Chemical Engineering Laboratory II MAY 2016

CDB 3052
CHEMICAL ENGINEERING LAB II
MAY 2016

EXPERIMENT NO. : 8B -- ACTIVATED CARBON ADSORPTION ISOTHERM & KINETICS

TASK B : ADSORPTION KINETICS
GROUP NO : B8
GROUP MEMBERS : GRACE NGU SOOK ERN 20006
MAHFUZOH BINTI ABU HASSAN 19902
MOHAMMAD AIMAN HAIKAL BIN ROSLAN 19379
VISHNU RAO A/L SUBBA RAE 19829
LAB INSTRUCTOR : MS. VARSHETA SELLAPPAH
EXPERIMENT DATE : 6TH JUNE 2016
SUBMISSION DATE : 13TH JUNE 2016

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TABLES OF CONTENTS

1) Introduction and Objectives…………………………………………………………………………………………………..2

2) Methodology…………………………………………………………………………………………………………………………4

3) Result and Discussion…………………………………………………………………………………………………………….6

4) Conclusion…………………………………………………………………………………………………………………………..18

5) Appendix……………………………………………………………………………………………………………………………..20

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1.0 INTRODUCTION AND OBJECTIVES

1.1 ABOUT ADSORPTION

Adsorption is the chemical separation process of substances, usually liquid or gas that are
required to be extracted from the system for further processes in molecular form. Adsorbates are
commonly known as substances which are attached to the surface and adsorbents are the agents
that provide the contact area for adsorption process to occur. In the adsorption process,
adsorbates will be attached to the surface of the adsorbent which are made up of multiple active
sites. The amount of tiny holes or pores on the adsorbent is vast in amount which provides larger
surface area for adsorption. This process will result with the concentration of the adsorbates in
the solution decreases with time as most of them are attached to the active sites (Define
Adsorption, 2016).

One of the examples of adsorption is the activated carbon mask. The usage of activated
carbon is seen very effective in filtering the sarin gas which is one of the toxic gases exists. Next,
the silica gel which is usually found in new shoes, functions to adsorb water, ensuring that the
soles of the shoe remain dry. It eliminates the natural humidity in the environment (Becker,
2016).

Adsorption Processes are analysed in two different contexts – Isotherms and Reaction
Kinetics. Our task was targeted towards studying reaction kinetics of the process. Reaction
kinetics or chemical kinetics is the rate of chemical processes which involves the elementary
processes, reactions or steps (Vallance, n.d.). The term – ‘kinetics’ deals with the study of
movement of molecules in the chemical process. Pseudo order terms must be understood as it
explains how the reaction of chemical species will yield the pattern of mathematical display in
terms of rate of reaction (Ng, 2014). Both pseudo-first-order and pseudo-second-order graphs
are plotted based on the linearized form of the equation models as shown in the table below. If
the any of the two kinetic model graphs yields a linear line, then the process fits the kinetic
model.

Kinetic models Equation model Linearized form

Pseudo-first order 𝑑𝑞𝑡 𝑞𝑡
= 𝐾1 (𝑞𝑒 − 𝑞𝑡 ) 𝑙𝑛 (1 – ) = 𝑙𝑛 𝑞𝑒 − 𝐾1 𝑡
𝑑𝑡 𝑞𝑒
OR
𝑘1
log(𝑞𝑒 − 𝑞𝑡 ) = log 𝑞𝑒 − 𝑡
2.303
Pseudo-second order 𝑑𝑞𝑡 𝑡 1 1
= 𝐾2 (𝑞𝑒 − 𝑞𝑡 )2 =( )+ ( ) t
𝑑𝑡 𝑞𝑡 𝐾2 𝑞𝑒2 𝑞𝑒
Table 1
1.2 ABOUT THE EXPERIMENT

The experiment that we are required to conduct is the adsorption process of methylene blue

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by activated carbon from the distilled water solution. In this case, adsorbent used is the
granulated activated carbon and the methylene blue acts as the adsorbate. As the adsorbate
contaminated the distilled water, the presence of activated carbon provides the contact area for
extracting out the contaminant.

We have conducted two experiments to study about this adsorption process. In the first
experiment, we manipulated the initial concentrations of methylene blue (MB) which are 10mg/L,
30mg/L and 50mg/L with constant volume of distilled water of 1 litre and amount of activated
carbon of 0.1 g. Next, the second experiment involved the manipulation of different amount of
activated carbon which was 0.1g, 0.3g and 0.5g with a fixed concentration of 50mg/L of
methylene blue solution.

