Abstract

This study investigates the adsorption of Cu(II) ions using carbon as the adsorbent,
focusing on the effects of solution pH and contact time. The batch method, chosen for its
simplicity, was employed to determine the variations in adsorption percentage and
adsorption capacity (Qc) under different conditions. At pH levels of 4, 5, 6, and 7, the
adsorption percentages were 33.2%, 61.6%, 76%, and 101.2%, respectively, with
corresponding Qc values of 1.68 mg/g, 3.08 mg/g, 3.8 mg/g, and 5.06 mg/g. These results
indicate that higher pH values enhance adsorption efficiency. Contact times of 10, 20, and
30 minutes yielded adsorption percentages of 32.8%, 43.6%, and 32.8%, respectively, with
Qc values of 1.64 mg/g, 2.18 mg/g, and 1.64 mg/g. The optimal contact time was
determined to be 20 minutes, as equilibrium was achieved quickly, with no significant
improvement observed beyond this duration. Overall, the study highlights the significant
influence of pH and the importance of optimizing contact time to enhance the adsorption of
Cu(II) ions using carbon.
 Chapter 1

Introduction

1.1 Objective of the study

To study the effects of solution pH and contact time on the adsorption process
using the batch method.

1.2 Literature review

Adsorption is a process where a gaseous, liquid, or solid substance, known as the
adsorbate, adheres to the surface of a solid or liquid, called the adsorbent or sorbent. In
liquid-gas or liquid-liquid adsorption systems, where the liquid acts as the adsorbent, the
layer that forms on the liquid's surface is referred to as a film or emulsion. In solid-gas or
solid-liquid systems, where the solid is the adsorbent, the surface layer is described by the
interfacial layer model, which can involve either physical or chemical adsorption. Physical
adsorption is driven by weak Van der Waals forces, while chemical adsorption involves the
formation of chemical bonds, such as ionic or covalent bonds, between the adsorbent and
the adsorbate. The most prevalent types of adsorption are physical and chemical
adsorption, with interactions based on Van der Waals forces or ion exchanges. The
adsorbent contains "adsorption sites," which are pores where adsorption potential is
highest. Since these interactions can overlap and are not mutually exclusive, many models
have been developed to understand and calculate the overall adsorption effects accurately.
(Alaqarbeh, 2021; Wang, 2020)

According to the principles of adsorption, this phenomenon happens as a result of

contact between adsorbate molecules and the adsorbent's surface. This explanation leads to
the conclusion that adsorbates are substances or materials containing molecules that create
an adhesive layer on an adsorbate when the two contact, whereas adsorbents are materials
on which the adsorption occurs. Activated carbon is a popular adsorbent because it is
inexpensive and the surface chemistry may be easily adjusted for a given use. Other
adsorbents include zeolites, silica gel, and metal organic frameworks. There are no
specifics for adsorbates because they contain all molecules that can be adsorbed on the
adsorbent's surface. Adsorbates include phenol, salicylic acid, ethanol, methylparaben, and
virtually any other chemical. (Bernal, 2018; Shabir, 2020; Patel, 2021)

An effective adsorbent should have a high adsorption capacity, rapid adsorption

kinetics, small pore size, extensive surface area, excellent porosity, significant micropore
volume, and a comprehensive pore network. These properties allow molecules to access
the interior of the adsorbent, making it suitable for the adsorption process (Priyanto et al,
2021). The molecular size of the adsorbate influences the adsorption process on the
adsorbent medium, especially on porous media; adsorbate molecules larger than the pore
size of the adsorbent will naturally have a slower adsorption rate compared to smaller
molecules; adsorbate molecules with high solubility are more difficult to separate from
their solvent, leading to less efficient adsorption. Adsorbate molecules with other
characteristics that need to be taken into account during the adsorption process include
molecular size, solubility, chemical composition, and others (Sirajuddin & Harjanto, 2018).

