EQUILIBRIUM, KINETIC AND THERMODYNAMIC STUDIES ON BIOSORPTION OF COPPER AND ZINC FROM MIXED SOLUTION BY Erythrina variegata orientalis

LEAF POWDER

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ABSTRACT The aim of the present investigation is to explore the feasibility of biosorption for the removal of copper and zinc from aqueous Cu-Zn mixed solution using freely and abundantly available plant based material Indian coral (Erythrina variegate orientalis) leaf powder. The effects of agitation time, biosorbent size and dosage, initial concentration of Cu-Zn in mixed solution, pH and temperature of the mixed solution on biosorption are determined. Batch investigations indicate that biosorption of Cu-Zn mixture is gradually increased with increase in pH from 1 to 6 (38.25 mg/g to 44.77 mg/g). The biosorption of Cu-Zn mixture is increased from 86.3 to 91.9 % (86.27 to 45.93 mg/g) with increase in biosorbent dosage from 1 to 2 g/L. 91.9 % (45.93 mg/g) of Cu-Zn mixture is removed from the mixed solution containing 100 mg/L of Cu and Zn agitated with 2 g/L of 45 m size adsorbent for an equilibrium agitation time of 30 min. The experimental data are well described by Langmuir (R2=0.99), Freundlich (R2=0.98) and Temkin (R2=0.98) isotherms. The sorption studies follow the second order rate expression (R2 = 0.99) and rate constant is 9.39 g/mg-min. The biosorption is found to increase with decrease in temperature of the mixed solution. From the thermodynamic parameters, sorption is found to be exothermic and reversible.

Introduction Land, water and air are the three precious gifts of nature to mankind. Mankind has a gift to live, and that should be of a good quality free of squalor, disease and deprivation. An important factor for quality of life is the environment in which man exists. Environmental health depends on air quality, water quality, nutrition levels, surroundings, industrial susceptibility and climatic conditions. Enhanced industrial activity during recent decades has led to the discharge of unprecedented volumes of waste water, which is a serious cause of environmental degradation [1]. Heavy metals due to their high toxicity, pose a serious thereat to biota and the environment [2]. Heavy metals, such as lead, copper, zinc, cadmium and nickel are among the most toxic pollutants present in marine, ground and industrial waste waters. In addition to their toxicity effects even at low concentrations, heavy metals can accumulate throughout the food chain, which leads to serious ecological and health hazards as a result of their solubility and mobility [3]. Although copper and zinc are essential trace elements, high levels can cause harmful health effects. Copper is also toxic to a variety of aquatic organisms, even at low concentrations [4]. The excessive intake of copper results in its accumulation in the liver and produces gastrointestinal problems, kidney damage, anemia and continued inhalation of copper containing sprays is linked with an increasing lung cancer among exposed workers [5]. One metal ion which is often released into the environment through industrial activities at concentrations of physiological and ecological concern is zinc. In the Dangerous Substances Directive (76/464/EEC) of the European Union, zinc has been registered as list 2 dangerous substances with environmental quality standards being set at 40 g/L for estuaries and marine water and at 45-500 g/L for fresh water depending on water hardness. Zinc is widely used in coating iron and other metals, in wood preservatives, catalysts, photographic paper, and accelerators for rubber vulcanization, ceramics, textiles, fertilizers, pigments and batteries [6] and as a consequence it is often found in the waste water arising from these processes. The commonly used procedures for removing metal ions from waste water include chemical precipitation, ion exchange, membrane separation, reverse osmosisi, evaporation and electro dialysis [7]. However, the application of these methods is often limited due to their inefficiency, high capital investment/operational costs. Though ionexchange resins and activated carbons are efficient in the removal of metals with high uptake capacities, their utilization may be prohibitively costly for treating large volumes of waste water [6]. Biosorption is a fast and reversible reaction of th heavy metals with biomass [8]. Biosorption can be defined as the ability of biological materials to accumulate heavy metals through metabolically mediated or physico chemical pathways of uptake [9]. The

term biosorbent includes the usage of dead biomass (such as fiber, peat and wool) as well as living plants and bacteria as sorbents. Biosorbent represent cheap filter materials often with high affinity and capacity [10]. The application of biosorption for the removal of individual copper and zinc using the adsorbents ulva fasciata sp. [3], marine algal biomass [4], cassava (manihot sculenta cranz) tuber waste [19], sugarbeet pulp and flyash[20] etc was reported in literature. The biosorption of copper was reported onto carbonate hydroxylapatite derived from eggshell waste [23], palm kernel fibre [17] etc. The investigations were carried out for the removal of zinc using the adsorbents like crab carapace [6], coir [10], tectona grndis L.f.leaves [9]. Based on literature review the biosorption of Cu and Zn from mixed solution by erythrina variegate orientalis leaf powder was carried out in this investigation. The other investigations and their results were tabulated in table 1. Table 1 Results of literature cited Adsorbent [Reference] Papaya wood [1] Ulva fasciata sp. [3] Marine algal biomass [4] Metal study Cu, Zn, Cd Cu, Zn Cu, Zn, Pb, Cd, Ni Cu Zn Cu (II), Zn(II), Pb(II) Cu2+, Pb2+ Zn Results t = 60 min, Langmuir isotherm, second order, Optimum pH= 5, Langmuir isotherm, qmax=26.88 mg/g for Cu and 13.5 mg/g for Zn Optimum pH= 5 for Cu and 5.5 for Zn, t= 60 min, Langmuir isotherm, qmax =1.14 mmol/g for Cu and 0.81 mmol/g for Zn t=20 min, Optimum pH=5, Langmuir isotherm, second order, K=0.0072 Optimum pH= above 4, qmax = 172.5 mg/g, t= 60 min, Langmuir isotherm, qmax = 98.85 mg/g for Cu and 48.85 mg/g for Zn Optimum pH=6, qmax = 4.64 (mg/g) for Cu, Kf = 0.662mmol/g t= 180 min, Optimum pH=5, Langmuir isotherm, qmax = 16.42 mg/g, second order, K=0.0165, exothermic. Optimum pH= 5.6, Freundlich isotherm, Kf = 0.021 mmol/g

