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P.C.

Chau (UCSD, 1999)

Diffusion in Concentrated Solutions


In the simplest terms, Fick's law of diffusion at constant temperature and pressure is
Ji = D i ci
We would have liked to make the statement as we would with Fourier's law in heat conduction and
stop. Unfortunately, we cannot do that; mass transport is not as simple as we may have thought.
As stated, the constitutive equation describes only diffusive flux and not the net flux of the
chemical species i. It is only under circumstances of dilute solutions that we can use Ficks law to
evaluate the net transport.
For concentrated solutions, meaning now general circumstances, the explanation of mass flux
from a molecular dynamics viewpoint is rarely grasped firmly by someone new to the topic. So
dont feel bad if you are lost the first time. The description is not complete until both the units and
the reference frame have been given. We'll give the concept of flux a slightly more detailed
explanation here.
We begin with the concept of a flux velocity. Let's consider a gas mixture with no external
imposed force. All the molecules will be in constant thermal motionBrownian motion. At
uniform temperature and pressure, the mean velocity of all the molecules would be zero, i.e., there
is no net flow (bulk motion) in any direction. However, the molecules could have finite mean
speed related to the thermal motion; this is a phenomenon described by the Maxwell-Boltzmann
equation in physical chemistry.
Now consider the situation when the gas mixture is nonuniform. The source of nonuniformity
is general; it may arise from external forces and temperature and not necessarily confined to
concentration gradients. Now for sure we expect the species i to have an average velocity vi in
some direction relative to a stationary coordinate. The transport of the species i, in terms of the
mass flux, is defined as
ni = i vi

(1)

where i is the mass density of species i. Note that the unit of mass flux is mass per area per time
[e.g., g.cm2.s1 ] in other words, the rate of mass transport per unit area. The velocity is also
called the flux velocity. If we divide Eq. (1) by the molecular weight of species i, we have now the
molar flux:
N i = ci v i
(2)
where ci = i/MWi is the molar concentration of species i.
A nonuniform mixture of molecules may have a resultant motion due to the motion of
individual molecules. We define for the mixture as a whole the mass average velocity:
v =

i v i 1
= i vi = i vi
i

(3)

where the summation is over all the species in the mixture. We also have used = i as the
total mass density and i = i/ is the mass fraction of species i. Again, we can divide the mass
definition by the molecular weight of each species and arrive at the molar average velocity of the
mixture:
c i v i 1
v* =
= ci vi = yi vi
(4)
ci
c
where we have used c = ci as the total molar density and yi = ci/c is the mole fraction of species
1

P.C. Chau (UCSD, 1999)

i. Thus v and v* are the mass fraction or mole fraction weighted average velocities.
In general, the motion of a mixture as a whole can be described by the total mass flux v, or
the total molar flux v*c, both in reference to a stationary coordinate system.
Of course, we would not expect the velocity of an individual species vi to be always the same
as the average velocity v or v*. We define the difference (vi v) or (vi v*) as the diffusion
velocities. From the terminology, we may guess ahead that the source of the difference is
concentration gradient. 1
We now define diffusive fluxes as relative to the average velocities. Again, we can use
either the mass diffusive flux:
ji = i (vi v)

(5)

or molar diffusive flux: 2


J*i = ci (vi v*)

(6)

We next see what properties we can derive for these fluxes. We begin with molar fluxes,
which properly reflect the distribution of gas molecules. If we substitute the definition of v* in
Eq. (6), we have

c
J *i = c i vi ci c j v j
j
Note that the summation index for all species is j. We know that Ni = civi, and yi = ci/c, so we
have the important result for the diffusive flux of species i:

J *i = N i y i N j

(7)

where, once again, J*i is the difference between the molar flux of the species and the rate of
transport of i due to the local molar flux (or bulk motion) of the mixture. Note that Nj is the
total molar flux of the mixture (identical to v*c). When the bulk motion contribution is
negligible, the transport is purely diffusive, Ni = J*i.
It is instructive and helpful to think of Eq. (7) as
N i = J*i + yi N j
in that the total molar flux of a species is the sum of Fickian diffusive flux and a contribution due
to the bulk motion of the entire mixture.
1

