CHEE 4704 - Chapter 1 - Fundamentals of Mass Transfer

CHEE 4704 – Separation Processes II
Chapter 1: Fundamentals of Mass Transfer

Instructor: Jon Totten
Lecture Notes: Jon Totten
Process Engineering and Applied Science
Dalhousie University
Fall 2023
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Outline
• Objectives
• Introduction
• Molecular Diffusion
○ Special Cases of Fick’s Law of Diffusion
○ Diffusion Coefficients
• Convection
○ Convective Mass Transfer Coefficients
• Conservation of Species
• Unsteady-State Mass Transfer
• Summary
• Self-Test
• References
CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

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Learning Objectives
Students should achieve the following learning outcomes:
○ Describe and apply Fick’s law of diffusion for molecular transport.
○ Describe and apply the forms of Fick’s law suitable for situations involving
equimolar counter-diffusion and diffusion through a stagnant film.
○ Apply relationships to calculate diffusivity coefficients for gases and liquids.
○ Describe and apply the equations for convective mass transfer.
o Use convective mass transfer correlations to calculate convective mass
transfer coefficients for different flow regimes and geometries.
○ Describe and apply the conservation of species equation.
○ Solve unsteady-state diffusion mass transfer problems in various
geometries using graphical methods and numerical methods.
Supplemental Reading: Geankoplis, C. J., et al. (2018). Transport Processes and Separation Process
Principles (5th ed.): Chapters 18 to 21, pp. 731 to 925.
Supplemental Reading: Seader, J. D., Henley, E. J., & Roper, D. K. (2018). Separation Process Principles
(3rd ed.): Chapter 3, pp. 85 to 119.
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Outline
• Objectives
• Introduction
• Convection
• Summary
• Self-Test
• References

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Introduction
• Many chemical process materials occur as mixtures of different
components in the gas, liquid, or solid phase.
• To separate or remove one or more of the components from its original
mixture, it must be contacted with another phase. The two phases are
brought into contact with each other so that a solute(s) can diffuse from
one to the other.
• The two-phase pair can be gas-liquid, gas-solid, liquid-liquid, or liquid-
solid.
• Mass transfer occurs in distillation, absorption/stripping, drying, liquid-
liquid extraction, adsorption, and membrane processes.

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Introduction
Types of Transport
• Mass transfer occurs whenever there is a concentration difference
within a material or fluid or between materials and fluids.
• There are two modes (or mechanisms) of mass transfer:
1. Diffusion (molecular diffusion + eddy diffusion)
2. Convection (advection + diffusion)
• Transfer of mass can occur through the random motion of molecules.
This is referred to as diffusion

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Introduction
Types of Transport
• Transfer of mass can also occur through the bulk motion of fluids. This
is referred to as advection.
• Advection usually occurs simultaneously with diffusion. The combination
of the two is referred to as convection.
• Therefore, convection is comprised of two mechanisms:
○ Transfer due to random molecular motion (diffusion)
○ Transfer by bulk fluid motion (advection)

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Outline
• Objectives
• Introduction
• Convection
• Summary
• Self-Test
• References

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Molecular Diffusion
Fick’s First Law of Diffusion
Flow = Flux ⋅ Area
Mass Mass
Time Area⋅Time
For one-dimensional mass transfer in the y-direction:

mol A mol A
𝑁ሶ𝐴𝑦 = 𝐽𝐴𝑦 2 ⋅ 𝐴 m2
s m ⋅s

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Molecular Diffusion
Proportionality
Flux = ⋅ Gradient
Constant
Mass Diffusion Concentration

Area⋅Time Coefficient Gradient
For one-dimensional mass transfer in the y-direction:

mol A m2 𝑑𝐶𝐴 mol A/m3
𝐽𝐴𝑦 2 = −𝐷𝐴𝐵 ⋅
m ⋅s s 𝑑𝑦 m

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Molecular Diffusion
Fick’s law can also be written in terms of mole fraction, by substituting
the following into the flux equation:
mol A mol A mol mixture
𝐶𝐴 3 = 𝑦𝐴 ⋅𝐶
m mixture mol mixture m3 mixture
𝑑𝐶𝐴 𝑑𝑦𝐴
𝐽𝐴𝑦 = −𝐷𝐴𝐵 = −𝐶𝐷𝐴𝐵
𝑑𝑦 𝑑𝑦
where:
○ yA is the mole fraction of A
○ C is the total concentration of the mixture including all components (mol/m3)
and can often be treated as constant

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Molecular Diffusion
Although Fick’s law worked for some systems, early investigations found that it did not always
accurately describe diffusion in all systems.
This is because the diffusion of mass creates a bulk motion of mass (advection).
Stefan and Maxwell, using the kinetic theory of gases, proved that the mass flux relative to a
stationary coordinate system is a result of two contributions:
∗
𝑁
ด𝐴 = 𝐽ณ𝐴 + 𝐶ถ
𝐴𝑢
flux of total flux of mass flux of mass
mass transported transported by
transported by diffusion bulk motion of fluid
where:
○ 𝑁𝐴 is the molar flux relative to a set of stationary axes (mol A s-1 m-2)
○ 𝐽𝐴 is the molar flux relative to the molar-average velocity (mol A s-1 m-2)
○ CA is the concentration of A (mol A/m3)
○ u* is the average molar velocity (m/s)

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Molecular Diffusion
We are typically interested in determining the molar flux using stationary coordinates:
𝑁𝐴 = 𝐽𝐴 + 𝐶𝐴 𝑢∗ = 𝐶𝐴 𝑢𝐴
For a binary system, the molar-average velocity is given by the following equation:
1
𝑢 ∗ = 𝑦𝐴 𝑢𝐴 + 𝑦𝐵 𝑢𝐵 = (𝐶ถ
𝐴 𝑢𝐴 + 𝐶𝐵 𝑢𝐵 )
𝐶
𝑁𝐴 𝑁𝐵
Fick’s law can be used for JA:

𝑑𝑦𝐴
𝐽𝐴 = −𝐶𝐷𝐴𝐵
𝑑𝑦
Combining these equations gives the Fick’s rate equation (or Fick’s law with bulk motion):
𝑑𝑦𝐴
𝑁𝐴 = −𝐶𝐷𝐴𝐵 + 𝑦𝐴 𝑁𝐴 + 𝑁𝐵
𝑑𝑦

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Outline
• Objectives
• Introduction
• Convection
• Summary
• Self-Test
• References

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Special Cases of Fick’s Law of Diffusion

Equimolar Counter-Diffusion
Consider two large tanks connected by a small
diameter tube. Initially Tank 1 has a higher NA
partial pressure of gas A and Tank 2 has a PA1, PB1 PA2, PB2
higher partial pressure of gas B. P NB P
Once the valve is opened, there will be a flux of z=0 z = z1
A to the right (NA) and a flux of B to the left (NB). PA1 PB2
To maintain constant pressure, if a molecule of A PB1 PA2
diffuses from left to right, then a molecule of B
must replace it by diffusing from right to left.
This will result in equimolar counter-diffusion.
The molar flux of A relative to stationary coordinates will be equal in magnitude but in the
opposite direction to the molar flux of B relative to stationary coordinates:
𝑁𝐴 = −𝑁𝐵

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Equimolar Counter-Diffusion
Substituting NA = –NB into Fick’s law gives the following equation:
0
𝑑𝑦𝐴
𝑁𝐴 = −𝐶𝐷𝐴𝐵 + 𝑦𝐴 𝑁𝐴 − 𝑁𝐴
𝑑𝑧
𝑑𝑦𝐴
𝑁𝐴 = 𝐽𝐴 = −𝐶𝐷𝐴𝐵
𝑑𝑧
If the system is composed of ideal gases, this expression can be recast in terms of pressure.
𝑃𝐴
𝑃 𝑑 𝐷𝐴𝐵 𝑑𝑃𝐴
𝑃
𝑁𝐴 = − 𝐷 =−
𝑅𝑇 𝐴𝐵 𝑑𝑧 𝑅𝑇 𝑑𝑧
where: ○ yA is the mole fraction of A
○ NA is the molar flux relative to a set of stationary axes ○ P is the gas pressure (atm)
(mol A s-1 m-2) ○ R is the universal gas constant
○ JA is the molar flux relative to the molar-average velocity (8.206×10-5 m3 atm mol-1 K-1)
(mol A s-1 m-2)
○ T is the gas temperature (K)
○ C is the the total concentration of the mixture including all
components (mol/m3) ○ PA is the partial pressure of component A (atm)
○ DAB is the diffusion coefficient of component A in B (m2/s) ○ z is the position in the z-direction (m)

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Example 1: Equimolar Counterdiffusion
Ammonia gas (A) is diffusing through a uniform tube 0.10 m long
containing N2 gas (B) at 101325 Pa pressure and 298 K. At point 1, 𝑃𝐴,1 =
10130 Pa and at point 2, 𝑃𝐴,2 = 5070 Pa. The diffusivity 𝐷𝐴𝐵 = 0.230 ×
10−4 m2/s. Calculate the flux 𝑁𝐴 at steady state.

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Diffusion Through a Stagnant Film
It is possible for component A to diffuse through other molecules that
remain stationary or stagnant. Air (B)
(2)
Examples of this include the following:
○ Evaporation of pure benzene (A) into stagnant air (B). NA
z1 – z2
○ Absorption of NH3 vapour (A) through air (B) and into water.
(1)
This is also referred to as unimolecular diffusion. Liquid
benzene (A)
In this case, NB = 0.
NH3 (A) (1)
Air (B)
NA z1 – z2
(2)
CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023 Liquid water

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Diffusion Through a Stagnant Film
Substituting NB = 0 into Fick’s law gives the following equation :
𝑑𝑦𝐴
𝑁𝐴 = −𝐶𝐷𝐴𝐵 + 𝑦𝐴 𝑁𝐴 − 0
𝑑𝑧
𝐶𝐷𝐴𝐵 𝑑𝑦𝐴
𝑁𝐴 = −
1 − 𝑦𝐴 𝑑𝑧
Again, this can be recast for use with ideal gases at constant pressure:
𝑃𝐴
𝑃 𝐷𝐴𝐵 𝑑 𝑃 𝐷𝐴𝐵 𝑃 𝑑𝑃𝐴
𝑁𝐴 = − =−
𝑅𝑇 1 − 𝑃𝐴 𝑑𝑧 𝑅𝑇 𝑃 − 𝑃𝐴 𝑑𝑧
𝑃
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Example 2: Diffusion Through a Stagnant Film
A thin film of water (5 mm) is exposed to CO2 (solubility = 615×10-6 mol
CO2/mol liquid) on one side and He (solubility = 6.997×10-6 mol He/mol
liquid) on the other side. Consider He to be essentially insoluble in water.
What is the flux of CO2 through the water film?

