THERMODYNAMIC POTENTIALS, PHASE TRANSITION AND LOW TEMPERATURE PHYSICS

Syllabus: Unit II - Thermodynamic potentials : Internal Energy; Enthalpy; Helmholtz free

energy; Gibbs free energy and their significance; Maxwell's thermodynamic relations (using
thermodynamic potentials) and their significance; TdS relations; Energy equations and Heat
Capacity equations; Third law of thermodynamics (Nernst Heat theorem)

Thermodynamics deals with the conversion of heat energy to other forms of energy or
vice versa in general.
A thermodynamic system is the quantity of matter under study which is in general
macroscopic in nature. Examples: Gas, vapour, vapour in contact with liquid etc..
Thermodynamic stateor condition of a system is one which is described by the
macroscopic physical quantities like pressure (P), volume (V), temperature (T) and
entropy (S).
The physical quantities like P, V, T and S are called thermodynamic variables. Any
two of these variables are independent variables and the rest are dependent variables.
A general relation between the thermodynamic variables is called equation of state.
The relation between the variables that describe a thermodynamic system are given by
first and second law of thermodynamics.

According to first law of thermodynamics, when a substance absorbs an amount of

heat dQ at constant pressure P, its internal energy increases by dU and the substance
does work dW by increase in its volume by dV.
Mathematically it is represented by 𝒅𝑸 = 𝒅𝑼 + 𝒅𝑾 = 𝒅𝑼 + 𝑷 𝒅𝑽….(1)
If a substance absorbs an amount of heat dQ at a temperature T and if all changes
that take place are perfectly reversible, then the change in entropy from the second
𝒅𝑸
law of thermodynamics is 𝒅𝑺 = or 𝒅𝑸 = 𝑻 𝒅𝑺….(2)
𝑻
From equations (1) and (2), 𝑻 𝒅𝑺 = 𝒅𝑼 + 𝑷 𝒅𝑽
This is the basic equation that connects the first and second laws of thermodynamics.
The functions of the state variables, P, V, T and S,together with the two laws of
thermodynamics that gives the complete knowledge of the state of a system are called
thermodynamic functions or thermodynamic potentials.

Thermodynamic potentials are extensive state variables of dimensions of energy.

Their purpose is to allow for simple treatment of equilibrium for systems interacting
with the environment. These functions are the energy functions formed by combining
the basic thermodynamic variables.
The four fundamental thermodynamic potentials are1. Internal energy (U), 2.
Enthalpy or total heat function (H), 3. Helmholtz function (F) and 4. Gibbs function
(G).

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 THERMODYNAMIC POTENTIALS, PHASE TRANSITION AND LOW TEMPERATURE PHYSICS
Internal Energy (U) :Internal energy of a system is the energy possessed due to
kinetic energy and potential energy of the constituents of the system. Kinetic energy
refers to energy possessed by the molecules by virtue of its motion and potential
energy is due to intermolecular forces.

1. From the first and second laws of thermodynamics𝑇 𝑑𝑆 = 𝑑𝑈 + 𝑃 𝑑𝑉

or 𝒅𝑼 = 𝑻 𝒅𝑺 − 𝑷 𝒅𝑽…..(1) This equation gives the change in internal energy of a
system in terms of variables P. V. T and S.
2.From first law, 𝑑𝑄 = 𝑑𝑈 + 𝑃 𝑑𝑉,
𝑑𝑄 𝑑𝑈 𝑑𝑉
Dividing both the sides of the above equation by dT, we get𝑑𝑇 = +𝑃
𝑑𝑇 𝑑𝑇
𝜕𝑄 𝜕𝑈
At constant volume, (as dV = 0) the above equation would be ( 𝜕𝑇 ) = ( 𝜕𝑇 ) = 𝐶𝑉
𝑉 𝑉
where CV is the specific heat at constant Volume.
Also, for an adiabatic process (no exchange of heat) dQ = 0.
Thus 0 = dU + PdV or dU = - PdV
For a isochoric process (Constant volume, i.e. dV = 0), from the above relation, dU = 0.
Thus internal energy of a system is a constant in a isochoric - adiabatic process.
This potential is also called Isochoric – Isentropic potentialwhere thermodynamic
potential is the internal energy U and the independent variables are Entropy S and
volume V.

Enthalpy (H) :
Consider two states 1 and 2 of a thermodynamic system. If 𝑈1 and 𝑈2 are the internal
energies, then if 𝑑𝑄 is the heat absorbed by the system, from first law
dQ = (𝑈2 − 𝑈1 ) + dW. If work is done at constant pressure due to change in volume,
then 𝑑𝑊 = 𝑃(𝑉2 − 𝑉1 ). Thus (𝑈2 − 𝑈1 ) = 𝑑𝑄 − 𝑃(𝑉2 − 𝑉1 ) or (𝑈2 + 𝑃𝑉2 ) − (𝑈1 + 𝑃𝑉1 )) =
𝑑𝑄
Thus 𝐻2 − 𝐻1 = 𝑑𝑄 where in general 𝐻 = 𝑈 + 𝑃𝑉
Enthalpy of a system is the total heat energy of a systemgiven by H = U + PV…(1)
1.When a system undergoes an infinitesimal process from an initial equilibrium state
to a final equilibrium state, dH = dU + P dV + V dP,,,,,,(2) (by differentiating (1) )
From first law. dQ = dU + PdV.…(3) Thus eqn. (2) is dH = dQ + V dP
𝑑𝐻 𝑑𝑄 𝑑𝑃
Dividing both the sides of the above equation by dT, we get 𝑑𝑇 = +𝑉
𝑑𝑇 𝑑𝑇
𝜕𝐻 𝜕𝑄
At constant pressure, (as dP = 0) the above equation would be ( 𝜕𝑇 ) = ( 𝜕𝑇 ) = 𝐶𝑃
𝑃 𝑃
where CP is the specific heat at constant pressure. Also dH = T dS + V dP and Q = TdS

2. Since dH = dQ + V dP, the change in enthalpy during isobaric process (constant

pressure dP = 0) is the heat transferred (iedH = dQ ). Thus the latent heat measured

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during phase transition (e.g. melting, boiling, sublimation) is simply the change in
enthalpy.i.e. Hf – Hi = Q or 𝐻𝑓 − 𝐻𝑖 = ∫ 𝐶𝑃 𝑑𝑇 .(since dQ = CPdT). This indicates isobaric
process.

3.For an adiabatic process, dQ = 0. Thus for adiabatic and isobaric process, dH = 0.

Thus H is a constant.
The potential is also called isentropic – isobaric potentialwhere independent
variables are entropy S and pressure P.

Note :In a throttling process, enthalpy remains constant as explained below.

A process in which a gas at high pressure passes through a porous material into a low
pressure region is the throttling process. During this process U + PV remains
constant.Applying first law to the throttling process, Q = Uf – Ui + (-W) (W is negative as work
is done on the system). Here Q = 0, and W = - (PfVf – PiVi) Thus 0 = Uf – Ui + PfVf - PiVi or Ui
+ PiVi = Uf + PfVf
orHi = Hf. . Thus initial enthalpy of a system is equal to the final enthalpy of the system in a
throttling process.

Comparison of properties of U and H for a hydrostatic system

Internal energy (U) Enthalpy (H)
Free expansion (irreversible) Throttling process (irreversible)
Ui = Uf Hi = Hf
In general dU = dQ – PdV and In general dH = dQ + VdP and
𝜕𝑈 𝜕𝐻
( ) = 𝐶𝑉 ( ) = 𝐶𝑃
𝜕𝑇 𝑉 𝜕𝑇 𝑃
Isochoric process Isobaric process
Uf – Ui = QV Hf – Hi = QP
For an ideal gas For an ideal gas
𝑓 𝑓
𝑈𝑓 − 𝑈𝑖 = − ∫ 𝐶𝑉 𝑑𝑇 𝐻𝑓 − 𝐻𝑖 = − ∫ 𝐶𝑃 𝑑𝑇
𝑖 𝑖
For a adiabatic process For a adiabatic process
𝑓 𝑓
𝑈𝑓 − 𝑈𝑖 = − ∫ 𝑃𝑑𝑉 𝐻𝑓 − 𝐻𝑖 = − ∫ 𝑉𝑑𝑃
𝑖 𝑖
Nearly equilibrium state Nearly equilibrium state
𝑑𝑈 = 𝑇 𝑑𝑆 − 𝑃 𝑑𝑉 dH = T dS + V dP
𝜕𝑈 𝜕𝑈 𝜕𝐻 𝜕𝐻
( 𝜕𝑆 ) = 𝑇 and (𝜕𝑉 ) = −𝑃 ( 𝜕𝑆 ) = 𝑇 and ( 𝜕𝑃 ) = 𝑉
𝑉 𝑆 𝑃 𝑆

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 THERMODYNAMIC POTENTIALS, PHASE TRANSITION AND LOW TEMPERATURE PHYSICS
Helmholtz Function :From the first and second law of thermodynamics
𝑇𝑑𝑆 = 𝑑𝑈 + 𝑑𝑊 If heat is exchanged between the system and surroundings at constant
temperature 𝑇𝑑𝑆 = 𝑑(𝑇𝑆). Thus 𝑑𝑈 = 𝑑(𝑇𝑆) − 𝑑𝑊 𝑜𝑟 𝑑(𝑈 − 𝑇𝑆) = −𝑑𝑊 where
(𝑈 − 𝑇𝑆) = 𝐹 called Helmoltz free energy or work function
The Helmholtz function (called Helmholtz free energy) is defined as F = U - TS
For an infinitesimal reversible process,
dF = dU – TdS – SdT (by differentiating above equation)
From laws of thermodynamics TdS = dU + PdV
Hence dF = dU – (dU + PdV) – SdT or dF = - PdV – SdT
Thus for a reversible isothermal process (for a isothermal process, temperature
remains constant i.e. dT = 0) dF = - PdV
𝑓
Thus 𝐹𝑓 − 𝐹𝑖 = − ∫𝑖 𝑃𝑑𝑉
Hence the change of Helmholtz function during a reversible isothermal process equals
the work done on the system.
For a reversible isothermal and isochoric process dF = - PdV = 0 or F = constant. (In a
𝜕𝐹
isochoric process, Volume is constant. Thus dV = 0)Also, from dF = - PdV – SdT(𝜕𝑉) =
𝑇
𝜕𝐹
− 𝑃 and (𝜕𝑇) = −𝑆
𝑉
The potential is also called isothermal – isochoric functionwhere independent
variables are temperature T and volume V.

