METU Chem. Eng. Dept.

Ch.E. 320 Chem. Eng. Lab I

EXPERIMENT 38
MEASUREMENT OF GASEOUS DIFFUSION COEFFICIENT


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OBJECTIVE
The purpose of this experiment is to determine the diffusion coefficient of acetone
during its evaporation from its liquid level.
PRELIMINARY WORK
Review the theoretical aspects of diffusion in gases.
Review steady-state and quasi steady-state diffusion of a gaseous species A
in a stagnant gas B.
Use of Fick's Law to evaluate mass transfer rate of a gas in the presence and
absence of convective effects
Appropriate references are cited at the end of this manual.
Experiment place: A Blok Room A-106
OUTLINE OF THE EXPERIMENTAL METHOD
When two phases of different concentrations, originally at equilibrium with their
surroundings, are contacted, a concentration gradient is created and mass
transfer starts until a new equilibrium is reached. In case of no motion or
convection, species move through the interphase by diffusion from high to low
concentration regions until new and homogeneous solutions result.

One experimental method of measuring the gaseous diffusion coefficient, D
AB
, in
binary gas systems is by diffusion of vapour A from a volatile liquid into another
gas B in an arrangement of Stefan tube, as shown in Figure 1. The experimental
method due to Winklemann has the liquid contained in a narrow diameter vertical
tube, maintained at a constant temperature, and a gas stream is passed over the
top of the tube to ensure that the partial pressure of the vapor is transferred from
the surface of the liquid to the air stream by molecular diffusion. The volatile liquid
METU Chem. Eng. Dept.
Ch.E. 320 Chem. Eng. Lab I
Experiment 38
Gaseous Diffusion Coefficient


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A is convenienly selected from among organic solvents, such as ethanol,
methanol, or acetone, or water may also be studied.

Figure 1. Evaporation of acetone inside the capillary tube with air flow

This arrangement allows the maintenance of a partial pressure difference within
the capillary tube between the evaporating liquid surface and the flowing air
stream. The partial pressure p
A2
at the top surface of capillary is kept as zero by
flowing air stream. The partial pressure p
A1
in gas-liquid interface adjacent to
liquid surface can be taken as the vapor pressure p
*
A
the species A. Diffusion of
A through B occurs in the gas-filled tube and the evaporating liquid surface level
decreases down by time.

The process is clearly an unsteady-state situation. The rate of evaporation and
hence the change in liquid level by time is so slow, however, approximation of a
quasi steady-state process brings in negligible error and steady-state mass flux
expressions can be utilized.

Steady-state diffusion of only one of the two species in binary mixtures of ideal
gases (diffusion of A through stagnant B) starts with the Ficks law
J = - D
AB
.C/x (Eqn. 1)
where,
J : Diffusion flux in x direction, kmole/m
2
.sec
C: Concentration, kmole/m
3

METU Chem. Eng. Dept.
Ch.E. 320 Chem. Eng. Lab I
Experiment 38
Gaseous Diffusion Coefficient


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X: Distance through which diffusion occurs, m
D
AB
: Diffusion coefficient (diffusivity), m
2
/s
and becomes
N
A
(1-y
A
) = - D
AB
.dC
A
/dx = - (D
AB
.P
T
/R.T). dy
A
/dx (Eqn. 2)
where,
N
A
= Molar diffusion flux, kmole/m
2
.s
y
A
= Mole fraction of species A, dimensionless
P
T
= Total pressure, Pa
R = Gas constant, m
3
.Pa/kmole.K
T = Temperaure of the environment, K
This equation can be integrated over x for the diffusion distance L, and after
changing mole fractions to partial pressures and rearranging, to give
N
A
= - (D
AB
.P
T
/R.T.L). (p
A1
-p
A2
) / p
BM
(Eqn. 3)
where
p
A1 -
p
A2
= p
A
= Partial pressure difference of A, Pa
p
BM
= Logarithmic mean of the partial pressures p
B1,
p
B2
, of B, Pa
The rate of mass transfer due to evaporation by time can be written as
N
A
= (
L
/M). dx/dt (Eqn.4)
where,

L
= Liquid density of A, kg/m
3

M = Molecular weight of A
The approximation of quasi steady-state operation allows to equate the equations
3 and 4, where for simplicity the variable distance x is changed to L
N
A
= - (D
AB
.P
T
/R.T.L). (p
A1
-p
A2
) / p
BM
= (
L
/M). dL/dt (Eqn. 5)
Integration from time t=0 to t=t for L=L
0
to L=L yields,
t = (R.T. p
BM
.
L
/ 2. D
AB
.P
T
.M.p
A
).(L
2
-L
0
2
) (Eqn. 6)
METU Chem. Eng. Dept.
Ch.E. 320 Chem. Eng. Lab I
Experiment 38
Gaseous Diffusion Coefficient


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The change in diffusion distance is very small to measure correctly unless too
long times are allowed. It is however possible to rearrange the Equation 5 into a
linear form of the type
Y = AX+B (Eqn. 7)
where,
Y = t / L-L
0
A = R.T. p
BM
.
L
/ 2. D
AB
.P
T
.M.p
A

