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457454 Physical Chemistry Quantum Chemistry

457454 Physical Chemistry Quantum Chemistry

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Published by: el_cachero on Feb 07, 2010
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04/19/2013

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Consider a homogeneous substance consisting of two phases α and β at a constant
T and V.

Suppose some amount of material, dn, goes from αβ

(dAα)T =−PdVαμαdn
(dAβ)T =−PdVβ +μβdn
(dA)T,V =−P

= 0 since V is constant

z }| {
(dVα +dVβ) +¡μβμα

¢dn

For a spontaneous process A deceases (dA < 0)

At equilibrium dA = 0. This implies μβ = μα is the condition for equilibrium.

When α, β denote liquid (or solid) and vapor phases, then for a given T, the
pressure of the system when μβ = μα is the called the vapor pressure of the
material at temperature T.

296

For phase changes at constant T and P then (dG)T,P = ¡μβμα

¢dn. So again

μβ = μα is the condition for equilibrium.

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