"

Adsorption from Solution

An Experiment To Illustrate the Langmuir Adsorption Isotherm
Davld G. Duff, Sheina M. C. Ross, and D. Huw Vaughan
Paisley College of Technology, High Street. Paisley, Renfrewshire PA1 2BE. Scotland

The study of adsorption is important for an understand- Recommended Volumes of SoMlon*

ing of such processes as heterogeneous catalysis, chromato-
graphic analysis, and the dyeing of textiles. However, there Experiment No. Vol. of solution A (mL) Vol. of solution B(mL)
are few simple and easily performed experiments available -
1 25
to illustrate the quantitative aspects of adsorption.' The 2 40 -
purpose of the present paper is to describe a simple experi- 3 60 -
ment to illustrate the ahs&ption process from solution and 4 80 -
its auantitative treatment using the L a n m u i r adsorption 5 100 -
isotherm. Also, the constants of the ~ a n i m u i radsorption 6 150 -
isotherm, for example, the limiting amount adsorbed by the 7 - 25
adsorbent, may be evaluated, and this in turn allows an n - A"

approximate evaluation of its specific surface area.

Furthermore. the use of sand as an adsorbent in this ex-
periment has an important potential environmental applica-
tion. Effluent from plants in the dyeing industry contains
highly colored species as well as appreciable quantities of
materials with a biological oxygen demand (BOD) and sus-
pended solids. Water pollution regulations now require
treatment of these wastes prior to discharge. Whereas hio-
logical treatment processes are generally efficient for BOD
and suspended solids removal, they are largely ineffective
for removing color from the waste. The discharge of highly
colored waste is not only aesthetically displeasing hut also
hinders light penetration and may in consequence upset
hiological processes in a river. In addition the dyes may be
toxic to some oreanisms and hence cause the destruction of
aquatic commu~ities.The most commonly used adsorbent
for treatment of textile effluents is activated charcoal, but
this is relatively expensive. However, sand is a cheap and
commerciallv available material that mav have potential in
the treatment of effluents.
Experlrnenlal Procedure
The adsorbent used in the experiment was ordinary hrown
"Builder's sand", which was first sieved to remove particles
of diameter 2 1 mm. The sand was then washed several
times with copious amounts of water and finally dried in an
oven at 100 "C.
A rommercially available sample of the chloride salt of the
basic dye Malachite Green ICI 42000) was used to prepare
two stock
-~ dve solutions in 25% methanol-water IVA'I.
~ ~~
. . . The
first stock skution (solution A) had anabsorbance of -2.0
and the second (solution B) an absorbance of -1.0. when
measured a t the in,,
of the dye (610 nm) and in a 1.0-em cell.
The value for the molar absorptivity for the dye a t ,A, in
this solution was found to be 6.0 X 10' dm3 mol-' cm-', and
this gives a value for the concentration of solution A of 3.3 X
.. --.
-.-... .
Accurately weighed samples of -1.0 a of the sand were
placed in eight grate 250-mL conicalflasks, and the vol-
umes of the two solutions indicated in the table were added
to the respective flasks. The flasks were then stoppered with
rubber stoppers wrapped in metal foil and shaken \.igorously
ona mechanicalshaker for -2.3 h. At theend of this time the
absorbances of the solutions in the flasks were measured a t
I Dunlcz, 8. L. J. Chem. Educ. 1961,38,357-358; Dandy, A. J. J.
Chem. Educ. 1964, 41, 47; Hanson, J. C.; Stafford, F. E. J. Chem.
Educ. 1965,42,88-91; Brina, R.; De Banisti, A. J. Chem. Educ. 1987,
64,175-176.