Gibbs Function (G) :

For enthalpy 𝐻 = 𝑈 + 𝑃𝑉. For a infinitesimal change dH = TdS + VdP
If the system is isothermal and pressure is remaining constant, from above equation
𝑑𝐻 = 𝑑(𝑇𝑆) or 𝑑(𝐻 − 𝑇𝑆) = 0. Thus 𝐻 − 𝑇𝑆 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 where 𝐻 − 𝑇𝑆 = 𝐺 is called
Gibbs free energy.
The Gibbs function (Gibbs free energy) is defined as G = H – TS or G =U + PV - TS
For an infinitesimal reversible process,
dG = dH – TdS - SdTAlsodH = TdS + VdP
Hence dG = (TdS + VdP) –TdS - SdT or
dG = VdP – SdT
𝜕𝐺 𝜕𝐺
Also (𝜕𝑃) = 𝑉 and (𝜕𝑇 ) = −𝑆
𝑇 𝑃
For a reversible isothermal and isobaric
process dG = 0 or G = constant. (In a isobaric
process, pressure is constant. Thus dP = 0).
The potential is also called the isothermal –
isobaric potential where the independent
variables are temperature and pressure P.

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Significance of thermodynamic potentials

A mechanical system is said to be in stable equilibrium if the potential energy of the
system is minimum. For example heat flows from higher to lower temperature region
till equilibrium is achieved. Also water flows from higher to lower level to achieve
minimum potential energy.
As U, H, F and G are all energy functions in thermodynamics, they behave similar to
potential energy in mechanics.
1. In an isochoric – adiabatic process, the internal energy tends to a minimum.
2. In an isobaric – adiabatic process, the enthalpy tends to a minimum.
3. In an isochoric – isothermal process, the Helmholtz free energy tends to a
minimum.
4. In an isobaric – isothermal process, the Gibbs free energy tends to a minimum.

Maxwell’s thermodynamic relations

Maxwell’s equations refer to relations between the thermodynamic variables that hold
at any equilibrium state of a hydrostatic system. They provide relationships between
measurable quantities and those which either cannot be measured or difficult to
measure.
If a relation exists between the variables x, y and z, then z can be expressed in terms
𝝏𝒛 𝝏𝒛
of x and y as 𝒅𝒛 = (𝝏𝒙) 𝒅𝒙 + (𝝏𝒚) 𝒅𝒚
𝒚 𝒙
𝜕𝑧 𝜕𝑧
Let (𝜕𝑥) = 𝑀 and (𝜕𝑦) = 𝑁, then 𝒅𝒛 = 𝑴 𝒅𝒙 + 𝑵 𝒅𝒚 ….(1)
𝑦 𝑥
Partially differentiating M with respect to y and N with respect to x, we get
𝜕𝑀 𝜕2𝑧 𝜕𝑁 𝜕2𝑧
( 𝜕𝑦 ) = and ( 𝜕𝑥 ) = .
𝑥 𝜕𝑥𝜕𝑦 𝑦 𝜕𝑥𝜕𝑦

𝝏𝑴 𝝏𝑵
The right hand side of the above equation is same. Thus( ) = ( 𝝏𝒙 ) …(2)
𝝏𝒚 𝒙 𝒚
This is the condition for exact differential and is applicable to all thermodynamic
potentials. This result is applied to the four exact differentials, dU, dF, dH and dG, to
get the Maxwell equations.

1. First Maxwell equation -Internal energy :From the first law of thermodynamics
𝑑𝑄 = 𝑑𝑈 + 𝑑𝑊 = 𝑑𝑈 + 𝑃 𝑑𝑉 and from the second lawdQ = TdS
Combining the above two relations, 𝑇𝑑𝑆 = 𝑑𝑈 + 𝑃 𝑑𝑉……(3)
Or 𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 …….(4)
Comparing eqn. (1) with (4), 𝑀 = 𝑇, 𝑁 = −𝑃, 𝑥 = 𝑆 𝑎𝑛𝑑 𝑦 = 𝑉
𝝏𝑻 𝝏𝑷
Substituting these variables in eqn. (2) (𝝏𝑽) = − ( 𝝏𝑺 ) ….(5)
𝑺 𝑽

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 THERMODYNAMIC POTENTIALS, PHASE TRANSITION AND LOW TEMPERATURE PHYSICS

2. Second Maxwell equation - Helmholtz Function :The Helmholtz function (is

defines as F = U - TS
For an infinitesimal reversible process,dF = dU – TdS – SdT
From laws of thermodynamics TdS = dU + PdV
Hence dF = dU – (dU + PdV) – SdT or dF = - PdV – SdT…..(6)
Comparing eqn. (1) with (6), 𝑀 = −𝑃, 𝑁 = −𝑆, 𝑥 = 𝑉 𝑎𝑛𝑑 𝑦 = 𝑇
𝝏𝑷 𝝏𝑺 𝝏𝑺 𝝏𝑷
Substituting these variables in eqn. (2) (𝝏𝑻 ) = (𝝏𝑽) or (𝝏𝑽) = (𝝏𝑻 ) …..(7)
𝑽 𝑻 𝑻 𝑽

3. Third Maxwell equation - Enthalpy (H) : Enthalpy of a system is the total heat
energy of a systemgiven byH = U + PV
When a system undergoes an infinitesimal process,dH = dU + P dV + V dP
From laws of thermodynamics TdS = dU + PdV
Thus dH = TdS + V dP ….(8)
Comparing eqn. (1) with (8), 𝑀 = 𝑇, 𝑁 = 𝑉, 𝑥 = 𝑆 𝑎𝑛𝑑 𝑦 = 𝑃
𝝏𝑻 𝝏𝑽
Substituting these variables in eqn. (2) (𝝏𝑷) = (𝝏𝑺 ) …..(9)
𝑺 𝑷

4. Fourth Maxwell equation - Gibbs Function (G) : The Gibbs function is defined as
G = H – TS or For an infinitesimal reversible process,dG = dH – TdS - SdT
AlsodH = TdS + VdP ,Hence dG = VdP – SdT……..(10)
Comparing eqn. (1) with (10), 𝑀 = 𝑉, 𝑁 = −𝑆, 𝑥 = 𝑃 𝑎𝑛𝑑 𝑦 = 𝑇
𝝏𝑽 𝝏𝑺 𝝏𝑺 𝝏𝑽
Substituting these variables in eqn. (2) (𝝏𝑻) = − (𝝏𝑷) or (𝝏𝑷) = − (𝝏𝑻)
𝑷 𝑻 𝑻 𝑷
…..(11)

Note :To remember the Maxwell’s relations – remember the sentence T VSpecial Programme,
taken clockwise along a circle as shown
First relation – Start from T and read anticlockwise (negative) T - P – S - V T
Second relation – Start from S and read clockwise (positive) S – P – T – V
P V
Third relation – Start from T and read clockwise(positive) T – V – S – P
Fourth relation – Start from S and read anticlockwise(negative) S – V – T - P S

The TdS equations

1. First TdSequation : The entropy of a pure substance can be imagined as a
𝜕𝑆 𝜕𝑆
function of T and V. This can be written as 𝑑𝑆 = (𝜕𝑇) 𝑑𝑇 + (𝜕𝑉) 𝑑𝑉
𝑉 𝑇
𝜕𝑆 𝜕𝑆
Multiplying the above equation throughout by T, 𝑇𝑑𝑆 = 𝑇 (𝜕𝑇) 𝑑𝑇 + 𝑇 (𝜕𝑉) 𝑑𝑉
𝑉 𝑇
…..(1)

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 THERMODYNAMIC POTENTIALS, PHASE TRANSITION AND LOW TEMPERATURE PHYSICS
𝜕𝑆 𝜕𝑄
For a reversible process TdS = dQ. Thus 𝑇 ( ) = ( ) = 𝐶𝑉 , …(2) where 𝐶𝑉 is the
𝜕𝑇 𝑉 𝜕𝑇 𝑉

specific heat at constant volume.

