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Sucgang, Mark Anthony N.

BS ChE 5

03/31/2016
MA2

Adsorption Isotherm Of Acetic Acid Solutions On Activated Carbon


Sucgang, Mark Anthony N.
Abuan, Rebecca Grace A.
Agudo, Anna Leslie C.
Balicha, Eloisa Myra H.
ABSTRACT
The purpose of the experiment was to study the adsorption isotherm of acetic acid solutions on activated carbon. To observe
if this system will obey the Freundlich or Langmuir equation, different concentrations of acetic acid were prepared and equilibrated
with 1 gram of activated carbon. After shaking for a 10-20 minutes it was set aside undisturbed for a week in a place where the
relatively constant temperature is 24 C. A sample from each solution was then titrated with a standardized sodium hydroxide solution.
The amount of equilibrium concentration and weight of acetic acid adsorbed was then calculated. From the data gathered, the
Freundlichs and Langmuirs linear equation were used to observe if they obey the said equations. Comparing the values of r from
Freundlich equation of 0.9572 and 0.9734 from those of Langmuir equation having r values of 0.9504 and 0.9523, the system obeys
both equation but Freundlich equation is more favored. Thus, Freundlich isotherm is better in describing the adsorption of acetic acid
on activated carbon.
Keywords: acetic acid, activated carbon, adsorption, isotherm, titration
INTRODUCTION
specific type of carbon and a known substance, there is a
Adsorption is the adhesion of atoms, ions, or
relationship between the amount of adsorbed matter per unit of
molecules from a gas, liquid, or dissolved solid to a surface.
weight of carbon and the equilibrium concentration in the
Adsorption is a process in which molecules from gas (or
solution, when temperature is constant. This relationship is
liquid) phase land on, interact with and attach to solid
called isotherm.
surfaces. It is a separation process in which some materials,
Adsorption isotherm is the relation between the
(adsorbate) is concentrated from a bulk vapor or liquid has on
amount of substance adsorbed by an adsorbent and the
to the surface of a porous solid (adsorbent). The reverse
equilibrium pressure or concentration at constant temperature.
process of adsorption, i.e. the process in which adsorbed
The shape of isotherm can be described in various
molecules escape from solid surfaces, is called desorption.
mathematical ways. Some of the well-known is the Langmuir
Adsorption appears to be good for the treatment of effluents.
and Freundlich isotherm.
The first thing for an efficient adsorption process is the search
The chemical reaction for a monolayer adsorption can be
for a low cost adsorbent with high adsorption capacity and
represented as follows:
second it should be biodegradable. There are many examples
A + S AS
of adsorbents, some of which are activated carbon (adsorbs
where AS represents a solute molecule bound to a surface site
organics), silica gel (adsorbs moisture), activated alumina
on S. The equilibrium constant
(adsorbs moisture), zeolites & molecular sieves and synthetic
Kads for this reaction is given by:
resins. The commonly used adsorbing agent is the activated
[ AS]
Kads=
carbon, in this experiment activate carbon will be used to
equation [1.1]
[ A ] [S ]
study about the adsorption isotherms of acetic acid solutions
on activated carbon. All activated carbon may look the same
[A] denotes the concentration of A, while the other two terms
to the naked eye, but pore size and structure makes a huge
[S] and [AS] are two-dimensional analogs of concentration
difference on how well impurities are adsorbed. Adsorption of
and are expressed in units such as mol/cm2. The principle of
gases by solids depends on the nature of adsorbent, nature of
chemical equilibrium holds with these terms. The complete
gas being adsorbed, area of adsorbent, temperature and
form of the Langmuir isotherm considers (Eq.1.1) in terms of
pressure of the gas. Surface adsorption to a solid falls into two
surface coverage q which is defined as the fraction of the
broad categories; Physisorption or Physical adsorption and
adsorption sites to which a solute molecule has become
Chemisorption or Chemical adsorption. If the force of
attached. An expression for the fraction of the surface with
attraction existing between adsorbate and adsorbent are
unattached sites is therefore (1 - q). Given these definitions,
Vander Waals forces, the adsorption is called physical
we can rewrite the term [AS]/[S] as
adsorption. It is also known as Vander Waals adsorption. In
[ AS ]

the physical adsorption, the force of attraction between the


=
equation [1.2]
[ S] 1
adsorbate and the adsorbent are very weak, therefore this type
of adsorption can be easily reversed by heating or be
Now we express [A] as C and rewrite (Eq. 1) as:
decreasing the pressure. While if the force attraction existing

between adsorbate and adsorbent are almost same strength as


Kads=
chemical bonds, the adsorption is called chemical adsorption.
equation [1.3]
C(1)
It is also known as Langmuir adsorption. In the chemisorption
the force of attraction is very strong, therefore adsorption
Rearranging, we obtain the final form of the Langmuir
cannot be easily reversed. Chemisorption process is best
adsorption isotherm:
described by the Langmuir isotherm.
Kads C
=
The amount of substance that can be adsorbed on
equation [1.4]
1+ Kads C
activated carbon depends on the nature of the substance and its
concentration, the surface structure of the activated carbon and
the temperature of the solution. For a treatment system with a

