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INTERNATIONAL JOURNAL OF ENVIRONMENTAL SCIENCES Volume 3, No 1, 2012

© Copyright by the authors - Licensee IPA- Under Creative Commons license 3.0

Research article ISSN 0976 – 4402

Received on February 2012 Published on July 2012 453

Adsorption of Copper (II) ion onto chitosan/sisal/banana fiber hybrid

composite Bakiya lakshmi K

1, Sudha P N

2

1- Part – Time Research Scholar, Department of chemistry, Manonmanium Sundaranar

University, Tirunelveli, Tamil Nadu, India

2- Department of Chemistry, DKM College for Women, Vellore, Tamil Nadu, India

[email protected]

doi:10.6088/ijes.2012030131044

ABSTRACT

An investigation was made on the biosorption of Copper (II) ions onto chitosan (CS)/sisal

fiber (SF)/banana fiber (BF) hybrid composite from an aqueous solution using batch

adsorption studies. Chitosan/sisal/banana fiber hybrid composite were prepared by solution

mixing method. The prepared composite was confirmed by FTIR, X-ray, DSC and SEM

measurements. The efficiency of adsorption was evaluated by varying pH of the solution,

contact time and adsorbent dose. At an optimum pH (pH=5), the maximum uptake of Cu (II)

ions by CS/SF/BF composite was found to be 169 mg/g. The data were described with the

help of Freundlich, Langmuir, Tempkin, Dubinin – Radushkevich, isotherm models. It was

found that the Freundlich isotherm model provided the best fit for the adsorption of Cu (II)

ion. The obtained kinetic datas were tested by pseudo-first order, pseudo-second order and

intra-particle diffusion models. From the Kinetic studies pseudo-second order reaction was

well fitted to the data. Studies also showed adsorption proceeds through the intra-particle

diffusion mechanism. This current work suggests that chitosan/sisal/banana fiber hybrid

composite was highly economic and efficient in removing the copper (II) ions from aqueous

solution.

Key words: Chitosan, siSal fiber, Banana fiber, hybrid, Biocomposite, adsorption, kinetics,

metal removal.

1. Introduction

Give a man a fish, and he can eat for a day. But teach a man how to fish, and he will be dead

of mercury poisoning- Charles Haas.

This is the current status of pollution in the world. However, almost all the natural resources

have been exploited to the core, due to the population bloom, rapid industrialization and

urbanization activities. Since WATER is known as elixir of life and a universal solvent which

is supposed to be the pure and abundantly available? But the present scenario of water is

terribly pathetic. It is highly polluted by the organic and inorganic pollutants.

Environmental pollution by heavy metals has become a major threat due to their non bio

degradability, bio – accumulating tendency, toxicity and causing various diseases and

disorders (Hasan et al., 2007). These toxic heavy metals are present in the environment due to

natural and man made activities. To meet the demand of the raising population endless

number of industries (like fertilizers and pesticides, Tanneries, batteries, thermal power plant,

steel plants, etc,) (Lantzy and Mackenzie, 1979; Nriagu, 1979; Ross, 1994) have been

Adsorption of Copper (II) ion onto Chitosan/sisal/Banana fiber hybrid composite

Bakiya lakshmi , Sudha P N

International Journal of Environmental Sciences Volume 3 No.1, 2012 454

constructed across the world. But these industries are discharging their waste water into

nearby streams or rivers without treating the effluent. This was the root cause for the heavy

metals enter into the environment. One among the heavy metal is copper. According to WHO

(The World Health Organization) guidelines the maximum permissible limit of copper in

drinking water is 1.5mg/L. In case of higher intake, it affects the functions of capillaries,

kidneys, liver and causes central nervous disorders. (Kalavathy et al., 2005).

Thereby it is most important to remove or control the heavy metal contamination in aqueous

streams. Several conventional methods have been employed to remove heavy metals. To cite

a few methods chemical precipitation, reverse osmosis, electrolysis, coagulation and

adsorption. However, often these methods are complicated in operation, possible secondary

pollution (Saeed and Iqbal, 2005) expensive; require high running and maintenance costs,

ineffective at low concentration (Rengaraj et al., 2004).

Biosorption technique is one of the most preferred methods to remove copper (II) ions from

the industrial waste water. This is because adsorption technique is more efficient, economical

and eco – friendly. (Volesky, 1990). Several adsorbents such as activated sludge(Yesim sag

et al, 2003), Banana peel(Hossain M A et al, 2012; Renata S D Castro et al, 2011), tire

rubber(Maria Alexandra-Franco et al, 2011), fungus(Xiao Xiao et al, 2010), Lignin(Dinesh

Mohan et al, 2006), Coir pith(Kavitha D, Namasivayam C, 2007) inorganic colloids

(Subramanian and Yiocoumi, 2001), modified goethite (Li et al., 2007) etc, have been used

for the removal of heavy metals.

Recently tremendous research has been going in natural fiber reinforced polymer composites.

