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Claussius clayperon equation

The Clausius-Clapeyron equation describes the relationship between pressure and temperature during phase changes of a substance in equilibrium. It establishes that the change in pressure with respect to temperature is proportional to the change in entropy and volume during the phase transition. The equation is derived from the principle that free energy remains constant between two phases at equilibrium, leading to the conclusion that dP/dT = ΔS/ΔV.

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18 views

Claussius clayperon equation

The Clausius-Clapeyron equation describes the relationship between pressure and temperature during phase changes of a substance in equilibrium. It establishes that the change in pressure with respect to temperature is proportional to the change in entropy and volume during the phase transition. The equation is derived from the principle that free energy remains constant between two phases at equilibrium, leading to the conclusion that dP/dT = ΔS/ΔV.

Uploaded by

mohamed2003imran
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Claussius clayperon equation

• The equilibrium can in any of the following two phases:


(i) Solid and Liquid, S = L, at the melting point of the solid.
(ii) Liquid and Vapor, L = V, at the boiling point of the solid.
(iii) Solid and Vapor, S = V, at the sublimation temperature of the solid.
(iv)One crystalline form and another crystalline form as, for example, rhombic and
monoclinic sulphur, SR = SM.

• Let us consider any two phases (say, solid and liquid) which
belongs to same substance and are in equilibrium with each
other at a given temperature and pressure. We know that in a
reversible reaction, the reaction can be change from one phase
to another by proceeding infinitesimally slow.
For example, by providing heat infinitesimally slowly to a system
containing any substance like solid can be changed into any form
like liquid at the same temperature and pressure. Similarly, by
withdrawing heat infinitesimally slow form system we can get
back the solid from the liquid without change in temperature
and pressure.
• As the system remains in a state of equilibrium, the free energy
change of either process will be zero.

Hence we conclude that in the two phases at equilibrium with each other,
equal amount of a given substance must have exactly the same free
energy.
Let us suppose a pure substance which is initially in phase A and then
changes to phase B. Both the phases are in equilibrium with each
other at given temperature and pressure.
Let GA be the free energy per mole of the substance in the initial phase A
and GB be the free energy per mole of the substance in the final phase
B and we know that the two phases at equilibrium with each other
having equal amount of a given substance have exactly the same free
energy.
GA = GB
Hence, there will be no free energy change, i.e.
∆G = GB – GA = 0
If the temperature of the above system is raised from T to T + dT
as well as the pressure from P to P + dP so that equilibrium will
maintained. The relationship between dT and dP can be obtained
from thermodynamics.
At the new temperature and pressure let the free energy per
mole of the substance in phase A be GA + dGA and that in phase B be
GB + dGB. As the two phases are still in equilibrium, hence their free
energy will be equal to each other i.e.

GA + dGA = GB + dGB ………………….. (1)

According to thermodynamics,
dG = VdP – SdT ……………….. (2)
• The above equation gives the change of free
energy when a system undergoes a change of
temperature dT and a change of pressure dP.
For phase A the equation (2) can be written as:
dG A = VA dP – SA dT
And
For phase B can be written as:
dG B = VB dP – SB dT
as GA = GB, hence, from equation (1),
dGA = dGB
therefore,
V GA dP – SA dT = VB dP – SB dT

dP / dT = (SB – SA) / (VB – VA)


as VA and VB are molar volumes of the pure
substance in the two phases A and B respectively.
Hence difference between them i.e. (VB – VA)
represents the change in volume when one mole
of the substance passes from initial phase A to
final phase B.
It can be represented as ∆V = VB – VA. Similarly entropy
change would be given as ∆S = SB – SA. Hence,
dP / dT = ∆S / ∆V
if the heat exchanged reversibly per mole of the
substance during phase transformation be q at
temperature T , then the change in entropy i.e. ∆S will
be given as:
∆S = q / T
Hence, dP / dT = q / T ∆V
• This equation is known as Clapeyron-Clausius
Equation.
• After comparing 187 and 190 equation we can
conclude that the content included in the
second bracket must beequal to zero
• We can say

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