The main objectives of this experiment (B) are:

1. To study the adsorption kinetics of the experiment by determining whether the
process is a Pseudo-first order or Pseudo-second order reaction.
2. To determine its respective kinetic constants.
3. To determine the effect of different concentrations of methylene blue.
4. To determine the effect of different concentrations of activated carbon used.

The general findings of our experiment include that the concentration of methylene blue
decreases over time until equilibrium is reached in which the reverse reaction is then favored,
causing an increase of concentration. Besides, the higher the concentration of the methylene
blue solution, the longer it takes to reach the breaking point which indicates that good
adsorption takes place in a longer period. Next, the mass of methylene blue adsorbed per mass
of activated carbon increases over time. Finally, the adsorption of methylene blue by activated
carbon fits the pseudo-second order reaction.

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2.0 METHODOLOGY

We have conducted two experiments:

Experiment A: To study the reaction kinetics of blue adsorption by activated carbon with the
variation of concentration of methylene blue
Experiment B: To study the reaction kinetics of methylene blue adsorption by activated carbon
with the variation of mass of activated carbon

2.1 APPARATUS USED

The apparatus used in this experiment include:
1. 5 sets of 3 L beaker
2. Laboratory shaker
3. Weighing balance
4. 2 sets of 10 ml Pipette
5. UV Spectrophotometer
6. Stopwatch
7. Glass Columns
8. Container to contain methylene blue and granular activated carbon

2.2 MATERIALS USED

1. Granulated Activated Carbon; sieved, washed of fines, and dried to constant weight at 105
degree Celsius
2. Methylene blue dry powder

2.3 EXPERIMENT A: To study the reaction kinetics of methylene blue adsorption by activated
carbon with the variation of concentration of methylene blue
1. UV Spectrophotometer is turned on to let it warm up for 15 minutes.
2. 10 mg, 30 mg and 50 mg of methylene blue powder is weighted on a weighing balance.
3. 3 beakers filled with equal volume of 1L of distilled water are prepared.
4. The methylene blue powder is poured respectively into all 3 beakers filled with 1L distilled
water to form 10mg/L, 30mg/L and 50 mg/L methylene blue solution.
5. 3 sets of 0.1 g of activated carbon are prepared.
6. Place the beakers of prepared solution under the agitators.
7. The agitator is pre-set to 120 RPM before being turned on.
8. As the agitator is set to ‘START’, the activated carbon sets are then poured simultaneously into
the respective beakers at time zero.
9. At a time interval of 15 minutes, the agitator is stopped and 10 ml of sample is pipetted out of
each beakers.
10. Each 10 ml sample is filled in the glass columns used for UV Spectrophotometer.
11. A bottle is filled with pure distilled water as a control solution and is used to calibrate the UV
Spectrophotometer.
12. The absorbance index of each 10 ml sample is analysed using the UV spectrophotometer and
the data obtained are recorded.
13. The agitator is turned on again and the 9th procedure is repeated for 60 minute (until

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equilibrium is reached).
14. The data obtained are tabulated and attached in the appendix.
15. Then, the calculation for determination of pseudo-first order and second order is performed.

2.4 EXPERIMENT B: To study the reaction kinetics of methylene blue adsorption by activated
carbon with the variation of mass of activated carbon

The procedure for experiment B follows the procedure of experiment A except:

1. For the 2nd step, three set of 50 mg/L methylene blue powder is weighted on the weighing
balance
2. For the 5th step, 0.1g, 0.3g and 0.5g of activated carbon are prepared.
3. All other steps are repeated for duration of 60 minutes.
4. The data obtained are tabulated and attached in the appendix.
5. Then, the calculation for determination of pseudo-first order and second order is performed.

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3.0 RESULTS AND DISCUSSION

3.1 EXPERIMENT A: To study the reaction kinetics of methylene blue adsorption by activated
carbon with the variation of concentration of methylene blue

The following graphs are obtained for this experiment:

Removal Efficiency (%) vs Time (min)

100
Removal Efficiency (%)

80

60

40

20

0
0 10 20 30 40 50 60 70
Time, t (min)

10 mg/L Methylene Blue 30 mg/L Methylene Blue 50 mg/L Methylene Blue

Graph 1: Removal Efficiency vs time graph

Concentration (mg/L) vs time (min)

3.5
Concentration of methylene blue in the solution

3
2.5 y = -0.0006x + 3.1158
R² = 0.0644
2
1.5 y = -0.003x + 1.9096
R² = 0.3285
1
(mg/L)

0.5 y = 0.0002x + 0.7881

R² = 0.001
0
0 15 30 45 60 75
Time (min)

10 mg/L Methylene Blue 30 mg/L Methylene Blue

50 mg/L Methylene Blue Linear (10 mg/L Methylene Blue)
Linear (30 mg/L Methylene Blue) Linear (50 mg/L Methylene Blue)

