 𝜕𝑆
𝑇( )
𝜕𝑇 𝐻

𝜕𝑀
𝜕𝑇 −𝑇 ( )
𝜕𝑇 𝐻
( ) =
𝜕𝐻 𝑆 𝜕𝑄
𝑇( )
𝜕𝑇 𝐻

𝜕𝑇 𝑇 𝜕𝑀
( ) = − ( )
𝜕𝐻 𝑆 𝐶𝐻 𝜕𝑇 𝐻

𝜕𝑄
( ) = 𝐶𝐻 ,
𝜕𝑇
𝑡ℎ𝑒 𝑠𝑝𝑒𝑐𝑖𝑓𝑖𝑐 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑚𝑎𝑔𝑛𝑎𝑡𝑖𝑐 𝑓𝑖𝑒𝑙𝑑 𝐻.
𝐽𝑜𝑢𝑙𝑒⁄
𝑇ℎ𝑒 𝑢𝑛𝑖𝑡 𝑖𝑠 𝑚𝑜𝑙𝑒 𝐾
Since the process is carried out adiabatically, we may write,

𝑇 𝜕𝑀
𝑑𝑇 = − ( ) ⋅ 𝑑𝐻
𝐶𝐻 𝜕𝑇 𝐻
Therefore, when a field changes from H1 to H2, the change in temperature.

𝐻2
𝑇 𝜕𝑀
𝛥𝑇 = − ∫ ( ) ⋅ 𝑑𝐻
𝐶𝐻 𝜕𝑇 𝐻
𝐻1
Differentiating eq. (1) with respect to T,
𝜕𝑀 𝐶𝑉𝐻
( ) =− 2
𝜕𝑇 11 𝑇

𝐻2
𝑇 𝐶𝑉𝐻
𝛥𝑇 = − ∫ − 2 ⋅ 𝑑𝐻
𝐶𝐻 𝑇
𝐻1

𝐻2
𝐶𝑉
𝛥𝑇 = ∫ 𝐻 ⋅ 𝑑𝐻
𝐶𝐻 𝑇
𝐻1

𝐶𝑉
𝛥𝑇 = (𝐻22 − 𝐻12 )
2𝐶𝐻 𝑇
If the magnetic field is reduced from H1 = H to H2 = 0, then the change in
temperature will be
𝐶𝑉
𝛥𝑇 = − ⋅ 𝐻2
2𝐶𝐻 ⋅ 𝑇
❖ Conclusion: -
a) The temperature of the paramagnetic substance decreases in
decreasing the magnetizing field H and, so and so
b) Greater is the initial field H and lower is the initial temperature
T, grater is the temperature fall ∆𝑇,
It should be noted that the quantity CV is the curie constant
per mole. If 1 gm of paramagnetic substance (salt) is taken, then
CV would stand for curie constant per gram.