二(N,N-二乙基二硫代氨基甲酸)烷基黄原酸合钴(Ⅲ)与二丙胺和二丁胺反应的动力学

本文采用分光光度法研究了在甲醇介质中(N,N-二乙基二硫代氨基甲酸)烷基黄原酸合钴(Ⅲ)与二丙胺,二正丁胺在298.2K～313.2K(R=Me,Et,n-Pr)的反应动力学及机理.结果表明对配合物是准一级反应,对二正丁胺是分数级.反应速率随着基团R的增加而减小,随着温度的增加而增加,随着溶剂中水含量的增大而增加.提出了一种含有前期平衡的反应机理.据此导出了一个能够解释实验事实的速率方程,求得了速控步骤的速率常数,并给出了相应的活化参数.     

二(烷基黄原酸)合铂(Ⅱ)与哌啶在苯介质中连串取代反应的动力学及机理

研究了二(境基黄原致)合铂(Ⅱ)[Pt(S₂COR)₂(R=Me,Et,n-Pr,n-Bu,Am)]与哌啶连串取代反应动力学,提出了包括前期平衡的反应机理,据此导出的速率方程圈满地解释了全部实验事实.计算了前期平衡常数和速控步骤的速率常数,并对加成物的结构作了合理推断,计算了各活化参数和两个反应系的等动力学温度β₁=283±7K和β₂=263±25K.     

二(N,N-二乙基二硫代氨基甲酸)烷基黄原酸合钴(Ⅲ)与二丙胺和二丁胺反应的动力学

本文采用分光光度法研究了在甲醇介质中二(N,N-二乙基二硫代氨基甲酸)烷基黄原酸合钴(Ⅲ)与二丙胺,二正丁胺在298.2K～313.2K(R=Me,Et,n-Pr) 的反应动力学及机理.结果表明对配合物是准一级反应,对二正丁胺是分数级. 反应速率随着基团R的增加而减小,随着温度的增加而增加,随着溶剂中水含量的增大而增加.提出了一种含有前期平衡的反应机理.据此导出了一个能够解释实验事实的速率方程,求得了速控步骤的速率常数,并给出了相应的活化参数     

二过碘酸合铜(III)氧化乙醇胺的动力学及机理

近年来，三价铜的过碘酸配合物作为氧化剂在有机物的定量测定中得到广泛的应用问．Movius风和Murthy门分列报导了二过碘酸合铜（Ill）氧化一元醇的反应动力学，但二者所得结果有一定的差别·由于C“m）处于最高氧化态，反应体系又比较复杂·目前人们对它的认识并不太清楚·本文就CU（）氧化乙醇胺（则进行了动力学及机理的研究·1实验部分所用仪器及测定人。s的实验手续同前文＊．2结果与讨论2．1准一级速车常教k。bs的求得在D川。三IO可＊u（m）IO条件下，以w人一＊。）对时间土的图为直线，表明反应对［Cb（Ill）］为一级·准一级速…     

钴配合物催化的乙烯与三烷基铝置换反应动力学研究

研究了用钴配合物催化的乙烯与三异丁基铝的置换反应动力学. 置换反应速率相对于烷基铝浓度、配合物浓度及乙烯压力呈一级关系. 置换反应速率的动力学方程为r=1.4 ×106[R3Al][Cat.][pC2H4]. 反应的活化能为71.9 kJ/mol.     

高效液相色谱法研究二(烷基黄原酸)合钯(II)间的配体交换反应动力学

高效液相色谱法, 由于其分辨率高和检测浓度低, 在研究反应物和产物的结构和物理化学性质极为相似的反应中显示出独特的本领, 本文利用高效液相色谱法, 在12-32℃(研究了二(烷基黄原酸)合钯(II)间的配体交换反应动力学.     

Fe(III)与2,3-二羟基苯磺酸钠配位反应的动力学研究

[H⁺]在0.01～0.70 mol•L^－1范围内, 离子强度为1.00 mol•L^－1, [Fe(III)]>>[配体]、[H⁺]>>[配体]的条件下, 研究了Fe(III)与2,3-二羟基苯磺酸钠(Tiron)的配位反应. 发现当[H⁺]≤3.00×10^－2 mol•L^－1时, [Fe(III)]²对反应速率有明显的贡献. 求得了相关反应的动力学参数, 从而揭示了FeOH²⁺和与Tiron配位的解离反应途径及的缔合反应机制, 并提出了该配位反应的可能机理.     

