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Fundamentals of Mass Transfer

What is 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 (to reach equilibrium).

The transport of one constituent from a region of higher concentration to that of a lower
concentration is called mass transfer.

i.e. mass transfer is meant to be the tendency of a component in a mixture to travel from a region of
higher concentration to that of lower concentration.

Examples:

Many of our day to day experiences also involve mass transfer, for example:

a) A lump of sugar added to a cup of coffee eventually dissolves and then eventually diffuses to
make the concentration uniform. This process begins with the dissolution of sugar from the
surface of each crystal into the neighboring liquid. The sugar in solution is then
transported across the liquid (by diffusion and convection) from the higher concentration
area to the lower concentration area..
b) Water evaporates from ponds to increase the humidity of passing-air-stream
c) Perfumes present a pleasant fragrance which is imparted throughout the surrounding
atmosphere.
Note: There is a difference between mass and momentum transfer.

What is the difference between momentum and mass transfer?

Momentum transfer involves bulk transport of the continuum while mass transfer involves the
transport of species within the bulk continuum. Continuum could be stationary or itself mobile.

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Importance of mass transfer:

What is the importance of mass transfer?

Field of mass transfer involves some of the most typical chemical engineering problems:
 Design and operation of chemical process equipment involves preparation of reactants,
carrying out chemical reactions (diffusion controlled reactions), and separation of the
resultant products.
 Ability to carry out the above operations largely rests on the proficiency of principles of mass
transfer, which is largely the domain of chemical engineers.
The transfer of mass within a fluid mixture or across a phase boundary is a process that plays a
major role in many industrial processes (biological and chemical). Examples of such:

Name the important processes involving mass transfer.

 Distillation: Differential distillation, equilibrium flash vaporization, steam distillation, batch
and continuous fractionation, binary and multi-component distillation, azeotropic and
extractive distillation, and so on.
 Absorption: Used for separation of acidic impurities from mixed gas streams, for example,
CO2, H2S, SO2 , other organics such as carbonyl sulfide (COS) and mercaptans, NH3, HCN,
and NOx, VOC control in environmental cleanup, odor control, wastewater stripping, and so
on.
 Adsorption (absorption and adsorption play an important role in environmental engineering)
 Liquid–Liquid and Solid–Liquid Extraction: Pharmaceuticals and foods, extraction and
refining of fats and oils, dewaxing and aromatic extraction from lube oils, leaching of ores,
and so on.
 Crystallization.
 Drying.
 Ion exchange.
 Membrane Separation Processes: Based on molecular size differences:
 Gas–gas, gas–liquid, liquid–liquid.
 Liquid membranes, for example, for H2S removal.
 Reverse osmosis.

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 Biological processes: include the oxygenation of blood and the transport of ions across
membranes within the kidney.
Mechanism of mass transfer

The mechanism of mass transfer depends upon the dynamics of the system in which it occurs.

Mass can be transferred by two mechanisms, namely:

a. Molecular diffusion (Random molecular motion in quiescent fluids)

b. Convection (where mass is transferred from a surface into a moving fluid, aided by the
dynamic characteristics of the flow)

These two distinct modes of transport, molecular mass transfer and convective mass transfer, are
analogous to conduction heat transfer and convective heat transfer.

1. Molecular mass transfer

1.1.Properties of a mixture

Mass transfer always involves mixtures. Consequently, we must account for the variation of
physical properties which normally exist in a given system. When a system contains three or
more components, as many industrial fluid streams do, the problem becomes un-widely very
quickly. The conventional engineering approach to problems of multi-component system is to
attempt to reduce them to representative binary (i.e., two components) systems.