In this present work, the new combination of chitosan with embedded sisal and banana fibers

(chitosan/sisal/banana hybrid fiber composite) was successfully prepared and implemented

for removing the copper (II) ions from the aqueous solution.

On comparing the properties of some inorganic fibers, natural fibers are superior to them

owing to their low cost, easily available, less dense in nature, biodegradability and light in

weight. (Samir Kumar Acharya et al., 2011). Some of the natural fibers such as jute (Dipa

Ray et al, 2007), pine apple leaf fiber (Manoranjan Biswal et al, 2009), Banana and sisal fiber

(Idicula M et al, 2005), coir (Bettini S H P et al, 20 10), kenaf (Annie kamala Florence J et al,

2011) have been used as the resin for synthetic or Bio matrices. One or more fibers can be

embedded to the single matrix is called Hybrid fiber composites (Smita Mohanty, Sanjay,

Nayak, 2006.).

In this study sisal and banana fibers were used as the reinforcing agent onto chitosan matrix.

Sisal fiber are extracted from the plant leaves Agave sisalana which is mainly cultivated in

India, Indonesia, and east African countries (Favaro et al., 2010). Banana (Musaceae) plant is

cultivated in tropical and sub tropical areas. The fiber is obtained from the stem (modified)

called a pseudostem. (Abdul Khalil et al, 2006).

Chitosan is the most abundant biopolymer next to cellulose. It has been used for about three

decades in water purification processes. Chitosan is the deacetylated product of chitin

(Rinaudo, 2006), it is a natural polysaccharide present in crab, shrimp, lobster, coral jelly fish,

butterfly, lady bug etc., (Zhou et al., 2009). Since chitosan has free amino groups can acts as

better chelating agent than chitin. (Yang and Zall, 1984). The special properties of chitosan

include biocompatibility, biodegradability, and drug –absorption enhancement. Thus chitosan

could be considered as a green polymer applicable in analytical chemistry, water treatment,




agriculture, food ingredients (Chien et al., 2007), cosmetics (Ravi Kumar et al., 2004), bio-

medicine (Du et al., 2009), and pharmaceutical materials (Macquarie, 2005), Biotechnology

(Mao et al., 2001).

Figure 1: Deacetylation of chitin to chitosan (Saifuddin, Nomanbhay, Kumaran palanisamy,

2005)

The main objective of this work is to test the newly prepared chitosan/sisal/banana fiber

hybrid composite as an adsorbent to recover copper ions from aqueous solution. Equilibrium

and kinetic studies were made as a function of pH, adsorbent dosage and contact time. The

analyzed equilibrium data were fitted to Freundlich, Langmuir, Tempkin, Dubinin-

Radushkevich (D-R) isotherm equations to find the best fit model.

2. Materials and methods

2.1 Materials

Chitosan was purchased from India sea foods, Cochin, Kerala. The sisal fiber in this study

was purchased from vibrant nature, Chennai. And the banana fiber was collected from the

fields of Gingee Town which is located in Villupuram district, Tamilnadu. All the chemicals

used in this study such as copper sulphate (CuSO4.5H2O), NaOH, HCl and Acetic acid was of

analytical grade.

2.2 Preparation of chitosan/sisal/banana fiber hybrid composite

About 1g of chitosan (92% deacetylation from chitin of crab shell) was dissolved in 10ml of

acetic acid (8%) which is stirred in a vertical mechanical stirrer for 30 minutes. A whitish

homogeneous viscous gel was formed between chitosan – acetic acid.

The sisal fibers and banana fibers were cut into dust fiber. Both the fibers were mixed to the

chitosan with the help of glass stirrer for thorough reinforcement of fibers to the chitosan.

2.3 Characterization of composite

The formation CS/SF/BF composite was confirmed by Fourier Transform Infra red

Spectroscopy (FTIR) whereas crystalline nature by X-ray diffraction method. Thermal

stability was determined by Thermo gravimetric analysis (TGA) and Differential Scanning

Calorimetry (DSC) and Scanning Electron Microscopy (SEM) is employed to study the

morphological structure of the composite.




2.3.1 Standard solution

About 0.786 mg of copper sulphate was dissolved in 1000 ml double distilled water (DDW).

The exact concentration of Cu (II) ion was determined by mass equilibrium equation

Q = (C0 - Ce) V/m (1)

Where C0 = initial concentration of copper (mg/L).

Ce = equilibrium concentration of copper (mg/L).

V = volume of copper (II) solution (L)

M = mass of the adsorbent (g).

From the stock solution, the desired concentration of metal ion was freshly prepared.

