ADSORPTION OF Cu (II) AND Ni (II) FROM AQUEOUS

SOLUTION BY CANISTEL (Pouteria campechiana):

EQUILIBRIUM, KINETICS AND THERMODYNAMICS STUDIES

A Thesis Proposal
Presented to the
Faculty of the College of Science
Pamantasan ng Lungsod ng Maynila

In partial fulfilment
of the requirement for the degree
Bachelor of Science in Chemistry

By:
Jesamyn L. Camagong

CONTENTS

INTRODUCTION

1.1 Objectives of the Study

1.2 Scope and Limitations

2
3

RELATED LITERATURE
2.1 Canistel
2.2 Metal Ions
2.2.1 Toxicity of Copper (II)
2.2.2 Toxicity of Nickel (II)
2.3 Common Waste Water Treatment
2.3.1 Chemical Precipitation
2.3.2 Ultrafiltration
2.3.3 Ion Exchange
2.3.4 Reverse Osmosis
2.4 Adsorption: Alternative Method
2.5 Adsorption Process
2.5.1 Physical
2.5.2 Chemical
2.6 Adsorption Isotherm
2.6.1 Langmuir Isotherm
2.6.2 Freundlich Isotherm
2.6.3 Temkin Isotherm
2.6.4 Dubinin-Radushkevich Isotherm
2.6.5 Redlich-Peterson
2.7 Adsorption Kinetics
2.7.1 Pseudo-first order model
2.7.2 Pseudo-second order model
2.7.3 Interparticle Diffusion

2.8 Adsorption Thermodynamics

2.9 Adsorbent Derived from Different Materials

METHODOLOGY
3.1
3.2
3.3
3.4

Materials (Reagents or Samples)

Preparation of the Canistel as an Adsorbent
Base Treatment
Characterization
3.4.1 FT-IR
3.4.2 SEM
3.4.3 BET
3.5 Preparation of Metal Ions

19

3.6Adsorptio Equilibrium
3.7 Adsorption Kinetics
3.8 Adsorption Thermodynamics
3.9 Statistical Analysis
BUDGET PROPOSAL
GANTT CHART

CHAPTER 1

INTRODUCTION
Heavy metal pollution is one of the major problems worldwide. Water
pollution as one of these issues attracted a lot of concerns to people. The cause
of this problem is due to the expansion of industrial activities [1]. The presence
of heavy metals in the environment is a potential problem to the quality of the
water because of its high toxicity.
Copper which is naturally present in the environment can be harmful to
human when exposure is more than 15ppm. Acute copper poisoning intake can
cause nausea, vomiting, diarrheal and there are some cases studied that if not
cured can cause death [5]. The presence of copper in the water system was
because of its improper disposal and copper mining [6]. Consequently, in order
to avoid water pollution, treatment is needed before disposal [1].
Nickel is an element that occurs naturally but skin exposure of greater
than 1-5ppm can cause skin allergy and irritation. On the other exposure to high
level of nickel may results cancers of the lung [7]. Wearing jewelleries containing
nickel is the most common reason an individual is exposed to nickel. Avoidance
from wearing jewelleries containing nickel may limit the exposure.
Several treatment have been developed for removing copper and nickel
from water such as chemical precipitation, ultra filtration, adsorption, ion
exchange

[4],

reverse

osmosis,

oxidation,

reduction[6]

and

electrolysis.

Chemical precipitation used expensive sulfidic precipitant and it is not possible to

do electro winning from precipitate. In addition, ultrafiltration cannot remove
dissolved substances unless they are first adsorbed (with activated carbon).
Furthermore, reverse osmosis requires a consumption of high specific energy

and also electro winning of copper may not be possible because of the chloride in
the concentrate.
Adsorption among all the method is highly effective and economical [4]. It
is the cheapest method because the materials used are low cost. For most of the
studies conducted low cost material has been a parameter in choosing the
adsorbent material. This introduced the usage of agricultural waste for treating
water system. Several by products are already used as a metal adsorbent but
canistel peel has not reported.
In this study canistel peel will be use as the adsorbent. Canistel (pouteria
campechiana) fruit is a round or ovoid, smooth and glossy. The peel and flesh of
this fruit is yellow. Since highly cost commercial adsorbent materials are not
practical to use so, this work will use an agricultural waste like canistel peel to
remove heavy metal like copper in the water system.

