CDB3052

CHEMICAL ENGINEERING LAB II

September 2018
Laboratory Report

Experiment : 9

Experiment Name : Activated Carbon Adsorption Isotherm & Kinetics

Group : A5

Toh Jian Heng 24042

Manniin Waynthenn A/L Anparasu 24055
Group Members : Muhammad Afiq Isyraf Bin Ishak 23692
Anis Farahin Ahmad 23523
Kabilasini A/P Mana Mohan 23921

Lab Demonstrator : Hanan Mohsin

Date of Submission : 14th October 2018

 1.0 INTRODUCTION & OBJECTIVES

Activated charcoal which also known as activated carbon, is a type of

processed carbon which has small and low volume pores that increase the surface area.
It is used widely in industrial application as it is available for adsorption or chemical
reactions. Other applications of activated carbon are medical, environmental,
agricultural uses, mercury scrubbing and purification of gas, chemical, and distilled
alcoholic beverage (Bansal, 2005). In the field of chemical engineering, activated
carbon is used successfully in treating gas, vapor, and liquid. In water treatment
processes, activated carbon is able to impart colour, taste and odor to the water by
removing the organic compounds contained in the water. The removal of
contaminant is attained through a process called adsorption where contaminants react
and adhere to the surface of activated carbon which is then removed from the water.

Adsorption is the adhesion or attachment of molecules, atoms and ions which

are called as adsorbate from a gaseous, liquid or solution onto the surface of an
adsorbent which is activated carbon (Marsh, 2006). It is able to take place as the
porosity of activated carbon offers a wide surface area. The pores should be slightly
larger than the molecules that are being adsorbed as it is crucial to match the pore size
of the activated carbon with the molecule that is trying to be adsorbed. The adsorbates
are then trapped within the internal pore structure of activated carbon by Van Der
Waals forces or different bond of attraction and accumulate onto the solid surface.
There are two types of adsorption which are physical adsorption and chemisorption.
The adsorbates are held on the surface of the pore walls by weak forces of attraction
such as Van Der Waals forces or London dispersion forces is called physical
adsorption while for chemisorption, it involves strong forces of attraction such as
chemical bonds between adsorbates and the pore wall of the activated carbon.
Chemisorption is irreversible since the process involves a strong chemical bond
between adsorbate and the adsorbent which is activated charcoal in this case.

The relation between the amount of adsorbate being adsorbed on to the surface
of adsorbent can be defined by adsorption isotherm. Some of the examples of
adsorption isotherm will be Freundlich isotherm, Langmuir isotherm and the linear
isotherm. For this experiment, only Freundlich and Langmuir isotherm will be
compared. Freundlich isotherm actually portrays the quantity of gas adsorbed by unit

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mass of solid adsorbent with pressure at a particular temperature. The only limit of
this isotherm is that it is able to fail at high pressures. Thus, at high pressures the rate
of adsorption saturates beyond a particular point for this isotherm (Porter, 1982).

The second common isotherm for adsorption as mentioned will be Langmuir

isotherm. This isotherm describes the relationship between the number of active sites
of the adsorption surface and pressure. The most prominent assumptions are that the
adsorption layer must be monolayer, all the active sites are of same size and shape and
also there can only be a fixed number of adsorption sites. Just like Freundlich
isotherm, the Langmuir isotherm also has its own limitation where this isotherm is
only valid at low pressure conditions (Porter, 1982; Osman, 1994).

The objective of this experiment is to investigate the properties of adsorption

of activated carbon by studying the equilibrium isotherms, adsorption kinetics and
operational characteristics of a reactor. In this experiment, activated charcoal is used
to remove the contaminant which is known as methylene blue and required to achieve
70% of removal efficiency. There are two parts of the experiment which are the
measurement of methylene blue is kept constant of 20 mg and different measurement
of activated carbon with 2g, 4g, and 6g while the second part is the measurement of
activated carbon is kept constant at 6 g and different measurement of methylene blue
which are 5 mg, 10 mg, 20 mg, and 30 mg. The data of the experiment for both parts
are obtained, recorded and tabulated and the best fit of adsorption isotherm and its
isotherm constant are calculated respectively. The most accurate isotherm will be
determined through the experiment where the Regression (R2) value from the graph
will be used to compare which isotherm has the closest Regression value with one.
Therefore, the isotherm with the closest value will be the more accurate one.

