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INTERNATIONAL JOURNAL OF ENVIRONMENTAL SCIENCES Volume 2, No 2, 2011 

© Copyright 2010 All rights reserved Integrated Publishing Association 

Research article ISSN 0976 – 4402 

Adsorption of Copper (II) and Nickel (II) Ions on Chitin/Polyvinyl Alcohol 

Binary Blend: Kinetics and Equilibrium Studies 

Hema.S 1 , Kumaran.T. M 2 , Sudha.P.N 3 

1- Part Time Research Scholar, Department of Chemistry, Manonmanium Sundaranar 

University, Tirunelveli, Tamilnadu, India. 

2- Part Time Off Campus Scholar, Dravidian University, Kuppam, Andhra Pradesh, India. 

3- Department of Chemistry, DKM College for Women, Vellore, Tamilnadu, India 

parsu8@yahoo.com 

doi:10.6088/ijes.00202020023 

ABSTRACT 

The presence of toxic heavy metals in electroplating industrial effluent is a pervasive and 

serious pollution problem. The ability of chitin binary blend as an adsorbent for Cu and Ni 

ions in aqueous solution was studied. Chitin was blended with poly(vinyl alcohol) in the 

presence of formaldehyde as a cross linking agent. Removal of Cu and Ni has been found to 

be pH, contact time and adsorbent dosage dependent. Adsorption isotherm studies indicated 

that the adsorptive behavior of metal ions on chitin/PVA binary blend satisfies Freundlich 

assumptions and follows pseudo second order kinetic model. Results show that the 

chitin/PVA binary blend is a good adsorbent for the removal of copper and nickel ions from 

metal solution. 

Keywords: Chitin, poly (vinyl alcohol), formaldehyde, binary blend, effluent. 

1. Introduction 

Water is an essential matter to human and other living organism. Water is polluted in many 

ways like effluent of leather and chemical industries and dye industries (Sudha, 2010). 

Presence of highly toxic heavy metals and synthetic chemicals in ground water, surface water, 

drinking water and aqueous effluent has impact on human and aquatic life (Meena, 2005). 

Heavy metal pollution is a pervasive and extremely serious environmental problem. The 

present situation of heavy metal pollution in many developing countries is even more serious 

largely attributed to their low environmental conscious and also their desire for excess 

economic benefits. Some metal ions such as Hg and Cd are highly toxic even in low 

concentration of 0.001 to 0.1 mg/L (Alkorta et al., 2004; Wang, 2002). So removal of heavy 

metals from waste water is important to protect public health. 

The methods used for the removal of heavy metals include filtration, precipitation, adsorption, 

ion exchange, reverse osmosis and electrolysis etc. These processes may be efficient but 

expensive (Crist et al., 1996). As a result, biological methods such as bio sorption may 

provide an attractive alternate to physio-chemical methods (Kapoor and Viraraghavan, 1995; 

Pagnanelli et al., 2000). Bio sorption is a feasible option because it is both efficient and cheap, 

compared with other conventional methods and having the advantage of low operating cost, 

minimization of volume of chemicals and biological sludge to be disposed off and high 

efficiency in detoxifying very dilute effluents (Ramya et al., 2011). Bio sorbents are prepared 

from naturally abundant waste or bio mass. Recently numerous approaches have been studied 

for the development of cheaper and more effective adsorbents such as fungi (Acosta et al., 

2004), algae (Gupta et al., 2001), Seaweeds (Kratochvil et al., 1998; Elangovan et al., 2008), 

Received on September 2011 Published on November 2011 636

Adsorption of Copper (II) and Nickel (II) Ions on Chitin/Polyvinyl Alcohol Binary Blend: Kinetics and 

Equilibrium Studies 

Micro organisms (Sahin and Ozturk, 2005; Fan et al., 2008) have been used for water 

treatment. Polysaccharides are renewable resources which are currently being explored 

intensively for their application in water treatment (Gupta and Ravikumar, 2000). 