Ulva fasciata sp.[5] Crab carapace [6] Phanerochate chrysosporium[7] Barley straws [8] Tectona grndis L.f.leaves [9] Coir[10]

Zn

Palm kernel fibre [17] Cassava (manihot sculenta cranz) tuber bark waste [19] Sugarbeet pulp(SBP)[20] Flyash (FA) [20] Black carrot residues[21]

Cu Cu, Zn, Cd Cu, Zn Cu, Zn Cu (II), Mn (II),Co(II), Ni(II) Cu, Zn, Cd, Pb Cu(II), Cd(II) Zn (II) Cu (II), Pb(II), Ni(II) Cu, Pb, Cd Cu, Zn, Cd

t= 60 min, Optimum pH= 5.01, second order, K= 0.1068 Langmuir isotherm , second order, K= 5.76 x 10-3 for Cu and 5.80x10-3 for Zn Freundlich isotherm, qmax (mg/g) = 0.0024 for Cu and 0.0027 for Zn Langmuir isotherm, qmax (mg/g) = 0.180 for Cu and 0.170 for Zn Optimum pH=5.25, Langmuir isotherm, qmax (mg/g)= 8.745, first order, k= 7.0x103, endothermic Optimum pH>6.0 for Cu and pH>6.5 for Zn t=60 min, Langmuir isotherm, qmax = 142.86 mg/g, Optimum pH=4, Langmuir isotherm, qmax = 37.45 mg/g t= 30 min, Langmuir isotherm t= 24hr, Optimum pH= 3, Langmuir and Freundlich isotherms, second order, K= 0.0716 Optimum pH= 5, Langmuir isotherm

Caulerpa lentllifera[22] Carbonate hydroxylapatite derived from eggshellwaste[23] Calymperes erosum [24] PEI-modified biomass[25] Indigenous isolate enterobacter sp.[26] Exhausted coffee grounds[27] Sago waste [28] Seaweeds [29] Chitosan [30]

Cu, Pb t= 24 hrs, Optimum pH= 4.5 to 5.5, Langmuir isotherm, qmax= 12.42 mg/g second order, R2 = 0.99 Zn (II) Optimum pH= 5.5, Langmuir model, qmax= 135.5 mg/g, second order, K= 0.0003 at 250 mg/L, endothermic Zn (II) t= 6 min, Optimum pH=7,Langmuir and Freundlich isotherms, endothermic

Experimental Biosorbent preparation The Erythrina variegata orientalis is a fast growing, dense, medium-large deciduous tree growing to 15-25 m height spread over 12-15 m with 80-100 year life. The Indian coral trees are abundantly and freely available in rural India and can be discarded without regeneration. The analyses of the leaves indicate the presence of scoulerine, saponin, hydrocyanic acid. Erythrinine (an alkaloid) having properties identical to those of hypaphorine (C14H18N2O2), (+) coreximine, l-Reticuline, erybidine [11]. The matured leaves were collected from Andhra University College campus, Visakhapatnam. The IR spectrum and XRD of Erythrina variegate orientalis leaf powder was indicated the presence of hydroxyl and carboxy moities as major functional groups. The BET surface area of the adsorbent is 22.08 m2/g with a cumulative volume of 7.05 mL/g at STP and monolayer of 5.07 cm3/g[12]. These leaves were thoroughly washed with water to remove dust and water soluble impurities. The leaves were further washed with necessary distilled water to free them of color and turbidity. The leaves were dried under sunlight and powdered. The dry leaf powder was sieved to different fractions (i.e. 45 m, 75 m, 106 m and 212 m) using rotap sieve shaker. These size fractions were preserved in glass bottles for use as a biosorbent. Preparation of stock solution 3.898 gm of 99% CuSO4.5H2O and 4.443 gm of ZnSO4.7H2O were dissolved in 1L of distilled water to prepare 1000 mg/L of copper and zinc mixed stock solution. Samples of different concentrations were prepared from this stock solution by appropriate dilutions. 100 mg/L of mixed solution was prepared by diluting 100 mL (containing50 mL of Cu and 50 mL of Zn) of mixed stock solution with distilled water in 1000 mL volumetric flask up to the mark. Similarly solutions with different concentrations of CuZn mixture (25 mg/L, 50 mg/L, 125 mg/L and 150 mg/L) were prepared. Procedure 50 mL of mixed solution containing 50 mg/L of Cu and 50 mg/ L of Zn was shaken in a 250 mL conical flask and treated with 2 g/L of 45 m size biosorbent for 30 min on an orbital shaker at 180 rpm and 303 K. The sample was settled and filtered through a Whatman filter paper. Then the filtrate was analyzed in an Atomic Absorption Spectrophotometer (Perkin Elmer-AA Analyst-200 (air-acetylene oxidizing flame), wave length for Cu was 324.8 nm and wave length for Zn 213.9 nm) for final concentration of Copper and Zinc separately and the sum is as the final concentration of Cu-Zn mixture. The same procedure was repeated to study the other parameters such as agitation time (t), biosorbent size (dp), biosorbent dosage (w), initial concentration of Cu Zn mixture in the mixed solution (Co), pH of the mixed solution and temperature (T) on biosorption