𝜕𝑆 𝜕𝑃
Also from Maxwell’s second relation, (𝜕𝑉) = (𝜕𝑇 ) ….(3)
𝑇 𝑉
𝝏𝑷
Substituting (2) and (3) in (1) we get 𝑻𝒅𝑺 = 𝑪𝑽 𝒅𝑻 + 𝑻 (𝝏𝑻) 𝒅𝑽
𝑽
This is the first TdS equation.
Application – Consider one mole of a van der Waals gas undergoes isothermal
expansion from volume Vi to Vf, then to find the amount of heat transferred,
𝜕𝑃
From the first TdS equation𝑇𝑑𝑆 = 𝐶𝑉 𝑑𝑇 + 𝑇 (𝜕𝑇 ) 𝑑𝑉 ….(1)
𝑉
𝑎
From van der Waals equation, (𝑃 + )(𝑉 − 𝑏) = 𝑅𝑇
𝑉2
𝑅𝑇 𝑎 𝜕𝑃 𝑅
or𝑃 = − , thus . (𝜕𝑇 ) = ……(2)
𝑉−𝑏 𝑉2 𝑉 𝑉−𝑏

For an isothermal change dT = 0. The TdS equation becomes

𝑅
𝑇𝑑𝑆 = 0 + 𝑇 𝑑𝑉 (by inserting (2) in (1) along with dT = 0)
𝑉−𝑏
𝑉 𝑑𝑉 𝑉 −𝑏
Hence heat transferred is 𝑄 = ∫ 𝑇𝑑𝑆 = 𝑅𝑇 ∫𝑉 𝑓 𝑉−𝑏 . Thus 𝑄 = 𝑅𝑇 𝑙𝑛 𝑉𝑓−𝑏 .
𝑖 𝑖

2. Second TdS equation

If entropy of a pure substance is regarded as a function of T and P, then
𝜕𝑆 𝜕𝑆
𝑑𝑆 = ( ) 𝑑𝑇 + ( ) 𝑑𝑃
𝜕𝑇 𝑃 𝜕𝑃 𝑇
𝜕𝑆 𝜕𝑆
Multiplying the above equation throughout by T, 𝑇𝑑𝑆 = 𝑇 (𝜕𝑇) 𝑑𝑇 + 𝑇 (𝜕𝑃) 𝑑𝑃 … . . (1)
𝑃 𝑇
𝜕𝑆 𝜕𝑄
As 𝑇 (𝜕𝑇) = (𝜕𝑇 ) = 𝐶𝑃 … (2) where 𝐶𝑃 is the specific heat at constant pressure.
𝑃 𝑃
𝜕𝑆 𝜕𝑉
From Maxwell’s fourth equation (𝜕𝑃) = − (𝜕𝑇 ) …..(3)
𝑇 𝑃
𝝏𝑽
Putting (2) and (3) in (1), we get 𝑻𝒅𝑺 = 𝑪𝑷 𝒅𝑻 − 𝑻 ( ) 𝒅𝑷 . This is the second TdS
𝝏𝑻 𝑷

equation.

Application : 1. To find the amount of heat transferred during an isothermal change

of pressure. As temperature is a constant, the second TdS can be written as
𝜕𝑉
𝑇𝑑𝑆 = −𝑇 (𝜕𝑇 ) 𝑑𝑃 (putting dT = 0 in TdS equation)
𝑃
𝜕𝑉
The heat 𝑄 = ∫ 𝑇𝑑𝑆 = − 𝑇 ∫ (𝜕𝑇 ) 𝑑𝑃
𝑃
1 𝜕𝑉
As the volume expansivity is 𝛽 = ( ) , We obtain 𝑄 = −𝑇 ∫ 𝑉𝛽𝑑𝑃
𝑉 𝜕𝑇 𝑃

In most of the solids and liquids, β behave similarly. Thus V and β can be taken out of
integration sign by taking their averages. We obtain,
𝑓
𝑄 = −𝑇𝑉̅ 𝛽̅ ∫𝑖 𝑑𝑃 = −𝑇𝑉̅ 𝛽̅ (𝑃𝑓 − 𝑃𝑖 ) .

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 THERMODYNAMIC POTENTIALS, PHASE TRANSITION AND LOW TEMPERATURE PHYSICS
It is seen from this result that, as the pressure is increased isothermally, heat will flow
out if 𝛽 is positive. In case of water as 𝛽 is negative (between 00 and 40C), an
isothermal increase of pressure causes an absorption of heat.
Application 2. : Reversible adiabatic change of pressure.Since entropy remains
constant (dS = 0). The TdS equation is
𝜕𝑉 𝜕𝑉
𝑇𝑑𝑆 = 0 = 𝐶𝑃 𝑑𝑇 − 𝑇 (𝜕𝑇 ) 𝑑𝑃 or 𝐶𝑃 𝑑𝑇 = 𝑇 (𝜕𝑇 ) 𝑑𝑃
𝑃 𝑃
𝑇 𝜕𝑉 𝑇𝑉𝛽
or 𝑑𝑇 = ( ) 𝑑𝑃 = 𝑑𝑃
𝐶𝑃 𝜕𝑇 𝑃 𝐶𝑃

In a solid or a liquid, increase of pressure produces only a small change of

𝑇𝑉𝛽
temperature. Also CP does not vary. Hence above equation is ∆𝑇 = (𝑃𝑓 − 𝑃𝑖 ).
𝐶𝑃

It is clear from the above discussion that an adiabatic increase of pressure will
produce an increase of temperature in any substance with a positive expansivity and a
decrease in temperature in a substance with a negative expansivity.

Energy equations
1. First energy equation : If a pure substance undergoes infinitesimal reversible
process between two equilibrium states, the change in internal energy is (from the two
laws of thermodynamics) 𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉
𝑑𝑈 𝑑𝑆
Dividing by dV we get =𝑇 −𝑃
𝑑𝑉 𝑑𝑉
U, S and P are regarded as functions of T and V. If T is held constant, the derivatives
𝜕𝑈 𝜕𝑆
become partial derivatives. i.e.(𝜕𝑉 ) = 𝑇 (𝜕𝑉) − 𝑃 ,
𝑇 𝑇
𝜕𝑆 𝜕𝑃
Using Maxwell’s second relation (𝜕𝑉) = (𝜕𝑇 ) in the above equation, we get
𝑇 𝑉
𝝏𝑼 𝝏𝑷
(𝝏𝑽 ) = 𝑻 (𝝏𝑻) − 𝑷. This is the first energy equation.
𝑻 𝑽

An example of the usefulness of this equation is as follows

(a) Ideal gas
𝑛𝑅𝑇 𝜕𝑃 𝑛𝑅
For an ideal gas 𝑃 = Differentiating(𝜕𝑇 ) = …..(1)
𝑉 𝑉 𝑉
𝜕𝑈 𝜕𝑃
From the energy equation (𝜕𝑉 ) = 𝑇 (𝜕𝑇 ) − 𝑃 …..(2)
𝑇 𝑉
𝜕𝑈 𝑛𝑅
Equation (1) in (2) gives (𝜕𝑉 ) = 𝑇 −𝑃 =𝑃−𝑃 =0
𝑇 𝑉

Therefore U does not depend on V but is a function of T only.

(b) Van der Waals gas (1 mol) :

𝑅𝑇 𝑎
From the van der waals equation for one mole of a gas 𝑃 = − …..(1)
𝑉−𝑏 𝑉2
𝜕𝑃 𝑅
Differentiating (𝜕𝑇 ) = ……(2)
𝑉 𝑉−𝑏

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 THERMODYNAMIC POTENTIALS, PHASE TRANSITION AND LOW TEMPERATURE PHYSICS
𝜕𝑈 𝜕𝑃
From the energy equation ( ) = 𝑇 ( ) −𝑃 ………(3)
𝜕𝑉 𝑇 𝜕𝑇 𝑉
𝜕𝑈 𝑅 𝑅𝑇 𝑎 𝑎 𝜕𝑃 𝑎
Putting (1) and (2) in (3) (𝜕𝑉 ) = 𝑇 − + = or 𝑇 (𝜕𝑇 ) − 𝑃 =
𝑇 𝑉−𝑏 𝑉−𝑏 𝑉2 𝑉2 𝑉 𝑉2
𝜕𝑃
As 𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 and substituting for TdS from the relation𝑇𝑑𝑆 = 𝐶𝑉 𝑑𝑇 + 𝑇 (𝜕𝑇 ) 𝑑𝑉
𝑉
𝜕𝑃 𝜕𝑃
We get 𝑑𝑈 = 𝐶𝑉 𝑑𝑇 + 𝑇 (𝜕𝑇 ) 𝑑𝑉 − 𝑃𝑑𝑉 = 𝐶𝑉 𝑑𝑇 + [𝑇 (𝜕𝑇 ) − 𝑃] 𝑑𝑉
𝑉 𝑉
𝑎 𝑎
Thus 𝑑𝑈 = 𝐶𝑉 𝑑𝑇 + 𝑉 2 𝑑𝑉 and 𝑈 = ∫ 𝐶𝑉 𝑑𝑇 − + 𝑐𝑜𝑛𝑠𝑡.
𝑉
It follows, therefore, that the internal energy of a van der Waals gas increases as the
volume increases, with the temperature remaining constant.