Fe(III)与2,3-二羟基苯磺酸钠配位反应的动力学研究

[H+]在0.01～0.70mol?L-1范围内,离子强度为1.00mol?L-1,[Fe(III)]>>[配体]、[H+]>>[配体]的条件下,研究了Fe(III)与2,3-二羟基苯磺酸钠(Tiron)的配位反应.发现当[H+]≤3.00×10-2mol?L-1时,[Fe(III)]2对反应速率有明显的贡献.求得了相关反应的动力学参数,从而揭示了FeOH2+和FeOH24+与Tiron配位的解离反应途径及FeOH32+的缔合反应机制,并提出了该配位反应的可能机理.     

二过碘酸合铜(III)氧化氨基丙酸的动力学

高氧化态的过渡金属通常借助与适当多齿配体螯合能稳定存在．例如二羟基二过碘酸合镍（IV）［1，2］和二过碘酸合铜（皿）[3，4]等在适当pH下都是良好的氧化剂．近期Morius[3]和Murthy[4]等人进行了Cu(III）对一元醇、醛等有机化合物的氧化反应动力学研究，两者所得结果有一定的差别．例如前者得出反应对于过碘酸为一1．0级，而后者为一0．45级．由于这类反应比较复杂，而且钢在许多包含有电子转移的生物化学过程中起着重要的作用问，因此对这类反应体系进一步探讨有一定的意义·及实验部分（1）试剂和仪器a一氨基丙酸和其它试剂都不低…     

二(氢过碘酸)合银(III)配离子氧化愈创甘油醚的反应动力学及机理

在碱性介质中,用传统的分光光度法研究了Ag(III)配离子,即[Ag(HIO6)2]5-,氧化药物分子愈创甘油醚的动力学及其机理.用质谱鉴定了氧化产物;反应对Ag(III)和愈创甘油醚均为一级;在温度25.0-40.0℃范围内,通过分析[OH-]和[IO4-]tot对反应速率的影响,二级速率常数有以下表达式:k′=(ka kb[OH-])K1/｛f([OH-])[IO4-]tot K1｝,在25.0℃及离子强度0.30mol·L-1时,对此反应有ka=(2.6±1.2)×10-2mol-1·L·s-1,kb=(2.8±0.1)mol-2·L2·s-1,及K1=(4.1±0.4)×10-4mol·L-1,求出了涉及ka,kb的活化参数,并据此推出反应机理为反应体系中的[Ag(HIO6)2]5-配离子在前期平衡后,反应活性中心与药物分子形成Ag(III)-过碘酸-愈创甘油醚分子三元配合物,配位甘油醚分子通过两个平行途径将两电子传递给中心原子Ag:一个途径无OH-离子参与,另一途径有OH-参与完成.     

The oxidation of carbohydrazide by the 12-tungstocobaltate(III) ion in acidic medium: Kinetics and mechanism

The redox reaction between the 12-tungstocobaltate(III) ion and carbohydrazide is first order with respect to both the oxidant and the substrate. The observed pseudo first-order rate constant, k_obs, is retarded by increasing the concentrations of H⁺ and alkali metal ion (Li⁺, Na⁺ and K⁺). There is a linear correlation between the k_obs and the concentrations of carbohydrazide and H⁺ ion, but the plots of k_obs against the concentrations of the alkali metal ions is non-linear. However, the same data is applicable to the Davies equation for the effect of the ionic strength on the k_obs.     

Kinetics of the Ru(III) catalyzed oxidation of formaldehyde and acetaldehyde by alkaline hexacyanoferrate(III)

The kinetics of ruthenium(III) catalyzed oxidation of formaldehyde and acetaldehyde by alkaline hexacyanoferrate(III) has been studied spectrophotometrically. The rate of oxidation of formaldehyde is directly proportional to [Fe(CN) _3– ⁶ ] while that of acetaldehyde is proportional tok[Fe(CN) _3– ⁶ ]/{k +k[Fe(CN) _3– ⁶ ]}, wherek, k andk are rate constants. The order of reaction in acetylaldehyde is unity while that in formaldehyde falls from 1 to 0. The rate of reaction is proportional to [Ru(III)] _T in each case. A suitable mechanism is proposed and discussed.

