Final Exam Formula Sheet

Chemical Engineering Thermodynamics II/ CHME312

Vapor Liquid Equilibria

𝐵 𝑦𝑖 𝐾1 𝑧𝑖 𝐾𝑖
ln 𝑃𝑖𝑠𝑎𝑡 = 𝐴𝑖 − 𝑖 𝑦𝑖 𝑃 = 𝑥𝑖 𝛾𝑖 𝑃𝑖𝑠𝑎𝑡 𝐾𝑖 = 𝛼1,2 = 𝑦𝑖 =
𝑇+𝐶𝑖 𝑥𝑖 𝐾2 1+(𝐾𝑖 −1)𝑉

Solution Thermodynamics
̅𝑖 = (𝜕[𝑛𝑀])
𝑀 ̅1 = 𝑀 + 𝑥2 𝑑𝑀
𝑀 ̅2 = 𝑀 − 𝑥1 𝑑𝑀
𝑀 ̅𝑖
𝑀 = ∑ 𝑥𝑖 𝑀
𝜕𝑛𝑖 𝑇,𝑃,𝑛𝑗≠𝑖 𝑑𝑥1 𝑑𝑥1
𝑖𝑔 𝑖𝑔 𝑖𝑔 𝑖𝑔
Ideal gas mixing 𝐻𝑚𝑖𝑥 = ∑ 𝑦𝑘 𝐻𝑘 (𝑇) 𝑈𝑚𝑖𝑥 = ∑ 𝑦𝑘 𝑈𝑘 (𝑇)
𝑖𝑔 𝑖𝑔 𝑖𝑔 𝑖𝑔
𝑆𝑚𝑖𝑥 = ∑ 𝑦𝑘 𝑆𝑘 (𝑇, 𝑃𝑘 ) − 𝑅 ∑ 𝑦𝑘 ln 𝑦𝑘 𝐺𝑚𝑖𝑥 = ∑ 𝑦𝑘 𝐺𝑘 (𝑇, 𝑃𝑘 ) + 𝑅𝑇 ∑ 𝑦𝑘 ln 𝑦𝑘

𝐺𝑅 1 𝐻𝑅 𝑃 𝑍−1 𝐵𝑃 𝑃𝑟
Fugacity coefficient of pure gases ln 𝜑 = = [ − 𝑆 𝑅 ] = ∫0 𝑑𝑃 = = (𝐵0 + 𝜔𝐵1 )
𝑅𝑇 𝑅 𝑇 𝑃 𝑅𝑇 𝑇𝑟
𝑓 1 𝐻−𝐻 ∗
𝜑 = [𝜑 0 ][𝜑1 ]𝜔 ln = [ − (𝑆 − 𝑆 ∗ )]
𝑓∗ 𝑅 𝑇
0.422 0.172
𝐵0 = 0.083 − 𝐵1 = 0.139 −
𝑇𝑟1.6 𝑇𝑟4.2
Cubic EOS: ln 𝜑 = 𝑍 − 1 − ln(𝑍 − 𝛽) − 𝑞. 𝐼 Cubic EOS Parameters in Table 3.1 (Page 98)
𝛽
𝑖𝑓 𝜀 = 𝜎 𝐼=
𝑃𝑟 𝜓 𝛼(𝑇𝑟 ) 𝑍−𝛽 𝑍+𝜀𝛽
𝛽=Ω 𝑞= 𝑍 = 1 + 𝛽 − 𝑞𝛽 (𝑧+𝜀𝛽)(𝑍+𝜎𝛽) { 1 𝑍+𝜎𝛽
}
𝑇𝑟 Ω𝑇𝑟
𝑖𝑓 𝜀 ≠ 𝜎 𝐼= ln [ ]
𝜎−𝜀 𝑍+𝜀𝛽
1 𝑃 𝑉𝑖𝐿
Pure liquids 𝑓𝑖𝐿 = 𝑓𝑖𝑠𝑎𝑡 exp [ ∫ 𝑠𝑎𝑡 𝑉𝑖𝐿 𝑑𝑃] ≅ 𝑓𝑖𝑠𝑎𝑡 exp [ (𝑃 − 𝑃𝑖𝑠𝑎𝑡 )]
𝑅𝑇 𝑃𝑖 𝑅𝑇
Gas mixtures
𝐺̅ 𝑅 𝑃 𝑍̅ −1 𝐵̅𝑖 𝑃
ln 𝜑̂𝑖 = 𝑖 = ∫0 𝑖 𝑑𝑃 = 𝛿𝑖𝑗 ≡ 2𝐵𝑖𝑗 − 𝐵𝑖𝑖 − 𝐵𝑗𝑗
𝑅𝑇 𝑃 𝑅𝑇
For binary mixtures: 𝐵̅1 = 𝐵11 + 𝑦22 𝛿12 𝐵̅2 = 𝐵22 + 𝑦12 𝛿12
1
For multicomponent mixtures: 𝐵̅𝑘 = 𝐵𝑘𝑘 + ∑𝑖 ∑𝑗[𝑦𝑖 𝑦𝑗 (2𝛿𝑖𝑘 − 𝛿𝑖𝑗 )]
2
1 1
𝜔𝑖𝑗 = (𝜔𝑖 + 𝜔𝑗 ) 𝑍𝑐,𝑖𝑗 = (𝑍𝑐,𝑖 + 𝑍𝑐,𝑗 ) 𝑇𝑐,𝑖𝑗 = √𝑇𝑐,𝑖 𝑇𝑐,𝑗 (1 − 𝑘𝑖𝑗 ) 𝑇𝑟,𝑖𝑗 = 𝑇/𝑇𝑐,𝑖𝑗
2 2
1 1 3
1 3 3 𝑍𝑐,𝑖𝑗 𝑅 𝑇𝑐,𝑖𝑗 𝑅 𝑇𝑐,𝑖𝑗 0 1
𝑉𝑐,𝑖𝑗 = [ (𝑉𝑐,𝑖 + 𝑉𝑐,𝑗 )] 𝑃𝑐,𝑖𝑗 = 𝐵𝑖𝑗 = (𝐵𝑖𝑗 + 𝜔𝑖𝑗 𝐵𝑖𝑗 )
2 𝑉𝑐,𝑖𝑗 𝑃𝑐,𝑖𝑗
0 0.422 1 0.172
𝐵𝑖𝑗 = 0.083 − 𝐵𝑖𝑗 = 0.139 −
𝑇𝑟1.6 𝑇𝑟4.2
𝑖𝑗
𝑖𝑗
2
1 𝜕𝑉 −1 𝜕𝑉 (1−𝑇 )7 𝑉2
For Liquids 𝛽 = ( ) 𝜅= ( ) 𝑉𝐿𝑠𝑎𝑡 = 𝑉𝑐 𝑍𝑐 𝑟 ln = 𝛽∆𝑇 − 𝜅 ∆𝑃
𝑉 𝜕𝑇 𝑃 𝑉 𝜕𝑃 𝑇 𝑉1