2. Second energy equation :The change of internal energy is (from the two laws of
thermodynamics) 𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉
𝑑𝑈 𝑑𝑆 𝑑𝑉
Dividing this equation by dP, we get =𝑇 − 𝑃 𝑑𝑃
𝑑𝑃 𝑑𝑃
Where U, S and V are imagined to be functions of T and P. If T is held constant, the
derivatives become partial derivatives, and
𝜕𝑈 𝜕𝑆 𝜕𝑉
( ) = 𝑇 ( ) −𝑃( )
𝜕𝑃 𝑇 𝜕𝑃 𝑇 𝜕𝑃 𝑇
𝜕𝑆 𝜕𝑉
Using Maxwell’s fourth relation ( ) = − ( ) , the above equation becomes,
𝜕𝑃 𝑇 𝜕𝑇 𝑃
𝝏𝑼 𝝏𝑽 𝝏𝑽
(𝝏𝑷) = − 𝑻 (𝝏𝑻) − 𝑷 (𝝏𝑷) This is the second energy equation.
𝑻 𝑷 𝑻

Heat capacity equations – Expression for difference in molar specific heat

capacities :The first and the second TdS equations are given by
𝜕𝑃 𝜕𝑉
𝑇𝑑𝑆 = 𝐶𝑉 𝑑𝑇 + 𝑇 (𝜕𝑇 ) 𝑑𝑉 ….(1) and 𝑇𝑑𝑆 = 𝐶𝑃 𝑑𝑇 − 𝑇 (𝜕𝑇 ) 𝑑𝑃 …….(2)
𝑉 𝑃
Equating the above equations, we get,
𝜕𝑉 𝜕𝑃
𝐶𝑃 𝑑𝑇 − 𝑇 ( ) 𝑑𝑃 = 𝐶𝑉 𝑑𝑇 + 𝑇 ( ) 𝑑𝑉
𝜕𝑇 𝑃 𝜕𝑇 𝑉
𝜕𝑉 𝜕𝑃
Solving for dT we get, 𝐶𝑃 𝑑𝑇 − 𝐶𝑉 𝑑𝑇 = 𝑇 (𝜕𝑇 ) 𝑑𝑃 + 𝑇 (𝜕𝑇 ) 𝑑𝑉
𝑃 𝑉
𝜕𝑉 𝜕𝑃
or (𝐶𝑃 − 𝐶𝑉 ) 𝑑𝑇 = 𝑇 ( ) 𝑑𝑃 + 𝑇 ( ) 𝑑𝑉
𝜕𝑇 𝜕𝑇 𝑃 𝑉
𝜕𝑃 𝜕𝑉
𝑇( ) 𝑇( )
𝜕𝑇 𝑉 𝜕𝑇 𝑃
or𝑑𝑇 = (𝐶 𝑑𝑉 + 𝑑𝑃 ……(3)
𝑃 − 𝐶𝑉 ) (𝐶𝑃 − 𝐶𝑉 )
𝜕𝑇 𝜕𝑇
As dT is a perfect differential, 𝑑𝑇 = (𝜕𝑉) 𝑑𝑉 + (𝜕𝑃) 𝑑𝑃 …..(4)
𝑃 𝑉
Equating coefficients of dP and dV of equations (3) and (4)
𝜕𝑃 𝜕𝑉
𝜕𝑇 𝑇( ) 𝜕𝑇 𝑇( )
𝜕𝑇 𝑉 𝜕𝑇 𝑃
(𝜕𝑉) = (𝐶𝑃 − 𝐶𝑉 )
……..(5) and (𝜕𝑃) = (𝐶𝑃 − 𝐶𝑉 )
…..(6)
𝑃 𝑉
Both the above equations yields the same relation after rearranging, ie.,

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 THERMODYNAMIC POTENTIALS, PHASE TRANSITION AND LOW TEMPERATURE PHYSICS
𝜕𝑃
𝑇( ) 𝜕𝑃 𝜕𝑉
𝜕𝑇 𝑉
𝐶𝑃 − 𝐶𝑉 = 𝜕𝑇 = 𝑇 (𝜕𝑇 ) (𝜕𝑇 ) ………(7)
( ) 𝑉 𝑃
𝜕𝑉 𝑃

Consider P as a function of T and V, since dP is a perfect differential,

𝜕𝑃 𝜕𝑃
𝑑𝑃 = ( ) 𝑑𝑉 + ( ) 𝑑𝑇
𝜕𝑉 𝑇 𝜕𝑇 𝑉
If the changes take place at constant pressure, dP = 0. Then,
𝜕𝑃 𝜕𝑃 𝜕𝑃 𝜕𝑃
0 = (𝜕𝑉) 𝑑𝑉 + (𝜕𝑇 ) 𝑑𝑇 or (𝜕𝑇 ) 𝑑𝑇 = − (𝜕𝑉) 𝑑𝑉
𝑇 𝑉 𝑉 𝑇
𝜕𝑃 𝜕𝑃 𝜕𝑉
or(𝜕𝑇 ) = − (𝜕𝑉) (𝜕𝑇 ) ……(8)
𝑉 𝑇 𝑃

𝝏𝑽 𝟐 𝝏𝑷
Substituting (8) in (7) we get, 𝑪𝑷 − 𝑪𝑽 = − 𝑻( ) (𝝏𝑽)
𝝏𝑻 𝑷 𝑻
The above equation shows that
𝜕𝑃 𝜕𝑉 2
1. Since (𝜕𝑉) is always negative for all known substances and (𝜕𝑇 ) must be
𝑇 𝑃
positive, then 𝐶𝑃 − 𝐶𝑉 can never be negative or 𝐶𝑃 can never be less than 𝐶𝑉 .
2. As𝑇 → 0, 𝐶𝑃 → 𝐶𝑉 , or at absolute zero the two heat capacities are equal.
𝜕𝑉
3. 𝐶𝑃 = 𝐶𝑉 when (𝜕𝑇 ) = 0. For example, at 40C, at which density of water is a
𝑃
maximum, 𝐶𝑃 = 𝐶𝑉
𝜕𝑃 𝑅 𝜕𝑉 𝑅
4. For a perfect gas of 1 mole, PV = RT, (𝜕𝑇 ) = and (𝜕𝑇 ) =
𝑉 𝑉 𝑃 𝑃
𝜕𝑃 𝜕𝑉
From equation (7) 𝐶𝑃 − 𝐶𝑉 = 𝑇 (𝜕𝑇 ) (𝜕𝑇 ) . Putting the above conditions in (7)
𝑉 𝑃
𝑅 𝑅 𝑇𝑅 2 𝑇𝑅 2
we get, 𝐶𝑃 − 𝐶𝑉 = 𝑇 ×𝑉 ×𝑃 = = =𝑅 Thus 𝐶𝑃 − 𝐶𝑉 = 𝑅 called
𝑃𝑉 𝑅𝑇
Mayer’s equation.

To find the ratio of specific heat capacities :The two TdS equations are
𝜕𝑃 𝜕𝑉
𝑇𝑑𝑆 = 𝐶𝑉 𝑑𝑇 + 𝑇 (𝜕𝑇 ) 𝑑𝑉….(1) and 𝑇𝑑𝑆 = 𝐶𝑃 𝑑𝑇 − 𝑇 (𝜕𝑇 ) 𝑑𝑃 …….(2)
𝑉 𝑃
At constant entropy, the equations become
𝜕𝑃 𝜕𝑉
𝐶𝑉 𝑑𝑇 = − 𝑇 (𝜕𝑇 ) 𝑑𝑉….(3) and 𝐶𝑃 𝑑𝑇 = 𝑇 (𝜕𝑇 ) 𝑑𝑃 …..(4)
𝑉 𝑃
𝜕𝑉
𝐶𝑃 ( ) 𝜕𝑃
𝜕𝑇 𝑃
Dividing (4)/(3) we get, = −[ 𝜕𝑃 ] (𝜕𝑉)
𝐶𝑉 ( ) 𝑆
𝜕𝑇 𝑉
𝝏𝑷
𝜕𝑉 𝑪𝑷 ( )
𝝏𝑽 𝑺
But the quantity in the square bracket is equal to − (𝜕𝑃) . Therefore = 𝝏𝑷
𝑇 𝑪𝑽 ( )
𝝏𝑽 𝑻

1 𝜕𝑉
The adiabatic compressibility is defined as 𝜒𝑆 = − ( )
𝑉 𝜕𝑃 𝑆
1 𝜕𝑉 𝑪𝑷 𝝌𝑺
Also 𝜒 = − ( ) We therefore have = = 𝜸
𝑉 𝜕𝑃 𝑇 𝑪𝑽 𝝌

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 THERMODYNAMIC POTENTIALS, PHASE TRANSITION AND LOW TEMPERATURE PHYSICS
Third law of thermodynamics – Nernst heat theorem
Statements : By no finite series of processes is the absolute zero attainable.
The entropy change associated with any isothermal reversible process of a condensed
system approaches zero as the temperature approaches zero. This is the Nernst
statement of third law of thermodynamics.
Explanation :Experiments show that the fundamental feature of all cooling processes is that
the lower the temperature achieved, the more it is to go lower. For example the colder the
liquid is , the lower is the vapour pressure, and the harder it is to produce further cooling by
pumping away the vapour. The third law is known as principle of unattainability of absolute
zero. Just as the second law of thermodynamics , the third law has the alternative statement.
The Nernst statement is the result of experiments leading to calculation of the way the entropy
change of a condensed system during a reversible, isothermal process ST behaves as T
approaches zero.
From the third law, it is observed that, heat capacities of a system vanish at absolute zero.
Also the coefficient of volume expansion of any substance vanishes at absolute zero. These
facts shows the unattainability of absolute zero.

Descriptive questions
1. (a) What are thermodynamic potentials? Explain.
(b) Distinguish between internal energy and enthalpy of a system consisting of a system
consisting of a pure substance.
2. (a) What is Helmholtz function? Show that it represents the free energy of the system in a
reversible isothermal process or the energy available for work.
(b) What is Gibbs function? Show that it represents the free energy of the system in a
reversible isothermal-isobaric process.
(c) Give the significance of thermodynamic potentials.
3. Derive Maxwell’s thermodynamic relations from thermodynamic potentials.
4. (a) Obtain the first TdS equation from the Maxwell’s thermodynamic relations.
(b) Explain an application of first TdS equations.
5. (a) Obtain second TdS equation from the Maxwell’s thermodynamic relations.
(b) Explain an application of second TdS equations.
6. Obtain the first energy equation and second energy equation from the TdS equation.
7. (a) Arrive at the expression for the difference in molar specific heats using TdS equation.
(b) Give the significance of the expression of the difference in molar specific heats.
8. (a) Arrive at the expression for ratio of specific heats using TdS equation.
(b) State and explain third law of thermodynamics.

