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Mathematical modelling and simulation of chemical

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engineering process
Dr Sourav Mondal
Chemical Engineering, IIT KHARAGPUR
Lecture 04 : Constitutive relations – mass transfer and thermodynamics
Basic principle

Developed by considering a mole

of a component in a multicomponent
mixture which reaches Frictional Driving

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steady motion as the consequence resistance force

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of the balance between two
opposing forces, the mass transfer

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driving force and the frictional
resistance
Mass transfer driving force
At constant T & P, species i experiences a force (per mole), acting in the direction of z
𝜕𝜇𝑖
𝐹𝑖 = −
𝜕𝑧 𝑇,𝑃

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The chemical potential for component i in ideal phases:

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d𝑦𝑖
For gas: 𝜇𝑖 = 𝜇𝑖0 + 𝑅𝑇 ln 𝑃𝑖 = 𝜇𝑖0 + 𝑅𝑇 ln 𝑦i 𝑃 d𝜇𝑖 = 𝑅𝑇
𝑦𝑖

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For liquid: 𝜇𝑖 = 𝜇𝑖∗ + 𝑅𝑇 ln 𝑥𝑖 d𝜇𝑖 =
d𝑥
𝑅𝑇 𝑖
𝑥𝑖

For non-ideal phases: use fugacity (gas) or activity (liquid) coefficients

for correction.
 Frictional resistance

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𝑥𝐴
𝐹𝐵 = −𝑅𝑇 (𝑢𝐵 − 𝑢𝐴 )
𝐷𝐵𝐴

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𝑥𝐵

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𝐹𝐴 = −𝑅𝑇 (𝑢𝐴 − 𝑢𝐵 ) Generalising for the 𝐹 = −𝑅𝑇Σ𝑛−1 𝑥𝑗 (𝑢 − 𝑢 )
𝐷𝐴𝐵 multi − components 𝑖 𝑗=1
𝐷𝑖𝑗 𝑖 𝑗

In a unit volume of the mixture, the forces will be:

𝑥𝐵 𝑥𝐴 𝐶𝑇 𝑥𝐴 𝑥𝐵 𝐶𝑇
On A: 𝑥𝐴 𝐶𝑇 𝐹𝐴 = −𝑅𝑇 (𝑢𝐴 − 𝑢𝐵 ) On B: 𝑥𝐵 𝐶𝑇 𝐹𝐴 = −𝑅𝑇 (𝑢𝐵 − 𝑢𝐴 )
𝐷𝐴𝐵 𝐷𝐵𝐴

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Complete picture Frictional Driving
resistance force

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 Diffusion in a binary mixture

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The interaction (frictional) term involves the knowledge of relative velocities.

We need therefore to specify another single piece of information, which will fix the
velocity or flux relative to a fixed reference frame.
 Specification 1: Equimolar counter-diffusion
𝜕𝐶𝐴 1 𝜕𝐶𝐵 1
− = (𝐶𝐵 𝑁𝐴 − 𝐶𝐴 𝑁𝐵 ) and − = (𝐶 𝑁 − 𝐶𝐵 𝑁𝐴 )
𝜕𝑧 𝐶𝑇 𝐷𝐴𝐵 𝜕𝑧 𝐶𝑇 𝐷𝐵𝐴 𝐴 𝐵

The fluxes of A & B are equal

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and opposite (e.g. distillation)
𝑁𝐴 = −𝑁𝐵

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𝜕𝐶𝐴 𝜕𝐶𝐵
Therefore, 𝑁𝐴 = −𝐷𝐴𝐵 and 𝑁𝐵 = −𝐷𝐵𝐴
𝜕𝑧 𝜕𝑧

This looks like the Fick’s law, but here we do not have the
condition of being dilute or stagnant!
Specification 2: Stagnant component (Stefan’s condition)
𝜕𝐶𝐴 1 𝜕𝐶𝐵 1
− = (𝐶𝐵 𝑁𝐴 − 𝐶𝐴 𝑁𝐵 ) and − = (𝐶 𝑁 − 𝐶𝐵 𝑁𝐴 )
𝜕𝑧 𝐶𝑇 𝐷𝐴𝐵 𝜕𝑧 𝐶𝑇 𝐷𝐵𝐴 𝐴 𝐵

