CL255 Equations

Real mixture/pure component properties

Extensive properties Intensive molar property Intensive mixture

(for single component or (for single component or mixtures) partial molar property
mixtures) (for mixtures)
Gibbs phase rule Gibbs phase rule
𝐹 =𝐶−𝑃+2 𝐹 =𝐶−𝑃+2
𝐾 𝐾
Mole balance 𝑑𝑁𝑖 𝑑𝑁𝑖
= ∑(𝑁̇𝑖 )𝑘 = ∑(𝑁̇𝑖 )𝑘
𝑑𝑡 𝑑𝑡
𝑘=1 𝑘=1
Energy balance 𝐾 𝐾
𝑑𝑈 𝑑𝑉 𝑑𝑈 𝑑𝑉
= ∑(𝑁̇𝐻)𝑘 + 𝑄̇ + 𝑊̇𝑠 − 𝑃 = ∑(𝑁̇𝐻)𝑘 + 𝑄̇ + 𝑊̇𝑠 − 𝑃
𝑑𝑡 𝑑𝑡 𝑑𝑡 𝑑𝑡
𝑘=1 𝑘=1
Entropy balance 𝐾 𝐾
𝑑𝑆 𝑄̇ 𝑑𝑆 𝑄̇
̇
= ∑(𝑁̇𝑆)𝑘 + + 𝑆𝑔𝑒𝑛 ̇
= ∑(𝑁̇𝑆)𝑘 + + 𝑆𝑔𝑒𝑛
𝑑𝑡 𝑇 𝑑𝑡 𝑇
𝑘=1 𝑘=1
𝐻 = 𝑈 + 𝑃𝑉 𝐻 = 𝑈 + 𝑃𝑉 𝐻𝑖 = 𝑈𝑖 + 𝑃𝑉𝑖
𝐴 = 𝑈 − 𝑇𝑆 𝐴 = 𝑈 − 𝑇𝑆 𝐴𝑖 = 𝑈𝑖 − 𝑇𝑆𝑖
𝐺 = 𝐻 − 𝑇𝑆 𝐺 = 𝐻 − 𝑇𝑆 𝐺𝑖 = 𝐻𝑖 − 𝑇𝑆𝑖
1 𝜕𝑁𝜃 𝜕𝜃
𝜃 = 𝑁𝜃 = ∑ 𝑁𝑖 𝜃𝑖 𝜃= ∑ 𝑁𝑖 𝜃𝑖 = ∑ 𝑥𝑖 𝜃𝑖 𝜃𝑖 = ( ) =( )
𝑖
𝑁 𝜕𝑁𝑖 𝑇,𝑃,𝑁 𝜕𝑁𝑖 𝑇,𝑃,𝑁
𝑖 𝑖 𝑗≠𝑖 𝑗≠𝑖
Change of property upon mixing Δ𝑚𝑖𝑥 𝜃 = 𝜃(𝑇, 𝑃, {𝑥}) − ∑ 𝑥𝑖 𝜃𝑖 (𝑇, 𝑃)
Δ𝑚𝑖𝑥 𝜃 = 𝜃(𝑇, 𝑃, {𝑥}) 𝑖
− ∑ 𝑁𝑖 𝜃𝑖 (𝑇, 𝑃) = ∑ 𝑥𝑖 (𝜃𝑖 (𝑇, 𝑃, {𝑥}) − 𝜃𝑖 (𝑇, 𝑃))
𝑖 𝑖
Constant volume heat capacity 𝜕𝑈 𝜕𝑆 𝜕𝐻𝑖 𝜕𝑆𝑖
𝐶𝑉 = ( ) = 𝑇 ( ) 𝐶𝑃,𝑖 = ( ) = 𝑇( )
𝜕𝑇 𝑉 𝜕𝑇 𝑉 𝜕𝑇 𝑃 𝜕𝑇 𝑃
𝜕𝐻 𝜕𝑆
Constant pressure heat capacity 𝐶𝑃 = ( ) = 𝑇 ( )
𝜕𝑇 𝑃 𝜕𝑇 𝑃
1 𝜕𝑉 𝐶𝑃 = ∑ 𝑥𝑖 𝐶𝑃,𝑖
Isothermal compressibility 𝜅𝑇 = − ( ) 𝑖
𝑉 𝜕𝑃 𝑇

