DETERMINATION OF ADSORPTION ISOTHERM OF ACETIC ACID ON ACTIVATED

CHARCOAL

AIM

To determine the adsorption isotherm of acetic acid on activated charcoal.

To determine the adsorption constant (k) and the maximal adsorbed substance amount of
acetic acid per gram of charcoal (Amax) of Langmuir isotherm.

INTRODUCTION

In this experiment the adsorption isotherm of acetic acid on activated charcoal along with
the adsorption constant (k) and the maximal adsorbed substance amount of acetic acid per
gram of charcoal (Amax) of Langmuir isotherm were to be determined.

ABSTRACT

Adsorption of acetic acid from aqueous solution onto activated carbon was investigated
and evaluated the adsorption constant (k) and the maximal adsorbed substance amount of
acetic acid per gram of charcoal (Amax) of Langmuir isotherm which were found to be
0.0000004115 mol-1 dm3 and 0.00048146 mol.g-1 respectively . The contact time value used in the
experiment for acetic acid adsorption onto the activated carbon was 20 minute. Greater
amount of acetic acid adsorbed with increase in the initial concentration of acetic acid and
increase in amount of adsorbent used. Adsorption data was modeled using the Langmuir
isotherms.

THEORY

Adhesion of atoms, ions, bimolecular or molecules of gas, liquid or dissolved solids to a

surface is called adsorption. This process creates a film of the adsorbate –the molecules or
atoms being accumulated, on the surface of the adsorbent.

Examples:

 Activated charcoal adsorbs gases like CO2 , SO2, Cl2 etc.

 Pt or Ni metal kept in contact with a gas adsorbs the gas - Hydrogenation of oils.
 Animal charcoal, when added to acetic acid solution and shaken vigorously, adsorbs
acetic acid.
 Molasses is decolorized by activated charcoal.

The molecules of gases or liquids or the solutes in solutions adhere to the surface of the
solids. In adsorption process, two substances are involved. One is the solid or the liquid on
which adsorption occurs and it is called adsorbent. The second is the adsorbate, which is
the gas or liquid or the solute from a solution which gets adsorbed on the surface.
Adsorbent: The substance on whose surface the adsorption occurs is known as adsorbent.

Adsorbate: The substance whose molecules get adsorbed on the surface of the adsorbent
(i.e. solid or liquid) is known as adsorbate. Adsorption is different from absorption. In
absorption, the molecules of a substance are uniformly distributed in the bulk of the other,
whereas in adsorption molecules of one substance are present in higher concentration on
the surface of the other substance.

Types of adsorption: Depending upon the nature of forces existing between adsorbate
molecules and adsorbent, the adsorption can be classified into two types:

1. Physical adsorption (physisorption): If the force of attraction existing between

adsorbate and adsorbent are Vander Waal’s forces, the adsorption is called physical
adsorption. It is also known as Vander Waal’s adsorption. In physical adsorption the force
of attraction between the adsorbate and adsorbent are very weak, therefore this type of
adsorption can be easily reversed by heating or by decreasing the pressure.

2. Chemical adsorption (chemisorptions): If the force of attraction existing between

adsorbate and adsorbent are almost same strength as chemical bonds, the adsorption is
called chemical adsorption. It is also known as Langmuir adsorption. In chemisorptions the
force of attraction is very strong; therefore adsorption cannot be easily reversed.

Factors affecting adsorption: The extent of adsorption depends upon the following
factors:

a. Nature of adsorbate and adsorbent.

b. The surface area of adsorbent.
c. Activation of adsorbent.
d. Experimental conditions. E.g., temperature, pressure, etc.
Langmuir isotherm: Langmuir isotherm in 1916, Irving Langmuir published an
isotherm for gases adsorbed on solids, which retained his name. It is an empirical
isotherm derived from a proposed kinetic mechanism. It is based on four
hypotheses:
a. The surface of the adsorbent is uniform, that is, all the adsorption sites are
equal.
 b. Adsorbed molecules do not interact.
c. All adsorption occurs through the same mechanism.
d. At the maximum adsorption, only a monolayer is formed: molecules of
adsorbate do not deposit on other, already adsorbed, molecules of adsorbate,
only on the free surface of the adsorbent.

For liquids (adsorbate) adsorbed on solids (adsorbent), the Langmuir isotherm (Figure 1)
can be expressed by:

m = Amax Kc/1+Kc

Where: m – is the substance amount of adsorbate adsorbed per gram (or kg) of the
adsorbent, the unit is mol g-1, resp. mol.kg-1
Amax – is the maximal substance amount of adsorbate per gram (or kg) of the adsorbent, the
unit is mol g-1, resp. mol.kg-1
k – Is the adsorption constant (mol-1 dm3)
c – Is the concentration of adsorbate in liquid (mol dm-3)
In practice, activated carbon is used as an adsorbent for the adsorption of mainly organic
Compounds along with some larger molecular weight inorganic compounds such as iodine
and mercury.