For now, we should remind ourselves that we have made no explicit assumption on the origin
of the flux velocity of an individual velocity, vi , and thus for that matter also the origin of v or
v*. In essence, the flux velocity vi embeds diffusive and convective velocities.
The average velocities v and v* are a result of superimposed molecular motions of all kinds
and they generally manifest in bulk motion of the mixture. When the molecules of an individual
species do not move on average as the same as the bulk fluid, i.e., vi v or vi v*, it may arise
from heterogeneity in physical properties of the mixture. One possibility is severe temperature
gradient and thermal diffusion. However, under most circumstances, we only need consider
gradients in concentration and thus mass diffusion.
2
Note that we now have the choices of using ni and ji in mass units or Ni and J*i in molar
units. In B.S.L. (Table 16.1), you may find a bewildering combinations of other possibilities.
Ignore them for now. Stay with the most common and simple definitions.
2

P.C. Chau (UCSD, 1999)

We can manipulate Eq. (7) a bit to give

J *i = N i y i N i
j

Nj
Nj
= Ni 1 yi
Ni
j Ni

(7a)

where the term (1 yi Nj/Ni ) is called the drift factor. The idea is that the diffusive flux J*i in
Eq. (7) is likened to evaluating the "drift" of the species i relative to the bulk motion of the
mixture.
If we now sum Eq. (7) over all species, we have

i J *i = i N i i y i j N j = 0

(8)

since yi = 1. The important result is that the sum of molar diffusion fluxes is zero under all
circumstances.3 In a binary mixture, it means that we must have
J*A = J*B

(9)

We now state the Fick's law of diffusion. For a binary mixture at constant temperature and
pressure, the diffusive flux of species A is
J*A = DAB cA

(10)

where DAB is the binary diffusion coefficient 4 and cA is the concentration gradient. For gas
phase system and problems that may have temperature and pressure variations, Fick's law is more
properly defined as
J*A = c DAB yA

(10a)

to ensure that the driving force is entirely due to concentration gradient and not changes in molar
concentration, c.
For a binary mixture, the molar flux of the species i as state in Eq. (7) is

N A = c DAB y A + y A (N A + N B)

(11)

Repeating the comment after Eq. (7): the molar flux of A, NA, is the Fickian diffusive flux (first
term on the right) superimposed on the flux of species A resulting from the bulk fluid motion (the
second term).

This is the major source of confusion, and would likely remain so until you take a graduate
level course! Eq. (8) is the sum of diffusive fluxes. It does not mean that the molar flux of the
mixture v* is zero. Recall that vi is defined in reference to a stationary coordinate, but Ji is
defined in reference to v*. Loosely speaking, the "drift" of all the species in a mixture evens out
and all the molecules on average follow the bulk motion of the mixture.
Under circumstances when we do not have externally imposed force or fluid flow, the molar
average velocity v* of a gas mixture is nearly zero, while in a liquid mixture, it would be the mass
average velocity v that is nearly zero. The text by Cussler is the best to clear up this point.
4
In an introductory course, we invariably stays with binary mixtures. When we have
multicomponent mixtures, we would use the notation, for species i, Di,m. Solutions to non-dilute
multicomponent diffusion also requires the so-called Stefan-Maxwell equation.
3

P.C. Chau (UCSD, 1999)

When we solve a problem, we need to know (or make a reasonable assumption of) NB as a
function of NA. One simple scenario is equimolar countertransport where NA = NB which is
equivalent to stating that v* = 0.5 Another simple situation is that NB = 0, i.e., the species B
molecules remain essentially stagnant. We can also consider NB = 0 when we have a dilute
mixture of A.
We finish by repeating two classic textbook examples.
Example 1. Stefan diffusion tube