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CL255- List of thermodynamic equations/relations Prof. A. Chatterjee, Department of Chemical Engineering, IIT Bombay
Thermal expansion coefficient 1 𝜕𝑉
𝛼=( )
𝑉 𝜕𝑇 𝑃
𝜕𝑉
𝑉 −𝑇( )
Joule-Thomson coefficient 𝜕𝑇 𝑃
𝜇=−
𝐶𝑃
Thermodynamic functions 𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 𝑑𝑈𝑖 = 𝑇𝑑𝑆𝑖 − 𝑃𝑑𝑉𝑖
(for closed system)
𝜕𝑃 𝑑𝐻𝑖 = 𝑇𝑑𝑆𝑖 + 𝑉𝑖 𝑑𝑃
𝑑𝑈 = 𝐶𝑉 𝑑𝑇 + [𝑇 ( ) − 𝑃] 𝑑𝑉
𝜕𝑇 𝑉
𝑑𝐴𝑖 = −𝑃𝑑𝑉𝑖 − 𝑆𝑖 𝑑𝑇
𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃
𝑑𝐺𝑖 = 𝑉𝑖 𝑑𝑃 − 𝑆𝑖 𝑑𝑇
𝜕𝑉
𝑑𝐻 = 𝐶𝑃 𝑑𝑇 + [𝑉 − 𝑇 ( ) ] 𝑑𝑃
𝜕𝑇 𝑃

𝐶𝑃 𝜕𝑉
𝑑𝑆 = 𝑑𝑇 − ( ) 𝑑𝑃
𝑇 𝜕𝑇 𝑃

𝑑𝐴 = −𝑃𝑑𝑉 − 𝑆𝑑𝑇

𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇

Thermodynamic functions Single component Mixture

(for open system) 𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 + 𝐺𝑑𝑁 𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 + ∑ 𝐺𝑖 𝑑𝑁𝑖
𝑖
𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃 + 𝐺𝑑𝑁
𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃 + ∑ 𝐺𝑖 𝑑𝑁𝑖
𝑖
𝑑𝐴 = −𝑃𝑑𝑉 − 𝑆𝑑𝑇 + 𝐺𝑑𝑁
𝑑𝐴 = −𝑃𝑑𝑉 − 𝑆𝑑𝑇 + ∑ 𝐺𝑖 𝑑𝑁𝑖
𝑖
𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 + 𝐺𝑑𝑁
𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 + ∑ 𝐺𝑖 𝑑𝑁𝑖
𝑖

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CL255- List of thermodynamic equations/relations Prof. A. Chatterjee, Department of Chemical Engineering, IIT Bombay
Maxwell relations 𝜕𝑇 𝜕𝑃
( ) = −( )
𝜕𝑉 𝑆 𝜕𝑆 𝑉