of Cu Zn. The range of the experimental parameters investigated in this biosorption studies are compiled in table-2. Table- 2 Experimental parameters investigated Parameter Agitation time, t, min Biosorbent size, dp, m Biosorbent dosage, w, g/L Initial concentration of Cu-Zn mixture, Co, mg/L pH of the mixed solution Temperature, K Values 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 60, 120 & 180 45, 75, 106 & 212 1, 2, 5 & 10 25, 50, 75, 100, 125 & 150 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11& 12 283, 293, 303, 313 & 323

The percentage removal of copper and zinc is calculated as: % removal = (C0-Ce) x 100/ C0 (1)

where Co and Ce are the initial and final concentrations of the cu-zn in the mixed solution. The metal uptake is calculated as: qe = {(Co- Ce) V} / w (2)

where qe is the metal uptake(mg/g), V is the volume of the mixed solution and w is the dosage of the biosorbent. Adsorption isotherms Adsorption isotherm is important to develop an equation that accurately represents the results and can be used in design of sorption systems [16]. Three adsorption modelsFreundlich, Langmuir, and Temkin were used to describe the equilibrium between adsorbed metal ions of Cu- Zn mixture on Erythina variegate orientalis leaf powder at a constant temperature. According to the Freundlich equation [13], the amount of substance adsorbed per gram of adsorbent (qe) is related to the equilibrium concentration (Ce) as: qe = Kf Cen or log qe = n log Ce + log Kf .. ........... (3) (4)

where Kf (mg/g) is the constant indicative of the relative adsorption capacity of the adsorbent and n is the constant indicative of the intensity of the adsorption.

The Langmuir model [14], is valid for monolayer adsorption onto a surface containing a finite number of identical sites. It is probably the most popular isotherm model due to its simplicity and its good agreement with experimental data. It could be described by the linearised form: (Ce/qe) = 1/(Ka qmax) +Ce/qmax .... (5)

where qmax the maximum amount adsorbed, Ka is an equilibrium adsorption constant, Ce is the concentration of the adsorbate at equilibrium and qe is the amount adsorbed at equilibrium in unit mass of the adsorbent. By plotting a graph between C e and (Ce/qe), qmax and Ka can be determined from the slope (1/qmax) and the intercept (1/Ka qmax). The Temkin isotherm equation [15] describes the behavior of many adsorption systems on heterogeneous surface and it is based on the following equation: qe= RT ln (atCe)/bt (6)

The linear form of temkin isotherm can be expressed by Eq. (7): qe = A+B ln Ce (7)

where R is the gas constant, T absolute temperature (K), A (= RT/b t ln at) and B (= RT/ bt) isotherm constants respectively. Kinetics of sorption The order of adsorbate- adsorbent interactions has been described by using various kinetic models. In the case of adsorption preceded by diffusion through a boundary, the kinetics in most cases follows the pseudo- first-order rate equation of Lagergren[16] : (dqt/dt) = kad (qe - qt) (8)

where qt and qe are the amount adsorbed at time t and at equilibrium, and k ad is the rate constant of the pseudo-first-order adsorption process. The integrated rate law, after applying the initial condition of qt=0 at t=0, is log (qe - qt) = log qe (kad /2.303) t (9) Plot of log (qe-qt) versus t gives a straight line for first-order kinetics, which allows computation of the adsorption rate constant, kad. The pseudo-second-order kinetics [17] may be expressed as: dqt/dt = k (qe-qt)2 (10)

is applicable. For the boundary conditions t=0 to t=t and qt=0 to qt=qt, the integrated form of the equation is 1/(qe-qt) = (1/qe) + kt that can be written as (t /qt) = (1/ kqe2) + (t/qe) . (12) (11)