2.4 Batch adsorption studies

Batch adsorption experiment was performed at 300C as a function of various parameters for

the removal of Cu (II) onto chitosan/sisal/banana hybrid fiber composite. For each

experimental run, 100 ml aqueous Cu (II) solution was taken in 250ml conical flask and

agitated with 1g of CS/SF/BF composite in orbit shaker at fixed speed of 160 rpm. The extent

of adsorption with respect to time was studied in the range of 30 -360 min. whereas pH was

varied between 4 to 8. The pH of each solution was adjusted by adding either dilute NaOH or

HCL solution. The efficiency of adsorption was studied by varying the adsorbent dosage

from 1 to 6g for 1hr contact time. And the adsorbate was removed by filtration through

whatmann filter paper No: 41 (Hanif et al., 2007). The residual concentration of Cu(II) was

determined by Atomic absorption spectroscopy(AAS) using varian AAA 220FS.To avoid the

interference effect, supernatant solution was filtered before to the analysis. After analysis, the

solution was treated according to standard methods (Clesceri et al., 1989).

3. Result and discussion

3.1 Characterization of the hybrid composite

3.1.1 FTIR analysis

The FTIR spectrum of chitosan and CS/SF/BF hybrid composite are depicted in (fig 2a & 2b)

respectively.

Figure 2: FTIR spectrum of (a) pure chitosan (b) chitosan/sisal/banana hybrid fiber

composite

(a)

(b)




FTIR spectrum of pure chitosan shows a strong broad peak at 3454.75cm-1

due to –OH group

and –NH stretching vibration. The two sharp peaks at 1640 cm-1

and 1592 cm-1

due to amide

I and II groups. Peak at 1087cm-1

indicates C-O stretching and 1485cm-1

due to C-N

stretching. Bands at 2923.08 cm-1

is due to –CH stretching vibration of =CH-O-CH2 (C-O-C)

stretching vibration respectively.

In the case of CS/SF/BF composite a broad peak occurs at 3413.74 cm-1

due to –OH

stretching of carboxyl groups in fibers and amide group of chitosan. The shift in this peak

confirms the intermolecular hydrogen bonding and the strong polymerization of CS/SF/BF

composite. A peak at 2921.45 cm-1

refers to aliphatic C-H stretching. The peaks at 1611.26

cm-1

due to amide I band (Liu et al., 2001).

3.1.2 XRD analysis

The X- ray diffraction of pure chitosan and the CS/SF/BF hybrid composite are shown in

figure 3a and 3b. The typical crystalline peak of chitosan appeared at 2θ = 20o. In the XRD

spectrum of the composite (figure 2b) it was observed that intensity of the peak around 2θ =

20o was weakened and a broad peak appeared at 2θ = 41

o shows significant reduction in the

crystallinity and the increased amorphous nature in the composite compared to the pure

chitosan. This result clearly states that chitosan was strongly interacted between sisal and

banana fibers.

Figure 3: XRD of (a) pure chitosan, (b) chitosan/sisal/banana hybrid composite.

3.1.3 DSC analysis

DSC is an important analytical tool in determining the thermal stability of the composite. (Qu

et al., 2000). Two stage of heating process was done for the DSC analysis. The first stage

heating is used to decrease the water content in the films and release the stress.

The DSC curve of pure chitosan and CS/SF/BF hybrid composite is depicted in figure 4a and

4b. The figure 4b revealed that the pair of broad endothermic peak at 117oC and 177

oC is due

to the loss of water from chitosan while a high intense exothermic peak at 297.14oC due to

decomposition of glycoside units (Guinesi and Cavalheiro, 2006). From the single glass

transition temperature, we conclude that CS/SFBF hybrid composite has formed. From table

1, increasing Sisal fiber and banana fiber contact decreased the crystalline nature of pure

chitosan. This is greatly due to the interaction between fibers and acetyl glucosamine groups

in chitosan (Neto et al., 2005). Hence the degree of crystallinity for the CS/SF/BF hybrid




composite was lesser than the pure chitosan, which was consistent with the result of X- ray

diffraction studies.

Table 1: Fiber variation data ( Fiber vs crystalline nature)

S.No Sample ToC ∆H(J/g)

1 Chitosan 312.26 194.1

2 CS/SF/BF 297.08 58.01

Figure 4: DSC of (a) pure chitosan (b) CS/SF/BF hybrid composite.

3.1.4 Morphological Studies of CS/SF/BF Hybrid Composite

The scanning electron micrograph of the surface and cross section of CS/SF/BF hybrid

composite are shown in fig 5a and 5b respectively. The composite modified the surface

morphology of chitosan matrix significantly making it useful for water treatment. The SEM

image of CS/SF/BF hybrid composite revealed an irregular, rough surface (i.e. heterogeneous

phase) and composite immiscibility nature.

Figure 5: Scanning electron micrographs of (a) surface (b) cross section of CS/SF/BF hybrid

composite

(a)

(b)




3.2 Factors influencing the Adsorption of Copper (II) ion

3.2.1 Effect of pH

Figure 6 shows the adsorption of metal ions was strongly influenced by pH. Under highly

acidic conditions (i.e. pH = 1 to 2) removal of Cu (II) ion was found to be very less. This may

be due to the competition between hydrogen ion and metal ion for the same adsorbent site.

(Puranik and Paknikar, 1999). However, adsorption increases gradually till pH= 4 and

increase drastically pH>4. At higher pH > 5.0 the adsorptive removal of Cu (II) ion decreases.