𝜕𝑇 𝜕𝑉
( ) =( )
𝜕𝑃 𝑆 𝜕𝑆 𝑃

𝜕𝑃 𝜕𝑆
( ) =( )
𝜕𝑇 𝑉 𝜕𝑉 𝑇

𝜕𝑉 𝜕𝑆
() = −( )
𝜕𝑇 𝑃 𝜕𝑃 𝑇
Thermodynamic identities 𝜕𝐻 𝜕𝑈
( ) =( ) =𝑇
𝜕𝑆 𝑃 𝜕𝑆 𝑉

𝜕𝐺 𝜕𝐻
( ) =( ) =𝑉
𝜕𝑃 𝑇 𝜕𝑃 𝑆

𝜕𝑈 𝜕𝐴
( ) = ( ) = −𝑃
𝜕𝑉 𝑆 𝜕𝑉 𝑇

𝜕𝐴 𝜕𝐺
( ) = ( ) = −𝑆
𝜕𝑇 𝑉 𝜕𝑇 𝑃
Other relations 𝜕𝑈 𝜕𝐻 𝜕𝐴 𝜕𝐺 𝜕𝑈 𝜕𝐻 𝜕𝐴
𝐺=( ) =( ) =( ) =( ) 𝐺𝑖 = ( ) =( ) =( )
𝜕𝑁 𝑆,𝑉 𝜕𝑁 𝑆,𝑃 𝜕𝑁 𝑇,𝑉 𝜕𝑁 𝑇,𝑃 𝜕𝑁𝑖 𝑆,𝑉,𝑁 𝜕𝑁𝑖 𝑆,𝑃,𝑁 𝜕𝑁𝑖 𝑇,𝑉,𝑁
𝑗≠𝑖 𝑗≠𝑖 𝑗≠𝑖
𝜕𝐺
=( )
𝜕𝑁𝑖 𝑇,𝑃,𝑁
𝑗≠𝑖
Gibbs-Duhem equations At constant temperature and pressure

∑ 𝑥𝑖 𝑑𝜃𝑖 = 0
𝑖
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CL255- List of thermodynamic equations/relations Prof. A. Chatterjee, Department of Chemical Engineering, IIT Bombay
Fugacity and fugacity coefficient 𝐺(𝑇, 𝑃) − 𝐺 𝐼𝐺 (𝑇, 𝑃) 𝐺𝑖 (𝑇, 𝑃, {𝑥}) − 𝐺𝑖 (𝑇, 𝑃, {𝑥})
𝐼𝐺𝑀
𝑓(𝑇, 𝑃) = 𝑃 exp ( ) 𝑓𝑖 (𝑇, 𝑃, {𝑥}) = 𝑃 exp ( )
𝑅𝑇 𝑅𝑇
1 𝑃 𝑅𝑇
= 𝑃 exp ( ∫ (𝑉 − ) 𝑑𝑃) 1 𝑃
𝑅𝑇 0 𝑃 = 𝑥𝑖 𝑃 exp ( ∫ (𝑉𝑖 (𝑇, 𝑃, {𝑥})
𝑅𝑇 0
𝐼𝐺𝑀
− 𝑉𝑖 (𝑇, 𝑃, {𝑥})) 𝑑𝑃)

𝑓(𝑇, 𝑃) 𝑓𝑖 (𝑇, 𝑃, {𝑥})

𝜙(𝑇, 𝑃) = 𝜙𝑖 (𝑇, 𝑃, {𝑥}) =
𝑃 𝑥𝑖 𝑃

lim 𝑓(𝑇, 𝑃) = 𝑃 lim 𝑓𝑖 (𝑇, 𝑃, {𝑥}) = 𝑥𝑖 𝑃

𝑃→0 𝑃→0

𝑓𝑖 (𝑇, 𝑃, {𝑥}) 1 𝑃
ln = ∫ (𝑉𝑖 (𝑇, 𝑃, {𝑥}) − 𝑉𝑖 (𝑇, 𝑃, {𝑥})) 𝑑𝑃
𝑥𝑖 𝑓𝑖 𝑅𝑇 0
Excess property Δ𝑚𝑖𝑥 𝜃(𝑇, 𝑃, {𝑥}) = Δ𝐼𝑀
𝑚𝑖𝑥 𝜃(𝑇, 𝑃, {𝑥}) + 𝜃
𝑒𝑥

