Kinetics and Mechanism of Iridium（Ⅲ）-Catalyzed Oxidation of Ethanol Amine by Cerium（ Ⅳ ） in Sulfuric Acid Media

In this study, the kinetics and mechanism of the iridium(Ⅲ)-catalyzed oxidation of ethanol amine(EAN) by cerium(Ⅳ) in a sulfuric acid medium was investigated using titrimetric technique of redox in a temperature range of 298—313 K. It was found that the reaction is of first order with respect to Ce(Ⅳ) and Ir(Ⅲ), and a positive fractional order with respect to EAN. It was also found that the pseudo-first-order([EAN][Ce(Ⅳ)]) rate constant kobs decreases with the increase of [H ] and [HSO-4]. Under the protection of nitrogen gas, the reaction system can initiate the polymerization of acrylonitrile, indicating the generation of free radicals. On the basis of the experimental results, a suitable mechanism was proposed. From the dependence of kobs on the concentration of hydrogen sulfate, Ce(SO4)2 was found to be the kinetically active species. The rate constants of the rate-determining step together with the activation parameters were evaluated.     

铬(III)离子催化铈(IV)离子氧化四氢糠醇的反应动力学及机理

在酸性介质中用氧化还原滴定法研究了铈(IV)离子在铬(III)离子催化作用下,于25～40℃区间氧化四氢糠醇的反应动力学.结果表明反应对铈(IV)和四氢糠醇均为一级.准一级速率常数kobs随催化剂[Cr(III)]增加而增大,亦随[H+]增加而增大,而随[HSO-4]增加而减小.在氮气保护下,反应不能引发丙烯酰胺聚合,说明在反应中没有自由基产生.提出了催化剂、底物和氧化剂间生成双核加合物的反应机理.通过kobs与HSO-4的依赖关系,并结合Ce(IV)在溶液中的平衡,找到了本反应体系的动力学活性物种是Ce(SO4)2.还计算出一些速率常数及相应的活化参数.     

铬(III)离子催化铈(IV)离子氧化四氢糠醇的反应动力学及机理

在酸性介质中用氧化还原滴定法研究了铈(IV)离子在铬(III)离子催化作用下, 于25～40 ℃区间氧化四氢糠醇的反应动力学. 结果表明反应对铈(IV)和四氢糠醇均为一级. 准一级速率常数k_obs随催化剂[Cr(III)]增加而增大, 亦随[H^＋]增加而增大, 而随增加而减小. 在氮气保护下, 反应不能引发丙烯酰胺聚合, 说明在反应中没有自由基产生. 提出了催化剂、底物和氧化剂间生成双核加合物的反应机理. 通过k_obs与的依赖关系, 并结合Ce(IV)在溶液中的平衡, 找到了本反应体系的动力学活性物种是Ce(SO₄)₂. 还计算出一些速率常数及相应的活化参数.     

Kinetics and Mechanism of the Cerium(IV) Oxidation of Arnold's Base and the Protonation and Hydroxylation of Michler's Hydrol Blue

In aqueous H₂SO₄, Ce(IV) ion oxidizes rapidly Arnold's base((p-Me₂NC₆H₄)₂CH₂, Ar₂CH₂) to the protonated species of Michler's hydrol((p-Me₂NC₆H₄)₂CHOH, Ar₂CHOH) and Michler's hydrol blue((p-Me₂NC₆H₄)₂CH⁺, Ar₂CH⁺). With Ar₂CH₂ in excess, the rate law of the Ce(IV)-Ar₂CH₂ reaction in 0.100 M H₂SO₄ is expressed -d[Ce(IV)]/dt = k_app[Ar₂CH₂]₀[Ce(IV)] with k_app = 199 ± 8M^?1s^?1 at25°C. When the consumption of Ce(IV) ion is nearly complete, the characteristic blue color of Ar₂CH⁺ ion starts to appear; later it fades relatively slowly. The electron transfer of this reaction takes place on the nitrogen atom rather than on the methylene carbon atom. The dissociation of the binuclear complex [Ce(III)ArCHAr-Ce(III)] is responsible for the appearance of the Ar₂CH⁺ dye whereas the protonation reaction causes the dye to fade. In highly acidic solution, the rate law of the protonation reaction of Michler's hydrol blue is -d[Ar₂CH⁺]/dt = k_obs[Ar₂CH⁺] where K_obs = ((ac + 1)[H*] + bc[H⁺]²)/(a + b[H⁺]) (in HClO₄) and k_obs= ((ac + 1 + e[HSO₄^?])[H⁺] + bc[H⁺]² + d[HSO₄^?] + q[HSO₄^?]²/[H⁺])/(a + b[H⁺] + f[HSO₄^?] + g[HSO₄^?]/[H⁺]) (in H₂SO₄), and at 25°C and μ = 0.1 M, a = 0.0870 M s, b = 0.655 s, c = 0.202 M^?1s^?1, d = 0.110, e = 0.0070 M^?1, f = 0.156 s, g = 0.156 s, and q = 0.124. In highly basic solution, the rate law of the hydroxylation reaction of Michler's hydrol blue is -d[Ar₂CH⁺]/dt = k_OH[OH^?]₀[Ar₂CH⁺] with k_OH = 174 ± 1 M^?1s^?1 at 25°C and μ = 0.1 M. The protonation reaction of Michler's hydrol blue takes place predominantly via hydrolysis whereas its hydroxylation occurs predominantly via the path of direct OH attack.     

