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Derive The Gibbs-Duhem Equation and Give Its Applications?

The Gibbs-Duhem equation relates the chemical potentials of the components in a mixture at equilibrium. It can be derived from the Gibbs free energy expression. The Gibbs-Duhem equation has applications in calculating partial molar quantities and partial vapor pressures from experimental data. The Nernst heat theorem states that the entropy and heat capacity differences between products and reactants approach zero as temperature approaches absolute zero. The Clapeyron-Clausius equation relates the change in pressure to the change in temperature during a first-order phase transition at a fixed composition. It can be derived using thermodynamic relationships and considering two phases in equilibrium.

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517 views4 pages

Derive The Gibbs-Duhem Equation and Give Its Applications?

The Gibbs-Duhem equation relates the chemical potentials of the components in a mixture at equilibrium. It can be derived from the Gibbs free energy expression. The Gibbs-Duhem equation has applications in calculating partial molar quantities and partial vapor pressures from experimental data. The Nernst heat theorem states that the entropy and heat capacity differences between products and reactants approach zero as temperature approaches absolute zero. The Clapeyron-Clausius equation relates the change in pressure to the change in temperature during a first-order phase transition at a fixed composition. It can be derived using thermodynamic relationships and considering two phases in equilibrium.

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kannan2030
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© © All Rights Reserved
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Derive the Gibbs-Duhem Equation and give

its Applications?
Gibbs-Duhem Equation
The Gibbs free energy can be defined in two different ways once by subtracting off combinations
of entropy S, enthalpy H and temperature T and other as a sum of chemical potentials and
amounts of species. The fact that they are equal gives a new relation known as “Gibbs-Duhem
Relation.” The Gibbs-Duhem relation helps us to calculate relationships between quantities as a
system which remains in equilibrium. One example is the Clausius-Clapeyron equation which
states that two phases at equilibrium with each other having equaled amount of a given substance
must have exactly the same free energy i.e. it relates equilibrium changes in pressure to changes
in temperature as a function of material parameters.

Deriving the Gibbs-Duhem equation from thermodynamics state equations is very easy. The
Gibbs free energy G in equilibrium can be expressed in terms of thermodynamics as:

dG = μ1 dn1 + n1 dμ1 + μ2 dn2 + n2 dμ2……….. μj dnj + nj dμj


= (μ1 dn1 + μ2 dn2 + ……… μj dnj) + (n1 dμ1 + n2 dμ2 +……….. nj dμj)

At constant temperature and pressure, the above equation can be written as:
n1 dμ1 + n2 dμ2 +……….. nj dμj = 0
∑ ni dμi = 0 …………………….. (1)
Because at constant temperature and pressure, (μ1 dn1 + μ2 dn2 + ……… μj dnj) = dG
The equation (1) is known as the Gibbs-Duhem equation.

Applications of Gibbs-Duhem equation:


(i) Gibbs-duhem equation is helpful in calculating partial molar quantity of a binary mixture by
measuring the composition of the mixture which depends on the total molar quantity.

(ii) Gibbs-duhem equation is helpful in calculating the partial vapor pressures by calculating the
total vapor pressure. All these calculations require a curve-fitting procedure. Using tabulated
experimental data the accuracy of the calculated quantities was found to be comparable to the
accuracy of the original experimental data.

Define the Nernst Heat Theorem


The Nernst Heat Theorem
Let us consider the Gibbs-Helmholtz equation which includes chemical reaction i.e.:
∆G – ∆H = T (∂ (∆G)/∂T) P ………………………………….. (1)
Where ∆G ——-> change in free energy
∆H ——-> change in enthalpy

At absolute zero i.e. T = 0,


Equation (1) will become:
∆G = ∆H

A scientist Richard measures the E.M.F. of the cells at different temperatures. He found that the
value of ∂ (∆G)/∂T decreases with decrease in temperature.

Hence from this it is concluded that ∆G and ∆H tends to approach each other more and more
closely as the temperature is lowered. Nernst discovered that ∂ (∆G)/∂T tends to approach to zero
as the temperature is lowered to absolute zero. This is known as Nernst Heat Theorem.

Mathematically, The Nernst Heat Theorem can be expressed as:


Lt (T –> 0) [∂ (∆G) / ∂T] P = Lt (T –> 0) [∂ (∆H) / ∂T] P = 0 ………………………….. (2)
Where Lt means limiting value.

From the second law of thermodynamics,


[∂ (∆G) / ∂T] P = – ∆S ……………………. (3)
And [∂ (∆H) / ∂T] P = ∆CP …………………… (4)
Where ∆S ———-> Entropy change of the reaction
∆CP ——-> difference in the heat capacities of the products and the reactants.

From equation (2), (3) and (4), we will get:


Lt (T –> 0) ∆S = 0
Lt (T –> 0) ∆CP = 0

This means that entropy change of a reaction tends to approach to zero and the difference in the
heat capacities of the products and the reactants also tends to approach to zero as the temperature
is lowered to absolute zero.

Explain Clapeyron-Clausius Equation and


also give its derivation
Clapeyron discovered an important fundamental equation which helps in finding the extensive
application in one component, two phase system and by Clausius from second law of
thermodynamics. Hence this fundamental equation is known as Clapeyron-Clausius Equation.
One of the uses of this equation is to determine if a phase transition will occur in a given
situation

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

Thus, dP / dT = q / T (VB – VA)


This equation is known as Clapeyron-Clausius Equation.

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