National Journal of Chemistry,2008, Volume 31, 400-414 المجلد الواحد والثالثون2008-المجلة القطرية للكيمياء Removal of Neutral Red Dye from Aqueous Solution by Adsorption onto Rice Bran Rafah Muhammed Thiyab Department of Chemistry, College of Science, Al-Kufa University. (NJC) (Received on 9 /10 /2007) (Accepted for publication 19/6 /2008) Abstract This work is concerned with the study of locally available rice bran (Oryza sativa L) as an adsorbent for the removal of neutral red dye from solution as low-cost adsorbent in wastewater treatment for the removal of color which comes from textile dyes or other industries. Adsorption process were occurred at different acidity of solution (pH=3, 7, 11). The experiments were repeated at different temperatures (20, 30, 40, 50°C) in order to measure the thermodynamic parameters (ΔHº, ΔGº, ΔSº). Rice bran showed good adsorption capacity against neutral red dye and can extract the dye from aqueous solution. Adsorption isotherms of neutral red dye on bran from aqueous solution obeyed Freundlich adsorption isotherm indicating the heterogeneity of rice bran surface. The thermodynamic parameter values are calculated as follow: ΔHº=-44.92 KJ.mol-1, ΔGº=-5.06 KJ.mol-1, ΔSº=-136.05 J.mol-1.ºK-1 In conclusion, adsorption of on rice bran is exothermic process with relatively high thermodynamic parameters values. The adsorption enhanced by decreasing temperature and with increasing acidity of the medium. It can be concluded from the results of the present study that the process of adsorption of neutral red dye on rice bran may be used effectively to remove the dye from aqueous medium. 400 المجلة القطرية للكيمياء 2008-المجلد الواحد والثالثون National Journal of Chemistry,2008, Volume 31, 400-414 الخالصة يعنى هذا البحث بدراسة مادة متوفرة محلياً (نخالة الرز) كمادة مازة ألزالة صبغة ( (N-Rمن المحلول كمادة مازة رخيصة (أوقليلة الكلفة) في معالجة مياه الفضالت الصناعية من معامل األنسجة والصناعات األخرى إلزالة اللون. أجريت عملية األمتزاز عند درجات حامضية مختلفة ) (pH=3, 7, 11كما وأعيدت التجربة عند أربعة درجات ح اررية مختلفة ) (20, 30, 40, 50°Cلحساب الدوال الثرموديناميكية (.)∆Sº, ∆Gº, ∆Hº أظهرت نخالة الرز سعة أمتزاز جيدة لصبغة N.R.كما ونستطيع أستخالصها من المحلول المائي . درست أيزو ثرمات األمتزاز ووجدت أنطباقية لمعادلة فرندلش عليها مشيرةالى عدم تجانس سطح نخالة الرز. تم حساب القيم الثرموديناميكية وكاألتي : ΔHº=-44.92 KJ mol-1, ΔGº=-5.06 KJ mol-1, ΔSº=-136.05 J mol-1 ºK-1 وبالنتيجة االمتزاز على نخالةالرز باعث للح اررة وذلك من قيم الدوال الثرموديناميكية العالية نسبيا. أفضل امتزاز ظهر بنقصان درجه الح اررة مع زيادة حامضية الوسط . ويمكن إن نستنتج من نتائج الدراسة الحالية بان عمليه امتزاز صبغه األحمر المتعادل على نخالةالرز قد تستعمل عمليا الزاله الصبغة من الوسط المائي. مفاتيح الكلمات :نخالة الرز-األحمر المتعادل – االمتزاز process of adsorption; the concentration Introduction of adsorbate (substance being adsorbed), ;adsorbent surface adsorb substances from aqueous medium temperature, onto their surface, however only some solubility, few solid materials have the selective adsorbent and adsorbate molecules and adsorption strength, both of were tested of the ionic area Any solid has some tendency to pH, chemical state adsorbate to capacity the kinetic effect ( 3, 4, 5). molecules. The adsorbate may be atoms, Different adsorbents ions or molecules (adsorbate) of organic )(6, 7, 8 for their ability to remove and extract (1, different dyes from aqueous solutions Many factors can influence the 401 compound, color, odor, moisture etc.. )2 . المجلد الواحد والثالثون2008-المجلة القطرية للكيمياء National Journal of Chemistry,2008, Volume 31, 400-414 (10, 1/40 that of activated carbon, which , and agriculture products (16, would lower the cost of wastewater which used widely as adsorbents in treatment significantly. Additionally, the the adsorption processes for different use of rice bran is significant from the substances from solution including metal aspect of effective utilization of waste ions (18, 19, 20), and organic pollutants (21). matter (26). including activated charcoal 11, 12, 13, 14, 15) 17) (9) , clays Some active surface materials Rice bran has a good adsorptive have important applications in medicine activity against different substances arises including different pesticides from an from their high adsorption capability as physical antidotes in the aqueous solution treatment of acute poisoning by toxic 29) substances and drug overdosage and as a drug carrier (24) vary in (22, 23) dichloromethane, . Dietary fibre is composition (27, 28, , metal ions , several organic compounds, such as chloroform, tetrachloride, carbon trichloroethylene, tetrachloroethylene, and benzene (30). mainly composed of plant cell walls which (26) and Neutral red used in (31, 32) the properties according cell type and plant measurement of cytotoxicity species. In addition to polysaccharides, apoptosis measurement the walls of some plant cell types contain photosynthesis inhibitor in different light the hydrophobic polymers lignin or dependent species (34). Neutral red stains suberin that may produce surface activity both normal and cancer mitotic cells, but (25) . One of these important dietary fibers uptake by living mitotic cancer cells is is rice bran from rice (Oryza sativa L.). distinctly higher than in normal cells (35). (33) It is a by-product of making polished rice from brown rice. Therefore, rice bran is very inexpensive, costing 1/50– Cl - + N(CH3)2 N CH 3 N H NH3 Neutral Red: 3-amino-7(dimethylamino)-2-methyl-hydrochloride. 402 , cell , and National Journal of Chemistry,2008, Volume 31, 400-414 Rice bran, among in vitro the adsorb environmental المجلد الواحد والثالثون2008-المجلة القطرية للكيمياء anothers, This work is concerned with the hydrophobic, study of locally available rice bran as an mutagen 1,8- adsorbent for the removal of neutral red dinitropyrene and other mutagens. Direct dye from solution as low-cost adsorbent mechanisms of protection of cancer by in wastewater treatment for the removal fibers of color which comes from textile dyes include the adsorption of carcinogens onto undegraded dietary or other industries. fibres which pass out of the intestinal Experimental tract in the faeces (25, 36) . A- Adsorption process In one research, dietary fibers have the Commercial ability to nonspecific adsorption of T4 rice bran (Oryza sativa L.) was obtained from locally (37) . Adsorption of the vital dye, neutral markets. It was cleaned and dried at red was previously studied on the matrix 50˚C for two hours and kept in an of the calcium-binding "vesicles" from the green alga airtight container. A volume of 10 (38) . milliliters The term adsorption isotherm of different (2, 4, 6, 8, 10, 12, 14, and 16mg/L) was of adsorption (Qe) or (X/M) with the concentration eight concentrations of neutral red solutions refers to the relation between the extent equilibrium of shaken with 0.05g of dried rice bran the adsorbent at a certain temperature in a adsorbate in solution (Ce) at constant thermostated shaker bath at shaking temperature. (X) is the amount of dye speed 60cycle/minute for 30 minutes adsorbed in milligrams by (M) grams of which is measured experimentally as a the adsorbent (23). time needed for reaching the equilibrium The process of adsorption from state. After the equilibrium time is solution is more complicated than the elapsed, the mixtures were centrifuged at corresponding process of gas adsorption a speed of 3000Xg for 10 minutes. on solid surface. The solvent effect and Acidity of the solutions were adjusted the complicated interaction between using few drops of 0.1N HCl or 0.1N solvent molecules and dye molecules to NaOH solutions. Absorbencies were be adsorbed have to be taken into measured at the maximum wave length account. (λmax) 403 of neutral red solutions المجلد الواحد والثالثون2008-المجلة القطرية للكيمياء National Journal of Chemistry,2008, Volume 31, 400-414 depending on the pHs used in the adsorbate molecules on the surface while experiment. The maxima used were the