Activated carbon, also called activated charcoal or activated coal, is a general term that
includes carbon material mostly derived from charcoal. For all three variations of the name,
“activated" is sometimes substituted by "active." By any name, it is a material with an
exceptionally high surface area. Just one gram of activated carbon has a surface area of
approximately 500 m² (for comparison, a tennis court is about 260 m²). The three main
physical carbon types are granular, powder and extruded (pellet). All three types of
activated carbon can have properties tailored to the application. Activated carbon is
frequently used in everyday life, in – industry, food production, medicine, pharmacy,
military, etc. In pharmacy, activated charcoal is considered to be the most effective single
agent available as an emergency decontaminant in the gastrointestinal tract. It is used after
a person swallows or absorbs almost any toxic drug or chemical.

APPARATUS
6 boiling flasks (250 ml), 6 Erlenmeyer’s flasks (250 ml), 6 funnels, 3 burettes (50 ml), 10
titrimetric flasks,3 pipettes, Holders for funnel, Holders for burettes, Filtering paper,
Weasels for weighing coal, Spoon, rubber stoppers, solution of acetic acid (c = 1 mol dm-3),
solution of NaOH (c = 0.2 mol dm-3), activated charcoal, phenolphthalein

PROCEDURE

 The aqueous solutions of acetic acid were prepared into a numbered flask following
the scheme which was given in the table Table 1? The total volume of each solution
was 60 ml and flasks fitted with stoppers where used.

Flask No. V (acetic acid) V(distilled water)

[cm3] [cm3]
1 6 54
2 12 48
3 18 42
4 30 30
5 42 18
6 60 0

 10 ml of the solution was transferred from each flask into numbered titrimetric
flask. Final volume of acetic acid solution was VA = 50 ml per flask.

 The actual concentration of acetic acid in flasks was determined by titration in this
way: For titration, the volume in each titrimetric flask was modified a defined
volume of the each titrimetric flask. a defined volume of the solution was taken
away, to obtain in each flask the volume as given in the Table 2

Table 2 Volumes of the acetic acid solutions (V) used for titration before and after
 Adsorption
Titrimetric flask No. 1 2 3 4 5 6

volume solution – 10 10 5 5 5 2
V[ml]

 1-2 drops of phenolphthalein were added and the solution was titrated by NaOH.
 Once the endpoint was reached the burette value was read. The volume of the base
(X0i) - ml that was required to reach the endpoint write down to the Table 3.
  Actual concentration of acetic acid before adsorption (Ci0) in the flask No.1-6 was
calculated, respectively according Equation 2:

Ci0 = X0i CT / V [mol dm-3] (2)

Where:
X0i – is the volume of the titrant before adsorption (NaOH)
CT – is the volume of the titrant (NaOH)
V – is the volume of the analyte (from Table 2)

 Practical balance and weasels where used for weighing coal as 6 portions of
activated charcoal, each portion 5 g where obtained and weighed. The accuracy of
weighing was with accuracy 0.01 g.
 The activated charcoal was put into numbered flasks with stoppers (1 portion per
flask).
 The flasks where plugged with stoppers and shaken. the process of adsorption was
in Progress and we waited for 20 minutes,. the mixtures where mixed several times
by flasks shaking within this period.
 The mixtures where filtered into clean and dry flasks. To avoid disturbing effect of
adsorption of acetic acid into filtering paper, the first portion of filtration was
removed, app. 5 ml.
 The final concentration of acetic acid (Ci ) in each of the flasks after adsorption was
determined
 From each solution, transfer the asked volume into clean and dry titrimetric flask,
again following Table 2.
 Points 4-6 were repeated, and from the consumed base (Xi) from Table 3 the
concentration of acetic acid (Ci ) was determined after adsorption according
Equation 3:

Ci = Xi CT / V [mol dm-3] (3)

Where: Xi – is the volume of the titrant after adsorption (NaOH)

CT and V – are the same values as in Equation 2
Write measured values (Xi ) and calculated values (Ci ) down to the Table 3.
Finishing experiment, used flasks, pipettes and others were washed carefully.

RESULTS
TABLE 1
NO. 1 2 3 4 5 6
INITIAL 0.00 4.80 14.50 22.60 0.00 12.30
FINAL 4.80 14.50 22.60 34.90 17.00 1.90
VOLUME USED 4.80 9.30 8.10 12.30 17.00 10.40

TABLE 3
NO. 1 2 3 4 5 6
INITIAL 0.00 13.40 20.40 32.40 49.20 18.60
FINAL 4.40 4.40 13.40 20.40 33.40 8.20
VOLUME USED 4.40 9.00 7.00 12.00 15.80 10.40