Figure 1: Types of adsorption Figure 2: Adsorption

of activated charcoal
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 2.0 METHODOLOGY/ EXPERIMENTAL PROCEDURES

METHODOLOGY

This experiment was to investigate the effect on the reaction kinetics of methylene
blue adsorption by activated carbon (activated charcoal C5510) with the variation of
concentration of methylene blue. The objective was achieved in part B, by
manipulating the initial concentrations of methylene blue solution, 5 mg/L, 10 mg/L,
20 mg/L and 30 mg/L. The mass of the granulated activated carbon was kept constant
for the experiment, which is 6 g.

The experiment unit consists of the followings:

 Granular Activated Carbon (Activated Charcoal C5510)

 Methylene Blue
 Distilled Water
 Beaker (1 Liter)
 Volumetric Flask (1 Liter)
 Laboratory Electrical Stirrer
 Electronic Balance
 Weighing Aluminum Foil
 Spatula
 Vial Bottles
 UV Spectrophotometer
 Pipette
 Filter Paper
 Filter Funnel

EXPERIMENTAL PROCEDURES

Part A: To attain at least 70% removal efficiency of methylene blue using activated
carbon as an adsorbent

1. The UV spectrophotometer was switched on to allow it to warm up for 15

minutes.

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2. 3 sets of 20 mg methylene blue powder were weighed on the electronic
balance by using aluminum foil.
3. The 3 sets of methylene blue powder were then inserted into 3 different
volumetric flasks with 1 liter capacity, respectively.
4. 1 liter of distilled water was added into each volumetric flask and the mixture
was mixed well. Methylene blue solution with concentration of 20 mg/L was
obtained.
5. The methylene blue solution was then transferred from volumetric flasks into
3 different beakers.
6. The activated carbon weighed for 2g, 4g and 6g were placed into the 3 beakers
respectively.
7. All 3 breakers were placed under the electrical stirrer and were stirred at
200rpm for 10 minutes.
8. After 10 minutes, 10ml sample solution from each beaker was obtained by
using pipette and they were transferred into 3 different vial bottles. UV
spectrophotometer was used to obtain the absorbance reading by the means of
UV-Vis ray.
9. The absorbance reading obtained was recorded as the initial value. The
samples were placed back into their respective beakers.
10. Steps 8 to 9 were repeated until at least 70% of removal efficiency was
achieved. The percentage of removal efficiency was calculated by using the
formula shown below:

( ) ( )
where
C0 = initial concentration of methylene blue solution (mg/L)
Ci = concentration of methylene blue solution at time, t (mg/L)
11. The amount of adsorbent (activated carbon) would be determined from step 10
at which the amount with the shortest time recorded to reach 70% removal
efficiency would be used.

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Part B: To determine the best fit of adsorption isotherm (Langmuir Isotherm/
Freundlich Isotherm) and its respective isotherm constants

1. 5mg, 10mg, 20mg and 30mg of methylene blue powder were newly weighed
on the electronic balance.
2. The weighed methylene blue powder was transferred into 4 different
volumetric flasks respectively and the flasks were labeled.
3. 1 liter of distilled water was added into each volumetric flask and 4 sets of
methylene blue solution with concentration of 5mg/L, 10mg/L, 20mg/L and
30mg/L were obtained.
4. Methylene blue solutions of 4 different concentrations were then transferred
into 4 beakers respectively and the beakers were labeled.
5. Each methylene blue solution was analyzed on the initial absorbance reading
by using the UV spectrophotometer. The readings obtained were recorded at
t=0.
6. 4 sets of granulated activated carbon with the amount obtained from part A
were prepared and were added into the 4 different beakers.
7. All beakers were placed under electrical stirrer and were stirred at a speed of
200rpm. The stopwatch was started quickly once the stirrer was switched on.
The process was left for 10 minutes.
8. After 10 minutes of stirring, two sets of 10ml sample solutions from each
beaker were taken by using pipette and were transferred into vial bottles. UV
spectrophotometer was used to obtain the absorbance reading by the means of
UV-Vis ray.
9. The absorbance reading obtained was recorded as the initial value. The
samples were placed back into their respective beakers.
10. Steps 8 and 9 were repeated for a total period of time until the equilibrium was
reached.
11. Once the equilibrium was achieved, the solutions from each beaker were
filtered by using filter paper and filter funnel in order to remove any
disintegrated activated carbon.
12. The data obtained were tabulated and attached in the Appendices.
13. The calculations were done to determine whether the process is a Langmuir
isotherm or a Freundlich isotherm.