λmax=539 nm for pH=7, λmax=543 nm (equation) consider heterogeneity of the for pH=3, λmax=428 nm for pH=11 surface and the formation of more than using one layer is probable. The linear form of UV-Visible spectrophotometer (Apple®) and then converted into Freundlich adsorption Freundlich absolute concentration readings through isotherm is: 1 log Ce n -- (2) log Qe log k the calibration curve. The experiments isotherm were repeated at different temperatures Where k and n are Freundlich (20, 30, 40, 50°C) in order to measure constants characteristics of the system, the thermodynamic parameters (ΔHº, including the adsorption capacity and the ΔGº, ΔSº). adsorption intensity, respectively (4, 23). B-Adsorption Isotherms Calculations: C-Adsorption Thermodynamics: Two main theories have been adopted to order to obtain a adsorption thermodynamical state of the adsorption Langmuir process, the adsorption experiments were adsorption isotherms which represented repeated at different temperatures (20, by the linear equation: 30, isotherms. describe In The first, Ce 1 Ce Qe ab a ….(1) 40, 50°C) to measure the thermodynamic parameters (ΔHº, ΔGº, ΔSº). The equilibrium constant (K) for the adsorption process at each Where (a) represents a practical temperature is calculated from division limiting adsorption capacity when the of the quantity of dye adsorbed on the surface bentonite surface on the quantity of dye is fully covered with a monolayer of adsorbate. The constant b still present is the equilibrium adsorption constant K Qe * 0.05 Ce * 0.01 -----(3) which related to the affinity of the Where binding sites (24). in (0.05g) solution:- represent the The applicability of these equations on weight of the clay that has been used and the adsorbent-adsorbate (solute) system (0.01) represents the volume of the dye assume the formation of one layer of solution used in the adsorption process. 404 National Journal of Chemistry,2008, Volume 31, 400-414 المجلد الواحد والثالثون2008-المجلة القطرية للكيمياء The change in free energy (∆Gº) adsorbents for removing dyes from could be determined form the equation:- aqueous solutions in different industries G RT ln K -----(4) (39, 40, 41) Where R is the gas constant (8.314 Adsorption isotherms of neutral red dye J.mole-1.ºK-1) and T is the absolute on bran from aqueous solution obeyed temperature. Freundlich adsorption isotherm (Figure . The heat of adsorption (∆Hº) may be (1)). This fact obtained from the obtained from the vant Hoff's equation:- applicability of the linear form of H cons tan t RT ---(5) Freundlich Where K is the equilibrium (2)). Table (1) showed the Freundlich constant when Ce approaches to zero at constants that indicated the adsorption certain temperature. It obtained from capacity (k) plotting (Ln K) of each concentration adsorption against corresponding Ce. Plotting (In temperatures. In general, the results of K) versus (1/T) should produce a straight Table (1) indicated the decrease in line with a slope =(-∆Hº/R) from which adsorption capacities and intensities as the enthalpy (∆Hº) of the adsorption temperature process is obtained. isotherms of different dyes on different ln K from Gibbs indicating as adsorbents for different dyes in order to obtain cheep, available, (n) non the at intensity of four increases. heterogeneity surfaces (4, 23). used high different Adsorption (29, 30, 31, 42) were also obeyed Freundlich isotherm equation: Results and Discussion substances and surfaces including rice bran G H TS ---- (6) Many with correlation coefficient values (Figure The change in entropy (∆Sº( was calculated equation toxic 405 of these المجلد الواحد والثالثون2008-المجلة القطرية للكيمياء National Journal of Chemistry,2008, Volume 31, 400-414 Table (1): Freundlich constants (k and n) of adsorption of methylene blue on bentonite clay surface at three temperatures. Where k refers to the adsorption capacity and n refers to the adsorption intensity. T logk K 1/n n 293 0.313 2.058 1.142 0.876 313 -0.262 0.548 1.349 0.741 323 -0.365 0.432 1.398 0.716 333 -0.615 0.243 1.868 0.535 3.5 3 Qe (mg/g) 2.5 2 1.5 Tem p=20C Tem p=30C 1 Tem p=40 Tem p=50C 0.5 0 0 0.5 1 1.5 2 2.5 3 3.5 4 Ce (mg/L) Figure (1): Adsorption isotherms of neutral red on rice bran at different temperatures (20, 30, 40, and 50°C). 