An Experiment Illustrating Both the Langmuir and Freundlich Isotherms
J. H. Pofgieler Division of Physical Metallurgy, Council for Mineral Technology, Private Bag X3015. Randburg. Republic of South Africa
Adsorption and adsorption processes are important fields of study in physical chemistry. They form the basis for under standing phenomena such as heterogeneous catalysis, chro matomanhic analvsis. dveine of textiles. and clarification of various effluents.'~cti\.atedcarbon finds particular applica tion in the rlarificntion of effluents, includine the removal of coloring matter from various types of solution and the elimi nation of organic suhstances from treated Dotable water (especially Gihalomethanes) and waste water. However, findine simple and easilv ~erformahleex~eriments to illus trate the quantitative as&& of adsorption can be very difficult. A number of such experiments were described in some previous issues of _{t}_{h}_{i}_{s} Journal (15). The present investigation describes the adsorption of methylene blue, a rationic organic dyestuff commonly used for trarer studies in water rrsearch, on activated rarbon. Althoueh it has been claimed (2) in a orevious investienti(m using Gfferent adsorhents, that meth;lene blue adsiption ohevs the Frumkin tvDe of adsor~tionisotherm. it was found in the present case tiobey hoth'the ~an~muir'and Freund lich isotherms better for the specific type of adsorhent used.
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..
Experlmental Procedure
The adsorbent used in the experiment was a commercial activated carbon, the physical characteristics of which are given in Table 1. A methylene blue solution with a concentration of 25 mgL was pre pared from analyticalgrade reagent and distilled water. The posi tion of maximum absorbance (A,,,) of this solution was determined
to be
at 630 nm on a Speetronic 20 spectrophotometer. Coneentra
tions of 525 mgL of this methylene blue solution were found to obey the BeerLambert law. Adsorption isotherms were obtained as follows: Accurately weighed samples of between 0.001 g and 0.100 g of adsorbent were olaced in seven seoarate 250mL conical flasks. each containine 100
ical shaker for 72
h to reach equilibrium. At the end of this time
analysis of the supernatant solution in each flask was carried out by
spectrophotometry at 630 nm. All the ducted at 25 "C.
experimental runs were con
Treatment of Results
The derivation of the Langmuir, Freudlich, and Frumkin adsorption isotherms is dealt with in most physical chemis try textbooks. It will therefore suffice to state only the final form of each equation in this discussion. The Langmuir adsorption isotherm may he written as
where x = amount of solute (MB) adsorbed per mass of adsorbent (act.C), x, = limiting amount of adsorbate that can be taken up per mass of adsorbent,K = a constant, and c = concentration of the solute in the solution that is in equi librium with the adsorbent. Thus the plot of 1/x against llc should be linear with agradient of l/x,Xand intercept of I/ x, on the 1/x asis. The equation describing the Freundlich isotherm can he defined as
logr =logK+%,logc
_{(}_{2}_{)}
where K, n = constants and x, c have the same meaning as in theLangmuir isotherm. It is clear from eq 2 that aplot of log
x against log c should yield a straight line with a slope of and an intercept of log K.
'I,
The equation describing the Frumkin isotherm can be written as
u = log (0155.55) + 2aOl2.303
_{(}_{3}_{)}
where" = log (8(1 8).c), 0 = M/M,d,, M = the amount of dye adsorbed at equilibrium, Mads= the maximum amount of dve adsorbed at equilibrium (2.48 mg in this experiment), and c~,d= constant;, whilec has rhesame meaning as before. Plotting the first member against 0 should yield a straight
line
~.
if the Frumkin isotherm is oheved. From the interce~t
~
~
with the ordinate 0 is obtained wgile a can be calculated
from the slooe. The experimental data points ~ummarizedin'l'ahle 2 were fitted toall three isotherms, which arerra~hirall~ represenr ed in Figures 13. The dotted line in e&hfigure iepresents a linear reeression fit to the results. However, since adsorption data are of a nonlinear nature, nonlinear regression was also performed on each set of data points. These nonlinear re gression fits are represented as solid lines in Figures 13. The correlation coefficients obtained with both kinds of regres sion for all three adsorption isotherms are summarized in Table 3. Except in the case of the Langmuir isotherm, non linear regression fits produced better correlation coefficients and thus more accurate constants than are obtained with the
~~
~

Table 1.
Physical Properlles of the Adsorbent
BET surface area, m2/g 
9501050 
Pore vol~me.em3 
0.80.9 
lodlne number (mglg) 
9001000 
Apparent denshy, g/cm3 
0.460 
Effective partide size, mrn 
0.81.1 
Abrasion number 
7580 
Table 2. Experlrnental Adsorptlon Data 
[wafter 

Activated 
lniiiai h4E 
Final blB 

carbon 
mass before 
mass after 
Mass of 

mass 
adsorption 
adsorption 
MB adsorbed 
adsorption 
(mg) 
(me) 
(mg) 
(mg) 
(mg/dm3) 
Volume 68 
Number 4 
April 1991 
349 
FW~1. Application of me F~mkinequ~~o~
to me experlmentai datawinls
determined lor lha adsorption 01 melhylene blue on an activated carbon at 25
OC.
Figure 3. Application 01 lha Freundlich equation to the experimental data
points determined iwme adsorption of rnethylene blue on an activated cmon
_{a}_{t} _{2}_{5} _{O}_{C}_{,}
40.0
Table 3.
Correlallon Coelflclents for Llnear and Nonlinear
Regresalon Fllr ol Dlflerent Adsorption Isolhermr
35.0

30.0

25.0

20.0

15.0

Carelation 
Coefficient 

Type of 
Linear 
Nonlinear 
aasorptlon isolherm 
regression 
regression 
Frumkin 
0.940 
0.984 
Langmuir 
0.998 
0.998 
Freundlich 
0.987 
0.992 
Table 4.
Langmulr and Freundllch Isotherm Constants
0.0 
1.0 
2.0,3.0 
4.0 
5.0 
6.0 
Typed regression 
Figure 2. Application of the Langmuir equation to Ite experimental data poinls 
Linear 

determined lor the 
adswptlon of methylene blue 
on an activatsd carbon at 25 
Nonlinear 

'C. 
ordinary linear regression. From these values it is clear that although the adsorption of methylene blue on Pyrex beads and Taz06 can be described by the Fmmkin isotherm (2), this is not the case for activated carbon. The correlation coefficient values in Table 3 also indicate that the data fit the Langmuir isotherm better than the Freundlich isotherm, both in the case of linear and nonlinear regression. It is furthermore evident that both the Langmuir and Freundlich isotherms describe the adsorption process very well and are better adhered to than the Frumkin isotherm. The values of the constants obtained for the Langmuir and Freundlich isotherms from both types of regression are given in Table 4.
k Langmuir 
K 
Fremdllch K 
n 

0.378 
0.358 0.0834 
1.66 

0.355 
0.401 0.0897 
1.50 

S = x,.N.a 
(4) 
where N = Avogadro's number and a = the area of the dye molecule. In this case the value of "a" for methylene blue can be taken as 120 AZ (6). This simple experiment brings to the student's attention the basic principles of adsorption as well as the application of more than one isotherm to describe the whole process. It also enables the student to judge the suitability of different types of regression fits to experimental data, to become acquainted with the measurement of specific surface area of the adsorbent, and to estimate an approximate value for it.
Calculation ol the Specllk Surlace Area of the Activated
_{C}_{a}_{r}_{b}_{o}_{n}
Uterature Cited
I. ~~ff,
D G.:R~~~,S.M.C.;V~U~~~~,D.H.
J. chern.~duc.
1%8,65,815816.
350 Journal of Chemical Education