Y
Ymax

equation [1.5]

and the isotherm can be expressed as:

C
1
C
=
+
Y KadsYmax Ymax

equation

[1.6]
This is the form of the isotherm we will use for our CharcoalAcetic Acid system.
At lower concentrations, an alternate isotherm
developed by Herbert F. Freundlich frequently describes the
data better. The Freundlich Isotherm is:
Figure 1.1 General Form of Langmuir Isotherms
If we define Y as the amount of adsorption in units of
moles adsorbate per mass adsorbant, and Ymax and the
maximal adsorption, then:
DESIGN AND METHODOLOGY
A. Preparation of Solutions
First 1000 mL of a 0.100N sodium hydroxide
(NaOH) solution was prepared. To prepare the solution,
about four grams of sodium hydroxide pellets were
weighed in the analytical balance. The pellets were then
dissolved in a small quantity of water and were
transferred to a 1000 mL volumetric flask. Sufficient
water was added until the mark to make up 1000 mL of
the solution. The solution was mixed thoroughly and was
transferred to a reagent bottle and was labeled.
Next 500 mL of 0.500N acetic acid (HAc) solution
was prepared. To prepare the solution, about 18 mL of
glacial acetic acid was pipetted carefully into a 500 mL
volumetric flask and enough water was added to reach the
mark. The solution was mixed thoroughly and was
transferred to a reagent bottle and was labeled.
The titrant solution, which was the NaOH solution,
was standardized using potassium phthalate (KHP). The
amount needed for standardizing the solution was
weighed using the analytical balance and was placed in an
Erlenmeyer flask. This amount of KHP was dissolved
with a small amount of water. A few drops of
phenolphthalein were added to the flask and was titrated
with the NaOH solution. A second standardization was
done.
The normality of the titrant solution was
determined up to four digits.
B. Preparation of Adsorption Solutions
For the preparation of the adsorption solutions, 100
mL each of N/4, N/8, N/16, N/32 and N/64 HAc
solutions. The volume of N/2 or 0.500N HAc solution
required in the preparation of these solution was
computed. The computed volumes were pipetted into
different 100 mL volumetric flasks and enough water was
added to these flasks until the mark. These solutions were
mixed thoroughly and 80 mL of these solutions were
transferred to properly labeled Erlenmeyer flasks and
corks were placed as stoppers. A second set of these
solutions were made for the second trial.
Approximately one gram of activated carbon was
weighed using an analytical balance and was transferred

Y =k C

ln

equation [1.7]

where the Freundlich parameters k and n are empirically


determined. A plot of log Y vs. log C allows for a
determination of these parameters.

to an Erlenmeyer flask containing the prepared solution. This


was done to the other Erlenmeyer flasks. The weight of the
activated carbon placed in each erlenmeyer flask was carefully
recorded. The contents of the twelve flasks were mixed
thoroughly for about 10 to 20 minutes, and were then left in a
place where the temperature remained relatively constant. The
prepared solutions were left for a week to let the solution
adsorbed by activated carbon reach equilibrium.
C. Determination of the Equilibrium Concentrations
of the Solutions
After a week, the solutions were carefully removed from their
safekeeping place as not to disturb the solution. For each of
the solution, 10 mL of the clear liquid was pipetted into a
clean Erlenmeyer flask for titration. Small amount water was
added to the walls of the flasks.
A few drops of
phenolphthalein were placed in the solutions as an indicator
and were titrated with the standardized NaOH solution. A
second titration was done with the second set of prepared
solutions. The concentration of the original concentration was
calculated with N/2 equal to 0.5000N acetic acid solution.
After the titration the equilibrium concentration of the each
acetic acid solutions were calculated using the formula:
NHAcVHAc = NNaOHVNaOH
equation [2.1]
where NHAc is the equilibrium concentration of the acetic acid
solution, VHAc is the volume of acetic acid used, N NaOH is the
concentration of the standardized NaOH, and V NaOH is the
volume of the standardized NaOH used. The weight of the
acetic acid at equilibrium was also calculated using the
formula:

wt. of HAc =

(N)(MW)(L solution)
f

equation

[2.2]
where N is the calculated normality of the equilibrium
solution, MW is the molar mass of acetic acid, L solution is
the volume of acetic acid solution equilibrated with about 1
gram of activated carbon, and f is the equivalence per mole of
a substance. By deducting the weight of acetic acid in the
equilibrium solution from that in the original solution, the

weight of acetic acid adsorbed can be obtained. After which

the ratio of the weight of the acetic adsorbed per gram of


activated carbon was also calculated.

