Phenol removal from aqueous solution by adsorption and ion exchange mechanisms onto polymeric resins

The removal of phenol from aqueous solution was evaluated by using a nonfunctionalized hyper-cross-linked polymer Macronet MN200 and two ion exchange resins, Dowex XZ (strong anion exchange resin) and AuRIX 100 (weak anion exchange). Equilibrium experimental data were fitted to the Langmuir and Freundlich isotherms at different pHs. The Langmuir model describes successfully the phenol removal onto the three resins. The extent of the phenol adsorption was affected by the pH of the solution; thus, the nonfunctionalized resin reported the maximum loading adsorption under acidic conditions, where the molecular phenol form predominates. In contrast both ion exchange resins reported the maximum removal under alkaline conditions where the phenolate may be removed by a combined effect of both adsorption and ion exchange mechanisms. A theoretical model proposed in the literature was used to fit the experimental data and a double contribution was observed from the parameters obtained by the model. Kinetic experiments under different initial phenol concentrations and under the best pH conditions observed in the equilibrium experiments were performed. Two different models were used to define the controlling mechanism of the overall adsorption process: the homogeneous particle diffusion model and the shell progressive model fit the kinetic experimental data and determined the resin phase mechanism as the rate-limiting diffusion for the phenol removal. Resins charged after the kinetic experiments were further eluted by different methods. Desorption of nonfunctionalized resin was achieved by using the solution (50% v/v) of methanol/water with a recovery close to 90%. In the case of the ion exchange resins the desorption process was performed at different pHs and considering the effect of the competitive ion Cl⁻. The desorption processes were controlled by the ion exchange mechanism for Dowex XZ and AuRIX 100 resins; thus, no significant effect for the addition of Cl⁻ under acidic conditions was observed, while under alkaline conditions the total recovery increased, specially for Dowex XZ resin.     

717型阴离子交换树脂吸附水溶性芳香族有机污染物研究

研究了717型阴离子交换树脂对苯酚、苯甲酸和十二烷基苯磺酸钠(SDBS)等水溶性芳香族污染物吸附过程的基本化学问题.研究结果表明:717型树脂对苯酚、苯甲酸和SDBS的吸附过程均符合Lagergren二级吸附动力学方程,吸附速率均随着温度的升高而加快,吸附表观活化能Ea分别为13.2kJ/mol、59.5kJ/mol和48.1kJ/mol,吸附过程△H0和△S0均为正值,△G0均为负值,吸附能够自发进行;吸附等温模型符合Langmuir等温式;318K时,717型树脂在pH=9.1对SDBS的饱和吸附容量为360mg/g;在pH=10.2,对苯酚和苯甲酸的饱和吸附容量分别为194mg/g和286mg/g.用浓度均为0.5mol/L,体积比为5∶1的NaCl-NaOH混合溶液可快速洗脱树脂上吸附的污染物,洗脱率达98％以上.该树脂对水溶性芳香族污染物吸附容量大,易于再生和循环利用,可用于环境水体中水溶性芳香族有机污染物的吸附治理.     

Synthesis, characterization and metal adsorption properties of the new ion exchanger polymer 3-n-propyl(4-methylpyridinium) silsesquioxane chloride

The preparation and anion exchange properties of 3-n-propyl(4-methylpyridinium) silsesquioxane chloride polymer are described. This new polymer was prepared by the sol-gel processing method and is designated as SiPic+Cl-. It is insoluble in water and showed an anion exchange capacity of 1.46x10(-3) mol g-1. The adsorption isotherms of ZnCl2, CdCl2 and HgCl2 were determined from aqueous solutions and the adsorption equilibria simulations fit the model of fixed bidentate centers with the absence of lateral interactions and energetic heterogeneity between them. The metal ions diffuse into the solid solution interface and are dominantly present as MCl2-(4) species for Zn(II), MCl(2-)4 and MCl-3 species for Cd(II) and MCl-3 species for Hg(II).     