The fluxes one component, say B is

zero (e.g. membrane separation)

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𝑁𝐵 = 0

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𝜕𝐶𝐴 𝐶𝐵 𝜕𝐶𝐵 𝐶𝐵
=− 𝑁 and = 𝑁

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𝜕𝑧 𝐶𝑇 𝐷𝐴𝐵 𝐴 𝜕𝑧 𝐶𝑇 𝐷𝐴𝐵 𝐴

Stefan’s law
Note that even 𝑁𝐵 = 0, the spatial
𝜕𝐶𝐵
gradient of B still exists, in the
𝜕𝑧
𝐶𝑇 𝜕𝐶𝐴 positive direction of the diffusion of A
𝑁𝐴 = − 𝐷𝐴𝐵
𝐶𝑇 − 𝐶𝐴 𝜕𝑧
 Specification 3: Stagnant & dilute component (Fick’s law)

𝐶𝑇 𝜕𝐶𝐴 considering the flux of one

Stefan’s law: 𝑁𝐴 = − 𝐷
𝐶𝑇 −𝐶𝐴 𝐴𝐵 𝜕𝑧 component to be zero, 𝑁𝐵 = 0

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Considering A to be dilute, 𝐶𝐴 ≪ 𝐶𝑇

𝑁𝐴 = −𝐷𝐴𝐵
𝜕𝐶𝐴
𝜕𝑧 N
(Fick’s law)
Mass transport equation

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𝜕𝐶
+ 𝐯 ⋅ 𝛻𝐶 = 𝛻 ⋅ 𝐷𝛻𝐶 + 𝑅
𝜕𝑡

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where 𝐯 is the fluid velocity field.
Thermodynamic relations
Dalton’s law ………………… 𝑃 = σ𝑖=1 𝑝𝑖 (non-reacting ideal gases)

Lewis-Randall Rule ………………… 𝑓ഥ𝑖 = 𝑦𝑖 𝑓𝑖

Raoult’s law ………………… 𝑝𝑖𝑣 = 𝑥𝑖 𝑝𝑖𝑣∗

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Henry’s law ………………… 𝑓ഥ𝑖 = 𝑥𝑖 𝐻𝑖

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𝐵
Antoine equation …… ln 𝑃𝑣 = 𝐴 − 𝐶+𝑇 (vap. pr. of pure species)

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𝐾2 Δ𝐻𝑟 1 1
Vant-Hoff’s Relation …… ln =− −
𝐾1 𝑅 𝑇2 𝑇1
𝑃2 𝜆 1 1
Clausius – Clapeyron equation ………… ln =− −
𝑃1 𝑅 𝑇2 𝑇1
Van-der Waals, Redlich-Kwong, Peng–Robinson,
Eqn. of state (real gases)
Virial Eqn., Benedict-Webb-Rubin, etc.
Gibbs free energy and phase equilibrium

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Gibbs free energy and phase equilibrium

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Thermodynamics of gas and liquid states
For an ideal gas at const. 𝑇, undergoing a change in state, the corresponding
change in free energy is equal to the work done ‘on’ the system

∫ d𝐺 = ∫ V d𝑝

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2 d𝑝

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⟹ Δ𝐺 = 𝑛𝑅𝑇 ∫1 [from the ideal gas relation: 𝑝𝑉 = 𝑛𝑅𝑇]
𝑝

Therefore, Δ𝐺 = 𝑛𝑅𝑇 ln
𝑝2
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⟹ 𝐺 = 𝐺 0 + 𝑛𝑅𝑇 ln 𝑝
Gas-liquid equilibrium
For any solution (in gas-liquid equilibrium),
𝑝=𝛼𝑥
𝑝: partial pressure of the component in the gaseous phase
𝛼: activity co-efficient

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𝑥: Liquid phase concentration

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At constant 𝑇 & 𝑃, the Gibb’s free energy is 𝐺 = 𝜇 𝑁

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So, 𝜇 = 𝜇0 + 𝑅𝑇 ln(𝛼 𝑥)

For ideal (dilute) solution, 𝛼 ∼ 1, 𝜇 = 𝜇0 + 𝑅𝑇 ln 𝑥

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