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Diffusion Through Cylinders
One-dimensional mass transfer can also occur in cylindrical or spherical
systems, and other geometries are possible.
The equimolar counter-diffusion rate in the radial direction through a
cylinder is given by Fick’s law:
𝑑𝐶𝐴
ሶ
𝑁𝐴 = 𝑁𝐴 𝐴 = −𝐷𝐴𝐵 𝐴
𝑑𝑟
where 𝐴 = 2𝜋𝑟𝐿. Note that A varies with r.
𝑑𝐶𝐴 dr
𝑁ሶ𝐴 = −2𝜋𝐿𝐷𝐴𝐵 𝑟
𝑑𝑟 r1 r2
𝑟2 𝐶𝐴2
𝑑𝑟
𝑁ሶ𝐴 න = −2𝜋𝐿 න 𝐷𝐴𝐵 𝑑𝐶𝐴
𝑟
𝑟1 𝐶𝐴1
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Diffusion Through Cylinders
If DAB is assumed to be constant, it can be taken out of the integral.
𝑟2
𝑁ሶ𝐴 ln = −2𝜋𝐿𝐷𝐴𝐵 𝐶𝐴2 − 𝐶𝐴1
𝑟1
2𝜋𝐿𝐷𝐴𝐵 𝐶𝐴1 − 𝐶𝐴2
𝑁ሶ𝐴 = 𝑟2
ln ൗ𝑟1
dr
r1 r2

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Diffusion Through Spheres
We can repeat this analysis for one-dimensional equimolar counter-
diffusion in the radial direction through a sphere:
𝑑𝐶𝐴
𝑁ሶ𝐴 = 𝑁𝐴 𝐴 = −𝐷𝐴𝐵 𝐴
𝑑𝑟
where 𝐴 = 4𝜋𝑟 2 . Note that A varies with r.
𝑑𝐶𝐴 dr
𝑁ሶ𝐴 = −4𝜋𝐷𝐴𝐵 𝑟2 r1
𝑑𝑟
𝑟2 𝐶𝐴2 r2
𝑑𝑟
𝑁ሶ𝐴 න 2 = −4𝜋 න 𝐷𝐴𝐵 𝑑𝐶𝐴
𝑟
𝑟1 𝐶𝐴1
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Diffusion Through Spheres
If DAB is assumed to be constant, it can be taken out of the integral.
1 1
−𝑁ሶ𝐴 − = −4𝜋𝐷𝐴𝐵 𝐶𝐴2 − 𝐶𝐴1
𝑟2 𝑟1
4𝜋𝐶𝐷𝐴𝐵 𝐶𝐴2 − 𝐶𝐴1
𝑁ሶ𝐴 =
1 1
−
𝑟2 𝑟1 dr
r1
r2

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Outline
• Objectives
• Introduction
• Convection
• Summary
• Self-Test
• References

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Diffusion Coefficients
The diffusion coefficient (DAB) (or mass diffusivity) is generally given for a
specific pair of chemical species (A and B) and is a measure of the speed at
which they diffuse into each other.
The diffusion coefficient depends on the pressure, temperature, and composition
of the system.
It is closely related to the density of the system, which greatly affects the mobility
of molecules.
The typical ranges for diffusion coefficients are as follows:
○ Gases 10-6 to 10-5 m2/s (diffusion is quickest)
○ Liquids 10-10 to 10-9 m2/s
○ Solids 10-14 to 10-10 m2/s (diffusion is slowest)
For a binary system:
𝐷𝐴𝐵 = 𝐷𝐵𝐴

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Diffusion coefficient (DAB) values for various species pairs can be found in
published data tables.
(Welty et al., 2015)

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Prediction of Diffusivity for Gases
• The diffusivity of binary gas mixture in the dilute gas region can be
predicted using the kinetic theory of gases.
• The Chapman-Enskog relation for predicting the diffusivity of a binary gas
pair of A and B molecules is:
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1.8583 × 10−7 𝑇 3/2 1 1
𝐷𝐴𝐵 = 2 +
𝑃𝜎𝐴𝐵 Ω𝐷,𝐴𝐵 𝑀𝐴 𝑀𝐵
where
o 𝐷𝐴𝐵 is diffusivity in m2/s
o 𝑇 is temperature in K
o 𝑀𝐴 is molecular weight of A in kg mass/kg mol
o 𝑀𝐵 is molecular weight of B in kg mass/kg mol
o 𝑃 is pressure in atm
o 𝜎𝐴𝐵 is average collision diameter
o Ω𝐷,𝐴𝐵 is collision integral based on Lennard-Jones potential

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• The Chapman-Enskog equation is relatively complicated to use because
the constants 𝜎𝐴𝐵 and Ω𝐷,𝐴𝐵 are difficult to estimate.
• The semiempirical method of Fuller et al., is often preferred. This
equation shows that 𝐷𝐴𝐵 is proportional to 1/𝑃 and to 𝑇 1.75 .
1 1 1/2
1.00× 10−7 𝑇 1.75
𝑀𝐴 + 𝑀𝐵
𝐷𝐴𝐵 =
where 𝑃 ∑ν𝐴 1/3 + ∑ν𝐵 1/3 2
o 𝑀𝐴 is molecular weight of A in kg mass/kg mol Note: This method can be used for
o 𝑀𝐵 is molecular weight of B in kg mass/kg mol nonpolar gases or for a polar-nonpolar
o 𝑃 is pressure in atm mixtures. It’s accuracy is not as good
of the Chapman-Enskog equation.
o ∑𝜈𝐴 is sum of structural volume increments in A
o ∑𝜈𝐵 is sum of structural volume increments in B
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Example 3: Prediction of Diffusivity of a Gas Mixture
Butanol (A) is diffusing through air at 1 atm. Using the Fuller et al. method,
estimate the diffusivity, 𝐷𝐴𝐵 , for the following temperatures and compare
with experimental data:
a) For 0°C (Experimental 𝐷𝐴𝐵 = 7.03×10-6 m2/s)
b) For 25.9°C (Experimental 𝐷𝐴𝐵 = 8.70×10-6 m2/s)
c) For 0°C and 2.0 atm (No Experimental 𝐷𝐴𝐵 )