Since hydrogen ions are abundantly present in solutions with lower pH, the surface
of the adsorbent becomes positively charged, which electrostatically attracts the negatively
charged dye molecules. Conversely, at higher solution pH, the adsorption ratio tends to
decline. The differences in adsorption equilibrium can be attributed to the physicochemical
properties and structure of the adsorbate and adsorbent. Therefore, maintaining the solution
pH slightly above 4 is recommended to achieve the highest adsorption capacity for the dye.
Ideally, the adsorption of the dye should occur under weakly acidic or neutral conditions
(Nguyen et al, 2020). Research on the effect of contact time on the adsorption of reactive
red-120 dye using bintaro shell adsorbent showed that varying the contact time between
10-90 minutes impacts the adsorption capacity. The results indicated an increase in
adsorption capacity from 10 to 30 minutes, with optimal adsorption conditions occurring at
40 minutes. Beyond 40 minutes, a decrease in adsorption capacity was observed due to
desorption, as the reduced number of active sites on the adsorbent surface led to the dye
forming a new layer that covered the adsorbent surface. Another study on the adsorption of
reactive red-120 dye using oil palm coir adsorbent with contact times ranging from 10 to
90 minutes found that optimal adsorption conditions occurred at a contact time of 30
minutes (Kurniawati and Indriyanti, 2021).

For data processing and modeling, removal efficiency was calculated using the
following equation:

𝐶𝑖−𝐶𝑓
Removal= 𝐶𝑖
× 100 %

where (Ci) is the initial concentration (mg/L) and (Cf ) is the final concentration (mg/L) of
thorium ions. Additionally, the adsorption capacity (q) represents the amount of ion
adsorbed on a given amount of adsorbent (mg/g), can be described by:

where (C0) and (Ce) are the initial and equilibrium concentrations of a particular substance,
respectively. Here, (V) denotes the volume of the solution (mL), and (m) is the mass of the
adsorbent (mg) (Pei et al, 2015).
 Chapter 3
Results and Discussion

3.1 Result
3.1.1 Table of Observation Results

No. Observation Treatment

Effect of Solution pH

1. 0.25 grams of activated carbon were The activated carbon was a black colored
weighed four times using an analytical powder.
balance, and were transferred unto 4
erlenmeyer flasks.

2. Unto the filled erlenmeyer flasks, 25 A clear Cu(II) solution was mixed with the
mL of 100 ppm Cu(II) solution were activated carbon.
added.

3. Using NaOH and HCl, the pH of the The pH indicator was used to show the
solutions were made to a pH of 4, 5, 6, colors corresponding with each pH, thus
and 7, respectively based on their indicating when each solution has the
erlenmeyer flask with the help of desired pH value.
universal pH indicators.

4. The erlenmeyer flasks were covered The shaker was left for 20 minutes, and the
using aluminum foils and shaken obtained solution was still mixed with
using a shaker at room temperature for activated carbon. No visible changes occur
20 minutes at 170 RPM. between the obtained mixtures.

5. The shaken flasks were then filtered The obtained filtrate was a clear solution,
using filter papers and glass funnels to while the black carbon was left on the
obtain the filtrates in a small vial. filter paper.

6. The obtained filtrates that contain Visible flames on the AAS, and
Cu(II) were then taken to an AAS for absorbance data was obtained in the
its absorbance value to be obtained. computer.

Effect of Contact Time

1. 0.25 grams of activated carbon were The activated carbon was a black colored
weighed thrice using an analytical powder.
balance, and was transferred unto 3
erlenmeyer flasks.
 2 Unto one of erlenmeyer flasks, 25 mL A clear Cu(II) solution was mixed with the
of 100 ppm Cu(II) solution were activated carbon.
added.

3 The erlenmeyer flasks were covered The shaker was left for 10, 20, and 30
using aluminum foils, and one of them minutes, and the obtained solution was still
was shaken using a shaker at room mixed with activated carbon. No visible
temperature for 10 minutes at 170 changes occur between the obtained
RPM, another was shaken for 20 mixtures.
minutes, and the last one for 30
minutes.

4. The shaken flasks were then filtered The obtained filtrate was a clear solution,
using filter papers and glass funnels to while the black carbon was left on the
obtain the filtrates in a beaker. filter paper.

5. The obtained filtrate that contains Visible flames on the AAS, and
Cu(II) was then taken to an AAS for absorbance data was obtained in the
its absorbance value to be obtained. computer.