406 المجلد الواحد والثالثون2008-المجلة القطرية للكيمياء LogQe National Journal of Chemistry,2008, Volume 31, 400-414 Temp=20C temp=30C Temp=40C Temp=50C 0.7 y = 1.1419x + 0.3134 R2 = 0.9961 0.5 0.3 0.1 -0.7 LogCe -0.5 -0.3 -0.1 0.1 -0.1 0.3 0.5 -0.3 y = 1.3488x - 0.2616 R2 = 0.9616 -0.5 y = 1.3975x - 0.3645 R2 = 0.9756 y = 1.8677x - 0.6146 R2 = 0.9602 -0.7 Figure (2): Linear form of Freundlich equation of adsorption of neutral red on rice bran at different temperatures (20, 30, 40, and 50°C). The study of the adsorption process of removal by rice bran was examined dye on rice bran requires taking the using nature of the surface and the chemical removal efficiencies varied from 22.2% composition into to 98.8%. The variation in the removal consideration. Rice bran contains lectin, efficiency of different pesticides was chitin of rice bran (43) 22 different pesticides. The , and myo-inositol derivatives studied, and the pesticides with high (44) . It has shown that different types of lipophilicity were found to be easily plant cell walls adsorbed a range of removed by rice bran (26). carcinogens heterocyclic Rice bran was the most effective of the aromatic amines which are like the adsorbents among different adsorbent chemical structure of neutral red dye. including charcoal and different natural Cell walls that contained lignin or and modified clays in removal of suberin organochlorine including adsorbed hydrophobic carcinogens particularly well. (25) environment (45). . The 407 compounds from المجلد الواحد والثالثون2008-المجلة القطرية للكيمياء National Journal of Chemistry,2008, Volume 31, 400-414 (46) approaches zero, could be obtained and for the adsorption isotherm shapes, the used for vant Hoff’s equation plotted adsorption isotherm of neutral red dye (Figure (4)). molecules on the rice bran surface is of The thermodynamical parameters values S2 type indicating the heterogeneity of are: the surface and the presence of different (ΔHº=-44.92 types KJ.mol-1, ΔSº=-136.05 J.mol-1.ºK-1). According to the Giles interpretation of forces between the dye ΔGº=-5.06 KJ.mol-1, molecules and the surface active sites. Free energy change and entropy values Rice among were measured at 298ºK. These values different lees materials is effective in are high and indicated a spontaneous adsorbing organochlorine compounds. adsorption process as seen in the There was a high correlation between the adsorption of other substances removal adsorbing supposed such as values that, moderate and nonspecific or interaction bran among different efficiency organochlorine chloroform, in compounds dichloromethane, from the occurs (40) . It is thermodynamic between dye benzene by lees materials and the molecules and the active sites of rice number of spherosomes from different bran surface. lees materials(47). The removal of these Exothermic process for the adsorption of organochlorine compounds and benzene neutral red on rice bran is consistent with by rice bran was conformed to the other adsorption processes (48) and differs Freundlich type and attributed to the from other which was endothermic uptake by intracellular particles called processes (49). spherosomes (30). In one study; adsorption of industrially Figure (3) showed the natural logarithm important dyes including methylene blue of equilibrium constants (LnK) against from equilibrium charcoal has been investigated. The concentration (Ce) of aqueous media for the activated adsorption of neutral red on rice bran calculated surface. The intercepts of the straight adsorption and the free energy indicated lines give the natural logarithm of that adsorption of dyes is favored at low equilibrium constants (LnK) from which temperatures. These results