Thermodynamic Potentials (Ch.

2)
[From: C. T. Sir]

3rd SEM (H) Class – 2

4. Adiabatic Demagnetisation:
One of the most powerful methods of producing very low temperatures is the adiabatic
demagnetisation of a paramagnetic salt. This method was first suggested independently
and almost simultaneously in 1926 by Giauque and Debye who, from theoretical
considerations, showed that a paramagnetic salt may be made to do magnetic work to
reach temperatures below 1K.

General principle – The principle of the method is based on temperature variation of

entropy for zero magnetic fields 𝐇 = 𝟎, and a field of 𝐇 = 𝐇𝟏 , say 15 KG or 1.5 Tesla, with
iron-ammonium alum shows that the entropy of the specimen is more with zero fields.
This is quite understandable if we consider the physics behind it: Due to thermal energy,
the spins of a paramagnetic sample are oriented at random when there is no field. But as
soon as a magnetic field is applied, the spins get partially aligned along the field-direction
and the entropy decreases, for the entropy of an ordered system is smaller.

This process of adiabatic demagnetisation through which the tremendous cooling can be
achieved with the ordered system of minimum entropy configuration, has two steps of
procedure which are

First stage: In the first stage when the salt specimen

gets cooled, down to about 1K by rapid evaporation
of liquid helium, the electromagnet is switched on
and the paramagnetic salt gets isothermally
magnetised. The heat produced on magnetisation is
conduced away by the helium gas to the liquid bath.

Second stage: In the second stage, the helium gas in

the interspace is pumped out to make the sample
thermally isolated and thus provide the necessary
adiabatic condition. The electromagnet is then
switched off slowly (taking several seconds) so that
the magnetic field reduces to zero, the process
being both adiabatic and reversible. As a result, the
paramagnetic salt is demagnetised without any
residual magnetism in it. The resulting molecular
orientations involve the expenditure of energy and this is obtained naturally from the
thermally insulated salt. Consequently, the salt is cooled to a sufficiently low
temperature. For instance, a temperature 0.003K was attained by this method by Kurti
and Simon using iron-ammonium alum as salt specimen; a temperature as low as 0.0014K
was reached by de Klerk and others with powdered crystals of chromium alum and
aluminium alum.

To measure such a low temperature, the magnetic susceptibility of the paramagnetic salt
sample was determined by a method of mutual inductance, the coils of the magnetic
thermometer being used for such measurements. But the actual value of the temperature
is computed by extrapolation method using a previously determined calibration curve
that represented the variation of magnetic susceptibility with temperature down to a
value of about 1K.

Theory – We give below an elementary treatment of the phenomenon of adiabatic

demagnetisation, the complete theory being somewhat involved.

The thermodynamic state of a paramagnetic substance, placed in a magnetic field of

strength 𝐁, is defined by the temperature 𝐓 and the magnetic moment 𝐌 only. The
𝛛𝐌
second 𝐓𝐝𝐒 - equation for a paramagnetic substance is 𝐓𝐝𝐒 = 𝐂𝐁 𝐝𝐓 + 𝐓( 𝛛𝐓 )𝐁 𝐝𝐁 where
𝐂𝐁 is the specific heat at constant magnetic field.

Since the process is adiabatic,

𝛛𝐌 𝐓 𝛛𝐌
𝐓𝐝𝐒 = 𝟎 ⟹ 𝐂𝐁 𝐝𝐓 + 𝐓( )𝐁 𝐝𝐁 = 𝟎 ⟹ 𝐝𝐓 = − ( ) 𝐝𝐁
𝛛𝐓 𝐂𝐁 𝛛𝐓 𝐁

𝛛𝐌
Now, for a paramagnetic substance, ( 𝛛𝐓 )𝐁 is always found to be negative. Also, since 𝐝𝐁 is
negative, the adiabatic demagnetisation of a paramagnetic salt will always lead to a drop
𝐓 𝛛𝐌
in temperature 𝐝𝐓 given by 𝐝𝐓 = − 𝐂 ( 𝛛𝐓 )𝐁 𝐝𝐁 . The phenomenon is therefore,
𝐁
sometimes termed as magneto-caloric effect.
𝐁
From Curie’s law 𝐌 = 𝐤 𝐓 so by differentiation

