Polymer-Plastics Technology and Engineering, 49: 14631472, 2010 Copyright # Taylor & Francis Group, LLC ISSN: 0360-2559

print=1525-6111 online DOI: 10.1080/03602559.2010.496423

The Removal of Hg (II) Ions from Laboratory Wastewater onto Phosphorylated Haloxylon ammodendron: Kinetic and Equilibrium Studies
A. Hashem1, A. M. Azzeer2, and A. Ayoub1
1 2

Faculty of Science and Arts at Shaqra, Shaqra University, Shaqra, Kingdom of Saudi Arabia Physics and Astronomy Department, King Saud University, Riyadh, Kingdom of Saudi Arabia

Haloxylon ammodendron (HA), a desert plant residue, has been utilized as adsorbent material for the removal of Hg (II) ions from laboratory wastewater after treatment with phosphoric acid to form Haloxylon ammodendron cellulose phosphate (HACP). Three levels of HACP having different phosphorous content were prepared. The HACP samples were characterized by estimating the phosphorous content as well as FT-IR spectra. Using the batch experimental systems, the removal of Hg (II) on the HACP particles was investigated. The data of the adsorption isotherm was tested by the Langmuir, Freundlich and Temkin models. The removal processes of Hg (II) onto HACP particles could be well described by pseudo-second order model. The adsorption rate of mercury was affected by the initial heavy metal concentration, initial pH, adsorbent dose and agitation time and temperature as well as extent of modication. The adsorption experiments indicated that the HACP particles have great potential for the removal of Hg (II) from laboratory wastewater. The maximum adsorption capacity (Qmax) of the HACP towards Hg (II) ions was found to be 384.6 and 416.7 and 476.2 mg/g at 30, 40 and 50 C, respectively. Similarly, the Freundlich constant, n values were found to be 6.6, 4.4 and 3.8 at 30, 40 and 50 C, respectively. The thermodynamics constants of the adsorption process: DH , DS and DG were evaluated. Keywords Adsorption isotherm; Adsorption kinetic; Haloxylon ammodendron; Hg (II) removal; Phosphorylation; Thermodynamic; Wastewater

INTRODUCTION Heavy metal pollution is an environmental problem of worldwide concern. The heavy metals, such as mercury, lead, copper, cadmium, zinc and nickel are among the most common pollutants found in industrial efuents. Even at low concentrations, these metals can be toxic to organisms, including humans[1]. The removal and recovery of toxic metals from aqueous efuents have received much attention in recent years. Among the many methods available to reduce heavy metals
Address correspondence to A. Hashem, Faculty of Science and Arts at Shaqra, Shaqra University, Shaqra, Kingdom of Saudi Arabia. E-mail: alihashem2000@yahoo.com

concentrations from wastewater, the most common are chemical precipitation, ion-exchange, and reverse osmosis. Precipitation methods are particularly reliable but require large settling tanks for the precipitation of sludges and a subsequent treatment is needed[2]. Ion-exchange has the advantage of allowing the recovery of metallic ions, but it is expensive and sophisticated. Mercury can be found in signicant amounts in wastes from chloro-alkali manufacturing plants, electrical and electronics manufacturing, and sulde ore roasting operations. Mercury is the most harmful to humans, plants and animals. Exposure to Hg can have toxic effects on reproduction, the central nervous system, liver, and kidney, and cause sensory and psychological impairments. Therefore, all countries have taken measures to reduce mercury exposure through comprehensive prevention strategies including environmental standards that require removal of mercury from industrial efuents. Adsorption is an alternative technique for heavy metal removal. The activated carbon is the most widely used adsorbent material. In fact, use of activated carbon is comparatively expensive with difculties in regeneration and this has led to a large volume of work trying to develop low cost adsorbents[3]. Agricultural by-products, mainly cellulosic in composition, constitute one of the most abundant renewable resources in the world. Chemical modication of agricultural wastes through etherication or esterication or graft copolymerization is promising technique for modifying its physical and chemical properties to improve the adsorption property toward heavy metals. Agricultural wastes such as sawdust[4,5], sunower stalks[6,7], peanut hull[8] and Alhagi residues[9,10] are considered one of the low cost unconventional adsorbents, have been examined for potential use as inexpensive adsorbents for heavy metal removal. In this work, we attempt to explore the adsorption behavior of new low-cost adsorbent based on HA. HACP were prepared by the reaction with conc. phosphoric acid at high temperature in presence of urea as catalyst.