If the pseudo-second order kinetics is applicable, the plot of t/qt versus t gives a linear relationship, that allows computation of qe, k and kqe2 . Thermodynamics of adsorption According to Lechatelier principle, the amount adsorbed at a given concentration decreases as temperature increases. During adsorption, physical changes like spontaneity of adsorption and experimental results like rate constant of that particular adsorption process will be effected with the changes in three thermodynamic parameters. Enthalpy change (H), entropy change (S) and change in Gibbs free energy (G) due to transfer of unit mole of solute from solution to the solid-liquid interface. These values can be obtained by carrying out the adsorption experiments at different temperatures. The biosorption data were obtained at temperatures (283 K, 293 K, 303 K, 313 K and 323 K). The thermodynamic parameters for adsorption were evaluated from the well known relation [18]: log K = - G/ (2.303RT) = - H/ (2.303 RT) + (S/2.303 R)......... (13) where K= qe/Ce. Plot of log (qe/Ce) versus (1/T) yields a straight line with slope =- H/ (2.303 R) and intercept = S/(2.303R). RESULTS AND DISCUSSION Effect of agitation time: The equilibrium agitation time is determined by plotting the % removal of Cu-Zn against agitation time in fig. 1 for biosorbent sizes of 45, 75, 106 and 212 m using 0.1g (2 g/L) dosage for C0=100 mg/L. The % removal of Cu-Zn mixture is found to be very quick and equilibrium is attained in 30 min. The percent removal for 45 m, 75 m, 102 m and 212 m sizes are 91.86%, 89.89%, 83.98% and 78.31% respectively. 20-30 min of equilibrium agitation time had been reported for the removal of Cu and Zn by cassava tuber bark waste [19]. An equilibrium agitation time of 60min was reported for cu and zn by the adsorbents papaya wood [1], sugar beet pulp and flyash [20], marine algal biomass [4]. The equilibrium contact time of 30 min for Cu (II) adsorption by black carrot

(Daucus carota L.) residue was observed by Guzel [21]. Equilibrium agitation time of 60 min was reported for copper removal by palm kernel fiber [17]. Effect of adsorbent size and dosage: The effect of biosorbent size on % removal of Cu-Zn mixture was shown in fig.2 with % removal as a function of dp for dosages of 1, 2, 5, 10 g/L. It is observed that the % removal of metal decreases with increase in biosorbent size. With decrease in biosorbent size, surface area of the biosorbent increases and more number of active sites on the biosorbent are exposed to the adsorbate, resulting in increased metal uptake (qe =9.335mg/g).The maximum removal of 93.09% was observed with 45 m particle size at the dosage of 10g/L with a metal uptake capacity of 9.335mg/g. The percent removal was decreased from 86.27% to 77.20% for the adsorbent sizes 45 to 212 m at 1g/L biosorbent dosage. Percent removal of mixture was increased from 86.27% to 93.09% with an increase in adsorbent dosage from 1 to 10 g/L (fig. 3). The change in % removal is very small when biosorbent dosage (w) is increased from 2 to 10 g/L (i.e., 91.86% to 93.09%). Therefore optimum biosorbent dosage of 2 g/L is used to study the remaining parameters. The adsorbent size of 75m was used for zinc by tectona grandis L. f leaves biomass. They revealed that the metal uptake of zinc on tectona grandis L. f leaves decreases from 4.3866 to 3.256 mg/g with the increased particle size from 75 m to 212 m. It is well known that decreasing the average particle size of the adsorbent increases the surface area, which in turn increases the adsorption capacity [9]. Effect of pH of the mixed solution: The effect of pH on biosorption of Cu-Zn mixture is shown in fig.4 for 2 g/L of 45 m biosorbent size varying pH from 1 to 10. The % biosorption of Cu-Zn mixture is increased gradually from pH = 1 to 6 (76.5% to 89.55%) and decreased gradually beyond pH value of 6 (86.25% to 80%). At less pH values % biosorption is low because the metal ions will compete with H+ ions for appropriate sites on the adsorbent surface. However, with increasing pH (upto neutral value), this competition weakens and metal ions replace H+ ions bound to the adsorbent or forming part of the surface functional groups such as OH, COOH. As pH is increased from 6, OH - ions will be increased and these will compete with metal ions. Formation of precipitation is also observed beyond pH 8. Apiratikul, et al [22] observed a formation of precipitation of heavy metal at pH>6 for cu and pH>6.5 for zn. The pH of 5+0.2 is used for the adsorption of Cu and Zn by green macroalga. A pH of 5 has been fixed for the adsorption of both Cu and Zn by cassava tuber bark waste [19]. Saeed et al [1] investigated that, at pH=5 the optimum biosorption was reached with 97.3% removal of Cu and 66.6% removal of Zn. Pehlivan et al [20] had identified the maximum overall uptake of copper by SBP as 30.9mg/g at pH=5.5 and by flyash 7mg/g at pH=5. They also reported the maximum uptake of zinc by SBP as 35.6mg/g at pH=6 and by flyash 7.84mg/g at pH=4. Kumar et al [3] reported optimum pH=5 for Cu and Zn removal with 0.1 g/L and 26.88 mg/g and metal capacity respectively. In all the above investigations maximum removal was reported in the pH