𝛛𝐌 𝐁 𝐤
( 𝛛𝐓 )𝐁 = −𝐤 𝐓𝟐 We thus get 𝐓𝐝𝐓 = 𝐂 𝐁𝐝𝐁
𝐁

If the magnetic field decreases from 𝐁𝐨 to zero and if 𝐓𝐨 𝐚𝐧𝐝 𝐓𝐟 be the respective initial
and final temperatures, the total drop in temperature is obtained by integrating above
equation
𝐓𝐟 𝐤 𝐨 𝐤
𝐓𝐨
𝐓𝐝𝐓 =𝐂 𝐁𝐨
𝐁𝐝𝐁 ⟹ 𝐓𝐟𝟐 − 𝐓𝐨𝟐 = − 𝐂 𝐁𝐨𝟐 [Assuming that 𝐂𝐁 does not vary with
𝐁 𝐁
𝐤
temperature in the relevant range]. Thus we get 𝐓𝐟 − 𝐓𝐨 = − 𝟐𝐂 𝐁𝐨𝟐 where
𝐁 𝐓𝐚𝐯
 𝟏 𝐤
𝐓𝐚𝐯 = 𝟐 (𝐓𝐟 + 𝐓𝐨 ) = average temperature of the specimen. So finally ∆𝐓 ≃ − 𝟐𝐂 𝐁𝐨𝟐
𝐁 𝐓𝐚𝐯

which shows that the drop in temperature is proportional directly to 𝐁𝐨𝟐 and inversely
to 𝐂𝐁 .

Note. In fact, 𝐂𝐁 varies with temperature as 𝐂𝐁 = 𝐚𝐓 𝟑 , a being a constant. Using this

𝟓𝐤
relation we get on integration, 𝐓𝐟𝟓 − 𝐓𝐨𝟓 = − 𝟐𝐚 𝐁𝐨𝟐 and this shows finally 𝐓𝐟 < 𝐓𝐢 i.e. the
fall in temperature.

5. Application of Clausius – Clapeyron Equation: Young and Kirchhoff’s

Equation of 1st Order Phase Transformation: Saturated Vapour Pressure:

𝐝𝐩 𝐋
We have from Clapeyron Equation in 1st Order phase transition 𝐝𝐓 = 𝐓 𝐯 −𝐯 . If we now
𝐟 𝐢
take vaporization of liquid, we then have 𝐯𝐟 = 𝐯𝐠 and 𝐯𝐢 = 𝐯𝐥 then for 𝐯𝐠 ≫ 𝐯𝐥 , we get
𝐝𝐩 𝐋
= 𝐓𝐯 where is latent heat of vaporization. If we assume that the vapour satisfies ideal
𝐝𝐓 𝐠
𝐕
gas equation 𝐏𝐕 = 𝐑𝐓, we get 𝐯𝐠 = 𝐌 where 𝐌 is the molecular weight.
𝐝𝐩 𝐋𝐌 𝐋𝐌𝐏 𝐝𝐏 𝐌𝐋 𝐝𝐓 𝐌𝐋 𝐁
So we get = = ⇒ = . 𝐓𝟐 ⇒ 𝐥𝐧𝐏 = − + 𝐀 = 𝐀 + 𝐓 ------------- (1)
𝐝𝐓 𝐓𝐕 𝐑𝐓 𝟐 𝐏 𝐑 𝐑𝐓
𝐌𝐋
where 𝐀 is a constant and 𝐁 = − .
𝐑

This equation (1) is known as Young’s equation which gives saturation vapour pressure at
several temperatures.
After that Kirchhoff considered that latent heat varies linearly withy temperature such
that 𝐋 = 𝐚 + 𝐛𝐓 where 𝐚 and 𝐛 are constants. Thus for that consideration, we have from
equation (1)
𝐝 𝐁 𝐌𝐋 𝐌 𝐌𝐚 𝐌𝐛 𝐌𝐚 𝐌𝐛
𝐥𝐧𝐏 = − 𝐓𝟐 = 𝐑𝐓𝟐 = 𝐑𝐓𝟐 𝐚 + 𝐛𝐓 = + 𝐑𝐓 ⇒ 𝐥𝐧𝐏 = − 𝐑𝐓 + 𝐥𝐧𝐓 + 𝐂 ---------- (2)
𝐝𝐓 𝐑𝐓 𝟐 𝐑

This equation (2) is comparatively more exact expression to give the variation of
saturation vapour pressure with temperature and this equation is known as Kirchhoff’s
equation.

