Regeneration of Rhodamine B Loaded Modified Biosorbent by a Self‐Cleaning Eluent: TiO2 Hydrosol

Waste beer yeast was modified by pyromellitic dianhydride to improve its adsorption capacity for rhodamine B (RhB). Results showed that the adsorption capacity of the modified biomass for RhB was 600 mg g^?1, which was about five times than that obtained on the unmodified biomass. Dye loaded modified biomass was regenerated by (1) a common eluent: HNO₃ solution and (2) a self‐cleaning eluent: TiO₂ hydrosol, while the pH of both systems varied from 1 to 4. Desorption experimental results showed that low desorption rates were obtained in both systems after the first desorption cycle. A large volume of HNO₃ solution was needed to obtain high desorption rate, and a concentrated solution of RhB was left, which brought a secondary pollution. As a self‐cleaning eluent, acid TiO₂ hydrosol acted both as eluent and photocatalyst. The desorbed RhB could be photodegraded under sunlight irradiation and the same hydrosol could be used in the next desorption cycle without losing its activity, which could economize large volumes of solvent. The results showed an adsorption capacity of the regenerated biosorbent for RhB of 450 mg g^?1 by using hydrosol with pH 2 as eluent after four desorption/photodegradation cycles.     

Adsorptive Removal of Acid Blue 15: Equilibrium and Kinetic Study

Activated carbons prepared from sunflower seed hull have been used as adsorbents for the removal of acid blue 15 (AB‐15) from aqueous solution. Batch adsorption techniques were performed to evaluate the influences of various experimental parameters, e. g., temperature, adsorbent dosage, pH, initial dye concentration and contact time on the adsorption process. The optimum conditions for AB‐15 removal were found to be pH = 3, adsorbent dosage = 3 g/L and equilibrium time = 4 h at 30°C. The adsorption of AB‐15 onto the adsorbent was found to increase with increasing dosage. It was found from experimental results that the Langmuir isotherm fits the data better than the Freundlich and Temkin isotherms. The maximum adsorption capacity, Q_m (at 30°C) was calculated for SF1, SF2, and SF3 as 75, 125 and 110 mg g^–1 of adsorbent, respectively. It was found that the adsorption follows pseudo‐second order kinetics. The thermodynamic parameters such as ΔG°, ΔH°, and ΔS° were also evaluated. The activated carbons prepared were characterized by FT‐IR, SEM and BET analysis.     

Cercis siliquastrum Tree Leaves as an Efficient Adsorbent for Removal of Ag(I): Response Surface Optimization and Characterization of Biosorption

The Cercis siliquastrum tree leaves are introduced as a low cost biosorbent for removal of Ag(I) from aqueous solution in a batch system. FT‐IR, XRD analysis, and potentiometric titration illustrate that the adsorption took place and the acidic functional group (carboxyl) of the sorbent was involved in the biosorption process. In addition, it was observed that the pH beyond pH_pzc 4.4 is favorable for the removal procedure. The effect of operating variables such as initial pH, temperature, initial metal ion concentration, and sorbent mass on the Ag(I) biosorption was analyzed using response surface methodology (RSM). The proposed quadratic model resulting from the central composite design approach (CCD) fitted very well to the experimental data. The optimum condition obtained with RSM was an initial concentration of Ag(I) of 85 mg L^?1, pH = 6.3 and sorbent mass 0.19 g. The applicability of different kinetic and isotherm models for current biosorption process was evaluated. The isotherm, kinetic, and thermodynamic studies showed the details of sorbate‐sorbent behavior. The competitive effect of alkaline and alkaline earth metal ions during the loading of Ag(I) was also considered.     