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To achieve the goal, the work comprises the following studies: (i) preparation of three levels of HACP using different amount of conc. phosphoric acid at 150 C; (ii) characterization of native and modied HA by estimation of % P and FT-IR spectroscopy; (iii) establishment of the factors affecting the adsorption of Hg (II) by HACP such as: pH of adsorbate, adsorbent and adsorbate concentrations, contact time, adsorption temperature and extent of modication; (iv) the ability of adsorption experimental data of Hg (II) onto HACP to obey Langmuir, Freundlich and Temkin isotherms; (v) evaluation of the kinetic and thermodynamic parameters for Hg (II) ion adsorption onto HACP. EXPERIMENTAL Materials Adsorbent. HA, a desert plant is widely spread in Kingdom of Saudi Arabia and Libya. There is no previous report used HA as adsorbent material for removal of heavy metal. The roots were separated from the stems and leaves, washed with distilled water several times to remove the surface adhered particles and water soluble particles and dried at 80 C in an electric oven for 24 h and ground using a mixer, and sieved to pass through a 100200 mm. The roots were chosen because they contain the highest percentage of the cellulose content. Reagents. Phosphoric acid, urea, EDTA, mercuric acetate, ethanol, sodium carbonate, acetic acid were of analytical reagent grade supplied by Merck Company, Germany. Methods Phosphorylation Procedure. Three levels of HACP with various phosphorous content were prepared by keeping other reaction conditions constant and varying the amount of phosphoric acid according to a reported method[11] as shown in Table 1. The reaction was carried out as follows: To a 400 ml beaker containing 10 g of HA with particle sizes in the range 100200 mm was added to a know weight of urea (dissolved in the least amount of water) and different amounts of conc. phosphoric acid under continuous stirring with a spatula until a homogeneous TABLE 1 The characteristics of samples of HA cellulose phosphate Phosphoric acid (mmole=l) 0 43.11 86.22 172.45 Adsorption capacity (mg=g) at 30 C 30.5 166.3 230.7 384.6

paste was obtained. The paste was then transferred to a Pyrex Petri dish and placed in an air-circulated oven at 150 C for 2 h. The thermally treated sample was subsequently cooled to room temperature and ground. The soluble by-products and any un-reacted phosphoric acid were removed by washing the sample several times with a water= ethanol (20:80) mixture, and nally dried at 100 C for 2 h. FT-IR Spectroscopy. The FT-IR spectra of unmodied HA and HACP were recorded on a Nexus 670 FT-IR spectrometer, Nicolet, USA, in the spectral range 4000400 cm1 with a resolution of 4 cm1 using the KBr disk technique. Adsorption Studies. The adsorbate solution of 1001000 mg=l were prepared by dissolving certain weights of mercuric acetate in certain volumes of distilled water. The pH (26) of the solutions was adjusted with acetic acid or sodium carbonate solution. Equal volumes (100 ml of each) of the previously prepared metal ion solutions were placed in the corresponding number of 125 ml Erlenmeyer asks each of which containing 0.05 g of the adsorbent and the whole asks were shaken at 30 C in a thermostatic water-bath at 150 rpm for 2 h. At the end of agitation time, the metal ion solutions were separated by ltration. The blank experiments were simultaneously carried out without the adsorbent. The extent of metal ion adsorption onto adsorbent was calculated mathematically by measuring the metal ion concentration before and after the adsorption through direct titration against standard EDTA solution. The amount of mercury adsorbed, qe (mg=g) on HACP was calculated according to the following equation: qe Co Ce V l W 1

where Co and Ce are the initial and nal concentrations of metal ion, mg=l. V is the volume of metal ion (l), W is the weight of HACP (g). Determination of Phosphorous Content of Adsorbent. The phosphorous content of the HACP as % P was determined according to the reported method[12]. RESULTS AND DISCUSSION Phosphorus can be covalently attached to the cellulose chain via a reaction of hydroxyl groups to give: phosphate groups CellOP(O)(OH)2, phosphite groups CellO P(OH)2, or phosphonic acid groups CellP(O)(OH)2. The derivatives of pentavalent phosphorus, i.e., H3PO4, P2O5, organic phosphates, and POCl3 are most frequently used to obtain phosphorous containing cellulose derivatives. The reaction between cellulose and phosphoric acid is supposed to proceed predominantly at the hydroxyl group of the C-6 atom of cellulose polymer according to Scheme 1.