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 3.0 RESULTS & DISCUSSIONS

Part A: To attain at least 70% removal efficiency of methylene blue using activated
carbon as an adsorbent

In this experiment, methylene blue was used as the adsorbate and activated
charcoal C5510 was used as the adsorbent. A series of activated charcoal with
different masses were used (2g, 4g, and 6g accordingly with the same concentration
of methylene blue which is 20mg/L. To reach the objective of the experiment, the
removal efficiency was calculated for every absorbance reading by using the formula:

( ) ( )

where
C0 = initial concentration of methylene blue solution (mg/L)
Ci = concentration of methylene blue solution at time, t (mg/L)

Table 1: Table of absorbance reading for different amount of adsorbent

Amount of Adsorbent (g)

Time 2 4 6
(min) Absorbance Reading
st nd rd st
1 2 3 Avg 1 2nd 3rd Avg 1st 2nd 3rd Avg
0 0.278 0.277 0.278 0.278 0.269 0.267 0.268 0.268 0.272 0.272 0.273 0.272
10 0.232 0.231 0.231 0.231 0.218 0.215 0.224 0.219 0.218 0.215 0.219 0.217
20 0.183 0.183 0.183 0.183 0.173 0.176 0.161 0.170 0.163 0.160 0.165 0.163
30 0.120 0.126 0.129 0.125 0.109 0.109 0.112 0.110 0.109 0.105 0.104 0.106
40 0.105 0.103 0.101 0.103 0.086 0.085 0.087 0.086 0.058 0.061 0.059 0.059

Table 2: Table of removal efficiency percentage for different amount of adsorbent

Amount of Adsorbent (g)

Time
2 4 6
(min)
Removal Efficiency (%)
0 0 0 0
10 16.91 18.46 20.22
20 34.17 36.57 40.07
30 55.04 58.96 61.03
40 62.95 67.91 78.31

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 Removal Efficiency (%) vs Time (min)
90

80

70
Removal Efficiency (%)

60

50
2g
40 4g
30 6g

20

10

0
0 10 20 30 40 50
Time (min)

Figure 3: Graph of removal efficiency against time for different amount of adsorbent

Based on the graph of removal efficiency against time, we can analyze that 6g
of activated charcoal C5510 at the 40th minute had achieved its removal efficiency
exceeding 70%. Below is the calculation for the removal efficiency for the 6g of
activated carbon at t=40min:

( ) ( )

Comparing to other amounts which are 2g and 4g, we can observe that both
amounts had not exceeded the 70% removal efficiency at t=40 min. The reason for
this result might come from the presence of methylene blue particles which are yet to
be adsorbed by the activated carbon. Therefore, since the amount of adsorbent used
for 20 mg/L of methylene blue solution which helps to achieve the 70% removal
efficiency is 6g, the same amount will be used for the second part of the experiment
which is to determine the best fit of adsorption isotherm and its respective isotherm
constants.

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Part B: To determine the best fit of adsorption isotherm (Langmuir Isotherm/
Freundlich Isotherm) and its respective isotherm constants

For this part of the experiment, the amount activated carbon used were
determined to be 6 g and were added to different concentration of methylene blue
solutions which are 5 mg/L, 10 mg/L, 20 mg/L and 30 mg/L to investigate on the best
fit adsorption isotherm and its respective isotherm constants for the experiment. Four
beakers with the solutions were stirred at 200 rpm and at 10 minute intervals, samples
were collected where the absorbance values were measure by the UV-
Spectrophotometer.

Absorbance Reading VS Methylene Blue

Concentration (mg/L)
0.35 0.324
y = 0.0108x - 0.0071
0.3
R²= 0.9941
Absorbance Reading

0.25
0.197
0.2

0.15
0.109
0.1
0.046
0.05

0
0 5 10 15 20 25 30 35
Concentration of Methylene Blue Solution (mg/L)

Figure 4: Calibration curve of absorbance reading against concentration of methylene

blue solution at t = 0 min.

The calibration graph was obtained by taking the first reading of the
absorbance value for the concentration of methylene blue solution at t = 0min. From
the graph, the linear equation obtained has a relation of y = 0.0108 x - 0.0071.

From the equation, we can determine that the gradient of the graph is 0.0108.
The y-intercept of the graph obtained is -0.0071 while the regression (R2) value

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obtained is 0.9941, which signifies that this model is accurate to display the result.
This equation can be used to obtain the initial and final concentration of solution.

