Pharos University

Faculty of Engineering
Petrochemical Department

MASS TRANSFER
LECTURE (2)

1. FLUXES:
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.

Fick's first law defines the diffusion of component A in an

isothermal, isobaric system, for diffusion in only the z direction, the
Fick,s rate equation is:

Where JA,Z is the molar flux in the z direction relative to the molar-
average velocity, dcA/dz is the concentration gradient in the z
direction, and DAB, is the mass diffusivity or diffusion coefficient for
component A diffusing through component B. A more general flux
relation that is not restricted to isothermal, isobaric systems:

flux = (overall density) (diffusion coefficient) (concentration

gradient)

An equivalent expression for jA,z, the mass flux in the z direction

relative to the mass-average velocity, is:
Where dA/dz is the concentration gradient in terms of the mass
fraction. When the density is constant, this relation simplifies to:

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 differences induced by the
density differences that resulted from the concentration variation.

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:

By rearranging above equations:

As the component velocities, vA,Z and vB,Z are velocities relative to

the fixed z axis, the quantities cAvA,Z and cBvB,Z are fluxes of
components A and B relative to a fixed z coordinate; accordingly, we
symbolize this new type of flux as:

Substituting these symbols into above equation, we obtain a

relation for the flux of component A relative to the z axis:
 This relation may be generalized and written in vector form as:

It is important to note that the molar flux, NA is a resultant of the two

vector quantities:
- c DAByA the molar flux, JA, resulting from the concentration gradient.
This term is referred to as the concentration gradient contribution;
and yA (NA + NB) = cAV 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.

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:

nA = - DAB + wA (nA+ nB)

This relation may be generalized and written in vector form as:

Where:

Under isothermal, isobaric conditions, this relation simplifies to:

As previously noted, the flux is a resultant of two vector quantities:

- DAB A the mass flux, jA, resulting from a concentration gradient; the
concentration
gradient contribution.

A ( nA + nB ) = A v, the mass flux resulting as component A is carried

in the bulk flow
of the fluid; the bulk motion contribution.

2. DIFFUSION COEFFICIENT:
Fick's law of proportionality, DAB, is known as the diffusion coefficient,
which may be
obtained from equation:

The mass diffusivity has been reported in cm2/s: the SI units are m2/s,
which is a factor 10-4smaller.

The diffusion coefficient depends upon the pressure, temperature, and

composition of the
system. Experimental values for the diffusivities of gases, liquids, and
solids are tabulated in Appendix Tables J. 1, J.2, and J.3, respectively. As
one might expect from the consideration of the mobility of the
molecules, the diffusion coefficients are generally higher for gases (in
the range of 5 x 10-6 to 1 x 10-5 m2/s), than for liquids (in the range of
10-10 to 10-9 m2/s), which are higher than the values reported for solids
(in the range of 10-14to 10-10 m2/s). In the absence of experimental data,
semi theoretical expressions have been developed which give
approximations, sometimes as valid as experimental values due to the
difficulties encountered in their measurement.

2.1 GAS MASS DIFFUSIVITY:

Hirschfelder et al. presented an equation for the diffusion coefficient
for gas pairs of non-polar, non-reacting molecules:

Where DAB is the mass diffusivity of A through B, in cm 2/s; T is the

absolute temperature,
in K; MA, MB are molecular weights of A and B, respectively; P is the
absolute pressure, in atmospheres; AB is the "collision diameter," in A;
and D is the "collision integral" for
molecular diffusion, a dimensionless function . Appendix Table K.1 lists
D as a function of kT/AB , k is the Boltzmann constant, which is 1.38 x
10-16 ergs/K, and AB is the energy of molecular interaction for the binary
system A and B, in ergs. Unlike the other two molecular transport
coefficients, viscosity and thermal conductivity, the diffusion coefficient
is dependent on pressure as well as on a higher order of the absolute
temperature.

This information is available for only a very few pure gases. Appendix
Table K.2 tabulates these values.

For a binary system composed of non-polar molecular pairs, the

parameters of the pure
component may be combined empirically by the following relations:

The Hirschfelder equation is often used to extrapolate experimental

data. For moderate
ranges of pressure, up to 25 atm, the diffusion coefficient varies
inversely with the pressure. Higher pressures apparently require dense
gas corrections; unfortunately, no satisfactory correlation is available
for high pressures. Equation also states that the diffusion coefficient
varies with the temperature as T 3/2/ D varies. Simplifying
Hirschfelder, we can predict the diffusion coefficient at any
temperature and at any pressure below 25 atm from a known
experimental value by:

3/2
DAB,T2 = DAB,T1* * *

In Appendix Table J.l, experimental values of the product DABP are listed
for several gas pairs at a particular temperature. Using this equation,
we may extend these values to other temperatures.

EXAMPLE (1):
Evaluate the diffusion coefficient of carbon dioxide in air at 20 C and
atmospheric pressure. Compare this value with the experimental value
reported in appendix table J.I.

SOLUTION:

From Appendix Table K.2, the values of and A/k are obtained:

Substance in A A/k
CO2 3.996 190
Air 3.617 97

T = 20+273=293K, P= 1 atm
 D = 1.047

M CO2 = 44 g/gmol, Mair =29 g/gmol

Substituting these values in Hirschfelder equation:

From Appendix Table J.l for CO2 in air at 273 K, 1 atm, we have DAB =
0.136 cm2/s
To correct for the differences in temperature, the following equation is
applied:

3/2
DAB,T2 = DAB,T1* * *

3/2
DAB,T2 = 0.136*(

At T= 273 K:

D = 1.074

By substituting this value in the previous equation:

 3/2
DAB,T2 = 0.136*( = 0.155 cm2/s

We readily see that the temperature dependency of the "collision

integral" is very small.
Accordingly, most scaling of diffusivities relative to temperature
includes only the ratio (T1/T2)3/2.