are differ the equilibrium constants, when Ce from the result of our research indicating 408 values on heat of National Journal of Chemistry,2008, Volume 31, 400-414 المجلد الواحد والثالثون2008-المجلة القطرية للكيمياء the ability of bentonite as a better interactions between the surfaces and the adsorbent when the adsorption occurs at dyes, which include hydrogen bonding, high temperature as it happen really in electrostatic, different industries (50). interactions. The results of this work can be compared with other papers related to and hydrophobic The mechanism of adsorption the was best described with a model that adsorption of different dyes on different included adsorbents in order to treat the waste complexation of ion forms of the water from different industries and compounds, solution speciation, the laboratories (51, 52). presence of other competitor ions in rice The adsorption of dichloromethane and bran surface, and the exchangeable pore chloroform by rice bran was observed waters over the range of pH 1-11. Therefore, adsorption amounts may explained by rice bran is applicable for treatment of dependency of adsorption on the relative wastewater over a wide pH range. energies Dichloromethane adsorbate-solvent, was successfully cation may exchange, also of affect surface (53) . The adsorbent-adsorbate, and adsorbate- removed from water samples with an adsorbate interactions (54). These findings average removal efficiency of 70% after may be applied for the adsorption of dye 60 minutes when rice bran was added to on rice bran surface in our study. water samples containing from 0.006 to Conclusion: 100 mg/L dichloromethane (30). Adsorption of on rice bran is exothermic Adsorption of neutral dye on rice process with relatively high bran showed a decrease in basic solution thermodynamic parameters values. The and mildly good adsorption capacity in adsorption neutral and acidic solution (Figures (5 & temperature and with increasing acidity 6)). This may be due to the complex of the medium. It can be concluded from interaction among solvent, solute, and the results of the present study that the surface in response to the changing in process of adsorption of neutral red dye acidity. The adsorption results can be on rice bran may be used effectively to explained by considering the textural remove the dye from aqueous medium. properties of the rice bran and the 409 enhanced by decreasing المجلد الواحد والثالثون2008-المجلة القطرية للكيمياء National Journal of Chemistry,2008, Volume 31, 400-414 2.5 Temp=20C Temp=30C Temp=40C Temp=50C y = 0.2528x + 2.0772 R2 = 0.9556 2 Ln K 1.5 1 y = 0.212x + 0.7863 R2 = 0.5845 y = 0.2638x + 0.4636 R2 = 0.9158 y = 0.4548x - 0.1958 R2 = 0.8607 0.5 0 0 0.5 1 1.5 2 2.5 3 3.5 4 Ce (mg/L) Figure (3 ): Natural logarithm of equilibrium constants (LnK) against equilibrium concentration (Ce) of adsorption of neutral red on bentonite clay surface. The intercept represent the (LnK) when Ce approaches to zero at certain temperature. y = 5.4032x - 16.382 R2 = 0.991 1.8 Ln K 1.3 0.8 0.3 2.9 -0.2 3 3.1 3.2 3.3 3.4 (1/T)*1000 °K Figure (4): Correlation of equilibrium constants ,when Ce approaches to zero of adsorption of neutral red on rice bran at (20, 30, 40, and 50°C) according to the vant Hoff's equation. 410 3.5 National Journal of Chemistry,2008, Volume 31, 400-414 المجلد الواحد والثالثون2008-المجلة القطرية للكيمياء 3.5 3 pH=3 Qe (mg/g) 2.5 pH=7 pH=11 2 1.5 1 0.5 0 0 2 4 6 8 10 12 14 Ce (mg/L) Figure (5): Adsorption isotherms of neutral red on rice bran at different pHs (3, 7, 11) at 20°C. pH=3 pH=7 0.6 pH=11 y = 1.1419x + 0.3134 R2 = 0.9961 y = 0.8305x - 0.0801 R2 = 0.9122 0.4 0.2 0 -0.5 LogCe -0.3 -0.1 0.1 0.3 0.5 0.7 0.9 -0.2 -0.4 LogQe -0.7 -0.6 y = 0.5898x - 0.6983 R2 = 0.9784 -0.8 Figure (6): Linear form of Freundlich equation of adsorption of neutral red on rice bran on three different pHs at 20°C. 411 1.1 National Journal of Chemistry,2008, Volume 31, 400-414 9. 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