B
z=L

In a common scenario, a capillary tube is partly filled with a volatile


organic liquid A, while air (species B) is blown across the top. Of course,
the species A will diffuse slowly upward. A typical exercise is to find the
concentration (mole fraction) profile of A along the capillary. As we will
see in most mass transport problems, this is not a very useful result. What
we want is the flux of A, and from this quantity, we can estimate the rate of
decrease of the liquid level and the molecular diffusivity of A in B.

h(t)

z=0
Pure A

The solution of this problem is based on several important


Figure. E1
assumptions:
(1) Species A is volatile and the mass transport is more than just pure diffusion. That is, we need
to invoke Eq. (11).
(2) Air is not soluble in the liquid A, and the molar flux NB = 0 between z = 0 and z = L.7 Thus
even as species A is evaporating, air is essentially stagnant in the capillary.
(3) In a race between tortoises, the mass transport within the capillary is rather "quick" compared
with the rate of decrease of the liquid level h(t). Hence, we apply the quasi-steady state
assumption to the diffusional problem in the capillary.
Based on a shell balance at steady state for species A, we arrive at

dN A
=0
dz

(E1-1)

in the capillary, meaning that the molar flux NA is a constant. Now, with Eq. (7), we also have

N A = c DAB

dy A
+ yA NA ,
dz

(E1-2)

or

NA =

c DAB dy A
.
(1 y A ) dz

(E1-2a)

With constant c and DAB, substitution of (E1-2a) in (E1-1) leads to

d
1 dy A = 0 ,
dz 1 y A dz

(E1-3)

Note that while v* = 0 when we have a so-called equal exchange of molecules NA = NB , the
mass average velocity is nonzero, v 0. That's because molecule weights are different.
6
Not everyone calls this the Stefan tube problem. It is just as commonly referred to as
"diffusion in a stagnant gas film."
7
This fact also follows from (E1-1). Like species A, NB is also constant. Since B is not
soluble in A, the net flux of B at z = 0 is zero, which implies that NB is zero everywhere in the
capillary.
4

P.C. Chau (UCSD, 1999)

which is subjected to boundary conditions yA(0) = yAo, and yA(L) = yAL. The solution is 8
z/L

1 y AL
1 yA
=
1 y Ao
1 y Ao

(E1-4)

The key is to appreciate that the concentration profile is nonlinear. We only expect a linear profile
when we have pure diffusion. And you can certainly plot (E1-4) with the computer to get a better
feel on the nonlinearity of the problem.
Our next agenda is to find the flux NA. The key is never use the final solution which often
leads to a mess before things get cleared up. You can sense that in (E1-4). The smart move is to
make use of the intermediate integration step where we have the gradient dyA/dz (see footnotes to
E1-4). With that and (E1-2a), we can find easily

NA =

c DAB
1 y AL
ln
1 y Ao
L

(E1-5)

which of course is a constant as consistent with (E1-1). It is easy to see that when yAo 1, and
hence also yAL 1, (E1-5) reduces to

NA

c DAB
(y Ao y AL) ,
L

(E1-6)

which is a long-winded way to come back and see why with dilute solutions, we can approximate a
problem with only the pure diffusive term. On this note, one question for you: how do you find
values for yAo and yAL?
Our final step of this problem comes back to the drop in liquid level. We cannot lose sight
that we are solving a quasi-steady state problem. Something else must be changing in time! We
can evaluate the loss of species A by matching the mass flux:

A dh = N A M w,A ,
dt

(E1-7)

where A is the mass density, and MW,A is the molecular weight of A. From here, we need to
substitute (E1-6) into (E1-7) and make a statement how L also changes in time.
We may note that at t = 0, we have L = Lo and h = ho, and hence L = (Lo + ho) h. So the
algebra is much cleaner if we keep L as the variable and use dL/dt = dh/dt instead. You'd be darned
if you can't develop the remaining steps in solving a problem.
Before we leave this example, let's revisit Eq. (E1-2). Even as NB = 0, the diffusive flux J*B
is not. In (E1-2), both terms on the right, the diffusive flux and the bulk motion contribution for
A, are positive. The analogous equation for B is