This may be due to the formation of insoluble copper hydroxide. (El-said et al., 2010). The

maximum removal efficiency was 89.0% at the optimum pH of 5.

Figure 6: Effect of pH on the uptake of Cu

2+ ion by the CS/SF/BF hybrid composite.

3.2.2 Effect of adsorbent dose

The effect of varying the adsorbent amount from 1 to 6 g, while keeping other parameters

such a pH and contact time constant. Figure (7) reveals that the adsorption of metal ions

gradually increased by increasing its dosage.

Figure 7: Effect of adsorbent dose on the uptake of Cu

2+ ion by the CS/SF/BF hybrid

composite.

The adsorption capacity increases rapidly on increasing the adsorbent dose till 3g. This may

be attributed to the large surface area in turn number of adsorption sites. (Mall et al. 2006).

The maximum removal of Cu (II) ion was 87.4% at 3g of adsorbent. Further addition of




CS/SF/BF composite did not show any significant removal of metal ion. Thus the maximum

adsorption had taken place at the optimum dose of 3g hence the metal ion in the solution

remains constant. (Namasivayam et al., 1998).

3.2.3 Effect of Contact time

Figure 8 indicates the uptake of Cu (II) ions was increased as the contact time increases. The

rapid removal of Cu (II) ion was noticed (from 45.3 to 87.5%) with the contact time variation

from 30 to 240 mins, respectively. This is because at the early stage, more number of

potentially active/vacant sites is available for adsorption. As the contact time increases

maximum number of sites got adsorbed to the metal ions. Hence it is difficult for the metal

ion to search for the very fewer remaining sites. Therefore rate of adsorption decreases in the

later. (El-said et al. 2010). Hence 240 min was found to be an optimum treatment time

(Guinesi and cavalheiro, 2006).

Figure 8: Effect of contact time on the uptake of Cu2+

ion by the CS/SF/BF hybrid composite.

3.3 Adsorption equilibrium studies

Equilibrium adsorption isotherm is the basis to design the adsorption process. In this study

Freundlich, Langmuir, Tempkin and Dubinin – Radushkevich (D-R) isotherm models were

studied.

3.3.1 Freundlich Adsorption Isotherm

In 1906, H M F Freundlich proposed an empirical equation in order to study the relationship

between concentration of metal ion in the adsorbent and at equilibrium solution (Mahajan and

sud 2011).

It is expressed by the following equation

qe = Kf(Ce)1/n

(2)

Taking logarithm on both sides, equation (2) becomes

log qe = log Kf + 1/n log Ce (3)




Where Kf and n represents Freundlich constants (Teng and Hsieh, 1998), Ce is the

equilibrium concentration (mg/L), qe is the solid phase ion concentration (mg/L).

The value of Kf and n determines the nature of the curve and extent of the adsorption. Higher

the value of Kf (Kf = 1.8849) and less than unity is the value of 1/n (0.8510), indicates the

beneficial sorption of Cu (II) ions onto CS/SF/BF composite. (Teng and Hsieh, 1998).

0 1 2 30.0

0.5

1.0

1.5

2.0

2.5

logce

log

Ye

Figure 9: Freundlich isotherm for copper.

3.3.2 Langmuir Adsorption Isotherm

Langmuir Predicts the adsorption is a monolayer that too on a completely homogeneous

surface without any interaction between the adsorbed species. (Neto et al., 2011).

Inspite of some drawbacks in Langmuir isotherm model it helps us to fix the optimum

operation conditions for adsorption process. (Bailey 1999). The linearized form of Langmuir

isotherm model is stated as

Ceq/Cads = bCeq/KL + 1/KL (4)

Where Cads = concentration of adsorbed metal ions (mg/g)

Ceq = equilibrium concentration of metal ion in solution (mg/dm3)

KL = Langmuir constant (dm-3

/g)

Cmax = maximum metal ion adsorbed onto 1g of adsorbent (mg/g)

The constant b and KL are related to the enthalpy of adsorption (Schmuchl et al., 2001). A

linearized plot of Ceq/Cads against Ceq gives the values of KL and b respectively.

The correlation coefficient (R2) value and the value of slope less than unity confirms that

considerable amount of adsorption had taken place. Fitting the experimental data to one

particular isotherm model is not necessarily to imply that a ‘pure’ adsorption phenomenon

has taken place (Mark, 2006; Volesky 1990).




Copper

0 50 100 150 2000.6

0.8

1.0

1.2

1.4

Ceq (mg/dm3)

Ce

q/Y

ad

s (

g/d

m3)

Figure 10: Langmuir isotherm for copper

3.3.3 Tempkin Isotherm

Tempkin model suggested that distribution of uniform binding energy. Always heat of

adsorption falls linearily and there is an interaction between the adsorbate and adsorbing

species. (Tempkin and Pyzhev, 1940). It is expressed as

qe = B ln A + B ln Ce (5)

Where, B = RT/b

‘A’ = Tempkin isotherm constant.