3.1.1 Experimental Results Data

3.1.1.1 Effect of Solution pH
Cu (II) standard solution absorbance:
No Sample Absorbance

1 10 ppm 0.0145

2 20 ppm 0.0279

3 30 ppm 0.0352

4 40 ppm 0.0443

Cu (II) sample absorbance:

No Sample Absorbance

1 pH 4 0.0397

2 pH 5 0.0255

3 pH 6 0.0120

4 pH 7 0.0057

3.1.1.2 Effect of Contact Time

Cu (II) Sample Absorbance:
No Sample Absorbance

1 10 Minutes 0.0399

2 20 Minutes 0.0345

3 30 Minutes 0.0399

3.2 Calculation
3.2.1 Standard curve and linear regressions of Cu (II) with concentration:

3.2.2 Calculation Formulas

Standard Cu (II) Regression : y = 0.001x + 0.0063
𝐶𝑜 − 𝐶𝑠
% Adsorption : 𝐶𝑜
𝑥 100%
(𝐶𝑜 − 𝐶𝑠) 𝑉
Qc : 𝑊
mg/g
With:
Y = Absorbance Value
X = Concentration (ppm) → used to find the Cs value
Co = concentration of substance before adsorption (mg/L)
Cs = concentration of substance after adsorption (mg/L)
V = volume of solutions (L)
W = adsorbent mass (g)
Qc = adsorption capacity (mg/g)

3.2.3 Effect of Solution pH Calculations

Sample 1 (pH 4)
Cs : 0.0397 = 0.001x + 0.0063
 : 0.001x = 0.0334
Cs = 33.4 ppm
50 𝑝𝑝𝑚 − 33.4 𝑝𝑝𝑚
% Adsorption : 50 𝑝𝑝𝑚
𝑥 100%
: 33.2 %
(50 − 33.4)𝑝𝑝𝑚 (0.025 𝐿)
Qc : 0.25 𝑔𝑟𝑎𝑚
: 1.68 mg/g

Sample 2 (pH 5)
Cs : 0.0255 = 0.001x + 0.0063
: 0.001x = 0.0192
Cs = 19.2 ppm
50 𝑝𝑝𝑚 − 19.2 𝑝𝑝𝑚
% Adsorption : 50 𝑝𝑝𝑚
𝑥 100%
: 61.6 %
(50 − 19.2)𝑝𝑝𝑚 (0.025 𝐿)
Qc : 0.25 𝑔𝑟𝑎𝑚
: 3.08 mg/g

Sample 3 (pH 6)
Cs : 0.0120 = 0.001x + 0.0063
: 0.001x = 0.0120
Cs = 12 ppm
50 𝑝𝑝𝑚 − 12 𝑝𝑝𝑚
% Adsorption : 50 𝑝𝑝𝑚
𝑥 100%
: 76 %
(50 − 12)𝑝𝑝𝑚 (0.025 𝐿)
Qc : 0.25 𝑔𝑟𝑎𝑚
: 3.8 mg/g

Sample 4 (pH 7)
Cs : 0.0057 = 0.001x + 0.0063
: 0.001x = -0.0006
Cs = -0.6 ppm
50 𝑝𝑝𝑚 − (−0.6) 𝑝𝑝𝑚
% Adsorption : 50 𝑝𝑝𝑚
𝑥 100%
: 101.2 %
(50 − (−0.6))𝑝𝑝𝑚 (0.025 𝐿)
Qc : 0.25 𝑔𝑟𝑎𝑚
: 5.06 mg/g

When presented as a table, these results gave such:

Concentration Adsorption
Sample pH Value Absorbance % Adsorption
(ppm) Capacity (mg/g)

1 4 0.0397 33.4 33.2 % 1.68 mg/g

2 5 0.0255 19.2 61.6 % 3.08 mg/g

 3 6 0.0120 12 76 % 3.8 mg/g

4 7 0.0057 -0.6 101.2 % 5.06 mg/g

3.2.4 Effect of Contact Time Calculations

10 Minutes
Cs : 0.0399 = 0.001x + 0.0063
: 0.001x = 0.0336
Cs = 33.6 ppm
50 𝑝𝑝𝑚 − 33.6 𝑝𝑝𝑚
% Adsorption : 50𝑝𝑝𝑚
𝑥 100%
: 32.8 %
(50 − 33.6)𝑝𝑝𝑚 (0.025 𝐿)
Qc : 0.25 𝑔𝑟𝑎𝑚
: 1.64 mg/g