Surface-charging behavior of Zn-Cr layered double hydroxide

A Zn-Cr layered double hydroxide (LDH) having the formula Zn(2)Cr(OH)(6)Cl(0.7)(CO(3))(0.15)2.1H(2)O was synthesized and characterized by powder X-ray diffraction, infrared spectroscopy, acid-base potentiometric titration, mass titration, electrophoretic mobility, and modeling of the electrical double layer. Adsorption of alizarin was also performed in order to show some particular features of the HDL. Net hydroxyl adsorption, which increases with increasing pH and decreasing supporting electrolyte concentration, takes place above pH 5. The electrophoretic mobility of the particles was always positive and it decreased when the pH was higher than 9. An isoelectric point of 12 could be estimated by extrapolating the data. The modified MUSIC model was used to estimate deprotonation constants of surface groups and different adsorption models were compared. Good fit of hydroxyl adsorption and electrophoresis could be achieved by considering both OH(-)/Cl(-) exchange at structural sites and proton desorption from surface hydroxyl groups. The modeling, in agreement with alizarin adsorption, indicates that most of the structural positive charge of the LDH is screened at the surface by exchanged anions and negatively charged surface groups. It also suggests that only structural charge sites initially neutralized by chloride ions are active for anion exchange. The remaining sites are blocked by carbonate and do not participate in the exchange.     

pH-mediated dual-cloud point extraction as a preconcentration and clean-up technique for capillary electrophoresis determination of phenol and m-nitrophenol

pH-mediated dual-cloud point extraction (dCPE) technique for capillary electrophoresis (CE) determination of phenol and m-nitrophenol is proposed in this paper. This technique for the preconcentration and clean-up of the two analytes includes two steps through simple pH-mediation. The analytes are transferred into surfactant-rich phase in the first step (under acidic condition) with Triton X-114 as the extractant because the two analytes become hydrophobic in acidic solution. They were back-extracted into alkaline aqueous phase in the second cloud point step. Because the concentration of Triton X-114 in the final aqueous solution after dCPE is only around critical micelle concentration, its adsorption on the inner wall of capillary and its possible influence on electrophoretic separation are eliminated. Baseline separation of phenol and m-nitrophenol is realized in a 60 cm x 75 microm i.d. capillary at 18 kV using 50 mM boric acid solution (pH 9.5). The preconcentration factors are 24.0 for phenol and 22.5 for m-nitrophenol. The detection limits of phenol and m-nitrophenol are 2.0 x 10(-6) mol L(-1) and 2.5 x 10(-6) mol L(-1), respectively. The proposed method was successfully applied to the determination of two analytes in spiked natural water samples.     

单一阴离子交换柱同时分离有机酸和无机阴阳离子

研究了用乙二胺四乙酸（ＥＤＴＡ）作淋洗液时，性质迥异的有机酸、无机阴离子和碱土金属离子（Ｃａ＾２＋、Ｍｇ＾２＋）在同一阴离子交换柱上的同时分离以及保留机理，结果表明，在离子交换机理之外，非离子交换机理对有机酸及钙镁的ＥＤＴＡ络阴郭的保留行为起一定的辅助作用，９种有机酸和无机阴阳离子在１０ｍｉｎ内得到了较好的分离。各离子的电导检测灵敏度在１０＾－９至１０＾－１１ｍｏｌ，能满足环境和食吕分析的要求。     

酸性溶液中β-苯胺基苯丙酮在铁上的吸脱附行为

用极化曲线法研究了０．５ｍｏｌ·Ｌ－１硫酸溶液中β－苯胺基苯丙酮（ＰＡＰ）在铁－溶液界面的吸脱附行为及Ｃｌ－,Ｉ－的影响．结果表明,ＰＡＰ的吸附遵循Ｆｌｏｒｙ－Ｈｕｇｇｎｓ等温式;在较正的极化电位区出现阳极脱附现象．讨论了两种粒子联合吸附方式与浓度的关系,提出可根据吸附粒子的脱附电位与其浓度关系来推断联合吸附的理论模型     

酸性媒染紫-示波计时电位法测定天然水和饮用水中铝

报道酸性媒染紫（ＳＶＲＳ）－示波计时电位法测定天然水及饮用水中铝。在０．８５ｍｏｌ／Ｌ　ＮＨ３·Ｈ２Ｏ－ＮＨ４Ｃｌ－５×１０－５ｍｏｌ／Ｌ ＳＶＢＳ（ｐＨ８．８）底液中,Ａｌ－ＳＶＲＳ络合物在－１．０５Ｖ电位处产生灵敏切口,切口深度与铝浓度成正比,可用于定量分析。线性范围为１×１０－７～６×１０－６ｍｏｌ／Ｌ． ＲＳＤ为５．５％ （ｎ＝１０,２×１０－７ｍｏｌ／Ｌ）,检测限为５×１０－８ｍｏｌ／Ｌ。本法特点为：在碱性条件下,无需加热,无需通氮除氧,无需预富集,大大减少了分析时间。仪器简单,方法灵敏准确,特别适用于天然水和饮料中Ａｌ的分析。对实际水样进行了分析,与ＩＣＰ／ＡＥＳ法所测结果基本一致。     