‘b’ = constant related to heat of sorption.

‘R’ = gas constant (8.314 J/mol//k).

‘T’ = absolute temperature (K)

The isotherm constants A and b are obtained from the plot of qe verses ln Ce. The data are

listed in table 2.

2 4 6

-50

0

50

100

150

200

lnCe

qe

Figure 11: Tempkin isotherm for copper




3.3.4 Dubinin – Radushkevich (D-R) isotherm

This isotherm was proposed by Dubinin – Radushkevich in 1947. It assumes that the porous

nature of the adsorbent determines the rate of adsorption. (Dubinin, 1960). The linearized

equation of D-R isotherm can be stated as

Ln qe = ln qm – βε2 (6)

Where, qe = equilibrium concentration of metal ion on the adsorbent (mol/g).

qm = maximum adsorption capacity (mol/g)

β = activity coefficient of mean free energy (mol2/J

2)

ε = Polanyi potential.

The value of E can be calculated from

ε = RT ln (1+ 1/ Ce) (7)

A linearized plot of ln qe Vs E2 enables to determine the value of B and qm from the slope and

intercept. From the value of activity coefficient B, biosorption mean free energy E (KJ/mol)

is determined as follows

E =1/ (-2B) ½

(8)

The calculated D-R constants and mean free energy for adsorption are shown in Table 2. The

numerical value of mean free energy E calculated from Dubinin – Radushkevick (D-R)

isotherm model was 0.7843 kJ/mol. If the value of E lies between 8 – 16 kJ/mol, the process

is said to follow chemical ion exchange while E < 8 kJ/mol then the process follows physical

adsorption (Horsfall et al, 2004). In the current study the biosorption process of Cu (II) onto

CS/SF/BF follows physical adsorption.

Copper

0 1 2 3 40

2

4

6

e2

lnq

e

Figure 12: D-R isotherm for copper.

Table 2: Isotherm constants for copper (II) adsorption onto CS/SF/BF hybrid composite

Isotherm model Parameters CS/SF/BF hybrid

composite

Cm

KL 0.7706

b 0.0022

Langmuir

R2 0.7389




KF 1.8849

1/n 0.8509

Freundlich

R2 0.9990

A 10.03

b 33.09

Tempkin

R2 0.8516

QD 4.589

E 0.7843

D – R

R2 0.8365

3.4 Adsorption kinetic studies

The controlling mechanism or rate determining step of Cu (II) uptake on the adsorbent was

studied by Lagregan pseudo first order, second order and intra-particle diffusion models

(Mahajan and sud, 2011). From the literature Biosorption of divalent metal ions by various

adsorbents mostly followed pseudo – second order reaction. (Ho, 2001; Krishnan, 2003).

3.4.1 Pseudo –first order model

This model assumes that rate of adsorption is directly proportional to the number of

adsorption sites on the adsorbent. The pseudo first order kinetic equation may be expressed as

log (qe – qt) = logqe – k1t/2.303 (9)

where qe and qt are the amount of Cu2+

ions adsorbed (mg/g) at equilibrium and at time t,

(min) respectively, and k1 is the equilibrium constant.

Thus a plot of log (qe – qt) against is drawn to calculate the intercept and slope. The

low correlation coefficient R2 value (R

2 = 0.9734) shows the inapplicability of the model.

100 200 300 400

-1

0

1

2

3

Time(min)

log

(qe-q

t)

Figure 13: Pseudo first order kinetics for copper.

3.4.2 Pseudo second order model: This model describes the rate of adsorption is based on the square of number of vacant sites

on the adsorbent. The pseudo second order kinetic is given below

t/qt = 1/k2qe2 + t/qe (10)




A plot of t/qt against t predicts the values of second order rate constant k2. The obtained

correlation coefficient (R2) value is found to be 0.9977.

On comparing the correlation coefficient R2

of pseudo first order and second order kinetic

model the latter one shows the higher value hence the adsorption follows pseudo second

order kinetics. (Hanif et al., 2007).

Figure 14: Pseudo second order kinetics for copper.

3.4.3 Intra – particle diffusion model

This model describes about the diffusion of the adsorbate (particle) from the outer surface

into the pores of the composite. (Weber and Morris, 1963). It is also known as Weber and

Morris equation is given as

qt = Kd t0.5

+ I (11)

Where Kd is the particle diffusion rate constant (mg/g/min1/2

), I characterizes the extent of

diffusion. A plot of qt Vs t0.