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Prediction of Diffusivity for Liquids
• Equations for predicting diffusivities of dilute solutes in liquids are semi-
empirical, since the theory of diffusion in liquids in not well established.
• The Stokes-Einstein equation is for very large spherical molecules (A)
diffusing in a liquid solvent (B) of small molecules as follows:
9.96 × 10−16 𝑇
𝐷𝐴𝐵 = 1/3
where 𝜇𝑉𝐴
o 𝜇 is dynamic viscosity of solution in Pa∙s
o 𝑉𝐴 is solute molar volume at its normal boiling point in m3/kg mol
• This equation only applies to large sphere molecules >1000 molecule
weight or when the molar volume is >0.500 m3/kmol.
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• For smaller solute molar volumes, the Stokes-Einstein equation does not
hold.
• The Wilke-Chang equation can be used for most general purposes where
the solute (A) is dilute in the solvent (B).
𝑇
𝐷𝐴𝐵 = 1.173 × 10−16 𝜙𝑀𝐵 1/2
𝜇𝐵 𝑉𝐴0.6
where
o 𝐷𝐴𝐵 is diffusivity in m2/s Note: 𝝓 = 2.6 for water, 1.9 for methanol,
o 𝑇 is temperature in K 1.5 for ethanol, 1.0 for benzene, 1.0 for
o 𝑀𝐵 is molecular weight of B in kg mass/kg mol ether, 1.0 for heptane, and 1.0 for other
o 𝜇𝐵 is dynamic viscosity of B in Pa∙s unassociated solvents.
o 𝑉𝐴 is solute molar volume at its normal boiling point in m3/kg mol
o 𝜙 is an association parameter of the solvent

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Outline
• Objectives
• Introduction
• Convection
• Summary
• Self-Test
• References

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Convection
• Consider the transfer of a volatile component A from a surface to a fluid
moving at a steady velocity of u∞. The concentration of A in the bulk
fluid is CA∞ = 0.
• Because of the concentration difference, there will be a mass flux from
the surface and into the fluid.
• The flux from surface must equal
the diffusion flux from the interface CA
into the fluid (no advection at the u
surface).
y
• Mass balance at the interface: NA
𝑑𝐶𝐴
𝑁𝐴 = −𝐷𝐴𝐵 ቤ x
CA = CAs
𝑑𝑦 𝑦=0

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Convection
• We assume that the concentration difference within the fluid occurs
within a small layer or film thickness of width δ.
• The gradient at the surface can then be approximated as a difference
through the boundary layer:
𝑑𝐶𝐴 𝐶𝐴∞ − 𝐶𝐴 𝑠
ቤ ≈
𝑑𝑦 𝑦=0 𝛿
CA
u
y
NA
x
CA = CAs

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Convection
• Therefore, the molar flux into the fluid can be written as follows:
𝑑𝐶𝐴 𝐷𝐴𝐵
𝑁𝐴 = −𝐷𝐴𝐵 ቤ = 𝐶𝐴 𝑠 − 𝐶𝐴∞ = 𝑘c 𝐶𝐴 𝑠 − 𝐶𝐴∞
𝑑𝑦 𝑦=0 𝛿
where
○ DAB is the diffusion coefficient of component A (volatile component) in B (flowing fluid) (m2/s)
○ δ is the film thickness (m)
○ CA∞ is the concentration of A in the CA
free flowing stream (mol A/m3) u
○ CAs is the concentration of A in the fluid directly
above the interface at y = 0 (mol A/m3)
y
○ kc is the convective mass transfer coefficient (m/s) NA
• The value of kc is usually determined x

experimentally and formulated into semi- CA = CAs
empirical correlations.

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Outline
• Objectives
• Introduction
• Convection
• Summary
• Self-Test
• References

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Convective Mass Transfer Coefficients

Dimensionless Numbers
• Experimental data for mass-transfer coefficients obtained using different
fluids, velocities, and geometries are correlated using dimensionless
numbers.
• The most important dimensionless number is the Reynolds number:
Inertial Force 𝜌𝑢𝐿
Re = =
Viscous Force 𝜇
where
o 𝜌 is density in kg/m3
o 𝑢 is velocity in m/s Note: In packed beds the superficial
velocity, 𝒖′ is often used. 𝒖 = 𝒖′ /𝜺
o 𝐿 is characteristic length in m
o 𝜇 is dynamic viscosity in Pa∙s

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• The Schmidt number is the ratio of the viscous diffusion rate to the
molecular diffusion rate. The Schmidt number relates the relative
thickness of the hydrodynamic layer and mass boundary layer.
• The Schmidt number is defined as:
Viscous Diffusion Rate 𝜇
Sc = =
Molecular Diffusion Rate 𝜌𝐷𝐴𝐵
where
o 𝜌 is density in kg/m3
o 𝜇 is dynamic viscosity in Pa s

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• The Sherwood number is a dimensionless number used in many mass
transfer operations.
• The Sherwood number is the ratio of the convective to the diffusive mass
transfer rate in the fluid at the surface.
Convective Mass Transfer Rate 𝐿
Sh = = 𝑘𝐶
Diffusion Mass Transfer Rate 𝐷𝐴𝐵
where
o 𝑘𝐶 is mass transfer coefficient in m/s
o 𝐿 is characteristic length in m

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• Often the mass transfer coefficient is correlated as a dimensionless
factor, which is related to the Sherwood number and mass transfer
coefficient.
𝑘𝐶 2/3 Sh
JD = Sc =
𝑢 ReSc1/3

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Mass Transfer for Flow Past Single Sphere
The following equation is an alternative for mass transfer involving gases:
0.6 < Sc < 2.7
Sh = 2 + 0.552 Re0.53 Sc1/3
1 < Re < 48000
The following equation is an alternative for mass transfer involving liquids:
Sh = 2 + 0.95 Re0.5
𝐷 Sc 1/3
2 < Re < 2000
Sh = 0.347 Re0.62
𝐷 Sc 1/3 2 × 103 < Re < 17 × 103

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Mass Transfer to Packed Beds
The following equation for mass transfer involving gases:
0.4548 0.3 < 𝜀 < 0.5
JD = Re−0.407
𝜀 10 < Re < 10000
The following equation mass transfer involving liquids:
1.09 165 < Sc < 70000

JD = Re−2/3
𝜀 0.0016 < Re < 55
0.250 165 < Sc < 10690

JD = Re−0.31
𝜀 55 < Re < 1500
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Example 4: Estimation of the Mass Transfer Coefficient
Calculate the value of the mass-transfer coefficient and the flux for mass
transfer from a sphere of naphthalene to air at 45°C and 1 atm flowing at a
velocity of 0.305 m/s. The diameter of the sphere is 25.4 mm. The
diffusivity of naphthalene in air at 45°C is 6.92 × 10-6 m2/s and the vapour
pressure of solid naphthalene is 0.555 mmHg.