20 Minutes
Cs : 0.0345 = 0.001x + 0.0063
: 0.001x = 0.0282
Cs = 28.2 ppm
50 𝑝𝑝𝑚 − 28.2 𝑝𝑝𝑚
% Adsorption : 50𝑝𝑝𝑚
𝑥 100%
: 43.6 %
(50 − 28.2)𝑝𝑝𝑚 (0.025 𝐿)
Qc : 0.25 𝑔𝑟𝑎𝑚
: 2.18 mg/g

30 Minutes
Cs : 0.0399 = 0.001x + 0.0063
: 0.001x = 0.0336
Cs = 33.6 ppm
50 𝑝𝑝𝑚 − 33.6 𝑝𝑝𝑚
% Adsorption : 50𝑝𝑝𝑚
𝑥 100%
: 32.8 %
(50 − 33.6)𝑝𝑝𝑚 (0.025 𝐿)
Qc : 0.25 𝑔𝑟𝑎𝑚
: 1.64 mg/g

When presented as a table, these results gave such:

Concentration Adsorption
Sample Contact Time Absorbance % Adsorption
(ppm) Capacity (mg/g)

1 10 Minutes 0.0399 33.6 32.8 % 1.64 mg/g

2 20 Minutes 0.0345 28.2 43.6 % 2.18 mg/g

3 30 Minutes 0.0399 33.6 32.8 % 1.64 mg/g

3.3 Procedure Analysis
The tools used in this experiment includes an analytical balance to weigh the
required activated carbon, erlenmeyer flasks to mix the adsorbents and adsorbates, a shaker
to mix the both and induce the adsorption property, glass funnels to be used in conjunction
with filter paper to filter the mixture, and beakers to hold the final filtrate, and for it to be
used in the AAS. Finally, an AAS (Atomic Absorption Spectrometry) spectrophotometer
was used to measure the absorbance, and through calculations the concentration of the final
solution.
The materials used in this experiment includes activated carbon to act as the
adsorbent where the adsorption phenomenon will occur, and a Cu(II) solution as the
adsorbate, which will get adsorbed onto the adsorbent.
In this experiment, to first determine the effect of solution pH, the adsorbent in the
form of activated carbon was a fixed 0.25 grams, which was weighed and put onto 4
separate erlenmeyer flasks. Onto these prepared activated carbons, the same 50 ppm Cu
(II) solution was added as much as 25 mL, which is then added with a few drops of NaOH
and HCl, to create solutions with a pH of 4, 5, 6, and 7. The addition of Cu (II) solution
was used as the copper atom can be measured using AAS in the measurement step later.
The mixture of Cu (II) and carbon was then mixed in a shaker for 20 minutes at room
temperature and 170 RPM to stimulate the adsorption phenomenon. The obtained mixture
is then filtered, so that the filtrate is left in vials, ready for AAS measurement. The
obtained AAS absorbance data is then processed to be as a graph, and compared with the
available standard data and regression data.
In the second part of the experiment, the effect of different contact times are studied
instead. Here, 3 analytes are used, all three using a fixed amount of 0.25 grams of activated
carbon, though with a different shaking time. All three mixtures are treated as the first part
of the experiment, though without any pH alterations, then shaken with different times.
One flask was shaken for 10 minutes, another 20 minutes, and the last one was shaken for
30 minutes. The obtained filtrate of copper is measured using the AAS as before, the
absorbance value of all solutions will be measured, and similarly as before, compared
using the available standard data and regression.
3.2.4 Result Analysis
Based on the results of this experiment, the absorbance of the solutions after its
interaction with the adsorbent will always result in a lower value when measured. This is
our main focus on this experiment, as this proves that the adsorbent used here (activated
carbon) will be able to adsorb the adsorbates, thus reducing the final concentration in the
solution. When measuring using the AAS, standards are used, and during this experiment,
the standard data was used from 10 to 40 ppm (at intervals of 10), which give the linear
regression of:
y = 0.001x + 0.0063
In the first experiment that studies the effect of solution’s pH, it was shown that the
absorbance of the 4, 5, 6, and 7 pH corresponds to 0.0397, 0.0255, 0.0120, and 0.0057
respectively. The result as shown has a trend of a lower value as a higher pH was used.
From these obtained data, results from the varying pH from 4 to 7 revealed corresponding
concentrations of 33.4 ppm, 19.2 ppm, 12 ppm, and -0.6 ppm respectively. The negative
value resulted due to the standard used not being measured from 0, which if it was (by
adding a 0 that corresponds to 0 absorbance), the regression would change, forming a
positive number for this data, though requiring all obtained data to be re-calculated. The