1.1 Objectives of the Study

The following were the objectives of this research:
I.
To characterize the unmodified and modified canistel powder.
II.
to produced an adsorbent from the canistel peel
III.
to modify canistel peel powder by base treatment
IV.
to remove Cu (II) and Ni (II) from the wastewater using the
V.

canistel peel powder

to determine the adsorption

equilibrium,

kinetics

and

thermodynamic parameters
1.2 Scope and Limitations
In this study, the base modified canistel (Pouteria campechiana) peel will
be use as an adsorbent for the removal of copper and nickel in artificial
wastewater. Different isotherm models will be involved to describe adsorption

process such as Langmuir, Freundlich, Temkin, Dubinin-Radushkevich, and

Redlich-Petrson. The following kinetic models will also be used such as Pseudofirst order model, Pseudo-second order model and Interparticle Diffusion.
Thermodynamic parameters including H, G and S will also be determined.
This study will only be concern in the initial measurement of the
parameters to be use such as the pH but the pH during and after the experiment
cannot be regulated. The analytical concentration shall be treated as a whole.

CHAPTER II

RELATED LITERATURE
2.1 Canistel
Egg fruit or commonly known as Canistel (Pouteria campechiana) is a
tropical fruit belonging to the family of Sapotaceae. Canistel trees can reach the

height of 25m and have a trunk diameter up to 1.5m. Leaves are green and
glossy and are held together at the end of the branches. Fruits are usually round
or ovoid, smooth and glossy. Canistel is pale orange-yellow in color when fully
ripe [2]. The plant of canistel is believed to b native of Southern Mexico and
most countries of Central America. The tree was introduced to the Philippines by
the Spaniards.

2.1 Metal Ion

2.2.1 Toxicity Copper
Copper is a mineral that occurs naturally in soil. It is an essential nutrient
for humans and plants. Too little is unhealthy and too much can lead to copper
poisoning. Copper (Cu) [21] is a reddish brown metal that is high ductility and
malleability. It is a metal with very high thermal and electrical conductivity. Pure
copper is soft and malleable. Copper (II) ions are water soluble
Copper imbalance can result from: environmental copper exposure, zinc
deficiency and the copper personality. Copper poisoning can be triggered by
stressed, excessive copper stored in live (>15ppm) and destruction of red blood
cell.
Copper [42] strongly complexes to sludge, and it occurs mainly in the
organic phase. Only a small fraction of the copper will be found in the solution as
ionic copper (Cu2+). All heavy metals have its specific pH, for copper it is 5.5.

2.2.2 Toxicity of Nickel

Nickel [41] is a very hard metal that occurs naturally in soils and volcanic
dust. Nickel is released to the atmosphere by windblown dust, volcanoes,

combustion of fuel oil, municipal incineration, and industries involved in nickel

refining, steel production, and other nickel alloy production. The form of nickel
emitted to the atmosphere is dependent upon the source.
Nickel salts of strong acids and organic acids are soluble in water, whereas
salts of weak inorganic acids are insoluble. Nickel is resistant to corrosion by air
and water.
The general population can be exposed to nickel via inhalation. Too much
exposure to nickel can cause an allergic contact dermatitis; the primary targets
of toxicity appear to be the respiratory tract following inhalation exposure.
2.3 Common Waste Water Treatment
Chemical

precipitation

is

an

effective

treatment

for

removing

contaminants in water. The substance removability from water depends on the

solubility of the various complexes formed in water [9]. Chemicals are added to
form particles which settle and remove contaminants. The treated water is
properly disposed or reused. It can also be used in a small or large scale.
Ultrafiltration is a very competitive treatment compare to the conventional
once. Ultrafiltration is necessary in producing safe water as far as disease is
concerned. Today, more than 2 millions 3/d of drinking water is produced
worldwide through ultrafiltration. More than 50 UF plants for producing drinking
water from surface water are in operation in the world.
Application of UF for drinking water supply can be in form of single
operation without any pre-treatment except a common screen filter. UF can be