Oreganum Stalks as a New Biosorbent to Remove Textile Dyes from Aqueous Solutions

In the present study, Oreganum onites L. stalks in natural and chemically modified with HNO³ and H³PO⁴ used as adsorbent for removal of both acidic and basic dyes from waters. The adsorption was studied as a function of pH and contact time by batch method. All tested biosorbents were characterized by FT‐IR, scanning electron microscopy, and measuring the pH dependence of the zeta potential. The adsorption isotherms were fitted to Langmuir isotherm. The maximum adsorption capacity of dyes was 280.73 mg g^?1 for Basic Red 18, 147.06 mg g^?1 for methylene blue and 112.36 for Acid Red 111, which is comparable to that of other lignocellulosic materials. The modification process was considerably increased the biosorption capacity of lignocellulosic material, resulting in a 56–63% increase in the biosorption capacity of basic dyes and a 125% increase in the biosorption capacity of acidic dye. The present study illustrated that the most effective factors in the adsorption of basic dye were surface charge and acidic groups on lignocellulosic biosorbents, while non‐electrostatic forces as well as electrostatic forces were also effective in the adsorption of acidic dye. In conclusion, Oreganum stalks can be considered as a very prospective adsorbent for the removal of tested basic and acidic dyes.     

Removal of Organic Dyes in Environmental Water onto Magnetic‐Sulfonic Graphene Nanocomposite

A magnetic‐sulfonic graphene nanocomposite (G‐SO₃H/Fe₃O₄) was synthesized and characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and X‐ray diffraction. It was used for removal of three cationic dyes: safranine T (ST), neutral red (NR), victoria blue (VB), and three anionic dyes: methyl orange, brilliant yellow, and alizarin red, from environmental water. The experimental conditions were optimized, including pH, amount of adsorbent, adsorption kinetics, adsorption isotherms, ionic strength, etc. The results show that G‐SO₃H/Fe₃O₄ can adsorb cationic dyes more efficiently and selectively than anionic dyes at pH 6.0. In the first 10 min of adsorption time, more than 93% of the cationic dyes were removed by the sorbent. Adsorption kinetics follow the pseudo‐second‐order kinetic model well. The adsorption isotherm coincided with Langmuir and Freundlich adsorption models. The maximum adsorption capacities of G‐SO₃H/Fe₃O₄ for ST, NR, and VB dyes were 199.3, 216.8, and 200.6 mg g^?1. The adsorbed cationic dyes were eluted by using different pH values of ethanol as the solvent. The established method was simple, sensitive, and rapid, and was suitable for the adsorption of cationic dyes in environmental water.     

Study of the Interaction Mechanism in the Biosorption of Copper(II) Ions onto Posidonia oceanica and Peat

A systematic approach was used to characterize the biosorption of copper(II) onto two biosorbents, Posidonia oceanica and peat, focusing on the interaction mechanisms, the copper(II) sorption–desorption process and the thermal behavior of the biosorbents. Sorption isotherms at pH 4–6 were obtained and the experimental data were fitted to the Langmuir model with a maximum uptake (q_max) at pH 6 of 85.78 and 49.69 mg g^?1, for P. oceanica and peat, respectively. A sequential desorption (SD) with water, Ca(NO₃)₂, and EDTA was applied to copper‐saturated biosorbents. Around 65–70% copper(II) were desorbed with EDTA, indicating that this heavy metal was strongly bound. The reversibility of copper(II) sorption was obtained by desorption with HCl and SD. Fourier transform IR spectroscopy (FTIR) analysis detected the presence of peaks associated with OH groups in aromatic and aliphatic structures, CH, CH₂, and CH₃ in aliphatic structures, COO^? and COOH groups and unsaturated aromatic structures on the surface of both biosorbents, as well as peaks corresponding to Si? O groups on the surface of peat. The results of SEM‐EDX and FTIR analysis of copper‐saturated samples demonstrated that ion exchange was one of the mechanisms involved in copper(II) retention. Thermal analysis of biosorbent samples showed that copper(II) sorption–desorption processes affected the thermal stability of the biosorbents.     

Removal of Cu2+ and Pb2+ Ions Using CMC Based Thermoresponsive Nanocomposite Hydrogel

