Mass Transfer

Operations

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Mass Transfer…

What is MT?

Why does it occur??

What are its applications???

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What is MT?
• Operations which involves changes in chemical composition in phases
• Within a single phase
• Between phases
• Through direct contact
• Through indirect contact

• With or without bulk movement, but always with diffusion

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Why does MT occur?

• Driving force
• Concentration
• Chemical potential

• Phase equilibria

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Where is MT applicable?

• Mixing
• Separation

• Method/technique
• Equilibrium
• Rate

(Google Images)

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Mass Transfer Operations

• Direct contact between immiscible phases
• Gas-liquid (distillation, absorption)
• Gas-solid (drying, adsorption)
• Liquid-liquid (extraction)
• Liquid-solid (crystallization, leaching, adsorption)
• Solid-solid

• Indirect contact between immiscible phases

• Membranes (permeation, dialysis, osmosis)

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Gradient driven transfer

Name Transfer Process Flux Gradient
Newton’s viscosity Molecular 𝑑 𝜌𝑢 Momentum
𝜏𝑦𝑥 = −𝜈
law Momentum 𝑑𝑦 concentration
Viscous flow 𝑑 2 𝑑𝑝
Poiseuille law 𝑢=− Pressure
through circular pipe 32𝜇 𝑑𝑥
Viscous flow in 𝑘 𝑑𝑝
Darcy’s law 𝑢=− Pressure
porous medium 𝜇 𝑑𝑥
𝑞 𝑑(𝜌𝐶𝑝 𝑇)
Fourier’s law Conduction = −𝛼 Energy
𝐴 𝑑𝑥
𝑑𝐶
Fick’s law Diffusion 𝐽𝐴 = −𝐷 Concentration
𝑑𝑥

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Gradient driven transfer

T C

T = f(x) C = f(x)
q N
dT/dx dC/dx

x x

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Additional considerations in MT
• Phase equilibria
• Mixture
• Multicomponent system, who’s composition keeps varying.
• Convective mass flux
• Diffusional flux causes mass flux, i.e. change in center of mass.
• High mass flux effect
• Strong convective mass flux can have significant effect on velocity.
• Effect of latent heat
• Latent heat of substances changes with composition, i.e. transfer of matter is accompanied
with energy transfer. Especially when associated with phase change.

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Diffusion
• Molecular diffusion
• Movement of individual molecules through a medium/phase is caused by virtue
thermal energy.

• Free path – distance travelled between collisions.

• Velocity – dependent on temperature.

• Eddy or turbulent diffusion

• Rapid movement of relatively large volume of fluid.
• Within each eddy, uniformity is achieved through molecular diffusion.

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Fick’s Law of Diffusion

[J] = mol/(s.m2)
𝑑𝐶𝐴
Molar flux, 𝐽𝐴 = −𝐷𝐴𝐵
𝑑𝑧 [C] = mol

[DAB] = m2/s

First reported by A. Fick (1855): salt dissolution in water.

For ideal solution, DAB = DBA.

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Generalized Fick’s Law

For component A diffusing in B with a bulk movement in the direction Z,
𝑑𝑥𝐴
𝑁𝐴 = 𝑁𝐴 + 𝑁𝐵 𝑥𝐴 − 𝐶𝐷𝐴𝐵
𝑑𝑧

When xA is very small,

N is the flux relative to a fixed position & J is the flux relative to the average
molar velocity of all the constituents.
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Gas phase diffusion

• Molecular diffusion in a binary gas mixture
• Steady state condition
• Constant cross section
• Ideal gas
• Uniform temperature

• Limiting cases
• Diffusion of A through non-diffusing B – Stefan diffusion
• Equimolar counterdiffusion of A & B
• Non-equimolar counterdiffusion of A & B

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Diffusion of A through non-diffusing B (1)

Since B is non-diffusing, 𝑁𝐵 = 0
For gas, 𝑝𝐴
𝑥𝐴 =
𝑃
𝑃
𝐶=
𝑅𝑇

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Diffusion of A through non-diffusing B (2)

Since P is constant, 𝑃 = 𝑝𝐴0 + 𝑝𝐵0 = 𝑝𝐴𝑙 + 𝑝𝐵𝑙 ⇒ 𝑃 − 𝑝𝐴0 = 𝑝𝐵0
𝑃 − 𝑝𝐴𝑙 = 𝑝𝐵𝑙
𝑝𝐴0 − 𝑝𝐴𝑙 = 𝑝𝐵𝑙 − 𝑝𝐵0

Log Mean
𝑝1 − 𝑝2
𝑝𝐵𝑀 ≡
ln 𝑝1 /𝑝2

Generalizing,
𝐷𝐴𝐵 𝑃 𝑃 − 𝑝𝐴 𝐷𝐴𝐵 𝑃 𝑝𝐴0 − 𝑝𝐴
𝑁𝐴 = ln or, 𝑁𝐴 =
𝑅𝑇𝑧 𝑃 − 𝑝𝐴0 𝑅𝑇𝑧 𝑝𝐵𝑀

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Equimolar Counterdiffusion
Equimolar ⇒ 𝑁𝐴 = −𝑁𝐵

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Non-equimolar counterdiffusion
Consider the reaction, 2𝐶 + 𝑂2 → 2𝐶𝑂

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Example 1.1
A tube, 0.25 m long & 1.5 mm dia. connects 2 tanks containing N2 and H2
gases respectively. Both components diffuse in the opposite directions.
The mole fraction of N2 in the tanks were 0.7 & 0.25 respectively, at one
particular instant during diffusion. The mass diffusivity of N2-H2 mixture
is 7.84×10-5 m2/s. If P = 101.3 kPa & T = 298 K, determine the following:
a) Rate of diffusion of N2 in kmol/h and kg/h.
b) Velocity of species with reference to stationary coordinates as function
of concentration.