6. Clausius Equation of 1st Order Phase Transition: Negative Specific Heat of

Saturated Steam:

This equation is also known as second latent equation which is related with second order
phase transition. If 𝐬𝐢 and 𝐬𝐟 are the respective specific entropies at 1st and 2nd phase then
we have
𝐋 𝐝 𝐋 𝐝𝐬𝐟 𝐝𝐬 𝐝𝐋 𝐋 𝐝𝐬 𝐝𝐬
𝐬𝐟 − 𝐬𝐢 = 𝐓 . In this case we can have 𝐝𝐓 = − 𝐝𝐓𝐢 ⇒ 𝐝𝐓 − 𝐓 = 𝐓 𝐝𝐓𝐟 − 𝐓 𝐝𝐓𝐢 = 𝐜𝐟 − 𝐜𝐢
𝐓 𝐝𝐓
Here 𝐜𝐢 and 𝐜𝐟 are respective specific heats at initial and final phase.

Particularly, if we now take vaporization, i.e. the transition from liquid to vapour phase
then 𝐜𝐟 will be the specific heat at final saturated vapour phase and then it can be
denoted by (𝐜𝐟 )𝐬 .

Again at the time of boiling, the liquid and its saturated vapour are in contact with each
other, we can also denote 𝐜𝐢 by (𝐜𝐢 )𝐬 and in that case we get
𝐝𝐋 𝐋
− 𝐓 = (𝐜𝐟 )𝐬 − (𝐜𝐢 )𝐬 ----------------- (1)
𝐝𝐓

This equation (1) is known as Clausius equation which is also known as second latent heat
equation which basically gives the variation of latent heat with temperature. Here for
specific entropy, let us take

𝛛𝐬 𝛛𝐬 𝐝𝐬 𝛛𝐬 𝛛𝐬 𝐝𝐏
𝐬 = 𝐬 𝐓, 𝐏 ⇒ 𝐝𝐬 = ( )𝐏 𝐝𝐓 + ( )𝐓 𝐝𝐏 ⇒ 𝐓( )𝐬𝐚𝐭 = 𝐓( )𝐏 + 𝐓( )𝐓 ( )𝐬𝐚𝐭
𝛛𝐓 𝛛𝐏 𝐝𝐓 𝛛𝐓 𝛛𝐏 𝐝𝐓
𝛛𝐯 𝐝𝐏
So saturated specific heat is given by 𝐜𝐬 = 𝐜𝐏 − 𝐓(𝛛𝐓)𝐏 (𝐝𝐓)𝐬𝐚𝐭 [By using Maxwell’s
relation]
𝛛𝐯 𝐝𝐏 𝛛𝐯 𝐝𝐏
Thus we have (𝐜𝐟 )𝐬 = (𝐜𝐏 )𝐟 − 𝐓( 𝛛𝐓𝐟)𝐏 (𝐝𝐓)𝐬𝐚𝐭 , (𝐜𝐢 )𝐬 = (𝐜𝐏 )𝐢 − 𝐓( 𝛛𝐓𝐢)𝐏 (𝐝𝐓)𝐬𝐚𝐭

Hence from equation (1) we get

𝐝𝐋 𝐋 𝐝𝐏 𝛛𝐯𝐟 𝛛𝐯𝐢
− = (𝐜𝐟 )𝐬 − (𝐜𝐢 )𝐬 = (𝐜𝐏 )𝐟 − (𝐜𝐏 )𝐢 − 𝐓( )𝐬𝐚𝐭{( )𝐏 − ( )𝐏 }
𝐝𝐓 𝐓 𝐝𝐓 𝛛𝐓 𝛛𝐓
𝐝𝐋 𝐋 𝐝𝐏 𝛛𝐯 𝛛𝐯
Finally we get = 𝐓 + (𝐜𝐏 )𝐟 − (𝐜𝐏 )𝐢 − 𝐓(𝐝𝐓)𝐬𝐚𝐭 {( 𝛛𝐓𝐟)𝐏 − ( 𝛛𝐓𝐢)𝐏 } ------------------ (2)
𝐝𝐓

This equation (2) gives another form of Clausius equation for vaporisation of liquid in 1st
order phase transition.