Graph 2: Concentration of methylene blue solution vs Time Graph

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Breakthrough Curve: C/Co vs time (min)

y = -0.0001x + 0.0637
0.12 R² = 0.3285
0.1
0.08
y = 2E-05x + 0.0788
C/Co

0.06 R² = 0.001

0.04
0.02 y = -1E-05x + 0.0623
R² = 0.0644
0
0 15 30 45 60
Time, t

10 mg/L Methylene Blue 30 mg/L Methylene Blue

50 mg/L Methylene Blue Linear (10 mg/L Methylene Blue)
Linear (30 mg/L Methylene Blue) Linear (50 mg/L Methylene Blue)

Graph 3: Breakthough curve: C/Co vs time graph

qt(mg MB/g AC) vs time (min)

600
Mass of methylene blue adsorbed per mass of

500 y = 6.2569x + 187.54

R² = 0.5005
400
activated carbon (mg/g)

300
y = 3.7755x + 112.36
200 R² = 0.504

100
y = 1.2267x + 36.847
0 R² = 0.4992
0 20 40 60 80

Time, t
10 mg/L Methylene Blue
30 mg/L Methylene Blue
50 mg/L Methylene Blue

Graph 4: Graph of Mass of methylene blue adsorbed per mass of activated carbon used, qt
vs time, t

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Pseudo-first order: log( qe-qt) vs time

2.5
2 y = -0.0269x + 1.1401
1.5 R² = 0.4846
log (qe-qt)

1
0.5
y = -0.0248x + 0.9297
0 R² = 0.261
-0.5 0 10 20 30 40 50 60 + 1.496870
y = -0.04x
R² = 0.8092
-1
-1.5
time, t

10 mg/L Methylene Blue 30 mg/L Methylene Blue

50 mg/L Methylene Blue Linear (10 mg/L Methylene Blue)
Linear (30 mg/L Methylene Blue) Linear (50 mg/L Methylene Blue)

Graph 5: Pseudo-first-order graph: Log (qe-qt) vs time,t

Pseudo-second order : t/qt vs time

(min-g GAC/mg MB) vs time (min)
0.7
0.6 y = 0.0108x + 0.0007
R² = 0.9997
0.5
t/qt(min-g/mg)

0.4
y = 0.0035x + 0.0001
0.3 R² = 1
0.2
y = 0.0021x + 6E-06
0.1 R² = 1
0
0 10 20 30 40 50 60 70
Time,t (min)

10 mg/L Methylene Blue 30 mg/L Methylene Blue

50 mg/L Methylene Blue Linear (10 mg/L Methylene Blue)
Linear (30 mg/L Methylene Blue) Linear (50 mg/L Methylene Blue)

Graph 6: Pseudo-second-order graph: t/qt(min-g/mg) vs time,t(min)

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3.2 EXPERIMENT B: To study the reaction kinetics of methylene blue adsorption by activated
carbon with the variation of mass of activated carbon

Removal Efficiency (%) vs time (min)

100
Removal Efficiency (%)

80
60
40
20
0
0 10 20 30 40 50 60 70
Time, t

100 mg Activated Carbon 300 mg Activated Carbon 500 mg Activated Carbon

Graph 1: Removal Efficiency vs time graph

Concentration (mg/L) vs time (min)

3.2
Concentration of methylene blue in the

3.1
y = -0.0005x + 3.113
3 R² = 0.04
y = -0.0005x + 3.0339
R² = 0.0079
solution (mg/L)

2.9
2.8
y = -0.0047x + 3.0989
2.7 R² = 0.6831
0 15 30 45 60 75
Time (min)

100 mg Activated Carbon 300 mg Activated Carbon

500 mg Activated Carbon Linear (100 mg Activated Carbon)
Linear (300 mg Activated Carbon) Linear (500 mg Activated Carbon)

Graph 2: Concentration of methylene blue solution vs Time Graph

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Breakthrough Curve: C/Co vs time (min)

0.065
0.064 y = -9E-06x + 0.0607
0.063 R² = 0.0079
0.062
0.061 y = -9E-06x + 0.0623
C/Co

0.06 R² = 0.04
0.059
0.058
0.057 y = -9E-05x + 0.062
0.056 R² = 0.6831
0.055
0 15 30 45 60
Time, t (min)

100 mg Activated Carbon 300 mg Activated Carbon

500 mg Activated Carbon Linear (100 mg Activated Carbon)
Linear (300 mg Activated Carbon) Linear (500 mg Activated Carbon)

Graph 3: Breakthough curve: C/Co vs time graph

qt (mg MB/gAC) vs time(min)