In this study, carboxymethylcellulose (CMC) based thermoresponsive nanocomposite hydrogel was synthesized for the removal of Cu²⁺ and Pb²⁺ ions from aqueous solutions. To prepare nanocomposite hydrogel, graft copolymerization of N‐isopropyl acrylamide (NIPAm) and acrylic acid (AA) onto CMC was carried out in Na‐montmorillonite (MMT)/water suspension media and ammonium persulfate (APS) used as initiator. The chemical structures of hydrogels were characterized by Fourier transform infrared (FT‐IR) and X‐ray diffraction spectroscopy (XRD). Lower critical solution temperature (LCST), pH responsivity, swelling, and deswelling properties of the hydrogels were also examined. In addition competitive and non‐competitive removal of Cu²⁺ and Pb²⁺ studies were carried out. According to heavy metal sorption studies results, removal capacities of nanocomposite hydrogel for both metal ions were found to be higher than those of pure hydrogel. The analyzed adsorption data showed that the adsorption process of Cu²⁺ and Pb²⁺ could be explained by pseudo‐second order kinetic model. Moreover, according to competitive sorption studies, it is found to be that both hydrogels are more selective to Cu²⁺ ion rather than Pb²⁺.     

Selective Preconcentration of Trace Amounts of Cu(II) With Surface‐Imprinted Multiwalled Carbon Nanotubes

In this study, a new sorbent is synthesized using surface imprinting technique. Cu(II)‐imprinted multiwalled carbon nanotube sorbent (Cu(II)‐IMWCNT) is used as the solid phase in the solid‐phase extraction method. After the preconcentration procedure, Cu(II) ions are determined by high‐resolution continuum source atomic absorption spectrometry. A total of 0.1 mol L^?1 ethylenediaminetetraacetic acid (EDTA) is used to remove Cu(II) ions from the sorbent surface. The optimum experimental conditions for effective preconcentration of Cu(II), parameters such as pH, eluent type and concentration, flow rate, sample volume, sorbent capacity, and selectivity are investigated. The synthesized solid phase is characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The maximum adsorption capacities of Cu(II)‐IMWCNT and non‐imprinted solid phases are 270.3 and 14.3 mg g^?1 at pH 5, respectively. Under optimum experimental conditions for Cu(II) ions, the limit of detection is 0.07 μg L^?1 and preconcentration factor is 40. In addition, it is determined to be reusable without significant decrease in recovery values up to 100 adsorption–desorption cycles. Cu(II)‐IMWCNT have a high stability. To check the accuracy of the developed method, certified reference materials, and water samples are analyzed with satisfactory analytical results.     

Sulfur and Carbon Co‐doped TiO2 Composite Fabricated by Lignosulphonate and Its Suitability for Removal of Cadmium

Highly toxic divalent cadmium causes serious environmental issues. To quickly monitor and/or efficiently remove this potentially toxic metal ion as well as to explore its interfacial chemistry with metal oxides, a sulfur and carbon co‐doped titania (S/C‐TiO₂) composite is synthesized via a facile sol‐gel method with the assistance of sodium lignosulphonate (SLS). The prepared composite displays a well‐crystallized TiO₂ nanostructure comprising the anatase phase. Both S and C, which are derived from the SLS template, are found to enter the TiO₂ lattice. The S/C‐TiO₂ composite exhibits a porous structure with a wide pore size distribution. The newly synthesized composite shows adsorption capability for the potentially toxic metal Cd(II). The adsorption process requires <5 min to reach equilibrium. The measured equilibrium adsorption capacity is 19.42 mg g^?1, which is twice as high as that of bare TiO₂. The removal efficiency is as high as 97%. Moreover, the materials are suitable for contaminated solutions over a wide range of pH values and various initial cadmium concentrations. A mechanism for the enhanced adsorption behavior is also proposed.     

Synthesis and Characterization of Poly(2‐hydroxyethylmethacrylate‐hydroxyapatite) a Novel Composite for the Removal of Lead(II) from Aqueous Solutions

In the present study, a novel adsorbent, poly (2‐hydroxyethylmethacrylate‐hydroxyapatite) [P(HEMA‐Hap)], was prepared and characterized. The synthesis was achieved by means of free‐radical polymerization and a number of structural characterization methods, including FT‐IR, XRD, TGA, SEM, BET‐porosity, and swelling tests. Pb²⁺ adsorption was performed using a series of pH, time, and temperature ranges. The reusability of the composite was also tested. The results obtained indicated that the novel adsorbent is able to bind Pb²⁺ ions with strong chemical affinity. The adsorption results were fitted to the classic Langmuir, Freundlich, and Dubinin–Radushkevich (D–R) sorption models. Thermodynamic parameters obtained demonstrated that the sorption process was spontaneous (ΔG < 0), endothermic (ΔH > 0), as expected. The process was also consistent with the pseudo‐second‐order model, and chemical adsorption was determined to be the rate‐controlling step. It was also shown that the composite could be used for five consecutive adsorption processes.     