range of 5 to 6 for both Cu and Zn. In the present investigation, maximum removal of Cu - Zn mixture (89.55%) was obtained at pH = 6 for 2 g/L of 45 m size biosorbent in 100 mg/L of mixed solution. Effect of initial concentration of Cu-Zn mixture: Fig.5 represents the variation in biosorption of Cu-Zn mixture with initial concentration of cu-zn mixed solution. Results from the plots indicate that the % removal of Cu-Zn mixture is decreasing (from 92.23% to 85.99%) significantly with an increase in initial concentration of Cu-Zn mixed solution Co from 25 mg/L to 150 mg/L. The metal uptake capacity was increased from 11.53 mg/g to 64.49 mg/g as the concentration of mixture was increased. The effect of initial copper ion concentration (50 to 250 mg/dm3) on copper ion uptake onto palm kernel fiber was studied by Yuh- Shan Ho et al [17]. They reported that the amount of cu ions adsorbed at equilibrium increased with an increase in initial Cu ion concentration. The removal of cu ions increased from 4.451 to 13.07 mg/g when the initial copper ion concentration was increased from 50 to 250 mg/dm3 at pH 5.01. Lu et al [6] increased the initial zn2+ concentration from 10 to 140 mg/L and the removal efficiency was decreased rapidly from 99% to 65.25 % on small crab carapace particles. Freundlich, Langmuir and Temkin isotherms Freundlich isotherm is drawn for the present data between log Ce and log qe in fig.6. The resulting line has the correlation coefficient of 0.98. The following equation is obtained: log qe = 0.790 log Ce + 0.858, R2= 0.98 . (14)

The slope (n) of the above equation is 0.79 this value satisfies the condition of 0 < n< 1 indicating favorable adsorption. Langmuir isotherm, drawn in fig.7, has good linearity correlation coefficient of 0.99 indicating strong binding of Cu-Zn mixed solution to the surface of erythrina variegata orientalis leaf powder. The data are well correlated by the equation: (Ce/qe) = 0.008 Ce + 0.146, R2 = 0.99 (15)

To study the suitability of Temkin isotherm, a graph is plotted between ln Ce and qe in fig.8. The resulted equation is: qe = 22.44ln Ce - 6.44, R2 = 0.98 .. (16)

R2= 0.98 indicates that the Temkin isotherm is suitable for the present study. Freundlich, Langmuir and Temkin constants obtained in the present investigation are compiled in table 3.

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Table-3 Freundlich, Langmuir and Temkin constants for Cu-Zn mixed solution Langmuir isotherm qmax(mg/g) ka 125 856.16 R2 0.99 Freundlich isotherm Kf N R2 7.095 0.79 0.98 Temkin isotherm at bt R2 (L/mg) 0.75 112.26 0.98

Kinetics of biosorption: In order to determine the order and rate of the biosorption, 50 mL of mixed solution was taken in each of fourteen 250 mL conical flasks. 2 g/L of 45 m size biosorbent was added to each sample. The contents of conical flasks were shaken in an orbital shaker for different agitation times (1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 60, 120 and 180). Similar procedure was adopted for the biosorbent dosages of 0.05 gm, 0.25 gms and 0.5 gms (1, 5 and 10 g/L) with 45 m biosorbent size. The pseudo first order Lagergren plot of log (qeqt) versus agitation time (t) for biosorption of cu-zn mixture for biosorbent size of 45 m and at different biosorbent dosages 1, 2, 5 and 10 g/L erythrina variegata orientalis leaf powder was drawn in fig 9. The resulting equations and constants are shown in table-4. Table -4 Lagergren equations and its coefficients w, g/L 1 2 5 10 dp, m 45 45 45 45 Equation log (qe-qt) = 0.042 t +1.36 log (qe-qt) = 0.028 t + 1.073 log (qe-qt) = 0.0316 t+0.687 log (qe-qt) = 0.0314 t+0.375 kad, min-1 0.096 0.0644 0.0727 0.723 R2 0.99 0.95 0.95 0.90

To identify the suitability of rate equation, the second order rate equation is applied for the present data and the plots of (t/qt) versust are drawn in fig. 10. The pseudo second order model based on equation (11), considers the rate -limiting step as the formation of chemisorptive bond involving sharing or exchange of electrons between the adsorbate and adsorbent. The second order rate equations obtained from the graph are shown in table 5. 11

Table-5 Pseudo-second-order equations and its coefficients w, g/L 1 2 5 10 Equation (t/qt) = 0.011 t + 0.010 (t/qt) = 0.022t + 0.022 (t/qt) = 0.055 t + 0.054 (t/qt) = 0.109 t + 0.111 k x 104, g/(mg-min) 82.9 9.39 0.61 0.07 R2 0.99 0.99 0.99 0.99

So, second order rate equation better explains the interactions of Cu-Zn mixture than the first order rate equation as the R values are higher in case of second order rate equations. Thermodynamics of biosorption The biosorption data are obtained for various initial concentrations of the mixed solution adding 2 g/L of 45 m size adsorbent. Fig. 11 indicates that increased temperature results in lower % removal of cu-zn mixed solution. The Vant Hoffs plot (log (qe/Ce) as a function of (1/T)) is shown in fig 12. The change in enthalpy ( H), change in entropy( S) and change in Gibbs free energy ( G) for Cu-Zn mixture at various concentrations are given in table-6. Table -6 Thermodynamic parameters for various initial concentrations Co, Initial concentration of mixture, mg/L 50 100 150 H kJmol-1 -17.23 -14.36 -9.956 S kJmol-1 K-1 -44.34 -37.70 -25.12 G kJmol-1 293 K 303 K 313 K 13.00 11.06 7.37 13.45 11.43 7.62 13.89 11.81 7.87