𝐼𝑀
𝜃 𝑒𝑥 = ∑ 𝑥𝑖 (𝜃𝑖 (𝑇, 𝑃, {𝑥}) − 𝜃𝑖 (𝑇, 𝑃, {𝑥}))
𝑖
𝑒𝑥
= ∑ 𝑥𝑖 𝜃𝑖
𝑖

𝑒𝑥 𝜕𝑁𝜃 𝑒𝑥 𝐼𝑀
𝜃𝑖 =( ) = 𝜃𝑖 − 𝜃𝑖
𝜕𝑁𝑖 𝑇,𝑃,𝑁
𝑗≠𝑖

𝑒𝑥 𝐼𝑀 𝑓𝑖
𝐺𝑖 = 𝐺𝑖 − 𝐺𝑖 = 𝑅𝑇 ln
𝑥𝑖 𝑓𝑖

For liquids and solids, the activity coefficient is defined as

𝑓
𝛾𝑖 (𝑇, 𝑃, {𝑥}) = 𝑖
𝑥𝑖 𝑓𝑖

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CL255- List of thermodynamic equations/relations Prof. A. Chatterjee, Department of Chemical Engineering, IIT Bombay
Ideal mixture versus ideal gas mixture

Ideal mixture Ideal gas mixture

Gas or liquid mixture that obeys at all temperatures, pressures and Gas mixture that obeys at all temperatures, pressures and
compositions compositions
𝐼𝑀 𝐼𝐺𝑀
𝐻𝑖 (𝑇, 𝑃, {𝑥}) = 𝐻𝑖 (𝑇, 𝑃) 𝑈𝑖 (𝑇, 𝑃, {𝑥}) = 𝑈𝑖𝐼𝐺 (𝑇)
and and
𝐼𝑀 𝐼𝐺𝑀 𝑅𝑇
𝑉𝑖 (𝑇, 𝑃, {𝑥})
= 𝑉𝑖 (𝑇, 𝑃). 𝑉𝑖 (𝑇, 𝑃, {𝑥}) = 𝑉𝑖𝐼𝐺 (𝑇, 𝑃) =
.
Here 𝐻𝑖 (𝑇, 𝑃) and 𝑉𝑖 (𝑇, 𝑃) are real fluid properties. Concept of ideal 𝑃
Here 𝑈𝑖𝐼𝐺 (𝑇) and 𝑉𝑖𝐼𝐺 (𝑇, 𝑃) are ideal gas properties. Concept of ideal
mixture is an idealization.
gas mixture is an idealization. The ideal gas mixture follows the ideal
gas law