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 THERMODYNAMIC POTENTIALS, PHASE TRANSITION AND LOW TEMPERATURE PHYSICS

Syllabus :Phase transitions of the first order : Melting, vaporization and sublimation;
Condition of equilibrium of phases in terms of Gibbs potential; Clausius-Clapeyron equation -
elevation of boiling point, depression of freezing point; Equilibrium between phases - triple
point

Phase transition is a process of change of state of matter.For example from solid to

liquid state or liquid to vapour state or vapour state to solid state ie. Melting,
vapourisation and sublimation. Other known phase transition is change of system of
one crystalline modification to another.

A first order phase transition is one in which a system absorbs heat or releases heat
without any change in pressure or temperature but the entropy and volume of the
system changes.
Example : Change of state on heating - The constant temperature at which change of
state from solid to liquid occurs isMelting point. Similarly from liquid to vapour state
is the Boiling pointand from solid to vapour state is Sublimation.
The heat energy cannotproduce both a change of state and a change in temperature
simultaneously.
ste
The specific latent heat of fusion is Vapourisation
1000C am
te wa
the heat energy required to change ter Lv
m
unit mass of a substance from the
per Melting
solid to the liquid state at its melting atu 0 C
0
Lf
point. In case of water Lf= 3.35 x re
- 250C
105Jkg-1. The specific latent heat of
Heat energy
vapourisation is the quantity of heat
required to change unit mass of a substance from the liquid to the vapour state
without a change in temperature i.e at the boiling point. Lv =2.26 x 106J kg-1. The
variation of temperature of ice with heat energy when heated is as shown above.

Characteristics of first order phase transition

1.During the phase transition, pressure and temperature remains constant and both
entropy and volume undergoes change.
2.In this phase transition, the Gibbs energy remains constant in both the phases but
the first derivative of Gibbs energy with respect to pressure and temperature is
discontinuous at the transition point.
The Gibbs function is defined as G = H – TS …….(1) or G = F + PV
For an infinitesimal reversible process,dG = dH – TdS - SdTAlso dH = TdS + VdP
Hence dG = (TdS + VdP) –TdS - SdT or dG = VdP – SdT

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 THERMODYNAMIC POTENTIALS, PHASE TRANSITION AND LOW TEMPERATURE PHYSICS
𝜕𝐺
At constant temperature dT = 0. Thus ( ) = 𝑉 …..(2)
𝜕𝑃 𝑇
𝜕𝐺
And at constant pressuredP = 0. Thus (𝜕𝑇 ) = −𝑆. …..(3)
𝑃
𝜕𝑉
3.From the T dS equation, 𝑇𝑑𝑆 = 𝐶𝑃 𝑑𝑇 − 𝑇 (𝜕𝑇 ) 𝑑𝑃
𝑃
𝜕𝑆
As dP = 0, the above equation is 𝑇𝑑𝑆 = 𝐶𝑃 𝑑𝑇 or 𝐶𝑃 = 𝑇 (𝜕𝑇) …….(4)
𝑃
For the first order phase transitions the variations of G, V, S and CP with temperature
are as shown in the graphs.
Volume
Gibb’s function Entropy Heat capacity
G V
S CP
Phase (f)
Phase (i) Phase (i) Phase (i)
Phase (i) Phase (f) Phase (f) Phase (f)

T T T T

To show that Gibb’s function is a constant during first order phase transition
Consider a system of liquid and vapour in equilibrium state. The temperature and
pressure of the system are constants in both the phases. Thus the product of specific
value of functions U, S, V and G and their masses are equal to the thermodynamic
coordinates U, S, V and G.
If g1 and g2 are the Gibb’s function of the two phases ie. Liquid and vapour with m1
and m2as their masses, then G = m1 g1 + m2 g2 ………(1) where G is the Gibb’s
potential of the whole system. If a small quantity of liquid changes to vapour, then
differentiating the above equation, 𝑑𝐺 = 𝛿𝑚1 𝑔1 + 𝛿𝑚2 𝑔2
As this process take place at constant temperature and pressure, ie under isothermal
and isobaric condition, Gibb’s potential does not change ie. dG = 0.
The above equation becomes 0 = 𝛿𝑚1 𝑔1 + 𝛿𝑚2 𝑔2
Or 𝛿𝑚1 𝑔1 = − 𝛿𝑚2 𝑔2
In a closed system, the gain in mass of vapour 𝛿𝑚2 is equal to loss in mass of liquid
𝛿𝑚1.Thus 𝛿𝑚1 = − 𝛿𝑚2 . Thus 𝒈𝟏 = 𝒈𝟐 .
Thus the value of Gibb’s function in the two phases are equal.

Clausius - Clapeyron equation

Consider an enclosed system of liquid with its saturated vapour in equilibrium. As the
system is undergoing isothermal and isobaric change, Gibb’s potential is a constant
during the phase change. ie. 𝑔1 = 𝑔2 …..(1)
Let temperature change from T to T + dT and pressure from P to P + dP. Then for
equilibrium condition 𝑔1 + 𝑑𝑔1 = 𝑔2 + 𝑑𝑔2 ………(2)
Using the condition (1) in (2) we get 𝑑𝑔1 = 𝑑𝑔2

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 THERMODYNAMIC POTENTIALS, PHASE TRANSITION AND LOW TEMPERATURE PHYSICS
𝑑𝑔1 𝑑𝑔2
If the condition of saturation is satisfied, then ( ) =( ) …..(3)
𝑑𝑇 𝑠𝑎𝑡 𝑑𝑇 𝑠𝑎𝑡
As the pressure is also changing from P to P + dP, we have
𝜕𝑔 𝜕𝑔
𝑑𝑔 = ( ) 𝑑𝑇 + ( ) 𝑑𝑃
𝜕𝑇 𝑃 𝜕𝑃 𝑇
𝜕𝑔 𝜕𝑔 𝜕𝑔 𝜕𝑃
Dividing throughout by 𝑇 , we get (𝜕𝑇 ) = (𝜕𝑇 ) + (𝜕𝑃) (𝜕𝑇 ) ………(4)
𝑃 𝑇
As change in Gibb’s function is given by dg = VdP-SdT
𝜕𝑔 𝜕𝑔
We have (𝜕𝑃) = 𝑉 and (𝜕𝑇 ) = −𝑆.
𝑇 𝑃
𝜕𝑔 𝜕𝑃
Putting these values in equation (4) (𝜕𝑇 ) = −𝑆 + 𝑉 (𝜕𝑇 )
𝑠𝑎𝑡
𝜕𝑔 𝜕𝑃
The above equation for the two phases can be written as ( 𝜕𝑇1 ) = −𝑆1 + 𝑉1 (𝜕𝑇 )
𝑠𝑎𝑡
𝜕𝑔2 𝜕𝑃
And ( 𝜕𝑇 ) = −𝑆2 + 𝑉2 (𝜕𝑇 )
𝑠𝑎𝑡
𝜕𝑃 𝜕𝑃
Now, by substituting above equations in (3) we get −𝑆1 + 𝑉1 (𝜕𝑇 ) = −𝑆2 + 𝑉2 (𝜕𝑇 )
𝜕𝑃 𝑆2 − 𝑆1
(𝜕𝑇 ) = ……(5)
𝑉2 − 𝑉1
𝑑𝑄
The amount of heat absorbed dQ = T dS = T (S2 – S1) or 𝑆2 − 𝑆1 = 𝑇
As phase change occurs at constant temp. if L is the latent heat and m is the mass of
𝑚𝐿 𝐿
the system, then dQ = mL. Thus 𝑆2 − 𝑆1 = . If m = 1, then 𝑆2 − 𝑆1 = …..(6)
𝑇 𝑇
𝒅𝑷 𝑳
By substituting for change of entropy from (6) in (5), we get =
𝒅𝑻 𝑻 (𝑽𝟐 − 𝑽𝟏 )
This equation is called Clausius – Clapeyron equation.

Applications of Clausius – Clapeyron equation

1. Effect of pressure on the boiling point of liquids :
When a liquid changes its state to vapour state, its volume increases. That is V2 is
greater than V1. This means, V2 – V1 is a positive quantity. From the Clausius-
𝒅𝑷 𝑳 𝒅𝑷
clapeyron equation, = , if V2 – V1 is positive, then (𝒅𝑻) is also positive.
𝒅𝑻 𝑻 (𝑽𝟐 − 𝑽𝟏 )

Thus, as the pressure is increased, the boiling point also increases. In case of water, it
boils at a temperature greater than 1000C if the pressure is increased beyond 1
atmosphere.
2. Effect of pressure on the melting point of solids:
When a solid changes its state to liquid state, its volume increases. That is V2 is
greater than V1. This means, V2 – V1 is a positive quantity. From the clausiusclapeyron
𝒅𝑷 𝑳 𝒅𝑷
equation, = , if V2 – V1 is positive, then ( ) is also positive. Thus as the
𝒅𝑻 𝑻 (𝑽𝟐 − 𝑽𝟏 ) 𝒅𝑻

pressure is increased, the melting point also increases. Eg. Wax and sulphur.
In case of ice, gallium and bismuth V2 is less than V1. That is V2 – V1 is a negative
𝒅𝑷
quantity. Thus (𝒅𝑻) is a negative quantity. This means, as pressure is increased, the

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 THERMODYNAMIC POTENTIALS, PHASE TRANSITION AND LOW TEMPERATURE PHYSICS
melting point decreases. In case of ice whose melting point is 00C, at 1 atmosphere, it
will be less than this value at higher pressures.

