Cambridge University Engineering Department

Engineering Tripos Part IIA

Module 3A6: Heat and Mass Transfer

Some Notes on Mass Transfer

Dr. Christos Markides

cnm24@cam.ac.uk

NOTE: Unless otherwise stated, the Einstein Summation Convention is used

throughout, with
.

22

nd

CNM
of February, 2008

1. Background:
The definition of the Material or Substantive Derivative operator is:

Conservation of mass, or continuity,

or, in vector calculus notation, and thus in any (all) co-ordinate system(s):

Then, for any scalar , and using Eqn. 2:

In one, planar dimension, with v = w = 0, Eqns. 2 and 3 become:

In one, cylindrical dimension, with u = uz = 0, Eqn. 3 becomes:

In one, spherical dimension, with u = u = 0, Eqn. 3 becomes:

For one-dimensional,
respectively:

incompressible

flows,

Eqns.

5,

and

become,

In addition, conservation of species (mass) gives,

where Ficks law has been used for the molecular diffusive mass flux
, in exactly the same way that Fouriers law of heat
conduction was used for the molecular diffusion (conduction) of heat. The reader
is asked to refer also to Section 2: Diffusive (Ficks law) and advective
mass/molar flux.
Note that, if we sum Eqn. 9 throughout, over all species i:

Hence, we see that Eqn. 9 is an equation for the conservation of mass of species
i, such that if we sum over all i, we get back to the equation for the
conservation of the total mass of all species.

In vector calculus notation, and thus in any (all) co-ordinate system(s):

Note that, similarly to above, if we sum over all i:

In one, planar, cylindrical or spherical dimension, Eqn. 10 becomes, respectively:

In this course you will concentrate on one-dimensional, incompressible flows and

fluids with constant D. In these situations, Eqns. 11 simplify to,

From left to right in Eqns. 12, the terms represent: unsteadiness, advection,
volumetric species mass generation/chemical reaction (also the chemical source
term), and molecular diffusion.
You will deal with both non-reactive (

) and reactive (

) mass transfer. In

reactive mass transfer you will be presented with homogeneous and

heterogeneous reactions, and further you will only encounter these reactions in
steady, stagnant conditions, i.e. in absence of unsteadiness and advection.
Heterogeneous reactions do not occur throughout the volume of the fluid, so that
in this case,

, as with non-reactive mass transfer.

In non-reactive mass transfer you will be expected to solve steady diffusion with
non-zero advection, or non-zero bulk flow, that is,

steady diffusion with zero advection, or stagnant mass transfer with no bulk flow,

and unsteady diffusion, but never with advection:

In the latter case, you will only ever be presented with the planar geometry of
Eqn. 15a, and further will not be expected to actually solve Eqn. 15a and obtain
the error function solution itself. Instead, you might face a question in which you
are asked to obtain the result by being guided through it, and/or to use this
result.

In reactive mass transfer (homogeneous reactions) you will only be expected to

treat so-called reactive-diffusive problems, which are steady and with no
advection, resulting in:

2. Diffusive (Ficks law) and advective mass/molar flux:

So far we have considered governing equations of Yi, the mass fraction of species
i. The solutions, dealt with in detail in the following Sections, will yield the
spatial distributions of Yi, and in the case of unsteady mass transfer the temporal
evolution of these distributions.
However, one might in fact be interested in the mass flux of species i, denoted
by Gi, and which is defined as the mass flow rate of i per unit cross-sectional
flow area, A:

It can be seen from above, that given Yi, the definition of Gi is of limited
usefulness, since we still require ui. Instead, it is best to think of the total mass
flux of species i as the sum of an advective part and a diffusive part,

and where the diffusive contribution is given by Ficks law, here presented in
vector calculus notation,

such that, in one-dimension:

Note that, by summing over Eqn. 18, we can obtain a further property of the
diffusive mass flux:

This existence of two contributions to the mass flux can also be seen directly by
considering Eqn. 9:

In addition, and similarly to above, one can define the molar flux of species i,
denoted by Ji:

where c is the total molar concentration and ci is the molar concentration of

species i, and,

in an analogous way to,

with n being number of moles and m mass.

