MASS DIFFUSION

INTRODUCTION
Whenever there is an imbalance of a commodity in a medium, nature tends to redistribute it
until a “balance” or “equality” is established. This tendency is often referred to as the driving
force, which is the mechanism behind many naturally occurring transport phenomena.

The commodity simply creeps away during

redistribution, and thus the flow is a diffusion
process. The rate of flow of the commodity is
proportional to the concentration gradient dC/dx,
which is the change in the concentration C per unit
length in the flow direction x, and the area A
normal to flow direction.

kdiff is the diffusion coefficient of the medium, which is a measure of how fast a commodity
diffuses in the medium, and the negative sign is to make the flow in the positive direction a
positive quantity (note that dC/dx is a negative quantity since concentration decreases in
the flow direction). 2
The diffusion coefficients and thus diffusion rates of gases depend
strongly on temperature.
The diffusion rates are higher at higher temperatures.
The larger the molecular spacing, the higher the diffusion rate.
Diffusion rate: gases > liquids > solids

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ANALOGY BETWEEN HEAT AND MASS TRANSFER

We can develop an understanding of mass transfer in a short time with little

effort by simply drawing parallels between heat and mass transfer.

Temperature
The driving force for mass transfer is the
concentration difference.
Both heat and mass are transferred from
the more concentrated regions to the
less concentrated ones.
If there is no difference between the
concentrations of a species at different
parts of a medium, there will be no mass
transfer.

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Conduction
Mass is transferred by conduction (called diffusion) and convection only.

Rate of mass Fick’s law of

diffusion diffusion

 A  = kg 3A
m
DAB is the diffusion coefficient (or mass
diffusivity) of the species in the mixture
CA is the concentration of the species in the
mixture

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Heat Generation
Heat generation refers to the conversion of some form of energy such as
electrical, chemical, or nuclear energy into sensible thermal energy in the
medium.
Some mass transfer problems involve chemical reactions that occur within
the medium and result in the generation of a species throughout.
Therefore, species generation is a volumetric phenomenon, and the rate of
generation may vary from point to point in the medium.
Such reactions that occur within the medium are called homogeneous
reactions and are analogous to internal heat generation.
In contrast, some chemical reactions result in the generation of a species at
the surface as a result of chemical reactions occurring at the surface due to
contact between the medium and the surroundings.
This is a surface phenomenon, and as such it needs to be treated as a
boundary condition.
In mass transfer studies, such reactions are called heterogeneous reactions
and are analogous to specified surface heat flux.
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Convection
Mass convection (or convective mass transfer) is the mass transfer mechanism between a
surface and a moving fluid that involves both mass diffusion and bulk fluid motion.
Fluid motion also enhances mass transfer considerably.

In mass convection, we define a concentration

boundary layer in an analogous manner to the
thermal boundary layer and define new
dimensionless numbers that are counterparts
of the Nusselt and Prandtl numbers.

Newton’s law
of cooling

Rate of mass
convection
hmass  = m
s

hmass the mass transfer coefficient

As the surface area
Cs − C a suitable concentration difference across
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the concentration boundary layer.
MASS DIFFUSION
Fick’s law of diffusion states that the rate of diffusion of a
chemical species at a location in a gas mixture (or liquid or
solid solution) is proportional to the concentration gradient
of that species at that location.

1 Mass Basis
On a mass basis, concentration is expressed in terms of
density (or mass concentration).

The density of a mixture at a location is equal to the sum of

the densities of its constituents at that location.

The mass fraction of a species ranges between 0

and 1, and the sum of the mass fractions of the
constituents of a mixture be equal to 1. 8
2 Mole Basis
On a mole basis, concentration is expressed in terms of molar concentration
(or molar density), which is the amount of matter in kmol per unit volume.

9
Special Case: Ideal Gas Mixtures
At low pressures, a gas or gas mixture can conveniently be approximated as an ideal
gas with negligible error.
The total pressure of a gas mixture P is equal to the sum of the partial pressures Pi of
the individual gases in the mixture..
Here Pi is called the partial pressure of species i, which is
the pressure species i would exert if it existed alone at the
mixture temperature and volume (Dalton’s law of additive
pressures).
Then using the ideal gas relation PV = NRuT where Ru is the
universal gas constant for both the species i and the
mixture, the pressure fraction of species i can be
expressed as

The pressure fraction of species i of an ideal gas

mixture is equivalent to the mole fraction of that
species and can be used in place of it in mass
transfer analysis.
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Fick’s Law of Diffusion:
Stationary Medium Consisting of Two Species
Fick’s law of diffusion

Here jdiff, A is the (diffusive) mass

flux of species A (mass transfer
by diffusion per unit time and
per unit area normal to the
direction of mass transfer, in
kg/s·m2) and is the
(diffusive) molar flux (in
kmol/s·m2).
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Binary diffusion coefficient or mass
diffusivity, DAB: The constant of
proportionality in Fick’s law.
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1. The diffusion coefficients, in general, are highest in gases and lowest in solids.
The diffusion coefficients of gases are several orders of magnitude greater than
those of liquids.
2. Diffusion coefficients increase with temperature. The diffusion coefficient (and
thus the mass diffusion rate) of carbon through iron during a hardening process, for
example, increases by 6000 times as the temperature is raised from 500°C to
1000°C. 13
Diffusion of water
vapor in air