Triple point of water

The triple point of a substance is the temperature and pressure at which three phases (gas,
liquid, and solid) of that substance may coexist in thermodynamic equilibrium.
For example, the triple point temperature of mercury is at −38.8344 °C, at a pressure of 0.2
mPa.
The triple point of water is used to define the kelvin, the SI base unit of thermodynamic
temperature.
The number given for the temperature of the triple point of water is an exact definition rather
than a measured quantity.
The single combination of pressure and temperature at which pure water, pure ice, and pure
water vapour can coexist in a stable equilibrium occurs at exactly 273.16 kelvins (0.01 °C) and
a pressure of 611.73 pascals ( 0.006037 atm). At that point, it is possible to change all of the
substance to ice, water, or vapor by making infinitesimally small changes in pressure and
temperature.
Triple point is the intersection on a phase
diagram where three phases coexist in
equilibrium. The most important application of
triple point is water, where the three-phase
equilibrium point consists of ice, liquid, and
vapour.
The line TC gives the vapor pressure of liquid
water up to the critical point C. Along this line,
liquid and vapor coexist in equilibrium. At
temperatures higher than that of point C,
condensation does not occur at any pressure.
The line TB is the vapour pressure of solid ice,
which is a plot of the temperatures and pressures at which the solid and vapour are in
equilibrium. Finally, line TA gives the melting point of ice and liquid water. The plot shows the
temperatures and pressures at which ice and liquid water are in equilibrium.
(Note: At the dashed line TD, liquid water can be cooled below the freezing point to give
supercooled water.)
This explanation show that two phases are in equilibrium along the three solid lines. But
when these lines intersect at one point C, three phases coexist in equilibrium. This
intersection is the triple point, where a substance may simultaneously melt, evaporate, and
sublime.

1. Mention the characteristics of a first order phase transitions?

2. Obtain the condition of equilibrium of phases in terms of Gibbs potentials.
3. Derive the first order phase transition or Clausius-Clapeyron equation.

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 THERMODYNAMIC POTENTIALS, PHASE TRANSITION AND LOW TEMPERATURE PHYSICS
4. Explain the applications of Clausius-Clapeyron equation.
5. Write a note on triple point of water.

1 Calculate change in boiling point of water by taking the normal boiling point as
100 C with the latent heat of vapourization as 2.26 × 106 𝐽𝑘𝑔−1 , specific volume of water
0

1 m3 and that of steam is 2.676 m3 and change in pressure is 1 atmosphere (1

atmosphere 1.015 × 105 𝑁𝑚−2 .
𝑑𝑃 𝐿 𝑇(𝑉2 − 𝑉1 )
[ = 𝑜𝑟 𝑑𝑇 = 𝑑𝑃 = 𝟐𝟕. 𝟗𝟕𝟎 𝑪 (here T = 373 K) (Here the transition
𝑑𝑇 𝑇 (𝑉2 − 𝑉1 ) 𝐿
is from water to steam 𝑉1 = 1 𝑚3 𝑎𝑛𝑑 𝑉2 = 2.676 𝑚3) ]

2 Calculate the depression in melting point of water assuming normal melting point
of ice as 00C, latent heat of ice as 3.35 × 105 𝐽𝑘𝑔−1 Specific volume of water is 1× 10−3
m3 and that of ice is 1.091× 10−3 m3 and change in pressure is 1 atmosphere.
𝑑𝑃 𝐿 𝑇(𝑉2 − 𝑉1 )
[ = 𝑜𝑟 𝑑𝑇 = 𝑑𝑃 = −𝟎. 𝟎𝟎𝟕𝟒𝟎 𝑪 ( here T = 273 K. The depression
𝑑𝑇 𝑇 (𝑉2 − 𝑉1 ) 𝐿
in freezing point means decrease in freezing point. Thus 𝑉1 = 1 × 10−3 𝑚3 𝑎𝑛𝑑 𝑉2 =
1.091 × 10−3 𝑚3) Negative sign is taken due to decrease in melting point of ice with
increase in pressure ]

3 Mercury melts at -40°C at 1 atmosphere pressure. Its density is 13590 kg𝑚−3. The density of
solid mercury is 14190 kg𝑚−3 and the latent heat of fusion is 9786J𝑘𝑔−1 . What would be the
melting point of mercury at 800 atmosphere.
[ T = - 400C = 273 – 40 =233K, dP = P2 – P1 = 800 – 1 = 799 atm. = 838 × 105 𝑁𝑚−2.
𝑇(𝑉 − 𝑉 )
Specific Volume V1 = 1/13590 m3, V2 = 1/14190 m3 𝑑𝑇 = 2 1
𝑑𝑃 = 5.916 𝐾
𝐿
Melting point = −𝟒𝟎 + 𝟓. 𝟗𝟏𝟔 = −𝟑𝟒. 𝟎𝟖°𝐂 (Here pressure is increasing and melting
point also increases as it is Mercury. The value of V1 is at 1atm and V2 at 800atm.)
Thus positive sign is taken for dT ]

4 Calculate the pressure required to lower the melting point of ice by 1°C, L=3.35 × 105 𝐽𝑘𝑔−1,
specific volume of water at 0°C = 1000𝑚3 , specific volume of ice at 0°C = 1091𝑚3 .
𝑑𝑃 𝐿 𝐿
[ = 𝑜𝑟 𝑑𝑃 = 𝑇 (𝑉 − 𝑉 ) 𝑑𝑇 = −13.46 𝑎𝑡𝑚. , pressure required to lower the
𝑑𝑇 𝑇 (𝑉2 − 𝑉1 ) 2 1
melting point is P = 1 + 13.46 = 14.46 atm. (Here melting point is lowered from 00C starting from
water to ice. Thus V1 = 1000𝑚3 and V2 = 1091𝑚3 ) With increase in pressure melting point
decreases in case of water. Thus negative sign is taken ]

5 Calculate the change in boiling point of water when the pressure is increased by one
atmosphere. Boiling point of water at the atmospheric pressure is 373 K Specific volume of
water is 1m3 and Specific heat of steam is 1.671 m3 and the specific latent heat of steam is 2.268
× 106 JKg-1.
𝑇(𝑉2 − 𝑉1 )
[ 𝑑𝑇 = 𝑑𝑃 = 11.04 K ]
𝐿

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 THERMODYNAMIC POTENTIALS, PHASE TRANSITION AND LOW TEMPERATURE PHYSICS
6 Calculate the pressure required to lower the melting point of ice by 10C. Given Latent heat of
fusion of ice is 3.35 × 105 JKg-1, specific volume of water at 00C is 1000 m3 , specific volume of ice
at 00C is 1091 m3.
𝐿
[ 𝑑𝑃 = 𝑇 (𝑉 − 𝑉 ) 𝑑𝑇 = 14.4 𝑎𝑡𝑚. Here even though dT is negative pressure difference is
2 1
taken as positive ]

7 Calculate the depression in melting point of ice for an increase in the external
pressure of 2 atmosphere. Latent heat of ice as 3.35 × 105 𝐽𝑘𝑔−1 Specific volume of
water is 1× 10−3 m3 and that of ice is 1.01× 10−3 m3 at 00C. and 1 atmospheric
pressure = 105Nm-2.
𝑑𝑃 𝐿 𝑇(𝑉2 − 𝑉1 )
[ = , 𝑑𝑇 = 𝑑𝑃 = −0.00163 𝐾 ]
𝑑𝑇 𝑇 (𝑉2 − 𝑉1 ) 𝐿

8 Find the pressure at which water would boil at 1500C if the change in specific
volume when 1 kg of water is converted into steam is 1.676 m3. 1 atm = 105 𝑁𝑚−2 , L =
2.268 × 106 JKg-1 .
𝐿
[ 𝑉2 − 𝑉1 = 1.676, dT = 500C, T = 373 K 𝑑𝑃 = 𝑇 (𝑉 − 𝑉 ) 𝑑𝑇 = 1.814 × 105 , P =
2 1
(1 + 1.814 ) × 105 = 2.814 × 105 N𝑚−2 ]

Syllabus : Low Temperature Physics : Methods of producing low temperatures: (i)

Joule Thomson (Joule Kelvin / Throttling / Porous plug) experiment, Joule Thomson
Coefficient, inversion temperature (ii) Adiabatic demagnetization - working and theory

Liquefaction of gases : Regenerative cooling coupled with Joule Thomson cooling;

Adiabatic expansion with Joule Thomson cooling (qualitative)

Low Temperature Physics : The various experimental methods to produce very low
temperatures are 1) by adding salt to ice, 2) cooling by evaporation of a liquid under
reduced pressure (cascade process), 3) by
adiabatic expansion of a gas, 4) by Joule –
Thomson effect, 5) by regenerative cooling and 6)
adiabatic demagnetisation of a paramagnetic salt.