In order to understand the future discussions, let us first consider definitions and relations which
are often used to explain the role of components within a mixture.
1.2. Concentration of Species

Concentration of species in multi-component mixture can be expressed in many ways.

a. Mass concentration
For species A, mass concentration denoted by 𝝆𝑨 is defined as the mass of A, 𝒎𝑨 per unit
volume of the mixture.
𝒎𝑨
𝝆𝑨 = (1)
𝑽
The total mass concentration density  is the sum of the total mass of the mixture in unit volume:

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 𝝆 = ∑ 𝝆𝒊
𝒊

where 𝛒𝐢 is the concentration of species i in the mixture.

b. Molar concentration
Molar concentration of, A, 𝒄𝑨 is defined as the number of moles of A present per unit volume of
the mixture.
By definition,
𝒎𝒂𝒔𝒔 𝒐𝒇 𝑨
𝑵𝒖𝒎𝒃𝒆𝒓 𝒐𝒇 𝒎𝒐𝒍𝒆𝒔 =
𝒎𝒐𝒍𝒆𝒄𝒖𝒍𝒂𝒓 𝒘𝒆𝒊𝒈𝒉𝒕 𝒐𝒇 𝑨
𝒎𝑨
𝒏𝑨 =
𝑴𝑨 (2)

From equations 1 and 2:

𝒏𝑨 𝒎𝑨 𝝆𝑨
𝒄𝑨 = = =
𝑽 𝑽 𝑴𝑨 𝑴𝑨 (3)

Note:
𝒏 𝑷
For gas phase: PV = n R T from which 𝒄 = 𝑽 = 𝑹𝑻
𝑷𝑨
∴ 𝒄𝑨 =
𝑹𝑻

Q: What is the relation between mass and molar concentration?

1.3.Velocities
In a multi-component system the various species will normally move at different velocities; and
evaluation of velocity of mixture requires the averaging of the velocities of each species present.
If 𝒊 is the absolute velocity of species i with respect to stationary fixed coordinates, then mass-
average velocity for a multi-component mixture defined in terms of mass concentration is;
∑𝒏𝒊=𝟏 𝝆𝒊 𝒊 ∑𝒏𝒊=𝟏 𝝆𝒊 𝒊
𝝂= = (4)
∑𝒏𝒊=𝟏 𝝆𝒊 𝝆
𝒏

𝝂 = ∑ 𝒘𝒊 𝒗𝒊
𝒊=𝟎

By similar way, molar-average velocity of the mixture 𝑽 is:

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 ∑𝒏𝒊=𝟏 𝒄𝒊 𝒊 ∑𝒏𝒊=𝟏 𝒄𝒊 𝒊
𝑽= 𝒏 = (5)
∑𝒊=𝟏 𝒄𝒊 𝒄
𝒏

𝑽 = ∑ 𝒙 𝒊 𝒗𝒊
𝒊=𝟎

The velocity of a particular species relative to the mass-average or molar average velocity is
termed as diffusion velocity
i.e.
 Diffusion velocity relative to the mass average velocity = 𝒊 − 𝒗 (mass diffusion velocity)
 Diffusion velocity relative to the molar average velocity = 𝒊 − 𝑽(molar diffusion velocity)
1.4. Mole and mass fraction
The mole fraction for liquid and solid mixture is denoted by 𝐱 𝐀 and for gaseous mixtures it is
denoted by 𝐲𝐀 are the molar concentrations of species A divided by the molar density of the
mixtures.
𝒄𝑨
𝒙𝑨 = (6)
𝒄
and
𝒄𝑨
𝒚𝑨 = (7)
𝒄
by similar way, mass fraction of A in a mixture is;

𝝆𝑨
𝒘𝑨 = (8)
𝝆
A summary of the various concentration terms and of the interrelations for a binary system
containing species A and B is given in Table 1.

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Table 1 Concentrations in a binary mixture of A and B