阴离子树脂分离富集光度法测定尾矿中微量钼

研究了717型阴离子交换树脂柱分离-富集钼的条件,建立了分光光度法测定尾矿中微量钼的方法。在pH 7.5的条件下,钼以MoO42-形式被树脂定量吸附后,采用体积比1:1的2 mol/L HNO3和0.5 mol/L NH4NO3混合溶液洗脱,消除了绝大部分共存离子的干扰。结果表明,采用硫氰酸盐光度法,体系的最大吸收波长为460 nm,线性范围为0～120.0μg/L,检出限为1.3μg/L。对实际样品测定结果与ICP-AES法相符,6次测定值的RSD=3.3%,加标回收率在96.2%～105.7%之间。     

Adsorptive voltammetry of 2-(5-bromo-2-pyridyl)azo-5-[N-n-propyl-N-(3-sulfopropyl)amino]phenol on a carbon paste electrode in the presence of organic cations and polycation.

The adsorption of ion-association complexes on a carbon paste electrode (CPE) was investigated by cyclic voltammetry using an electroactive hydrophobic anion probe. The redox reactions of 2-(5-bromo-2-pyridyl)azo-5-[N-n-propyl-N-(3-sulfopropyl)amino]phenol (5-Br-PAPS), the analytical probe, were irreversible. The reduction of the azo group and the oxidation of the phenol were observed at -0.1 V and 0.9 V vs. SCE, respectively, in a 0.1 mol L(-1) H(2)SO(4) solution. The peak currents for the redox reaction increased with the concentration of the cationic surfactant and the accumulation time. The increase in the ratio of the peak current to the concentration of cationic surfactants was proportional to the hydrophobicity. The peak current for 5-Br-PAPS also increased when a polycation, polyhexamethylene biguanide hydrochloride, was added and was strongly dependent on the ionic strength and pH, in contrast to cationic surfactants.     

Adsorption Behavior of Metal Ions by Amidoxime Chelating Resins

In this work, the acrylonitrile (AN) – divinylbenzene (DVB) –methylacrylate (MA) resin was synthesized via suspension polymerization in the presence of toluene as diluent, and benzoylperoxide (BPO) as initiator. The effect of MA, toluene and alkaline treatment on the exchange capacity of the resin were investigated. The results showed that the anion exchange capacity decreased with an increase in the amount of MA, while alkaline treatment had no significant effect. Also, the cation exchange capacity increased with an increase in the amount of hydrophilic agent and reached a maximum point. The sorption equilibrium was achieved relatively fast within 40 mins, and the resin exhibited affinity towards lead (II), copper (II) and in particular uranium (VI). The adsorption of uranium was directly depended up on the pH value. Furthermore, the macroreticular chelating resin, containing amidoxime group had higher adsorption of uranium (VI) in comparison to other metal ions studied. Finally, the alkaline treatment enhanced the potential for much faster adsorption characteristics and the highly porous chelating resin provided a more favorable pore structure for the rapid rate of diffusion of metal ions.     

Synthesis of novel chitosan resin derivatized with serine moiety for the column collection/concentration of uranium and the determination of uranium by ICP-MS

A chitosan resin derivatized with serine moiety (serine-type chitosan) was newly developed by using the cross-linked chitosan as a base material. The adsorption behavior of trace amounts of metal ions on the serine-type chitosan resin was systematically examined by packing it in a mini-column, passing a metal solution through it and measuring metal ions in the effluent by ICP-MS. The resin could adsorb a number of metal cations at pH from neutral to alkaline region, and several oxoanionic metals at acidic pH region by an anion exchange mechanism. Uranium and Cu could be adsorbed selectively at pH from acidic to alkaline region by a chelating mechanism; U could be adsorbed quantitatively even at pH 3–4. Uranium adsorbed on the resin was easily eluted with 1 M nitric acid: the preconcentration (5-, 10-, 50- and 100-fold) of U was possible. The column treatment method was used prior to the ICP-MS measurement of U in natural river, sea and tap waters; R.S.D. were 2.63, 1.13 and 1.37%, respectively. Uranium in tap water could be determined by 10-fold preconcentration: analytical result was 1.46±0.02 ppt. The resin also was applied to the recovery of U in sea water: the recovery tests for artificial and natural sea water were 97.1 and 93.0%, respectively.     