Table 3: Average absorbance values for 5, 10, 20 and 30 mg/L of methylene blue
solution using 6g of activated carbon

Concentration of Methylene Blue Solution (mg/L)

Time (min) 5 10 20 30
Absorbance Reading
0 0.046 0.109 0.197 0.324
10 0.038 0.095 0.175 0.289
20 0.029 0.076 0.146 0.250
30 0.016 0.063 0.123 0.221
40 0.010 0.048 0.094 0.186
50 0.002 0.029 0.071 0.147
60 0.002 0.013 0.052 0.112
70 0.002 0.013 0.029 0.079
80 0.002 0.013 0.029 0.048
90 0.002 0.013 0.029 0.048

To achieve the objective of this experiment, the value of qe must be obtained

to determine the best fit of adsorption isotherm. The value of qe can be calculated
using the following equation:

( )

where
qe = equilibrium concentration of methylene blue adsorbed onto activated carbon
(mg/g)
= initial concentration of methylene blue solution (mg/L)
= equilibrium concentration of methylene blue solution (mg/L)
V = volume of solution (L) = 1L
m = mass of activated carbon used (g) = 6g

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The value of is used in the calculation to determine which adsorption isotherm this
experiment fits, either Langmuir isotherm or Freudlich isotherm.

For 5 mg/L of methylene blue solution:

C0 = 0.046

Ce = 0.002

( )

( )

a) Langmuir Isotherm

Linearized Langmuir isotherm model expression:

qe = equilibrium concentration of methylene blue adsorbed onto activated carbon

(mg/g)
q0 = monolayer adsorption capacity of the adsorbent (mg/g)
ce = equilibrium concentration of solution (mg/L)
b = Langmuir adsorption constant (L/mg)

A graph of ce/qe versus ce was plotted for the different concentration of methylene blue
solution using the experimental data to obtain this relation.

Table 4: Table of c0, ce, qe and ce/qe values

Concentration of
Methylene Blue c0 (mg/L) ce (mg/L) qe (mg/g) ce/qe (g/L)
Solution (mg/L)
5 0.046 0.002 0.007 0.273
10 0.109 0.013 0.016 0.813
20 0.197 0.029 0.028 1.036
30 0.324 0.048 0.046 1.043

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 ce/qe (g/L) VS ce (mg/L)
1.400

y = 15.349x + 0.4381
1.200
R²= 0.7211
1.000
ce/qe (g/L)

0.800

0.600

0.400

0.200

0.000
0.000 0.010 0.020 0.030 0.040 0.050 0.060
ce (mg/L)

Figure 5: Graph of ce/qe against ce

Figure 5 shows the relationship between ce/qe and ce, which displays the Langmuir
isotherm relation. The linear equation obtained from the graph plot is:

y = 15.349x + 0.4381

Calculations:

where the slope is identified to be 15.349 while the y-intercept is 0.4381. The
Regression (R2) value is determined to be 0.7211. The slope of the graph can be said

to be and the y-intercept can be said to be the value of . Thus, the value of q0

will be 0.065 mg/g while the value of b will be 35.11 L/mg.

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b) Freundlich Isotherm

Linearized Freundlich isotherm model expression:

( )

= adsorption capacity

n = adsorption intensity

A graph of log vs log was plotted by using the experimental data in order to
obtain the relation.

Table 5: Table of log qe and log ce values

Concentration of
Methylene Blue Solution ce (mg/L) qe (mg/g) log Ce log qe
(mg/L)
5 0.002 0.007 -2.6990 -2.1549
10 0.013 0.016 -1.8861 -1.7959
20 0.029 0.028 -1.5376 -1.5528
30 0.048 0.046 -1.3188 -1.3372

log qe vs log ce
0.0000
-3.0000 -2.5000 -2.0000 -1.5000 -1.0000 -0.5000 0.0000

-0.5000
y = 0.5701x - 0.6496
R²= 0.9702
-1.0000
log qe

-1.3188, -1.3372
-1.5376, -1.5528 -1.5000

-1.8861, -1.7959
-2.0000
-2.6990, -2.1549

-2.5000
log ce

Figure 6: Graph of log qe against log ce

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Figure 6 shows the relationship between log qe and log ce, which displays the
Freundlich isotherm relation. The linear equation obtained from the graph plot is:

y = 0.5701x - 0.6496

where the slope of the graph is 0.5701 while the y-intercept is -0.6496. The
Regression (R2) value for this graph is 0.9702, which is said to be very accurate to be
referred to. From this linear equation, we can comparatively obtain the values for n
and log kf where n = 1.754 while log kf is the y-intercept value of -0.6496. Thus, the
value of kf is 0.5223.