𝑃𝑉 𝐼𝐺𝑀 = 𝑁𝑅𝑇 = (∑ 𝑁𝑖 ) 𝑅𝑇
𝑖

𝑉 𝐼𝑀 (𝑇,
𝑃, {𝑥}) = ∑ 𝑥𝑖 𝑉𝑖 (𝑇, 𝑃) Δ𝑚𝑖𝑥 𝑉 𝐼𝑀 = 0 𝑉 𝐼𝐺𝑀 (𝑇,
𝑃, {𝑥}) = ∑ 𝑥𝑖 𝑉𝑖𝐼𝐺 (𝑇, 𝑃) Δ𝑚𝑖𝑥 𝑉 𝐼𝐺𝑀 = 0
𝑖 𝑖
𝐼𝑀 𝐼𝐺𝑀
𝑉𝑖 (𝑇, 𝑃, {𝑥}) = 𝑉𝑖 (𝑇, 𝑃) 𝑉𝑖 (𝑇, 𝑃, {𝑥}) = 𝑉𝑖𝐼𝐺 (𝑇, 𝑃)
𝑈 𝐼𝑀 (𝑇, 𝑃, {𝑥}) = ∑ 𝑥 𝑈 (𝑇, 𝑃) Δ𝑚𝑖𝑥 𝑈 𝐼𝑀 = 0 𝑈 𝐼𝐺𝑀 (𝑇, 𝑃, {𝑥}) Δ𝑚𝑖𝑥 𝑈 𝐼𝐺𝑀 = 0
𝑖 𝑖
𝑖 = ∑ 𝑥𝑖 𝑈𝑖𝐼𝐺 (𝑇, 𝑃)
𝑖
𝐼𝑀 𝐼𝐺𝑀
𝑈𝑖 (𝑇, 𝑃, {𝑥}) = 𝑈𝑖 (𝑇, 𝑃) 𝑈𝑖 (𝑇, 𝑃, {𝑥}) = 𝑈𝑖𝐼𝐺 (𝑇)
𝐻 𝐼𝑀 (𝑇, 𝑃, {𝑥}) = ∑ 𝑥𝑖 𝐻𝑖 (𝑇, 𝑃) Δ𝑚𝑖𝑥 𝐻 𝐼𝑀 = 0 𝐻 𝐼𝐺𝑀 (𝑇, 𝑃, {𝑥}) Δ𝑚𝑖𝑥 𝐻 𝐼𝐺𝑀 = 0
𝑖 = ∑ 𝑥𝑖 𝐻𝑖𝐼𝐺 (𝑇, 𝑃)
𝑖
𝐼𝑀 𝐼𝐺𝑀
𝐻𝑖 (𝑇, 𝑃, {𝑥}) = 𝐻𝑖 (𝑇, 𝑃) 𝐻𝑖 (𝑇, 𝑃, {𝑥}) = 𝐻𝑖𝐼𝐺 (𝑇)
𝑆 𝐼𝑀 (𝑇, 𝑃, {𝑥}) = ∑ 𝑥𝑖 𝑆𝑖 (𝑇, 𝑃) Δ𝑚𝑖𝑥 𝑆 𝐼𝑀 = −𝑅 ∑ 𝑥𝑖 ln 𝑥𝑖 𝑆 𝐼𝐺𝑀 (𝑇, 𝑃, {𝑥}) Δ𝑚𝑖𝑥 𝑆 𝐼𝐺𝑀 = −𝑅 ∑ 𝑥𝑖 ln 𝑥𝑖
𝑖 𝑖 = ∑ 𝑥𝑖 𝑆𝑖𝐼𝐺 (𝑇, 𝑃) 𝑖
− 𝑅 ∑ 𝑥𝑖 ln 𝑥𝑖 𝑖
𝑖 − 𝑅 ∑ 𝑥𝑖 ln 𝑥𝑖
𝑖

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CL255- List of thermodynamic equations/relations Prof. A. Chatterjee, Department of Chemical Engineering, IIT Bombay
 𝐼𝑀 𝐼𝐺𝑀
𝑆𝑖 (𝑇, 𝑃, {𝑥}) = 𝑆𝑖 (𝑇, 𝑃) − 𝑅 ln 𝑥𝑖 𝑆𝑖 (𝑇, 𝑃, {𝑥}) = 𝑆𝑖𝐼𝐺 (𝑇, 𝑃) − 𝑅 ln 𝑥𝑖
𝐴𝐼𝑀 (𝑇, 𝑃, {𝑥}) = ∑ 𝑥𝑖 𝐴𝑖 (𝑇, 𝑃) Δ𝑚𝑖𝑥 𝐴𝐼𝑀 = 𝑅𝑇 ∑ 𝑥𝑖 ln 𝑥𝑖 𝐴𝐼𝐺𝑀 (𝑇, 𝑃, {𝑥}) Δ𝑚𝑖𝑥 𝐴𝐼𝐺𝑀 = 𝑅𝑇 ∑ 𝑥𝑖 ln 𝑥𝑖
𝑖 𝑖 = ∑ 𝑥𝑖 𝐴𝐼𝐺
𝑖 (𝑇, 𝑃) 𝑖
+ 𝑅𝑇 ∑ 𝑥𝑖 ln 𝑥𝑖 𝑖
𝑖 + 𝑅𝑇 ∑ 𝑥𝑖 ln 𝑥𝑖
𝑖
𝐼𝑀 𝐼𝐺𝑀
𝐴𝑖 (𝑇, 𝑃, {𝑥}) = 𝐴𝑖 (𝑇, 𝑃) + 𝑅𝑇 ln 𝑥𝑖 𝐴𝑖 (𝑇, 𝑃, {𝑥}) = 𝐴𝐼𝐺
𝑖 (𝑇, 𝑃) + 𝑅𝑇 ln 𝑥𝑖

