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Characterization of hydroxybenzoic acid chelating resins: Equilibrium, kinetics, and isotherm profiles for Cd(II) and Pb(II) BHAVNA A. SHAH*1, AJAY V. SHAH2, RITESH V.TAILOR1 Department of Chemistry, Veer Narmad South Gujarat University, Surat-7, Gujarat, India.
2

Science and Humanity Department, Polytechnic, Vidyabharti trust, Umrakh, Bardoli-1, Gujarat, INDIA.

*Corresponding Author. Email: bhavna606@gmail.com Running title: UPTAKE OF CADMIUM AND LEAD Abstract: Chelating ion-exchange resins have been synthesized by polycondensation of ortho/para hydroxybenzoic acid with resorcinol/catechol employing formaldehyde as cross linking agent at 805 C in DMF. The resins were characterized by FTIR and XRD. The uptake behaviour of synthesized resins (SFR, SFC, pHFR and pHFC) for Cd(II) and Pb(II) ions have been studied depending on contact time, pH, metal ion concentration and temperature. The selectivity order of synthesized resin for Pb(II) is SFR>SFC>pHFR>pHFC and for Cd(II) is SFR>pHFR>SFC>pHFC. The sorption data obtained at optimized conditions were analyzed by Langmuir and Freundlich isotherms. Experimental data of all metal-resin system were best represented by Freundlich isotherm. SFR shows maximum sorption capacity for Cadmium (69.53mg/g) and Lead (169.32mg/g). The adsorption process follows first order kinetics and specific rate constant Kr was obtained by the application of Lagergan equation. Thermodynamic parameters Gads, Sads and Hads have been calculated for the metal-resin systems. The external diffusion rate constant (Ks) and intra-particle diffusion rate constant (Kid) were calculated by Spahn-Schlunder and Weber-Morris models respectively. The sorption process was found to follow intra-particle diffusion phenomenon. Keywords: chelating resin; SEM, kinetics; isotherm; distribution co-efficient INTRODUCTION In recent years, there has been a growing concern for the immobilization of metal ions introduced into water and wastewater bodies by the increasing human technological activities. It has been established beyond doubt that heavy metal ions in the environment (water, soil, and air) pose a very serious threat to the health of man. With the exponentially increasing population, the need for controlling heavy metal discharge, before toxic metal ions enter the complex ecosystem. 1

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Separation, removal, and enrichment of trace metals in aqueous solutions play an important role for the analysis of wastewaters, industrial and geological samples. The solid phase extraction of metal ion has gained rapid acceptance because of various advantages over other methods. The extraction of metal ions using chelating ion exchange resin is a green analytical method since it does not involve the use of toxic chlorinated organic solvents, which are very frequently used in conventional liquid-liquid extraction technique. The main objective of the most of the research on chelating resins, is preparation of insoluble functionalized polymers which can be provide more flexible working conditions together with good stability and high capacity for certain metal ions. The use of modified clay minerals for the adsorption of metal ions form aqueous solutions for the purpose of water purification or industrial wastewater treatment has been widely studied. These clay minerals, when used as colloids or powders, have been found to be equally efficient as ion exchange resin but it is difficult to recover the adsorbent from filters after use. This further renders the regeneration and possible reuse of the clay adsorbent very difficult. The kinetics of the adsorption of these toxic metal ions is needful in order to predict the rate at which these toxic metal ions are being removed from the aqueous solution. Adsorption kinetics also provides an insight mechanism of adsorption.1 Although a number of kinetic investigations have been carried out on the adsorption of Pb+2 onto peat,2 Pb+2 onto decaying leaves,3 Cd+2 onto hydrous Ferric oxide,4 Cu+2 and Pb+2 onto polysulfone and algae complex,5 Cr(IV) onto peat,6 Pb+2 on palm kernel fiber,7 Pb+2 onto Orthophosphate modified Kaolinite clay,8 Pb+2 and Cd+2 onto Tripolypphosphate-modified Kaolinite clay,9 to mention but a few. These adsorbents all showed good potential as low cost adsorbents in the adsorption of metal ions except that they exist in aqueous solution as either colloids or dispersed particles that are difficult to recover from filters. To address the problem of recovery of adsorbent after use from filters, this study focuses on the production of a water stable and mechanically strong adsorbent by synthesis of chelating ion exchange resin. This is subsequently used for the adsorption of Pb+2 and Cd+2. This study further considers the kinetics of the adsorption of Pb+2 and Cd+2 onto chelating ion exchange resin adsorbents. The effect of pH, metal ion concentration, temperature, the Pseudo-second order and Pseudo first order rate constants and kinetics of adsorbed Pb+2 and Cd+2 for all the resins. Kinetic adsorption data obtained are modeled against existing kinetic adsorption models. 2