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Solution Thermodynamics
Simplest Activity Model (Constant)
𝐺𝑖̅ 𝐸 𝐺𝐸 ln 𝛾1 = 𝐴 𝑥22 ln 𝛾2 = 𝐴 𝑥12
ln 𝛾𝑖 = = ∑𝑁
𝑖=1 𝑥𝑖 ln 𝛾𝑖
𝑅𝑇 𝑅𝑇
Wilson Model
𝑓̂𝑖 = 𝑥𝑖 𝛾𝑖 𝑓𝑖 𝑉𝑗 𝑎𝑖𝑗
𝛬𝑖𝑗 = exp [− ]
𝑉𝑖 𝑅𝑇
Margules Equation
𝛬12 𝛬21
ln 𝛾1 = − ln(𝑥1 + 𝑥2 𝛬12 ) + 𝑥2 ( − )
𝑥1 + 𝑥2 𝛬12 𝑥2 + 𝑥1 𝛬21

𝛬12 𝛬21
ln 𝛾2 = − ln(𝑥2 + 𝑥1 𝛬21 ) − 𝑥1 ( − )
𝑥1 + 𝑥2 𝛬12 𝑥2 + 𝑥1 𝛬21
Van Laar Model

NRTL Model
2
𝐺21 𝐺12 𝜏12
ln 𝛾1 = 𝑥22 [𝜏21 ( ) + ]
𝑥1 + 𝑥2 𝐺21 (𝑥2 + 𝑥1 𝐺12 )2
2
𝐺12 𝐺21 𝜏21
ln 𝛾2 = 𝑥12 [𝜏12 ( ) + ]
𝑥2 + 𝑥1 𝐺12 (𝑥1 + 𝑥2 𝐺21 )2

𝐺𝑖𝑗 = exp(−𝛼 𝜏𝑖𝑗 ) 𝜏𝑖𝑗 = 𝑏𝑖𝑗 /𝑅𝑇

Reaction Equilibrium
−Δ𝐺 𝑜 ∆𝐻0𝑜 𝑇 𝑇 ∆𝐶𝑃0 1 𝑇 ∆𝐶𝑃0
𝐾0 = exp ( 0 ) 𝐾1 = exp [ (1 − 0)] 𝐾2 = exp (∫𝑇 𝑑𝑇 − ∫𝑇 𝑑𝑇)
𝑅𝑇0 𝑅𝑇0 𝑇 0 𝑅𝑇 𝑇 0 𝑅

T
rC po rB
  C
  1 1



dT  r A T  To  T 2  To2  r T 3  To3  rD   
 R 2 3  T To
To
T
rC po  1 1 
T  C D
 



dT  r A ln    rB T  To  r T 2  To2  r  2  2
 RT  To  2 2 T To 
To

𝑃 −𝜈 −𝜈
For Gases: 𝐾 = ∏𝑖 𝑦𝑖 𝜈𝑖 = 𝐾 ( 0) ∏𝑖(𝜙̂𝑖 ) 𝑖
𝑃
𝑃𝑜 −𝑃
For Liquids 𝐾 = ∏𝑖 𝑥𝑖 𝜈𝑖 = 𝐾 exp [ ∑𝑖(𝜈𝑖 𝑉𝑖𝐿 )] ∏𝑖(𝛾𝑖 )−𝜈𝑖
𝑅𝑇

Useful Constants & Conversion Factors

1 kJ = 1 kPa.m3 1 bar = 100 kPa = 14.5 psi 𝑇(℉) = 1.8 𝑇(℃) + 32 1 m3 =103 L = 106 cm3
3
R = 8.314 kJ/kmol.K = 83.14 bar.cm /mol.K = 0.08205 L.atm/mol.K = 1.987 cal/mol.K
Atomic Weights: (C=12, H=1, O=16, N = 14)
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