283 K 12.56 10.68 7.11

323 K 14.33 12.19 8.12

The above results indicate that the heat of reaction (H) is negative. The negative value of H value indicates the biosorption is exothermic [32]. The negative value of S confirms the reversibility of the biosorption and the gradual increase in the S value with the concentration indicates that the process is tending towards irreversibility [18]. The spontaneity of the biosorption is demonstrated further by the increase in free energy change with temperature. The increase in G value with an increase in temperature indicates that the biosorption of Cu-Zn mixture is less favorable at high temperatures and also shows physical nature of the biosorption. From the above values of G, H and S

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obtained with erythrina variegate orientalis leaf powder show that the adsorbent has the potential to remove Cu-Zn from the mixed aqueous solutions.

CONCLUSIONS
(i) The optimum agitation time for the biosorption of Cu Zn mixture is 30 min. (ii) The % removal of Cu Zn mixture in mixed solution increases with decrease in biosorbent size and increase in the biosorbent dosage. (iii) The increase in the initial concentration of Cu - Zn mixture results in a decrease in % removal of Cu - Zn mixture. (iv) The % biosorption of cu-zn mixture is increased gradually from pH = 1 to 5.5 and decreased gradually beyond pH value of 5.5. (v) The biosorption data are well fitted to Freundlich, Langmuir and Temkin isotherms. (vi) The kinetics of biosorption of Cu -Zn mixture by erythrina variegata orientalis leaf powder is well described by second order kinetics than the first order kinetics. (vii) The percentage removal of Cu -Zn mixture decreases with increase in temperature. (viii) The negative value of H value indicates the biosorption is exothermic. The negative value of S confirms the reversibility of the biosorption and the gradual increase in the S value with the concentration indicates that the process is tending towards irreversibility. The increase in G value with an increase in temperature indicates that the biosorption of Cu-Zn mixture is less favorable at high temperatures. NOMENCLATURE Ce Co Cco Czo dp G Equilibrium concentration of Cu Zn mixture, mg/L Initial concentration of mixed solution comprising of copper and zinc, mg/L Initial concentration of copper in the mixed solution, mg/L Initial concentration of zinc in the mixed solution, mg/L Biosorbent size, m Change in Gibbs free energy, kJ /mole

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H kad k Kf Ka K n qe qt qmax R2 R S T t V w

Enthalpy change J/mole First order rate constant for Cu Zn mixture, min-1 Second order rate constant for the Cu Zn mixture, g/(mL-min) Freundlich coefficient for Cu Zn mixture, mg/g Langmuir biosorption constant Thermodyanamic constant(qe/Ce) Freundlich coefficient for Cu Zn mixture Amount of Cu Zn mixture adsorbed per unit mass of biosorbent at equilibrium, mg/gm Amount of Cu Zn mixture adsorbed per unit mass of biosorbent at time t (min), mg/gm Langmuir monolayer capacity, mg/gm Correlation Coeffitient Universal gas constant, 8.314 J / mole. K Entropy change, kJ /mole-K Absolute temperature, K Agitation time, min Volume of mixed solution, mL Biosorbent dosage, g/L

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REFERENCES 1. Asma Saeed , M. Waheed Akther and Muhammed Iqbal Removal and recovery of heavy metals from aqueous solution using papaya wood as a new biosorbent. Separation and Purification Technology, 45 (2005) 25-31 2. Volesky. B., Detoixification of metal- bearing effluents: biosorption for the next century Hydrometallurgy, 59 (2001) 203-216 3. Prasanna Kumar, Y., King, P. and Prasad, V.S.R.K., Comparison for adsorption modeling of Cu and Zn from aqueous solution by Ulvafaciata sp Journal of Hazardous Materials, B 1379 (2006) 1246-1251 4. Ping Xin Sheng, Yen-peng Ting, J. Paul Chen and Liang Hong Sorption of lead, copper, cadmium, Zinc and nickel by marine algal biomass: Characterization of biosorptive capacity and investigation of mechanisms Journal of Colloid and Interface Science, 275 (2004) 131-141 5. Prasanna Kumar, Y., King, P. and Prasad, V.S.R.K., Removal of copper from aqueous solution using Ulva fasciata sp.- A marine green algae Journal of Hazardous Materials, B 137(2006) 367-373 6. Shuguang Lu, Stuart W. Gibb and Emma Cochrane Effective removal of zinc ions from aqueous solutions using crab carapace biosorbent Journal of Hazardous Materials, 149(1) (2007) 208-217 7. Iqbal, M. and Edyvean, R. G. J., Biosorption of lead, copper and zinc ions on loofa sponge immobilized biomass of Phanerochaete chrysosporium Minerals Engineering, 17 (2004) 217223 8. Erol Pehlivan, Trkan Altun and Serife Utilization of barley straws as biosorbents for Cu2+ and Pb2+ ions Journal of Hazardous Materials, 164 (2009) 982986 9. Prasanna Kumar, Y., King, P. and Prasad, V.S. R. K., Zinc biosorption on Techtona grandis leaves biomass: Equillibrium and kinetic studies Chemical Engineering Journal, 124 (2006) 63-70 10. Kathrine Conrad and Hans Christian Bruun Hansen