percentage of Cu2+ uptake showed values of 33.2 %, 61.6 %, 76 %, and 101.2 %
respectively. Additionally, absorption capacity values derived from the calculations were
1.68 mg/g, 3.08 mg/g, 3.8 mg/g, and 5.06 mg/g respectively. These results gave a
relationship of pH, concentration, adsorption percentage, and Qc value. As shown by the
data, adsorption, and absorption capacity increases with increasing pH, while the
concentration of Cu2+ remaining in the solution decreases. The sample that exceeds the
100% limit has the same reasoning as before, which causes the calculation to be faulty.
This observed phenomenon goes accordingly with a research done by Demiral, 2016,
which states that activated carbon contains an R-OH group to mainly interact with the
copper ions through their negative and positive charge. When less pH is present, it means
that more H+ are available in the solution, thus negating the negative charge present,
making an R-OH2+ group available which will decrease the bonding between copper ions
and the OH group. The reverse will happen, when a high pH is present, an R-O- group may
occur, strengthening the bond between the adsorbent and the adsorbate.
The second experiment investigated how contact time between the adsorbent and
adsorbate will affect the adsorption process. The adsorbent and adsorbate are the same as
before, thus also using the same linear regression of Cu (II) standard. Here, the shaking
times are varied, with 10, 20, and 30 minutes of shaking. The absorption data that resulted
from this series of experiments corresponds to 0.0399, 0.0345, and 0.0399. These data
again corresponds to 33.6 ppm, 28.2 ppm, and finally 33.6 ppm respectively. The
percentage of Cu (II) being adsorbed was 32.8%, 43.6%, and 32.8%, with the adsorption
capacity of each data being 1.64 mg/g, 2.18 mg/g, and 1.64 mg/g respectively. From the
data, it was seen that sample 1 and 3 (10 and 30 minutes of shaking) gives the exact same
absorbance value, thus having the exact same data through and through. Observing the data
obtained, not enough is able to be deciphered to make a trend, as the same data between
sample 1 and 3. However, a similar research done by Suliestyah, 2020 shows that
generally, the longer the contact time, the more adsorption will occur, though it is not as
inline as the pH effect, as the same research also shows some abnormalities in the data
obtained, which means in some cases, there may be an optimal time in which the
adsorption will be the best, rather then always using the longest time of contact.
 Chapter 4
Closing Remarks
4.1 Conclusion
Based on the experiment that have been done, the absorbance obtained from measuring the
Cu (II) using an AAS after being adsorbed with activated carbon at different pH values from 4,
5, 6, and 7 corresponded to 0.0397, 0.0255, 0.0120, and 0.0057. Through the linear regression
obtained from the Cu (II) standard, those absorbance values correspond to 33.4 ppm, 19.2 ppm,
12 ppm, and -0.6 ppm respectively. The percentage of Cu (II) being adsorbed showed values of
33.2 %, 61.6 %, 76 %, and 101.2 % respectively. Additionally, absorption capacity values
derived from the calculations were 1.68 mg/g, 3.08 mg/g, 3.8 mg/g, and 5.06 mg/g respectively.
For the next experiment which studies the effect of contact time, 10, 20, and 30 minutes of
shaking variations were studied. The absorbance data obtained shows a result of 0.0399,
0.0345, and 0.0399, which when calculated using the same regression gives concentration
values of 33.6, 28.2, and finally 33.6 ppm respectively. Similar to the experiment done before,
this data gives a percentage of Cu (II) being adsorbed was 32.8%, 43.6%, and 32.8%, with the
adsorption capacity of each being 1.64 mg/g, 2.18 mg/g, and 1.64 mg/g respectively.
4.2 Recommendation
During the experiment, laborers have to keep any possible source of contamination away
from the samples, as it will affect the measurements, especially when a sensitive instrument
such as the AAS is used. Though not too precise, weighings are also important to keep check
on, as when a data is too strayed apart from what it should've been, the final results will also be
skewed. Finally, all measurements have to be done as precisely as possible, as mistakes may
lead to misleading data being used.