Zeta potential of anoxygenic phototrophic bacteria and Ca adsorption at the cell surface: possible implications for cell protection from CaCO3 precipitation in alkaline solutions

Electrophoretic mobility measurements and surface adsorption of Ca on living, inactivated, and heat-killed haloalkaliphilic Rhodovulum steppense, A-20s, and halophilic Rhodovulum sp., S-17-65 anoxygenic phototrophic bacteria (APB) cell surfaces were performed to determine the degree to which these bacteria metabolically control their surface potential equilibria. Zeta potential of both species was measured as a function of pH and ionic strength, calcium and bicarbonate concentrations. For both live APB in 0.1M NaCl, the zeta potential is close to zero at pH from 2.5 to 3 and decreases to -30 to -40 mV at pH of 5-8. In alkaline solutions, there is an unusual increase of zeta potential with a maximum value of -10 to -20 mV at a pH of 9-10.5. This increase of zeta potential in alkaline solutions is reduced by the presence of NaHCO(3) (up to 10 mM) and only slightly affected by the addition of equivalent amount of Ca. At the same time, for inactivated (exposure to NaN(3), a metabolic inhibitor) and heat-killed bacteria cells, the zeta potential was found to be stable (-30 to -60 mV, depending upon the ionic strength) between pH 5 and 11 without any increase in alkaline solutions. Adsorption of Ca ions on A-20s cells surface was more significant than that on S-17-65 cells and started at more acidic pHs, consistent with zeta potential measurements in the presence of 0.001-0.01 mol/L CaCl(2). Overall, these results indicate that APB can metabolically control their surface potential to electrostatically attract nutrients at alkaline pH, while rejecting/avoiding Ca ions to prevent CaCO(3) precipitation in the vicinity of cell surface and thus, cell incrustation.     

Platinum(II) and palladium(II) complexes of bisphosphine ligands bearing o-N,N-dimethylanilinyl substituents: a hint of catalytic olefin hydration

Platinum(II) and palladium(II) complexes of the potentially hexadentate P,N-donor ligand family Ar2P-X-PAr2 (X = (CH2)2 [dmape], cyclic-C5H8 [dmapcp]; Ar = o-N,N-dimethylanilinyl) are described. In CH2Cl2, the dmape complexes exist as equilibrium mixtures of MCl2(P,P'-dmape) and [MCl(P,P',N-dmape)]Cl isomers (M = Pd, Pt), governed by deltaH(o) = -19 +/- 4 kJ mol(-1) and deltaS(o) = -100 +/- 30 J mol(-1) K(-1) for M = Pt, and deltaH(o) = -11 +/- 7 kJ mol(-1) and deltaS(o) = -60 +/- 20 J mol(-1) K(-1) for M = Pd. The water-soluble dmapcp complexes exist solely in the [MCl(P,P',N-dmapcp)]Cl form, but the free and coordinated anilinyl rings in these complexes are in slow diastereoselective exchange. X-ray crystal structures for MCl2(P,P'-dmape) (M = Pd, Pt), and the [PdCl(P,P',N-dmape)]+ and [PtCl(P,P',N-dmapcp)]+ cations, are presented. Some of the complexes show marginal activity in water for the catalyzed hydration of maleic to malic acid, giving about 6-7% conversion in 24 h at 100 degrees C and substrate:catalyst loadings of 100:1. Attempts to synthesize a PdCl(P,P',N-dmapm)+ species led instead to isolation of [Pd(mu-Cl)(P,P'-dmapm)]2[PF6]2 (dmapm = Ar2PCH2Ar2).     