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Sorption of zinc and lead on coir Bioresource Technology, 98 (2007) 89-97 11. Compendium of Medicinal Plants, CSIR Publications, New Delhi, (5)(1999) 12. Rohini Kumar, P., Venkateswara Rao, M., Chitti Babu, N., Ravi Kumar, P. V. and Venkateswarlu, P., Utilization of erythrina variegate orientalis leaf powder for the removal of cadmium Indian Journal of Chemical Technology, 16(2009) 308-316 13. Langmuir, I., The constitution and fundamental properties of solids and liquids J. Am. Chem. Soc., 38 (1916) 2221-2295 14. Freundlich, H., Fundamentals of interface and colloid science: particulate colloids Colloid and Capillary Chemistry, Methuen, London, 1926 15. Runping Han, Zhu Lu, Weihua Zou, Wang Daotong, Jie Shi and Yang Jiujun Removal of copper (II) and lead (II) from aqueous solution by manganese oxide coated sand: II. Equilibrium study and competitive adsorption Journal of Hazardous Materials, B 137 (2006) 480-488 16. Lagergren, S., About the theory of so-called adsorption of soluble substances Sven. K. Vetenskapsa. Handlingar, 24 (1898) 1-39 17. Yuh-Shan Ho and Augustine E. Ofomaja Kinetic studies of copper ion adsorption on palm kernel fiber Journal of Hazardous Materials, B 137 (2006) 1796-1802 18. Arunima shrma and Krishna G. Bhattacharya Azardica indica (neem) leaf powder as a biosorbent for removal of Cd(II) from aqueous medium Journal of Hazardous Materials, B 125 (2005) 102-112 19. Horsfall Jr. M., Abia A. A. and Spiff. A., Kinetic studies on the adsorption of Cd, Cu and Zn from aqueous solutions by cassava (Manihot Sculenta Cranz) tuber bark waste Bioresource Technology, 97 (2006) 283-291 20. Pehlivan, E., Cetin, S. and Yanik B. H., Equillibrium studies for the sorption of zinc and copper from aqueous solutions using sugar beet pulp and fly ash Journal of Hazardous Materials, B 135 (2006) 193-199

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21. Fuat guzel, Hakan yakut and Giray topal Determination of kinetic and equilibrium parameters of the batch adsorption of Mn(II), Co(II), Ni(II) and Cu(II) from aqueous solution by black carrot (Daucus carota L.) residues., Journal of Hazardous Materials, 153 (2008) 1275-1287. 22. Ronbanchob Apiratikul, Taha F.Marhaba, Suraphong Wattanachira and Prasert Pavasant Biosorption of binary mixtures of heavy metals by green macro alga, Caulerp Lentillifera J. Sci. Tehnol., 26 (2004) 199-207 23. Wei Zheng, Xiao-ming Li, Qi Yang, Guang-mng Zeng, Xiang-xin Shen, Ying Zhang and Jing-jin Liu Adsorption of Cd(II) and Cu(II) from aqueous solution by carbonate hydroxylapatite derived from eggshell waste Journal of Hazardous Materials, 147 (2007) 534-539 24. Adesola Babarinde, N. A., Oyesiku, O. O., Oyebamji Babalola and Janet O. Olatunji Isothermal and thermodynamics studies of the Bioosorption of Zinc (II) ions by calymperes erosum Journal of Applied Science Research, 4 (6) (2008) 716-721 25. Shubo Deng, yen- Peng Ting Characterization of PEI- modified biomass and biosorption of Cu (II), Pb (II), Ni(II) Water resource 39 (2005) 2167-2177 26. Wei-bin Lu, Jun-Ji Shi, Ching-Hsiung Wang and Jo-Shu Chang Biosorption of Lead, Copper and Cadmium by an indigenous isolate Enterobacter Sp.1 possessing high heavy-metal resistance Journal of Hazardous Materials, B 134(2006) 80-86 27. Djati Utomo, H. and Hunter, K. A., Adsorption of heavy metals by exhausted coffee grounds as a potential treatment method for waste waters Journal of Surf. Sci. Nanotech., 4 (2006) 504-506 28. Quek , S. Y., Wase, D. A. J. and Forster, C. F., The use of sago waste for the sorption of lead and copper J Water Science, ISSN 24 (3) (1998) 251-256 29. R. Senthilkumar, K. vijayaraghavan, M. thilakavathi, P.v.R. Iyer and M. Velan Seaweeds for the remediation of waste waters contaminated with zinc (II) ions Journal of Hazardous Materials, B 136 (2006) 791-799 30. G. Karthikeyan, K. Anbalagan and N. Muthulakshmi Andal Adsorption dynamics and equilibrium studies on Zn (II) onto chitoson J. chem. Sci. 116(2) 119-127

17

31. Benaissa, H. and Elouchdi, M. A., Removal of Copper ions from aqueous solutions by dried sunflower leaves Chemical Engineering and Processing 46 (2007) 614-622 32. Anoop Krishnan and Anirudhan, T. S., Kinetic and equilibrium modeling of Cobalt(II) adsorption onto bagasse pith based sulphurised activated carbon Chemical Engineering Journal, 137 (2008) 246-251