RESULTS AND DISCUSSION


Room Temperature: 24C

Pressure: 24.96 in Hg

TRIAL 1
TABLE 3.1 Original Concentration of Acetic Acid Solution and Weight of Acetic Acid in the Original Solution
Original
Volume of
Weight of HAc in the
Volume of
Volume of
Concentration
Solution
Original Solution
HAc in
NaOH Used
Titration
N/2
0.4841 N
80 mL
2.3237 g
10 mL
45.7 mL
N/4
0.2421 N
80 mL
1.1621 g
10 mL
22.5 mL
N/8
0.1210 N
80 mL
0.5808 g
10 mL
10.8 mL
N/16
0.0605 N
80 mL
0.2904 g
20 mL
9.9 mL
N/32
0.0303 N
80 mL
0.1454 g
20 mL
4.3 mL
N/64
0.0151 N
80 mL
0.0725 g
40 mL
4.7 mL
TABLE 3.2 Equilibrium Concentrations, Weight of Acetic Acid Adsorbed per gram Activated Carbon
Equilibrium
Weight of HAc
Weight of
Weight of
Weight of HAc per
Concentration
at Equilibrium
HAc
Activated
gram of Activated
Adsorbed
Carbon
Carbon
N/2
0.4515 N
2.1672 g
0.1565 g
1.0 g
0.1565 g HAc/ g AC
N/4
0.2223 N
1.0670 g
0.0951 g
1.0 g
0.0951 g HAc/ g AC
N/8
0.1067 N
0.5112 g
0.0686 g
1.0 g
0.0686 g HAc/ g AC
N/16
0.0489 N
0.2347 g
0.0557 g
1.0 g
0.0557 g HAc/ g AC
N/32
0.0212 N
0.1018 g
0.0436 g
1.0 g
0.0436 g HAc/ g AC
N/64
0.0116 N
0.0557 g
0.0168 g
1.0 g
0.0168 g HAc/ g AC
Freundlich constants: k = 0.2323 n = 1.9262
Langmuir constants: a = 1.4449 b = 7.8429

r = 0.9572
r = 0.9504

TRIAL 2
TABLE 3.3 Original Concentration of Acetic Acid Solution and Weight of Acetic Acid in the Original Solution
Original
Volume of
Weight of HAc in the
Volume of
Volume of
Concentration
Solution
Original Solution
HAc in
NaOH Used
Titration
N/2
0.4841 N
80 mL
2.3237 g
10 mL
46 mL
N/4
0.2421 N
80 mL
1.1621 g
10 mL
22.7 mL
N/8
0.1210 N
80 mL
0.5808 g
10 mL
10.8 mL
N/16
0.0605 N
80 mL
0.2904 g
20 mL
10 mL
N/32
0.0303 N
80 mL
0.1454 g
20 mL
4.3 mL
N/64
0.0151 N
80 mL
0.0725 g
40 mL
4.3 mL
TABLE 3.4 Equilibrium Concentrations, Weight of Acetic Acid Adsorbed per gram Activated Carbon
Equilibrium
Weight of HAc
Weight of
Weight of
Weight of HAc per
Concentration
at Equilibrium
HAc
Activated
gram of Activated
Adsorbed
Carbon
Carbon
N/2
0.4545 N
2.1816 g
0.1421 g
1.0 g
0.1421 g HAc/ g AC
N/4
0.2243 N
1.0766 g
0.0855 g
1.0 g
0.0855 g HAc/ g AC
N/8
0.1067 N
0.5122 g
0.0686 g
1.0 g
0.0686 g HAc/ g AC
N/16
0.0494 N
0.2371 g
0.0533 g
1.0 g
0.0533 g HAc/ g AC
N/32
0.0212 N
0.1018 g
0.0436 g
1.0 g
0.0436 g HAc/ g AC
N/64
0.0106 N
0.0509 g
0.0216 g
1.0 g
0.0216 g HAc/ g AC

