LABORATORY EXPERIMENT

pubs.acs.org/jchemeduc

A Simple Adsorption Experiment

Gonzalo Guirado and Jose A. Ayllon*
Departament de Química, Universitat Autonoma de Barcelona, Campus UAB, 08193 Bellaterra, Spain

bS Supporting Information
ABSTRACT: The study of adsorption phenomenon is one of the
most relevant and traditional physical chemistry experiments
performed by chemistry undergraduate students in laboratory
courses. In this article, we describe an easy, inexpensive, and
straightforward way to experimentally determine adsorption iso-
therms using pieces of filter paper as the adsorbent and an organic
dye the as the adsorbate.
KEYWORDS: Upper-Division Undergraduate, Laboratory
Instruction, Physical Chemistry, Hands-On Learning/Manipulatives,
Applications of Chemistry, Surface Science, Equilibrium, UV
Vis
Spectroscopy

T he phenomenon of adsorption is a key topic included in

most physical chemistry courses and textbooks.1,2 The
adsorption of a molecule into a solid surface is the basis for a broad
spectrum of chemical applications and technologies, such as the
removal of contaminants from wastewater, chromatography, and
heterogeneous catalysis.3
7 The importance of this phenomenon
and the existence of either theoretical models (such as Langmuir or
BET isotherms) or experimental models (such as Freundlich and
Temkin isotherms), which make it possible to explain the adsorption
equilibrium process,8,9 has led to the publication of a considerable
number of related experiments in this Journal8
14 and in many chem-
istry laboratory manuals.15
17
The search for simple and workable experiments to study
chemical phenomena and test theoretical models is crucial for
increasing the number of experiments that each student can do
on a laboratory course, especially when working with a relatively
large number of students. Although the theoretical background
for this laboratory experiment is relatively simple, existing experi-
ments require a considerable amount of routine work. Here we
present a simple, inexpensive, and reproducible adsorption
experiment in which small pieces of filter paper are used as adsorbent.
It is well-known that several derivatives of agricultural waste, comp-
osed mainly of cellulose fibers, have been proposed as adsorbents for
dye wastewaters.18,19
Filter paper, which is composed of cellulose fibers, is the
simplest kind of commercially available, homogeneous paper that
can be used without the need for any pretreatment (cleaning,
thermal activation). Filter paper is also more easily manipulated
than powdered adsorbents because the quantity of adsorbent is
determined by cutting different sized pieces of paper. It also has a
large specific surface area that adsorbs a relatively high amount of
adsorbate.
The use of filter paper as an adsorbent introduces some other
important advantages in comparison with the experiments
reported in the literature when adsorption processes are inves-
tigated. First, long equilibration times can be employed to allow
the system to reach the equilibrium without using magnetic
stirrers or mechanical shakers.20 The reduction in necessary
equipment is especially important when large numbers of
students are simultaneously working in the laboratory, especially
considering that the clear definition of an isotherm curve requires
the determination of a relatively large number of data points.
Second, the use of a static system solves the problems associated
with the degradation or fragmentation of the adsorbent. Third,
dyes are typically used in low concentrations and filtration can be
problematic owing to significant amounts of dye that can be
adsorbed in the filter agent. Fourth, the use of filter paper elimi-
nates the need for filtration, a time-consuming step in classical
experiments. Finally, it is worth noting that filtration and agita-
tion are two routine tasks in most experimental laboratory work,
so forgoing these tasks will not have a negative influence on the
manual skills of undergraduate students and will help to avoid
experimental errors attendant with these processes.
UV
vis spectroscopy provides a convenient and rapid meth-
od for determining the concentration of dye molecules in
solution after exposure to a solid adsorbent. The dye concentra-
tion is simply determined by removing an aliquot and measuring
its absorbance at an appropriate wavelength. The difference in
optical density between the initial and equilibrated solutions
provides a measure of the amount of dye adsorbed. The approach
to equilibrium can also be readily monitored spectrophotome-
trically. Use of filter paper as the adsorbent provides a visually
appealing way to monitor dye adsorption by simple visual
inspection of the intensity of the filter paper color (Figure 1).
One can even test the reversibility of the adsorption process by
Published: March 11, 2011

Copyright r 2011 American Chemical Society and

Division of Chemical Education, Inc. 624 dx.doi.org/10.1021/ed100324s | J. Chem. Educ. 2011, 88, 624–628
Journal of Chemical Education
Figure 1. Photograph showing representative samples and denoting the
highly visual character of the experiment (top). Detail of several pieces of
filter paper after use as adsorbent (bottom).
placing the filter paper with the adsorbed dye in contact with pure
water, whereupon the solution becomes colored and color of the
paper diminishes.
Although it is important to remind the students that adsorp-
tion equilibrium is a temperature-dependent process, good
results can generally be obtained without taking special precau-
tions if the laboratory temperature is reasonably homogeneous
and constant throughout the experiment. We have found that
satisfactory results are obtained without the need for costly
temperature-control equipment.
This laboratory experiment is designed for students who have
achieved basic competence in chemistry and physical chemistry.
The rigor and depth of the explanations should be adapted
depending on the undergraduate course. In our case, these
experiments were performed by second-semester, third-year
students obtaining a chemistry degree. The students had the
ability to gather and interpret relevant scientific data and to
make judgments that include reflection on physical chemistry
phenomena.
Finally, it is worth remarking that the equipment required to
perform the experiments is a visible spectrophotometer or
colorimeter, a relatively inexpensive and common instrument
in chemistry laboratories. We have incorporated this simplified
adsorption lab into our physical chemistry lab curriculum since
2006. We worked with student groups of more than 30; each
student had their own material and took their own measure-
ments. After four years, approximately 250
300 students have
performed the experiment.
The first step in the experiment involves the preparation of the
solution and adsorbent and takes approximately 2 h. The
equilibrium situation has usually been reached after 24 or 48 h
depending on the type of cellulose filter paper. The students can
also verify whether the adsorption processes have reached the
equilibrium after 24 or 48 h. Determination of dye concentration
using spectrophotochemical techniques and cleaning material
takes two more hours. Data treatment using the most common
isotherm models (Langmuir or Freundlich) takes from 1 to 2 h.
Answering and discussing several related questions that can be
found in the Supporting Information takes from 1 to 2 h of
autonomous or cooperative student work. Thus, the workload
for the students is from 6 to 8 h.
625
LABORATORY EXPERIMENT
Figure 2. Molecular structure of Procion Red MX-5B (C19H10Cl2N6-
Na2O7S2).
’ EXPERIMENTAL DETAILS
Procion Red MX-5B (C19H10Cl2N6Na2O7S2, 615.33 g/mol)
is purchased from Sigma-Aldrich and used as received (Figure 2).
A concentrated acid stock solution of Procion Red MX-5
(40 mg/L, analytical-grade reagent) containing 0.001 M per-
chloric acid is prepared with distilled water. The position of
the absorbance maximum (λmax) of this solution is determined to
be at 540 nm using a UV
vis spectrophotometer. A calibration
curve (absorbance versus concentration) at 540 nm wavelength
is constructed using dye concentrations ranging between
1.5  10
6 M (1 mg/L) and 6.5  10
5 M (40 mg/L) for a
standard path length of 1 cm. Over this concentration range, the
dye solutions obey the Beer
Lambert law. A perchloric acid
solution (1.0  10
3 M) was used as diluent to avoid pH
variations.
Standard laboratory filter paper is purchased from Albet (filter
paper reams, #2504252). This inexpensive filter paper is usually
used for basic filtration, for the absorption of liquids, splatters,
and as a protector of laboratory furniture, worktables, trays, and
instruments. This sort of paper is composed basically of pure
cellulose fibers. For the adsorption study, a piece of filter paper is
cut into small pieces (3  4 cm) and accurately weighed. The
adsorbent pieces are placed in 12
14 separate 100 mL stoppered
glass bottles.
Adsorption isotherms are obtained as follows: 50 mL of
Procion Red MX-5 solutions (from 3 to 40 mg/L) are prepared
by dilution of the concentrated stock solution with a previously
prepared perchloric acid solution (1.0  10
3 M). The absor-
bance of each solution is measured at 540 nm before transferring
into a 100 mL stopper glass bottle where the adsorption experi-
ments are performed. The bottles are stored in a dark place
without mechanical shaking at room temperature (25 °C) for
24
48 h (1
2 days) to reach equilibrium. Aliquots of each
solution are taken and their absorption at 540 nm is measured.
’ HAZARDS
The adsorbent used in the experiment, paper filter (cellulosic
surface), presents no hazards; however, the use of an anionic
colored dye, such as Procion Red MX-5B as an adsorbate, may be
harmful. The use of a diluted perchloric acid solution, a corrosive
acid, requires the use of gloves and safety goggles. The perchloric
diluted solution (0.10 M) should be stored separately from other
reagents in a cool, dry, well-ventilated hood.
Undergraduate teaching laboratory staff, instructors or teach-
ing assistants prepare the diluted perchloric solution (0.10 M)
from perchloric concentrated acid. Concentrated perchloric acid,
especially, should be treated with the utmost caution. Perchloric
acid is a strong acid and reacts, often violently, with bases. Used
under ideal conditions it is safe, but it should never be heated in
contact with any organic matter, including alcoholic solutions.
dx.doi.org/10.1021/ed100324s |J. Chem. Educ. 2011, 88, 624–628
Journal of Chemical Education
The addition of water to the acid can result in a violent boiling of
the mixture; instead, add the acid slowly to the water.
’ TREATMENT OF THE RESULTS
The absorbances of 12 analytical-grade Procion Red MX-5
solutions (from 3 to 40 mg/L) are measured before performing
the adsorption experiments. According to the Beer
Lambert
law, the extinction molar coefficient at 540 nm (ε540) is deter-
mined in the concentration range of 1.5  10
6 M (1 ppm) to
6.5  10
5 M (40 ppm) for a standard path length (l) of 1 cm.
A540 ¼ l 3 ε540 3 c
Adsorption isotherms are obtained as described above. The
progress of the adsorption process on the cellulosic surface can
also be qualitatively followed by naked-eye analysis of each
solution. After the equilibrium process is reached, the absorbance
of each solution at 540 nm is measured.
The amount of substrate, S, adsorbed depends on the dye
solution concentration:
S þ adsorbent / S
adsorbent
Because there are two phases (solution and solid), the final
mathematical equation, which relates the amount of adsorbate
deposited on the adsorbent surface (ns) with the concentration of
the solute in the solution (Ceq) at room temperature, is known as
the adsorption isotherm. The Langmuir isotherm equation is
ns bCeq
¼ ð1Þ
nmax 1 þ bCeq
where the nmax term corresponds to the amount of adsorbate
molecules for monolayer coverage and b is a constant. Taking
into account that the relationship between ns/nmax corresponds
to the fraction of occupied adsorption sites on the solid surface
after equilibrium is reached and that w is the mass of adsorbent;
the plot of w/ns against 1/Ceq should be a linear plot for a
gradient of adsorbate concentrations:
 
w w w 1
¼ þ ð2Þ
ns nmax nmax b Ceq
Hence, w/nmax and b, which are two constant values for a given
adsorbate and type of filter paper and temperature, are directly
obtained from the intercept and the slope, respectively.
It is known that Langmuir’s Isotherm is only valid for the
description of some adsorption process.1,2 For those cases, in
which Langmuir’s isotherm would not properly describe the
adsorption process, the Freundlich isotherm appears to be a
suitable alternative. The Freundlich isotherm may fit better to a
set of experimental data points because it considers the existence
of interactions between the adsorbed molecules in neighboring
sites:
ns
¼ kCeq a ð3Þ
w
where k and a are empirical parameters. These parameters can be
determined, similar to the previous case, for a given adsorbate
and type of filter paper. Equation 4 can be obtained by lineariza-
tion of eq 3 (taking logarithms):
 
ns
ln ¼ ln k þ a ln Ceq ð4Þ
w distinguish a linear correlation for the set of data points
626
LABORATORY EXPERIMENT
Figure 3. Adsorption of Procion Red MX-5 into cellulose filter paper
(ns/w) as a function of the concentration of Procion Red MX-5 at the
equilibrium.
Table 1. Langmuir and Freundlich Isotherm Parameters
Adsorption Correlation to
Isotherm Equation Parameter
Langmuir 0.99 b = 9.6  104 L mol1
Freundlich 0.94 k = 2.8  10
4 La mol1
a g
1; a = 0.57
It is clear from eq 4 that if the process follows a Freundlich
isotherm, the plot of ln(ns/w) versus ln Ceq should lead to a
straight line with a slope of a and an intercept of ln k.
’ RESULTS AND DISCUSSION
The difference between the initial absorbance and the absor-
bance of solutions in equilibrium with adsorbent after 1
2 days
enables calculation of the amount of dye adsorbed to filter paper.
The determination of the number of hours or days required for
the system to reach equilibrium could also be established by the
students measuring the absorbance of solutions at different times
and showing that it does not change (Figure S2 in the Supporting
Information). The relation between this amount and the equi-
librium concentration clearly gives rise to a plateau suggesting the
saturation of the available adsorbent surface. Typical isotherm
and data adjustment are shown in Figure 3. Although ideally w
should be constant, experimentally it is found that there is a little
variation in the weight of paper pieces used as the adsorbent (less
than 5%). This variation could be assumed as an experimental
error source. Hence, rigorously speaking, in our case, the plot of
ns/w versus Ceq allows one to establish only the maximum for the
ns/w ratio, which is labeled as (ns/w)max
The experimental data points were fitted according to the
eqs 2 and 4 for the Langmuir and Freundlich isotherms,
respectively. The values of the parameters obtained for Langmuir
and Freundlich isotherms are given in Table 1. The data
corresponding to the 2
3 most diluted samples are excluded
in both cases because the optical density changes are too small to
be accurately measured. In the case of Langmuir isotherm, a good
linear correlation is obtained for an experimental set of data
points (Figure 4A), although it does not correlate to the whole
set of data points collected (see Figure S2 in the Supporting
Information). In the cases where the experimental data does not
correlate linearly with the Langmuir Model, the Freundlich
model can be tested. With the Freundlich isotherm, the dotted
line graphically represented in Figure 4B makes it possible to
dx.doi.org/10.1021/ed100324s |J. Chem. Educ. 2011, 88, 624–628
Journal of Chemical Education
Figure 4. (A) Application of Langmuir isotherm (eq 2) to the experi-
mental data points determined for the adsorption of Procion Red MX-5
on a piece of cellulose filter paper at room temperature. (B) Application
of Freundlinch isotherm (eq 4) to the experimental data points
determined for the adsorption of Procion Red MX-5 on a piece of
cellulose filter paper at room temperature.
Figure 5. (A) Scanning Electron Microscope (SEM) micrographs
showing the surface morphology of the cellulose fibers from the filter
paper. (B) Chemical structure of cellulose.