66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 Reagents and solutions

EXPERIMENTAL Analytical reagent (A.R) grade chemicals were used unless otherwise stated. Stock solutions (500mM) of metal ions were prepared by dissolving appropriate amounts of CdAc2 and PbAc2 in deionized water acidified with 5cm3 of the corresponding acid. The metal ion solutions were standardized by complexometric titration with EDTA using standard procedures.10 The working solutions of metal ions were obtained by dilution of the stock solutions with deionized water. The solutions were adjusted to a particular pH using buffers. Acetate buffer was used to adjust the pH in the ranges 3.5 to 6.5. The water samples from industry was collected, acidified with 2% HNO3 immediately, filtered, and stored in the glass bottles. Solutions of acids and alkalies were prepared by dissolving appropriate amount of the particular compound in deionized water and standardized by the literature methods. 10 Instruments A flame atomic absorption spectrometer (AAS: Electronic corporation of India Ltd, Hyderabad, INDIA, Model 4129) was used for the measurement of metals by employing an air-acetylene flame (air and acetylene flow rates: 10 dm3/min and 2.0 dm3/min, respectively). The line selected for monitoring Cd and Pb were 228.8 nm and 217.0 nm respectively. The analysis of each metal ion was carried out by AAS after appropriate dilution. Infra-Red spectra of the synthesized resin had been scanned in KBr pallets on FTIR Spectrophotometer (Shimadzu model-8201PC). The X-ray diffraction analysis (XRD) was performed by advanced Diffractometer (Bruker AXE D8). The surface morphology was analyzed using an optical photograph (Olympus SZX12) and scanning electron microscope (Philips XL30) at different magnifications. The sorption-desorption studies of both the metal ions were carried out by batch technique and columns of 0.5 cm internal diameter. For batch sorption technique, a mechanical shaker equipped with incubator (Hindustan Scientific, New Delhi, INDIA) with a speed of 200 strokes/min was used throughout the equilibration. Resin Synthesis Salicylic acid/p-Hydroxybenzoic acid (13.5 g, 0.1 moles) was taken in 250 cm3 round bottom flask and dissolved in DMF solvent (20 cm3) to give clear solution. A solution of resorcinol/catechol (11 g, 0.1 moles) in 10 cm3 DMF was added to above solution and stirred for 2 h. Formaldehyde (0.3 moles as 37%) was added and stirred for an hour. The Salicylic acid-Formaldehyde-Resorcinol (SFR), Salicylic acid-Formaldehyde-Catechol (SFC), pHydroxybenzoic acid-Formaldehyde-Resorcinol (pHFR) and p-Hydroxybenzoic acid3

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Formaldehyde-Resorcinol (pHFC) resins were synthesized by refluxing the above appropriate mixture at 805C in a water bath for 2-3 h with constant stirring during which the mixture gelled to a soft mass, which was dark brown in colour. A gel was separated from the reaction vessel and cured in an oven at 80-90C for 12h. As carboxylic acid group normally get decomposed above 100C, the resin was cured below 90C. The resulting resins were washed with DMF to remove monomer impurities and finally with deionised water. After complete washing cycle, the yields of the resins were found to be in the range 78-85%. These purified and dried resins were finely ground and passed through 50 mesh sieve and then 20 mesh sieve to get uniform particle size (20 to 50 meshes). The sieved resins were again washed with water, air dried at room temperature and stored in air tight polyethylene bottle. To convert the resin samples in H+ form, resins having uniform particle size were equilibrated with 1M HCl solution for 24 h and washed with deionized water till free from chloride, checked with silver nitrate solution. This H+ form of resins were used for batch and column studies. The physico-chemical properties viz. moisture content, solid %, apparent density, true density, void volume fraction, sodium exchange capacity were studied according to literature method.11 Batch sorption experiments The sorption properties such as effect of contact time, effect of pH, effect of metal ion concentration and effect of temperature have been studied by batch equilibration method at 302C according to literature methods.12 To study the effect of contact time on sorption of Cd(II) and Pb(II), accurately weighed (0.2500.001g) H+ form of dry resins having uniform particle size (20-50mesh) were taken in different glass stoppered bottles and equilibrated with buffer solutions of optimum pH value (pH of highest exchange) for 6 h. After decanting buffer solution, 50cm3 (200mM) metal ion solutions of the same pH was added. After equilibration time solutions were filtered with 0.02m membrane filter to separate the resin and solution. The amounts of unadsorbed metal ions were determined by AAS at fixed time intervals. To study the effect of pH on Cd(II) and Pb(II) uptake, it is necessary to buffer the resin at different pH. Different sets of accurately weighed (0.2500.001g) dry resin were equilibrated with buffer in different glass stoppered bottles for 6h, so that resin attained desired pH value. After 6h, buffer solutions were decanted and 50cm3 of 200mM metal ion solutions of varying pH from 3-7 were added. Metal ion solutions were equilibrated at room temperature (302C) for 6 h with intermittent shaking. The pH of the filtrate was measured 4

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and it was found that pH remain stable throughout the experiment (0.2). The unadsorbed metal ions were estimated after filteration. To study the effect of metal ion concentration on uptake of Cd(II) and Pb(II) ions by the synthesized resins. The accurately weighed (0.2500.001g) buffered resin were equilibrated with different concentration of metal ion solutions (50cm3) in the range of 50-300mM at the same pH value at room temperature for 6h with intermittent shaking. After 6h metal ion solutions were filtered and residual metal ions were estimated by AAS. To study the effect of temperature, equilibrium experiments were performed at fixed metal ion concentration (200mM) for fixed resin loading (0.2500.001g) and initial pH (different optimum pH for different resins for Cd(II) and Pb(II) ions) at four different temperatures 30, 40, 50 and 60C. Column chromatography Column/Ion exchange chromatography is a technique in which separation of the components of a mixture is brought about by taking advantage of their different selectivity coefficients/retention capacity of the column adsorbent/resin. The differences in the selectivity coefficient/retention capacity lead to different migration rates on column. The study of column chromatography for the separation of mixture and industrial effluent will provide an idea of its application at large level. Packing of column A calibrated 50cm3 glass column (0.5cm Internal diameter) fitted with a glass wool plug at the lower end was used as ion exchange column. The resin having various particle sizes (20-50mesh) was used to avoid chocking of column. Slurry of the resin was made in hot deionized water to avoid air entrapment and slowly poured into the column containing some water. To ensure that no air bubbles remained in the column and that the resin was uniformly distributed, the column was backwashed with deionized water. The column of 15.0cm length, without air bubble was prepared. However, the level of water must never be allowed to fall below the surface of the resin otherwise, the resin may dry up and channels may be formed in the resin bed. This column was used for the separation of Cd(II) and Pb(II) from the mixtures. RESULTS AND DISCUSSION Physico-chemical properties The physico-chemical properties of all the four synthesized resins are presented in Table 1. The moisture content of a resin furnishes a measure of its water loading capacity or its 5