600
Mass of methylene blue adsorbed per mass of activated

500
y = 6.2561x + 187.55
R² = 0.5004
400

300
y = 1.2602x + 37.521
carbon (mg/g)

R² = 0.5038
200

100 y = 2.0889x + 62.621

R² = 0.5004
0
0 20 40 60 80

Time, t (min)
100 mg Activated Carbon
300 mg Activated Carbon
500 mg Activated Carbon

Graph 4: Graph of Mass of methylene blue adsorbed per mass of activated carbon used, qt
vs time, t

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Pseudo-first order: log( qe-qt) vs time

3

2
log (qe-qt)

0 y = -0.0389x + 1.351
0 10 20 30 40 50 R² = 0.625760 70
-1 y = -0.0482x + 1.6981
y = -0.0422x + 1.1298 R² = 0.6597
-2 R² = 0.5972
time, t (min)

100 mg Activated Carbon 300 mg Activated Carbon

500 mg Activated Carbon Linear (100 mg Activated Carbon)
Linear (300 mg Activated Carbon) Linear (500 mg Activated Carbon)

Graph 5: Pseudo-first-order graph: Log (qe-qt) vs time,t

Pseudo-second order : t/qt (min-g GAC/mg

MB) vs time (min)
0.8
t/qt (min-g GAC/mg MB)

y = 0.0106x + 0.0003
0.6 R² = 1 y = 0.0064x + 4E-05
R² = 1
0.4
y = 0.0021x + 3E-06
0.2 R² = 1

0
0 10 20 30 40 50 60 70
Time,t (min)

100 mg Activated Carbon 300 mg Activated Carbon

500 mg Activated Carbon Linear (100 mg Activated Carbon)
Linear (300 mg Activated Carbon) Linear (500 mg Activated Carbon)

Graph 6: Pseudo-second-order graph: t/qt(min-g/mg) vs time,t(min

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3.3 DISCUSSION
There are two experiments that have been set up which are determining adsorption kinetics
and adsorption equilibria of the activated carbon.

3.3.1.0 EXPERIMENT A

For experiment A, the methylene blue solution was prepared with three different
concentrations which are 10 mg/L, 30mg/L and 50 mg/L respectively. The process variables
are shown in the table below:

Manipulated Variable Concentration of methylene blue solution (mg/L

Constant Variable 1. Volume of Distilled Water – 1Litre
2. Mass of activated carbon – 100 mg (0.1g)

3.3.1.1 Discussion on Graph 1: Removal Efficiency vs time Graph

The goal for our experiment was to achieve a minimum of 70% removal efficiency over
time. We plotted the removal efficiency vs time graph to ensure that the experiment
conducted was at least 70% removal efficiency of methylene blue by using activated carbon.
We can see that the adsorption process of methylene blue by activated carbon reached 70%
at the 11th minute and reached about 94% at 15 minutes continuously until the end of the
experiment. Based on Graph 6, it shows that the experiment was a success since the three
samples of solutions reaches above 70 % of removal efficiency at the time intervals in which
the samples were collected.

Since we had achieved our goal, we further analysed our data based on 5 different
graphs as follows:
Category Graphs Plotted
General 1. Concentration vs time Graph
2. C/Co vs time Graph
3. Mass of methylene blue adsorbed/ mass of granulated activated
carbon used, qt vs time Graph
Adsorption Kinetics 4. Pseudo-first order graph
5. Pseudo-second order graph

3.3.1.2 Relationship between absorbance value and concentration

The absorbance of methylene blue solution for the three samples was measured for 60
minutes at time interval of 15 minutes with the UV spectrophotometer. According to the
methylene blue calibration curve as provided in appendix 1, absorbance is directly
proportional to the concentration in methylene blue. The lower the absorbance reading,
the lower the concentration of the solution which indicates that more methylene blue had
being adsorbed by the activated carbon. From table obtained, our absorbance values for all
three samples were decreasing from time zero to the end of experiment.

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3.3.1.3 Discussion on Graph 2: Concentration of methylene blue vs time Graph

From 0 min through 60 min, the concentration of methylene blue obtained fluctuates.
However, by linear regression as shown in graph 2, we observed that 30 mg/L and 50 mg/L
show a negative gradient. This is because as time goes by, the methylene blue present in
the solution is adsorbed by the activated carbon. The graph for 10 mg/L methylene blue
solution shows a positive gradient because most of the methylene blue has been adsorbed
by the activated carbon at the early stage of the process (around 15 min). Once equilibrium
has reached, the activated carbon releases the methylene blue into the solution again as
the reaction now favour the production of methylene blue.

Comparing between the three samples, 50mg/L methylene blue has the highest points
because it has the highest concentration, while 30 mg/L methylene blue has the
intermediate points and 10mg/L has the lowest points.