After one integration of (E1-3), we can write


dy A
dy A
= (1 y A ) , or
= dz ,
dz
1 yA
where is an integration constant which can be found with
y AL
y Ao

dy A
=
1 yA

dz , or hence
0

1 ln 1 y Ao
=L
1 y AL

P.C. Chau (UCSD, 1999)

0 = c DAB

dy B
+ yB NA
dz

(E1-8)

where we have taken note of the fact that DBA = DAB.9 Here, the bulk motion contribution for B
(second term on the right) is positive, but the diffusive term is negative. We should "see" that
since the mole fraction of B is higher at the top (z = L) than at the bottom of the capillary. In fact,
we need these two terms counter to each other perfectly to achieve the zero net flux of B.
Furthermore, you should try this yourself: Add (E1-2) and (E1-8) together and the sum of the
two diffusive terms are zero, as we have derived in Eq. (8).

Example 2. Diffusion with heterogeneous chemical reaction


The main point of this example is to illustrate how we can get a
"drift" and deviate from pure diffusive flux even when the mixture is
dilute. Essentially, we see how a chemical reaction with the specific
stoichiometry selected may give rise to a molar flux, or loosely
speaking, reaction causes flow.

O2

CO

CO2

The situation is such that on a solid surface, we have some


oxidation reaction, say,
3C + 2O2 > 2CO + CO2

z =

z=0

Figure E2

(E2-1)

in which the number of moles is not conserved.


Oxygen in the bulk gas phase (say, mainly an inert nitrogen blanket) diffuses toward the
surface, while the products CO and CO2 diffuse away. The assumption is that the bulk gas
concentrations are uniform, and the necessary mass transport is effected within a "thin" gas film of
thickness . Furthermore, the mass transport is at steady state. It is clear that we want to apply Eq.
(7), the more general form of (11), to each species, and we'll use O2 as an illustration.
We need to find eventually Nj. Before that, we need to remember our chemical kinetics. The
rate of change of a species is ri = ir, where r is the rate of the chemical reaction and i is the
stoichiometric coefficient of species i in this reaction. Thus on the same basis (r = ri/i), we can
write
1/2 N O 2 = 1/2 N CO = N CO 2
or
Hence

NO2 = NCO = 2NCO2

(E2-2)

N j = N O 2 + N CO + N CO 2 = (1 1 1/2) N O 2 = 1/2 N O 2

(E2-3)

and Eq. (7) written for oxygen is

N O 2 = c DO 2 ,m

dy O 2
+ y O 2( 12 N O 2)
dz

or

NO2 =

c DO 2 ,m
(1 +

1
2

dy O 2
y O 2) dz

(E2-4)

For a binary mixture, yA + yB = 1, and thus yA + yB = 0. From Eq. (9) and (10a), we can
write c DAB yA = c DBA yB. Taken together, we have DAB = DBA for a a binary mixture.

P.C. Chau (UCSD, 1999)

where DO2,m denotes the diffusion coefficient of oxygen in the mixture. If the gas mixture is so
dilute such that there is negligible interaction among the O2, CO and CO2 molecules, we can use
the binary diffusion coefficient of oxygen in nitrogen, DO2,N2 as an approximation.
Even when the gas mixture is dilute, the flux is affected by the change in the number of
moles. In (E2-4), we see that the drift factor (1 + 1/2yO2) in this problem is larger than unity. The
molar flux of oxygen toward the surface is smaller than if there were only pure Fickian diffusive
flux.
You should now finish the example. The steps are very similar to the Stefan tube problem. A
steady state shell balance of oxygen in the gas film should lead to dNO2/dz = 0 as in (E1-1). With
prescribed boundary concentrations (mole fractions), the integration steps are just like those in
Example 1.