corresponding to intermediate concentration (5
20 ppm). As in
the case of the Langmuir isotherm, not all the experimental value
fits with the Freundlich Model (see Figure S2 in the Supporting
Information). Hence, it is possible to conclude that both isoth-
erms can be used to explain the phenomenon of adsorption in
some concentration range.
Students can also make a rough estimation of the specific
surface area of the filter paper using the value of (ns/w)max
obtained from the Langmuir isotherm adjustment. The area
covered by each dye molecule could be conjectured by knowing
its chemical structure and a bond distance from the literature or
by using free software programs with which the students can
open or draw the adsorbate structure (Figure 2). The students
are encouraged to discuss its interaction with the cellulose paper
627
LABORATORY EXPERIMENT
(Figure 5). The purpose of this discussion is to highlight the
intermolecular forces and to relate the insights into the adsorp-
tion process with the intermolecular interaction between the
Procion Red and the cellulose. Procion Red is an anionic azo dye
that can interact with the cellulose in different ways: by electro-
static forces through the sulfonic groups, by hydrogen bonding
through the several groups present in the molecule, by van der
Waals interactions though the conjugated planar π electrons, and
even by nucleophilic substitution in the triazine ring. Under our
experimental conditions, pH = 3, the nucleophilic substitution in
the triazine ring would not happen because the cellulose is in a
protonated form. Hence, the main interactions would be either
electrostatic forces though the sulfonic groups or hydrophobic
interactions through the conjugated planar π electron. Much
work has been done to understand such processes and it is clear
that hydrogen bonding, van der Waals forces, entropy, and
molecular shape are key drivers; however, which of these factors
dominates and how they interrelate is still an open question.21
To test whether the intermolecular interactions between the
adsorbate and adsorbent change at different pH values, we perfo-
rmed adsorption experiments at pH of 3, 5, and 7. The experi-
mental results show that the adsorption of the dye decreases
when the pH increases, the optimum pH value being 3. At pH
higher than 7 or lower than 3, the experiment is not possible due
to decomposition of the dye and the cellulose through undesired
reactions, respectively.
’ CONCLUSIONS
This experiment was developed for undergraduate students to
investigate the phenomenon of adsorption. The experimental
data was collected from more than 250 students over four academic
years and demonstrates that the proposed adsorption experiment
works well for the study of isotherm phenomena and allows students
to easily recognize the theoretical concepts and models (Langmuir
and Freundlich isotherms) from the mathematical treatment of the
collected experimental data. Moreover, from a practical point of
view, the experiment has several and important advantages in
comparison with previously reported experiments. The reactants,
adsorbate, and adsorbent are inexpensive, commercially available,
do not require any pretreatment to activate the surface area, and
are easy to handle. It is important to note the absence of both filtr-
ation processes and any expensive equipment. Finally, the use of a
dye makes it possible to follow the adsorption process in real time
and quantitatively (with the use of a standard visible spectro-
photometer) as well as qualitatively (naked eyed).
’ ASSOCIATED CONTENT
bS Supporting Information
Instructions for students and notes for instructors. This
material is available via the Internet at http://pubs.acs.org.
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: joseantonio.ayllon@uab.es.
’ ACKNOWLEDGMENT
The authors are pleased to acknowledge professors Xavier
Domenech and Iluminada Gallardo of the Department of Chemistry,
Universitat Autonoma de Barcelona for their contributions in the
dx.doi.org/10.1021/ed100324s |J. Chem. Educ. 2011, 88, 624–628
Journal of Chemical Education LABORATORY EXPERIMENT