5 gives the value of Kd and I from the slope and intercept. If it

gives a linear line and it passes through the origin then the intra particle diffusion is

considered to be the rate determining step. Fig (15) depicts two linear portions; the first part

of the curve is due to boundary layer diffusion, whereas the last part of the curve is due to the

diffusion of Cu2+

ions. Similar conclusions have been reported in the earlier studies of

adsorption of Zn (II) ions onto chitosan (Karthikeyan et al., 2004). Higher the value of Kd

more porous is the surface of the composite. Hence the rate of adsorption is more. The

diffusion rate parameters were shown in table (3):

Table 3: Parameters values calculated using pseudo first order, pseudo second order and intra

particle diffusion models for the biosorption of Cu (II) by CS/SF/BF hybrid composite

First order kinetic model Second order kinetic model Intra particle

diffusion model

k1(min-

1)

qe(mg/g

)

R2 k2

(mg/g/min)

qe

(mg/g)

R2 Kd

(mg/g/min0.5

)

R2

0.00822

7

282.97 0.956

0

0.005007 41.44 0.996

7

6.193 0.9012

From the above table 3 clearly indicates that the correlation coefficient R2 is higher for

pseudo second order model when compared to pseudo first order kinetics and intra-particle




diffusion model. This suggests that the adsorption was best fitted by the pseudo second order

model.

Figure 15: Intra particle diffusion kinetics for copper.

4. Conclusion

The composite CS/SF/BF hybrid composite was prepared successfully and it was confirmed

by FTIR, X ray, DSC and SEM analysis. From the above results it is obvious that sorption

efficiency was dependent on operating conditions such as pH, contact time, adsorbent dose.

The optimum pH for the maximum removal of Cu (II) ion from an aqueous solution is found

to be 5.0. Increase of adsorbent dose prominently increased the adsorption due to an increase

in the surface area. The equilibrium data were analyzed by Freundlich, Langmuir, Tempkin,

Dubinin- Radushkevich (D-R) isotherm models. The Freundlich adsorption isotherm

provided the best fit, suggesting multilayer layer adsorption on a heterogeneous surface. The

kinetic model indicates the adsorption of copper (II) ion from solution by CS/SF/BF hybrid

composite corresponds to the pseudo second order reaction. Also, Intra particle diffusion

study suggested that the diffusion of copper ions is very fast in the beginning and then

stabilizes slowly. The obtained results showed the prepared composite proves its high

efficiency in removing the copper (II) ions from aqueous solution. On the economical front

application of this (CS/SF/BF) hybrid composite for heavy metal removal could be tested in

industrial environments.

5. References

1. Abdul khalil H P S, Siti Alwani M, Mohd omar A K, (2006), Chemical composition,

anatomy, lignin distribution and cell wall structure of Malaysian plant waste fibers,

Bio resources,1(2), pp 220-232.

2. Abideen Idowu Adeogun, Andrew E. Ofudje, Mopelola Idowu, and sarafadeen O.

Kareem, (2011), Equilibrium, kinetic, and thermodynamic studies of the biosorption

of Mn(II) ions from aqueous solution by raw and acid treated corncob biomass,

BioResources,6(4), pp 4117-4134.

3. Annie kamala Florence J, Gomathi T and Sudha P N,(2011), Equilibrium adsorption

and kinetics study of chitosan-dust kenaf fiber composite, Archives of applied science

research, 3(4), pp 366-376.




4. Bailey, S.E., Olin, T.J., Brica, R.M., and Adrian, D.D., (1999), A review of

potentially low-cost sorbents for heavy metals, Water Research 33, 2469-2479.

5. Bettini S H P, Bicudo A B L C, Augusto I S, Antunes L A, Morassi P L, Con-datta R,

Bonse B C,(2010), Investigation on the use of coir fiber as alternative reinforcement

in polypropylene, Journal of applied polymer science,118, pp 2841-2848.

6. Chien.P.J, Sheu.F, and Yang.F.H, (2007), Effects of edible chitosan coating on quality

and shell life or sliced mango fruit, Journal of food engineering, 78, pp 225-229.

7. Clesceri.L.S, A.E.Greenberg and R.R.Trussel., (1989), Standard methods for the

examination of water and waste water, 17th

edition, APHA /AWWA/WPCF

publications, Washington D.C., part 3.

8. Dinesh Mohan, Charles U Pittman Jr, Philip H Steele,(2006) Single, binary and

multi-component adsorption of copper and cadmium from aqueous solution on Kraft

lignin- a biosorbent, Journal of colloid and interface science, 297, pp 489-504.

9. Dipa Ray, Suparna Sengupta, siba P Sengupta, Amar K Mohanty, Manjusri

Misra,(2007), A study of the mechanical and behavior of jute-fabric- reinforced clay-

modified thermoplastic starch-matrix composites, Macromolecular materials and

engineering, 292, pp 1075-1084.

10. Du C, Jin J, Li y, Kong X, Wei K, Yao J,(2009), Novel silk fibroin/hydroxyapatite

composite films; structure and properties, Material science and engineering, 29, pp

62-68.

11. El-said, A.G., Badawy, N.A., and Garamon, S.E., (2010), Adsorption of cd(II) and

Hg(II) onto natural adsorbent rice husk ash(RHA) from aqueous solutions: study in

single and binary systems, journal of American science. 6(12), pp 402-409.

12. Favaro S.L., etal.(2010), chemical, morphological and mechanical analysis of sisal –

fiber reinforced recycled high density polyethylene composites, eXpress polymer

letters, 4(8), pp 465-473.