Code sample Unmodied HA A B C

P% 0 1.5 3.1 5.5

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for OH groups of cellulose; a band at 2924 cm1 attributed to CH2 groups in cellulose structure. The IR spectrum of HACP (up) shows two new bands appeared: a band at 2369 cm1 corresponding to the POH bond, another one at 1653.4 cm1 corresponding to the P O bonds. Factors Affecting Adsorption of Hg (II) onto HACP Effect of pH. Earlier studies have indicated that the pH of adsorbate is an important parameter affecting adsorption of heavy metals. Figure 2 shows the adsorption capacity of Hg (II) as a function of pH (26) at xed adsorbent concentration, xed agitation time, xed adsorbate concentration at 30 C. It is clear from this gure that the adsorption capacity of Hg (II) onto HACP increases from 22.3 to 178.5 mg=g by increasing the pH from 2 to

SCH. 1. Reaction of cellulose with phosphoric acid to produce cellulose phosphate.

FT-IR Spectra Figure 1 shows the FT-IR spectra of modied HACP (up) and unmodied HA (down). The FT-IR spectra of unmodied HA (down) shows a large peak at 32503550 cm1 corresponding to the vibration of valence

FIG. 1. FT-IR spectra of HACP (up) and unmodied HA (down).

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On the other hand, the adsorption capacity (qe), or the amount of Hg (II) adsorbed per unit mass of adsorbent (mg=g), decreases by increasing the concentration of adsorbent (Fig. 3). The decrease in adsorption capacity with increasing the adsorbent concentration is mainly due to overlapping of the adsorption sites as a result of overcrowding of the adsorbent particles and is also due to the competition among Hg (II) ions for the surface sites[6]. Adsorption Isotherm (Effect of Adsorbate Concentration). The equilibrium adsorption isotherm is fundamental in describing the interactive behaviour between solutes and adsorbent, and is important in the design of adsorption system. Figure 4 shows equilibrium distribution of Hg (II) ions between the liquid phase, Ce (mg=l) and solid phase, qe (mg=g). The equilibrium curve plateau indicates the maximum adsorption capacity of Hg (II) ions on HACP at different temperatures (30, 40 and 50 C). As shown in Figure 4 the adsorption capacity of Hg (II) onto HACP increases with the increasing concentration of adsorbate and approaches the equilibrium at higher concentration of the adsorbate. Higher temperature result in higher adsorption capacity in the temperature range studied (3050 C). To simulate the adsorption isotherm, three models are used, the Langmuir, Freundlich and Temkin isotherms. Langmuir Isotherm. The Langmuir equation [13] was applied to the adsorption equilibrium of Hg (II) ions by HACP. The assumption of this model is based on the maximum adsorption corresponds to a saturated monolayer of adsorbate molecules on the adsorbent surface and the energy of adsorption is constant as well as there is no transmigration of adsorbate in the plane surface. The Langmuir model may be represented as follows: qe kL Ce 1 aL C e 2

FIG. 2. 30 C.

Effect of pH on the adsorption capacity of Hg(II) onto HACP at

5 and then remained at approximately the same level at pH 6. Under highly acidic conditions (pH 2) the adsorption capacity of mercury (II) is the lowest (22.3 mg=g) because metal binding sites on the adsorbent were closely associated with H3O and restrict the approach of metal cations as a result of the repulsion forces. However, adsorption capacity increased with increasing the pH of solution since the adsorbent surface could be exposed with negative charge with subsequent attraction with positive charge occurring onto the adsorbent surface. At a pH value higher than 6, the adsorption studied could not be carried out due to precipitation of Hg (II) as Hg (OH)2. Effect of Adsorbent Concentration (Adsorbent Dose). The effect of adsorbent concentration on both adsorption capacity and percent removal of mercury are shown in Figure 3. It is clear from this gure that the percent removal of mercury increases from 23.6 to 88.0 by increasing the concentration of adsorbent from 0.5 to 8 g=l and then remained at approximately the same level at higher adsorbent concentration. The increase in percent removal of Hg (II) with increasing adsorbent concentration in the rst range could be attributed to the greater availability of the exchangeable sites of the adsorbent. The leveling of the percent removal at higher adsorbent concentration could be attributed to the blocking of the available active sites on the adsorbent surface.

where Ce is the equilibrium concentration of Hg (II) ions (mg=l) and qe is the amount of mercury adsorbed (mg=g),

FIG. 3. Effect of adsorbent concentration on adsorption capacity of Hg (II) onto HCAP at 30 C.