Adsorption of Cationic Dyes from Aqueous Solution by Termite Feces,a Non‐Conventional Adsorbent

The adsorption of three cationic dyes (rhodamine B, RB; crystal violet, CV; and malachite green, MG) onto termite feces, a low‐cost adsorbent, was investigated. The adsorbent was characterized by IR spectroscopy, point of zero charge measurement, and the Boehm titration method. The adsorption follows the pseudo‐second‐order kinetic model and the Langmuir–Freundlich isotherm with maximum adsorption capacities of 95.53 mg g^?1 (RB), 75.71 mg g^?1 (CV), and 44.78 mg g^?1 (MG). The study of thermodynamics showed that the adsorption is a spontaneous and endothermic process. This works suggest that termite feces can be used as a new low‐cost adsorbent for cationic dye removal.     

Separation and Preconcentration of Boron with a Glucamine Modified Novel Magnetic Sorbent

A novel, simple method based on magnetic separation was developed for analytical purposes. In this method, N‐methyl‐D‐glucamine (NMDG) modified magnetic microparticles that were synthesized by using the sol‐gel method were used for the selective extraction and preconcentration of boron from aqueous solutions. This method combines the simplicity and selectivity of solvent extraction with the easy separation of magnetic microparticles from a solution with a magnet without any preliminary filtration step. The structure of the prepared γ‐Fe₂O₃‐SiO₂‐NMDG (magnetic sorbent) composites were characterized by using X‐ray diffraction (XRD), Transmission Electron Microscopy (TEM), and Fourier Transform Infrared Spectroscopy (FTIR). The influence of different parameters on the sorbent capacity, such as the sorption/desorption of boron, magnetic sorbent dosage, pH, equilibrium time, type, and amount of stripping solution, were evaluated by using the magnetic sorbent. Any equilibrium pH greater than 6 can be used for sorption. Desorption from the sorbent was carried out by using 1.0 M HCl. The sorption and desorption efficiency of the γ‐Fe₂O₃‐SiO₂‐NMDG was found as 92.5 ± 0.5% and 99.8 ± 6%, respectively.     

Adsorption of Cadmium from Aqueous Solution by Ficus religiosa Leaf Powder and Characterization of Loaded Biosorbent

The present investigation evaluates the adsorption effectiveness of Cd(II) ions on Ficus religiosa leaf powder (FRL). The experimental parameters chosen included time, pH, particle size, temperature, adsorbate, anion, and Pb(II) concentrations. The time data followed pseudo‐second‐order kinetics. Cd(II) adsorption increased from 1.38 to 75.17% with the increase in pH from 2 to 4 and further increase in pH to 5.5 resulted in its marginal increase to 77.52%. Based on regression coefficient values, the isothermic data fitted the various models in the order Langmuir > Redlich–Peterson > Temkin > Freundlich model. The maximum loading capacity of FRL was estimated to be 27.14 mg g^?1. The presence of Cl^?, , or Pb²⁺ exhibited adverse effect on Cd(II) uptake. The thermodynamic parameters of enthalpy (ΔH⁰) and entropy (ΔS⁰) were estimated to be 8.31 kJ mol^?1 and 38.22 J mol^?1 K^?1, respectively. SEM‐EPMA of the loaded FRL showed Cd(II) distribution at specific sites. The XRD patterns of Cd(II) loaded FRL sample showed disappearance of some peaks corresponding to β‐Ca(PO₃)₂; shifting of peaks and decrease in %RI corresponding to γ‐CaSO₄ phase. Positive shift of IR bands for the Cd(II) loaded sample was observed.     