Adsorption of fluoride, phosphate, and arsenate ions on a new type of ion exchange fiber

A new type of ion exchange fiber for the removal of fluoride, phosphate, and arsenate ions has been developed. A batch adsorption technique for investigating adsorption kinetic and equilibrium parameters and determining pH adsorption edges is applied. It is shown that the adsorption properties of the ion exchange fiber for fluoride, phosphate, and arsenate ions depend on the pH value and anion concentration. The adsorption of arsenate on the sorbent reaches a maximum of 97.9% in the pH value range of 3.5 to 7.0. The adsorption percentage of phosphate is more than 99% in the pH range of 3.0 to 5.5. The adsorption of fluoride on the ion exchange fiber is found to be 90.4% at pH 3.0. The Freundlich model can describe the adsorption equilibrium data of fluoride, arsenate, and phosphate anions. The sorption of the three anions on the ion exchange fiber is a rapid process, and the adsorption kinetic data can be simulated very well by the pseudo-second-order rate equation. The column performance is carried out to assess the applicability of the ion exchange fiber for the removal of fluoride, phosphate, and arsenate ions from synthetic wastewaters with satisfactory removal efficiency. The desorption experiment shows that fluoride ion sorbed by the fiber column can be quantitatively desorbed with 5 mL of 0.50 mol/L NaOH at elution rate of 1 mL/min, and 30 mL of NaOH is necessary for the quantitative recovery of phosphate and arsenate ions.     

锗(IV)-茜素红-VOSO4-EDTA体系极谱吸附催化波研究

报导了在酸性缓冲液中锗(IV)-茜素红-VOSO4-EDTA体系的配合吸附平行催化波的研究.锗的最低检出量为1.0x10^-^9mol.dm^-^3.研究了催化波的机理.     

Electrochemical determination of activation energies for methanol oxidation on polycrystalline platinum in acidic and alkaline electrolytes

The oxidation pathways of methanol (MeOH) have been the subject of intense research due to its possible application as a liquid fuel in polyelectrolyte membrane (PEM) fuel cells. The design of improved catalysts for MeOH oxidation requires a deep understanding of these complex oxidation pathways. This paper will provide a discussion of the literature concerning the extensive research carried out in acidic and alkaline electrolytes. It will highlight techniques that have proven useful in the determination of product ratios, analysis of surface poisoning, anion adsorption, and oxide formation processes, in addition to the effects of temperature on the MeOH oxidation pathways at bulk polycrystalline platinum (Pt(poly)) electrodes. This discussion will provide a framework with which to begin the analysis of activation energy (E(a)) values. This kinetic parameter may prove useful in characterizing the rate-limiting step of the MeOH oxidation at an electrode surface. This paper will present a procedure for the determination of E(a) values for MeOH oxidation at a Pt(poly) electrode in acidic and alkaline media. Values from 24-76 kJ mol(-1) in acidic media and from 36-86 kJ mol(-1) in alkaline media were calculated and found to be a function of applied potential and direction of the potential sweep in a voltammetric experiment. Factors that influence the magnitude of the calculated E(a) include surface poisoning from MeOH oxidation intermediates, anion adsorption from the electrolyte, pH effects, and oxide formation processes. These factors are all potential, and temperature, dependent and must clearly be addressed when citing E(a) values in the literature. Comparison of E(a) values must be between systems of comparable electrochemical environment and at the same potential. E(a) values obtained on bulk Pt(poly), compared with other catalysts, may give insight into the superiority of other Pt-based catalysts for MeOH oxidation and lead to the development of new catalysts which lower the E(a) barrier at a given potential, thus driving MeOH oxidation to completion.     

Synthesis of a large amino-phenolic cage. Synthesis, crystal structures, and acid-base and coordination behavior toward cations and anions