Volume 65 Number 9 September 1988 815

Figwe 1. Adsorption isotherm fa Malachite (+em on brown sand; x = grams
of dye adswbed by 1kg of sand. C = equilibrium concernration of dye. (g L-'.
0 = recommended ~olutions,X = other solutions.
the ,A, of the dye. Some of the solutions, especially those of
smaller total volume, were slightly cloudy a t the end of the
2.5 h and were centrifuged prior to measuring their ahsor-
bance.
I t was found that this method whereby a constant weight
of sand and a variable total volume of dye solution is used
gives reproducible results. In addition the experimental con-
ditions shown in the table are found to give final absorhance
values that can he measured conveniently using a l-cm cell,
while the final equilibrium conditions cover a wide range,
thus presenting the student with a convincing set of results
with which to test the Langmuir adsorption isotherm.
Treatment of Results
Many solids are ahle to adsorb solutes from solution, and
the relationship between the amount adsorbed and the con-
centration of solute (adsorbate) in solution a t equilihrium is
often described bv the Lanemuir adsomtion isotherm.
which is derived in.most advanced phgsicaichemistry text:
books. For adsorption of solutes from solution the isotherm
may be written
where x represents the amount of solute adsorbed (in moles
or grams) per unit mass of adsorbent (usually 1 kg) and c is
the concentration of soluce in the solution that is in eouilib-
rium with the adsorhent. x, is the limiting amount of adsor-
bate that can he taken up by unit mass of adsorbent, and K is
a constant. Both K and x, are constant for the particular
system being studied and for agiven temperature. A plot of x
against c shows that initially x increases as c increases, hut
then x tends to a limit, x,, as c becomes large.
The applicability of the Langmuir adsorption isotherm to
a particular system is usually tested by rearranging eq 1in
the form:
Thus a plot of l/x aeainst l/c should he linear with a eradient
llx,K and interce;t on the l l x axis of llx,.
The initial numher of moles, or erams. of solute in solution
is determined from the volume and initial concentration of
the stock solution. Measurement of the absorhance of the
solution when equilibrium is reached yields the equilibrium
concentration c and the final numher of moles, or grams, of
solute in solution. The difference between the initial and
818 Journal of Chemical Education
Figure 2. Langmuir plot of liw data in Figure 1.
final numher of moles. or erams. of solute vields the amount
of solute adsorbed for'thz particular weiiht of adsorhent.
A plot of x aeainst c for Malachite Green adsorbed on
brown sand is s&wn in Figure 1, which includes, in addition
to the eight recommended solutions. several others of differ.
ent initial conditions to illustrate that the system appears to
conform to the Langmuir adsorption isotherm over a wide
range of concentrations. Figure 2 shows the linear plot of the
data in Figure 1; points corresponding to very low and very
high values of c are omitted from this latter plot as these are
generally inherently inaccurate.
Calculation of the Speclllc Surtace Area of the Solid
I t is a relatively simple extension of the above experiment
to determine the approximate specific area, S, of the sdsor-
bent using the value of x, obtained from the linear plot in
Figure 2. Thus:
where N is Avoeadro's numher and "a" is the area of the dve
molecule.
In this case the value of "a" for Malachite Green can be
taken as equal to 2.25 nm', which is the value calculated for
the flatwise adsor~tionof Crystal Violet (CI 42555).a closelv
related mo~ecule.~
Popie13 has pointed out that in experiments of this type
care must be taken in interpreting the results to allow for
adsorption of the solvent, aggregation of the dye, and the
porosity of the solid adsorhent. In this particular case the
experimental conditions are such that a dilute methanolic
solution of dye is used with a relatively nonporous solid so
the complications arising from these three factors can be
neglected.
We have found that this simple experiment illustrating
the Langmuir adsorption isotherm can he extended to other
solutes and adsorhents. Thus we have obtained satisfactory
results using other basic dyes such as Crystal Violet and
other adsorbents such as white "Morar" sand and sawdust
(pine wood).
Giles. C. H. In Adsorption from Solution at the SolidLiquid hter-
face; Parfiit, G. D.; Rochester, C. H., Eds.: Academic: 1983: Chapter
7; Giles. C. H.: Agnihotri, V. G.: Mclver, N. J. Colloid interface Sci.
1975, 50. 24-31; Giles. C. H.; D'Silva. A. P. Trans. Faraday Soc.
1969,65,2516-2528.
Popiel, W. J. J. Chem. Educ. 1966, 43, 415-418.