Adsorption from Solution

Shoji-an Daradal
BS Chemical Engineering-3
Xavier University-Ateneo de Cagayan
Corrales Avenue, Cagayan de Oro,
Philippines

Jean Stefani Obsiana

BS Chemical Engineering-3
Xavier University-Ateneo de Cagayan
Corrales Avenue, Cagayan de Oro,
Philippines

Abstract The experiment deals with the adsorption of

acetic in charcoal using Freundlich and Langmuir
Isotherms. It is an example of a Physical absorption
wherein, van der Waals and dipole forces are the main
sources of attraction. Heat of adsorption was also
determined on this experiment and the type of reaction
which occurs based on the latter. The adsorption process
starts with the adding of approximately 1 gram of
charcoal into a flask with 100 mL acetic acid solution.
The amount of acid adsorb was then calculated and so is
the final concentration of the acid used. From that
results, the two isotherms will be made, which represents
a plot of the logarithm of the moles adsorbed versus the
logarithm of the solution concentration (Freundlich) and
a plot of the ratio of the concentration over the moles
adsorbed versus the concentration (Langmuir). As shown
in the graph, it was found out that Freundlich provides a
better fit to the data with an R-squared value of 0.9784.
The heat of absorption was also calculated to have an
amount of ??? which means that the reaction is ??? in
nature.

John Keno Ong

BS Chemical Engineering-3
Xavier University-Ateneo de Cagayan
Corrales Avenue, Cagayan de Oro,
Philippines

adsorbent, in this case active carbon (macro-pore

>50nm).
Micro transport: The movement of organic
material through the meso-pore and micro-pore

system of the adsorbent. (For active carbon, micropore <2nm; meso-pore 2-50nm)
Sorption: The physical attachment of organic
material on the surface of adsorbent (active
carbon) in the meso-pores and micro-pores of the
adsorbent (active carbon)

The activity level of adsorption is based on the

concentration of substance in the water, the temperature and
the polarity of the substance. A polar substance (a substance
which is good soluble in water) cannot or is badly removed
by active carbon, a non-polar substance can be removed
totally by active carbon. Every kind of carbon has its own
adsorption isotherm (as shown in Fig 1) and in the water
treatment business this isotherm is definite by the function
of Freundlich.[4]

Keywords- adsorption, Langmuir, Freundlich, van der

Waals, Dipole, isotherms, Heat of adsorption.

I. INTRODUCTION
Adsorption is the adhesion of atoms, ions, or
molecules from a gas, liquid, or dissolved solid to a surface.
This process creates a film of the adsorbate, the substance
being adsorbed, on the surface of the adsorbent, the
substance adsorbing.[1] It is operative in most natural
physical, biological, and chemical systems, and is widely
used in industrial applications such as activated charcoal,
synthetic resins and water purification.[2]
The adsorption process takes place in three steps:[3]

Macro transport: The movement of organic

material through the macro-pore system of the

Freundlich
function:

x
=K f C1e /n
m

Where
the
ratio x/m
is
Figure
1: Active
Carbon Adsorption Freundlich Isotherm
the adsorbed
substance per gram of active carbon, C e is the concentration
difference, and the Kf and n are specific constants.
Factors that influence the performan of active carbon in
water is are the:

The type of compound to be removed

Concentration of the compound to be removed
Presence of organic compounds

Another isotherm that can model the adsorptivity

of active carbon is the Langmuir isotherm. The Langmuir
adsorption model explains adsorption by assuming an
adsorbate behaves as an ideal gas at isothermal conditions.
At these conditions the adsorbate's partial pressure, p A, is
related to the volume of it, V, adsorbed onto a solid
adsorbent.[5]

At the start of the experiment, seven labelled flask

were added with approximately 1g of charcoal and with 100
ml different solutions of acetic acid, except for the seventh
flask, which was added with 100ml distilled water. An eight
flask was also added with 0.3M of acetic acid without any
charcoal. The flasks (8) were left to equilibrate for about a
week and were then filtered to separate the charcoal from
the liquid solution (discarding the first 10 mL filtrate). Two
25-ml aliquot of the filtrate was titrated with 0.1N
standardized NaOH solution using phenolphthalein as
indicator.

