Mass Transfer for Environmental Engineers

CEIC 2009

Week 1 August 2018

Overview: Todays objective is to introduce the concept of Flux in mass transfer

systems and applications.

Mass transfer is the term used to describe the movement of molecules between
phases (e.g. “solid to gas” or “gas to liquid”), across a physical interface (eg a
membrane) or within a phase in response to a driving force (concentration gradient or
microscopic movement of fluid).

To describe mass transfer we begin by identifying a two-dimensional plane1 that

exists at some coordinate (z) in the system defined by a given coordinate geometry
(eg Cartesian, spherical, cylindrical etc.).

For convenience we often use the term Flux to describe the amount of
material/molecules that move across the 2D plane per unit of time to define mass
transfer in that system. Consequently Flux has the units of molecules/area/unit time
(mol/m2/s).

Aim: By the end of Lectures 1, 2 & 3 and through practice in the class tutorial and
formal tutorial in week 3 you should be able to do the following;

1. Describe features of mass transfer systems in environmental engineering

2. Define the properties of flux in the context of mass transfer systems. This
includes;
o Dimensional analysis of flux
o Forms of concentration in liquids and gasses
o Factors that define flux
o Difference between steady state and non-steady state systems
3. Use Fick’s First Law to calculate the diffusive component of flux in terms of a
concentration gradient and a diffusion coefficient
4. Use some techniques for estimating Diffusion Coefficients for solids, liquids
and gases

First MT quiz: Items 1 through 4 will be used as the basis for our 1st quiz on mass
transfer that will be held in week 5

References and Resources: The material presented today is covered in more detail
in a number of text books. For example Chapters 1 and 2 of the book “Mass Transfer
– Fundamentals and Applications” by Hines and Maddox. (However, this book was
written for chemical engineers – all will be OK if you follow the notes and do the
tutorial problems!

1
See last slide of Mass transfer in environmental applications handout for an image
of the 2 D plane.
 1. The properties of “flux” in mass transfer problems

We begin by defining Flux of an individual component A across an imaginary, (or

real12), Two– Dimensional plane in terms of either a mass flux or molar flux.

Flux is a vector component a +ve sign indicates movement in +ve Z direction

whereas a –-ve sign indicates movement in –ve Z direction. In most cases we use a
–ve sign. This is a feature of Fick’s law because flux flows down the concentration
gradient

Concentration can be expressed in different terms depending on the phase (liquid or

gas) and the conditions of the system (temperature and pressure). The Development
of equations to describe flux makes use of mole fraction as a form of concentration.
This is convenient because mole fraction is dimensionless and many of the systems
we need to study and design (distillation, absorption etc) are based on mixtures that
are readily described in terms of mole fraction.

By convention, x is used to describe mole fraction in liquids and y is used for gases.

The problems in tutorial number 1 will give you some practice at manipulating the
different forms of concentration.

2
An example of a real interface is the interface between an air bubble and the surrounding liquid (Two
phases). An imaginary interface is a 2D plane in a single phase (eg. At a specified distance from a
smoke stack)
 2. Developing mathematical description for flux in a binary system (A & B)

Molar flux of component A can be influenced by movement on the molecular scale

and the bulk fluid scale. These two components of flux are referred to as the
diffusive and convective components. The symbol used to define flux when we are
dealing only with the diffusive component (MJA). This represents, the net number of
moles of A (kmol) passing across 1 m2 of plane area per second in response to a
concentration gradient and influence by movement on the molecular scale.

To account for flux due to movement in the bulk fluid we need to consider the velocity
of the molecule due to bulk fluid and diffusion (which is always present above
absolute zero (0oK).

In either case, if movement (molecular or mixing) can influence flux, then we use the
concept of velocity to begin to develop equations for flux. Velocity is a vector
quantity and can be used to specify the rate and the direction. However, if we specify
direction, you must include a frame of reference

Therefore, the Total Molar Flux (NA) which accounts for both diffusion and
convention can be expressed

NA = CAUA (kmols s-1 m-2)

Where, CA = Molar concentration (kmol m-3)

UA = velocity of A w.r.t. a fixed reference frame (m s-1)

However, Mixing does not discriminate! The frame of reference must include all
components of the system (A & B). So, define a molar average velocity of the mixture w.r.t. a fixed
reference frame.

UM = xAUA + xBUB

Let new coordinates move at this molar average velocity relative to a fixed frame of reference
where XA and XB are the mole fraction of A and B.

C AU A  C BU B N A  N B
UM  
C C

The expression for UM (In terms of molar flux for A & B) will be used to develop an
expression for the molar flux of element A that accounts for diffusion & mixing (convection).

The Molar flux of A (MJA) in a mixture relative to a set of coordinates that are moving at the
molar average velocity depends on;

• CA (molar concentration of A)
• Net velocity of A (Velocity of A minus the molar average velocity)

Therefore,

MJ A = CA(UA – UM) (Equation 1)

 3. Flux and Fick’s First Law

The next step is to add some terms to account for the contribution of diffusion.

Consider a binary mixture of two gases (i.e. 2-components, A & B) expressed as a mole
fraction FICK’S LAW says;
dy A
M J A  CD AB
dZ
Where,

yA = mole fraction of component A (-)

Z = distance (m)
C = molar concentration (kmol m-3)
MJA = molar flux of component A (kg m -2 s-1)
DAB = proportionality constant between flux and concentration gradient,
Defined as the molecular diffusion coefficient (m2 s-1)

Now equate Fick’s First Law with Equation 1;

dy A
 CD AB  C A (U A  U M )
dZ
Substituting, NA = CAUA and UM = (NA + NB)/C gives,
dy A
N A  CD AB  y A (N A  N B )
dZ
Therefore, total Flux includes terms for both diffusion and convection. This equation is the
starting point for all diffusion mass transfer problems!

4. Implications of diffusive and convective components of flux.

We have seen that flux of a species A can have a diffusive component which can be described in terms
of Fick’s first law (concentration gradient and diffusion of A) and a convective component that depends
on mixing (Velocity of A as well as the molar Average Velocity of A). Here are some special cases to
consider:

Case 1 - What if the molar flux of A and B are equal but in the opposite direction?

For example, consider Two gas streams moving at equal flux but in opposite directions (Assignment
1 Problem 4). In this case, NA = - NB so the total flux is governed by the diffusion coefficient of A in
B and the concentration gradient. (This is known as Equimolar counter diffusion)

Case 2- What if the concentration of A is small?

This is an example of corrosion in humid environments. If concentration of A is small then

convective flux (CAUA) becomes negligible compared with diffusion.

In each case convection is negligible – therefore mass transfer is diffusion controlled.

Lecture 1 MT Tutorial 1 Problems

The purpose of tutorial 1 is to give you some practice at converting

concentration from one form to another.

There are three ways to express concentration of species A in the gas

phase:
1. Partial pressure PA – which has units of pressure (Pa)
2. Mole fraction yA – which is dimensionless
3. Molar concentration – which has units of mol/m3

There are two ways to express concentration of species A in the gas phase:
1. Mole fraction xA – which is dimensionless
2. Molar concentration – which has units of mol/m3

The following expressions will help with the tutorial.