Mass transfer is the net movement of a species in a mixture from one

location to another. In separation operations, the transfer often takes

place across an interface between phases. Absorption by a liquid of a
solute from a carrier gas involves transfer of the solute through the
gas to the gas–liquid interface, across the interface, and into the
liquid. Mathematical models for this process—as well as others such
as mass transfer of a species through a gas to the surface of a porous,
adsorbent particle—are presented in this book.

Two mechanisms of mass transfer are: (1) molecular diffusion by

random and spontaneous microscopic movement of molecules as a
result of thermal motion; and (2) eddy (turbulent) diffusion by
random, macroscopic fluid motion. Both molecular and eddy
diffusion may involve the movement of different species in opposing
directions. When a bulk flow occurs, the total rate of mass transfer of
individual species is increased or decreased by this bulk flow, which
is a third mechanism of mass transfer.
Molecular diffusion is extremely slow; eddy diffusion is orders of
magnitude more rapid. Therefore, if industrial separation processes
are to be conducted in equipment of reasonable size, the fluids must
be agitated and interfacial areas maximized. For solids, the particle
size is decreased to increase the area for mass transfer and decrease
the distance for diffusion.

In multiphase systems the extent of the separation is limited by phase

equilibrium because, with time, concentrations equilibrate by mass
transfer. When mass transfer is rapid, equilibration takes seconds or
minutes, and design of separation equipment is based on phase
equilibrium, not mass transfer. For separations involving barriers
such as membranes, mass-transfer rates govern equipment design.
Diffusion of species A with respect to B occurs because of driving
forces, which include gradients of species concentration (ordinary
diffusion), pressure, temperature (thermal diffusion), and external
force fields that act unequally on different species. Pressure diffusion
requires a large gradient, which is achieved for gas mixtures with a
centrifuge. Thermal diffusion columns can be employed to separate
mixtures by establishing a temperature gradient. More widely applied
is forced diffusion of ions in an electrical field. This chapter begins by
describing only molecular diffusion driven by concentration
gradients, which is the most common type of diffusion in chemical
separation processes.
Emphasis is on binary systems, for which molecular diffusion theory
is relatively simple and applications are straight forward. The other
types of diffusion are introduced in §3.8 because of their importance
in bioseparations. Multicomponent ordinary diffusion is considered
briefly in Chapter 12. It is a more appropriate topic for advanced
study using texts such as Taylor and Krishna [1].
Molecular diffusion occurs in fluids that are stagnant, or in laminar
or turbulent motion. Eddy diffusion occurs in fluids when turbulent
motion exists. When both molecular diffusion and eddy diffusion
occur, they are additive. When mass transfer occurs under bulk
turbulent flow but across an interface or to a solid surface, flow is
generally laminar or stagnant near the interface or solid surface.
Thus, the eddy-diffusion mechanism is dampened or eliminated as
the interface or solid surface is approached.
Mass transfer can result in a total net rate of bulk flow or flux in a
direction relative to a fixed plane or stationary coordinate system.
When a net flux occurs, it carries all species present. Thus, the molar
flux of a species is the sum of all three mechanisms. If Ni is the molar
flux of i with mole fraction xi, and N is the total molar flux in moles
per unit time per unit area in a direction perpendicular to a stationary
plane across which mass transfer occurs, then
STEADY-STATE, ORDINARY MOLECULAR DIFFUSION
Imagine a cylindrical glass vessel partly filled with dyed water. Clear
water is carefully added on top so that the dyed solution on the
bottom is undisturbed. At first, a sharp boundary exists between
layers, but as mass transfer of the dye occurs, the upper layer becomes
colored and the layer below less colored. The upper layer is more
colored near the original interface and less colored in the region near
the top. During this color change, the motion of each dye molecule is
random, undergoing collisions with water molecules and sometimes
with dye molecules, moving first in one direction and then in another,
with no one direction preferred. This type of motion is sometimes
called a random-walk process, which yields a means square distance
of travel in a time interval but not in a direction interval. At a given
horizontal plane through the solution, it is not possible to determine
whether, in a given time interval, a molecule will cross the plane or
not. On the average, a fraction of all molecules in the solution below
the plane cross over into the region above and the same fraction will
cross over in the opposite direction. Therefore, if the concentration of
dye in the lower region is greater than that in the upper region, a net
rate of mass transfer of dye takes place from the lower to the upper
region. Ultimately, a dynamic equilibrium is achieved and the dye
concentration will be uniform throughout. Based on these
observations, it is clear that:
1. Mass transfer by ordinary molecular diffusion in a binary mixture
occurs because of a concentration gradient; that is, a species diffuses
in the direction of decreasing concentration.
2. The mass-transfer rate is proportional to the area normal to the
direction of mass transfer. Thus, the rate can be expressed as a flux.
3. Net transfer stops when concentrations are uniform.
mass transfer coeffìcient
The Sherwood number (Sh) (also called the mass transfer Nusselt
number) is a dimensionless number used in mass-transfer operation. It
represents the ratio of the convective mass transfer to the rate of diffusive
mass transport,