二羟基二过碘酸合镍(IV)氧化氨基丙酸的动力学

在碱性介质中研究了二羟基二过碘酸合镍（Ⅳ）配离子（DDN）氧化α－氨基丙酸的动力学，结果表明，反应对DDN为一级，对α－氨基丙酸为正分数级，准一级速率常数，k_(obs)，随［OH~－］增加而增加，随［IO~-_4］增加而减小，无盐效应也未检出自由基1/k_(obs)对［IO~-_4］有直线关系，表明二羟基一过碘酸合镍（Ⅳ）（DMN）是氧化剂的活性物种，据此很出了一个包括DDN与DMN存在前期平衡和内层一步双电子转移的反应机理．导出的速率方程园满地解释了全部实验现象，并且计算出速控步聚的速率常数，前期平衡常数和活化参数．     

Studies on the Preparation and Properties of Some Phenolic Derivatives of Tricyclopentadienyl Cerium (IV) and Bisindenyl Cerium (IV)

Reactions of tricyclopentadienyl cerium (IV) chloride (I) and bisindenyl cerium (TV) dichloride (II) with mono-, di-, and trihydroxy phenols have been studied and some phenoxide derivatives of (I) and (II) have been isolated. Infrared spectra and some physical characteristics of all these compounds are Reported.     

硫酸溶液中胶束催化Ce(IV)氧化D-甘露糖

Kinetics of D-mannose oxidation by cerium (IV) was studied in a sulfuric acid medium at 40℃ both in absence and presence of ionic micelles. In both cases, the rate of the reaction was first-order in D-mannose and in cerium(Ⅳ), which decreased with increasing [H2SO4]. This suggested that the redox reaction followed the same mechanism. The reaction proceeded through formation of an intermediate complex, which was proved by kinetic method. The complex underwent slow unimolecular decomposition to a free radical that reacted with cerium (Ⅳ) to afford the product. The catalytic role of cationic cetyltrimethylammonium bromide (CTAB) micelles was best explained by the Menger-Portnoy model. The study of the effect of CTAB also indicated that a negatively charged species was reactive form of cerium (Ⅳ). From the kinetic data, micelle-cerium (Ⅳ) binding and rate constants in micellar medium were evaluated.The anionic micelle of sodium dodecyl sulfate plays no catalytic role. The oxidation has the rate expression --d[Ce(Ⅳ)]= k1Kcl[D-mannose] [Ce(Ⅳ)]dt Different activation parameters for micelle catalyzed and uncatalyzed paths were also calculated and discussed.     

Micelle Catalyzed Oxidation of D-Mannose by Cerium (IV) in Sulfuric Acid

Kinetics of D-mannose oxidation by cerium (IV) was studied in a sulfuric acid medium at 40°C both in absence and presence of ionic micelles. In both cases, the rate of the reaction was first-order in D-mannose and cerium (IV), which decreased with increasing [H₂SO₄]. This suggested that the redox reaction followed the same mechanism. The reaction proceeded through formation of an intermediate complex, which was proved by kinetic method. The complex underwent slow unimolecular decomposition to a free radical that reacted with cerium (IV) to afford the product. The catalytic role of cationic cetyltrimethylammonium bromide (CTAB) micelles was best explained by the Menger-Portnoy model. The study of the effect of CTAB also indicated that a negatively charged species was the reactive form of cerium (IV). From the kinetic data, micelle-cerium (IV) binding and rate constants in micellar medium were evaluated. The anionic micelle of sodium dodecyl sulfate plays no catalytic role. The oxidation has the rate expression: -d[Ce(IV)]=k1Kc1[D-mannose][Ce(IV)]dt Different activation parameters for micelle catalyzed and uncatalyzed paths were also calculated and discussed.     