FIG. 4. Equillibrium adsorption isotherms of Hg (II) onto HACP at different temperatures.

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while the constants kL and aL are the Langmuir constant (l=g) and Langmuir isotherm constant (l=mg), respectively. It is possible to represent Eq. (2) in a linearized form as shown in Eq. (3): Ce 1 aL qe KL KL   Ce 3 pH 5

TABLE 2 Langmuir constants of Hg (II) onto HACP at different temperatures Temp. ( C) 30 40 50 aL (l=mg) 0.049 0.038 0.023 kL (l=g) 18.94 15.65 11.03 Qmax (mg=g) 384.6154 416.6667 476.1905 b (l=mg) 0.049 0.038 0.023 R2 0.996 0.999 0.998

Qmax. The adsorption capacity of Hg(II) onto HACP were 384.4, 416.7 and 476.2 mg=g at 30, 40 and 50 C, respectively. These values should be compared with the negligible value (30 mg=l) exhibited by the original plant residues without modication (Table 1). The value of the adsorption capacity, Qmax, increased with increasing temperature, i.e., temperature had a favorable effect on the adsorption process. The increased adsorption capacity of HACP towards Hg(II) ions at higher temperatures may be attributed to chemisorption rather than physisorption being the principal adsorption step. This may attributed to the chelation between the electron-donating nature of O- and P-containing groups in the HACP and electron-accepting nature in Hg (II). The linear plots (Fig. 5) of Ce=qe vs Ce give straight lines with the slope aL=kL and intercept 1=kL. The Langmuir constants of adsorption of Hg (II) ions onto HACP are listed in Table 2. The values of the correlation coefcients, R2 (Table 2) of Langmuir plots are over 0.99 for 3 temperatures indicate that the adsorption of Hg (II) onto HACP is tted well on the Langmuir isotherm (obey the Langmuir isotherm). The equilibrium constant kL may be used to determine the enthalpy of adsorption, DH. The relation between kL and Qmax is given by the following equation: kL Qmax b 4

factor or equilibrium parameter, RL, which expressed by the following equation: RL 1 1 b Co 5

where Co is the initial concentration of Hg (II) and b is mentioned before. The values of RL for the adsorption of Hg (II) ions at different initial concentrations onto HACP at the temperatures studied are listed in Table 4. It is clear from this table that the values of RL all lie in the range 0 < RL < 1, indicating that the adsorption process was favorable at all the temperatures studied. Freundlich Isotherm. The Freundlich model[15] was also applied to the adsorption of Hg(II) ions onto HACP. This model can be used for the non-ideal case involving heterogeneous sorption. The Freundlich equation is basically empirical and can be represented as in Equation (6): qe KF C 1=n 6

The logarithmic form of the Freundlich model is given by Equation (7): 1 log qe log KF log Ce n 7

where b is related to the energy of adsorption (l=mg). It has been reported that the effect of isotherm shape with a view to predicting if an adsorption system is favorable or unfavorable (Table 3)[14]. The essential features of Langmuir isotherm can be expressed in terms of a dimensionless constant separation

where qe is the equilibrium concentration of mercury on HACP (mg=g), Ce the equilibrium concentration of mercury in solution (mg=l) and KF (mg=g) and n are the Freundlich constants characteristic of the system, indicators of adsorption capacity and adsorption intensity, respectively. TABLE 3 Effect of separation factor, RL on isotherm shape RL value RL > 1 RL 1 0 < RL < 1 RL 0 Type of isotherm Unfavorable Linear Favorable Irreversible

FIG. 5. Langmuir adsorption plots of Hg (II) onto HACP at different temperatures.