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swelling capacity. Moisture content depends on many factors such as, on the composition of the resin matrix, the degree of cross-linking or the nature of the active groups and the ionic form of resins. The amount of cross linking in the bead has an impact on the moisture content of the bead and the moisture content in turn has an impact on the selectivity. A bead with high moisture content has a high porosity and the active groups are spaced further apart from each other for example strong acid cation resins contain about 50 % moisture. The percentage of moisture content of synthesized resins as shown in Table 1 ranges from 6.2-8.7. It has been observed that these resins have low range of percentage moisture content compared to the commercial resins. The resins synthesized from salicylicacid-furfuraldehyde-benzidine and phydroxybenzoicacid-furfuraldehyde-benzidine13 have lower moisture content (4.01% and 4.9% respectively) than the present synthesized resins. The resin synthesized from salicylicfurfuraldehyde-hexamine14 and salicylic acid-formaldehyde-m-cresol15 exhibited slightly higher moisture content (15.11% and 9.4% respectively) than the SFR, SFC, pHFR and pHFC resins. The difference in moisture content may be due to the different experimental conditions like media in which the resins are synthesized, polymeric backbones, degree of cross linking and functional groups involved. True density of synthesized resins is shown in Table 1, which is in the range of 1.126g/cm3 to 1.689g/cm3. The true density of commercial resins generally lies between 1.1g/cm3 to 1.7g/cm3. To avoid the floating of resin particles, true density must be more than one. Floating of resin particles is undesirable in chromatographic study, as it hampers formation of compact column. Optimum density and uniform particle size gives perfect column packing and performance of the column. The measurement of column density or apparent density is necessary as commercially it is sold on volume basis and packed on weight basis. Apparent density of synthesized polymer is given in Table 1. It is observed that apparent density of all resins is in the range of 0.84g/cm3 to 0.93g/cm3, which is comparable to the density of commercial resins. It may be because of charge in polymeric matrix, different functional group and the method of synthesis. The apparent density parameter gives an idea of probable length of the packed column for an ideal column chromatography study. The values of void volume fraction of resin are represented in Table 1. Void volume fraction of synthesized resin is in the range of 0.341 to 0.483. The appreciable values of void volume fraction help the diffusion of the exchangeable ion on the resin and hence increase the rate of exchange of ions. Minimum essential void volume provides better diffusion of exchangeable ions and thus feasibility of column operation. 6

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Table 1. FTIR Spectra of resins The FTIR spectra of SFR, SFC, pHFR and pHFC resins are displayed in Fig. 1. The strong band at 3446-3452 cm-1 is attributed to the (O-H) stretching of phenolic group. The presence of medium band at 2920-2926 cm-1 is due to the (C-H) stretching of methylene group.16 The medium strong band at 1630-1653 cm-1 can be assigned to (C=O) stretching of aromatic acid group. The weak medium band at 1390-1462 cm-1 is due to (C-H) deformation of methylene group.15, 17 The medium band at 769-775 cm-1 is due to the (C-H) bending of 1, 2, 3, 4-tetra substituted benzene ring.18 The medium band at 664-667 cm-1 attributed to the (C-H) bending of poly ethylene (CH2) _ bridges. Fig. 1 X-ray diffraction spectroscopy The XRD patterns of the compound provide information about crystalline or amorphous nature and region of compound that may co-exist in the same compound.19 The XRD patterns of all the four resins (SFR, SFC, pHFR and pHFC) are shown in Fig. 2. No sharp peaks are observed in the difractograms of all the resins and exhibit irregular pattern, which is a characteristic of the amorphous compound. Phenol-formaldehyde resin also exhibited similar XRD pattern, which confirms the amorphous nature of these four synthesized resins.20 Fig. 2 SEM and Optical photographs Surface analysis has found to be of great use in understanding the surface features of the material. The Scanning Electron Microscopic photographs of all the resins are shown in Fig. 3 at 500X magnification. Several observations were made of the resins before the photographs (SEM and optical) were taken to ensure that the photographed regions were representative of the overall resin. The optical photographs of synthesized resins show that the resins appear to be reddish brown to black in colour. Optical photographs of the synthesized resins exhibit that SFR resin is red in colour, pHFR resin appears brown in colour with rough surface, while SFC and pHFC observed to be black in colour with smooth surface. This indicates that Salicylic acid containing resins exhibit reddish-brown colour and catechol containing resins shows black colour. From the SEM photographs (Fig. 3) indicate that resin exhibits angular edges with regular fringes. The morphology of the resin shows a fringed micelle model of the crystallineamorphous structure. The fringes represent the transition material between crystalline and 7

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amorphous phases. The SEM photographs exhibits such spherulites, which are the aggregate of some crystallites present along with some amorphous regions. All the four resin exhibits amorphous character which is confirmed by their XRD patterns. Fig. 3 Effect of contact time The exchange of metal ions on resin exhibits the time dependent phenomenon. The rate of exchange for different metal ions is illustrated in Fig. 4. The graph shows that the time required for 50 % exchange (t12) of Cd(II) for SFR and SFC resin is 50min., pHFR is about 60min. and for pHFC it is 65min. The time required for 50% exchange (t12) of Pb(II) for SFR is 45min., for SFC is 55min., pHFR is about 55min. and for pHFC it is 60min. The fast rate of exchange in the beginning can be explained on the basis of law of mass action.21 The faster rate of exchange facilitates column chromatographic separation. Kinetics of metal ion exchange mainly depends on the various physical properties like particle size, pore size, physical core structure and diffusion of counter ion.15,
17

For 100% uptake of Cd(II), SFR,

pHFR and pHFC took 21h and SFC took 15h. For 100% uptake of Pb(II), SFR took 12h, SFC took 15h, pHFR and pHFC took 18h. So, 24h is considered as optimum time for complete equilibration of Cd(II) and Pb(II) ions and used for all the further experiments. Fig. 4 Effect of pH on exchange capacity The synthesized resins were used to study the effect of variation in pH on chelating ability of the synthesized resins towards Cd(II) and Pb(II) ions. The removal of metal ions from aqueous solution is highly dependent on pH of the solution that also affects the surface charges of the sorbent. The results are presented as exchange capacity against pH for both the metal ions in Fig. 5. The results show that the uptake of Cd(II) and Pb(II) ions were increased with increase in pH up to a certain value and thereafter it decreased. From the nature of the trend observed indicates that the cation exchange behaviour of this resin is similar to weak acid cation exchangers.17 Because in weak acid cation ion exchanger, the exchange capacity is pH dependent.19 The maximum uptake of SFR for Cd(II) and Pb(II) took place at pH 5, SFC for Cd(II) and Pb(II) took place at pH 5.5, pHFR exhibits maximum capacity for Cd(II) at pH 5.5 and for Pb(II) at pH 5, pHFC exhibits maximum capacity for Cd(II) at pH 5 and for Pb(II) at pH 5.5. The selectivity order for Pb(II) is SFR > SFC > pHFR > pHFC and for Cd(II) is SFR > pHFR > SFC > pHFC. Chelation and ion exchange, both the phenomenon are more favorable 8