1.5. Flux
Definition: 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. (Flux = concentration x velocity)

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 Flux

Molar flux Mass flux

Relative to Relative to the Relative to Relative to the

fixed molar average fixed mass average
coordinates velocity coordinates velocity

Equations describing flux

a. Molar flux
The molar flux is defined by two methods:
1. Relative to the molar average velocity
2. Relative to a fixed coordinates
 Molar flux relative to the molar average velocity
The basic relation for molecular diffusion defines the molar flux relative to the molar average
velocity, 𝐉𝐀 . An empirical relation for this molar flux, first postulated by Fick and, accordingly,
often referred to as Fick’s first law, defines the diffusion of component A in an isothermal,
isobaric system:
𝑱𝑨 = −𝑫𝑨𝑩 𝜵𝒄𝑨 (9)
For diffusion in only the z direction, the Fick’s rate equation is:
𝒅𝒄𝑨
𝑱𝑨,𝒛 = −𝑫𝑨𝑩 (10)
𝒅𝒛
where:
𝐉𝐀 : is the molar flux in the z direction relative to the molar average velocity,
𝐝𝐜
: is the concentration gradient in the z direction and
𝐝𝐳
𝑫𝑨𝑩 : the proportionality factor, is the mass diffusivity or diffusion coefficient for component A
diffusing through component B.
Note: (see example 1)
𝑫𝑨𝑩 = 𝑫𝑩𝑨 (Only for gases)

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A more general flux relation that is not restricted to isothermal, isobaric systems (general form)
is:
𝒅𝒚𝑨
𝑱𝑨,𝒛 = −𝒄𝑫𝑨𝑩 (11)
𝒅𝒛
where: 𝒄𝑨 = 𝒄 𝒚𝑨
Important note:
For a binary system with a constant average velocity in the z direction, the molar flux in the z
direction relative to the molar average velocity may also be expressed by:
𝑱𝑨,𝒛 = 𝒄𝑨 (𝒗𝑨,𝒛 − 𝑽𝒛 ) (12)
Initial experimental investigations of molecular diffusion were unable to verify Fick’s law of
diffusion. This was apparently due to the fact that mass is often transferred simultaneously by
two possible means:
(1) as a result of the concentration differences as postulated by Fick and
(2) by convection currents induced by the density differences that resulted from the
concentration variation. Steffan (1872) and Maxwell (1877), using the kinetic theory of gases,
proved that the mass (mole) flux relative to a fixed coordinate was a result of two contributions:
the concentration gradient contribution and the bulk motion contribution.

Clarification:
If a balloon, filled with a color dye, is dropped into a large lake, the dye will diffuse radially as a
concentration gradient contribution. When a stick is dropped into a moving stream, it will float
downstream by the bulk motion contribution. If the dye-filled balloon were dropped into the
moving stream, the dye would diffuse radially while being carried downstream; thus both
contributions participate simultaneously in the mass transfer.
 Molar flux relative to a fixed coordinates
Fluxes of components A and B relative to a fixed z coordinate; accordingly, we symbolize this
new type of flux that is relative to a set of stationary axes by:
𝑵𝑨 = 𝒄𝑨 𝒗𝑨 (13)
and
𝑵𝑩 = 𝒄𝑩 𝒗𝑩 (14)
where 𝒗𝑨 𝒂𝒏𝒅 𝒗𝑩 are velocities relative to the fixed axis.

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By equating equations 11 and 12 we obtain
𝒅𝒚𝑨
𝑱𝑨,𝒛 = 𝒄𝑨 (𝒗𝑨,𝒛 − 𝑽𝒛 ) = −𝒄𝑫𝑨𝑩
𝒅𝒛
which, upon rearrangement, yields
𝒅𝒚𝑨
𝒄𝑨 𝒗𝑨,𝒛 = −𝒄𝑫𝑨𝑩 + 𝒄𝑨 𝑽𝒛
𝒅𝒛
For this binary system, 𝑽𝒛 can be evaluated by equation (5)
∑𝒏𝒊=𝟏 𝒄𝒊 𝒊 𝟏
𝑽𝒛 = = (𝒄𝑨 𝒗𝑨,𝒛 + 𝒄𝑩 𝒗𝑩,𝒛 )
𝒄 𝒄
or
𝒄𝑨 𝑽𝒛 = 𝒚𝑨 (𝒄𝑨 𝒗𝑨,𝒛 + 𝒄𝑩 𝒗𝑩,𝒛 )