3.3.1.4 Discussion on Graph 3: Breakthrough Curve

The graph of C/Co vs time depicts the breakthrough curve. C/Co is the ratio of
concentration of methylene blue solution at time, t to its initial concentration against time.
The reason of plotting this graph is to allow us to determine the break point of the
adsorption. Break point occurs when the concentration of the methylene blue solution
leaving the activated carbon spikes as unadsorbed methylene blue begins to emerge.

Based on the values we obtained from our experiment, we can see that all three curves
fluctuate, they decrease first then increase. This is because as equilibrium state reaches, the
reaction favours the reverse reaction; while the reaction goes backward and releases more
methylene blue from the activated carbon, the reaction begins to reach equilibrium and
favours forward reaction again. This shows that adsorption is a transient process.

Based on this deduction, we can say that for the first equilibrium state, the breakpoint
of 10 mg/L methylene blue solution is at 15 minutes; breakpoint of 30 mg/L methylene
blue solution is at 30 minutes; and the breakpoint of 50 mg/L methylene blue solution is at
45 minutes. This trend shows that the higher the concentration of the methylene blue
solution, the longer the time of good adsorption by activated carbon because more
methylene blue is available for the separation process.

Comparing between the three samples, 10mg/L has the highest points because it has
the lower initial concentration than the rest. With that, the denominator is lower and
contributes to a higher ratio of concentration of methylene blue solution at time,t to initial
concentration of methylene blue solution at time 0.

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3.3.1.5 Discussion on Graph 4: Mass of methylene blue adsorbed/ mass of granulated

activated carbon used, qt vs time Graph

Graph 4 shows a positive gradient for both 30mg/L and 50 mg/L of methylene blue
solution while 10 mg/L shows a negative gradient graph. We deduce that as time increases,
mass of methylene blue adsorbed per mass of activated carbon increases as the activated
carbon gradually reaches its saturation point. When the activated carbon reaches it
saturation point, it will stop adsorbing methylene blue from the solution and it will go in
the reverse reaction, which explains the case of 10 mg/L methylene blue solution. As the
breakpoint of 10 mg/L methylene blue solution strikes at 15 min, the activated carbon
becomes saturated and the concentration of the methylene blue adsorbed by the activated
carbon decreases.

Comparing between the three samples, 50mg/L methylene blue has the highest points
because it has the highest concentration, while 30 mg/L methylene blue has the
intermediate points and 10mg/L has the lowest points.

3.3.1.6 Discussion on Graph 5 and 6: Adsorption Kinetics of Methylene Blue by Granulated

Activated Carbon

One of our main objectives of this experiment was to determine the adsorption kinetics
of our experiment by determining whether our adsorption process conforms to the the
linearized form of pseudo-first-order or pseudo-second-order. For this purpose, we have
plotted two graphs – log (qe-qt) vs t (pseudo-first-order) and t/qt vs t (pseudo second order)
and observe which graphs yield a linear graph for all three samples of methylene blue
solution. In the log (qe-qt) vs t graph, the gradient of the graphs were not showing
consistent trends and has a very low coefficient of determination, R2 , indicating that the
data are far from the fitted linear regression line. On the other hand, the graph of t/qt vs t
yields smooth linear graphs for all three samples and has a near to 1 R2 value, showing that
the data fits well with its fitted regression line. We can thus, conclude that the adsorption
process of methylene blue by activated carbon conforms to the pseudo-second order
reaction.

For Experiment A, with pseudo-second order reaction, the qe and K2 value obtained is as
follows:
Table 8: qe obtained from experiment
qe Experimental Value
10 mg Methylene Blue/ 30 mg Methylene Blue/ 50 mg Methylene Blue/
100 mg Activated Carbon 100 mg Activated Carbon 100 mg Activated Carbon
92.59259259 285.7142857 476.1904762

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Table 9: K2 obtained from experiment

K2 Experimental Value
10 mg Methylene Blue/ 30 mg Methylene Blue/ 50 mg Methylene Blue/
100 mg Activated Carbon 100 mg Activated Carbon 100 mg Activated Carbon
0.063 0.1225 19.44

3.3.2.0 EXPERIMENT B

Although this experiment is not required from the lab manual, we decided to conduct this
experiment to see if there are any changes by manipulating the amount of activated carbon used.
The process variables are shown in the following table:

Manipulated Variable Mass of activated carbon – 100 mg, 300 mg, 500 mg
Constant Variable 1. Volume of Distilled Water – 1Litre
2. Concentration of methylene blue solution – 50 mg/L

We had also conducted data analysis on the following graphs:

Category Graphs Plotted

General 1. Concentration vs time Graph
2. C/Co vs time Graph
3. Mass of methylene blue adsorbed/ mass of granulated activated
carbon used, qt vs time Graph
Adsorption Kinetics 4. Pseudo-first order graph
5. Pseudo-second order graph

3.3.2.1 Discussion on Graph 1: Removal Efficiency vs time Graph

The goal for our experiment was to achieve a minimum of 70% removal efficiency over
time. From the graph, we observed that the adsorption process of methylene blue by
activated carbon reached 70% at the 11.5th minute and reached about 94% at 15 minutes
continuously until the end of the experiment. Thus, the experiment achieved our goal.

