Académique Documents
Professionnel Documents
Culture Documents
John E. Crooks
Pharmacy Department, King's College, London, SW3 6LX, U.K
Diffusion is a well-known physico-chemical phenomenon
of great theoretical and practical importance, hut it is difficult to find a suitable teaching lahoratory experiment for the
measurement of diffusion constants. Diffusion is a slow process, and typical diffusion experiments require many hours.
Irinal r e ~ o r t e da s i m ~ l eex~erimentin which diffusion UD
from t h e bottom of speckophotometer cuvette was observed for as lone as 40 hours. Clifford and Orchia12 have
desrribed a diffus/on cell construrted from a Y-shaped stopcock harrel. A sidearm containing less than I mL of solvent is
connected to concentrated soluiion in the bore of the tap
barrel. At the end of a time period of 5 to45 minutes, the tap
is turned to isolate the sidearm. and the contents are removed for analysis. The concentration of the sample solution rises to onlv a few Der cent of that of the source solution
during the diffision time. This method is capable of considerable precision, hut requires some manual dexterity. Several hours are needed to show the progress of diffusion with
time, as each run only gives one point on the graph. Moskovits and Derewlany3 have reported an experiment in which a
concentrated solution is contained inside a dialvsis hap. The
bag is suspended in a large volume of stirred soivent and the
increase in solute concentration in that solvent is measured
a t a series of times. A whole run takes less than an hour, since
only a small fraction of the solute diffusing out is monitored,
and the time course of diffusion can he readilv seen. The
disadvantage of this experiment is that the measured quantity is not a simple diffusion coefficient, hut rather the permeability coefficient of the dialysis membrane. I t is therefore not possible to compare the results with published data.
A major problem in diffusion coefficient measurement is
to make sure that solute movement is solelv hv diffusion, i.e..
random molecular motion, and not by bulk liquid move:
ment, e.g., by convection. Bulk movement is prevented if the
liquid is held in a gel. Agel is a comparatively rigid structure
composed of a three-dimensional open network of polymer
chains, the voids filled with liquid. Small molecules, of solvent or solute, can move about in a gel as freely as in an
ordinarv
.liouid.
. This can easilv he shown hv measurine the
conductivity of an ionir solute in a cooling solutionof agar in
wawr. The conductivity falls as the temperature fall% hut
614
M&
=~
( D ~ I ~ L ~ ) ~ ~11)~
The details of the experimental procedure depend on the monitoring technique. The diffusion of a highly colored substance, such
as hromoohenol hlue. which can he monitored soeetroohotometrically, g w i a a n rffecti$;evisual display, whereas thb drffuwm of KCI.
mmiumd rondurrirnrrrically. giver a value readily compnrnbie
with puhliahed dntn. 'The procedure for bromuphenol hlue is described first.
The jelly mold is a length of thick-walled glass tubing, about 10
cm by 2 cm diameter, with one end ground flat. The tube has three
indentations toward the top to prevent the jelly cylinder from sliding down. The ground end is greased and pressed on to a glass tile to
hromomake a seal. A 5-mL samole of a solution of 35 me.. faoorox.)
. ..
phenol blue and 0.5g wdiurn acetatein 50 mL wnter isdilurrd to250
ml., nnd its abqorbanrr at 5NI n m (A,, is measured. The remaining
~~
When the jelly has reached room temperature, which takes about
314 hour, the glass tile is slid away to reveal a plane jelly surface. The
tube is clamped vertically, at such a height that the lower end will be
approximately 2 cm above the bottom of a 250-mL beaker containing 150 mL of water. The water is vigorously stirred hy a magnetic
stirrer. The clampstand is lifted up and set down so that the tube is
in the center of the beaker, and a stopwatch is started. Samples are
removed so that their ahsarhance, At, at 590 nm can he measured,
and then returned tothe beaker. Suitable times are 1,2,5,10,20,30,
40,55,70, and 90 min from the start. Then
MtlMo= (At/A,)(150l45)(5/250)
(2)
tee
Volume 66
Number 7
July 1989
615