Substituting this expression into our relation, we obtain

𝒅𝒚𝑨
𝒄𝑨 𝒗𝑨,𝒛 = −𝒄𝑫𝑨𝑩 + 𝒚𝑨 (𝒄𝑨 𝒗𝑨,𝒛 + 𝒄𝑩 𝒗𝑩,𝒛 )
𝒅𝒛
Substitute from equations (13) and (14) into the above equation we obtain:
𝒅𝒚𝑨
𝑵𝑨,𝒛 = −𝒄𝑫𝑨𝑩 + 𝒚𝑨 (𝑵𝑨,𝒛 + 𝑵𝑩,𝒛 ) (15)
𝒅𝒛
This relation may be generalized and written in vector form as:
𝑵𝑨 = −𝒄𝑫𝑨𝑩 𝛁𝐲𝐀 + 𝒚𝑨 (𝑵𝑨 + 𝑵𝑩 ) (16)
It is important to note that the above equations (15 and 16) the molar flux relative to fixed
coordinates, 𝑵𝑨 , is a resultant of the two vector quantities:
 −𝒄 𝑫𝑨𝑩 𝛁𝐲𝐀 : the molar flux, 𝐉𝐀 , resulting from the concentration gradient : This term is
referred to as the concentration gradient contribution; and
 𝒚𝑨 (𝑵𝑨 + 𝑵𝑩 ) = 𝒄𝑨 𝑽: the molar flux resulting as component A is carried in the bulk flow of
the fluid : This flux term is designated the bulk motion contribution. For stagnant medium
this term will be zero
Note:
If species A were diffusing in a multicomponent mixture, the expression equivalent to equation
(16) would be:
𝒏

𝑵𝑨 = −𝒄𝑫𝑨𝑴 𝛁𝐲𝐀 + 𝒚𝑨 ∑ 𝑵𝒊
𝒊=𝟏

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b. Mass flux
The mass flux is defined by two methods similar to molar flux:
1. Relative to the mass average velocity
2. Relative to a fixed coordinates
 Mass flux relative to the molar average velocity
For isothermal and isobaric system

General form

 Mass flux relative to a fixed coordinates:

For component A

and for component B

The mass flux, 𝑵𝑨 , relative to a fixed spatial coordinate system, is defined for a binary system in
terms of mass density and mass fraction by

Under isothermal, isobaric conditions, this relation simplifies to:

Table 2, Equivalent forms of the mass flux equation for binary system A and B

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Example 1:
Starting with Fick’s equation for the diffusion of A through a binary mixture of species A and B
as given by:

and Fick’s equation for the diffusion of B through the same binary mixture given by:

Example: Prove the two gas diffusivities, 𝑫𝑨𝑩 and 𝑫𝑩𝑨 , are equals.
Solution:

By adding the two equations

𝒅𝒚𝑨 𝒅𝒚𝑩
𝑵𝑨,𝒛 + 𝑵𝑩,𝒛 = −𝒄𝑫𝑨𝑩 − 𝒄𝑫𝑩𝑨 + (𝒚𝑨 + 𝒚𝑩 )(𝑵𝑨,𝒛 + 𝑵𝑩,𝒛 )
𝒅𝒛 𝒅𝒛
But:
(𝒚𝑨 + 𝒚𝑩 ) = 𝟏
𝒅𝒚𝑨 𝒅𝒚𝑩
∴ 𝒄𝑫𝑨𝑩 + 𝒄𝑫𝑩𝑨 =𝟎
𝒅𝒛 𝒅𝒛
𝒅𝒚𝑨 𝒅𝒚𝑩
𝒄𝑫𝑨𝑩 = −𝒄𝑫𝑩𝑨
𝒅𝒛 𝒅𝒛
𝒚𝑨 + 𝒚𝑩 = 𝟏

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 𝒅𝒚𝑨 𝒅𝒚𝑩
+ =𝟎
𝒅𝒛 𝒅𝒛
𝒅𝒚𝑨 𝒅𝒚𝑩
=−
𝒅𝒛 𝒅𝒛
∴ 𝑫𝑨𝑩 = 𝑫𝑩𝑨

Related types of mass transfer:

 In chemical reactions, there is a thermodynamic term called the chemical potential 𝝁𝒄 . The
driving force in chemical thermo dynamic is ∆𝝁𝒄 .
 The chemical potential is a function of concentration and is related by the equation:
𝝁𝒄 = 𝝁𝒐 + 𝑹𝑻 𝒍𝒏 𝒄𝑨
i.e. where a concentration difference exists there will be a chemical potential difference and
there will be at tendency to move toward equilibrium (mass transfer will occur)
 There are a number of other physical conditions in addition to difference in concentration
which will produce a chemical potential gradient (and we can obtain mass transfer by
applying it) such as:
 Temperature gradient
 Pressure difference (separation of a liquid mixture in a centrifuge by pressure diffusion)
 Difference in forces applied by external field, such as:
a. gravity (separation by sedimentation under the influence of gravity),
b. magnetic (magnetic separation of mineral mixtures through the action of magnetic force
field)and
c. electrical field (electrolytic precipitation due to an electrostatic force field)
The diffusion coefficient (Fick’s law proportionality𝑫𝑨𝑩 )
In this part we search for:
1. definition of diffusion coefficient
2. factors affecting diffusion coefficient
3. equations used to calculate the diffusion coefficient (for gas, liquid and solid)
 Definition of 𝑫𝑨𝑩 : the mass or molar flux per unit concentration gradient
 Factors affecting diffusion coefficient:
The diffusion coefficient depends on:

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a) temperature b) pressure c) composition of the system
Experimental values of the diffusivities of gases, liquids and solids are tabulated in appendices at
different conditions. See tables 3, 4 and 5.
Note: Diffusion in gases > liquids > solids
In the absence of experimental data, semitheoretical expressions have been developed which
give approximations, sometimes as valid as experimental values due to the difficulties
encountered in their measurement.

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Table 3, Binary mass diffusivities in gases

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Table 3, continued

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Table 4, Binary mass diffusivities in liquids

Table 5, Binary mass diffusivities in solids

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 Equations used to calculate the diffusion coefficient
Gas Mass Diffusivity
We need to calculate the gas mass diffusivity for polar and nonpolar gases in a binary system and
a multicomponent system.
Note:
The arrangement or geometry of the atoms in some molecules is such that one end of the
molecule has a positive electrical charge and the other side has a negative charge. If this is the
case, the molecule is called a polar molecule, meaning that it has electrical poles. Otherwise, it is
called a non-polar molecule. Whether molecules are polar or non-polar determines if they will
mix to form a solution or that they don't mix well together.
Examples of polar molecules of materials that are gases under standard conditions are: Ammonia
(NH3), Sulfur Dioxide (SO2) and Hydrogen Sulfide (H2S).
A non-polar molecule is one that the electrons are distributed more symmetrically and thus does
not have an abundance of charges at the opposite sides. The charges all cancel out each other.
Common examples of non-polar gases are the noble or inert gases, including Helium (He), Neon
(Ne), Krypton (Kr) and Xenon (Xe). Other non-polar gases include the Hydrogen (H2), Nitrogen
(N2), Oxygen (O2), Carbon Dioxide (CO2), Methane (CH4) and Ethylene (C2H4) molecules.
Summary:
The geometry of atoms in polar molecules is such that one end of the molecule has a positive
electrical charge and the other side has a negative charge. Non-polar molecules do not have
charges at their ends. Mixing molecules of the same polarity usually results in the molecules
forming a solution.
For binary gas mixture
Nonpolar gases
For gas pairs of nonpolar, nonreacting molecules Hirschfelder presented an equation for the
diffusion coefficient
𝟏 𝟏 𝟏/𝟐
𝟎. 𝟎𝟎𝟏𝟖𝟓𝟖 𝑻𝟑⁄𝟐 [𝑴 + 𝑴 ]
𝑨 𝑩
𝑫𝑨𝑩 =
𝑷 𝝈𝟐𝑨𝑩 𝛀𝑫

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The above equation was developed for dilute gases consisting of nonpolar, spherical monatomic
molecules. However, this equation gives good results for most nonpolar, binary gas systems over
a wide range of temperatures.
where:
𝑫𝑨𝑩 : is the mass diffusivity of A through B, in cm2/s
T: is the absolute temperature in k
𝑴𝑨 , 𝑴𝑩 are the molecular weights of A and B, respectively
P: is the absolute pressure in atmosphere
𝝈𝑨𝑩 : is the ‘‘collision diameter in 𝐀̇,(average diameter of atom A and B) (a Lennard–Jones
parameter)
𝝈𝑨 + 𝝈𝑩
𝝈𝑨𝑩 =
𝟐
𝝈𝑨 𝒂𝒏𝒅 𝝈𝑩 are obtained from table 6
𝛀𝑫 : collision integral in ergs (The collision integral is defined as the rate of change of the
distribution function) (from table 7)
𝒌𝑻
From table 7 the collision integral is a function of a dimensionless temperature 𝜺
𝑨𝑩

k: is the Boltzmann constant (1.38×10-16 ergs/K)

𝜺𝑨𝑩 : the energy of molecular interaction for the binary system A and B in ergs
Note:
𝜺𝑨𝑩 𝜺𝑨 𝜺 𝑩
= √
𝒌 𝒌 𝒌
𝜺𝑨 𝜺𝑩
𝒂𝒏𝒅 are obtained from table 6
𝒌 𝒌

Important note:
We can predict the diffusion coefficient at any temperature and at any pressure below 25 atm
from a known experimental value (from table 3) by using the equation:
𝑷𝟏 𝑻𝟐 𝟑/𝟐 𝛀𝑫,𝑻𝟏
𝑫𝑨𝑩,𝑻𝟐 ,𝑷𝟐 = 𝑫𝑨𝑩,𝑻𝟏 ,𝑷𝟏 ( )( )
𝑷𝟐 𝑻𝟏 𝛀𝑫,𝑻𝟐
𝛀𝐃,𝐓𝟏
If the temperature range is close, you can consider the ratio 𝛀 =𝟏
𝐃,𝐓𝟐

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Table 6, Values of the diameter of spherical molecules, 𝝈 (Lennard–Jones force constants)

20
Table 6, continued

21
Table 7, Values of the collision integral 𝛀𝑫 (Lennard–Jones Constants)

22
Table 7, continued

There is another empirical correlation for estimating the diffusion coefficient for nonpolar,
binary gas systems at low pressures such as the empirical correlation recommended by Fuller,
Schettler, and Giddings which permits the evaluation of the diffusivity when reliable Lennard–
Jones parameters, 𝝈 and 𝜺 are unavailable. The Fuller correlation is:
𝟏 𝟏 𝟏/𝟐
𝟏𝟎−𝟑 𝑻𝟏.𝟕𝟓 [𝑴 + 𝑴 ]
𝑨 𝑩
𝑫𝑨𝑩 = 𝟐
𝟏/𝟑 𝟏/𝟑
𝑷 [(∑ 𝝂)𝑨 + (∑ 𝝂)𝑩 ]
The diffusion volume 𝝂 is obtained from table 8
Table 8, Atomic diffusion volumes for use in estimating 𝑫𝑨𝑩 by method of Fuller, Schettler,
and Giddings (the equation shown above)

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Mass diffusivity in a binary polar gases mixture
For estimating diffusion coefficient for binary gas mixtures containing polar compounds,
𝟏/𝟐
𝟏 𝟏
𝟎.𝟎𝟎𝟏𝟖𝟓𝟖 𝑻𝟑⁄𝟐 [ + ]
𝑴𝑨 𝑴𝑩
Hirschfelder equation (𝑫𝑨𝑩 = ) is used; however the collision integral
𝑷 𝝈𝟐𝑨𝑩 𝛀𝑫

(𝛀𝑫 ) is evaluated from equations not from table 7 (see the equations in the reference book page
413)
Mass diffusivity in gas mixture of several components
Mass transfer in gas mixtures of several components can be described by theoretical equations
involving the diffusion coefficients for the various binary pairs involved in the mixture. The
following relation can be used (Wilke’s equation):
𝟏
𝑫𝟏−𝒎𝒊𝒙𝒕𝒖𝒓𝒆 =
𝒚′𝟐 ⁄𝑫𝟏−𝟐 + 𝒚′𝟑 ⁄𝑫𝟏−𝟑 + . . . + 𝒚′𝒏 ⁄𝑫𝟏−𝒏
where 𝑫𝟏−𝒎𝒊𝒙𝒕𝒖𝒓𝒆 is the mass diffusivity for component 1 in the gas mixture; 𝑫𝟏−𝒏 is the mass
diffusivity for the binary pair, component 1 diffusing through component n; and 𝒚′𝒏 is the mole
fraction of component n in the gas mixture evaluated on a component-1-free basis, that is
𝒚𝟐 𝒚𝟐
𝒚′𝟐 = =
𝒚𝟐 + 𝒚𝟑 + . . . +𝒚𝒏 𝟏 − 𝒚𝟏