used on its own for treating drinking water where the feed water is not too high
in terms of organic content.
Ion exchange is the process at which ion are transferred to a solid matrix.
In other words ions that are originally present in the solid were replaced by
different ions. It requires interchange in the material because the electro
neutrality of the solution must be maintained. It is physical separation process
since atom is reversely removed from the waste water. It involves the
regeneration of the ion exchanger by contacting the spent exchanger with a
concentrated solution of an ion which can replace the ions adsorbed on the
exchanger during the treatment process. Ion exchange is advantageous because
is capable of handling and separating components from dilute waste water and it
is possible to recycle components present in the waste and/or regenerating
chemicals.
Reverse Osmosis (RO) is a membrane process of purification which
removes most of the total dissolved solids (TDS) in water. RO has become an
important process for a wide variety of applications including: medical,
laboratory, desalination, industrial wastewater and drinking water. Electrical
conductivity is the most convenient method for testing RO water quality. In the
process of reverse osmosis, water is produced through forcing it to semi
permeable membranes at high pressure. The pH is also very useful in predicting
membrane life and the scaling potential of feed water. The higher the pH and
calcium, the more likely it is that scale will form on the membranes.

2.4 Adsorption: Alternative Method

Adsorption [32] is operative in most natural physical, biological, and

chemical systems, and is widely used in industrial applications such as activated
charcoal, synthetic resins and water purification. It is a process that occur when
a gas or liquid solute accumulates on the surface of a solid or a liquid forming a
molecular or atomic film. Adsorbate or solute is the material being adsorbed
while adsorbent is the solid material being used as the adsorbing phase. The
driving force for adsorption is the reduction in interfacial (surface) tension
between the fluid and the solid adsorbent because of the adsorption of the
adsorbate on the surface of the solid.
Many industrial wastewaters contain substances that are difficult to
remove, toxic or hazardous, volatile and cannot be transferred to the
atmosphere, present is very small concentrations that make and their removal
via other methods difficult. Adsorption is advisable to use typically used because
it can remove toxic or recalcitrant organic pollutants (especially halogenated but
also no n-halogenated), and to a lesser extent, inorganic contaminants, from the
wastewater. Adsorption also finds applications in tertiary wastewater treatment
as a polishing step before final discharge. It is commonly used in the treatment
of industrial wastewaters containing organic compounds not easily biodegraded
during secondary (biological) treatment or toxic.

2.5 Adsorption Isotherm

2.5.1 Langmuir Isotherm
Langmuir isotherm model is valid for adsorption onto a surface with a
finite number of identical sides. The binding sites have the same affinity for

adsorption of single molecular layer. There is no interaction between the

adsorbed molecules.
It is an empirical isotherm derived from a proposed kinetic mechanism.
For liquids (adsorbate) adsorbed on solids (adsorbent), the Langmuir can be
expressed by:

(1)

where qeq is the adsorbate loading (mg g1) at equilibrium, Ceq the equilibrium
concentration in the fluid (mg l1), qmax the adsorption capacity (mg g1) and
Ka sorption equilibrium constant (l mg1) [12].

Table 1.1.Capacities for Cu (II) of various adsorbents

Material Used

Modifying agent

Streptomyces
coelicolorA3(2)

66.66

Dehydrated Wheat
Bran

42.4

Algae Gracilaria
Modified
peel

orange

Capsicum annuum
seeds

Qmax (mg.g-1)

Methyl acrylate

Reference
[22]

[23]

2.527

[24]

289.0

[20]

4.47 x 10-4

[25]

Meranti Sawdust

32.051

Palm Kernel Fibre

3.169 x 10 -4

[21]
[26]

Table 1.2.Capacities for Ni (II) of various adsorbents

Material Used

Modifying agent

Qmax (mg.g-1)

Reference

Granulated
Activated Carbon

1.2827

[28]

Helix Aspera Shells

0.2273

[38]

Streptomyces
coelicolorA3(2)

416.6

[22]

Sugarcane Bagasse

2.80

[25]

Meranti sawdust

35.971

[21]

9.01

[36]

Bakers Yeast

HCl, Bromine

2.5.2 Freundlich Isotherm

In 1907, Freundlich isotherm is obtained on the assumption that the
sorption takes place on the heterogeneous surface. The sorption energy decrease
exponentially.
A linear form of the Freundlich equation is:

log q e

1
n log C e log K

(2)

where K and n are Freundlich adsorption isotherm constants (dm3 g1), the plot
of ln qe versus lnCe for the adsorption was employed [13].