3.3.2.2 Discussion on Graph 2: Concentration of methylene blue vs time Graph

Based on Graph 2, the graph points for the 500mg activated carbon solution is the
lowest when it is compared to the graph points of the 100 activated carbon solution and 300
mg activated carbon solution. This is because the 500mg activated carbon solution contains
more activated carbon than the 100mg solution and the 300mg solution. The higher amount
of activated carbon allows more methylene blue to be adsorbed onto its surface.

For all three samples, the graphs will decrease first then increase at some point of time.
This is because as time goes by, methylene blue will be adsorbed onto the surface of
activated carbon until reaches equilibrium state. Once they reached equilibrium state, the

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concentration then increases because the active carbons need to be reactivated and do so
by releasing the methylene blue adsorbed on its surface back to the solution

3.3.2.3 Discussion on Graph 3: Breakthrough Curve

From the graph of C/C0 vs time, the breakpoint for 100mg activated carbon is 15
minutes; the breakpoint for 100mg activated carbon is 30 minutes; the breakpoint for
100mg activated carbon is 45 minutes. The breakpoint is decided at the point at which the
C/Co value starts to increase indicating that the activated carbon has reached its saturation
point and needs to release the methylene blue back to the solution.

3.3.2.4 Discussion on Graph 4: Mass of methylene blue adsorbed/ mass of granulated

activated carbon used, qt vs time Graph

A positive gradient is obtained for all three graphs. This shows that mass of methylene
blue adsorbed per mass of activated carbon increases over time. Besides that, among all
three samples, 100 mg Activated Carbon shows the highest values while 500 mg Activated
Carbon shows the lowest values. This is because since the concentration of methylene blue
used is kept constant for each sample, more methylene blue is adsorbed in 1mg of activated
carbon/ 100 mg of activated carbon; while methylene blue adsorbed is highly distributed in
the entire 500 mg Activated carbon, thus 1mg of activated carbon/ 500 mg of activated
carbon will definitely adsorbed lesser methylene blue.

3.3.2.5 Reason for Conducting two experiments and Discussion on Adsorption Kinetics

Although the mass of the activated carbon does not have a direct effect on the linearized
form of pseudo-first-order and pseudo-second order, we notice that there is an effect of the
different mass of activated carbon on qt (which is the mass of methylene blue adsorbed/ mass of
activated carbon used). Since qt is found in the linearized form of both pseudo-first order and
pseudo-second order, we deduce that changing the mass of activated carbon will also change the
adsorption kinetics of the adsorption process. However, based on the graphs obtained for
pseudo-first order and pseudo-second order, we can see that the graphs still conform to
pseudo-second order which further validates the findings obtained from the first part of the
experiment.

For Experiment A, with pseudo-second order reaction, the qe and K2 value obtained is as
follows:
Table 8: qe obtained from experiment
qe Experimental Value
50 mg Methylene Blue/ 50 mg Methylene Blue/ 50 mg Methylene Blue/
100 mg Activated Carbon 300 mg Activated Carbon 500 mg Activated Carbon
476.1904762 156.25 94.33962264

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Table 9: K2 obtained from experiment

K2 Experimental Value
50 mg Methylene Blue/ 50 mg Methylene Blue/ 50 mg Methylene Blue/
100 mg Activated Carbon 300 mg Activated Carbon 500 mg Activated Carbon
1.47 1.024 0.374533333

Then, this brought us to another discussion, which is better for the study of adsorption
kinetics? Changing the concentration of methylene blue or mass of activated carbon?
Pseudo-first order and pseudo-second order are usually used to characterize when relation
between compositions of reacting species gets complicated. This then depends on the
approximation that when one of the reactant is present in large excess, the concentration is
hardly changed during the course of the reaction, then the order of the reaction is characterize
by the other reactant. In both experiments, activated carbon is remain in excess. However, in
experiment B, since concentration is kept constant and activated carbon is remain in excess,
there won’t be a significant effect on the reaction kinetics as compared to experiment A. Thus,
we deduce that Experiment A is a more useful approach for studying the adsorption kinetics of
the experiment.