𝐺 𝐼𝑀 (𝑇, 𝑃, {𝑥}) = ∑ 𝑥𝑖 𝐺𝑖 (𝑇, 𝑃) Δ𝑚𝑖𝑥 𝐺 𝐼𝑀 = 𝑅𝑇 ∑ 𝑥𝑖 ln 𝑥𝑖 𝐺 𝐼𝐺𝑀 (𝑇, 𝑃, {𝑥}) Δ𝑚𝑖𝑥 𝐺 𝐼𝐺𝑀 = 𝑅𝑇 ∑ 𝑥𝑖 ln 𝑥𝑖

𝑖 𝑖 = ∑ 𝑥𝑖 𝐺𝑖 (𝑇, 𝑃) 𝑖
+ 𝑅𝑇 ∑ 𝑥𝑖 ln 𝑥𝑖 𝑖
𝑖 + 𝑅𝑇 ∑ 𝑥𝑖 ln 𝑥𝑖
𝑖
𝐼𝑀 𝐼𝐺𝑀
𝐺𝑖 (𝑇, 𝑃, {𝑥}) = 𝐺𝑖 (𝑇, 𝑃) + 𝑅𝑇 ln 𝑥𝑖 𝐺𝑖 (𝑇, 𝑃, {𝑥}) = 𝐺𝑖𝐼𝐺 (𝑇, 𝑃) + 𝑅𝑇 ln 𝑥𝑖
Partial pressure for gas mixture Partial pressure
𝑃𝑖𝐼𝑀 = 𝑥𝑖 𝑃 𝑁𝑖 𝑅𝑇
𝑃𝑖𝐼𝐺𝑀 = 𝑥𝑖 𝑃 =
𝑉

In general, for any (real/ideal) gas mixture one can define the partial pressure as 𝑃𝑖 = 𝑥𝑖 𝑃.

Equation of state (shown only for binary mixtures)

Virial equation 𝑃𝑉 𝐵(𝑇) 𝐶(𝑇)

𝑍= =1+ + 2 +⋯
𝑅𝑇 𝑉 𝑉
𝑃𝑉
𝑍= = 1 + 𝐵′ (𝑇)𝑃 + 𝐶 ′ (𝑇)𝑃2 + ⋯
𝑅𝑇
Peng-Robinson (1976) 𝑅𝑇 𝑎(𝑇)
𝑃= −
𝑉 − 𝑏 𝑉(𝑉 + 𝑏) + 𝑏(𝑉 − 𝑏)
𝑎 = 𝑥12 𝑎11 + 2𝑥1 𝑥2 𝑎12 + 𝑥22 𝑎22
𝑏 = 𝑥1 𝑏1 + 𝑥2 𝑏2
where 𝑎12 = 𝑎21 = √𝑎11 𝑎22 (1 − 𝑘𝑖𝑗 ). 𝑘𝑖𝑗 is the binary interaction parameter.
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CL255- List of thermodynamic equations/relations Prof. A. Chatterjee, Department of Chemical Engineering, IIT Bombay
 van der Waals (1873) 𝑅𝑇 𝑎
𝑃= − 2
𝑉−𝑏 𝑉
with appropriate mixture rules for 𝑎 and 𝑏.
Redlich-Kwong (1949) 𝑅𝑇 𝑎𝑇 −1/2
𝑃= −
𝑉 − 𝑏 𝑉(𝑉 + 𝑏)
with appropriate mixture rules for 𝑎 and 𝑏.