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for the uptake of Pb(II) in case of Salicylic acid containing resin due to its smaller hydrated ion radius. An increase in pH increases the negatively charged nature of the sorbent surface. This leads to an increase in the electrostatic attraction between positively charged metal ions and negatively charged sorbent which results in increase in the uptake of metal ions. The decrease in the removal of metal ions at lower pH is due to the higher concentration of H+ ions present in the reaction mixture which compete with the metal ions for the sorption sites on the resin surface. The observed decrease in sorption at higher pH is due to the formation of insoluble hydroxy complexes of the metal ions.22 Though SFC and pHFC are found to possess low cross linking in their backbones, they exhibit comparatively higher exchange than salicylic acid-formaldehyde-m-cresol resin.15 This is due to tiny creaks and channels, which are clearly seen on the surface of SFC and pHFC resin (SEM photographs, Fig. 3). The breaking of large particles tends to open tiny creaks and channels on the particle surface of the material resulting in more accessibility to better diffusion, owing to smaller particle size. Fig. 5. SFR exhibits higher exchange capacity for both Cd(II) and Pb(II), while pHFC shows lower exchange capacity for Cd(II) and Pb(II) as compared to other synthesized resins (SFC and pHFR) under this study. Exchange capacity of Cd(II) is found less as compared to Pb(II) for all the synthesized resins under study (SFR, SFC, pHFR and pHFC). This can be explain on the basis of hydrated radius of Cd(II) and Pb(II). Cadmium having greater hydrated ion radius than Pb(II) ion. This will results in decrease in electrostatic attraction between the Cd(II) and coordinating group, lower the complex stability and hence lower the capacity. Effect of initial metal ion concentration on exchange capacity The amount of metal ion uptake increases with the increase in concentration of metal ions and remains constant with further increase in metal ion concentration Fig. 6. At lower concentration of metal ions, the number of metal ions available in solution is less as compared to the available sites on the sorbent.23 However, at higher concentration the available sites of exchange remain same whereas more metal ions are available for sorption and subsequently the exchange becomes almost constant then after. Similar trend in the sorption data have previously been reported for lead and chromium onto bagasse fly ash24 and for heavy metal onto salicylic acid-formaldehyde-m-cresol chelating resin.15 Cd(II) after 250mM concentration, sorption/ion exchange attains limiting value for SFR, SFC and pHFC and pHFR resins. In case of Pb(II) after 200mM concentration, uptake become constant for SFR 9

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and pHFC, while for SFC and pHFC it is 250mM. So, 200mM concentration is considered as an optimum concentration for all the resins and used for further experiments. Fig. 6 Effect of electrolyte concentration and pH on distribution coefficients of metal ions The distribution coefficient (Kd) values of the metal ions as a function of pH and concentration of electrolyte solution were studied. The Kd value decreases with increasing the electrolyte concentration and increases with increase in pH, which is presented in Table 2. The present investigation limits the distribution studies up to a certain pH for each metal ion to prevent the hydrolysis of metal ions at higher pH. To achieve a more distinct separation of metal ion in a shorter time, the maximum Kd value difference should be selected for optimized condition of chromatography. Table 2. Among all the resins under investigation, SFR resin shows higher Kd values, where pHFC exhibits lower Kd values. This may be explained based on stability constant or difference in energy of the complexes according to Irving and Williams.25 The chromatography separation of these two metal ions was employed by using SFR resin. From Table 2 it is clear that Pb(II) has distribution coefficient of 120.91 as compared to Cd(II) (0.0)at pH 5.0 and 0.5M tartaric acid concentration indicating the possibilities of chromatography separation of these two metal ions. Chromatographic separation of these metal ions was achieved and the recovery of Cd(II) was 90.7% and Pb(II) was 96.20%, which is shown in Fig. 7. Fig. 7 Effect of temperature and thermodynamic parameters The effect of temperature on the uptake of both Cd(II) and Pb(II) on synthesized resins was studied using the optimizing conditions of above experiments. The temperature was varied from 30 C to 60 C. It was observed that the uptake of Cd(II) and Pb(II) ions increase with the increase in temperature (Fig. 8) for all the metal-resins systems. The exchange is enhanced due to increase kinetic energy.26 The phenomenon of an ion-exchange depends on metal ion concentration and temperature. The surface energy of the SFC resin increases with temperature. Similar results have also been reported earlier for the ion exchange of Ni(II), Cu(II), Zn(II),Cd(II) and Pb(II) with Dowex 5028 and Amberlite IR 120.27 Fig. 8 The values of Hexch, Sexch and Gexch were also calculated from the slope and 10

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intercept of the Vant Hoff plot of the exchange of metal ions on SFC resin, the linear variation of lnKd with reciprocal temperature 1/T using the following relation: ln Kd = (Sads/R)- (Hads/RT) (1) where, Sexch is the entropy change for the process, Hexch is the enthalpy change for the process. The free energy of the adsorption and Gexch was calculated using the following Vant Hoff equation: Gads = -RT lnKd (2) The value of Hexch is negative which indicates an exothermic ion exchange process and it is likely that the chelation mechanism dominates (Table 3).28 The entropy (Sexch) is positive corresponding to an increase in degree of freedom of the system due to release of two hydrogen ions for the divalent metal ions under study.29 The negative values of Gexch indicate the feasibility of the process and also the spontaneity of the ion exchange process. The amount of metal ions uptake at equilibrium must increase with increasing temperature, because Gexch decrease with the rise in temperature of the solution. Table 3.

Sorption Isotherms Equilibrium is described by usual isotherm equations such as Langmuir and Freundlich isotherms. A preliminary screening of the corresponding equations has shown that Langmuir and Freundlich models best fit the experimental data and the following equations are used for the modeling of results. Langmuir model: Freundlich : (Ce/Qe) = (1/Qo b) + (Ce/Qo) log qe = log kf + (1/n) log Ce (3) (4)

where, Ce is the equilibrium concentration (mmol/g), Qe is the amount of adsorbed at equilibrium (mmol/g) and Qo and b are Langmuir constant related to adsorption capacity and energy of adsorption respectively. The liner plot of Ce/Qe versus Ce (Fig. not shown) indicate that ion uptake obeys Langmuir model. These constant Qo for Cd(II) are calculated as 69.53, 43.23, 52.47 and 38.84mg/g as maximum capacity for SFR, SFC, pHFR and pHFC respectively. The constant Qo of Pb(II) for SFR, SFC, pHFR and pHFC are calculated as 169.32, 143.23, 122.47 and 101.84mg/g respectively. The results were comparable with commercial resin Duolite GT-73 reported by Vaughan et al.30 The Qo of Duolite GT-73 for Cd(II) and Pb(II) were 106 and 122mg/g respectively. The values of Qo for synthetic resin methacrylic acid-co-ethyleneglycol dimethacrylate were 416.67 and 588.24mg/g for Cu(II) 11

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and Ni(II) respectively.23 Sorption energy constant of Cd(II) for SFR, SFC, pHFR and pHFC are 0.1048, 0.0721, 0.0831 and 0.0593dm3/mg respectively. Sorption energy constant of Pb(II) for SFR, SFC, pHFR and pHFC are 0.2732, 0.2461, 0.2382 and 0.1984dm3/mg respectively The essential characteristics of Langmuir equation can be expressed in terms of a dimensionless separation factor or equilibrium parameter, RL.31 The values indicates the isotherm to be either unfavourable (RL<1), linear (RL=1), favourable (0< RL <1) or irreversible (RL=0). The values of RL obtained for all the metal-resin systems are shown in Table 4. The RL value for both the metals Cd(II) and Pb(II)) under study are between 0 and 1 indicate sorption is favourable. Table 4. The adsorption capacity (Kf) and the adsorption intensity (1/n) are directly obtained from the slope and the intercepts of the linear plot of logqe versus logCe (Fig. not shown) respectively and data are given in Table 4. The value of 1/n thus determined is of the same magnitude as those of commercial macrorecticular chelating resin DuoliteGT-73 reported by Vaughan et al.30 The higher fractional values of 1/n signify that strong sorption forces are operative on the system. The magnitude of 1/n also gives indication of the favourability and capacity of the sorbent/sorbate system. The values n for both Cd(II) and Pb(II) are between 1 to 10 represents the favorable adsorption process.32 For all the metal-resin systems reported here, the exponent is 1<n< 2 showing beneficial adsorption (Table 4). Freundlich constants Kf of cadmium are calculated as 39.37, 29.71, 31.25, 21.31 and 1/n were calculated as 0.5231, 0.4831, 0.5101 and 0.4389 for SFR, SFC, pHFR and pHFC respectively. The constants Kf for lead were calculated as 71.75, 66.23, 54.11; 39.63dm3/g and 1/n were calculated as 0.7023, 0.6230, 0.5834 and 0.4982 for SFR, SFC, pHFR and pHFC respectively. It is well established fact that the ion-exchange phenomenon follows reversible first order kinetics, when a single species is considered on a heterogeneous surface.26 The specific rate constant Kr for the sorbent was determined by Langergan equation. log (qe q) = log qe _ (Kr t) / 2.303 (5) where qe and q (mg/g) are the amounts of metal ions adsorbed at equilibrium and at time t (min) respectively. The straight line plot of the log (qe-q) versus time t, (Fig. not shown) indicates the validity of the Langergran equation for the system and explains that process follows first order kinetics. The values of Kr for Cd(II)-resin systems were found to be 17.12310-3, 14.31510-3, 15.21710-3, 11.83110-3min-1 for SFR, SFC, pHFR and SFC respectively. The values of Kr for Pb(II)-resin systems were found to be 9.18710-3, 12

396 397 398 399 400 401 402 403 404 405 406 407 408 409 410 411 412 413 414 415 416 417 418 419 420 421 422 423 424 425 426 427 428

12.50110-3, 15.15710-3 and 15.33110-3min-1 for SFR, SFC, pHFR and SFC respectively. Similar trend of Kr values were reported by Prasad et al for Cu2+ (11.310-3min-1) and Ni2+ (9.910-3min-1) with synthetic resin methacrylic acid-co-ethyleneglycol dimethacrylate.23 Diffusion models Sorption kinetics are mainly controlled by various factors including, (i) solute transfer from the solution to the boundry film of the particle (bulk diffusion) (ii) diffusion from the film to the surface of the sorbent (external diffusion) (iii) diffusion from the surface to the intraparticular sites (intra-particle diffusion) (iv) solute adsorption by complexation or physico-chemical sorption or ion exchange. By providing sufficient agitation to avoid particle and solute gradients in the batch reactor, makes it possible to ignore bulk diffusion.23 The process of intra-particle diffusion and external diffusion may be the rate controlling steps. Several models have been described to discuss the effect of external diffusion and intra-particle diffusion of solute on adsorbent. In the present work Spahn and Schlunder model33 and Weber and Morris model34 have been chosen to describe the external diffusion and intra-particle diffusion respectively on the resin. Spahn and Schlunder model If external diffusion of metal cations (within the diffuse layers outside the sorbent) is the rate limiting step then the sorption data can be fitted into the following equation.23, 37 ln(Ct/Co) = -Ks (A/V) t (6) where, Ks is external diffusion coefficient, Co is initial metal ion concentration, Ct is concentration at time t, A/V is external sorption area to the total solution volume, t is sorption time. The external diffusion coefficient can be calculated from the slope of the straight line obtained from the plot of ln(Ct / C0) versus t (Fig. not shown). The external diffusion model shows excellent correlation with the sorption data, with high correlation coefficients (Table 5). This would indicate that the sorption of Cd(II) and Pb(II) ions under study is a probably a surface process occurring on the exterior of the resin particle. The external diffusion coefficient (Ks) values of Cd(II) and Pb(II) for SFR, SFC, pHFR and pHFC are calculated, the values are given in the Table 5. The values for external diffusion coefficient (Ks) for synthesized resins are in the range of 0.00125-0.00425 mmol/h for Cd(II) and 0.002490.00680 mmol/h for Pb(II). Similar type of results were observed by Anand et al,23 while studding the uptake behaviour of Cu(II) and NI(II) on methacrylic acid-co-ethylene glycol dimethacrylate polymer. Table 5. 13

429 430 431 432 433 434 435 436 437 438 439 440 441 442 443 444 445 446 447 448 449 450 451 452 453 454 455 456 457 458 459 460 Weber and Morris model An empirically found functional relationship, common to the most sorption processes, is that the uptake varies almost proportionally with t1/2, the Weber and Morris plot,34 with the contact time, t . qt = kid t1/2 + I (7) where, qt is amount of sorbate retained at time t, kid is intra-particle diffusion rate constant, I is thickness of the boundary layer. According to above Eq. (8), a plot of qt versus t1/2 (Fig. not shown) should be a straight line with a slope kid and intercept I when sorption mechanism follows the intra-particle diffusion process. Values of intercept give an idea about the thickness of boundary layer, i.e., larger the intercept the greater is the boundary layer effect.35 The values of I for all the resins for Cd(II) and Pb(II) are found in the range of 0.029-0.187 mmol/dm3 h1/2. The values intra particle coefficient (Kid) and I are given in Table 5. From the external diffusion and intra particle diffusion data, it can be concluded that diffusion process is mainly controlled by intra-particle diffusion. Analytical application Removal of toxic metal from industrial effluents The efficiency of metal ion recovery from industrial effluent was examined using SFR as representative of all synthesized resin. The effluents were collected from D. P. Chemicals Pvt. Ltd. GIDC, Ankleshwer and Plate Well, Padra Road, Atladara, Baroda for Cd(II) and Pb(II) respectively. The initial concentration of Cd(II) and Pb (II) in effluents were found to be 185mg/dm3 and 106mg/dm3 respectively. Industrial effluent analysis was carried out in a simple way by using synthesized resins. The SFR resin was filled in the column up to 15cm length. The filled resin was preequilibrium at optimum condition. A 100cm3 industrial effluent was passed down the column at a flow rate of 1cm3/min. Industrial effluent containing Cd(II) was collected from D. P. Chemicals. The resin column was pre-equilibrated at pH 5.0. The pH of the effluent (100cm3) was adjusted to 5.0 using buffer solution and passed through the resin column at flow rate of 1 cm3/min., followed by a thorough washing with water. The chelated cadmium was eluted with 1M tartaric acid solution at pH 5.0. It was found that the removal and recovery of cadmium from the effluent is quantitative. 14

461 462 463 464 465 466 467 468 469 470 471 472 473 474 475 476 477 478 479

The effluent containing Pb(II) was collected from Plate Well industry. The resin column was equilibrated at pH 5.0. The pH of the effluent was adjusted to 5.0 and pass through the resin column at a flow rate 1cm3/min. followed by thorough wash with deionized water. The chelated lead was eluted with 1M tartaric acid solution at pH 6.0. The results show 94.3 % Cd(II) and 95.1 % Pb(II) recovery from industry effluent using SFR resin. The synthesized resins can be adopted for the treatment of industrial wastewater. CONCLUSIONS Synthesized resins exhibit greater amorphous character with cracks and channels on their surfaces. The lower moisture content of resins indicates the high degree of cross-linking which shows somewhat high capacity of metal uptake. Void volume fraction of resin is relatively lower than other reported resin indicating the lower rate of exchange. Chelating ability for Cd(II) is SFR > pHFR > SFC > pHFC and for Pb(II) is SFR > SFC > pHFR > pHFC. Uptake of metals proceeds by both physical and chemical phenomenon confirmed by Langmuir and Freundlich applicability. Diffusion studies shows that the metal ion uptake process is mainly govern by intra-particle diffusion process. These synthesized resins can be used for removal of heavy toxic metals from aqueous media and industrial wastewater containing Cd(II) and Pb(II). The recovery metal from industrial effluent gives an idea about the utilization of synthesized resin for wastewater treatment.

15

480 481 482 483 484 485 486 487 488 489 490 491 492 493 494 495 496 497 498 499 500 501 502 503 504 505 506 507 508 509 510 511 512

REFERENCES 1. 2. 3. 4. 5. 6. 7. 8. 9. G. McKay, Y.S. Ho, Trans. Chem. E Part B. 77, (1999) 165 Y.S. Ho, C.Y.J. Ng, G. Mckay, Sep. Sci. Technol. 36(2), (2001) 241 R. Salim, M. M. Al-Subu, S. Qashoa, J. Environ. Sci. Health Part A Environ. Sci. Eng. 29, (1994) 2087 D. A. Dzombak, F. M. M. Morel, J. Colloid Interface Sci. 112, (1996) 588 U. S. Ramelow, C. N. Guidry, S. D. Fisk, J. Hazard. Mater. 46, (1996) 37 D. C. Sharma, C. F. Forster, Eur. J. Soil Sci. 46, (1994) 633 Y. S. Ho, A. E. Ofomaja, Process Biochem. 40, (2005) 3455 E. I. Unuabonah, K. O. Adebowale, B. I. Olu-Owolabi, J. Hazard. Mater. 144(1-2), (2007) 386 K. O. Adebowale, I. E. Unuabonah, B. I. Olu-Owolabi, Chem. Eng. J. 136, (2008) 99 10. A. I. Vogel, Quantitative Inorganic Analysis, 5th Ed., Longaman, London, (1989) 11. A. Helfferich, Ion exchange, McGraw-Hills, NewYork, USA, (1962) 12. R. Kunnin, Ion exchange resin, Wiley, London, (1958) 13. M. V. Vyas, R. N. Kapadia, Indian J. Technol., 18, (1980) 411 14. M. V. Vyas, R. N. Kapadia, Indian J. Technol., 19, (1981) 491 15. B. A. Shah, A. V. Shah, P. M. Shah, Iran. Polym. J., 15(10), (2006) 809 16. M. Patel, R. Manavalan, Indian J. Chem. 22A, (1983) 117 17. B. A. Shah, A. V. Shah, R. R. Bhatt, Iran. Polym. J., 16(3), (2007) 173 18. R. M. Silverstain, G.C. Bassler, Spectrometric Identification of Organic Compound, John Wiley and Sons. Inc., New York, (1991) 19. A. Tager, Physical Chemistry of Polymer, Mir Publisher, Moscow, (1978) 20. S. A. Johnson, E. S. Brighan, T. E. Mollouk, Chem. Mater., 9, (1997) 2448 21. F. Vernon, H. Eccles, Anal. Chim. Acta. 72, (1974) 331 22. B. A. Shah, A. V. Shah, B. N. Bhandari, R. R. Bhatt, J. Iran. Chem. Soc. 5(2), (2008) 252 23. S. Anand, H. H. Prasad, K. M. Popat, P., Indian J. Chem. Technol. 9, (2002) 385 24. V. K. Gupta, I. Ali, J. Colloid Interf. Sci. 271, (2004) 321 25. H. R. Irving, R. J. Williams, Chem. Rev. 56, (1956) 221 26. E. Pehlivan, T. Altum, J. Hazard. Mater. 134(B), (2006) 149 27. A. Demirbas, E. Pehlivan, F. Gode, T. Altun, G. Arslan, J. Colloid Interf. Sci. 282, (2005) 20 16

513 514 515 516 517 518 519 520 521 522 523 524

28. I. S. Lima, C. Airoldi, Thermochim. Acta. 421, (2004)133 29. A. Baraka, P. J. Hall, M. J. Heslop, J. Hazard. Mater. 140, (2007) 86 30. T. Vaughan, C. W. Seo, W. E. Marshall, Bioresor. Technol. 78, (2001) 133 31. D. K. Singh, M. Srivastava, J. Liq. Chrom. Related Technol. 29, (2006) 1433 32. I. B. Stephan, N. Sulochana, Indian J. Chem. Technol. 9, (2002) 201 33. H. Spahn, U. Schlunder, Chem. Eng. Sci. 30, (1975) 529 34. J. C. Morris, W. J. Weber, Removal of biologically resistant pollution from waste waters by adsorption in Advance in Water Pollution Research, Pergamon Press, New York, (1962) 35. I. D. Mall, V. C. Srivastava, N. Agarwal, I. M. Mishra, Colloids and Surfaces A: Physicochem. Eng. Aspects. 264, (2005) 17.

17

525 526 527 528 529 530 531

TABLE CAPTIONS TABLE I. Physico chemical properties of synthesized resin TABLE II. Kd value for synthesized resins in tartaric acid at different pH and concentration. TABLE III. Thermodynamic parameters for Cd(II) and Pb(II) adsorption on synthesized TABLE IV. Langmuir and Freundlich isotherms constants for metal-resin systems TABLE V. External and intra-particle diffusion rate constants for metal-resin systems.

18

532

TABLE I.
Properties % moisture % solid True density (dres), g/cm
3

SFR 7.0 93

SFC 6.2 93.8

pHFR pHFC 8.7 91.3 1.689 0.931 0.448 3.822 5.893 3.247 6.5 93.5 1.391 0.916 0.341 3.497 4.548 2.997

SD 0.5 0.5 0.03 0.006 0.005 0.2 0.200 0.05

1.126 1.210 0.842 0.883 0.453 0.483 4.931 4.027 5.02 2.67 4.473 2.209

Apparent density (dcol), g/cm3 Void volume fraction Sodium exchange capacity, mmol/g dry resin Concentration of fixed ionogenic group, mmol/cm3 Volume capacity, mmol/cm3

533 534

19

535

TABLE II. Resin Metal ion Cd(II) SFR Pb(II) Tartaric acid Conc./ M 0.1 0.2 0.3 0.5 1.0 0.1 0.2 0.3 0.5 1.0 0.1 0.2 0.3 0.5 1.0 0.1 0.2 0.3 0.5 1.0 0.1 0.2 0.3 0.5 1.0 0.1 0.2 0.3 0.5 1.0 0.1 0.2 0.3 0.5 1.0 0.1 0.2 0.3 0.5 1.0 3.0 565.00 370.81 252.11 98.23 31.47 828.23 517.00 390.32 152.71 171.13 69.5 52.1 29.3 17.4 143.1 118.2 72.9 55.5 42.3 29.7 96.3 78.5 69.2 54.2 37.5 24.9 19.5 16.2 60.5 32.1 15.1 8.5 Kd values at different pH 3.5 4.0 5.0 6.0 443.00 299.80 143.31 87.50 215.70 153.80 98.98 50.99 170.77 101.02 53.00 19.27 50.09 31.13 22.57 10.68 587.62 440.84 310.51 247.10 473.74 301.77 250.67 189.74 295.00 220.22 181.37 121.84 210.13 187.15 120.91 92.31 145.70 90.27 52.64 11.09 54.3 33.5 21.3 17.5 37.8 21.5 13.5 12.5 21.5 14.3 9.2 15.8 129.7 103.5 81.5 52.6 110.4 84.8 62.7 45.3 63.1 57.6 48.3 37.5 31.2 24.8 62.2 68.6 22.2 19.4 57.2 31.7 39.3 13.6 20.5 27.8 14.5 81.1 74.2 54.2 33.8 68.2 62.8 49.0 30.1 60.5 54.8 31.5 22.0 49.7 44.0 37.4 18.8 22.0 30.2 19.5 19.0 18.0 15.5 10.9 15.6 15.0 9.5 12.9 39.5 28.4 25.5 16.5 22.0 20.3 16.5 15.4 13.6 10.1 15.2 10.2 -

Cd(II) SFC Pb(II)

Cd(II) pHFR Pb(II)

Cd(II) pHFC Pb(II)

536 537

20

538 539 TABLE III.