13. Garima Mahajan and Dhiraj sud, (2011), Kinetics and equilibrium studies of

Chromium (VI) metal ion remediation by on Archias hypogeal shells: A green

approach, 6(3), pp 3324-3338.

14. Guinesi.L.S, and cavalheiroETG, (2006), The use of DSC curves to determine the

acetylating degree of chitin/chitosan samples, Thermochimica Acta, 444(2), pp 9281-

283.

15. Hanif, M.A., Nadeem, R., Bhatti. H.N., Ahmad, N.R., & Ansari, T.M., (2007), Ni(II)

biosorption by cassia fistula(golden shower) biomass, Journal of Hazardous materials,

139, pp 345-355.

16. Hasan. S.H., Talat.M, Rai.S, (2007), Sorption cadmium and zinc from aqueous

solution by water hyacinth (Eicchornia crassipes), BioResourceTechnology, 98, pp

918-928.

17. Ho.Y.S. N.g, J.C.Y., Mckay, G.,(2001), Removal of lead (II) from effluents by

sorption of peat using second order kinetics, Science and Technology. 36, 241-261.




18. Horsfall. M. Jnr, Spiff.A.I. and Abia A.A., (2004), studies on the influence of

mercaptoacetic acid(MAA) modification of cassava (manihot sculenta cranz) waste

from biomass on the adsorption of cu2+

and cd2+

from aqueous solution, Bulletin of

the Korean chemical society, 25(7), 969-976.

19. Hossain. M. A, Ngo H H, Guo W S and Nguyen T V, (2012), Biosorption of Cu(II)

from water by Banana peel based biosorbent: Experiments and models of adsorption

and desorption, Journal of water sustainability, 2(1), pp 87-104.

20. Idicula. M , Malhotra S K, Joseph K, Thomas S, (2005), effect of layering pattern on

dynamic mechanical properties of randomly oriented short banana/sisal hybrid fiber

reinforced polyester composite, Journal of Applied polymer science, 97, pp 2168-

2174.

21. Kavitha. D and Namasivayam C,(2007), Experimental and kinetic studies on

methylene blue adsorption by coir pith, Bioresources technology, 98, pp 14-21.

22. Kalavathy.M.H., Karthikeyan.T., Rajgopal.S., Mirinda.L.R., (2005), Kinetics and

isotherm studies of cu(II) adsorption onto H3PO4-activated rubber wood saw dust,

Journal of colloid and Interface science, 292, pp 354-362.

23. Karthikeyan.T., Rajgopal.S., and Mirinda.L.R., (2004) Cr(VI) adsorption from

aqueous solution by Hevea Brasilinesis saw dust activated carbon, Journal of

Hazrdous materials, 124, pp 192-199.

24. Krishnan.K.A., and Anirudhan, T.S., (2003), Removal of cadmium (II) from aqueous

solution by steam –activated sulphurised carbon prepared from sugar-cane bagasse

pith: Kinetics and equilibrium studies, Water SA., 29, pp 147-156.

25. Lantzy.R.J., Mackenzie.F.T.,(1979), Atmospheric trace metals: global cycles and

assessment of man’s impact, Geochim, Cosmochim.Acta, 43, pp 511-525.

26. Li.W., Zhang.S., and Shan.X.Q,(2007), Surface modification of goethite by phosphate

for enhancement of cu and cd adsorption, Colloids and Surfaces

A:Physiochem.eng.Aspects, 293, PP. 13-19.

27. Liu. X.F., Guan Y.L., Yang Z.D., Li Z.& Yao K.D.,(2001), Journal of Applied

Polymer Science, 79, pp 1324.

28. Macquarrie.D.J.,(2005), Modified mesoporous materials as acid and base catalysys’,

Nano porous Materials: Science and Engineering, In G.Q.Lu(Ed).

29. Mall.D.I., Srivatsava.V.C., and Agarwal.N.K., (2006), Removal of orange-G and

methyl violet dyes by adsorption onto bagasse fly ash – kinetic study and equilibrium

isotherm analyses, Dyes and pigments, 69, pp 210-223.

30. Manoranjan Biswal, smita Mohanty, sanjay K Nayak,(2009), Influence of originally

modified nanoclay on the performance of pineapple leaf fiber-reinforced

polypropylene nanocomposites, journal of applied polymer science,114, pp 4091-

4103.

31. Mao.H.Q., K.Roy., V.L.Troung-Le, K.A.Janes, K.Y.Lin, W.Yan, J.T.Augustand

K.W.Leong., (2001),’ Chitosan-DNA nanoparticles as gene carriers: Synthesis,




characterization and transfection efficiency, Journal of Control Release, 70, pp 399-

421.

32. Maria Alexandre-Franco et al(2011), Adsorption of cadmium on carbaneous

adsorbents developed from tire rubber, Journal of environmental management, 92, pp

2193-2200.

