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Lecture 5: Third Law of Thermodynamics Maxwell Relations Gibbs Free Energy

This document discusses the third law of thermodynamics and Maxwell relations. It begins by explaining how the third law states that the entropy of a substance approaches zero as the temperature approaches absolute zero in the limit of an infinite number of steps, but cannot actually reach zero in a finite number of steps. It then introduces Maxwell relations, which provide relationships between partial derivatives of thermodynamic quantities that can be used to express experimentally hard to measure quantities like entropy in terms of experimentally measurable ones. Specific Maxwell relations are shown and examples are given of how they can be used to rationalize results from experiments like Joule and Joule-Thomson experiments. Graphs are presented showing how Gibbs free energy varies with temperature and pressure.

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84 views14 pages

Lecture 5: Third Law of Thermodynamics Maxwell Relations Gibbs Free Energy

This document discusses the third law of thermodynamics and Maxwell relations. It begins by explaining how the third law states that the entropy of a substance approaches zero as the temperature approaches absolute zero in the limit of an infinite number of steps, but cannot actually reach zero in a finite number of steps. It then introduces Maxwell relations, which provide relationships between partial derivatives of thermodynamic quantities that can be used to express experimentally hard to measure quantities like entropy in terms of experimentally measurable ones. Specific Maxwell relations are shown and examples are given of how they can be used to rationalize results from experiments like Joule and Joule-Thomson experiments. Graphs are presented showing how Gibbs free energy varies with temperature and pressure.

Uploaded by

Chegg Bolthe
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Lecture 5: Third law of

thermodynamics;

Maxwell relations;

Gibbs free energy

Arti Dua

Department of Chemistry

IIT Madras

!
Third law of thermodynamics
Third law of thermodynamics
How to bring down the temperature of a substance?

Suppose the entropy of a substance, S(T, X) where X is p or V, is varied as a function of



temperature, then the temperature can be decreased by carrying out a series of isothermal

and isentropic processes, shown below

Can reach T= 0K in finite number of steps,



Can only reach T= 0K in infinite number of steps

but not allowed by the third law as Delta S

implying T = 0K can not be realized in practice.
does not approach zero as T approaches 0K
Fundamental Equations
For a closed system we have introduced all the state functions

Fundamental Equations:

Can derive Maxwell relations from fundamental equations...


Maxwell Relations

• Provide relationships between different partial


derivatives.

• Certain thermodynamic quantities, like
entropy, Helmholtz and Gibbs free energies
etc are hard to measure experimentally.

• Using Maxwell relations, one can express the
above quantities (S, A, G…) in terms of
experimentally measurable quantities.
Maxwell Relations

U is an exact differential

Maxwell Relations:
Maxwell Relations

Since A, G are exact differentials

Maxwell Relations:

These can be obtained from equation of state.


The Four most common Maxwell Relations

& ∂T # & ∂P #
$ ! = −$ !
% ∂V " S % ∂S "V

& ∂T # & ∂V #
$ ! =$ !
% ∂P " S % ∂S " P

& ∂S # & ∂P #
$ ! =$ !
% ∂V "T % ∂T "V

& ∂S # & ∂V #
$ ! = −$ !
% ∂P "T % ∂T " P
Using Maxwell Relations

Joule coefficient:

Joule Thomson coefficient:

We used these expressions to rationalize results in Joule and Joule Thomson experiments.

Ideal gas Real gas

U (T)
Using Maxwell Relations
The variation of Gibbs Free Energy with temperature

Gas
Because S>0 for all substances, G always

decreases when the temperature is raised.
G
Liquid
G decreases most sharply when the

Solid
entropy of the system is large

T
The variation of Gibbs Free Energy with temperature

Gibbs-Helmholtz equation

Can be used to calculate changes in physical


states and chemical reactions at constant p
The variation of Gibbs Free Energy with pressure
The variation of Gibbs Free Energy with pressure

Ideal gases:

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