If we now take specially vaporization of water then in that case since, latent heat of water
decreases with increase of temperature and near boiling point of water
𝐝𝐋
= −𝟎. 𝟔𝟒 𝐮𝐧𝐢𝐭 (as obtained experimentally), we then have
𝐝𝐓
for(𝐜𝐢 )𝐬 = 𝐬𝐩 𝐡𝐞𝐚𝐭 𝐨𝐟 𝐰𝐚𝐭𝐞𝐫 𝐚𝐭 𝟏𝟎𝟎𝐨 𝐂 = 𝟏. 𝟎𝟏, 𝐋 = 𝟓𝟒𝟎 𝐜𝐚𝐥/𝐠

We get from equation (1)

𝐝𝐋 𝐋 𝟓𝟒𝟎
(𝐜𝐟 )𝐬 = (𝐜𝐢 )𝐬 + − = 𝟏. 𝟎𝟏 − 𝟎. 𝟔𝟒 − = −𝟏. 𝟎𝟕 𝐜𝐚𝐥
𝐝𝐓 𝐓 𝟑𝟕𝟑

Thus the specific heat of saturated steam is negative which is also the experimental fact
7. Ehrenfest Equation of Second Order Phase Transition:
Since in second order phase transition, the 1st order derivative of Gibbs potential remains
continuous at transition, the entropy will then remain constant at transition. Thus in this
case of 2nd order phase transition, since 𝐬𝟏 = 𝐬𝟐 ⇒ 𝐝𝐬𝟏 = 𝐝𝐬𝟐 ------------------ (1)

We have for 𝐬 = 𝐬 𝐓, 𝐏
𝛛𝐬 𝛛𝐬 𝛛𝐬 𝛛𝐯 𝟏
𝐝𝐬 = (𝛛𝐓)𝐏 𝐝𝐓 + (𝛛𝐏)𝐓 𝐝𝐏 = (𝛛𝐓)𝐏 𝐝𝐓 − (𝛛𝐓)𝐏 𝐝𝐏 = 𝐓 𝐜𝐏 𝐝𝐓 − 𝐯𝛂𝐝𝐏 [By Maxwell’s
relation] where symbols have their usual meanings.]

Again since volume does not change in second order phase transition; this specific volume
must remain unchanged at transition and remain the same at both phases and then we
have
𝟏 𝟏
𝐝𝐬𝟏 = 𝐓 (𝐜𝐏 )𝟏 𝐝𝐓 − 𝐯𝛂𝟏 𝐝𝐏 and 𝐝𝐬𝟐 = 𝐓 (𝐜𝐏 )𝟐 𝐝𝐓 − 𝐯𝛂𝟐 𝐝𝐏

𝟏 𝟏
Thus from equation (1) we get (𝐜𝐏 )𝟏 𝐝𝐓 − 𝐯𝛂𝟏 𝐝𝐏 = (𝐜𝐏 )𝟐 𝐝𝐓 − 𝐯𝛂𝟐 𝐝𝐏
𝐓 𝐓

𝐝𝐏 (𝐜𝐏 )𝟐 −(𝐜𝐏 )𝟏
And then we get (𝐝𝐓)𝐬 = -------------------- (2)
𝐓𝐯 𝛂𝟐 −𝛂𝟏

Again for volume remaining unchanged at second order phase transition, we also get

𝐯𝟏 = 𝐯𝟐 ⇒ 𝐝𝐯𝟏 = 𝐝𝐯𝟐 --------------------- (3)

𝛛𝐯 𝛛𝐯
We have for 𝐯 = 𝐯 𝐓, 𝐏 , 𝐝𝐯 = (𝛛𝐓)𝐏 𝐝𝐓 + (𝛛𝐏)𝐓 𝐝𝐏 = 𝐯𝛂𝐝𝐓 − 𝐯𝐂𝐓 𝐝𝐏

Thus from equation (3) 𝐯𝛂𝟏 𝐝𝐓 − 𝐯(𝐂𝐓 )𝟏 𝐝𝐏 = 𝐯𝛂𝟐 𝐝𝐓 − 𝐯(𝐂𝐓 )𝟐 𝐝𝐏

𝐝𝐏 𝛂𝟐 −𝛂𝟏
Finally we get (𝐝𝐓)𝐯 = (𝐂 ------------------- (4)
𝐓 )𝟐 −(𝐂𝐓 )𝟏

These equations (2) and (4) are known as Ehrenfest equation of 2nd order phase transition.