Ordinary diffusion: The primary driving mechanism of mass diffusion is the

concentration gradient, and mass diffusion due to a concentration gradient is
known as the ordinary diffusion.
Temperature gradients in a medium can cause thermal diffusion (also called the
soret effect), and pressure gradients may result in pressure diffusion.
Forced diffusion: An external force field such as an electric or magnetic field applied
on a mixture or solution can be used successfully to separate electrically charged or
magnetized molecules (as in an electrolyte or ionized gas) from the mixture.
Knudsen diffusion: When the pores of a porous solid such as silica-gel are smaller
than the mean free path of the gas molecules, the molecular collisions may be
negligible and a free molecule flow may be initiated.
Surface diffusion: When the size of the gas molecules is comparable to the pore
size, adsorbed molecules move along the pore walls.
Brownian motion: Particles whose diameter is under 0.1 m such as mist and soot
particles act like large molecules, and the diffusion process of such particles due to
the concentration gradient is called Brownian motion.

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BOUNDARY CONDITIONS
(1) specified species concentration, which corresponds to specified temperature
(2) specified species flux, which corresponds to specified heat flux.

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Solubility: The maximum amount of solid that can be
dissolved in a liquid at a specified temperature.

Henry’s constant H: The product of the total

pressure of the gas mixture and the
proportionality constant.

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1. The concentration of a gas dissolved in a liquid is inversely
proportional to Henry’s constant. The larger the Henry’s
constant, the smaller the concentration of dissolved gases in
the liquid.
2. Henry’s constant increases (and thus the fraction of a
dissolved gas in the liquid decreases) with increasing
temperature. Therefore, the dissolved gases in a liquid can
be driven off by heating the liquid.
3. The concentration of a gas dissolved in a liquid is
proportional to the partial pressure of the gas. The amount
of gas dissolved in a liquid can be increased by increasing
the pressure of the gas. This can be used to advantage in the
carbonation of soft drinks with CO2 gas.

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 Henry’s Law and Air Pollution Control

Scrubbing Pollutants from Vent Streams

Scrubbing is a common name given the
unit operation normally known as gas
absorption.
In this process, mass is transferred from
the gas phase into a liquid for the
purposes of removing material from the
gas stream.
Wet packed scrubbers can achieve high
contaminant removals and can operate
at a variety of loads.
 Typical Scrubbing Applications:

• SO2 removal from stack gases

• H2S removal for odor and sulphur emission control
• SO3 removal from sulfuric acid plant vents
• Alcohol, ketone, ether, and aldehyde removal from vent streams
• Sulfuric and nitric acid emission control
• CO2 removal from gas streams
• Organics removal by use of heavy , large molecular weight solvents
• Removal of HCl, chlorine oxides, and chlorine
Design of Absorption Tower
 Henry’s Law and Dissolved Oxygen Concentration in Water

• What is the concentration of oxygen dissolved in water at 25 oC when the

solution is in equilibrium with air at 1 atm total pressure?
• pA = H ·xA
• The Henry’s law constant is 4.38 x 104 atm/mol fraction
• The partial pressure pA of oxygen (A) in air is 0.21 atm
• 0.21 = H ·xA = 4.38 x 104 · xA
• Solving ➔ xA = 4.80 · 10-6 mol fraction
• This means 0.000853 part O2 / 100 parts water
 Henry’s Law and Dissolved Oxygen Concentration in Water

• What is the concentration of oxygen dissolved in water at 25 oC when the

solution is in equilibrium with air at 1 atm total pressure?

• The Henry’s law pA = H ·xA

• The Henry’s law constant is 4.38 x 104 atm/mol fraction

• The partial pressure pA of oxygen (A) in air is 0.21 atm
• 0.21 = H ·xA = 4.38 x 104 · xA
• Solving ➔ xA = 4.80 · 10-6 mol fraction

• That means 0.000853 part O2 / 100 parts water

Henry’s Law and ice fishing
An approximate relation in this case for the
mole fractions of a species on the liquid and
gas sides of the interface is given by Raoult’s
law:

The concentration of the gas species i in the solid

at the interface Ci, solid side is proportional to the
partial pressure of the species i in the gas Pi, gas
side on the gas side of the interface and is
expressed as

Permeability: The product of the solubility of a gas and

the diffusion coefficient of the gas in a solid. It is a
measure of the ability of the gas to penetrate a solid.

DAB is the diffusivity of the gas in the solid. Permeability is inversely

proportional to thickness and has the unit kmol/s·bar. 25
Atmospheric air can be viewed as a mixture of dry air and
water vapor.
Atmospheric pressure is the sum of the pressure of dry air and
the pressure of water vapor (vapor pressure Pv)
Relative humidity: The ratio of the actual amount of moisture
in the air at a given temperature to the maximum amount air
can hold at that temperature.
The relative humidity ranges from 0 for dry air to 100 percent
for saturated air (air that cannot hold any more moisture).
Saturation pressure Psat: The partial pressure of water vapor in
saturated air.