Among various polysaccharide compounds identified, chitin and their derivatives (Ravikumar, 

2000) deserved particular attention. This polysaccharides are abundant, renewable bio 

degradable and are the best choice in water treatment (Bolto, 1995). Chitin is one of the most 

abundant polysaccharide in nature (Knorr, 1982) next to cellulose. It can be found in animals, 

Fungi, mushrooms and yeasts (Roberts, 1992). Chitin can be described as a bio polymer 

composed of N-acetyl-D-glucosamine , a chemical structure very close to cellulose except 

that the hydroxyl group in C-2 of cellulose being replaced by an acetamido group in chitin. It 

is worth noting that both chitin and chitosan are recogonized as excellent metal ligand, 

forming stable complexes with many metal ions (Chui et al., 1996). Chitin is superior to 

chitosan especially in the bio medical fields due to the fact that acetamido group in chitin is 

similar to the amide linkage of protein in living tissues (Muzzareli, 1985). 

Blending is an important process for developing industrial applications of polymeric 

materials and compatibility among components has a marked influence on the resulting 

physical properties of polymer blends (Folkes and Hope, 1985). Blending a natural polymer 

with a synthetic one seems to be a better way of preparing polymeric alloys to meet specific 

needs. Blending improves the mechanical and thermal properties of the individual polymer. 

Poly(vinyl alcohol) is a non toxic, water soluble, synthetic polymer with its excellent film 

forming properties. PVA is a good candidate for use as membranes and hydro gels (Hassan 

and Peppas, 2000; Kim et al., 1992). 

The aim of this study is to prepare binary blend of chitin with poly (vinyl alcohol) in the 

presence of formaldehyde as a cross linking agent. In the present study, the equilibrium 

studies of Cu (II) and Ni (II) were investigated. Experiments have been done as a function of 

pH, adsorbent dose and contact time. The adsorption capacity of Cu(II) and Ni(II) by 

chitin/PVA binary blend were determined using Langmuir and Freundlich equation and 

kinetic studies were done to identify the type of adsorption. Hence this information will be 

useful for further water treatment application. 

2. Materials and Method 

2.1. Materials 

Chitin was kindly gifted by India Sea Food, Cochin, Kerala, India. Poly(vinyl alcohol), 

formaldehyde and other chemicals used in the experiments are of analytical grade. 

2.2. Preparation of chitin binary blend: 

Chitin/poly (vinyl alcohol) binary blend film was prepared by mixing solutions of chitin with 

poly (vinyl alcohol) in the ratio 1:1. Chitin was dissolved in 15% of lithium chloride 

dissolved in DMSO. Poly (vinyl alcohol) was dissolved in water. These two polymers were 

blended in the ratio 1:1 and 10% of formaldehyde was added as a cross linking agent. The 

solution was stirred well and kept overnight at 5 °C to get dry film. 

2.3. Experimental process of removal of copper and nickel 

Hema. S, Kumaran. T. M, Sudha. P. N 

International Journal of Environmental Sciences Volume 2 No.2, 2011 

637

% Removal of Cu(II) and Ni(II) 



Batch studies were performed with different concentrations of nickel chloride and copper 

sulphate to investigate the amount of adsorption. The extent of removal of the two metal ions 

was investigated separately by changing the pH, adsorbent dose, and contact time. The pH of 

the solution was adjusted to different values with either NaoH or Hcl. The stoppered bottles 

were agitated at 30°C by orbital shaker at fixed speed, 160 rpm for various time intervals. 

The adsorbates were separated by Whattman filter paper and supernatant liquid was analyzed 

for residual concentration of the metal ion by atomic adsorption spectrophotometer. Triplicate 

runs differing by less than 1% of all the tests were achieved assuring the reproducibility of 

the obtained results. 