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TABLE 4 RL values based on Langmuir equation of Hg (II) onto HACP at different temperatures Initial conc., Co of Hg (II) (mg=l) 108 204 311 405 501 607 705 814 RL values 30 C 0.158498 0.09096 0.061634 0.048004 0.039131 0.032482 0.02813 0.024452 40 C 0.195414 0.114282 0.078082 0..061052 0.049893 0.041495 0.03598 0.031308 50 C 0.286362 0.175717 0.122754 0.097006 0.079835 0.06675 0.058083 0.050691 pH 5

TABLE 5 Freundlich constants of Hg (II) onto HACP at different temperatures Temperature ( C) 30 40 50 KF 9.49 7.40 6.36 n 6.565988 4.395604 3.762227 R2 0.962 0.90 0.96

Linear plots of log qe vs log Ce at different temperatures (Fig. 6) suggest the applicability of adsorption process of Hg (II) onto HACP on Freundlich isotherm. The values of KF and n were evaluated from the intercept and the slope of the plot and their numerical values are listed in Table 5. The n value gives an indication to favorability of adsorption. The values of n were 6.6, 4.4 and 3.8 at 30, 40 and 50 C, respectively (0 < n < 10) showing that the adsorption of Hg (II) ions onto HACP is favorable. The correlation coefcient, R2 values (Table 5) of Hg(II) by HACP were over 0.90 indicating that the adsorption of Hg(II) ions on HACP are tted well also on Freundlich isotherm (obey the Freundlich isotherm). Indeed, the system obeyed the Langmuir isotherm more closely than the Freundlich isotherm as is evident from a comparison of the values of the correlation coefcients, R2, listed in Tables 2 and 5, respectively. Temkin Isotherm. The Temkin isotherm is given by the following equation [16]. RT qe lnAT Ce bT

where R is the universal gas constant (8.31441 J mol1 K1), T is the absolute temperature (K), AT is the Temkin isotherm constant (g=mg) and bT is Temkin constant. The sorption data were analyzed according to the linear form of the Temkin isotherm and the linear plots are shown in Figure 7. Linear plots of qe vs ln Ce at different temperatures (Fig. 7) suggest the applicability of adsorption process of Hg (II) onto HACP on Temkin isotherm. The linear isotherm constants and correlation coefcients of Hg (II) onto HACP are presented in Table 6. The correlation coefcient, R2 values (Table 6) of Hg(II) onto HACP were over 0.935 indicating that the adsorption of Hg(II) ions on HACP are tted well also on Temkin isotherm (obey the Temkin isotherm). Effect of Contact Time. Figure 8 shows the effect of agitation time on adsorption capacity of Hg (II) onto HACP by using the concentration of 306, 407 and 609 mg=l at xed adsorbent concentration and at 30 C. The amount of Hg (II) adsorbed (mg=g) increases with the increase in agitation time and reached the equilibrium after 60 min for three concentrations (Fig. 8). It is clear that the adsorption capacity depends on the concentration of the Hg (II) ions. The adsorption curves are singles and continuous leading to saturation. Kinetics of Adsorption. The kinetic process leading up to the establishment of equilibrium between the liquid and solid phases may be described in terms of

FIG. 6. Freundlich adsorption plots of Hg (II) onto HACP at different temperatures.

FIG. 7. Temkin adsorption plots of Hg (II) onto HACP at different temperatures.

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TABLE 6 Temkin constants of Hg (II) onto HACP at different temperatures pH 5 Temperature ( C) 30 40 50 AT 5.633 1.050 0.471 bT 54.633 40.267 33.135 R2 0.9355 0.9444 0.9588

the pseudo-rst-order rate expression of Lagergren Equation,[17] which can be generally expressed by Trivedi et al. as follows: logqe qt log qe k1 t 2:303 First order 9

where qe and qt are the amounts of metal ion adsorbed onto the adsorbent at equilibrium and at time t (mg=g), respectively, and k1 (min1) is the rate constant for the pseudo-rst-order adsorption process. For the data obtained in the present study, the plots of log(qe qt) versus t as required by Eq. 9 for the adsorption of Hg (II) ions at initial concentrations of 306, 407 and 609 mg=l onto HACP (gure not show) gave correlation coefcients, R2, which had very low values for all the plots concerned. This indicated that the pseudorst-order rate expression could not be applied to the data obtained in the present study. Another widely used kinetic expression is the pseudo second-order[18], where the adsorption capacity is assumed to be proportional to the number of active sites on the adsorbent surface occupied by Hg (II) ions. The pseudo second-order kinetic rate law can be expressed as: t 1 t qt k2 q2 q tt e Second order 10