18

100

% removal of Cu-Zn mixture

90

80

70 w = 2 g/L V = 50 mL Co= 100 mg/L Cco= Czo= 50 mg/L pH = 5.5

dp, m
45 75 102 212

60

50 0 20 40 60 80 100 120 140 160 180 200

Agitation time, t, min Fig. 1 Influence of agitation time on % removal of Cu-Zn mixture

95

% removal of Cu-Zn mixture

90

85

80

w, g/L
1 2 5 10 20 40 60 80 100 120 140 160

t = 30 min V = 50 mL Co= 100 mg/L Cco= Czo= 50 mg/L pH = 5.5

75

180

200

220

240

Biosorbent size, dp, m Fig. 2 Variation of % removal of Cu-Zn mixture with biosorbent size

19

96

% removal of Cu-Zn mixture

94

92

90

t = 30 min V = 50 mL Co= 100 mg/L Cco= Czo= 50 mg/L dp = 45 m pH = 5.5

88

86 0 2 4 6 8 10 12

Biosorbent dosage, w, g/L Fig. 3 Influence of biosorbent dosage on % removal of Cu-Zn mixture

92

% removal of Cu-Zn mixture

90 88 86 84 82 80 78 76 74 0 2 4 6 8

w = 2 g/L t = 30 min V = 50 mL Co= 100 mg/L Cco= Czo= 50 mg/L dp = 45 m

10

12

pH of mixed solution

Fig.4 Effect of pH of mixed solution on % removal of Cu-Zn mixture

20

93

% removal of Cu-Zn mixture

92 91 90 89 88 87 86 85 0 20 40 60 80 100

t = 30 min w = 2 g/L dp= 45 m V = 50 mL pH = 5.5

120

140

160

Initial concentration of Cu-Zn mixture inmixed solution, Co, mg/L

Fig.5 % removal of Cu-Zn mixture as a function of initial concentration of Cu-Zn mixed solution

2.0 t = 30 min w = 2 g/L dp= 45 m V = 50 mL pH = 5.5

1.8

log qe

1.6
2

1.4
90 0.7 log C e+

; 51 0.8

88 0.9

1.2

log

q e=

1.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

log C e

Fig.6 Freundlich isotherm for biosorption of Cu-Zn mixture

21

0.34 0.32 0.30 0.28

6; 14 0. R=
2

99 0.

(Ce/qe), g/L

0.26 0.24 0.22 0.20 0.18 0.16 0.14 0 5 10

C /q e e = 0.

8 00

Ce

t = 30 min w = 2 g/L dp= 45 m V = 50 mL pH = 5.5

15

20

25

Ce, mg/L

Fig.7 Langmuir isotherm for biosorption of Cu-Zn mixture

70

60 50 40
4; .4 -6 98 0.

qe

30

qe

4 .4 22

ln

Ce

20 10 0 0.5 1.0 1.5 2.0 2.5

t = 30 min w = 2 g/L dp= 45 m V = 50 mL pH = 5.5

3.0

3.5

ln C e

Fig.8 Temkin isotherm for biosorption of Cu-Zn mixture

22

1.5 t = 30 min t = 30 min C0=100 mg/L C0=100 mg / L Cco=Czo=50 mg/L dp= 45 m d = 45 m V = p mL 50 pHV = 50 mL = 5.5 pH = 5.5

1.0

log (qe-qt)

0.5

0.0 w, g/L -0.5 1 2 5 10 0 5 10 15 20 25 30

-1.0

Agitation time, t, min

Fig.9 First order kinetics for biosorption of Cu-Zn mixture

t = 30 min C0= 100 mg / L dp= 45 m V = 50 mL pH = 5.5

w, 1 2 5 10

g/L
R
2

97 0.9

t / qt

.997 = 0 R
2

2 0.997 R =

0 0 5 10 15 20 25

R2 = 0.998
30 35

Agitation time, t, min

Fig.10 Second order kinetics for biosorption of Cu-Zn mixture

23

94 92 t = 30 min dp = 45 m w = 2 g/L V = 50 mL pH = 5.5

% removal of Cu-Zn mixture

90 88 86 84 82 80 78 280 290 300 310

C0, mg/L
50 100 150

320

330

Temperature, K

Fig. 11 Effect of temperature on % removal of Cu-Zinc mixture for different concentrations of mixed solution
.96 =0

0.8

0.7

t = 30 min w = 2 g/L dp= 45 m V = 50 mL pH = 5.5

(q e log

log(qe/Ce)

0.6

)= /Ce

6; .31 )-2 /T 0( 1 .90 0

0.5
(q e log

)= / Ce

9; .96 )-1 /T 0 (1 .75

2

. 94 =0

0.4

0.3

R 2; 1.31 /T)0 (1 0.52 )= / Ce (q e log

0.0031 0.0032 0.0033
-3 -1

= 0.

92

C0, mg/L
50 100 150 0.0035 0.0036

0.0030

0.0034

(1/T) X 10 , K

Fig.12 Effect of temperature on biosorption of Cu-Zn mixture (Van't Hoff plot)

24