3. Results and Discussion 

3.1. Factors influencing the adsorption of Cu(II) and Ni(II) ions 

Several parameters which influences the adsorption such as adsorbent dose, contact time, pH 

were investigated 

3.1.1. Effect of adsorbent dose 

Adsorption of Cu(II) and Ni(II) was found to depend on the adsorbent dose. So adsorption of 

Cu(II) and Ni(II) was studied by varying the adsorbent dose from 1gm to 5gm, while other 

parameters like time, and pH were kept constant. From Figure 1, it is evident that adsorption 

of Cu(II) and Ni(II) ions was generally increased with increased in the adsorbent dose. This is 

because higher dosage of adsorbent increases the surface area, thereby increasing the greater 

availability of exchangeable sites for the metal ions to get adsorbed. From the results it was 

evident that there was no further increase in adsorption when the adsorbent dose reached 

5gm/L. The maximum % removal of Cu(II) was about 90.09% at the dosage of 5gm and that 

for Ni(II) was about 89% at the same dose. Hence 5 gm was concluded as the optimum 

adsorbent dose. This results also suggests that after a certain dose of adsorbent, the adsorption 

of metal ion reaches maximum and hence the amount of ions bound on the adsorbent site and 

the amount of free ions in the solution remains constant with further increase in the adsorbent 

dose. 

90 

Cu(II) 

Ni(II) 

80 

70 

60 

50 

40 

1 2 3 4 5 

Adsorbent of Dose (gms) 

Figure 1: Percentage removal of Cu(II) and Ni(II) ions using chitin/PVA blend with different 

adsorbent dosage. 

3.1.2. Effect of contact time 

Adsorption of Cu(II) and Ni(II) was studied by varying the contact time from 60 minutes to 

240 minutes (1hr – 4hr) by keeping pH and adsorbent dose as constant. Results revealed that 



638





metal ion removal was increased with increase in contact time before equilibrium was 

reached (Figure 2). There was increase in the adsorption of Ni(II) from 58% to 73% when the 

time was increased from 60 minutes to 120 min. The percentage removal of Ni(II) remains 

constant (88%) at 240 min which shows that the equilibrium was attained even at 240 minute 

itself. Likewise, for the metal ion Cu(II) the rate of adsorption was increased with increase in 

the contact time from 1hr to 2hrs and remained constant (83%) at 4hrs. Thus from the results 

it is evident that the optimum contact time for maximum removal of Cu(II) was 240 min. The 

time parameter is a important factor because it brings us economical waste water treatment 

system. 

90 

85 

Cu(II) 

Ni(II) 

80 

75 

70 

65 

60 

55 

50 

45 

1.0 1.5 2.0 2.5 3.0 3.5 4.0 

Time (Hr) 

Figure 2: Percentage removal of Ni(II) and Cu(II) ions by chitin/PVA blend at different 

contact time. 

3.1.3. Effect of pH 

PH is an important parameter which obviously influences the removal efficiency of Cu(II) 

and Ni(II) ions from the solution. The results showed that Ni(II) and Cu(II) removal was 

maximum at a pH around 5 and decreases beyond 5 which is shown in Figure 3. The 

maximum removal of Ni(II) was about 82.3% at a pH 5 and that of Cu(II) was about 72% at 

the same pH. When the pH was greater than 5, copper ions starts precipitating as Cu(OH) 2 , 

and this fact was confirmed by Wang and Qin (2005). Decrease in adsorption at higher pH 

(pH>6) is due to the formation of soluble hydroxyl complexes (Meena et al., 2003). So the 

adsorption of Cu(II) and Ni(II) was found to depend mainly on solution pH. 

85 

80 

Cu(II) 

Ni(II) 

75 

70 

65 

60 

55 

50 

45 

40 

35 

30 

4 5 6 7 8 

pH 



639

Cads(mg/g) 



Figure 3: Percentage removal of Ni(II) and Cu(II) ions by chitin/PVA blend at different pH. 

3.2. Adsorption Isotherm 

3.2.1. Langmuir model 

Adsorption isotherm is important to describe how solutes interact with adsorbent. The 

Langmuir and Freundlich models are often used to describe equilibrium sorption isotherms. 

The most widely used Langmuir equation is valid for monolayer sorption on to a surface with 

a finite number of identical sites. The Langmuir equation has been frequently used to give the 

sorption equilibrium (Koumanova et al., 2002). The linearized Langmuir isotherm is as 

follows 

where 

C eq /C ads = bc eq /K L + 1/K L (1) 

C max = K L /b (2) 

C eq = equilibrium concentration of metal ion in solution (mg/dm 3 ) 

C ads = amount of metal ions adsorbed (mg/g) 

K L , b = Langmuir constants (dm 3 /g) 

C max 

= Maximum metal ion adsorption on to 1g of adsorbent (mg/g) 

The constant K L in Langmuir equation can be used to calculate the enthalpy of adsorption 

(Schmuchi et al., 2001). A plot of C eq /C ads against C eq gives the values of K L and b (Table 1). 