The synthesis and characterization of the new polyaza-phenolic-macrobicycle 32-hydroxy-1,4,7,10,13,16,19,22-octaazatricyclo-[11.11.7.1(26,30)]-diatriconta-26,28,Delta(30,32)-triene (L) are reported. L incorporates a 2,6-dimethyl-phenolic unit bridging two opposite amine functions of the [24]aneN(8) polyazamacrocyclic base to obtain a large cage. The basicity and binding properties of L toward Cu(II), Zn(II), and Cl(-) were determined by means of potentiometric measurements in aqueous solution (298.1 +/- 0.1 K, I = 0.15 mol dm(-3)). L can add up to six acidic protons, yielding the H(5)L(5+) species or the H(6)L(6+) species, depending on the ionic medium used. The molecular topology of L permits the formation of a highly positive three-dimensional cavity in the polyprotonated species that is able to host the chloride anion. This was detected both using potentiometric data, log K = 41.33 for the reaction L + 6H(+) + Cl(-) = H(6)LCl(5+), and in (35)Cl NMR experiments that showed interactions also with the H(5)L(5+) and H(4)L(4+) species. The anion is probably hosted inside the three-dimensional cavity of L, and stabilized by H-bonding interactions with the ammonium groups, as depicted in the crystal structure of the H(6)L(6+) cation reported. L forms mono- and dinuclear complexes with all the metal ions investigated; the dinuclear species are the only existing species with an L:M(II) molar ratio of 1:2 at pH higher than 6. The phenolate oxygen atom coordinates the two metal ions in a bridged disposition, drawing them inside the macrobicyclic cavity. The two metals were found to be quite isolated by the medium, and were coordinated by all the amine groups of L, as shown by the crystal structure of the dinuclear [Zn(2)H(-1)L](3+) species. This species can bind guests such as hydroxide and phosphate anions. Studies of anion binding in aqueous solution using pyrochatecol violet as the sensing guest revealed that the [Zn(2)H(-1)L](3+) species is able to bind one phosphate at physiological pH.     

Adsorption of Ni(II) on clays

The present work investigates the adsorptive interactions of Ni(II) ions with kaolinite, montmorillonite, and their poly(oxo zirconium) and tetrabutylammonium derivatives in aqueous medium. Batch adsorption studies were carried out with various Ni(II) concentrations, amount of clay adsorbents, pH, agitation time and temperature. The adsorption is strongly dependent on pH of the medium with enhanced adsorption as the pH turns from acidic to alkaline side till precipitation sets in. The process was very fast initially and maximum adsorption was observed within 180 min of agitation. The kinetics of the interactions, tested with pseudo first order Lagergren equation, second order kinetics, Elovich equation, liquid film diffusion model and intra-particle diffusion mechanism, showed better agreement with second order kinetics (k2 = 1.3 x 10(-2) to 5.3 x 10(-2) g/(mg min)). The adsorption data gave good fits with Langmuir and Freundlich isotherms and yielded Langmuir monolayer capacity of 2.75 to 21.14 mg/g and Freundlich adsorption capacity of 0.70 to 3.40 mg(1-1/n) l(1/n)/g for the clay adsorbents. The adsorption process was exothermic with Delta H in the range of -24.0 to -45.1 kJ/mol accompanied by decrease in entropy (DeltaS: -118.2 to -160.5 J/(mol K)) and Gibbs energy (Delta G: -34.6 to -49.5 kJ/mol). The results have shown that montmorillonite has the largest adsorption capacity followed by ZrO-montmorillonite, TBA-montmorillonite, kaolinite, ZrO-kaolinite and TBA-kaolinite. Introduction of ZrO- and TBA- groups into the clays reduced their adsorption capacity by blocking the available adsorption sites.     

Eu（Ⅲ）在Na基高庙子膨润土上的吸附作用：实验和构模研究

采用连续电位滴定法研究了不同离子强度下Na基高庙子膨润土（Na-BNT）的表面酸、碱性质;用批式法研究了温度为22±2℃时,离子强度从0．001到0．5mol／L、Eu（Ⅲ）浓度从10曲到10^-4mol／L、pH从3到10．5的广泛实验条件下,Eu（Ⅲ）在Na．BNT上的吸附作用;通过考虑发生在层间位点（1ayersites）和边位点（edgesites）上的表面反应,对比了双层静电模型与非静电模型对宏观实验数据的描述,结果表明,双层静电模型可以描述Na基高庙子膨润土的表面酸碱性质,但对除I=0．1mol／L以外其他离子强度下Eu（Ⅲ）的吸附难以作出合理描述;非静电模型可以定量描述广泛实验条件下Eu（Ⅲ）在Na基高庙子膨润土上的吸附作用,但对pH〉8时Na基高庙子膨润土的表面酸碱性质的描述不够理想;研究结果为解释和预N＋3价镧系和锕系元素在高庙子膨润土上的吸附作用提供了模型参考．