DATA TREATMENT
The amount of acetic acid adsorbed per gram of the charcoal mi (mmol g-1) in individual
flask was determined by using the following:

mi = ( Ci0- Ci)VA /g

Where: Ci0 – is concentration of acetic acid before adsorption (from Table 3, unit mol dm-3)
Ci – is concentration of acetic acid after adsorption (from Table 3, unit mol dm-3)
VA –is volume of the liquid phase used for adsorption (VA= 50 ml, change ml to
dm )
3

g – Is the mass of the adsorbent – charcoal (use 5 grams?)

i =1-6 is the number of flask

Table 3 Experimental data

Flask No. X0i Ci0 Xi Ci mi 1/Ci 1/mi
[ml] [mol dm-3] [ml] [mol.dm-3] [mmol g-1] [dm3 mol-1] [g mmol-1]

1 4.80 0.096 4.40 0.088 8E-05 11.36 12500.00

2 9.30 0.186 9.00 0.18 6E-05 5.56 16666.67
3 8.10 0.324 7.00 0.28 0.00044 3.57 2272.73
4 12.30 0.492 12.00 0.48 0.00012 2.08 8333.33
5 17.00 0.68 15.80 0.632 0.00048 1.58 2083.33
6 10.40 1.04 10.40 1.04 0 0.96 #DIV/0!
 18000.00
16000.00
y = 1170.1x + 2077.6
14000.00
12000.00
1/mi

10000.00
1/mi [g mmol-
8000.00 1]
6000.00 Linear (1/mi [g
mmol-1] )
4000.00
2000.00
0.00
0.00 5.00 10.00 15.00
1/Ci

Hence = 1170

= 2077

Hence =1/2077=0.00048146 mol.g-1 = 0.0000004115 mol-1 dm3

DISCUSSION
in this experiment the absorption constant (K) has been calculated to be 0.0000004115
mol-1 dm3, the Amax has also been calculated to be 0.00048146 mol.kg-1 and the value of m
which is the substance amount of adsorbed per gram of absorbent which was calculated for each
solution in its flask . Since the Amax is 0.00048146 mol.g-1 which means that 0.00048146
moles of acetic acid is the maximum amount that will be absorbed by one gram of activated
carbon. The adsorption is influenced by various factors, which include initial acetic acid
concentration, amount of adsorbent, nature of adsorbent, temperature, nature of adsorbent
and contact time. Analysis of the results shows that the acetic acid adsorption process on
activated carbon was increased as the initial concentration of acetic acid increased. The
initial acetic acid concentration is one of the most important factors that determine the
equilibrium concentration and in our experiment the initial concentrations were not high.
The activation energy for physisorption is also very low and hence it is practically a
reversible process. Effect of temperature: Since physical adsorption is an exothermic
process, it occurs more readily at lower temperatures and decreases with increase
in temperature (Le-Chatelier's Principle). With increase
in temperature, chemisorptions first increases as sufficient energy is being provided for
the molecules to reach the activation energy. But after certain degree it decreases, as the
further high temperature helps in breaking of the bond between the adsorbate and the
adsorbed molecules and our experiment took place at room temperature25oC. An effect of
contact time on removal of acetic acid by activated charcoal is of great importance in
adsorption since contact time depends on the nature of the system used. It is clear that
after a time of contact of 30 minutes with activated charcoal, the adsorbed amount of the
acetic acid does not vary practically any more and attained equilibrium at 30 min for acetic
acid according to literature which means that we were within the time limit as we used
20minutes. The amount adsorbed from a solution depends on the properties of the
adsorbent (chemical nature of the surface, dimension of the pores) those of the solution
and of its constituents. The effect of nature of adsorbent surface on adsorption is important
and in this experiment pellets where used which provided and fairly large surface area.

SOURCES OF ERRORS

Contaminated activated carbon and lack of proper apparatus such as beaker may have caused a
deviation.

Lack of distilled water in the laboratory used made cleaning used apparatus hard and
challenging.

RECOMMENDATION

The process of adsorption is a function of time too. It is important to put charcoal into flasks at the
same time, to provide adsorption for the same period in each flask.

Effective timers must be used so as to accurately time the 20minutes for the activated
carbon to adsorb the acetic acid as proper shaking with stoppers is being carried out
The process of adsorption would have been viewed better if the activated carbon was in
power form.

CONCLUSION
The adsorption behavior of acetic acid on activated carbon was studied and analysis of the
results shows that the acetic acid adsorption process on activated carbon was increased as
the initial concentration of acetic acid increased. From this study, the adsorption isotherm
studies were performed and from this the Langmuir separation factor is between 0 and 1
and hence the process of acetic acid adsorption on activated carbon is well fitted with the
Langmuir adsorption isotherm.
REFERENCE
Ernest J. Henley (2011), SEPARATION PROCESS PRINCIPLES with Applications Using Process
Simulators, (Fourth Edition). Elsevier Academic Press. (188,464).
Robert G. Mortimer (2008), Physical Chemistry. (Third Edition), Elsevier Academic Press.
(465,469).