The Schmidt number is a dimensionless number, named after the

German engineer Ernst Heinrich Wilhelm Schmidt (1892–1975).
The Schmidt number is defined as the ratio of momentum
diffusivity (kinematic viscosity) and mass diffusivity. It is used to
characterize fluid flows in which there are simultaneous momentum and
mass diffusion convection processes.
A Schmidt number of unity indicates that momentum and mass
transfer by diffusion are comparable, and velocity and
concentration boundary layers almost coincide with each other.
Mass diffusivity or diffusion coefficient is a proportionality
constant between the molar flux due to molecular diffusion and
the gradient in the concentration of the species (or the driving
force for diffusion). Mass diffusion in liquids grows with
temperature, roughly inversely proportional viscosity-variation
with temperature, so that the Schmidt number, Sc=ν/D, quickly
decreases with temperature.
Introduction of Mass Transfer
When a system contains two or more components whose concentrations vary from point to
point, there is a natural tendency for mass to be transferred, minimizing the concentration
differences within a system. The transport of one constituent from a region of higher
concentration to that of a lower concentration is called mass transfer.
MOLECULAR TRANSPORT
Substances may behave differently when subjected to the same gradients. Constitutive
equations identify the characteristics of a particular substance. For example, if the gradient is
momentum, then the viscosity is defined by the constitutive equation called Newton’s law of
viscosity. If the gradient is energy, then the thermal conductivity is defined by Fourier’s law
of heat conduction. If the gradient is concentration, then the diffusion coefficient is defined
by Fick’s first law of diffusion. Viscosity, thermal conductivity, and diffusion coefficient are
called transport properties
The concentration of a molecular species can be expressed in many ways
The mass (or molar) flux of a given species is a vector quantity denoting the amount of the
particular species, in either mass or molar units, that passes per given increment of time
through a unit area normal to the vector.

Diffusion is the process by which molecules, ions, or other small particles spontaneously
mix, moving from regions of relatively high concentration into regions of lower
concentration. This process can be analyzed in two ways. First, it can be described with
Fick's law and a diffusion coeffìcient, a fundamental and scientific description used in
the first two parts of this book. Second, it can be explained in terms of a mass transfer
coefficient

Fick's law states that the rate of diffusion of a substance across unit area (such as a surface or
membrane) is proportional to the concentration gradient.
Momentum, heat and mass transfer are called transport phenomena
Mass transfer is the basis for many biological and chemical processes. Biological processes
include the oxygenation of blood and the transport of ions across membranes
Mass transfer always involves mixtures.

where D AB is diffusivity or diffusion coefficient for component A diffusing through

component B, and dCA / dZ is the concentration gradient in the Z-direction.
The diffusion coefficient (D) is the amount of a particular substance that diffuses across a
unit area in 1 s under the influence of a gradient of one unit.
It is usually expressed in the units cm2 s−1.
3.4.02 Diffusion coefficient in the stationary phase (DS or DL)
The diffusion coefficient characterizing the diffusion in the stationary phase.
Diffusivity Fick’s law proportionality, D AB, is known as mass diffusivity (simply as
diffusivity) or as the diffusion coefficient. D AB has the dimension of L 2 / t, identical to the
fundamental dimensions of the other transport properties: Kinematic visc

Diffusivity is normally reported in cm2 / sec; the SI unit being m2 / sec.

Diffusivity depends on pressure, temperature, and composition of the system.
In table, some values of DAB are given for a few gas, liquid, and solid systems.
Diffusivities of gases at low density are almost composition independent, incease with the
temperature and vary inversely with pressure. Liquid and solid diffusivities are strongly
concentration dependent and increase with temperature.

General range of values of diffusivity:

Gases : 5 X 10 –6 ------------- 1 X 10-5 m2 / sec.
Liquids : 10 –6 ------------- 10-9 m2 / sec.
Solids : 5 X 10 –14 ------------- 1 X 10-10 m2 / sec.
In the absence of experimental data, semitheoretical expressions have been developed which
give approximation, sometimes as valid as experimental values, due to the difficulties
encountered in experimental measurements.
Fick's law for binary diffusion and define the diffusivity BABfo r the pair A-B. Then we
discuss briefly the temperature and pressure dependence of the diffusivity. After that we give
a summary of the theories available to predict the diffusivity for gases, liquids, colloids, and
polymers.
For binary gas mixtures at low pressure, %,, is inversely proportional to the pressure,
increases with increasing temperature, and is almost independent of the composition for a
given gas pair.
for liquids. At each temperature c9,,$ decreases toward zero with increasing pressure. With
decreasing pressure, ~ 9incr~eases" tow ard a low-pressure limit, as predicted by kinetic
theory
The molar flux is the number of moles per unit time per unit area
mass transfer coefficient is a diffusion rate constant that relates the mass transfer rate,
mass transfer area, and concentration change as driving force:[1]

Where:

 is the mass transfer coefficient [mol/(s·m2)/(mol/m3)], or m/s

 is the mass transfer rate [mol/s]

 is the effective mass transfer area [m2]

 is the driving force concentration difference [mol/m3].

This can be used to quantify the mass transfer

between phases, immiscible and partially miscible fluid mixtures (or
between a fluid and a porous solid[2]). Quantifying mass transfer allows for
design and manufacture of separation process equipment that can meet
specified requirements, estimate what will happen in real life situations
(chemical spill), etc.
Mass transfer coefficients can be estimated from many different
theoretical equations, correlations, and analogies that are functions of
material properties, intensive properties and flow regime
(laminar or turbulent flow). Selection of the most applicable model is
dependent on the materials and the system, or environment, being
studied.
Mass transfer coefficient units[edit]
 (mol/s)/(m2·mol/m3) = m/s