Diffusion through variable cross-sectional area

Diffusion through a conduit of non-uniform cross-sectional

area
• Component A is diffusing at steady state through a
circular conduit which is tapered uniformly as shown
in Figure
• At point 1 the radius is r1 and at point 2 it is r2
• A is diffusing through stagnant, non-diffusing B
Diffusion through a conduit of non-uniform cross-sectional
area

NB=0
NA(1-yA)=-CDAB. 𝒅𝒚𝑨
𝒅𝒛
NA(1-yA)= - PDAB. 𝒅𝒚𝑨
𝑹𝑻 𝒅𝒛
Using the geometry as shown, the variable radius r can be
related to position z in the path as follows:

The Equation is then substituted in the flux Equation to

eliminate r and then the Equation is integrated to obtain
On integration

Note that NA varies with z but is constant for all z

Evaporation of water from metal tube
• Suppose water in the bottom of a narrow metal tube is
held at constant temperature T.
• The total pressure of air (assumed dry) is P and the
temperature is T.
• Water evaporates and diffuses through the air. At a given
time t, the level is Z meter from the top as shown in Figure
• As diffusion proceeds, the level drops slowly. At any time
t, the steady state Equation holds, but the path length is Z.
Thus the steady state Equation becomes as follows
where NA and Z are variables:
Assuming a cross sectional area of 1 m2 (constant area), the
level drops dZ meter in dt s, and
ρA(dZ.1)/MA is the kmol of A that has been diffused. Then

Substituting the expression NA in Equation (2.26) and

integrating, one gets
The Equation represents the time tF for the level to drop from
a starting point of Zo meter at t = 0 to ZF at t = tF
 Diffusion from a sphere

There are lots of examples where diffusion can take place

through the spherical shape bodies. Some examples are:
• Evaporation of a drop of liquid
• The evaporation of a ball of naphthalene
• The diffusion of nutrients to a sphere-like microorganism in
a liquid
• Assume a constant number of moles ÑA of A diffuses from
a sphere (area = 4πr2) through stagnant B as shown in
Figure
 Assume a constant number of moles ÑA of A diffuses from a
sphere (area = 4πr2) through stagnant B as shown in Figure
From the Fick’s law of diffusion, the rate of diffusion can be
expressed as:
The differential equation

Integration with limit of PA2 at r2 and PA1 at r1

As r1<< r2 then 1/r2 = 0

The equation can be simplified if PA1 is small compared to P (A
dilute gas phase) PBM = P, 2r1 = D1; CA1 = PA1/RT
DIFFUSION COEFFICIENT: MEASUREMENT AND PREDICTION
The proportionality constant of Fick’s law is called diffusivity
or diffusion coefficient
It is defined as the ratio of the flux to its concentration
2 𝐽𝐴
gradient and its unit is m /s. DAB = 𝜕𝐶
− 𝐴
𝜕𝑥
It is a function of the temperature, pressure, nature and
concentration of other constituents.
Diffusivity decreases with increase in pressure ( DAB α 1/p)
for moderate ranges of pressures, upto 25 atm) because the
number of collisions between species is less at lower pressure.
The diffusivity is hardly dependent on pressure in case of liquid.
The diffusivity increases with increase in temperature (DAB α T 1.5)
because random thermal movement of molecules increases with
increase in temperature.
The diffusivity is generally higher for gases (in the range of 0.5×10–5
to 1.0 × 10-5 m2/s) than for liquids (in the range of 10–10 to 10-9 m2/s).
The diffusivity value reported for solids is even lower in the range of
10–13 to 10-5 m2/s. Diffusion is almost impossible in solids
because the particles are too closely packed and strongly held
together with no ‘empty space’ for particles to move through. Solids
diffuse much slower than liquids because intermolecular forces in
solid are stronger enough to hold the solid molecules together.
Measurement of gas-phase diffusion coefficient

There are several methods of experimental determination of

gas-phase diffusion coefficient
Two methods are (a) Twin-bulb method and (b) Stefan tube
method
Predictive Equations are sometimes used to determine
diffusivity. These may be empirical, theoretical or semi-
empirical
Twin-bulb method
Two large bulbs are connected by a narrow tube. The
schematic representation is shown in Figure.
In the beginning two bulbs are evacuated and all the three
valves [V1, V2 and V3] are kept closed.
Then V2 is opened and bulb 1 is filled with pure A at a
pressure P. After that V3 is opened and bulb 2 is filled with
pure B at the same pressure P. V1 is opened to diffuse A and
B at opposite direction. At steady state
where, a is cross sectional area of the connecting tube of
length l. If pA1 and pA2 are partial pressures of A in two bulbs
at any time
Analysis

Combining the above equation

𝑑(𝑝𝐴1−𝑝𝐴2 1 1
- ) = 𝑎𝑁𝐴𝑅𝑇( + )
𝑑𝑡 𝑉1 𝑉2
𝐷𝐴𝐵(𝑝𝐴1 − 𝑝𝐴2)
𝑁𝐴𝑅𝑇 =
𝑙
𝑑(𝑝𝐴1−𝑝𝐴2 𝑎𝐷𝐴𝐵(𝑝𝐴1 𝑝𝐴2 1 1
- ) = − )( + )
𝑑𝑡 𝑙 𝑉1 𝑉2
Applying the above boundary conditions, Equation is
integrated to obtain the expression of DAB as follows:
• Prob
(b) Stefan tube method
Stefan tube consists of a T tube made of glass, placed in a
constant temperature water bath.
Air pump is used to supply the air, passed through the T tube
as shown in Figure.
The volatile component is filled
in the T tube and air passed
over it by the pump and
change in the level is
observed by the sliding
microscope.
Let, at any time t, partial pressure of A at the Z distance
from the top of the vertical tube is pA1 and that at the top it
is pA2. The diffusional flux of A is given as:
Diffusion flux

The rate of evaporation is given by

Boundary conditions: t=0; Z=Z0 and t = t’; Z = Z’

On integration under the boundary conditions

The partial pressure of A at liquid surface, pA1 is equal to

vapor pressure at the same temperature.
The partial pressure of A at the top of the vertical tube, pA2 is
zero due to high flow rate of B.
The Predictive Equations:

Empirical: Fuller, Schettler and Giddings

T is temperature in K; MA, MB are molecular weights of A and

B; P is total pressure in bar
νA, νB are atomic diffusion volume in m3.
Theoretical: Chapman-Enskog Equation
A is an empirical coefficient equal to
D is the diffusion coefficient (cm2/s)
(m2/s)
D is
σAB is characteristic length parameter of binary mixture
in Å; ΩD is collision integral = f(kT/εAB); (dimensionless).
The values of r and e, such as those listed in Table, can be calculated
from other properties of gases, such as viscosity. If necessary, they ca
be estimated for each component empirically
where n is the molal volume of liquid at normal
boiling point, m3/kmol (estimate from Table 2.3),
and Tb is the normal boiling point in Kelvins. In
using Table 2.3, the contributions for the
constituent atoms are added together. Thus,
for toluene, C7H8. v = 7(0.0148) + 8(0.0037) - 0.015 = 0.1182.
Diffusion through air, when the constituents of the air remain in
fixed proportions. Is handled as if the air were a single substance.
Example: Estimate the diffusivity of ethanol vapor, C2H5OH, (A),
through air (B) at 1 std. atm pressure. 00 C.