3.4 ERRORS AND MODIFICATION

1. Error: The vial which contains the samples for the spectrophotometer has stains
methylene blue from previous experiments
Modification: Make sure the vials are cleaned thoroughly before conducting the
experiment to avoid staining which causes the reading of the spectrophotometer to
be inaccurate

2. Error: Fluctuating weight during weighing of methylene blue and granular activated
carbon
Modification: Make sure the glass walls of the electronic balance are closed during
reading of the weight of methylene blue and granular activated carbon in order to
attain a more accurate reading.

3. Error: The vials containing samples for the spectrophotometer contains droplets of
water
Modification: Make sure the vials are completely dry before pipetting the sample of
methylene blue solution in order to avoid the water droplets from causing error in
the reading of the spectrophotometer

4. Error: Pipette still contains residue from previous samples

Modifications: Wash the pipette thoroughly in order to remove any residue from the
previous samples and dry thoroughly before moving on to the next sample to avoid
errors in spectrophotometer reading

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5. Error: Parallax error during the filling in of 10mL vial samples. The inaccurate amount
of the methylene blue solutions will cause the absorbance index obtained from the UV
Spectrophotometer to deviate from its actual readings
Modification: Make sure the eye level is perpendicular to the meniscus level of the
samples.

4.0 CONCLUSION

From the task we were given, we were asked to (1) achieve at least a 70% removal of
efficiency of methylene blue using activated carbon and (2) to determine the adsorption
kinetics of the reaction as well as (3) its respective kinetic constants. We decided to carry out
two experiments in order to achieve this task. In the first we varied the concentration of
methylene blue in the solution and in the second we varied the mass of activated carbon.

We managed to achieve the first task which is to attain a removal efficiency of 70% of
methylene blue using the activated carbon. In both the experiments the removal efficiency
of methylene blue managed to reach about 94% at 15 minutes.

For both experiments, we found that concentration of methylene blue solution

decreases over time. This is because the methylene blue in the system is adsorbed by the
activated carbon as time passes. Once equilibrium has reached, the activated carbon
releases the methylene blue into the solution again as the reaction now favour the reverse
reaction -- production of methylene blue. Next, the higher the concentration of the
methylene blue solution allows longer time of good adsorption by activated carbon, causing
a longer period needed to reach the breakpoint. Besides that, mass of methylene blue
adsorbed per mass of activated carbon,qt increases over time as the activated carbon
gradually reaches its saturation point.

In order to determine the adsorption kinetics we plotted two graphs, log (qe-qt) vs t
(pseudo-first-order) and t/qt vs t (pseudo second order). We determine whether the
adsorption kinetics is pseudo first-order or pseudo-second order by observing which graph
yields a linear result. We manage to attain a mother linear graph in which all three samples
has a near to 1 R2 value using the linearized form of pseudo-second order. Thus, we can say
that the reaction conforms to a pseudo second-order reaction.

For Experiment B, we wanted to see if changing the mass of the active carbon would
affect the adsorption kinetics of the reaction. The higher the mass of activated carbon leads
to a higher amount of methylene blue to be adsorbed onto its surface. This causes the
solution with the greatest amount of activated carbon to reach its breakpoint later than the
rest. This however did not affect the adsorption kinetics of the reaction as it still conforms to
the pseudo second-order adsorption kinetics.

We also deduce that Experiment A would be better than Experiment B when it comes to
determining the adsorption kinetics. This is because the activated carbon in both
experiments would be in excess and the effect of changing the concentration of methylene

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blue will be more significant than changing the mass of activated carbon.

To conclude, we achieved our objectives and understand the importance of studying

reaction kinetics of adsorption process. Activated Carbon is a highly effective agent that
possesses high levels of micro porosity, thus having a high surface area to volume ratio of
adsorption process. It helps to treat toxic and waste in water and others which would help
Mother Earth. Hence, the use of activated carbon in the industries should be further
explored for the benefit of mankind.

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5.2 CALCULATIONS
Legend: MB= Methylene Blue; AC= Activated Carbon

NO. AIM VARIABLES INVOLVED FORMULAE USED

1. To find the average Trial1, Trial2, and Trial3 Average Absorbance=
value of absorbance Trial1 + Trial2, + Trial3
value. 3
2. To find the y,x; Y=0.177x; where it is
concentration with y=absorbance of MB on AC; calibration curve general
given absorbance x=concentration of MB at formula
value. Time,t.
3. To find the qt=mass of MB adsorbed/ 𝑉
qt= (Co-Ct)
concentration of MB on mass of AC used; 𝑚

AC. Co= initial conc. of MB;

Ct=conc. of of MB at t;
V=sample volume;
m=weight of AC.
4. To find ratio of C: conc. of MB at time, t; C
Ratio=
concentration of MB to Co=initial conc. of MB. Co

its initial concentration.