Freundlich constants: k = 0.1880 n = 2.2883


Langmuir constants: a = 1.5913 b = 10.1175

r = 0.9734
r = 0.9523

The experiment was done with two trials. Tables 3.1


and 3.3 shows the original concentration of the acetic acid
solution obtained by titrating it with the standardized NaOH
solution. The volume of solution was the volume of the acetic
acid in different concentrations equilibrated with about 1 gram
of activated carbon. The weight of acetic acid on the original
solution was obtained after the titration with the respective
volumes of acetic acid solution in different concentrations and
the corresponding volume of the standardized NaOH solution
used. When all the necessary data for the original solution
found in tables 3.1 and 3.3 are obtained and recorded, each
solution in different concentrations were equilibrated with
about 1 gram of activated carbon.
The other tables 3.2 and 3.4 shows the concentration
of acetic acid after each solution was equilibrated with about 1
gram of activated carbon. This was obtained by titrating each
solution with the standardized NaOH solution and using
equation [2.1]. The weight of acetic acid at equilibrium was
calculated using equation [2.2]. Then by deducting the weight
of the acetic acid in the equilibrated solution from its weight in

the original solution, the weight of acetic adsorbed can be


obtained. The respective weights of activated carbon put in
each solution was carefully recorded and the ratio of the
weight of acetic acid per gram of activated carbon is computed
by dividing the exact amount of activated carbon in each
concentration in each trial by the calculated weight of acetic
acid in their respective concentrations and trials.
The results show that the standardization of the acetic
acid solution was precise because the values of the volume of
the NaOH used were almost the same and had small
differences. The analytical balance used had accuracy up to
the first decimal and the constant weight of all the activated
carbon were obtained due to this. It is also evident that the
ratio of activated carbon and acetic, and weight of acetic acid
in the equilibrated solution were almost the same for each trial
with their respective concentrations except for concentrations
N/2 and N/64. This may be due to error in the titration process
where the change in color of the indicator was not observed
properly, however, the difference is not as high as to consider
that one of the trials was not performed properly.

Figure 3.1 Linear Curve of Freundlich Equation for First Trial


0
-0.5
-1
-1.5
-2
-2.5
-3
-3.5
-4
-4.5
y, ln y

ln y

Linear (y, ln y)

ln C

Figure 3.2 Linear Curve of Langmuir Equation for First Trial


3.5
3
2.5
2
1.5
1
0.5
0
y, C/y

C/ y

Linear (y, C/y)

Figure 3.3 Linear Curve of Freundlich Equation for Second Trial


0
-1
-2
ln y

y, ln y

-3

Linear (y, ln y)

-4
-5
-0.78859999999999997

-3.0078

ln C

Figure 3.4 Linear Curve of Freundlich Equation for Second Trial


3.5
3
2.5
2
1.5
1
0.5
0

y, C/y

C/ y

Linear (y, C/y)

From the given data, the Freundlich and Langmuir


constants were calculated using linear regression for each trial
and with the equations:
Freundlich Equation: ln y = ln k +
equation [3.1]
Langmuir Equation:

C
y

1
n

ln C

1
b
+
C
a
a

The r represents the closeness of the points from the


curve. This determines the best fit adsorption isotherm for the
experiment. Their values show that Freundlich isotherm is best
fit isotherm rather than the Langmuir isotherm for this
experiment as seen from a comparison of their curves and
points on the figures 3.1, 3.2, 3.3 and 3.4. The relatively
constant temperature considered during the period of the
experiment was 24C.

equation [3.2]
CONCLUSION AND RECOMMENDATION
The adsorption of acetic acid on activated carbon at
an approximately constant temperature 24C obeys the
Freundlich equation and Langmuir equation as can be seen by
the evaluated r or the closeness of the points to a curve, but the
best fit isotherm for the experiment was the Freundlich
isotherm which has lesser deviance of points to its curve.
Possible sources of error in this experiment can be
accounted mainly in inaccuracy of reading the measurements.
Failure to titrate or standardize the solutions also increases the
probability of obtaining values that are less likely to obey the
above mentioned equations. The preparation, especially the
transfer of exact amount of solutions, has a great impact on the
concentration the solution will have. Any excess or

insufficiency in the amount required will greatly affect the


result. Although instances that the procedure can be altered it
is best to do it as instructed for better comparison of results
with same level of possible errors.
References
Green, D. W. and R. H. Perry (2007). Perrys Chemical
Engineers Handbook, 8th Edition, Mcgraw-Hill.
Jonas, Leonard A., and Eric B. Sansone(1986). Prediction of
Activated Carbon Performance for Sequential Adsorbates,
Am. Ind. Hyg. Assoc.
Underhill, Dwight. W. (1987). Calculation of the
Performance of Activated Carbon at High Relative
Humidities.

Lando, J. B., and S. H.Maron (1974). Fundamentals of


Physical Chemistry, Macmillan.