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Outline
• Objectives
• Introduction
• Convection
• Summary
• Self-Test
• References

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Conservation of Species
Three-Dimensional Cartesian Coordinate System
• In a three-dimensional Cartesian coordinate system, the following species equation can
be written in vector notation form:
𝜕𝐶𝐴
+ 𝑢 ∙ ∇𝐶𝐴 = 𝐷𝐴 ∇2 𝐶𝐴 + 𝑅ሶ 𝐴,𝐺
𝜕𝑡
net rate of addition rate of addition of
rate of increase of rate of production or
of mass of A by mass of A by
mass of A mass of A
advection diffusion
(Accumulation Term) (Generation Term)
(Advection Term) (Diffusion Term)
• For the case of no advection (i.e., no fluid motion) and no production of species A by reaction, the
equation reduces to the following form:
𝜕𝐶𝐴
= 𝐷𝐴 ∇2 𝐶𝐴
𝜕𝑡
• This is often referred to as Fick’s second law of diffusion.

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Summary of Equations
𝜕𝐶𝐴
+ (𝑢 ∙ ∇)𝐶𝐴 = 𝐷𝐴 ∇2 𝐶𝐴 + 𝑅ሶ 𝐴,𝐺
𝜕𝑡
• Rectangular coordinates (𝑥, 𝑦, 𝑧),
𝜕𝐶𝐴 𝜕𝐶𝐴 𝜕𝐶𝐴 𝜕𝐶𝐴 𝜕 𝜕𝐶𝐴 𝜕 𝜕𝐶𝐴 𝜕 𝜕𝐶𝐴
+ 𝑢𝑥 + 𝑢𝑦 + 𝑢𝑧 = 𝐷 + 𝐷 + 𝐷 + 𝑅ሶ 𝐴,𝐺
𝜕𝑡 𝜕𝑥 𝜕𝑦 𝜕𝑧 𝜕𝑥 𝜕𝑥 𝜕𝑦 𝜕𝑦 𝜕𝑧 𝜕𝑧
• Cylindrical coordinates (𝑟, 𝜃, 𝑧),
𝜕𝐶𝐴 𝜕𝐶𝐴 𝑢𝜃 𝜕𝐶𝐴 𝜕𝐶𝐴 1 𝜕 𝜕𝐶𝐴 1 𝜕 𝜕𝐶𝐴 𝜕 𝜕𝐶𝐴

+ 𝑢𝑟 + + 𝑢𝑧 = 𝑟𝐷 + 2 𝐷 + 𝐷 + 𝑅ሶ 𝐴,𝐺
𝜕𝑡 𝜕𝑟 𝑟 𝜕𝜃 𝜕𝑧 𝑟 𝜕𝑟 𝜕𝑟 𝑟 𝜕𝜃 𝜕𝜃 𝜕𝑧 𝜕𝑧
• Spherical coordinates (𝑟, 𝜃, 𝜙),
𝜕𝐶𝐴 𝜕𝐶𝐴 𝑢𝜃 𝜕𝐶𝐴 𝑢𝜙 𝜕𝐶𝐴
+ 𝑢𝑟 + +
𝜕𝑡 𝜕𝑟 𝑟 𝜕𝜃 𝑟𝑠𝑖𝑛𝜃 𝜕𝜙
1 𝜕 𝜕𝐶𝐴 1 𝜕 𝜕𝐶𝐴 1 𝜕 𝜕𝐶𝐴
= 2 2
𝑟 𝐷 + 2 𝐷𝑠𝑖𝑛𝜃 + 2 2 𝐷 + 𝑅ሶ 𝐴,𝐺
𝑟 𝜕𝑟 𝜕𝑟 𝑟 𝑠𝑖𝑛𝜃 𝜕𝜃 𝜕𝜃 𝑟 sin 𝜃 𝜕𝜙 𝜕𝜙

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Summary of Equations: Molar Flux
𝜕𝐶𝐴
= −∇ ∙ 𝑁𝐴 + 𝑅ሶ 𝐴
𝜕𝑡
• Rectangular coordinates (𝑥, 𝑦, 𝑧),
𝜕𝐶𝐴 𝜕𝑁𝐴𝑥 𝜕𝑁𝐴𝑦 𝜕𝑁𝐴𝑧
=− + + + 𝑅ሶ 𝐴
𝜕𝑡 𝜕𝑥 𝜕𝑦 𝜕𝑧
• Cylindrical coordinates (𝑟, 𝜃, 𝑧),
𝜕𝐶𝐴 1𝜕 1 𝜕𝑁𝐴𝜃 𝜕𝑁𝐴𝑧
=− (𝑟𝑁𝐴𝑟 ) + + + 𝑅ሶ 𝐴
𝜕𝑡 𝑟 𝜕𝑟 𝑟 𝜕𝜃 𝜕𝑧
• Spherical coordinates (𝑟, 𝜃, 𝜙),
𝜕𝐶𝐴 1 𝜕 2 1 𝜕 1 𝜕𝑁𝐴𝜙
= − 2 (𝑟 𝑁𝐴𝑟 ) + (𝑁𝐴𝜃 𝑠𝑖𝑛𝜃) + + 𝑅ሶ 𝐴
𝜕𝑡 𝑟 𝜕𝑟 𝑟𝑠𝑖𝑛𝜃 𝜕𝜃 𝑟𝑠𝑖𝑛𝜃 𝜕𝜙