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TRANSIENT MASS DIFFUSION
The steady analysis is useful when determining the leakage rate of a species through a stationary
layer. But sometimes we are interested in the diffusion of a species into a body during a limited
time before steady operating conditions are established. Such problems are studied using
transient analysis.

Transient mass diffusion in a stationary medium is

analogous to transient heat transfer provided that
the solution is dilute and thus the density of the
medium is constant.
The analogous one-dimensional transient mass
diffusion problems satisfy these requirements:
1. The diffusion coefficient is constant. This is valid
for an isothermal medium since DAB varies with
temperature (corresponds to constant thermal
diffusivity).
2. There are no homogeneous reactions in the
medium that generate or deplete the diffusing
species A (corresponds to no heat generation).
3. Initially (t = 0) the concentration of species A is
constant throughout the medium (corresponds to
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uniform initial temperature).
 For the case of a semi-infinite medium with
constant surface concentration:

where CA, i is the initial concentration of species A at

time t = 0 and CA, s is the concentration at the inner
side of the exposed surface of the medium.

penetration depth
The penetration depth is proportional to the square root
of both the diffusion coefficient and time.

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 The penetration depth of zinc in
copper in 10 h is

The diffusion coefficients in solids are

typically very low (on the order of 10-9 to 10-
15 m2/s), and thus the diffusion process

usually affects a thin layer at the surface.

A solid can conveniently be treated as a semi-
infinite medium during transient mass
diffusion regardless of its size and shape
when the penetration depth is small relative
to the thickness of the solid.

Penetration depth: The location x where the

tangent to the concentration profile at the
surface (x = 0) intercepts the CA = CA, i line.
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DIFFUSION IN A MOVING MEDIUM
Many practical problems, such as the evaporation
of water from a lake under the influence of the
wind or the mixing of two fluids as they flow in a
pipe, involve diffusion in a moving medium
where the bulk motion is caused by an external
force.
Mass diffusion in such cases is complicated by
the fact that chemical species are transported
both by diffusion and by the bulk motion of the
medium (i.e., convection).
The velocities and mass flow rates of species in a
moving medium consist of two components: one
due to molecular diffusion and one due to
convection
We limit our consideration to systems that involve only two components (species
A and B) in one-dimensional flow (velocity and other properties change in one
direction only, say the x-direction). We also assume the total density (or molar
concentration) of the medium remains constant.

30
The velocity of a species at a location in this case is the diffusion velocity,
which is the average velocity of a group of molecules at that location moving
under the influence of concentration gradient. 31
Mass-average velocity V: The velocity that would be
measured by a velocity sensor such as a pitot tube, a
turbine device, or a hot wire anemometer inserted
into the flow.
Stationary medium (V = 0): A medium whose mass-
average velocity is zero. Therefore, mass transport in a
stationary medium is by diffusion only, and zero mass-
average velocity indicates that there is no bulk fluid
motion.
A MOVING MEDIUM

35
Anytime the species A diffuses in one direction, an
equal amount of species B must diffuse in the
opposite direction to maintain the density (or the
molar concentration) constant.
This behavior is closely approximated by dilute gas
mixtures and dilute liquid or solid solutions. For
example, when a small amount of gas diffuses into a
liquid, it is reasonable to assume the density of the
liquid to remain constant.

In the case of constant total concentration, the

diffusion coefficient of species A into B is equal to
the diffusion coefficient of species B into A.
36
On molar basis:

The rates of diffusion of species A and B must be

equal in magnitude but opposite in sign.

37
Special Case: Gas Mixtures at Constant Pressure
and Temperature
Consider a gas mixture whose total pressure and
temperature are constant throughout.

Ru = 8.314 kJ/kmol·K universal gas constant

The assumption of constant mixture density in such
cases will not be accurate unless the gas or gases with
variable concentrations constitute a very small
fraction of the mixture.
However, the molar density C of a mixture remains
constant when the mixture pressure P and
temperature T are constant since

The condition C = constant offers considerable

simplification in mass transfer analysis, and thus it is
more convenient to use the molar formulation when
dealing with gas mixtures at constant total pressure
and temperature 38
Diffusion of Vapor through a
Stationary Gas: Stefan Flow
Many engineering applications such as heat pipes, cooling ponds, and the familiar perspiration
involve condensation, evaporation, and transpiration in the presence of a noncondensable gas,
and thus the diffusion of a vapor through a stationary (or stagnant) gas.
To understand and analyze such processes, consider a liquid layer of species A in a tank
surrounded by a gas of species B, such as a layer of liquid water in a tank open to the
atmospheric air at constant pressure P and temperature T.

39
This relation is known as Stefan’s law, and
the induced convective flow
described that enhances mass diffusion is
called the Stefan flow.

40
Equimolar Counterdiffusion

equimolar counterdiffusion

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