Kinetics and Mechanism of the Oxidation of Some Thioacids by Hexamethylenetetramine-Bromine

Oxidation of thioacids by hexamethylenetetramine-bromine proceeds through an intermediate complex in the pre-equilibrium and its subsequent decomposition in the slow step.     

Kinetics and Mechanism of the Oxidation of 1,10-Phenanthroline by Diperiodatonickelate(IV)in Aqueous Alkaline Medium

 The title reaction was investigated in aqueous alkaline medium. A first order dependence on both [diperiodatonickelate(IV)] and [OH⁻] and an apparent fractional order in [1,10-Phenanthroline] was obtained. Addition of the reaction product has no effect on the reaction. The effects of dielectric constant, ionic strength, and temperature on the rate of the reaction were studied. A mechanism based on the experimental results is proposed, and the constants involved in the mechanism were evaluated. A good agreement between the observed and calculated rate constants at varying experimental conditions was obtained.     

Kinetics and Mechanism of the Oxidation of 1,10-Phenanthroline by Diperiodatonickelate(IV)in Aqueous Alkaline Medium

Summary.  The title reaction was investigated in aqueous alkaline medium. A first order dependence on both [diperiodatonickelate(IV)] and [OH⁻] and an apparent fractional order in [1,10-Phenanthroline] was obtained. Addition of the reaction product has no effect on the reaction. The effects of dielectric constant, ionic strength, and temperature on the rate of the reaction were studied. A mechanism based on the experimental results is proposed, and the constants involved in the mechanism were evaluated. A good agreement between the observed and calculated rate constants at varying experimental conditions was obtained. Received May 26, 2000. Accepted (revised) July 27, 2000     

Kinetics and Mechanism of Oxidation of Ethylene Glycol Monoethylether by Diperiodatonickelate（IV） in Alkaline Medium

The kinetics of oxidation of ethylene glycol monoethylether (EGE) by diperiodatonickelate(IV) ion (DPN) was studied by spectrophotometry in alkaline medium. The reaction rate showed first order dependence on Ni(IV) and positive fractional order with respect to EGE. The pseudo-first order rate conslants, kobs increased with the increase of [OH^-] and decreased with the increase of [IO4^- ]. Added salts had little effect on the rate and no free radical was detected. Based on these,the mechanism including the equilibrium between DPN and EGE was proposed. Furthermore, the activation parameters of the reaction were calculated.     

Kinetics and Mechanism of Oxidation of Adipic Acid by Ce(IV) Ion in Acidic Medium

Kinetic study of oxidation of adipic acid by Ce(IV) ion in aqueous solution of sulphuric acid shows that the reaction follows first order kinetics in both Ce(IV) and adipic acid and the over all reaction order ascertained is two. The specific rate constant increases with an increase in the concentration of adipic acid. Effects of hydrogen ion concentration, bisulphate ion and temperature have been studied in detail. Various kinetic parameters have been computed. The experimental findings are consistent with the mechanism involving rapid resersible formation of an activated complex between Ce(IV) and adipic acid followed by a rate determining step involving C-C bond fission.     

Kinetics of Central Ion Electroreduction in Cerium (IV)-Decatungstate

A general characteristics is given to the kinetics of electroreduction of cerium-decatugstate anions on mercury, polycrystalline gold, and the pyrolytic-graphite basis plane in acetate buffer solutions (pH 3.5-6.0). Based on the analysis of UV absorption spectra, the ratio of two reactant forms differing in the protonation degree in solutions under study is estimated. At a negatively charged mercury electrode, the reduction of the Ce(IV) central ion is shown to proceed as an outer-sphere process with classical manifestations of the psi-prime effect (polarization curves reveal a current minimum which deepens with supporting electrolyte dilution and an increase in the reactant negative charge). On the positively charged surface, the current is observed to increase with an increase in the supporting electrolyte concentration, which is interpreted in terms of the strong adsorption of the reactant and its coadsorption with cations. The gold electrode demonstrates pronounced effects of strong chemisorption. Adsorption complications observed on pyrolytic graphite are shown to become strongther for surfaces with more pronounced nonideal behavior. For low concentrations of atomar steps (apparently, for low coverages of pyrolytic-graphite surface with the adsorbed reactant), the quasireversible electron transfer with the rate increasing with increasing pH is observed.     

