Week4: Summary P age |1

For homogenous closed system of n moles

𝑑(𝑛𝑈) = 𝑇 𝑑 (𝑛𝑆) − 𝑃 𝑑 (𝑛𝑉) (34)


In terms of molar properties
(35)
𝑑𝑈 = 𝑇 𝑑𝑆 − 𝑃 𝑑𝑉

Typical units
𝑈: 𝐉 𝐦𝐨𝐥G𝟏 , 𝑆 ∶ 𝐉 𝐦𝐨𝐥G𝟏 𝐊 G𝟏 , 𝑉 ∶ 𝐦𝟑 𝐦𝐨𝐥G𝟏 𝑃: 𝐏𝐚, 𝑇 ∶ 𝐊, 𝑛 ∶ 𝐦𝐨𝐥𝐞𝐬

𝐻 = 𝑈 + 𝑃𝑉 𝐴 = 𝑈 − 𝑇𝑆 𝐺 = 𝐻 − 𝑇𝑆 (36)

𝑑𝐻 = 𝑇 𝑑𝑆 + 𝑉 𝑑𝑃 𝑑𝐴 = −𝑃 𝑑𝑉 − 𝑆 𝑑𝑇 𝑑𝐺 = 𝑉 𝑑𝑃 − 𝑆 𝑑𝑇 (37)

𝜕𝑈 𝜕𝑈 𝜕𝐻 𝜕𝐻 (38)
Z \ = 𝑇 Z \ = −𝑃 Z \ = 𝑇 Z \ = 𝑉
𝜕𝑆 ] 𝜕𝑉 ^ 𝜕𝑆 _ 𝜕𝑃 ^

𝜕𝐴 𝜕𝐴 𝜕𝐺 𝜕𝐺
Z \ = −𝑃 Z \ = −𝑆 Z \ = 𝑉 Z \ = −𝑆 (39)
𝜕𝑉 ` 𝜕𝑇 ] 𝜕𝑃 ` 𝜕𝑇 _

Maxwell’s relations
𝜕𝑇 𝜕𝑃 𝜕𝑇 𝜕𝑉
Z \ = − Z \ Z \ = − Z \
𝜕𝑉 ^ 𝜕𝑆 ] 𝜕𝑃 ^ 𝜕𝑆 _ (40)
𝜕𝑃 𝜕𝑆 𝜕𝑉 𝜕𝑆
Z \ = Z \ Z \ = − Z \
𝜕𝑇 ] 𝜕𝑉 ` 𝜕𝑇 _ 𝜕𝑃 `
(41)

m] p` m] (42)
𝑑𝐻 = 𝐶j 𝑑𝑇 + k𝑉 − 𝑇 lm` n o 𝑑𝑃 𝑑𝑆 = 𝐶j `
− lm` n 𝑑𝑃
_ _

𝜕𝑈 𝜕𝑉 𝜕𝑉 (43)
Z \ = −𝑇 Z \ − 𝑃 Z \
𝜕𝑃 ` 𝜕𝑇 _ 𝜕𝑃 `

For liquids
ms p` (44)
l n = (𝜅𝑃 − 𝛽𝑇)𝑉 𝑑𝐻 = 𝐶j 𝑑𝑇 + (1 − 𝛽𝑇) 𝑉 𝑑𝑃 𝑑𝑆 = 𝐶j − 𝛽𝑉 𝑑𝑃
m_ ` `
Week4: Summary P age |2

𝐺 𝐺 (45)
𝐺 𝑉 𝐻 𝜕l n 𝑉 𝜕l n 𝐻
𝑑Z \ = 𝑑𝑃 − 𝑑𝑇 x 𝑅𝑇 y = x 𝑅𝑇 y = − w
𝑅𝑇 𝑅𝑇 𝑅𝑇 w 𝜕𝑃 𝑅𝑇 𝜕𝑇 𝑅𝑇
` _


The residual property 𝑀{ at desired T , P is defined as
𝑀{ = 𝑀 − 𝑀}~ (46)

Note that M and 𝑀}~ are also at the same T and P.

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