The Langmuir isotherm is described by the equation:

c
c
1
=
+
N Nm k N m
Where Nm is the number of moles required to
cover one gram of charcoal with a monolayer of adsorbate,
and k is a function of temperature. The heat of adsorption
may be determined by measuring the concentration
necessary to achieve one-half of a monolayer of coverage as
a function of temperature by this equation: [6]

d ln c

dT

1
d ln (
)
kNm
=
dT

III. RESULTS AND DISCUSSION

Table 8.1
Flask #
1
2
3
4
5
6
7
8

Figure 2: Example of a Langmuir Isotherm on a Gas-Solid

Equilibria

II. EXPERIMENTAL SECTION

N
0.01104820
3
0.00938010
7
0.00543566
2
0.00472006
0.00222495
4
4.41767E06
0.00086117
2
0

c
0.0383680
92
0.0261538
71
0.0355983
24
0.0122823
3
0.0077054
03
4.50603E05
0.0063432
22
0.0057892
68

c/N
3.4727903
03
2.7882273
56
6.5490324
37
2.6021552
47
3.4631742
89
10.2
7.3658029
34
-------

This table represents the final concentration [c] of

acetic acid in every flask, the number of moles adsorbed
[N] and the ratio of the concentration to the number of
moles adsorbed [c/N]. The N and c values represented by
the 6th flask is the residual acidity that the solution got from
the activated carbon that was used as an adsorbent. All the
values were adjusted by subtracting the residual acidity to
the calculated experimental amount. If N will be plotted
against c c/N against c, the graphs below will be created:
Table 8.1

Langmuir isotherm originally is based on three

assumptions and the third assumption says that the ability of
a molecule to adsorb at a given site is independent of the
occupation of neighbouring sites. This means that there are
no interactions between molecules that are adsorbed.

N vs. c
0.05
0.04
f(x) = 2.97x + 0
R = 0.69

0.03
0.02

Linear ()

0.01
0
0

0.01

0.01

0.02

The above chart represents the linear relationship

of N with respect to c. As seen on that graph, the
relationship is not quite linear. The possible reason for this
could be due to experimental errors that took place in the
execution of the procedures for this experiment. The Rsquared value could attest the not-so-perfect linear
relationship of the data gathered.
Table 8.2

Table 8.3

0.05
c
c

f(x) = - 0x + 0.03
R = 0.19
0
2 4 6 8 10 12

Linear (c)

And by plotting the log of N with respect to the log of c the

graph would look like:
f(x) = NaN ln(x)
R = NaN

Freundlich Isotherm
-6

c/N
Log c
The graph doesnt fit the data that was plugged-in
and the R-squared value could attest that. The slopes value
is negative and the y-intercept is positive.

log c
-1.416029803
-1.582464028
-1.448570449
-1.910719242
-2.113204669
-4.346206356
-2.197690105
-2.237376327

The values represented on table 8.3 shows a direct

proportion of the logarithm of N and c, from flask 1 to 6.
The equation that was used for the plotting of these data is:

N=K c

Langmuir Isotherm

log N
-1.956708363
-2.027792212
-2.26474759
-2.326052446
-2.652679018
-5.354806528
-3.064910201
------

Flask #
1
2
3
4
5
6
7
8

0
-4
-2
0
-2+ 0.24
f(x) = 0.85x
R = 0.98 -4

Logarithmic ()
Linear ()

-6
Log N

The equation behind this Langmuir Isotherm is:

c
c
1
=
+
N Nm k N m
and based on the results represented by the equation on the
graph, the slope which represents 1/Nm has a value of
-0.0023. Nm is the number of moles required to cover one
gram of charcoal with a monolayer of adsorbate. The k on
that equation is a function of temperature.

As seen on this graph, there is a straight line

relationship between the log of N and of c. The 0.9784 Rsquared value could attest that Freundlich isotherm provides
a better fit to the data of this experiment.
Based on the equation of the line, the value of the
empirical constants k and a are found out to be 0.242 and
0.8504 respectively. The value for the k is equal to the yintercept and a is equal to the slope. The equation below
could provide a clearer view on why the latter two values
were obtained in such way:

d ln[ c]
H
=
2
dT
RT

log 10 ( N )=log 10 ( k ) +a log10 ( c )