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Boundary Conditions
• Solutions to the species equations must be constrained by physically realistic
initial and boundary conditions.
• Boundary conditions include:

1. Dirichlet conditions or boundary conditions of the first kind – 𝐶𝐴 is specified at the
boundary for 𝑡 > 0. Note that it is sometimes possible to use surface reaction
stoichiometry and rates to estimate a boundary value for 𝐶𝐴 .
2. Neumann conditions or boundary conditions of the second kind – 𝜕𝐶𝐴 /𝜕𝑛 is
specified for 𝑡 > 0. The condition 𝜕𝐶𝐴 Τ𝜕𝑛 = constant is used if the diffusive mass (or
molar) flux is specified at a point. If 𝜕𝐶𝐴 Τ𝜕𝑛 = 0 it is called the no flux BC and is used
for impermeable boundaries. Note that it is sometimes possible to use surface
reaction stoichiometry and rates to estimate a surface flux.
52/75
Boundary Conditions
3. Boundary conditions of the third kind: The flux is proportional to concentration
(𝜕𝐶𝐴 /𝜕𝑛 ∝ 𝐶𝐴 ). This condition frequently occurs when there is convection at a
boundary and is usually expressed as:
𝑁𝐴 ቚ = 𝑘𝑐 𝐶𝐴 𝑠 − 𝐶𝐴 ∞
𝑠
It is important to keep in mind that many other options are also possible, and that
the choice of boundary conditions has a large impact on the ultimate solution.

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Outline
• Objectives
• Introduction
• Convection
• Summary
• Self-Test
• References

54/75
Unsteady-State Mass Transfer

Concentration-Response Charts
Consider mass transfer in a long rectangular slab
of thickness 2L.
𝐶𝑖
The concentration at the surface is suddenly changed

to C1. If C1 < Ci, the slab will begin to transfer mass.
𝐶1
We can simplify the conversation of species balance in

rectangular coordinates to obtain the equation
for one-dimensional transient mass diffusion:
0 0 0 0 0 0
𝜕𝐶 𝜕𝐶 𝜕𝐶 𝜕𝐶 𝜕 𝜕𝐶 𝜕 𝜕𝐶 𝜕 𝜕𝐶
+ 𝑢𝑥 + 𝑢𝑦 + 𝑢𝑧 = 𝐷 + 𝐷 + 𝐷 + 𝑅ሶ 𝐺
𝜕𝑡 𝜕𝑥 𝜕𝑦 𝜕𝑧 𝜕𝑥 𝜕𝑥 𝜕𝑦 𝜕𝑦 𝜕𝑧 𝜕𝑧
𝜕𝐶 𝜕2𝐶
=𝐷 2
𝜕𝑡 𝜕𝑥
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Concentration-Response Charts L
Consider the case of transient mass transfer from a long plane slab
by symmetrical convection.
The initial and boundary conditions can be stated as follows:
-2 -1
𝐶h
∞ (W m 3K) )
(𝑚𝑜𝑙/𝑚 h𝐶(W m-2 K-1
∞ (𝑚𝑜𝑙/𝑚 )
3)
BC1: BC2: Initial condition: 𝑘𝑐T(𝑚/𝑠)

(°C) T (°C)
𝑘𝑐 (𝑚/𝑠)
𝜕𝐶 𝜕𝐶
𝑘𝐶 𝐶 − 𝐶∞ ቚ =𝐷 ቤ ቤ =0 C = Ci for all x
𝑥=±𝐿 𝜕𝑥 𝑥=±𝐿 𝜕𝑥 𝑥=0 x
We can define the following dimensionless variables:

𝐶 − 𝐶∞ 𝐷𝐴𝐵 𝑡 𝑥
Θℎ = Foℎ = 2 𝜉= +1
𝐶𝑖 − 𝐶∞ 𝐿 𝐿
𝐿2
𝐶 = 𝐶∞ + 𝐶𝑖 − 𝐶∞ Θℎ 𝑡= Foℎ 𝑥 =𝐿 𝜉−1
𝐷𝐴𝐵
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The following three slides present these graphical results for a plane slab, a long cylinder, and
a sphere.
○ For each shape, there are four plots. Each plot represents the results at a specific value of ξ (position
within solid).
○ Θh is plotted as a function of Bih for different constant values of Foh.
These charts can also be used for heat transfer problems.

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𝐶𝑖 − 𝐶∞
𝐶 − 𝐶∞
Plane Slab of Width 2L
Θℎ =
L
𝐶 − 𝐶∞
Θℎ =
-2 -1
(W m 3 )K )
𝐶∞h(𝑚𝑜𝑙/𝑚 h𝐶∞ m-2 K-1
(W(𝑚𝑜𝑙/𝑚 3)
)
𝐶 − 𝐶∞
T (°C) 𝑘𝑐 (𝑚/𝑠)
T (°C)
Θℎ =
x
Note the following: Fo =

𝐷𝐴𝐵 𝑡
𝐶 − 𝐶∞
𝐿2
○ The x-axis is on a logarithmic scale.
Θℎ =
○ You can also use this chart for walls of width L
with convection at x = L and insulation at x = 0. Biot number, 𝐵𝑖ℎ = 𝑘𝐶 𝐿/𝐷𝐴𝐵
(Lienhard and Lienhard, 2020)

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𝐶 − 𝐶∞
Long Cylinders of Radius ro
Θℎ =
ro
𝐶 − 𝐶∞
Θℎ =
-2 -1
𝐶∞h(𝑚𝑜𝑙/𝑚
(W m 3 )K )
T (°C)
𝐶 − 𝐶∞
Θℎ =
Note the following:
𝐷𝐴𝐵 𝑡
𝐶 − 𝐶∞
Fo =
𝑟𝑜 2
○ This chart uses a different definition of the
Θℎ =
characteristic length in the Biot number than
we saw before (Lc = ro).
Biot number, 𝐵𝑖ℎ = 𝑘𝐶 𝐿/𝐷𝐴𝐵