X = L-L
0

B = (R.T. p
BM
.
L
/ D
AB
.P
T
.M.p
A
.)L
0

QUESTIONS FOR PREPARATION
Answer the following questions to your lab notebook.
1. Define the Ficks first law of diffusion and write for the case of binary diffusion.
2. Why is there a negative sign in Ficks law?
3. What is the physical significance of diffusivity? How does it change according
to the state of matter? How does diffusivity depend on temperature?
4. For which conditions do we neglect or consider convective molar flux?
5. Derive the equation 2 for the species A diffusing through stagnant B and then
integrate it to obtain the Equation 3.
6. Derive the Equation 4 and use to obtain the Equation 6.
7. Rearrange the Equation 6 to obtain the Equation 7.

EXPERIMENTAL PROCEDURE
The apparatus consists essentially of a glass capillary tube placed in a
transparent-sided temperature controlled water bath. A horizontal glass tube is
fixed to the upper end of the capillary tube and air is blown through this by a
small air pump included within the unit. A microscope, with sliding vernier scale,
is mounted on a rigid stand alongside the thermostatic bath and is used to
measure the rate of fall of the solvent/air meniscus within the capillary (Figure 2).
METU Chem. Eng. Dept.
Ch.E. 320 Chem. Eng. Lab I
Experiment 38
Gaseous Diffusion Coefficient


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Fill the water bath with distilled water to approximately 25 mm from the top of the
bath. Partially fill the capillary tube with acetone to a depth of about 25 mm.
Remove the nut from the metal fitting. Carefully insert capillary tube through the
rubber ring, inside the metal nut until the top of the tube rests on the top of the
nut. Gently screw this assembly onto the top plate, with the T piece normal to
the microscope. Connect flexible air tube to one end of the T piece. With the
microscope set-up as shown, adjust the object lens to within 20-30 mm from the
tank.

Connect the mains cable to the electrical supply ensuring that the voltage of the
supply is correct to suit the equipment. Switch on the Residual Current Device
(RCD) at the right end of the equipment by raising the lever. Switch on the circuit
beaker at the right-hand end of the equipment by raising the lever.

Operate the heater switch and set the temperature controller to 40C. To display
the current setpoint of the controller press the SET key. To change the set point
press the increase or decrease key, as required, while pressing the SET
key.

To avoid the damage to the equipment do not set the temperature controller
above 60C. Check that the water heats to 40C and remains at constant
temperature (1C when settled).

Adjust the vertical height of the microscope until the capillary tube is visible; if the
capillary tube is not visible adjust the distance from the object lens to the tank
until it is. For a clearer and well defined view of the meniscus inside the capillary
tube, adjust the position of the viewing lens in or out of the microscope body as
necessary. Note that when viewing the capillary tube image will be upside down,
so that the bottom of the tube is at the top of the image. When the meniscus has
been determined, the sliding vernier should be aligned with a suitable graduation
on the fixed scale (Figure 2).
METU Chem. Eng. Dept.
Ch.E. 320 Chem. Eng. Lab I
Experiment 38
Gaseous Diffusion Coefficient


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Switch on the air pump. Check that a stream of air is delivered at the end of the
flexible tubing. The stream of air is only low velocity and may be detected by
placing the end of the flexible tube against the cheek. The flow can be varied if
necessary by adjusting the Hoffman clip on the flexible tube from the air pump.

Record readings of level change at every 10 minutes for at approximately 2
hours.



Figure 2. Experimental set-up for the gaseous diffusion apparatus
DATA TO BE RECORDED AND CALCULATIONS
1. Prepare a data sheet to record change in distance (L-L
o
) in millimeter as a
function of time (t) in minutes.
2. Record the ambient temparature and pressure.
METU Chem. Eng. Dept.
Ch.E. 320 Chem. Eng. Lab I
Experiment 38
Gaseous Diffusion Coefficient


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3. Obtain values of liquid density, molecular weight, and vapor pressure at the
evaporation temperature of the species that is to diffuse into air.
4. You should have graph paper and ruler when coming to the experiment.
Now during the experiment, plot a graph of t/(L-Lo) vs (L-Lo) and determine
the slope of the best-fit straight line from the graph.
5. Determine the diffusion coefficient using the equation 1.
6. Compare the experimental result with literature values.

SUGGESTED REFERENCES
1. Bird, R.B., Stewart, W.E., Lightfoot, E.N., Transport Phenomena, Wiley, 2
nd

Edition, 2007,
2. McCabe, W. L., Smith J. C., and Harriott, P., Unit Operations of Chemical
Engineering, 6
th
ed., McGraw Hill Company, New York, 2001
3. Sherwood, T.K., Pigford, R.L., Wilke, C.R, Mass Transfer, McGraw Hill
Kogakusha, 1975
4. Bennett, C.O., Myers, J.E., Momentum, Heat, and Mass Transfer, McGraw
Hill, 1962