Table 2.1 Freundlich constants for Cu (II) of various adsorbents

Material Used

1/n

Kf

Reference

(mg.g-1)

Ulvafasciatasp.

2.2163

2.2230

[39]

Treated oil shale ash

4.237

1.325

[40]

Dehydrated wheat bran

0.1408

26.2

[23]

Algae Gracilaria

0.3798

0.640

[24]

Modified Orange peel

18.93

0.504

[20]

0.4593

[25]

0.9900

[21]

Capsicum annuumseeds

7.16x10-3

Meranti Sawdust

1.460

Palm Kernel Fibre

3.488

7.03 x 10-4

[26]

Table 2.2.Freundlich constants for Ni (II) of various adsorbents

Material Used

1/n

Kf
(mg.g-1)

Reference

Helix Aspera Shells

0.833

0.2273

[33]

SpagnumPeat

0.1035

9.06

[21]

Streptomyces
coelicolorA3(2)

0.98

0.08

Natural iron-oxide coated

sand

0.98

0.99

Meranti Sawdust

1.483

0.99

[21]

Bakers Yeast

0.1700

3.73

[36]

[22]
[29]

2.5.3 Temkin Isotherm

The Temkin Isotherm assumes that the sorption is linear not logarithmic
as implied in the Freundlich isotherm. It is expressed as

RT
b

qe

RT
b

ln A

Ce

(3)

where, q is the amount of metal ions adsorbed at equilibrium (mg.g -1), Ce is the
equilibrium concentration (mg.L-1), A and b are the Temkin constants, R is the
universal gas constant, and T is the temperature of the system [14].

2.5.4 Dubinin-Radushkevich Isotherm

It is insufficient to explain the physical and chemical characteristic of
adsorption using the Freundlich and Langmuir Isotherm. D-R Isotherm is
commonly used to describe the sorption isotherm of the single solute systems. It
is more general since it rejects the homogeneous surface [11]. The D-S is
expressed as

ln qe ln V ' m K ' 2

(4)

where qe, the amount of adsorbed per unit weight (mg/g); K, Freundlich
constants related to adsorption capacity; Ce, the equilibrium concentration
(mg/L); n, Freundlich constants related to adsorption intensity.

2.5.5 Redlich-Peterson
In

describing

the

empirical

isotherm

for

redlich-peterson,

three

parameters are used, [KR], [aR], and [. The mechanism of adsorption is hybrid
[15].

(7)

2.6 Adsorption Kinetics

2.6.1 Pseudo-first order model
The pseudo-first rate order is expressed as follows:

1
1 K1

q t q1 q1t

(8)

where q1 and qt are the amounts of the substance ions adsorbed at equilibrium
and at time t (mg g1) and k1 is the pseudo-first-order rate constant (min1) of
adsorption. Values of k1 can be calculated from the slope of the plots of 1/qt
versus 1/t [16].

2.6.2 Pseudo-second order model

Pseudo-second order rate model was described in the literature in the

following form:

t
1 1
t

q t h q e 2

(9)

where, h is the initial sorption rate (mg g-1 min-1); k2 is the overall rate
constant for the sorption process (g mg-1 min-1); qe (2) is the amount of metal
ion adsorbed at equilibrium (mg/g); and qt is the adsorbed at time t (mg/g)
[16].
Table 3.1.Mechanisms of adsorption for Cu (II) and Ni (II)

Material Used

solute

Model

Reference

AlgaUndariapinnatifida

Cu (II)

2nd order

[30]