where k2 is the pseudosecond-order adsorption rate constant. This equation predicts that if the system follows pseudosecond-order kinetics, the plot of t=qe versus t should be linear. Plotting the experimental data obtained for the adsorption Hg (II) ions at initial concentrations of 306, 407 and 609 mg=l onto HACP according to the relationship given in Eq. (10) gave linear plots with correlation coefcients, R2, of 0.9988, 0.9997 and 0.9998, respectively, as shown in Figure 9 and Table 7, thereby indicating the applicability of the pseudosecond-order kinetic equation to the experimental data obtained in the present work. The experimental and calculated adsorption capacities for the three concentrations of Hg (II) ions studied, as well as the values of the pseudosecond-order rate constant, k2, are presented in Table 7. The rst-order and pseudosecond-order models cannot identify the diffusion mechanism and the kinetic results were then subjected to analyze by the intra-particle diffusion model. The intra-particle diffusion model[19] can be expressed by the following equation: qt k P t 2 C
1

11

where kp is the intra-particle diffusion rate constant (mg. g1 min1) and qt is the amount of solute adsorbed per unit mass of adsorbent. The data of solid phase metal concentration against time t at the initial concentrations of 306, 407 and 609 mg=l of Hg (II) were further processed for testing the rate of diffusion in the adsorption process. Adsorption process incorporates the transport of adsorbate from the bulk solution to the interior surface of the pores in HACP. The rate parameter for intra-particle diffusion, kp for the three concentrations of Hg (II) are measured according to Eq. 11. The plots of qt versus t1=2 for the concentrations of 306, 407 and 609 mg=l of Hg (II) are shown in Figure 10. Due to the mass transfer effect, the shape of qt versus t1=2 plot is curved at a small limit times. The plots for three concentrations of metal ions have the same

FIG. 8. Effect of agitation time on adsorption capacity of Hg (II) onto HACP using different adsorbate concentrations at 30 C.

FIG. 9. Pseudo second order reaction of Hg (II) onto HACP using different adsorbate concentrations at 30 C.

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TABLE 7 Pseudosecond-order adsorption rate constant, the calculated and experimental qe of Hg (II) onto HACP at different adsorbate concentrations Initial concentration of Hg(II) (mg=l) 306 407 609 Experimental qe (mg=g) 194 309 404 Calculated qe (mg=g) 204.1 312.5 416.7 Adsorption rate constant K2 (g=mg min) 0.0448 0.0152 0.01

Adsorbent HACP

R2 0.9988 0.9997 0.9998

features, the initial portion (curved) followed by linear portion and plateau. The initial curved portion is attributed to the bulk diffusion and the linear portion to the intra-particle diffusion. The values of kp (mg g1 min1) obtained from the slope of the straight lines (Fig. 11) are listed in Table 8. The values of R2 for the three plots are listed also in Table 8. The values of intercept, C (Table 8) give an idea about the boundary layer thickness, i.e., the larger the intercept, is the greater the boundary layer effect[20]. These values indicate that the adsorption of Hg (II) onto HACP may be follow the intra-particle diffusion mechanism. Mechanism of Removal. The HACP can be considered to be microporous biopolymer; therefore, pores are large enough to let Hg (II) ions through. The mechanism of Hg (II) adsorption on porous adsorbents may involve four steps: (i) diffusion of ions to the external surface of the adsorbent; (ii) diffusion of ions into the pores of the adsorbent; (iii) adsorption of the ion on the internal surface of the adsorbent. (iv) chelation between the electrondonating nature of O- and P-containing groups in the HACP and electron-accepting nature in Hg (II) as shown in scheme 2: Effect of Temperature. The temperature range used in this study was from 303 to 323 K. Thermodynamic parameters such as free energy change (4G ), enthalpy change (4H ) and entropy change (4S ) were calculated

from Equations (1214)[21]: DG  RT ln kL 12

where kL is the Langmuir constant, R is universal gas constant, 8.31441 J=mol K, and T is absolute temperature (K).

SCH. 2. Schematic representation of proposed complex structure between HACP and Hg (II) ions.

FIG. 10. Intraparticle diffusion of Hg (II) onto HCAP using different adsorbate concentrations at 30 C.

FIG. 11. Test of Intraparticle diffusion of Hg (II) onto HCAP using different adsorbate concentrations at 30 C.