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𝐶 − 𝐶∞
Spheres of Radius ro
Θℎ =
𝐶 − 𝐶∞
-2 -1
(W m 3K) )
h (𝑚𝑜𝑙/𝑚
𝐶∞
𝑘𝑐T(𝑚/𝑠)
(°C) ro
Θℎ =
𝐶 − 𝐶∞
Note the following:
Θℎ =
○ This chart uses a different definition of the
characteristic length in the Biot number than 𝐷𝐴𝐵 𝑡
𝐶 − 𝐶∞
Fo =
we saw before (Lc = ro). 𝑟𝑜 2
Θℎ =
Biot number, 𝐵𝑖ℎ = 𝑘𝐶 𝐿/𝐷𝐴𝐵

60/75

For the previous sets of curves, notice the following:
○ For a given Bih number and position, Θh
𝐷𝐴𝐵 𝑡
decreases from the initial value of 1 toward Fo =
𝐶 − 𝐶∞
𝐿2
a final value of 0 as Foh increases. In other
Θℎ =
words, C is initially equal to Ci and
approaches C∞ as time passes. Biot number, 𝐵𝑖ℎ = 𝑘𝐶 𝐿/𝐷𝐴𝐵
○ For larger values of Bih, the concentration

approaches C∞ more quickly. This is because
for large Bih, the convective mass transfer is more significant than the
conductive mass transfer.
○ When Bih < 0.1, C does not vary significantly within the object. This is
because conductive mass transfer is more significant than convective mass
transfer, which results in applicability of the lumped capacitance method.
61/75

Example 5: Unsteady-State Mass Transfer Using the Concentration
Response Charts
A large flat slab of wood 50 mm thick and initially containing 30 wt% moisture is
being dried using hot air on both sides. Since the slab is large and flat, end and
edge effects are negligible. The moisture content at the surface of the wood is
maintained at 5 wt% by flowing hot air over the surface of the wood. The diffusivity
of water vapour in the wood is approximately 1.03×10-8 m2/s. Calculate the time for
the center of the wood slab to reach a moisture content of 10 wt%.
yAs = 0.05 yAs = 0.05
L
Wood Air
DAB = 1.03×10-8 m2/s k c yA
+x
50 mm
62/75

Partial Differential Equations
• Partial differential equations (PDEs) are the basis of most complex
engineering models. Commonly, such systems even require the solution
of systems of PDEs.
• Two-dimensional transient mass diffusion:
𝜕𝐶 𝜕𝐶 𝜕𝐶
= 𝐷𝐴𝐵 2
+ 2
𝜕𝑡 𝜕𝑥 𝜕𝑦

63/75

• Mathematically, PDEs are often classified as being hyperbolic,
parabolic or elliptic, based on how information is propagated during
their solution. Consider the following equation:
𝜕2𝑢 𝜕2𝑢 𝜕2𝑢

𝐴 2+𝐵 +𝐶 2+𝐷 =0
𝜕𝑥 𝜕𝑥𝜕𝑦 𝜕𝑦
Two-dimensional steady- 𝜕 2 𝑁𝐴 𝜕 2 𝑁𝐴 𝑅ሶ 𝐴,𝐺

+ =
state mass transfer: 𝜕𝑥 2 𝜕𝑦 2 𝐷𝐴𝐵
Two-dimensional transient 𝜕𝑇 𝜕 2 𝑁𝐴 𝜕 2 𝑁𝐴
mass transfer: = 𝐷𝐴𝐵 +
𝜕𝑡 𝜕𝑥 2 𝜕𝑦 2
Wave equation:

64/75

• From a computational point of view, parabolic and hyperbolic PDEs can
be viewed as initial value problems. That is, they define how the value
of the dependent variable propagates “forward” in one of the independent
variables (typically time). For parabolic equations, this propagation is
normally monotonous. Conversely, for hyperbolic equations, the
propagation can oscillate (i.e., form waves).

65/75

• Elliptic PDEs can be viewed as boundary value problems. That is, the
goal is to find some static solution that satisfies conditions on the
boundaries.
• Note that the solution of elliptic PDEs typically requires an iterative solution
66/75

• Elliptic PDEs are usually converted into systems of linear or nonlinear
algebraic equations.
• Conversely, most parabolic PDEs and many hyperbolic PDEs can be
solved by converting the equations into systems of ODEs and then
applying typical methods for solution of systems of ODEs.
• The solution of PDEs is a complex topic and because this is a
separations course, we will only look at some of the basic solution
concepts (enough to give you a knowledge base that you can expand in
the future).

67/75

Spatial Discretization using Finite Differences
• Several methods are available to convert parabolic PDEs into systems of
ODEs and/or elliptic PDEs into systems of algebraic equations. In
general, this process is referred to as discretization.
• Perhaps the simplest of the available methods is called the finite
difference method (FDM). Other methods include the finite volume
method (FVM) and the finite element method (FEM).
• Most commercial software for packages for solving PDEs are based on
either the FVM or FEM, but the FDM is still useful for solving problems
with relatively simple geometries and to gain an understanding of the
overall approach.