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Example 1.2
A test tube, 1.5 cm dia. & 12 cm tall, is partly filled with a solution of
alkaline pyrogallate. The depth of the empty space above the solution is 5
cm. The temperature is 25°C and the total pressure is 1 atmosphere. Air
may be assumed to contain 21% O2 and 79% N2. The diffusivity of O2 in N2
at the given condition is 0.21 cm2/s.
a) Calculate the rate of absorption of O2 from air in the solution at steady
state if air flows gently over the open end of the test tube. Make plots
of the distribution of partial pressures of the gases along the diffusion
path.
b) Calculate the partial pressure gradient of O2 midway in the diffusion
path.

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Gas Phase Diffusion Coefficient (1)

• Experimentally through twin-bulb method and Stefan tube.

• Theoretical equation by Chapman & Enskog based on kinetic theory of

gases and Lennard-Jones potential.

3 1/2
−7 2 1 1
1.858 × 10 𝑇 +
𝑀𝐴 𝑀𝐵
𝐷𝐴𝐵 = 2
𝑃𝜎𝐴𝐵 Ω𝐷
T = absolute temperature, K
MA, MB = molecular weights of components A & B
P = Total pressure, atm
σAB = characteristic length parameter of the binary components, Å
ΩD = collision integral
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Gas Phase Diffusion Coefficient (2)

𝜎𝐴 + 𝜎𝐵
𝜎𝐴𝐵 =
2
𝑘𝑇
Ω𝐷 = 𝑓 𝜖𝐴𝐵 = 𝜖𝐴 𝜖𝐵
𝜖𝐴𝐵
5 1/3 𝜖
𝜎 = 𝑉𝑐 = 0.75𝑇𝑐
6 𝑘

σ&ε = Lennard-Jones potential parameters

Tc = Critical temperature, K
Vc = Critical volume, (cm3/gmol)

Range of gas phase diffusivity ~ 10-2 cm2/s

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Liquid Phase Diffusion Coefficient (1)

• Experimental through diaphragm cell.

• Prediction using Wilke-Chang equation:

0
1.173 × 10−16 𝜙𝑀𝐵 1/2
𝑇
𝐷𝐴𝐵 =
𝜇𝑣𝐴0.6

D0AB = Diffusivity of A in B at infinite dilution, m2/s.

T = Absolute temperature, K.
MB = Molecular weight of solvent.
𝜙 = Association factor for the solvent.
(for water = 2.26, methanol=1.5, non-associated solvent = 1.0)
µ = Viscosity of solution, N/m2s.
vA = Solute molar volume at the normal boiling point, m3/kmol.
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Liquid Phase Diffusion Coefficient (2)

• Stokes-Einstein equation for diffusivity:

𝑘𝑇
𝐷𝐴𝐵 =
6𝜋𝜇𝐵 𝑟𝐴

rA = Radius of solute molecules.

µB = Viscosity of solution, N/m2s.
T = Absolute temperature, K.
k = Boltzmann constant, 1.38×10-23 m2kg/s-2K-1

Range of liquid diffusivity ~ 10-5 cm2/s

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Example 1.3
Determine the diffusivity of acetic acid in a dilute aqueous solution at 20
ºC using Wilke-Chang equation.
Viscosity of water = 1.01 cP at 20 ºC.
Density of acetic acid at the normal boiling point = 1.014 g/cm3.

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Example 1.4
Determine the diffusivity of CO2 in air at 317.2 K and 101.3 kPa by Wilke-
Lee equation.
1
1/2
1 2 32 1 1 1 1 1
3.03 − 0.98 𝑇 × 10−4 𝑤ℎ𝑒𝑟𝑒, = +
𝑀𝐴𝐵 𝑀𝐴𝐵
𝐷𝐴𝐵 = 2
𝑀𝐴𝐵 2 𝑀𝐴 𝑀𝐵
𝑃𝜎𝐴𝐵 Ω𝐷

𝑚2 𝑁 kT/εAB ΩD kT/εAB ΩD
𝐷𝐴𝐵 = ; 𝑇 = 𝐾; 𝑃 = 2 ; 𝜎 = 𝑛𝑚
𝑠 𝑚 0.3 2.662 1.8 1.116
0.4 2.318 2.4 1.012
𝐹𝑜𝑟 𝐶𝑂2 , 𝐹𝑜𝑟 𝑎𝑖𝑟,
0.6 1.877 3.1 0.9406
𝜖 𝜖
𝜎 = 0.3996 𝑛𝑚; = 190 𝐾 𝜎 = 0.3617 𝑛𝑚; = 97 𝐾 0.9 1.517 3.9 0.8888
𝑘 𝑘
1.3 1.273 4.8 0.8492

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