33. Namasivayam.C., Prabha.D., and Kumutha.M., (1998),’ Removal of direct red and

acid brilliant blue by adsorption onto Banana pith, BioResources Technology, 64, pp

77-79.

34. Neto et al., (2011), Use of coconut bagasse as alternative adsorbent for separation of

copper(II) ions from aqueous solutions: Isotherms, kinetics, and

thermodynamicstudies, BioResources, 6(3), pp 3376-3395.

35. Nriagu.J.O.,(1979),Global inventory of natural and anthropogenic emissions of trace

metals to the atmosphere.Elsevier/Nature, 279, pp 409-411.

36. Puranik P.R., and K.M. Paknikar., (1999), Biosorption of lead, cadmium and zinc by

citrobacter strain MCM B-181: Characterization studies, Biotechnology progress, 15,

pp 228-237.

37. Qu X., Wirsen. A., Albertsson A-C. (2000), Effect of lactic /glycolic acid side chains

on the thermal degradation kinetics of chitosan derivatives, Polymer, 41, pp 4841-

4847.

38. Ravi Kumar. M.N.V.,(2000). A review of chitin and chitosan applications,

Reactive and Functional Polymers, 46(1), pp 1-27 .

39. Renata S D Castro et al, (2011), Banana peel applied to the solid phase extraction of

copper and lead from river water: Preconcentration of metal ions with a fruit waste,

Industrial and Engineering chemistry research, 50, pp 3446-3451.

40. Rengaraj.S., Kim.Y., Joo, C.K., and Yi.J., (2004), Removal of copper from aqueous

solution by aminated and protonated mesoporousaluminas: Kinetics and equilibrium,

Journal of Colloidal interface science, 273, pp 14-21.

41. Ross. S. M.,(1994), Toxic metals in soil-plant systems, Wiley,chichester,U.K.

42. Saeed. A., Iqbal. M., Akhtar. M.W., (2005), Removal and recovery of lead (II) from

single and multimetal (Cd, Cu, Ni, Zn) solution by crop milling waste (black gram

husk), J.Hazard.Mater. B117, pp 65-73.

43. Saifuddin M. Nomanbhay and Kumaran Palanisamy,(2005), Removal of heavy metal

from industrial waste water using chitosan coated oil palm shell charcoal, 8(1), 41-53.

44. Samir kumar Acharya, Punyapriya Mishra and Suraj Kumar Mehar, (2011), Effect of

surface treatment on the mechanical properties of Bagasse fiber reinforced polymer

composite, BioResources, 6(3), pp 3155-3165.

45. Schmuchl R, Krieg H.M. and Keizer. K, (2001), Adsorption of cu (II) and cr (VI) ions

by chitosan: Kinetics and equilibrium studies, Water SA, 27, pp 1.




46. Smita Mohanty., Sanjay K. nayak., (2006), Mechanical and Rheological

characterization of treated Jute-HDPE composites with a different morphology,

Journal of Reinforced Plastics and composites, 25(13), pp 1419-1439.

47. Subramanian. K. and Yiocoumi. S., (2001), Modeling kinetics of copper uptake by

inorganic colloids under high surface coverage conditions, Colloids surface, 191, pp

145-159.

48. Temkin. M., and Pyzhev.V. (1940), Kinetics of ammonia synthesis on promoted iron

catalysts, Actaphysiochim.USSR, 12, pp 217-222.

49. Teng, Hsisheng and Hsieh, Chien-To.,(1998), Influence of surface characterization on

liquid-phase adsorption of phenol by activated carbons prepared from bituminous

coal, Industrial and Engineering chemistry Research, 37(9), pp 3618-3624.

50. Volesky, B., (1990), Biosorption of heavy metals, Biotechnology progress, 11, pp

235-250.

51. W.J. Weber Jr., J.C. Morris, (1963), Kinetics of adsorption on carbon from solutions,

Journal of Sanitary Engineering Division .ASCE, 89, pp 31-60.

52. Xiao Xiao et al,(2010), Biosorption of cadmium by endophytic fungus

(EF)Microsphaeropsis sp. LSE10 isolated from cadmium hyper accumulator solanum

nigrum L, Bioresource technology, 101, pp 1668-1674.

53. Yesim Sag, Berya Tatar, Tulin kutsal,(2003), Biosorption of Pb(II) and Cu(II) by

activated sludge in batch and continuous-flow stirred reactors, Bioresource

technology,87, pp 27-33.

54. Zhanhua Huang, Shouxin Liu, Bin Zhang, Lili Xu, Xiaofeng Hu,(2012), Equilibrium

and kinetic studies on the adsorption of Cu(II) from the aqueous phase using a β-

cyclodextrin-based adsorbent, Carbohydrate polymers, 88, pp 609-617.

55. Zhou. L.Y., Wang.Z., Liu and Q.Huang,(2009), Characterics of equilibrium, kinetics

studies for adsorption of Hg(II), Cu(II) and Ni(II) ions by thiourea-modified magnetic

chitosan microspheres, Journal of Hazardous materials., 161, pp 995-1002.

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