Figures 4 and 5 explain the isotherm of sorption Cu(II) and Ni(II) ions by chitin PVA blend. 

The isotherm is characterized by the initial region, which is represented as being concave to 

the concentration axis. The isotherm begins to reach a plateau , which can typically be 

described by the Langmuir isotherm (Parfitt and Rochester, 1983). 

800 

600 

400 

200 

0 

0 100 200 300 400 500 

C eq (mg/dm 3 ) 

Figure 4: Isotherm for the adsorption of Cu(II) ions onto chitin/PVAblend. 



640

Ceq/ Cads(gm/dm3) 

Cads(mg/g) 

Ceq/ Cads(gm/dm3) 



600 

400 

200 

0 

0 100 200 300 400 500 


Figure 5: Isotherm for the adsorption of Ni(II) ions onto chitin/PVA blend. 

The Langmuir equation was used to describe the data derived from the adsorption of 

Cu(II)and Ni(II) ions by chitin/PVA binary blend adsorbent over the entire concentration 

range studies (Figures 6 and 7). 

4.0 

3.5 

3.0 

2.5 

2.0 

1.5 

0 100 200 300 400 500 

Ceq (mg/dm 3 ) 

Figure 6: Langmuir plot for the adsorption of Cu(II) ions by chitin/PVA blend. 

5 

4 

3 

2 

1 

0 

0 100 200 300 400 500 


. Figure 7: Langmuir plot for the adsorption of Ni(II) ions by chitin/PVA blend. 



641



Table 1: Langmuir adsorption isotherm constants and C max value 

Metal ions 

Langmuir constants 

Cu(II) K L (dm 3 /g) b(dm 3 /mg) C max (mg/g) R 2 

Ni(II) 2.183 0.003266 668.40 0.9403 

1.545 0.005641 273.88 0.9382 

R L the separation factor is used to predict if an adsorption system is “favourable” or “un 

favourable” (Ngah and Musa, 1998). R L is given by 

R L = 1/1+bC f (3) 

where C f = Final concentration of the metal ion (mg/dm 3 ) 

b = Langmuir adsorption equilibrium constant (dm 3 /g) 

The parameter indicates the isotherm shape according to Table 2. Table 3 explains the 

R L values for different final concentration of Cu(II) and Ni(II) ions. If the R L values are in the 

range of 0

log qe 



3.2.2. Freundlich model 

The widely used empirical Freundlich equation based on a heterogeneous surface is given by 

log q e = log K F + 1/n log C e (4) 

where K F , n are Freundlich constants (mg/g). K F and n can be determined from linear plot of 

log q e against log C e . The linear regression plot of Freundlich isotherm for Cu(II) and Ni(II) 

uptake by chitin/PVA blend is shown in the Figures 8 and 9. 

A comparison between Langmuir and Freundlich isotherm models is tabulated in Table 4. 

The Freundlich constants K F, n, and R 2 determined from model indicated that this model 

better describes the adsorption process in comparison to the Langmuir model. 

3.0 

2.5 

2.0 

1.5 

1.0 

0 1 2 3 

log C e 

Figure 8: Freundlich plot for the adsorption of Cu(II) ions by chitin/PVA blend. 

3.0 

log q e 

2.5 

2.0 

1.5 

0 1 2 3 

log C e 

Figure 9: Freundlich plot for the adsorption of Ni(II) ions by chitin/PVA blend. 