For calculating 𝑫𝟏−𝟐 , 𝑫𝟏−𝟑 and 𝑫𝟏−𝒏 use the Hirschfelder equation (for polar or nonpolar gases
according to the conditions) or Fuller equation for nonpolar gases.
Important note:
For a dilute multicomponent gas mixture, the diffusion coefficient of the diffusing species in the
gas mixture is approximated by the binary diffusion coefficient of the diffusing species in the
carrier gas (the carrier gas is the gas of high percentage)

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Liquid mass diffusivity
Compare between gas diffusion coefficient and liquid diffusion coefficient.
liquid diffusion coefficients (table 4) reveals that they are several orders of magnitude smaller
than gas diffusion coefficients and that they depend on concentration due to the changes in
viscosity with concentration and changes in the degree of ideality of the solution. While from the
Hirschfelder equation there is no dependency on concentration for gas diffusion coefficient.
How is liquid mass diffusivity calculated?
For diffusion of nonelectrolyte solutes in low concentration solutions (dilute solutions), there are
two theories for explanations:
1. The Eyring theory: according this theory the liquid is treated as a quasi-crystalline lattice
model interspersed with lattice holes. The solute jumps into the holes within the lattice
model.
2. The hydrodynamical theory: this theory states that the diffusion coefficient is related to the
mobility of solute molecules and it defines the diffusion coefficient as the net velocity of the
molecule while under the influence of a unit driving force.
Equations used to calculate the liquid mass diffusivity
A. Stokes-Einstein equation (developed from the hydrodynamical theory)
𝒌𝑻
𝑫𝑨𝑩 =
𝟔𝝅𝒓𝝁𝑩
𝑫𝑨𝑩 : is the diffusivity of A in dilute solution, cm2/s 𝒌: Boltzman constant (1.38×10-6 erg/K)
T: absolute temperature, K r: solute particle radius
𝝁𝑩 : Solvent viscosity, centipoise
The above equation shows that the liquid diffusion coefficient depends on the solute radius and
solvent viscosity which both affect the mobility of the molecule.
The above equation can be written in the form:
𝑫𝑨𝑩 𝝁𝑩
= 𝑪𝒐𝒏𝒔𝒕𝒂𝒏𝒕
𝑻
Note:
We can predict the diffusion coefficient at any temperature 𝑻𝟐 from an experimental value at 𝑻𝟏
from the equation:
𝑫𝟏 𝝁𝟏 𝑫𝟐 𝝁𝟐
=
𝑻𝟏 𝑻𝟐

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 B. Wilke and Chang equation (developed from the two theories for nonelectrolytes in dilute
solution)
𝑫𝑨𝑩 𝝁𝑩 𝟕. 𝟒 × 𝟏𝟎−𝟖 (𝝓𝑩 𝑴 𝑩 )𝟏/𝟐
=
𝑻 𝑽𝟎.𝟔
𝑨

𝑫𝑨𝑩 : is the diffusivity of A through liquid solvent B, cm2/s 𝑴 𝑩 :molecular weight of the solvent
T: absolute temperature, K 𝝁𝑩 : solution viscosity, centipoises
𝑽𝑨 : molecular volume of solute at normal boiling point, cm3/g.mol (from table 9 and 10)
𝝓𝑩 : association parameter for solvent B (from table 11)

Table 9, Molecular volumes at normal boiling point for some commonly encountered
compounds

Table 10, Atomic volumes for complex molecular volumes for simple substances

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Table 11, Recommended values of the association parameter, 𝝓𝑩 , for a few common solvents.