3. Steady, 1-D, incompressible, non-reacting flows and fluids with
constant D:
For steady, planar one-dimensional, incompressible flows and fluids with constant
D, and by using Eqn. 8a, Eqn. 12a simplifies to:

For steady, cylindrical one-dimensional, incompressible flows and fluids with

constant D, and by using Eqn. 8b, Eqn. 12b simplifies to:

For steady, spherical one-dimensional, incompressible flows and fluids with

constant D, and by using Eqn. 8c, Eqn. 12c simplifies to:

Furthermore, for steady, one-dimensional, incompressible, non-reacting flows and

fluids with constant D, Eqn. 21 that is the same as Eqn. 13a, becomes,

Eqn. 22 that is the same as Eqn. 13b, becomes,

and Eqn. 23 that is the same as Eqn. 13c, becomes:

4. Steady, 1-D, incompressible, non-reacting stagnant mass transfer

with constant D:
For steady, one-dimensional, incompressible, non-reacting stagnant mass
transfer with constant D, all velocities are zero, u = ur = 0, and Eqns. 24, 25 and
26 that are the same as Eqns. 14a, 14b and 14c collapse to, respectively:

It is straightforward to integrate twice, and apply (two) suitable boundary

conditions, in order to obtain the distributions of Yi in each case:

5. Unsteady, 1-D planar, incompressible, non-reacting stagnant mass

transfer with constant D:
The solution of Eqn. 15a,

is identical to the error function solution for unsteady, one-dimensional planar

heat transfer in a solid with constant properties, with the thermal diffusivity
being replaced here by the molecular diffusivity D:

6. Steady, 1-D, incompressible, reacting stagnant mass transfer with

constant D:
In reactive mass transfer one finds homogeneous reactions, which are volumetric
(that is, they occur throughout the volume of the fluid), and heterogeneous
reactions that are not volumetric, but surface phenomena (in that they occur on
the surface of catalysts). Note that not all catalysis results in heterogeneous
reactions. The former appear as relations for
boundary conditions, with

in Eqns. 16, but the latter as

. Hence, for heterogeneous reactions, the

governing equations look exactly like Eqns. 27, in Section 4: Steady, 1-D,
incompressible, non-reacting stagnant mass transfer with constant D, and the
solutions look exactly like Eqns. 28 in the same section.
For homogeneous reactions, the governing equations are:

A chemical reaction between two reactants R1 and R2, producing a product P, is

an expression of conservation of mass:

You will be expected to be familiar with zeroth and first order chemical reactions.
In these reactions we have,

where

is the molar production rate of P (in kmols/s), k is the reaction rate

constant, and ci is the molar concentration of species i (in kmols/m3). You must
be careful that the units of kj depend on the order of the reaction, such that in
Eqn. 31a these are kmols/s, whereas in Eqn. 31b they are m 3/s.
It is customary to deal with molar quantities in chemical kinetics, but we need to
obtain the mass reaction rate

of the various species (reactants and products) if

we are to proceed here. This is straightforward,

where MWi is the molecular weight of species i.

Furthermore,

and

can be obtained from Eqns. 31 depending on the type of the reaction.

One final point is that in first order reactions, you will need to turn ci into a mass
based quantity, since the molar reaction rate in Eqn. 31 involves ci,

and Eqns. 31 become:

Hence, for a zeroth order reaction, Eqns. 16 become,

where the sign of the chemical source term is positive for the product, i being
P, and negative for the reactants, i being R1, or R2.
The solution of Eqn. 36a, for geometries with planar symmetry, is,

For A and B we can use suitable boundary conditions for Yi, such as at x = 0, Yi,o,
or

, Yi,.

The solution of Eqn. 36b, for cylindrically symmetric geometries, is,

The solution of Eqn. 36c, for spherically symmetric geometries, is,

Similarly, for a first order reaction, we can substitute the chemical source term
from Eqn. 35b into Eqns. 16. For example, in order to find YR1 in a planar
geometry:

For a spherical geometry, we can make the following substitution:

Note that, in all solutions of second order linear, ordinary differential equations,
the
exponentials
can
written
as
sinhs
and
coshs:
, 2A = D + C, 2B = D C.