643

log(qe-qt) 



Table 4: Comparison of Langmuir and Freundlich isotherm parameters 

Metal 

ions 

Langmuir isotherm 

Freundlich isotherm parameters 

parameters 

Q max (mg/g) K L (dm 3 /g) b(dm 3 /g) R 2 K F (mg/g) n R 2 

Cu(II) 668.40 2.183 0.003266 0.9403 3.665 1.180 0.9986 

Ni(II) 273.88 1.545 0.005641 0.9382 8.3965 1.46 0.9971 

3.3. Kinetic studies of adsorption 

In order to study the controlling mechanism of adsorption process such as mass transfer and 

chemical reaction, the first order and second order equation were used to test the 

experimental data (Chiou, 2003, Chiou and Li, 2002) is given as 

log (q e – q t ) = log q e – k 1 t/2.303 (5) 

Where q e and q t are the amount of Cu(II) and Ni(II) adsorbed on adsorbent (mg/g) at 

equilibrium and at time t, respectively, k 1 is the rate constant of first order adsorption min -1 . 

The straight line plots of log (q e –q t ) against t was used to determine the rate constant k 1, and 

correlation coefficient R 2 values of Cu(II) and Ni(II) under different concentration range were 

calculated from these plots (Figures 10 and 11). The second order equation may be expressed 

as (Sag 2002, Wu et al., 2000) 

t/q t = 1/k 2 . q e 2 + 1/q e (6) 

where k 2 is the rate constant of second order adsorption (g mg -1 min -1 ). The straight line plot 

of t/q t against t have been tested to obtain rate parameters and it suggests the applicability of 

this kinetic model to fit the experimental data (Figures 12 and 13). 

1.5 

1.0 

0.5 

0.0 

-0.5 

100 200 300 

t(min) 

-1.0 

Figure 10: Pseudo-first-order sorption kinetic plot of Cu (II) on chitin/PVA binary blend. 



644

t/qt(min g mg -1 ) 

log(qe-qt) 

t/qt(min g/mg) 



1.0 

0.5 

0.0 

-0.5 

100 200 300 

t(min) 

-1.0 

-1.5 

Figure 11: Pseudo-first-order sorption kinetic plot of Ni(II) on chitin/PVA binary blend. 

6 

4 

2 

0 

0 100 200 300 

t(min) 

Figure 12: Pseudo-second -order sorption kinetic plot of Cu (II) on chitin/PVA binary blend. 

8 

6 

4 

2 

0 

0 100 200 300 

t(min) 

Figure 13: Pseudo-second-order sorption kinetic plot of Ni (II) on chitin/PVA binary blend. 



645



Metal 

ions 

Table 5: Comparison between pseudo-first-order and pseudo-second-order kinetic 

models for Cu(II) and Ni(II) sorption by chitin/PVA binary blend. 

Pseudo first order 

Kinetics 

Q e (mg/g) k 1 x10 -2 

Experimental Values 

Pseudo second order 

Kinetics 

min -1 (g/mg/min) 

R 2 Q e (mg/g) Q e (mg/g) k 2 

Cu(II) 156.10 9.5 0.9057 39.4 65.4 0.01783 0.9896 

Ni(II) 117.6 9.1 0.9092 32.2 51.59 0.02035 0.9990 

R 2 

The results of the kinetic parameters for Cu(II) and Ni(II) adsorption are given in Table 5. 

Based on the correlation coefficients, the adsorption of Cu(II) and Ni(II) is well described by 

the second order equation. In many cases, the first order equation does not fit well to the 

whole range of contact time and is generally applicable over the initial stage of adsorption 

process (Mc Kay, 1999). In many cases, the second order equation correlates well to the 

adsorption behavior may involve valency forces through sharing of electrons between metal 

cations and adsorbent. 

4. Conclusion 

The bio polymer chitin was blended with poly(vinyl alcohol) in the ratio 1:1 using 

formaldehyde as a cross linking agent. The prepared blend was subjected to adsorption 

studies and the results showed that the adsorbent dose, contact time, and pH had a marked 

influence on the removal of Cu(II) and Ni(II) ions from metal solution. Atomic adsorption 

studies were done to examine the extent of adsorption of Cu(II) and Ni(II) by chitin/PVA 

blend. The adsorption isotherm could be well fitted by Freundlich equation. The adsorption 

process could be best described by second order equation. It can be concluded that 

chitin/PVA binary blend is an effective adsorbent for the collection of Cu(II) and Ni(II) from 

waste water. 

Acknowledgement 

The Authors thank the authorities of DKM college, Thiruvalluvar University, Vellore, 

Tamilnadu, India for their support. 

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