碱性介质中分光光度法研究二羟基二（过碘酸）合银（III）配离子氧化一些二元醇的反应动力学及机理

The kinetics of oxidation of ethylene glycol and 1,3-butylene glycol by dihydroxydiperiodatoargentate（Ⅲ） in alkaline medium have been studied by spectrophotometry in the range of 298.2-318.2 K. It is shown that the reaction was first order with respect to each reductant and Ag（Ⅲ）, and kobs increased with an increase of [OH^-]. A plausible mechanism of reaction involving a pre-equilibrium of adduct formation between complex and reductants was proposed, which could be applied to explain all experimental phenomena, and the activation parameters of the ratedetermining step have been also calculated.     

铱(III)离子催化铈(IV)离子氧化四氢糠醇的动力学及机理

在酸性介质中用氧化还原滴定法研究了铈(IV)离子在痕量铱(III)离子催化作用下，于298~313 K区间氧化四氢糠醇(THFA)的反应动力学. 结果表明，反应对铈(IV)离子为一级，对铱(III)离子也为一级，对四氢糠醇的表观反应级数为正分数. 准一级速率常数kobs随[H+]增加而增大，而随[HSO₄－]增加而减小. 在氮气保护下，反应能引发丙烯腈聚合，说明在反应中有自由基产生. 通过kobs与[HSO₄－]的依赖关系，找到本反应体系的动力学活性物种是Ce(SO₄)₂，并计算出平衡常数，速控步骤的速率常数及相应的活化参数.     

铱（III）离子催化铈（IV）离子氧化异丁醇的反应动力学及机理

在酸性介质中用氧化还原滴定法研究了铈（IV）离子在痕量铱（III）离子催化作用下,于25～40 ℃区间氧化异丁醇（BA）的反应动力学.结果表明反应对铈（IV）离子为一级,对异丁醇的表观反应级数为正分数.准一级速率常数kobs随[H＋]及催化剂[Ir(Ⅲ)]增加而增大,随[HSO4-]增加而减小.在氮气保护下,反应不能引发丙烯酰胺聚合,说明在反应中没有自由基产生.提出了催化剂、底物和氧化剂间生成双核加合物的反应机理,通过kobs与HSO4-的依赖关系,找到本反应体系的动力学活性物种是Ce(SO4)2＋,并计算出平衡常数、速控步骤的速率常数及相应的活化参数.     

Mechanistic Study of Oxidation of Palladium(II) by Cerium(IV) in Aqueous Acid

The kinetics of oxidation of Pd^II by Ce^IV have been studied spectrophotometrically in HClO₄ media at 40 °C. The reaction is first order each in [Ce^IV] and [Pd^II] at constant [H⁺]. Increasing [H⁺] accelerates the reaction rate with fractional order in [H⁺]. The initially added products, palladium(IV) and cerium(III) do not have any significant effect on the reaction rate. At constant acidity, increasing the added chloride concentration enhances the rate of reaction. H₃Ce(SO₄)₄⁻ and PdCl₄²⁻ are the active species of oxidant and reductant respectively. The possible mechanisms are proposed and the reaction constants involved have been determined.     

Liquid-Phase Oxidation of Some Aromatic Aldehydes,Hydrocarbons, and Alcohols by Cerium(IV) Catalyzed by Iridium(III) in Acidic Medium

Addition of traces of iridium(III) chloride with cerium(IV) sulfate (catalyst–substrate ratio (1:2994 to 1:10,000) in traditional water-bath heating resulted in the oxidation of p-chlorobenzaldehyde, p-nitrobenzaldehyde, benzyl alcohol, p-methoxy benzyl alcohol, p-xylene, and p-nitrotoluene dissolved in acetic acid to give 77%, 90%, 21.7%, 88.6%, 86.2%, and 18% yields of the products, respectively, while catechol and resorcinol polymerized. Oxidation of aldehydes and alcohols resulted as usual in the corresponding acids and aldehydes, respectively, while p-xylene and p-nitrotoluene gave p-tolualdehyde and p-nitrobenzoic acid. Conditions were obtained for getting the highest yields under the experimental conditions.