Diffusivity of Volatile

Expt. No. 2
Liquids

OBJECTIVE: 1. Understand Ficks law as it relates to the unimolecular diffusion of

a volatile organic compound in a stagnant column of air.
2. Measure and compare the evaporation rates for different volatile
organic compounds in a stagnant column of air.
3. Determine the experimental diffusivity values from the
evaporation data.
4. Compare the experimental diffusivity value with values reported
in the literature or value predicted by an empirical equation.

APPARATUS: a) Volatile liquids (ammonia solution, HCl, methanol)

b) Analytical balance
c) Ruler
d) Cotton/ Stopper
e) Test tubes
f) Erlenmeyer flask
g) Stopwatch/ Any time-measuring device

THEORY:

Molecular diffusion is the transfer or movement of individual molecules

through a fluid by random molecular movements (Geankoplis, 1993). In the
diffusion process, the molecules of interest flow from regions of high
concentration to low concentration. Molecular diffusion can occur in both
directions with the system. In the case of the diffusion tube experiment,
however, acetone diffuses through non-diffusing air, which is passed over the
top of the test tube containing the acetone. The air is allowed into the test
tube, but does not diffuse into the acetone.

Diffusion is the mass transfer of an individual component through a

stagnant mixture due to a concentration gradient.

The rate of diffusion is described by Ficks law:

 dc A
J A DAB
dz

where JA = molar flux of A in the z direction, relative to the total

flow [mol/cm2s]
DAB = diffusivity, [cm2/sec]
cA = molar concentration of A [mol/cm3]
z = direction of concentration gradient [cm]

In diffusion, mass transfer occurs via random movements at the

molecular level. Note that the system must be stagnant for Ficks law to apply; if
bulk mixing or turbulence is present, the overall rate of mass transfer will be
much greater than predicted due to convective transport.

Diffusivities in gases can be predicted with considerable accuracy

from kinetic theory. The theoretical correlations have been modified in the light
of experimental data to give the Chen and Othmer semi-empirical equation:

0.01498T1.81 (1MA + 1/MB )0.5

DAB = 2
p(TcA TcB )0.1405 (V0.4 0.4
cA + VcB )

where:
MA, MB = molecular weights of components A & B respectively, g/mol
p = Pressure, atm
T = Temperature, K
TcA, TcB = critical temperatures of A & B respectively, K
VcA, VcB = critical molar volumes of A & B respectively, cm 3/mol

Gas diffusion occurred when diffusion of vapor takes place from volatile
liquid into another gas (air). This process used same concept as mass transfer
where one constituent is transported from region of higher concentration to that
of a lower concentration.

PROCEDURE:
 First, we gathered and cleaned all the materials and apparatus needed
for the experiment. Next, we prepared three different volatile compounds
(hydrochloric acid, methanol and ammonia solution) available in the
laboratory. To prevent convection in the cylinder, we selected these
compounds since hydrochloric acid, methanol and ammonia solution are
heavier than air in terms of molecular weight.

Then, we used a ruler to measure the test tubes to make sure that the test
tubes have a length to diameter ratio of at least 4.0 since the diffusion path must
be at least 4 times the diameter of the tubes. In this experiment, we used test
tubes with 1 cm diameter and 12 cm of tube length.

We measured 10 ml of each compound in the fume hood to prevent

inhalation of these chemicals and we placed the samples in beakers with
appropriate labels to avoid any confusion. We covered the beakers to prevent
these compounds from evaporating before the experiment proper.

Next, we transferred the samples in the test tubes that were prepared
beforehand. We measured the initial weight of each samples using the
analytical balance, and the initial height of the samples in the test tubes using a
ruler. After determining the initial weights and heights of the compounds, we
placed the samples in the fume hood and we ensured that the test tubes were
vertically upright by placing it in a test tube rack.

We then removed the cover from each test tube to start the experiment.
We let the samples stand by and evaporate for thirty minutes. We monitored the
temperature using a thermometer. After thirty minutes, we covered the test
tubes and measured the weight and height remained in the test tubes. We
repeated these procedures for three trials, thirty minutes of evaporation for each
trial.

After we have obtained all the necessary data, we cleaned up and

returned all the borrowed materials and apparatus in the laboratory.

DIAGRAM:
See next page.

DATA AND RESULTS:

 Time (min) 0 30 60 90 120
Ammonia
122.7287 122.6564 122.2364 121.9523 121.8602
Weight of Solution
Substance
HCl 128.6489 128.5703 128.4196 128.2298 127.9653
+
Container
Methanol 126.9545 126.8803 126.7177 126.7007 126.4067

COMPUTATIONS:

Using the Chen and Othmer semi-empirical equation:

0.01498T1.81 (1MA + 1/MB )0.5

DAB = 2
p(TcA TcB )0.1405 (V0.4 0.4
cA + VcB )

where:
MA, MB = molecular weights of components A & B respectively, g/mol
p = Pressure, atm
T = Temperature, K
TcA, TcB = critical temperatures of A & B respectively, K
VcA, VcB = critical molar volumes of A & B respectively, cm 3/mol

Given that:
T = 29oC (302.15K)
P = 1 atm
Component A = sample substance
Component B = air

For Methanol,

1.81
0.01498(302.15 )((132.04)+ (1/29))0.5
DAB = 2
0.4 0.4
1(512.5 x 132.45)0.1405 ((117) + (91.47) )
117.757
DAB = =0.1504
782.994

For HCl,

1.81
0.01498(302.15 )((136.461)+ (1/29))0.5
DAB = 2
0.4 0.4
1(324.65x 132.45)0.1405 ((81) + (91.47) )
 114.972
DAB = =0.1817
632.739

For NH4OH,

1.81
0.01498(302.15 )((135.05)+ (1/29))0.5
DAB = 2
0.4 0.4
1(405.65x 132.45)0.1405 ((72.47) + (91.47) )
115.993
DAB = =0.1855
625.417

REFERENCES:

Warren L. McCabe, Julian C. Smith and Peter Harriott, Unit Operations of

Chemical Engineering, Sixth Edition, McGraw-Hill Book Co. (2001).
Robert H. Perry and Don W. Green, Chemical Engineers Handbook, Eighth
Edition, McGraw-Hill Book Co., (2008).
C.J. Geankoplis, Transport Processes and Unit Operations, Third Edition,
Prentice Hall PTR (1993).

PICTURES: