@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I2@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (2) 2013 Removal of Birlliant Green Dye From Aqueous Solution by Adsorption Onto Modified Clay Dunya Edan Al-Mammar Dept. of Chemistry / College of Science / University of Baghdad Received in : 21 February 2013 , Accepted in : 10 June 2013 Abstract Application of a Fe-bentonite nano clay (Fe-BNC) as modified clay has been investigated for the removal of birlliant green (BG) from aqueous solutions. Atomic force microscope measurements give a detailed information on pore shape and pore size distribution about the clay. These measurements show that the average diameter of the improved clay is 346.84 nm. Batch adsorption experiments were carried out for the removal of (BG) from aqueous solutions onto Fe-BNC. Equilibrium data were fitted to Freundlich and Langmuir isotherm equations and the isotherm constants were determined. Thermodynamic parameters such as free energy, entropy and enthalpy, have been calculated. For the modified clay the study of adsorption rate constants has been carried out using lagergrens first order rate equations for the adsorption processes and it is found to follow first order rate kinetics. In addition, an activation energy of sorption has also been determined. Keywords : Adsorption, Birlliant green dye, bentonite. 206 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I2@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (2) 2013 Introduction Dyes and coloring materials are frequently used in some industries such as; textile, dye stuff manufacturing, leather tanning, food preparation, paper production that produce a high colored waste effluents [1]. The discharge of effluents is one of the potential sources of contamination and pollution [2], and also can consume the dissolve oxygen in water which is required by aquatic life. Some of these dyes were found to be toxic to some organisms and cause allergic dermatitis, skin irritation and mutation in man. It was reported that dyes are resistant to light and moderate oxidative agents, so they cannot be completely removed by conventional biological treatment process, including activated sludge and anaerobic digestion [3]. Birlliant green (BG), is known to be used in several industries including leather products, dying wool, silk and jute. It is also used in distilleries [4]. In addition to its high risk of cancer and many other diseases to human, this dye is highly toxic to the microbial populations in BG-containing water, therefore it is so important to develop a system that can be used to remove this dye from the water. Precipitation, coagulation, ozonization, ion exchange as well as adsorption methods are the conventional methods used for the removal of this dye [5]. Among the various treatments available for the removal of dyes, adsorption technique is one of the most effective treatment methods due to simplicity and high efficiency, as well as the availability of a wide range of adsorbents. Some materials like fly ash, clays, alumina, activated carbon and some agricultural byproducts have been as adsorbents for removal of dyes from industrial wastewaters [6]. It was found that the use of the clay materials as an adsorbent has many advantages in comparison of other adsorbant due to the low cost, lack of toxicity and good potential for ion exchange. The clay materials have a high specific surface area which gave these materials unique properties and were used in several application [7]. Lately, many studies have reported the use of nano-particels and cause a significant breakthrough in many areas of applied sciences. In particular, nano-particles smaller than 100 mm were found to be important in natural systems due to the high surface area, surface activity and their associated properties of adsorbing to organic and other trace metal contaminants [8]. This work examines the efficiency of using modified nano-clays to remove BG by measuring the adsorption data. Materials and method Materials Adsorbate :All chemicals (such as Fe(NO3)3.9H2O and Na2CO3) used in the experiments were analytical grad chemical and were obtained from Merck. Stock solutions of the test reagent were made by dissolving the dye in distilled water. The dye, Birlliant green sulfate, chemical formula: C27H34N2O4S. Molar mass= 482.65, λmax: 625 nm (measured value) was supplied by Merck. The chemical structure of birlliant green sulfate is shown in Figure (1) Adsorbent: The adsorbent, bentonite clay was collected from Al-Sufra in Al-Rutba, Iraq. It was supplied by geological survey and mining-Iraq. The components of this clay are SiO2 (56.77%), Al2O3 (15.67%), MgO (3.42%), K2O (0.06%), Na2O (1.11%), Fe2O3 (5.12%), CaO (4.48%) and loss of Ignition L.O.T (12.49%). Preparation of Fe-bentonite nano composite The Fe-BNC was prepared through the following steps [9]. Firstly an aqueous dispersion of bentonite clay was prepared by adding 10 gm bentonite clay to 500 ml H2O under vigorous stirring for (3 hrs.) at room temperature. Secondary, sodium carbonate was added slowly as a powder into a vigorously stirred (0.2 M) solution of iron nitrate for (3 hrs.) such that a molar ratio of (1:1) for [Na+]/[Fe+3] was established. Thirdly, 500 ml solution obtained from the second step was added drop by drop into the dispersion of bentonite clay prepared in the first 207 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I2@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (2) 2013 step under vigorous stirring. Fourthly, the suspension was stirred for (3 hrs.) followed by ageing at 100ºC in an autoclave for (48 hrs). Finally, 1000 solution containing Fe-bentonite nano clay was obtained [10]. The modified clay was separated from the solution by filtration, then dried in oven at 100 ℃ and stored in desiccators. Characterization measurement The atomic force microscopy (AFM) study carried out by (AA 3000, Angstrom Advanced IUC. USA) Fig.(2) shows typical AFM Top-view of (I) clay, (II) Fe-BNC. The results show that the average diameter for the clay is 699.22 nm, while the pore diameter of Fe-bentonite clay is about (300-400)nm with an average of 346.84 nm, it means that the pore diameter of the Fe-BNC is smaller than that of the clay. Methods Adsorption studies The adsorption of BG on to the modified clay was investigated in a batch system. Equilibrium experiments were carried out by containing 0.5 gm of modified clay to 50 ml of dye solution of different initial concentrations (5-20 ppm). A series of round bottom flasks were then shaken at a constant speed of 100 rpm in a shaker (CRIFFIN FLASK SHAKER) for 30 min (Equilibrium time) at four temperatures in the range (283-303)K. The dye solution was separated from the adsorbent by filtration residual concentration of dye in supernatant was estimated spectrophotometrically by monitoring the absorbance at 625 nm λmax using UV-Vis spectrophotometer (UV-1800 shimadzu). Amount of adsorbed dye molecules per gm of solid was determined as follows: Qe = (Co-Ce) V/W…..……….(1) Where, Co is the initial concentration of BG (mg/L), Ce is the equilibrium concentration of dye (mg/L), V is the volume of the solution (L) and (W) is the mass of the Fe-BNC (g). The removal efficiency (R) is defined as: [11] Removal of dye (%) = [(Co-Ce)/Co] x 100…..……….(2) Isotherm modeling The isotherm models of Langmuir [12], Freundlich [13] were fitted to describe the equilibrium adsorption. Langmuir isotherm Qe = KL Ce/ 1 + aCe…..……….(3) The linear form of the Langmuir isotherm equation is represented in the following formula: Ce/Qe = 1/KL + a/KL.Ce…..……….(4) Where Ce is the supernatant concentration at equilibrium state of the system (mg.L-1), Qe is the amount of dye adsorbed per unit weight of adsorbent (mg.g-1), assuming a mono layer of adsorbate up taken by the adsorbent, KL, a is the Langmuir affinity constant. Langmuir equation used to evaluate thermodynamic parameters of the ongoing process and also to know the nature adsorption. Freundlich isotherm The empirical Freundlich equation based on sorption on heterogeneous surface is given by equation: Qe = Kf (Ce)1/n…..……….(5) Where Kf is the freundlich constant related with adsorption capacity mg.g-1 (mg.L-1)-1/n and n is the freundlich exponent (dimensionless). This model is rearranged to the linear form by taking logarithms on both sides. Log Qe = log Kf + 1/n log Ce…..……….(6) 208 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I2@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (2) 2013 Batch kinetic studies Rate constant study The specific rate constant for each adsorption process was calculated using Lagergren's first order rate expression [14] ln (qe-qt) = ln qe - Kad t …..……….(7) Where qe (mg.g-1) and qt (mg.g-1) are the amounts of dye adsorbed at equilibrium and at any time t (min) respectively. Kad is the rate constant of adsorption (min-1). Results and Discussion Effect of initial dye concentration The effect of the dye (BG) concentration on adsorption properties of the bentonite and Fe-BNC are shown in Table (1) and Figure (3). It is apparent that the percentage removal of dye increases with increase in initial dye concentration [15], probably due to the greater availability of exchangeable sites for the adsorbents. Nonetheless, adsorbate saturation of the adsorbent sites may occur on increasing concentration of the dye solution causing no further adsorption of the dye molecules. As seen from the values of removal efficiency of the two adsorbents the R% values of the Fe-BNC larger than that of the bentonite clay. This indicates that Fe-BNC is effective for the removal of (BG) from aqueous solution Effect of temperature Fig. (4) shows the sorption kinetics of BG removal at 283, 293 and 303 K by plotting the dye uptake capacity qt versus time at the initial dye concentration of (10 ppm). Increasing the temperature reduced the sorption capacity of Fe-BNC clay. Thus, when increasing the temperature from 283 K to 303 K the removal of dye decreased, this may be due to a tendency for the dye molecules to escape from the solid phase to the bulk phase with an increase in temperature of the solution [16]. During kinetic study it has been seen that the removal of dye was rapid in the initial stages of constant time and gradually with time until equilibrium. This decreasing removal rate towards the end, suggests formation of monolayer coverage of dye molecules on the outer surface of the adsorbent and pore diffusion onto inner surface of the adsorbent particulars through the film due to continuous agitation maintained during the experiments [17]. The rate constant for the adsorption of dye on modified clay was determined using Lagergren equation [7]. The kinetic data of adsorption BG (Co= 10 ppm) onto the modified clay was shown in Table (2). The straight line plots of (ln qe-qt versus t), Fig. (5) confirm that process of removal is governed by first order kinetics. The values of Kad were determined by slops the graphs of Fig. (5) were listed in Table (3). All the fits show very good correlation coefficients. Fig. (6) shows a linear relationsship between the logarithm of rate constant and the reciprocal of temperature. The activation energy for the adsorption process Ea, was calculated using the Arrhenius equation [18] ln Kad = ln A – Ea/RT …..……….(8) Where A is referred to as the Arrhenius factor. R is the universal gas constant (8.314 J.mol- 1.K-1), T is the absolute temperature (K). The rat constant Kad listed in Table (3) was applied to estimate the activation energy of the adsorption. A value of (11.626 K.J.mol-1) for Ea was obtained from the slop of an ln Kad versus 1/T plot with a R2 of 0.981. Because the value of E is high, it is concluded that the adsorption kinetic of (BG) onto Fe-BNC involved a chemical reaction in the adsorption process 209 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I2@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (2) 2013 Adsorption isotherm The linear plots of Ce/Q versus Ce show that the adsorption obeys Langmuir isotherm model [19], Fig. (7), and indicates formation of mono layer of the dye around adsorbent particles and once a dye molecule occupies a site, no further adsorption takes place at that site. KL and a were determined from the slop and intercept of the plot and are presented in Table (4). The essential characteristic Langmuir isotherm can be expressed by a dimensional constant called equilibrium parameter, RL [20] that is defined by RL= 1 1+ KLCο ………(9) Where, KL is the Langmuir constant at (L.mg-1) and Co is the initial concentration. The value of RL indicates the shape of the isotherm to be either unfavorable (RL > 1), linear (RL = 1), favorable (0 < RL < 1) or irreversible (RL = 0). As shown in Table (5), RL value decreases with the concentration and its values between 0 and 1 at different concentrations indicate favorable adsorption of dye onto Fe-BNC clay. linear plot of ln Qe versus ln Ce shows that the adsorption follows freundlich isotherm model as well Fig. (8), Kf and n were calculated from the intercept and slop of the plot. The fitting results, i.e isotherm parameters and the coefficients of determination, R2 are shown in Table (4). It can be seen in Fig. (8) that freundlich isotherm fits the data better than Langmuir isotherm. This is also confirmed by the high value of R2 in case of freundlich (0.99) compared to Langmuir (0.962). The freundlich constant n is primarily related to the strength of adsorption. Given fixed Co and Kf the smaller the constant, the stronger the adsorption bond. As shown in Table (4), the (n) values of all the clays sample are less than (1), indicating that for this adsorbent the increased adsorption would promote the clay sorption capacity, and predominant adsorption mechanism would be chemical adsorption rather than physical adsorption [21]. The value of Kf increased on the increase of temperature indicating that higher temperature favored BG sorption on to Fe-BNC clay [22]. Fig. (9): Shows that the adsorption isotherms of BG on Fe-BNC clay is S-type according to the Giles classification. Thermodynamic parameters To calculate thermodynamic parameters of the ongoing process, another Langmuir form equation used [23]: Ce Qe = 1 b + Ce…………(10) Where b is the maximum adsorption quantity for dye solutions at different temperatures and could be obtained from the plot of Ce/Qe vs. Ce fig (7) The relation between log b and 1/T fig (10) is used to estimate ∆H and ∆S using the following formulas: 𝑏 = 𝑎 exp �− ∆H RT � … … … . . (11) 𝑎 = exp( ∆S/𝑅) … … … (12) log 𝑏 = ∆𝑆 2.303𝑅 − ∆𝐻 2.303𝑅 1 𝑇 … … … . . (13) The ∆𝐺 value was calculated from the following equation: ∆𝐺 = ∆𝐻 − 𝑇∆𝑆 … … … … . . (14) The estimated thermodynamic parameters are listed in Table (6). The positive value of enthalpy change (ΔH) confirms an endothermic nature of the enduring process whereas the negative values of free energy (ΔG) suggest feasibility and spontaneous nature of the process. The values of (ΔG) decrease with the increase of temperature indicated that the adsorption was more favorable at higher temperature. Positive values of entropy (ΔS) revealed that the adsorption process was irreversible and random at the solid/liquid in interface during the 210 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I2@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (2) 2013 sorption of BG onto and Fe-BNC and showed that a good affinity of the adsorbent materials towards the dye, also the positive value of ΔS suggested some structural change of BG and Fe-BNC clay, and favored complexion and sorption stability [24]. Similar results were also observed on the adsorption of some dyes on to de-oiled soya [25], bentonite [26], neem leaf [27] and hen feathers [28]. Conclusion It can be concluded that Fe-NBC can be successfully used as low cost adsorbents for removal of BG from waste waters. Equilibrium data were fitted to freundlich and Langmuir adsorption isotherm models. The thermodynamic parameters indicated that the adsorption is feasible, endothermic and spontaneous in nature. Kinetic studies were verified for lagergrens first order, and the adsorption of (BG) follows first order Kinetics more. References 1. Chen, Y. M. ; Tsao, T. M. and Wang, M. K.(2011) "Removal of Crystal Violet and Methylene Blue from Aqueous Solution Using Soil Nano Clays"; Inter. Conference on Environment Science and Engineering, 8: 252-254. 2. Sharma, Y. C.; Singh, B. and Uma,(2009) ''Fast Removal of Malachite Green by Adsorption on Rice Husk Activated Carbon''; The Open Environmental Pollution and Toxicology Journal, 1: 74-78. 3. Vipasiri, V.; Shaomin, L.; Bo, J.; Chris, W. K. C. and Chris, S.(2009) "Kinetic study and equilibrium isotherm analysis of Congo Red adsorption by clay materials"; Chemical Engineering J.148:354-364. 4. Rajeshkannan, R.; Rajasimman, M. and Rajamohan, N.(2010) "Removal of Malachite Green from Aqueous Solution Using Hydrilla verticillata Optimization, Eqnilibrium and Kinetic Studies''; Inter. J. of Civil and Environmental Engineering, 2(4): 222-229. 5. Nigam, P.; Armour,G.; Banat, I. M., Singh, D. and Marchant, R.(2000) "Physical removal of textile dyes from effluents and solid state fermentation of dye adsorbed agricultural residues "; Biorsource Technology, 72: 219-226. 6. Pavan, F. A.; Dias, S. L.; Lima, E. and Benvenutti, E.( 2008) "Removal of Congo red from aqueous solution by anilinepropylsilica xerogel"; Dyes and Pigments, 76: 64-69. 7. Tulin, B. L. and Gamze, G.(2009) "Removal of basic dyes from aqueous solutions using natural clay"; Desalination, 249: 1377-1379. 8. Roco, M.C. , Li , B.C. , Fissan, H.J. , Schoonman J., Hayashi, C. and Oda M.(1998) "Reviews of national research programs in nanoparticle and nanotechnology research "; J. of Aerosol science , 29:749-760. 9. Feng, J.; Hu, X. and Yue, P. L.(2005) "Discoloration and mineralization of orange (II) by using a bentonite clay-based Fe nanocomposite film as a heterogeneous photo-Fenton catalyst"; Water Research, 39:89-96. 10. Feng, J.; Hu, X. and Yue, P. L.(2004) "Novel bentonite clay-based Fe nanocomposite as a heterogeneous catalyst for photo-Fenton discoloration and mineralization of orange (II)"; Environ, Sci. Technol, 38:269-275. 11. Langmuir, I. (2007) "Constitution and fundamental properties of solids and liquids (I): Solids"; J. Hazard Mater, 139:57-66. 12. Fytianos, K.;Voudias, E. and Kokkalis, E.(2000) "Sorption-desorption behavior of 2,4- dichlorophenol by marine sediments"; Chemospher, 40:3-6. 13. Negi, A. S. and Anand, S. C.(2007); ''A textbook of physical chemistry''; Second Edition, New age international (P) LTd. Publishers, New Delhi. 211 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I2@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (2) 2013 14. Guen, S.; Yao, B.; Adouby, K. and Ado, G. (2007) "Kinetics and thermodynamics study of lead adsorption onto activated carbons from coconut and seed hull of the palm tree"; J. Environ. Sci. Tech, 4(1): 11-17. 15. Abdullah, N.A.; Othaman, R.; Abdullah,I.; Jon, N. and baharum , A. (2012) "Studies on the adsorption of phenol red dye using silica-filled ENR/PVC beads"; J. of Emerging Trends in Engineering and Applied Sciences, 3(5): 845- 850. 16. Yeddon, N. and Bensmaili, A. (2005) ''Kinetic models for the sorption of dye from aqueous solution by clay-wood sawdust mixture"; Desalination, 185: 499-508. 17. Mumin, M. A.; Kha,. M. M. R,; Akhter, K. F. and Uddin, M. J. (2007) "Potentiality of open burnt clay as an adsorbent for the removal of congo red from aqueous solution"; Int, J. Environ, Sci, Tech, 4(4):525-532. 18. Weng, C. H. and Pan, Y. F.(2007) ''Adsorption of a cationic dye (methylene blue) onto spent activated clay"; J. of Hazardous Materials, 144: 355-362. 19. Sonawane, S.; Chaudhari, P.; Ghodke, S.; Phadtare, S. and Meshram, S. (2009) "Ultrasound assisted adsorption of basic dye onto organically modified bentonite (nano clay)"; J. of Scientific and Industrial Research, 68:162-167. 20. Hall, K.R.; Eagleton, L.C.; Acrivos, A. and Vermeulen, T.(1966)"Pore and solid diffusion kinetics in fixed bed adsorption under constant pattern conditions "; J.Eng. Chem. Fundam. , 4:212-219. 21. Jiang, J. Q . and Zeng, Z.(2003) "Comparison of modified montmorillonite adsorbents part (II): The effects of the type of raw clays and modification conditions on the adsorption performance"; Chemophere, 53: 53-62. 22. Pan, X. and Zhang, D.(2009) "Removal of malachite green from water by firmian simplex wood fiber"; Electronic J. of Biotechnology, 12(4):1-10. 23. Dawood, J.S.(2006) "Adsorption study of lead ions on the surfaces of ion exchange resin and some Iraqi clays "; M.Sc. Thesis, univ. Baghdad. 24. Donat, R.; Akdogan, A.; Erden, E. and Cetisli, H.(2005) "Thermodynamics of Pb+2 and Ni+2 adsorption onto natural bentonite from aqueous solutions"; J. of Colloid and interface science, 286(1): 43-52. 25. Mittal, A.; Krishnan, L. and Gupta, V. K.(2005) "Removal and recovery of malachite green from wastewater using an agricultural waste material, de-oiled soya"; Separation and Purification Technology, 43(2): 125-133. 26. Bulut, E.; Ozacar, M. and Sengil, I.(2008) "Adsorption of malachite green onto bentonite equilibrium and Kinetic studies and process design"; Micro porous and Meso porous Materials, 115(3):234-246. 27. Bhattacharyya, Krishua, G. and Sarma, A.(2003) "Adsorption characteristics of the dye, Brilliant green, on Neem leef powder"; Dyes and Pigments, 57(3): 211-222. 28. Mittal, A.(2006) ''Adsorption kinetics of removal of a toxic dye, Malachite green from wastewater by using hen feathers''; J.of Hazard Materials, 133(1-3): 196-202. 212 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I2@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (2) 2013 Table (1): Removal efficiency for the adsorbents used in the adsorption of BG. 25 20 15 10 5 Co (ppm) 97.90 97.47 96.62 95.56 91.24 R% for bentonite 99.20 99.05 98.70 98.42 97.63 R% for Fe-BNC Table (2): Kinetic data of adsorption (10 ppm) BG dye onto Fe-BNC at temperature range (283-303) K. (ln qe - qt) qe-qt x 10-4 qt x 10-3 qe x 10-3 Time (min) Temp. (K) -8.70 -9.03 -9.43 -9.72 1.60 1.20 0.80 0.60 0 9.29 9.33 9.37 9.39 9.45 9.45 5 10 15 20 30 283 -8.839 -9.115 -9.567 -10.1519 1.45 1.10 0.70 0.39 0 9.265 9.30 9.34 9.371 9.41 9.41 5 10 15 20 30 293 -9.088 -9.231 -9.660 -10.31 1.13 0.98 0.64 0.33 0 9.251 9.266 9.295 9.331 9.364 9.364 5 10 15 20 30 303 Table (3): Rat constant at different temperatures 303 293 283 T/K 0.088 0.0805 0.0668 Kad (min.-1) 11.626 Ea (K.J.mol-1) Table (4): Freundlich and Langmuir parameters for BG adsorption on Fe-BNC clay Freundlich isotherm Langmuir isotherm T(K) R2 n Kf (mg.g-1) R 2 a (mg/g) KL (L/mg) 0.998 0.999 0.999 0.998 0.7174 0.7233 0.7219 0.7179 0.0962 0.1011 0.1036 0.1050 0.923 0.914 0.962 0.953 3.562 3.994 3.919 4.055 0.1886 0.2288 0.2323 0.2541 283 293 298 303 213 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I2@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (2) 2013 Table (5): Analysis of Langmuir isotherm at 283 K 25 20 15 10 5 Initial dye concentration Co (ppm) 0.1699 0.2096 0.2763 0.3585 0.5256 RL Table (6): Thermodynamic parameters for the adsorption of BG onto Fe-BNC ΔS (J.mol-1.K-1) ΔH (J.mol-1) ΔG (J.mol-1) T(K) 28.786 = = = 5169.7 = = = -2976.7 -3264.5 -3408.5 -3552.4 283 293 298 303 Fig. (1): The chemical structure of birllint green sulfate. 214 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I2@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (2) 2013 Fig. (2):(I) AFM images of clay. (II) AFM images of Fe-BNC clay (a)The 2D, cross section (b) 3D and (c) Pore size distribution diagram 215 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I2@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (2) 2013 Fig. (3): Effect of initial dye concentration on equilibrium adsorption of BG on to (I) bentonite (II) Fe-BNC Fig. (4): Kinetics of BG uptake by Fe-BNC at several initial temperatures Fig. (5): Lagergrens plot for kinetic modeling of the adsorption process of BG on Fe- BNC clay at different temperatures Fig. (6): Arrhenius equation of adsorption of BG on Fe-BNC 0.0092 0.00925 0.0093 0.00935 0.0094 0.00945 0.0095 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 qt (mg.L-1) t (min.) -2.75 -2.7 -2.65 -2.6 -2.55 -2.5 -2.45 -2.4 -2.35 0.0032 0.0033 0.0034 0.0035 0.0036 ln Kad 1/T (K) 283 K 293 K 303 K 283 K 293 K 303 K 216 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I2@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (2) 2013 Fig. (7): Langmuir's isotherm plot for the adsorption of BG on Fe-BNC [(a) 283, (b) 293, (c) 298, (d) 303K] Fig. (8): Plot of Freundlich adsorption isotherms of BG on Fe-BNC [(a) 283, (b) 293, (c) 298, (d) 303K] 0 1 2 3 0 0.1 0.2 0.3 Ce/Qe Ce (mg/L) (b) 0 1 2 3 0 0.1 0.2 0.3 Ce/Qe Ce (mg/L) (d) 0 1 2 3 0 0.1 0.2 0.3 Ce/Qe Ce (mg/L) (c) 0 1 2 3 4 0 0.1 0.2 0.3 Ce/Qe Ce (mg/L) (a) -4 -3 -2 -1 0 -3 -2 -1 0 ln Qe ln Ce (a) -4 -3 -2 -1 0 -3 -2 -1 0 ln Qe ln Ce (b) -4 -3 -2 -1 0 -3 -2 -1 0 ln Qe ln Ce (c) -4 -3 -2 -1 0 -3 -2 -1 0 ln Ce ln Qe (d) 217 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I2@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (2) 2013 Fig. (9): Adsorption isotherm of BG on Fe-BNC at 298 K Fig. (10): Relation of log b against 1/T where T/K 0 0.05 0.1 0.15 0.2 0.25 0 0.1 0.2 0.3 Qe (mg/L) Ce (mg/L) 0.54 0.55 0.56 0.57 0.58 0.59 0.6 0.61 0.62 0.0033 0.00335 0.0034 0.00345 0.0035 0.00355 log b 1/T (K) 218 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I2@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (2) 2013 ازالة الصبغة الخضراء اللمـــاعة من محالیلھا المائیـة بإمتزازھا على سطح الطین المحور دنیـــا عیــــدان محمــــد قســــم الكیمیــــاء / كلیـــة العلـــوم / جامعـــة بغـــداد 2013حزیران 10 ، قبل البحث في : 2013 شباط 21استلم البحث في : الخالصة درس استعمال استخدام طین البنتونایت النانوي كطین محور الزالة الصبغة الخضراء اللماعة من محالیلھا المائیة. واستخدم مجھر القوة الذریة لغرض الحصول على شكل المسام وتوزیعھ ، وتبین ان معدل قطر المسام للطین المحور ھو على سطح الطین المحور الزالة الصبغة من محالیلھا المائیة. وتبین ان . واجریت وجبات من تجارب االمتزاز 346.81 االمتزاز یتبع متساوي درجة الحرارة لكل من لنكمایر وفرندلش، واوجدت قیم الثوابت لكل منھما. وامكن حساب قیم الدوال لیة االمتزاز بأستخدام معادلة الثرمودینامیكیة مثل الطاقة الحرة ، واالنتروبي ، واالنثالبي. واوجد ثابت السرعة لعم لكركرین وتبین أن عملیة االمتزاز تتبع حركیة المرتبة االولى فضالً عن ذلك تم تعیین طاقة التنشیط لعملیة االمتزاز. االمتزاز، الصبغة الخضراء اللماعة، البنتونایت.الكلمات المفتاحیة : 219 | Chemistry