Note: the molecular volume = the sum of atomic volume of each elemnet present
Example: the molecular volume of C2H5OH = 𝟐𝑽𝑪 + 𝟔𝑽𝑯 + 𝑽𝑶
If data for computing the molar volume of solute at its normal boiling point, 𝑽𝑨 , are not
available, the following equation is used:
𝑽𝑨 = 𝟎. 𝟐𝟖𝟓 𝑽𝟏.𝟎𝟒𝟖
𝑪

where 𝑽𝑪 is the critical volume of species A in cm3/g.mol (from tabulated data)

C. Hayduk and Laudie equation (for diffusion in water)
It is a special form of Wilke equation for evaluating diffusion coefficient of nonelectrolytes in
water
𝑫𝑨𝑩 = 𝟏𝟑. 𝟐𝟔 × 𝟏𝟎−𝟓 𝝁−𝟏.𝟏𝟒
𝑩 𝑽−𝟎.𝟓𝟖𝟗
𝑨

Examples:
1. The Stokes–Einstein equation is often used to estimate the molecular diameter of large
spherical molecules from the molecular diffusion coefficient. The measured molecular
diffusion coefficient of the serum albumin (an important blood protein) in water at infinite
dilution is 5.94×10-7 cm2/s at 293 K. Estimate the mean diameter of a serum albumin
molecule.
Solution:
𝒌𝑻
𝑫𝑨𝑩 =
𝟔𝝅𝒓𝝁𝑩
𝒌𝑻
𝒓=
𝟔𝝅𝝁𝑩 𝑫𝑨𝑩
Water viscosity at 293 𝝁𝑩 = 𝟗𝟗𝟖 × 𝟏𝟎−𝟑 𝒄𝑷
𝒓 = 𝟑. 𝟔𝟑𝟕 𝒏𝒎

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2. Estimate the liquid diffusivity of methanol in water at 283 K.
Solution:
𝝁𝑩 = 𝟏. 𝟏𝟒 𝒄𝒑 𝑴𝑩 = 𝟏𝟖
𝝓𝑩 = 𝟐. 𝟐𝟔 𝑽𝑪𝑯𝟑 𝑶𝑯 = 𝟏𝟒. 𝟖 + 𝟒(𝟑. 𝟕) + 𝟕. 𝟒 = 𝟑𝟕
Substitute in the equation:
𝑫𝑨𝑩 𝝁𝑩 𝟕. 𝟒 × 𝟏𝟎−𝟖 (𝝓𝑩 𝑴 𝑩 )𝟏/𝟐
=
𝑻 𝑽𝟎.𝟔
𝑨

𝑫𝑨𝑩 = 𝟏. 𝟑𝟑𝟔 × 𝟏𝟎−𝟓 𝒄𝒎𝟐 /𝒔

Note:
 For the above example we can apply for Stokes-Einstein equation to estimate the atomic
radius
 the selection of the equation to be used to evaluate the liquid mass diffusivity depends on the
available data.
 It is important to note that liquid diffusivities 𝑫𝑨𝑩𝑳 and 𝑫𝑩𝑨𝑳 are not equal as were the gas
diffusivities at the same temperature and pressure.
Solid Mass Diffusivity
Applications of solid diffusion:
1. In semiconductors manufacture process: where impurity atoms, commonly called dopants,
are introduced into solid silicon to control the conductivity in a semiconductor device.
2. The hardening of steel: results from the diffusion of carbon and other elements through iron
Mechanism of solid diffusion:
Vacancy diffusion and interstitial diffusion are the two most frequently encountered solid
diffusion mechanisms
a) Vacancy diffusion b) Interstitial diffusion

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Factors affecting solid diffusion coefficient:
1. Type of solute
2. Type of solvent (host metal)
3. Temperature
The solid-phase diffusion coefficient depends on temperature and has been observed to increase
with increasing temperature according to an Arrhenius equation of the form:

𝑫𝑨𝑩 = 𝑫𝒐 𝒆−𝑸⁄𝑹𝑻

 𝑫𝑨𝑩 is solid diffusion coefficient for the  𝑫𝒐 is a proportionality constant of units

diffusing species A within solid B consistent with 𝑫𝑨𝑩 (from tables)
 Q is the activation energy (J/mol)  R is the thermodynamic constant
(8.314 J/mol·K)
 T is the absolute temperature (K)

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