Comparing the results of the two isotherms,
Freundlich obviously provided a better fit on the data
calculated and obtained in this experiment. The main reason
for this, is that Freundlich Isotherm corresponds to a
logarithmic change and it considers the role of substratesubstrate interactions on the surface. This means that there
is indeed an interaction that happens on the adsorption
surface and that the final concentration of the solution is
dependent of the number of moles ad sorbed per gram of
adsorbent.
Table 8.4
Flask #

ln [c]0.5

1
2
3
4
5
6
7
8

-3.260529115
-3.643758081
-3.335456721
-4.399593644
-4.86583357
-10.00750997
-5.060368476
-5.151749377

Temperature
(K)
301.15
301.15
301.15
301.15
301.15
301.15
301.15
301.15

Table 8.4 is a representation of the concentration

necessary to achieve one-half of monolayer coverage as a
function of temperature. These values will help in
determining the amount of the heat of adsorption. The graph
below was created based on the data which the table shows:

Heat of Adsorption
400
Temperature (K)

f(x) = + 301.15
200
Linear ()
R = 0
0
-20 -10 0
ln (c)

The calculation of the heat of adsorption follows

the equation:

That means that the slope value multiplied by the

gas constant and the temperature in kelvin is equal to the
heat of absorption. For this experiment, the calculated
amount was 3.779 x10-8 J. The positive sign implies that the
reaction is endothermic.

IV. ERROR ANALYSIS

Most errors encountered on this experiment were
caused by personal errors especially in handling with the
materials used. Parallax error could also be one of the
factors which affected the results of this experiment, it is
really very important during titration that an accurate
amount should be noted. Another factor is the instrumental
errors caused by some dysfunction of the instruments used,
like the analytical balance which was used in weighing the
adsorbent (charcoal).

V. CONCLUSION
From the results obtained in performing this
experiment, the Freundlich isotherm was found out to have
a better fit to the data since its R-squared value is 0.9784,
which is very close to 1 compared to the Langmuir
Isotherm. It was also evident that adsorption and
concentration indeed has a direct relationship, this means
that as the adsorption increases, the concentration adsorbed
also increases. The heat of adsorption has a value of 3.779
x10-8 J. The positive sign implies that the reaction is
endothermic.

VI. REFERENCES
[1] Adsorption. (n.d.). Retrieved 19 February, 2016, from

https://en.wikipedia.org/wiki/Adsorption.
[2] Adsorption. (n.d.). Retrieved 19 February 2016, from
http://www.fpharm.uniba.sk/fileadmin/user_upload/english/
Physical_Chemistry/5-Adsorption.pdf.
[3] Burton, F. & Tchobanoglous, G. (1991). Adsorption. In
Wastewater Engineering: Treatment Disposal Reuse (3rd
ed, p. 317). New York: McGraw-Hill.
[4] Active Carbon Adsorption. (n.d.). Retrieved 19
February, 2016, from
http://www.lenntech.com/library/adsorption/adsorption.htm

[5] Langmuir Adsorption Model. (n.d.). Retrieved 19

February, 2016, from
https://en.wikipedia.org/wiki/Langmuir_adsorption_model

1.
c=

VII. APPENDICES
Microsoft excel was used on this experiment to
employ an easy calculation of the data presented above. The
formulas used by obtaining such were the following (below
the photo):

Ave . conc . of NaOH x Vol. NaOH disp.

Volume of Solution
moles of acid adsorbed
gram of charcoal

2.

N=

3.

H=slope x R T 2

Flask #
1
2
3
4
5
6
7
8

Initial Moles
0.015
0.012
0.009
0.006
0.003
0
0.0015
0.003

Standardization of NaOH:

Continuation of the table:

1.
1
204.22
Conc . of NaOH =
Voluume dispensed (L)
wt . KHP x

Run

Final Moles
0.003836809
0.002615387
0.003559832
0.001228233
0.00077054
4.50603E-06
0.000634322
0.000578927

Volume
Dispensed
(mL)

27.60

26.35

Average

26.975

Conc. Of
NaOH
0.088707971
94
0.092916130
00
0.090812050
97

Calculation of N and c and H:

Moles
adsorbed
0.011163191
0.009384613
0.005440168
0.004771767
0.00222946
-4.50603E06*
0.000865678
0.002421073
*residual acidity

Final
Adjusted
Moles
0.011158685
0.009380107
0.005435662
0.004767261
0.002224954

Mass of
charcoal
1.01
1
1
1.01
1

4.50603E-06

1.02

0.000861172
0.002416567

1
0