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TABLE 8 Rate parameters of intra-particle diffusion at different initial concentrations of Hg (II) onto HACP at different adsorbate concentrations Initial conc. of Hg(II) Kp (mg=g min1=2) Adsorbent (mg=l) HACP 306 407 609 8.9852 6.5872 8.3247 Intercept (C) 100.35 234.58 311.88

R2 0.9333 0.920 0.9014

that the HACP with the higher extent of modication has more P content, which increases the adsorption ability toward Hg(II) through stronger complexation. Current data suggest that the phosphate groups introduced in the molecular structure of the cellulose component of the HA via esterication using phosphoric acid play a more effective role in the Hg(II) adsorption process than those in the unmodied (HA) as shown in Table 1. CONCLUSIONS Haloxylon ammodendron (HA), a desert plant has been utilized as starting material for preparation of reactive adsorbent for removal of Hg (II) from laboratory wastewater. Three samples of reactive adsorbent were prepared via reaction of HA with different amounts of phosphoric acid in presence of urea as catalyst at high temperature. The HACP samples were characterized by estimation the phosphorous content expressed as % P. Adsorption studies have been carried out to determine the effect of agitation time, pH, adsorbent concentration, extent of modication, and adsorbate concentration on the adsorption capacity of Hg(II) ions onto HACP. The adsorption capacity, qe (mg=g), of Hg(II) onto HACP increases by increasing the temperature. Langmuir, Freundlich and Temkin models were applied in the adsorption studies. The maximum adsorption capacity (Qmax) of the HACP towards Hg (II) ions was found to be 384.6 and 416.7 and 476.2 mg=g at 30, 40 and 50 C, respectively. Similarly, the Freundlich constant, n was found to be 6.6, 4.4 and 3.8 at 30, 40 and 50 C, respectively. Application of standard thermodynamic equations allowed the values of 4Go, 4Ho and 4So for the adsorption process to be determined. Negative values obtained for 4Ho over the temperature range 3050 C indicated that the adsorption process was exothermic. The negative values obtained for 4So demonstrated the decreasing randomness at the solid=solution interface during the adsorption of Hg (II) ions onto HACP. REFERENCES
1. Sheng, P.X.; Ting, Y.P.; Chen, J.P.; Hong, L. Sorption of lead, copper, cadmium, zinc, and nickel by marine algal biomass: characterization of biosorptive capacity and investigation of mechanisms. J. Coll. Interf. Sci. 2004, 275, 131141. 2. Ozer, A.; Ekiz, H.I.; Ozer, D.A. Comparative study of the biosorption of cadmium (II) ions to S. Leibleinii and R. Arrhizus. Chim. Acta Turcica 1997, 25, 6367. 3. Thomas, J.; Crittenden, B.W. Adsorption Technology and Design, Butterworth: Heinemann, Oxford, p 14, 1998. 4. Hashem, A.; Elhmmali, M.M.; Hussein, A.H.; Senousi, M.A. Utilization of sawdust-based materials as adsorbent for wastewater treatment. Polym. Plastics Technol. Eng. 2006, 45, 821827. 5. Hashem, A.; Abdel-Halim, E.; Maauof, H.A.; Ramadan, M.A.; Abo-Okeil, A. Treatment of sawdust with polyamine for wastewater treatment. Energy Educ. Sci. Technol. 2007, 19, 4558.

The Langmuir enthalpy change, 4H of adsorption as a function of temperature is given by Equation 13:   kL2 T2 T1 : DH  R ln kL1 T2 T1 13

where kL1 and kL2 are the Langmuir constants at 313 and 303 K, respectively. The negative values of 4G (Table 9) indicate spontaneous nature of adsorption of Hg (II) onto HACP. Negative values of 4H (Table 9) suggest the exothermic nature of adsorption. The entropy change (4S ) was calculated from Equation 14: DS  DH  DG  T 14

The negative value of 4S shows the decrease in randomness at the solid= solution interface during the adsorption of Hg (II) onto HACP. The increase in adsorption capacity of Hg (II) onto HACP at higher temperature (Table 2) may be attributed to the enlargement of pore size or activation of the adsorbent surface[22]. Effect of Extent of Modication. Table 1 shows the effect of % P of the HACP on their adsorption capacity of Hg(II) from laboratory wastewater. Evidently, increasing the extent of modication is accompanied by an increase in the adsorption capacity of HACP. It is logical

TABLE 9 Thermodynamic parameters of adsorption of Hg (II) onto HACP at different temperatures 4H 4S Temperature 4G (kJ=mol) (kJ=mol) (kJ=mol K) Adsorbent (K) HACP 303 313 323 7.41 40.73 6.45 5.29 11.44 0.664 9.17

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