Joule – Kelvin (Thomson) effect

Principle When a gas is made to expand

without doing external work and without
allowing any heat to enter or leave it during the
expansion, then, if the molecules of the gas
attract one another, internal work will have to
be done in pulling them apart. This can be

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 THERMODYNAMIC POTENTIALS, PHASE TRANSITION AND LOW TEMPERATURE PHYSICS
achieved at the expense of heat energy of the gas. This results in cooling. This is
called Joule Thomson effect. If the molecules of the gas repel each other, then
there is heating. If there is no intermolecular forces, there is no change in
temperature.

The porous plug experiment Theprinciple of this experiment is to drive a

gas by a compressor at a constant pressure through a porous plug and
measure the temperature of the gas as it enters and leaves the plug.

Construction :The porous plug G consists of a porous material, such as

cotton, wool, silk, etc., having a number of fine holes or pores and is thus
equivalent to a number of narrow orifices in parallel.

The porous plug is positioned between two perforated brass plates and
enclosed in a boxwood tube B. The plug is surrounded by a non-conducting
jacket to prevent any heat from entering or leaving the gas. B is surrounded by
a brass case D full of cotton wool, which serves as a thermal insulator. The
box-wood tube is fitted on both sides with copper tubes CC. The lower of these
in connected to a compression pump P through a copper spiral S. The whole
apparatus is placed in a water bath to ensure constant temperature

Experiment :The compressed gas is allowed to suffer throttle expansion through

the porous plug G. The temperature of the gas on the two sides of the plug are
measured with platinum resistance thermometers T 1 and T2. The gas is
allowed to flow for about an hour in order to obtain the steady state.

The experiment is repeated for various differences of pressure on the two

sides of the porous plug. The initial pressure of the gas is measured by a
manometer at the entrance into the lower copper tube, while its final pressure
is that of the atmosphere. Different gases are investigated over a wide range of
temperatures.

Joule and 'I'homson experimented on air, oxygen, nitrogen and carbon

dioxide between 4°C and 1000C, the initial and final pressures being 4·5 and 1
atmosphere respectively.

The results of the experiment

1) At sufficiently low temperature all gases show a cooling effect in passing

through the porous plug. But at ordinary temperatures most gases show
a cooling effect, while hydrogen shows a heating effect.
2) The fall in temperature is proportional to the difference of pressure on
the two sides of the porous plug. The greater the difference of pressure,
the greater the drop in temperature.
3) The fall in temperature per atmosphere difference of pressure decreases
as the initial temperature of the gas is raised, becomes zero at a
particular temperature, which is different for each gas, and above this

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 THERMODYNAMIC POTENTIALS, PHASE TRANSITION AND LOW TEMPERATURE PHYSICS
temperature there is no more fall but rise in temperature. The
temperature, at which the Joule-Thomson effect changes sign, i.e., the
cooling effect becomes heating effect, is called the temperature of
inversion.

Theory of the experiment

Let P1, V1and U1 be the initial pressure, volume and internal energy of the gas. After
undergoing the throttling process (passing through porous plug) let P1, V2and U2 be
the final values respectively.(P2< P1)
The net work done by the gas on the piston 𝑊 = 𝑃2 𝑉2 − 𝑃1 𝑉1
As no heat enters or leaves the system, work has to be done at the expense of internal
energy.𝑈1 − 𝑈2 = 𝑃2 𝑉2 − 𝑃1 𝑉1 or 𝑈1 + 𝑃1 𝑉1 = 𝑈2 + 𝑃2 𝑉2
orH1 = H2 where H = U + PV called enthalpy or total heat of the system which is a
constant. Thus Joule Kelvin expansion is isenthalpic.
Let H be a function of temperature and pressure, Thus H = H(T, P)
𝜕𝐻 𝜕𝐻
𝑑𝐻 = ( 𝜕𝑇 ) 𝑑𝑇 + ( 𝜕𝑃 ) 𝑑𝑃……(1)
𝑃 𝑇
𝜕𝐻
but ( 𝜕𝑇 ) = 𝐶𝑃 , specific heat at constant pressure.
𝑃
𝜕𝐻
Thus 𝑑𝐻 = 𝐶𝑃 𝑑𝑇 + ( 𝜕𝑃 ) 𝑑𝑃 …….(2)
𝑇

But H = U + PV, dH = dU + P dV + V dPAlso dQ = dU + PdV = T dS

Comparing the two equations dH = T dS + V dP
𝜕𝐻 𝜕𝑆
Differentiating with respect to pressure, ( 𝜕𝑃 ) = 𝑇 (𝜕𝑃) + 𝑉 ….(3)
𝑇 𝑇
𝜕𝑆 𝜕𝑉
From Maxwell’s fourth relation (𝜕𝑃) = − (𝜕𝑇 ) ……(4)
𝑇 𝑃
𝜕𝐻 𝜕𝑉
From (3) and (4) we get ( ) = −𝑇 ( ) + 𝑉 …..(5)
𝜕𝑃 𝑇 𝜕𝑇 𝑃

𝜕𝑉
Substituting (5) in (2) we get 𝑑𝐻 = 𝐶𝑃 𝑑𝑇 + [−𝑇 (𝜕𝑇 ) + 𝑉] 𝑑𝑃 ….(6)
𝑃

Since Joule – Thomson expansion is isenthalpic, dH = 0 ,

𝜕𝑉 𝜕𝑉
Thus 0 = 𝐶𝑃 𝑑𝑇 + [−𝑇 (𝜕𝑇 ) + 𝑉] 𝑑𝑃 or𝐶𝑃 𝑑𝑇 = [𝑇 (𝜕𝑇 ) − 𝑉] 𝑑𝑃
𝑃 𝑃

𝝏𝑻 𝟏 𝝏𝑽
Or 𝜇 = ( ) = [𝑻 ( ) − 𝑽] ……..(7)
𝝏𝑷 𝑪 𝝏𝑻 𝑯 𝑷 𝑷
𝝏𝑻 𝑻𝟐 𝝏 𝑽
𝝁 = ( ) = [ ( ) ]……(8)
𝝏𝑷 𝑪 𝝏𝑻 𝑻
𝑯 𝑷 𝑷
𝝏𝑻
where 𝝁 = (𝝏𝑷) is called the Joule Thomson coefficient which is the measure of
𝑯
change in temperature with pressure at constant enthalpy.

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 THERMODYNAMIC POTENTIALS, PHASE TRANSITION AND LOW TEMPERATURE PHYSICS
Since P2<P1 ,dPis negative. Thus, if µ is positive, then dT is negative implying cooling
effect. Similarly if µ is negative, then dT is positive implying heating effect. If µ is zero,
then no heating or cooling effect.
The physical reason for the above is the following
From equation (1) , since dH = 0 ,
𝜕𝐻 𝜕𝐻 𝜕𝐻 𝜕𝐻 𝜕𝑇 𝜕𝐻 𝜕𝑇
0 = ( 𝜕𝑇 ) 𝑑𝑇 + ( 𝜕𝑃 ) 𝑑𝑃 or ( 𝜕𝑇 ) 𝑑𝑇 = − ( 𝜕𝑃 ) 𝑑𝑃or (𝜕𝑃) = − ( 𝜕𝑃 ) (𝜕𝐻)
𝑃 𝑇 𝑃 𝑇 𝑇 𝑃

𝜕𝑇 𝜕𝐻 𝜕𝑇 𝜕𝐻 1
𝜇= ( ) = − ( ) ( ) = − ( )
𝜕𝑃 𝐻 𝜕𝑃 𝑇 𝜕𝐻 𝑃 𝜕𝑃 𝑇 𝐶𝑃
𝜕𝐻 𝜕𝑈 𝜕
Since H = U + PV, ( 𝜕𝑃 ) = ( 𝜕𝑃 ) + {𝜕𝑃 (𝑃𝑉)}
𝑇 𝑇
𝝏𝑻 𝟏 𝝏𝑼 𝝏
𝝁 = (𝝏𝑷) = − 𝑪 [(𝝏𝑷) + {𝝏𝑷 (𝑷𝑽)}]In this equation it is observed that Joule Thomson
𝑯 𝑷 𝑻
coefficient is made up of two terms – the first term is the measure of deviation from
Joule’s law and the second term is the deviation from the Boyles’ law.
For the perfect gas, both the terms are zero. Thus µ = 0. For real gases, the first term
produces cooling effect and the second term may produce cooling or heating effect
depending on the temperature and pressure.