A Study: Removal of Cu(II), Cd(II), and Pb(II) Ions from Real Industrial Water and Contaminated Water Using Activated Sludge Biomass

This study aims to remove of Cu²⁺, Cd²⁺, and Pb²⁺ ions from solution and to investigate the adsorption isotherms, adsorption kinetics, and ion‐exchange affinities of these metals using waste activated sludge (AS) biomass. The adsorptions of the metals on biomass were optimal at an acidic pH value of 6.0 based on its monolayer capacities. Maximum monolayer capacities of AS biomass (q_max) were calculated as 0.478, 0.358, and 0.280 mmol g^?1 for Cu²⁺, Cd²⁺, and Pb²⁺, respectively, and the adsorption equilibrium time was found as 60 min for each metal. The adsorbed amount of metal rose with increasing of initial metal ion concentration. The equilibrium adsorption capacity of AS for initial 0.25 mmol L^?1 metal concentration was determined as 0.200, 0.167, and 0.155 mmol g^?1 for Cu²⁺, Cd²⁺, and Pb²⁺ ions, respectively. These relevant values were determined as 0.420, 0.305, and 0.282 mmol g^?1 for Cu²⁺, Cd²⁺, and Pb²⁺ ions, respectively, when initial metal concentration was 0.50 mmol L^?1. In the multi‐metal sorption system, the adsorption capacity of AS biomass was observed in the order of Cu²⁺ > Cd²⁺ > Pb²⁺. In the presence of 100 mmol L^?1 H⁺ ion, the order of ion‐exchange affinity with H⁺ was found as Cu²⁺ > Cd²⁺ > Pb²⁺. The adsorption kinetics were also found to be well described by the pseudo‐second‐order and intraparticle diffusion models. Two different rate constants were obtained as k_i1 and k_i2 and k_i1 (first stage) was found to be higher than k_i2 (second stage).     

The Seashell Wastes as Biosorbent for Reactive Dye Removal from Textile Effluents

This study investigates structural and adsorption properties of the powdered waste shells of Rapana gastropod and their use as a new cheap adsorbent to remove reactive dye Brilliant Red HE‐3B from aqueous solutions under batch conditions. For the powder shells characterization, solubility tests in acidic solutions and X‐ray diffraction (XRD), scanning electron microscopy (SEM), energy‐dispersive X‐ray spectroscopy (EDX), Fourier transform IR spectroscopy (FT‐IR) and thermogravimetric analyses were performed. The results revealed that the adsorbent surface is heterogeneous consisting mainly from calcium carbonate layers (either calcite or aragonite) and a small amount of organic macromolecules (proteins and polysaccharides). The dye adsorptive potential of gastropod shells powder was evaluated as function of initial solution pH (1–5), adsorbent dose (6–40 g L^?1), dye concentration (50–300 mg L^?1), temperature (5–60°C), and contact time (0–24 h). It was observed that the maximum values of dye percentage removal were obtained at the initial pH of solution 1.2, shells dose of 40 g L^?1, dye initial concentration of 50–50 mg L^?1 and higher temperatures; the equilibrium time decreases with increasing of dye concentration. It is proved that the waste seashell powder can be used as low cost bioinorganic adsorbent for dyes removal from textile wastewaters.     

Removal of Copper,Nickel, and Zinc Ions from Electroplating Rinse Water

Removal of copper, nickel, and zinc ions from synthetic electroplating rinse water was investigated using cationic exchange resin (Ceralite IR 120). Batch ion exchange studies were carried out to optimize the various experimental parameters (such as contact time, pH, and dosage). Influence of co‐existing cations, chelating agent EDTA on the removal of metal ion of interest was also studied. Sorption isotherm data obtained at different experimental conditions were fitted with Langmuir, Freundlich, Redlich–Peterson, and Toth models. A maximum adsorption capacity of 164 mg g^?1 for Cu(II), 109 mg g^?1 for Ni(II), and 105 mg g^?1 for Zn(II) was observed at optimum experimental conditions according to Langmuir model. The kinetic data for metal ions adsorption process follows pseudo second‐order. Presence of EDTA and co‐ions markedly alters the metal ion removal. Continuous column ion exchange experiments were also conducted. The breakeven point of the column was obtained after recovering effectively several liters of rinse water. The treated rinse water could be recycled in rinsing operations. The Thomas and Adams–Bohart models were applied to column studies and the constants were evaluated. Desorption of the adsorbed metal ions from the resin column was studied by conducting a model experiments with Cu(II) ions loaded ion exchange resin column using sulfuric acid as eluant. A novel lead oxide coated Ti substrate dimensionally stable (DSA) anode was prepared for recovery of copper ions as metal foil from regenerated liquor by electro winning at different current densities (50–300 A cm^?2).     