c) Discussions

From the results obtained for both Langmuir and Freundlich Isotherm models,
the best fit of the isotherms can be compared by determining the Regression (R 2)
values of both isotherms. For Langmuir isotherm, the Regression value obtained was
0.7211 while the Regression value obtained for Freundlich isotherm was 0.9702.
Regression value is a statistical measure of how close the values are to the fitted
regression line. Thus, when comparing both the isotherms, Freundlich isotherm has a
closer value to 1 which defines that the Freundlich isotherm is more accurate
compared to the Langmuir isotherm for this experiment. It also proved that this is the
reason why Freundlich isotherm is most commonly used in environmental
engineering and specifically drinking water treatment application.

d) Errors and Recommendations

A few errors were encountered during the experiment and they had to be
modified so that the data obtained was accurate enough for data analysis. First of all,
the electronic balance reading might not be accurate since it is very sensitive towards
any movement in the surrounding. Therefore, the balance should be calibrated
properly before the experiment and the experiment should be carried out in a confined
space where less air movement is observed. Parallax error occurred too as the
readings of the flasks and beakers were not taken accurately. Eye level must be placed
perpendicularly to the scale reading in order to reduce this error.

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 4.0 CONCLUSION

Adsorption is defined as the adhesion of a chemical species on the surface of

particles and is usually used in removing various forms of pollutants such as
pesticides, colorings, pesticides and inorganic chemicals. This method is widely used
in wastewater treatment in removing harmful substances. In this experiment, activated
charcoal C5510 is used as the adsorbent. Activated charcoal is a type of activated
carbon which is highly porous in which surface-active materials will be adsorbed to
its surface. Activated charcoal is an effective adsorbent because of its large surface
area since it is in powder form for this experiment.

In this particular experiment, activated charcoals of three different amounts (2g,

4g and 6g) were added into three beakers which contain same concentration of
methylene blue solution. By using the UV-spectrophotometer, the absorbance values
were obtained. With the interval time of 10 minutes for every trial, the removal
efficiency of methylene blue was calculated using the formula stated in the discussion
part. It is observed that for 6 g of activated charcoal, the removal efficiency reached
78.31% at the 40th minute while for 2g and 4g of activated charcoal samples; they
were still yet to reach 70% of removal efficiency. Therefore, 6g of activated carbon
was chosen to be the constant variable for the second part of the experiment.

The process of adsorption is often studied through graphs known as isotherms. It

is the graph between the amounts of adsorbate (x) adsorbed on the surface of
adsorbent (m). Several isotherm models have been developed to describe adsorption,
including the linear, Freundlich, and Langmuir isotherms. For part B of this
experiment, we used Freundlich isotherm and Langmuir isotherm models to achieve
the objective. The objective was to determine the best fitting adsorption isotherm and
its respective isotherm constants. Graphs for linearized models of both Langmuir and
Freundlich isotherms are plotted where the best fit of the graphs were observed. The
Regression (R2) values were observed where the Regression value of Freundlich
isotherm which is 0.9702 was closer to 1 compared to the value of Langmuir isotherm,
which is 0.7211. Hence, it can be concluded that the Freundlich isotherm is more
accurate compared to Langmuir isotherm and it fits this experiment the best. All in all,
the objective of the experiment was achieved with the theory proved that Freundlich
isotherm is the most commonly applied isotherm in environmental engineering field.

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 5.0 REFERENCES

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https://www.crcpress.com/Activated-Carbon-Adsorption/Bansal-
Goyal/p/book/9780824753443

Adsorption Energetics, Models, and Isotherm Equations. (2005). Activated Carbon

Adsorption,67-143. doi:10.1201/9781420028812.ch2

Adsorption isotherm, kinetic and mechanism studies of some substituted phenols on

activated carbon fibers. (2009, November 17). Retrieved from
https://www.sciencedirect.com/science/article/pii/S1385894709007955

Bansal, R. C., & Goyal, M. (2005). Activated carbon adsorption. Boca Raton: Taylor &
Francis.

Marsh, H., & Reinoso, F. R. (2006). Activated carbon. Boston: Elsevier.

Osman, M. Y. (1994). Activated carbon adsorption: Effects of pore size distribution on

adsorption isotherms and kinetics of polymers.

Porter, K. E., & Jenkins, J. D. (1982). Separation process.

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