Expression for Inversion temperature

The temperature, at which the Joule-Thomson effect changes sign, i.e., the
cooling effect becomes heating effect, is called the temperature of inversion.
𝑎
The van der waals equation of state is(𝑃 + ) (𝑉 − 𝑏) = 𝑅 𝑇 ….(1)
𝑉2
𝑎 𝑎𝑏
Simplifying 𝑃𝑉 + − 𝑃𝑏 − = 𝑅𝑇
𝑉 𝑉2
𝑎 𝑎𝑏 𝑅𝑇 𝑎 𝑎𝑏
𝑃𝑉 = 𝑅𝑇 − 𝑉 + 𝑃𝑏 + or 𝑉= − 𝑃𝑉 + 𝑏 +
𝑉2 𝑃 𝑃𝑉 2
𝑅𝑇 𝑎 𝑎𝑏𝑃
Replacing PV by RT, we get 𝑉 = − 𝑅𝑇 + 𝑏 + ……(2)
𝑃 𝑅2𝑇 2
𝜕𝑉 𝑅 𝑎 2𝑎𝑏𝑃
Differentiating with respect to T, (𝜕𝑇 ) = 𝑃 + 𝑅𝑇 2 − 𝑅2𝑇 3 …….(3)
𝑃
𝑅𝑇 𝑎 𝑎𝑏𝑃 𝑅 𝑉−𝑏 𝑎 𝑎𝑏𝑃
From (2) = 𝑉 − 𝑏 + 𝑅𝑇 − or = + 𝑅𝑇 2 − …..(4)
𝑃 𝑅2𝑇 2 𝑃 𝑇 𝑅2𝑇 3
𝜕𝑉 𝑉−𝑏 2𝑎 3𝑎𝑏𝑃
Substituting (4) in (3) and simplifying (𝜕𝑇 ) = + 𝑅𝑇 2 −
𝑃 𝑇 𝑅2𝑇 3

𝜕𝑉 2𝑎 3𝑎𝑏𝑃
Or 𝑇 (𝜕𝑇 ) = 𝑉 − 𝑏 + 𝑅𝑇 −
𝑃 𝑅2𝑇 2

𝜕𝑉 2𝑎
or𝑇 (𝜕𝑇 ) − 𝑉 = –𝑏 …….(5) The term involving the product of a and b is neglected.
𝑃 𝑅𝑇

𝜕𝑇 1 𝜕𝑉
The J – T coefficient is 𝜇 = (𝜕𝑃) = 𝐶 [𝑇 (𝜕𝑇 ) − 𝑉] ……(6)
𝐻 𝑃 𝑃

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 THERMODYNAMIC POTENTIALS, PHASE TRANSITION AND LOW TEMPERATURE PHYSICS
𝝏𝑻 𝟏 𝟐𝒂
Substituting (5) in (6) 𝝁 = ( ) = [ – 𝒃] ……(7)
𝝏𝑷 𝑯 𝑪𝑷 𝑹𝑻

For the real gases, the cooling or heating effect depends on van der waals constants a
and b.
𝟐𝒂
Case 1 If the intermolecular forces are very strong i.e., a >> b then >𝑏 .
𝑹𝑻

Hence µ > 0. Thus cooling effect takes place.

𝟐𝒂
Case 2 If the intermolecular forces are weak i.e., b > a then < 𝑏 . Hence µ < 0.
𝑹𝑻
Thus heating effect takes place.
𝟐𝒂
Case 3 If𝑹𝑻 = 𝒃then µ = 0, there is no heating or cooling

Thus Joule – Thomson effect changes sign at the temperature Ti called inversion
𝟐𝒂
temperature given by 𝑻𝒊 = .
𝑹𝒃
Thus, it is clear that if the initial temperature of a real gas is more than inversion
temperature, heating effect is produced. If the initial temperature is less than
inversion temperature and then passed through porous plug, cooling effect is
produced. It is called regenerative or Joule Thomson cooling.
Relation between inversion temperature and critical temperature
𝟐𝒂
The inversion temperature is 𝑻𝒊 = 𝑹𝒃 …..(1)
𝟖𝒂
The critical temperature is𝑻𝑪 = ……(2)
𝟐𝟕 𝑹 𝒃
𝑇𝑖 𝟐𝒂 𝟐𝟕 𝑹 𝒃 𝟐𝟕
Dividing (1) by (2) = × = = 𝟔. 𝟕𝟓or𝑻𝒊 = 𝟔. 𝟕𝟓 𝑻𝑪
𝑇𝐶 𝑹𝒃 𝟖𝒂 𝟒

Difference between Adiabatic expansion and Joule Thomson effect

S. No. Adiabatic expansion Joule Thomson effect

1 Work is done by the gas. Work is done by the gas or on the
gas.
2 Larger cooling of gas is produced. Smaller cooling of gas is produced.
3 Reversible process Irreversible process
4 Cooling is produced even in an ideal Joule Thomson effect is zero. i.e., no
gas heating or cooling is produced in an
ideal gas
5 Real gases produce only cooling It can be cooling or heating effect in
effect. case of real gases.

Adiabatic demagnetisation

It is a process of cooling. The principle is that a paramagnetic salt heats up when

placed in a magnetic field and cools down when removed from the magnetic field
adiabatically. This is called adiabatic demagnetisation.

Vijaya College : II Semester B.Sc. Physics Dr. K S Suresh 21

 THERMODYNAMIC POTENTIALS, PHASE TRANSITION AND LOW TEMPERATURE PHYSICS
Principle The process of magnetising a substance involves doing work on the
substance, which will slightly heat the substance. This work done in aligning the
elementary magnets (atoms of the substance) in the field direction is stored in the
substance in the form of magnetic energy. If such a substance is demagnetised
adiabatically, it has to do work and the energy required for this is drawn from within.
This results in the cooling of the substance.

Experimental setup :The experimental arrangement is as shown. The sample

Gadolinium sulphate which is a paramagnetic saltis suspended in a vessel
surrounded by liquid helium taken in the dewar flask D1. Itis surrounded by liquid
hydrogen taken in the dewar flask D2. The whole arrangement is kept between the
poles of a strong electromagnet.

The magnetic field is switched on so that the specimen is magnetised. The heat
generated during this process is removed by introducing hydrogen gas into the
chamber A and then pumping it out using a high vacuum pump so that the specimen
is thermally isolated. The specimen attains the temperature of the liquid helium which
is being pumped so that it boils
under reduced pressure. This
temperature is in the range of 1 K.
When the magnetic field is switched
off, adiabatic demagnetisation of the
specimen takes place and its
temperature falls.

According to Curie law the magnetic

susceptibility of a substance is
inversely proportional to the absolute
temperature. By measuring the
magnetic susceptibility of the substance using a mutual inductance coil, before and
after the demagnetisation, the final temperature is computed.Temperature in the
range of 0.001 K was attained by many researchers by using this method.
𝜒1 𝑇2
Theory :According to Curie’s law 𝜒 𝑇 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑜𝑟 𝜒2
= 𝑇1
where 1 and 2 are the
𝜒
susceptibility of the salt at temperatures T1 and T2 respectively.Or 𝑇2 = 𝜒1 𝑇1 …..(1)
2

From first law of thermodynamics dQ = dU + dW = dU + P dV

From second law dQ = T dS. Thus T dS = dU + P dV …..(2)
When a paramagnetic salt is placed in a magnetic field of flux density B, intensity of
magnetisation increases (dI). Thus work dome on the salt is dW = B dI.
Thus equation (2) becomes T dS = dU + P dV - BdI
As the process is carried out at constant pressure, dV = 0.
Thus T dS = dU – BdI …..(3)

Vijaya College : II Semester B.Sc. Physics Dr. K S Suresh 22

 THERMODYNAMIC POTENTIALS, PHASE TRANSITION AND LOW TEMPERATURE PHYSICS
Comparing (2) and (3) – B corresponds to P and Icorresponds to V.
𝜕𝑇 𝜕𝑉
From Maxwell thermodynamic equation (𝜕𝑃) = ( 𝜕𝑆 ) , Replacing P by – B and V by I
𝑆 𝑃
𝜕𝑇 𝜕𝐼 𝜕𝐼 𝜕𝑇 𝜕𝑇 𝜕𝐼 𝜕𝑆
we get − (𝜕𝐵) = (𝜕𝑆) = (𝜕𝑇) (𝜕𝑆 ) or(𝜕𝐵) = − (𝜕𝑇) / (𝜕𝑇) ……(4)
𝑆 𝐵 𝐵 𝐵 𝑆 𝐵 𝐵
𝜕𝑄 𝜕𝑆 1 𝜕𝑄 𝜕𝑆 𝑚 𝐶𝐵
As dQ = T dS or𝜕𝑆 = . Thus = (𝜕𝑇 ) or = ….(5)
𝑇 𝜕𝑇 𝑇 𝐵 𝜕𝑇 𝑇

where m is the mass of the specimen and CB is the specific heat at constant magnetic
𝜕𝑇 𝜕𝐼 𝑚 𝐶𝐵
field. Hence (𝜕𝐵) = − (𝜕𝑇) /
𝑆 𝐵 𝑇

𝜕𝑇 𝑇 𝜕𝐼 𝑻 𝝏𝑰
or( ) = − ( ) or 𝝏𝑻 = − (𝝏𝑻) 𝝏𝑩 ….(6)
𝜕𝐵 𝑆 𝑚 𝐶𝑃 𝜕𝑇 𝐵 𝒎 𝑪𝑩 𝑩
This gives the fall in temperature due to adiabatic demagnetisation.

Liquefaction of gases
1. Cascade process – It uses series of liquids with successively lower boiling points to
reach low temperatures in stages.

The apparatus used by Kamerlingh Onnes consists of three units, each of which
comprises of a compression pump and acondenser. In the first unit methyl
chloride is liquefied. Since the critical temperature of methyl chloride is -143"C,
it can beIiquefiedat the room temperature with a pressure of a few atmospheres.

Compressed methyl chloride gas from

pump P, is passed through the spiral
tube (shown straight in the figure)
inside the condenser A, while cold
water is circulated through the outer
jacket
of A. Liquid methyl chloride thus
obtained is made to circulate the jacket
of the condenser B of the second unit,
which is connected to
the suction side of P1, this enables the
liquid methyl chloride, which normally
boils at -240C to evaporate under reduced
pressure and
produce a fall of temperature to about - 90°C in B.

Compressed ethylene from pump P2ispassed through the spiral tube inside B. sinceit
has a critical temperature of 100C,it is readily liquefied in B maintained at about –
900C by the continuous circulation of liquid methyl chloride through it. Liquid
ethylene formed in B is made to flow round the jacket of the condenser C of the third
unit at the same time allowed to evaporate under reduced pressure by connecting the

Vijaya College : II Semester B.Sc. Physics Dr. K S Suresh 23