Concentration Distributions in Different Phases at Laminar

Concentration Distributions in different Phases
at Laminar Flow
1
MASS BALANCES; BOUNDARY CONDITIONS
Having selected an appropriate system, the law of conservation of mass of species A in a binary system
is written over the volume of the material in the following form:
The conservation statement may, of course, be expressed in terms of moles. The chemical species A
may enter or leave the system by diffusion (i.e., by molecular motion) and also by virtue of the overall
motion of the fluid (i.e., by convection), both of these being included in NA. In addition, species A may
be produced or consumed by homogeneous chemical reactions.
After a balance is made on a finite thickness by means of above equation, we then let the thickness
become infinitesimally small. As a result of this process a differential equation for the mass (or molar)
flux is generated. If, into this equation, we substitute the expression for the mass (or molar) flux in
terms of the concentration gradient, we get a differential equation for the concentration.
When this differential equation has been integrated, constants of integration appear, and these have to
be determined by the use of boundary conditions.
2
The BOUNDARY CONDITIONS are very similar to those used in heat conduction (see Chapter 10.1):
3
DIFFUSION THROUGH A STAGNANT GAS FILM
We want to analyze the diffusion system

shown in the right hand side Figure in which
liquid A is evaporating into gas B. We imagine
there is some device that maintains the liquid
level at z =z1. Right at the liquid-gas interface,
the gas-phase concentration of A, expressed as
mole fraction, is 𝑥𝐴1 . This is taken to be the
gas-phase concentration of A corresponding to
equilibrium with the liquid at the interface.
That is, 𝑥𝐴1 is the vapor pressure of A divided
by the total pressure, 𝑝𝐴𝑣𝑎𝑝 /𝑝, provided that A
and B form an ideal gas mixture and that the
solubility of gas B in liquid A is negligible. A
stream of gas mixture A-B of concentration
𝑥𝐴2 flows slowly past the top of the tube, to
maintain the mole fraction of A at 𝑥𝐴2 for z=
z2. The entire system is kept at constant
temperature and pressure.
4
To simplify the problem, we neglect the effect of velocity profile in r-direction and assume
that there is no dependence of the z-component of the velocity on the radial coordinate. When
this evaporating system attains a steady state, there is a net motion of A away from the
interface and the species B is stationary. Hence the molar flux of A with considering NBz = 0 is
given by
For an ideal gas mixture the equation of state is p = cRT, so that at constant temperature
and pressure c must be a constant. Furthermore, for gases DAB is very nearly independent
of the composition. Therefore, can be moved to the left of the derivative operator to get
5
This is a second-order differential equation for the concentration profile expressed as mole fraction
of A. Integration with respect to z gives
6
7
(a) Derive expressions for diffusion through a hypothetical spherical stagnant gas
film surrounding a droplet of liquid A
(b) Extend these results to describe the diffusion in a non-isothermal film in
which the temperature varies radially according to
where T1 is the temperature at r = r1. Assume as a rough approximation that varies

as the 3/2 -power of the temperature:
Problems of this kind arise in connection with drying of droplets

and diffusion through gas films near spherical catalyst pellets.
8
9
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We study diffusion in both nonreacting and reacting systems. We want to distinguish between two reaction
types:
HOMOGENEOUS, in which the chemical change occurs in the entire volume of the fluid, and
HETEROGENEOUS, in which the chemical change takes place only in a restricted region, such as the
surface of a catalyst. The rate of production of a chemical species by homogeneous reaction appears as a
source term in the differential equation obtained from the shell balance, just as the thermal source term
appears in the shell energy balance. The rate of production by a heterogeneous reaction, on the other hand,
appears not in the differential equation, but rather in the boundary condition at the surface on which the
reaction occurs.
In order to set up problems involving chemical reactions, some information has to be available about the rate
at which the various chemical species appear or disappear by reaction. This brings us to the vast subject of
chemical kinetics, that branch of physical chemistry that deals with the mechanisms of chemical reactions
and the rates at which they occur.
11
Mentioning the notation to be used for the CHEMICAL RATE CONSTANTS:
in which RA [=] moles/cm3.s and CA [=] moles/cm3. The index n indicates the "order” of the reaction, for
a first-order reaction, k”’ [=] l/s.
in which NAZ [=] moles/cm2 .s and CA [=] moles/cm3. Here k” [=] cm/s. Note that the triple prime on the
rate constant indicates a volume source and the double prime a surface source.
12
Example: Let us now consider a simple
model for a catalytic reactor, such as that
shown in Fig. 18.3-la, in which a reaction
2A→B is being carried out.
We imagine that each catalyst particle is

surrounded by a stagnant gas film through
which A has to diffuse to reach the catalyst
surface, as shown in Fig. 18.3-lb At the
catalyst surface we assume that the reaction
2A→B occurs instantaneously, and that the
product B then diffuses back out through the
gas film to the main turbulent stream
composed of A and B.
The main goal is to get an expression for the
local rate of conversion from A to B when
the effective gas-film thickness and the
main stream concentrations 𝑥𝐴0 and 𝑥𝐵0
are known.
13
For the situation depicted in Fig. 18.3-lb, there is one mole of B moving in the minus z
direction for every two moles of A moving in the plus z direction. We know this from the
stoichiometry of the reaction. Therefore we know that at steady state
By making a mass balance on species A over a thin slab of thickness ∆z in the gas film:
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15
One point deserves to be emphasized: Although the chemical reaction occurs
instantaneously at the catalytic surface, the conversion of A to B proceeds at a finite rate
because of the diffusion process, which is “in series” with the reaction process. Hence we
speak of the conversion of A to B as being diffusion controlled.
In the example above we have assumed that the reaction occurs instantaneously at the
catalytic surface. In the next example we show how to account for finite reaction kinetics
at the catalytic surface.
16
17
Note once again that we have obtained the rate of the combined reaction and diffusion process.
Note also that the dimensionless group 𝐷𝐴𝐵 /𝑘"1 𝛿 describes the effect of the surface reaction kinetics
on the overall diffusion-reaction process. This group is known as the second Damkohler number'.
Evidently we get the result in Eq. 18.3-9 in the limit as Da → ∞.
A Da is a useful ratio for determining whether diffusion rates or reaction rates are more ‘important’
for defining a steady-state chemical distribution over the length and time scales of interest.
18
DIFFUSION WITH A HOMOGENEOUS CHEMICAL REACTION
Here gas A dissolves in liquid B in a beaker and diffuses isothermally into the liquid phase. As it
diffuses, A also undergoes an irreversible first-order homogeneous reaction: 𝐴 + 𝐵 → 𝐴𝐵. An example
of such a system is the absorption of CO, by a concentrated aqueous solution of NaOH.
19
The MASS BALANCE on species A over a thickness Δz of the liquid phase becomes:
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Concentration Distributions in different Phases

We want to analyze the diffusion system

where T1 is the temperature at r = r1. Assume as a rough approximation that varies

Problems of this kind arise in connection with drying of droplets

We imagine that each catalyst particle is

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