laboratory and helpful discussions and the Chemistry Department at

the University for the use of its facilities and instruments. The authors
greatly appreciate an anonymous reviewer for his valuable comments
and language corrections that improved the article very much.

’ REFERENCES
(1) Atkins, P.; de Paula, J. Physical Chemistry, 8th ed.; Oxford
University Press: Oxford, 2006.
(2) Levine, I. N. Physical Chemistry, 5th ed.; Mc Graw-Hill: Boston,
MA, 2002.
(3) Oliveira, L. C. A.; Rios, R. V. R. A.; Fabris, J. D.; Lago, R. M.;
Sapag, K. J. Chem. Educ. 2004, 81, 248–250.
(4) Thalody, B.; Warr, G. G. J. Chem. Educ. 1999, 76, 956–958.
(5) Davranche, M.; Lacour, S.; Bordas, F.; Bollinger, J.-c. J. Chem.
Educ. 2003, 80, 76–78.
(6) Lynam, M. M.; Kilduff, J. E.; Weber, W. J., Jr. J. Chem. Educ. 1995,
72, 80–84.
(7) Rybolt, T.; Burrell, D. E.; Shults, J. M.; Kelley, A. K. J. Chem. Educ.
1988, 65, 1009–1010.
(8) Geng, X.; Zebolsky, D. M. J. Chem. Educ. 2002, 79, 385.
(9) Duff, D. G.; Ross, S. M. C.; Vaughan, D. H. J. Chem. Educ. 1988,
65, 815–816.
(10) Pofgieler., J. H. J. Chem. Educ. 1991, 68, 349–350.
(11) Fernandes, D. L. A.; Xavier, A. M. R. B.; Portugal, I.; Da Silva,
F. A.; Silva, C. M. J. Chem. Educ. 2005, 82, 919–923.
(12) Poce-Fatou, J. A.; Gil, M. L. A.; Alcantara, R.; Botella, C.;
Martín, J. J. Chem. Educ. 2004, 81, 537–539.
(13) Tribe, L.; Barja, B. C. J. Chem. Educ. 2004, 81, 1624–1627.
(14) Brina, R.; De Battisti, A. J. Chem. Educ. 1988, 64, 175–176.
(15) Garland, C. W.; Nibler, J. W.; Shoemaker, D. P. Experiments in
Physical Chemistry, 8th ed.; McGraw Hill Higher Education: New York,
2008.
(16) Davison, A. W.; van Klooster, H. S.; Bauer, W. H. Laboratory
Manual of Physical Chemistry, 3rd ed.; Wiley: New York, 1941.
(17) Sime, R. J. Physical Chemistry: Methods, Techniques, and Experi-
ments (Saunders Golden Sunburst Series); Harcourt Brace College
Publishers: Philadelphia, PA, 1990.
(18) Hameed, B. H. J. Hazard. Mater. 2009, 162, 939–944.
(19) Osma, J. F.; Saravia, V.; Toca-Herrera, J. L.; Couto, S. R.
J. Hazard. Mater. 2007, 147, 900–905.
(20) Paria, S.; Manohar, C.; Khilar, K. C. Ind. Eng. Chem. Res. 2005,
44, 3091–3098.
(21) Bird, J.; Brough, N.; Dixon, S.; Batchelor, S. N. J. Phys. Chem. B
2006, 110, 19557–19561.

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