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26491797 457454 Physical Chemistry Quantum Chemistry[1]

26491797 457454 Physical Chemistry Quantum Chemistry[1]

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Published by: rajasebastian on May 21, 2011
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02/12/2013

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Consider the first law for a reversible change at constant volume.

dU = dq +dw = dqPexdV

(18.6)

From our earlier discussion of heat capacity dq = CVdT (CV since constant vol-
ume). So,

dU = CVdT

(18.7)

but also dU = TdS. So

dS = CVdT

T =⇒4S = Z T2

T1

CV
T dT.

(18.8)

127

A very similar derivation can be done for a reversible change at constant pressure
(we can not do it quite yet) to yield

4S = Z T2
T1

CP
T dT

(18.9)

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