5. To find the percentage C: conc. of MB at time, t; Co − C
%= x 100
removal of MB by AC. Co=initial conc. of MB. Co
6 To find the qe M: gradient 1
𝑚=
experimental value for Qe: equilibrium value of 𝑞𝑒
pseudo second order mass of MB adsorbed/ mass
reaction of AC
7 To find the K2 C: intercept 1
𝑐= ( )
experimental value for K2: kinetic constant 𝐾2 𝑞𝑒2
pseudo second order Qe: equilibrium value of
reaction mass of MB adsorbed/ mass
of AC

SAMPLE CALCULATION

From the table above:

1) To find the average value of adsorbance value.

Trial1+ Trial2,+ Trial3
Average value of adsorbance value=
3

0.547+0.545+0.546
For Methylene Blue of 50mg/L = 3
= 𝟎. 𝟓𝟒𝟔 𝐦𝐠/𝐋

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2) To find the concentration with given absorbance value. By using the calibration curve as
shown below:

From the result:

y=0.177x;
y is 0.549 of 10 mg/L of Methylene Blue at 15 minutes of the stirring period;

Hence,
0.549 𝒎𝒈
= 𝟑. 𝟏𝟎𝟐 of Methylene Blue adsorped with 0.1g of Activated Carbon after 15 minutes.
0.177 𝑳

3) To find the concentration of MB on AC.

𝑉
By using the formulae provided : qt= (Co-Ct) 𝑚;

mg mg 1L
At 15 minutes, qt= (10 L
− 3.102
L
) 100mg of AC

qt= 0.069 mg of Methlene Blue per 100 mg of Activated Carbon.

4) To find ratio of concentration of MB to its initial concentration.

At 15 minutes, the ratio of concentration of Methylene Blue at t to its initial
concentration as follow:

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C
Ratio=Co;

3.102mg/L
= = 0.3102.
10mg/L

5) To find the percentage removal of MB by AC.

At 15 minutes, the percentage of as follow:
Co−C
= Co
x 100;

10mg/L−3.102mg/L
= x 100 = 68.98% removal of Methylene Blue adsorbed by 100 mg of
10mg/L

Activated Carbon.
6) To find the qe experimental value
From pseudo-second order reaction, the gradient is 1/qe.
Experiment A
For 10 mg/L of methylene blue solution, m = 0.0108.
Thus from the equation m= 0.0108 = 1/qe,
Qe = 1/0.0108 = 92.59259259
Experiment B
For 100 mg activated carbon, m = 0.0021.
Thus from the equation m= 0.0021 = 1/qe,
Qe = 1/0.0021 = 476.1904762

7) To find the K2 experimental value

From pseudo-second order reaction, the intercept is c= 1/(k2*qe^2).
Experiment A
For 10 mg/L of methylene blue solution, c= 0.0007.
Thus from the equation c= 0.0007 = 1/(k2*qe2,
K2 = 1/(0.0007*(92.59259259)2 )= 0.063
Experiment B
For 100 mg activated carbon, c= 0.000003.
Thus from the equation c= 0.000003 = 1/(k2*qe2,
K2 = 1/ (0.000003*(476.1904762)2 )= 1.47

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5.3 PICTURES OF APPARATUS AND MATERIALS

MATERIALS

Figure 1: Granular Activated Carbon and Methylene Blue Used

APPARATUS

Figure 2: 1 Litre Beakers and Laboratory Shaker Used

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Figure 3: Weighing Balance Used

Figure 4: UV Spectrophotometer used

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Figure 5: Glass column used for the obtained samples

Figure 6: Container used to contain methylene blue and activated carbon

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OBSERVATION

Figure 7: 10mg/L Methylene Blue; 50 mg/L Methylene Blue and 30 mg/L Methylene Blue

** Notice the difference in saturation of the blue colour after 15 minute: 10mg/L remains
the lightest blue, 50 mg/L remains the darkest blue.

5.4 REFERENCES

 Define adsorption? What is the difference between adsorption and

absorption? Define Adsorption. Retrieved from
http://www.thebigger.com/chemistry/surface-chemistry on 8th June 2016.
 Becker, A. Demand Media. Examples of Adsorption. Retrieved from
http://education.seattlepi.com/examples-adsorption-5183.html on 8th June
2106.
 The significance of pseudo-first order and pseudo-second order in adsorption process.

Retrieved from https://www.researchgate.net/post on 8th June 2016.

 Adsorption Isotherm. (2010). Retrieved from

http://www.chemistrylearning.com/ on 8th June 2016.

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