Metal Ion Resin T/ K 293 303 313 323 293 303 313 323 293 303 313 323 293 303 313 323 293 303 313 323 293 303 313 323 293 303 313 323 293 303 313 323 1/T /K-1 3.30 10-3 3.19 10-3 3.09 10-3 3.00 10-3 3.30 10-3 3.19 10-3 3.09 10-3 3.00 10-3 3.30 10-3 3.19 10-3 3.09 10-3 3.00 10-3 3.30 10-3 3.19 10-3 3.09 10-3 3.00 10-3 3.30 10-3 3.19 10-3 3.09 10-3 3.00 10-3 3.30 10-3 3.19 10-3 3.09 10-3 3.00 10-3 3.30 10-3 3.19 10-3 3.09 10-3 3.00 10-3 3.30 10-3 3.19 10-3 3.09 10-3 3.00 10-3 Kd 7.92 8.12 8.41 8.67 4.65 4.95 5.10 5.29 5.19 5.32 5.49 5.69 4.41 4.67 4.93 5.06 9.65 9.92 10.51 10.87 8.05 8.27 8.63 8.79 7.47 7.61 7.92 8.11 7.12 7.56 7.73 8.02 lnKd 2.069 2.094 2.129 2.159 1.539 1.592 1.619 1.667 1.646 1.671 1.703 1.739 1.484 1.541 1.595 1.621 2.267 2.294 2.352 2.386 2.086 2.113 2.155 2.174 2.011 2.029 2.069 2.93 1.963 2.022 2.045 2.071 Go /kJ mol-1 -5.041 -5.276 -5.541 -5.799 -3.622 -3.712 -3.739 -4.801 -4.371 -4.391 -4.406 -4.409 -3.701 -3.722 -3.735 -3.739 -4.803 -4.812 -4.835 -4.853 -3.845 -3.892 -3.911 -3.923 -2.588 -2.591 -2.607 -2.615 -4.782 -5.094 -5.311 -5.492 Ho /kJ mol-1 -6.141 So /J K-1 mol-1 17.13

SFR

SFC Cd(II) pHFR

-7.003

19.14

-7.113

18.23

pHFC

-5.135

13.39

SFR

-4.794

10.57

SFC Pb(II) pHFR

-4.819

11.97

-7.021

19.56

pHFC

-5.153

15.25

540 541 542 543 544 545 21

546

TABLE IV.
Metal ions Resins Langmuir constant b/ dm mg Qo/ mg g-1 RL
3 -1

Freundlich constant Kf / dm3 g-1 1/n R2 35.41 68.72 54.70 21.35 71.75 66.23 54.11 39.63 0.4152 0.9886 0.7215 0.9934 0.5123 0.9862 0.5216 0.9912 0.7023 0.9925 0.6230 0.9914 0.5834 0.9887 0.4982 0.9974

SFR SFC Cd(II) pHFR pHFC SFR SFC Pb(II) pHFR pHFC

0.1048 0.0721 0.0831 0.0593 0. 2732 0.2461 0.2382 0.1984

69.53 43.23 52.47 38.84 169.32 143.23 122.47 101.84

0.219 0.202

0.9627 0.9787

0.2141 0.9791 0.198 0.341 0.322 0.281 0.263 0.9687 0.9892 0.9974 0.9972 0.9983

547 548

22

549 550 TABLE V.

Metal ions Resin SFR Cd(II) SFC pHFR pHFC SFR Pb(II) SFC pHFR pHFC External Diffusion Intra-particle diffusion Ks 0.00425 0.00125 0.00193 0.00187 0.00680 0.00355 0.00249 0.00283 R2 0.978 0.977 0.938 0.987 0.942 0.963 0.993 0.983 Kid 0.102 0.0310 0.0504 0.0301 0.134 0.0807 0.0443 0.0439 I 0.029 0.063 0.094 0.039 0.119 0.187 0.173 0.062 R2 0.987 0.990 0.992 0.990 0.989 0.997 0.978 0.995

551 552 553 554

23

555 556 557 558 559 560 561 562 563 564 565 566 567 568

FIGURES CAPTIONS Fig.1. FTIR spectra of synthesized resins Fig. 2. XRD pattern of synthesized resins. Fig. 3. SEM photograph of synthesized resins at 500X magnification. Fig. 4. Time dependence of the fraction of metal ion uptake of synthesized resins. Condition: C0=200mM, W=0.25g, V=50cm3, T=302 C Fig. 5. Metal ion uptake capacity of synthesized resins as a function of pH. Condition: C0=200mM, W=0.25g, V=50cm3, T=302 C Fig. 6. Metal ion uptake capacity of synthesized resins as a function of initial metal ion concentration. Condition: W=0.25g, V=50cm3, T=302 C Fig. 7. Chromatographic separation of Metal ions by SFR resin Fig. 8. The metal uptake capacity of synthesized resins as a function of temperature Condition: C0=200mM, W=0.25g, V=50cm3

24

569 570

571 572 573

Fig. 1

25

574 575 576

577 578 579 580 581

Fig. 2

26

582 583

SFC

SFR

584 585 586 587

pHFC

pHFR

Fig. 3

27

588

589 590 591

Fig. 4

28

592 593 594 595 596

597 598 599 Fig. 5

29

600 601

602 603 604

Fig. 6

30

605 606

607 608 609

Fig. 7

31

610 611 612

613 614 615 616

Fig. 8

32