Degradation of Rhodamine B and Safranin‐T by MoO3:CeO2 Nanofibers and Air Using a Continuous Mode

One‐dimensional MoO₃ nanofibers doped with Ce (MoO₃ : CeO₂) are synthesized by a method combining a sol‐gel process and an electrospinning technique. The resulting MoO₃ : CeO₂ is characterized by X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), Fourier transform infrared (FT‐IR) spectroscopy, and scanning electron microscopy (SEM). The catalytic degradation of rhodamine B and safranin‐T with MoO₃ : CeO₂ nanofiber catalyst is investigated in a continuous flowing mode using air (O₂) as an oxidant. The results show that rhodamine B and safranin‐T are degraded effectively and the removal efficiencies are 98.3%, and 98.5%, respectively. In addition, the organic dyes are totally mineralized to simple inorganic species such as CO₃^–, Cl^– and NO₃^–.     

Preparation,Characterization of a Novel Chelating Resin Functionalized with o‐Hydroxybenzamide and Its Application for Preconcentration of Trace Metal Ions

A stable extractor of metal ions was synthesized through azo linking of o‐hydroxybenzamide (HBAM) with Amberlite XAD‐4 (AXAD‐4) and was characterized by elemental analyses, IR spectral, and thermal studies. Its water regain value and hydrogen ion capacity were found to be 12.93 and 7.68 mmol g^?1, respectively. The optimum pH range (with the half‐loading time [min], t_1/2) for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) ions were 2.0–4.0 (5.5), 2.0–4.0 (7.0), 2.0–4.0 (8.0), 4.0–6.0 (9.0), 4.0–6.0 (12.0), and 2.0–4.0 (15.0), respectively. Comparison of breakthrough and overall capacities of the metals ascertains the high degree of column utilization (>70%). The overall sorption capacities for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) ions were found to be 0.29, 0.22, 0.20, 0.16, 0.13, and 0.11 mmol g^?1 with the corresponding preconcentration factor of 400, 380, 380, 360, 320, and 320, respectively. The limit of preconcentration was in the range of 5.0–6.3 ng mL^?1. The detection limit for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) were found to be 0.39, 0.49, 0.42, 0.59, 0.71, and 1.10 ng mL^?1, respectively. The AXAD‐4‐HBAM has been successfully applied for the analysis of natural water, multivitamin formulation, infant milk substitute, hydrogenated oil, urine, and fish.     

Adsorption Performance and Mechanism in Binding of Azo Dye by Raw Bentonite

The adsorption behavior of methyl orange (MO) from aqueous solution onto raw bentonite (RB) sample was investigated as a function of parameters such as pH, inorganic anion, contact time, and temperature. The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms. Langmuir adsorption capacity was found to be 34.34 mg/g at pH 4.0. The pseudo‐first‐order, pseudo‐second‐order kinetic, and the intra‐particle diffusion models were used to describe the kinetic data. The values of the energy (E_a), enthalpy (ΔH^≠), and entropy of activation (ΔS^≠) were calculated as 38.62 kJ/mol, 36.04 kJ/mol, and ?150.05 J/mol K, respectively, at pH 4.0.     

Modeling the Removal of Reactive Red 120 on Pistachio Husk

In this study, the adsorption of reactive red 120 (RR 120) on pistachio husk, and the modeling of the adsorption was investigated. Characterization of the pistachio husk was confirmed by Fourier transform infrared spectroscopy. The pH_zpc of pistachio husk was found to be pH 8.5. Increasing the initial pH value decreased (p < 0.01) the amount of dye adsorbed. However, increasing the initial dye concentration from 50 to 900 mg/L at pH 1 increased (p < 0.01) the equilibrium dye uptake from 20.83 to 182.10 mg/g. Results indicated that this adsorbent had great potential for the removal of RR 120 dye. The logistic model was found to be the most suitable of the kinetic and equilibrium models tested to describe the adsorption of the dye. The parameters determined from the logistic model were well correlated with the initial dye concentration, and were seen to increase with the increasing initial dye concentration, but this was not observed from pseudo‐second order kinetics.