Activity coefficient models (shown only for binary mixtures)

Origin Form
Ideal solution theory Ideal case 𝐺 𝑒𝑥 = 0
Regular solution theory Regular solution is a mixture for which 𝐺 𝑒𝑥 = (𝑥1 𝑉1 + 𝑥2 𝑉2 )𝜙1 𝜙2 (𝛿1 − 𝛿2 )2
(1927) Δ𝑚𝑖𝑥 𝑆 = 𝑥1 ln 𝑥1 + 𝑥2 ln 𝑥2 and Δ𝑚𝑖𝑥 𝑉 = 0. 𝑅𝑇 ln 𝛾1 = 𝑉1 𝜙22 (𝛿1 − 𝛿2 )2
However, Δ𝑚𝑖𝑥 𝐻 ≠ 0. Regular solution 𝑅𝑇 ln 𝛾2 = 𝑉2 𝜙12 (𝛿1 − 𝛿2 )2
theory is equivalent to van Laar theory. 𝑥𝑖 𝑉 𝑖 Δ𝑣𝑎𝑝 𝑈𝑖
1/2
Volume fraction 𝜙𝑖 = , solubility parameter 𝛿𝑖 = ( ) ,
𝑉𝑚𝑖𝑥 𝑉𝑖
Δ𝑣𝑎𝑝 𝑈𝑖 is the internal energy change (per mole) upon vaporization,
and molar volume for mixture is 𝑉𝑚𝑖𝑥 = 𝑥1 𝑉1 + 𝑥2 𝑉2
One-constant Margules Empirical 𝐺 𝑒𝑥 = 𝐴𝑥1 𝑥2
equation (1895)
Two-constant Margules Empirical 𝐺 𝑒𝑥 = 𝑥1 𝑥2 (𝐴 + 𝐵(𝑥1 − 𝑥2 ))
equation
Redlich-Kister (??) General polynomial form suggested to fit 𝐺 𝑒𝑥 = 𝑥1 𝑥2 (𝐴 + 𝐵(𝑥1 − 𝑥2 ) + 𝐶(𝑥1 − 𝑥2 )2 + ⋯ )
excess properties
van Laar model (1913) Empirical 𝛼
ln 𝛾1 =
𝛼𝑥1 2
(1 + )
𝛽𝑥2
𝛽
ln 𝛾2 =
𝛽𝑥 2
(1 + 𝛼𝑥2 )
1
Wilson equation (1964) Statistical mechanical 𝐺 𝑒𝑥 = −𝑥1 ln(𝑥1 + 𝑥2 Λ12 ) − 𝑥2 ln(𝑥2 + 𝑥1 Λ21 )

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CL255- List of thermodynamic equations/relations Prof. A. Chatterjee, Department of Chemical Engineering, IIT Bombay
 Non-random two liquid Statistical mechanical 𝐺 𝑒𝑥 𝜏21 𝐺21 𝜏12 𝐺12
= 𝑥1 𝑥2 ( + )
(NRTL) (1968) 𝑅𝑇 𝑥1 + 𝑥2 𝐺21 𝑥2 + 𝑥1 𝐺12
Flory-Huggins solution Statistical mechanical Δ𝑚𝑖𝑥 𝐻 = 𝜒𝑅𝑇(𝑥1 + 𝑚𝑥2 )𝜙1 𝜙2
theory (1941) (for polymers) Δ𝑚𝑖𝑥 𝑆 = −𝑅(𝑥1 ln 𝜙1 + 𝑥2 ln 𝜙2 )
𝑉2
𝑚=
𝑉1
𝑥1 𝑉1
𝜙1 =
𝑥1 𝑉1 + 𝑥2 𝑉2
UNIversal QUAsiChemical Statistical mechanical
(UNIQUAC) (1975) (group contribution method)
UNIquac Functional-group Statistical mechanical
Activity Coefficient (group contribution method)
(UNIFAC) (1975)
Analytical solution of Statistical mechanical
groups (ASOG) (1979) (group contribution method)

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CL255- List of thermodynamic equations/relations Prof. A. Chatterjee, Department of Chemical Engineering, IIT Bombay