68/75

Example 6: Unsteady-State Mass Transfer Using PDEs
Carbon dioxide is being absorbed into a solution. Once dissolved, the dissolved carbon dioxide is
converted into another species. The transient one-dimensional diffusion-reaction process is
governed by the following partial differential equation (PDE):
𝜕𝐶 𝜕2𝐶
= 𝐷 2 − 𝑘𝐶
𝜕𝑡 𝜕𝑥
where C is the dissolved carbon dioxide concentration (kmol/m3), t is time (s), x is distance (m), D
is the diffusion coefficient for dissolved carbon dioxide in the solution (m2/s), and k is the first-
order reaction rate constant (s-1). Assume that: 𝐷 = 1.5 × 10−9 m2/s and k = 35 s-1. Additionally,
assume that the initial condition and boundary conditions to be,
kmol
𝐶ቚ =0 𝐶ቚ = 0.03𝐶ቚ =0
𝑡<0 𝑥=0 m3 𝑥=0.0001
Use the finite difference method (FDM) with 6 node points (not including false nodes) to convert
the PDE into a system of ODEs. Remember to apply the boundary conditions to derive unique
equations at the boundary nodes.
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• To apply the FDM, we first divide the geometry up into a series of node
points. The simplest approach is to use equally-spaced node points. For
the one-dimensional in the example we could use:
• Note that we can use more node points if we would like a more accurate
solution. Also note that we have defined an endpoint outside of the
geometry. The purpose of this point will become apparent when we write
the equations.
70/75

• We can now approximate the second derivative in the governing PDE
using a finite difference approximation. To do this, we first note that we
can approximate the first derivative at intermediate points around any
point by a central difference. Recall the central difference formula from
calculus:
𝜕𝑓 𝑓 𝑥 + Δ𝑥 − 𝑓 𝑥 − Δ𝑥
ቤ ≈
𝜕𝑥 𝑥 2Δ𝑥
• We will use a central difference because it is more accurate than forward

or backward differences (second-order accuracy as opposed to first-
order accuracy).

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• Let’s then look at point 2 as an example. The first derivative can be
approximated at two intermediate points (1.5 and 2.5) around this point
as:
𝜕𝐶 𝐶2 −𝐶1 𝜕𝐶 𝐶3 −𝐶2
ቚ
𝜕𝑥 1.5
≈
Δ𝑥
ቚ ≈
𝜕𝑥 2.5 Δ𝑥
• The second derivative at point 2 is then simply the difference between the
two first derivatives around this point:
𝜕𝐶 𝜕𝐶 𝐶3 − 𝐶2 𝐶2 − 𝐶1
ฬ − ฬ
𝜕2𝐶 𝜕𝑥 2.5 𝜕𝑥 1.5 Δ𝑥 − Δ𝑥 𝐶3 − 2𝐶2 + 𝐶1
2 อ ≈ = =
𝜕𝑥 Δ𝑥 Δ𝑥 Δ𝑥 2
2

72/75
Outline
• Objectives
• Introduction
• Convection
• Summary
• Self-Test
• References

73/75
Summary
• This chapter introduced the fundamentals of mass transfer for separation
processes.
• Fick’s law of diffusion and special cases of Fick’s law including equimolar
counterdiffusion and diffusion through a stagnant film were discussed.
• Diffusion coefficients for gases can be estimated using the Fuller method
and liquids can be estimated using the Wilke-Chang equation.
• The procedure was shown for calculating mass transfer coefficients for
various geometries and fluids including spheres and packed beds.
• Graphical and numerical solutions to unsteady-state mass transfer
problems were discussed.

74/75
Self-Test
1. What is the proportionality constant for mass transfer? What kinds of
systems tend to have high values for it?
2. Why does the original formulation of Fick’s law not work for all
systems?
3. Describe equimolar counter-diffusion. What form of Fick’s law should
be used?
4. Describe diffusion through a stagnant film. What form of Fick’s law
should be used?
5. Describe the two mechanisms that occur during convective transport.

75/75
References
Chapra, S.C., Canale, R.P., Numerical Methods for Engineers, 7th ed., McGraw-Hill, New York, 2015.
Geankoplis, C.J., Hersel, A.A., Lepek, D.H. (2018). Transport Processes and Separation Process Principles,
5th ed. Pearson Education.
McCabe, W.L., Smith, J.C., Harriott, P., Unit Operations of Chemical Engineering, 7th ed., McGraw-Hill, New
York, 2005.
Plawsky, J.L., Transport Phenomena Fundamentals, 3rd ed., CRC Press, Boca Raton, 2014.
Press, W.H., Teukolsky, S.A., Vetterling, W.T., Flannery, B.P., Numerical Recipes in C: The Art of Scientific
Computing, Cambridge University Press, Cambridge, 1992.
Seader, J.D., Henley, E.J., Roper, D.K. (2011). Separation Process Principles: Chemical and Biochemical
Operations, 3rd ed. John Wiley & Sons Inc., New Jersey.
Wankat, P.C. (2012). Separation Process Engineering: Includes Mass Transfer, 3rd ed. Prentice-Hall, New
Jersey.
Welty, J., Rorrer, Gregory L., & Foster, David G. (2015). Fundamentals of momentum, heat, and mass
transfer (6th ed.). Hoboken, NJ: Wiley.

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CHEE 4704 – Separation Processes II

Chapter 1: Fundamentals of Mass Transfer

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

For one-dimensional mass transfer in the y-direction:

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

Mass Diffusion Concentration

For one-dimensional mass transfer in the y-direction:

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

Fick’s law can be used for JA:

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

Special Cases of Fick’s Law of Diffusion

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

Special Cases of Fick’s Law of Diffusion

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

Special Cases of Fick’s Law of Diffusion

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

Special Cases of Fick’s Law of Diffusion

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023 Liquid water

Special Cases of Fick’s Law of Diffusion

Special Cases of Fick’s Law of Diffusion

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

Special Cases of Fick’s Law of Diffusion

Special Cases of Fick’s Law of Diffusion

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

Special Cases of Fick’s Law of Diffusion

Special Cases of Fick’s Law of Diffusion

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

(Welty et al., 2015)

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

• The value of kc is usually determined x

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

Convective Mass Transfer Coefficients

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

Convective Mass Transfer Coefficients

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

Convective Mass Transfer Coefficients

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

Convective Mass Transfer Coefficients

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

Convective Mass Transfer Coefficients

CHEE 4704 – Chapter 1 | Jon Totten, Fall 2023

Convective Mass Transfer Coefficients

1.09 165 < Sc < 70000

0.250 165 < Sc < 10690

Convective Mass Transfer Coefficients