AlgaUndariapinnatifida

Ni (II)

2nd order

[30]

Algae Gracilaria

Cu (II)

2nd order

[31]

Modified Orange peel

Cu (II)

2nd order

[20]

Capsicum annuumseeds

Cu (II)

2nd order

[32]

Maize Cob

Cu(II)

2nd order

[34]

Cassava Waste

Cu (II)

2nd order

[33]

Meranti Sawdust

Cu (II)

1st, 2nd order

[21]

Meranti Sawdust

Ni (II)

1st, 2nd order

[21]

Fired Coal Fly Ash

Cu (II)

2nd order

[35]

Bakers Yeast

Ni (II)

2nd order

[36]

Zeolite X

Ni (II)

2nd order

[37]

2.6.3 Interparticle Diffusion

The intraparticle diffusion equation can be written as follows:
1

qt k pt 2 C

(10)

where C is the intercept and kp, the intraparticle diffusion rate constant (mg g1
min1/2) [16].

2.7 Adsorption Thermodynamics

Adsorption thermodynamic parameters are useful in determining whether
the reaction is endothermic or exothermic and the spontaneity of adsorption
[17]. Thermodynamic parameters such as change in enthalpy (H), free energy
change (G) and entropy change (S) can be estimated using equilibrium
constant with changing temperature. The free energy reaction is given by the
following equation:

G = -RT ln Ka

(11)

where _G is standard free energy change, J; R the universal gas constant, 8.314
J mol1 K1 and T the absolute temperature, K.
Free energy change indicates that the higher the negative value reflects a
more energetically favorable adsorption and the degree of spontaneity of the
adsorption process [18].
The plot of ln KL as a function of 1/T yields a straight line from which (H)
and (S) can be calculated from the slope and intercept, respectively [19].

ln K L

G
S

RT
RT
R

(12)

Table 4.1.Thermodynamic value for Cu (II) and Ni (II) of various adsorbents

________________________________________________________________

Material Used

G
(kJ/mole)

H
(kJ/mole)

S
(kJ/moleK)

Reference

________________________________________________________________
Andesite Products

16.502

4.0406

61.69

[27]

Natural
iron-oxide
coated sand

20.91

52.32

0.25

[29]

Palm Kernel Fibre

-8.57

5.3677

0.0463

[26]

Helix aspera shell

-1318.7

Natural
iron-oxide
coated sand

-24.4

45.75

0.23

[29]

Bakers Yeast

23.519

30.702

23.658

[36]

[38]

CHAPTER III

METHODOLOGY
3.1 Materials
The canistel peel that will be used in this study will be collected from the
local market. The concentrations of (NO3)3.9H2O and Ni (NO3)2.6H2O which are

of analytical grade will be used to prepare the metal ions Cu (II) and NI (II). For
the base treatment, NaOH will be used.
The instrument that will be used for drying the canistel peel is the 500
watts halogen lamp. The samples will be tested using AAS, FT-IR and SEM
services.

3.2 Preparation of Canistel Peel Adsorbent

Canistel peel will be used as the original material for the preparation of
adsorbent. The canistel peel will be collected from the local market. Clean the
canistel peel with distilled water; chop in small pieces and dry using 500 watts
halogen lamp. Grind the dried peel. The ground peel will be sieved to make the
size of the particles 80m. After sieving, boil it for 15 minutes to remove the
colour. To modify the substrate, treat 5g of canistel peel with 25ml of 0.1M NaOH
and for the remaining potion, used it as the unmodified. Neutralize the treated
substrate by washing it with distilled water. As the pH neutralizes dry again the
substrate. Do constant weighing of the substrate.

3.3 Base Treatment

The ground samples will be mixed with 0, 0.10, 0.25, and 0.50mol/L
NaOH, and then will be stirred at 400 r/min for 30 min. Treatment of the sample
with 0.50 mol/L NaOH for 60 and 120 min will also conducted for determining
the optimum treatment time. After each base treatment, the samples will be
filtered, wash extensively with distilled water until the final pH of the washing
reached neutral. The sample will be dried in oven at 80C. The treated samples
will be sieved.

3.4 Characterization of Unmodified and Modified Adsorbent

The pH will be determined by adding 1 g of canistel peel powder in 50mL
distilled water, stirred and the final pH will be measured after 24 hours.

In

addition, the Fourier transform infrared (FTIR) instrument will be used in the
analysis. . Spectra of the samples will be collected by KBr disk method by
blending 100mg adsorbent and KBr will be triturated with mortar and pestle for
10 minutes.
The BET specific surface areas were determined by standard multipoint
techniques of nitrogen adsorption using a Micromeritics Gemini 2360 instrument.
The untreated and modified canistel peel powder will be heated at 60 C for 2h
before specific surface areas were measured.
The scanning electron micrograph (SEM) of the canistel peel powder and
metal ions loaded canistel peel powder at bar length equivalent to 20_m,
working voltage 15 kV with 250 magnification

3.5 Preparation of Metal Ions

All chemicals that will be used are of analytical grade. The stock solution
of Copper and Nickel ions will be prepared from in1.0g L -1 concentration using Cu
(NO3)3.9H2O and Ni (NO3)2.6H2O.

3.6 Adsorption Equilibrium

Adsorption equilibrium experiment will be carried out by contacting 0.2 g
of powdered canistel peel with 100 ml of metal ion solution of different initial
concentrations ranging from 60 to 140 mg/dm3. A series of such conical flasks

will be maintained at 299 K. Equilibrium concentrations of Cu (II) and Ni (II) will

be determined by Atomic Absorption Spectrophotometer.

3.7 Adsorption Kinetics

The studies of the kinetics of adsorption will be carried out at 30 C. One
hundred ml of the solution containing the desired quantity of the metal ion will
be treated with 0.5 g of canistel peel in stoppard conical flasks for the different
times using a temperature-controlled stirrer. The solution will be filtered out and
will be analyzed for its metal ion concentrations using Atomic Absorption
Spectrometer, AAS.

3.8 Adsorption Thermodynamics

One-hundred milligram sample of the powdered canistel peel will be
added into a 100-mL solution of the Cu (II) and Ni (II) separately at initial
concentration of 50ppm. Different samples will be soaked to water and let it to
stand with a temperature of 303 K, 333 K and 363 K for 6 hours for three trials.
The solution will be filtered out and will be analyzed for its metal ion
concentrations using Atomic Absorption Spectrometer, AAS.

3.9 Statistical Analysis

The Pearson r is the measure of the strength of linear dependence
between two variables X and Y. Paired T-test will be used to determine any
significant difference in terms of adsorptive capacities of modified and nonmodified adsorbents for Ni (II) and Cu (II).

BUDGET PROPOSAL

ITEM/SERVIC
E

Canistel

UNIT COST

49/
1000 g

NO. OF
UNITS
NEEDE
D

TOTAL
COST

SUPPLIER/
INSTITUTION

4000 g

196.00

Super Market

100-ml peanut
butter plastic
containers

2.80/ pc

500pcs

840.00

Divisoria Market

Halogen lamp

250/pc

1pc

250.00

Handyman Hardware

Distilled water

70/10L

100L

700.00

SM Supermarket

6g

240.00

Metal ions
(Cu(II) and
Ni(II))

Cu(II)40/g
Ni(II)40/g

6g

240.00

Lithium Lab Supplies

Sodium
hydroxide,
Concentrated

3.00/
Ml

100ml

KBr
Zip lock bags
Whatmann
Filter paper No.
41

300.00

Lithium Lab Supplies

500.00

Lithium Lab Supplies

53.00/pack

3 packs

159.00

Adams

2.50/pc

100pcs

250.00

Lithium Lab Supplies

700.00

DLSU-Manila

900.00

DLSU-Manila

3,000.00

DLSU-Manila

2,250.00

Manila

AAS services
FT-IR Services

300/sample

SEM Services

1,000/sample

Printing and
bookbinding
TOTAL

10,285.00

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2004
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[16] Adnan O zcan, A. Safa O zcan, Sibel Tunali, Tamer Akar, Ismail Kiran,
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