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Die Kinetik der Ru(III)-katalysierten Oxidation von Formaldehyd und Acetaldehyd mittels alkalischem Hexacyanoferrat(III)

Zusammenfassung Die Untersuchung der Kinetik erfolgte spektrophotometrisch. Die Geschwindigkeitskonstante der Oxidation von Formaldehyd ist direkt proportional zu [Fe(CN) _3– ⁶ ], währenddessen die entsprechende Konstante für Acetaldehyd proportional zuk[Fe(CN) _3– ⁶ ]/{k +k[Fe(CN) _3– ⁶ ]} ist, wobeik,k undk Geschwindigkeitskonstanten sind. Die Reaktionsordnung für Acetaldehyd ist eine erste, die für Formaldehyd fällt von erster bis zu nullter Ordnung. Die Geschwindigkeitskonstante ist in jedem Fall proportional zu [Ru(III)] _T . Es wird ein passender Mechanismus vorgeschlagen.

     

Kinetics and mechanism of the ruthernium(III) catalyzed oxidation of propane-1,3-diol by alkaline hexacyanoferrate(III)

The kinetics of oxidation of propane-1,3-diol by alkaline hexacyanoferrate (III) catalyzed by ruthenium trichloride has been studied spectrophotometrically. A reaction mechanism involving the formation of an intermediate complex between the substrate and the catalyst is proposed. In the rate-determining step this complex is attacked by hexacyanoferate(III) forming a free radical which is further oxidized.     

Ruthenium (III) catalysed and uncatalysed oxidation of torsemide by hexacyanoferrate (III) in aqueous alkaline medium: A kinetic comparative approach

The kinetics approach of oxidation of torsemide (TOR) by hexacyanoferrate (III) [HCF (III)] has been identified spectrophotometrically at 420 ​nm in the alkaline medium in the presence and absence of catalyst ruthenium (III) at 25 ​°C, by keeping ionic strength (1 ​× ​10⁻² ​mol ​dm⁻³) constant. The reaction exhibits at the stoichiometry ratio 1:2 of TOR and HCF (III), for uncatalysed and catalysed reactions. In the absence and presence of the catalyst, the order of the reactions obtained for TOR and HCF (III) was unity. However, the rate of the reactions enhanced by the increase in the concentration of catalyst, as well as the rate increases with an increase in alkaline concentration. The activation parameters for the reaction at the slow step were identified, and the effect of temperature on the rate of the reaction was analysed. A suitable mechanism has been demonstrated by considering the obtained results. The derived rate laws are reliable with analysed experimental kinetics.     

铂单晶电极表面下不可逆反应动力学(III)

在本系列研究论文Ⅰ[1]和Ⅱ[2]报导的结果基础上，进一步发展动力学数据解析方法．通过改变反应体系的温度，首次获得甲酸在Pt（100），Pt（110），Pt（111）电极上直接氧化反应的表观活化Gibbs自由能（△G≠0）．在实验选定的标准状态下，即0．0V／SCE、298．15K和1．013×105Pa下，来算得到。还发现传递系数β在实验温度范围（283．15～303．15K）不随温度变化，但随电极表面原子排列结构变化，大小次序与△G≠0的变化一致．     

Ruthenium(III) catalysed oxidation of l-leucine by a new oxidant,diperiodatoargentate(III) in aqueous alkaline medium

The kinetics of Ru(III) catalysed oxidation of l-leucine by diperiodatoargentate(III) (DPA) in alkaline medium at 298 K and a constant ionic strength of 0.60 mol dm⁻³ was studied spectrophotometrically. The oxidation products are pentanoic acid and Ag(I). The stoichiometry is [l-leucine]:[DPA] = 1:2. The reaction is of first order in Ru(III) and [DPA] and has less than unit order in both [l-leu] and [alkali]. The oxidation reaction in alkaline medium has been shown to proceed via a Ru(III)–l-leucine complex, which further reacts with one molecule of monoperiodatoargentate(III) (MPA) in a rate determining step followed by other fast steps to give the products. The main products were identified by spot test and spectral studies. The reaction constants involved in the different steps of the mechanism are calculated. The catalytic constant (K_c) was also calculated for the Ru(III) catalysed reaction at different temperatures. From the plots of log K_c versus 1/T, values of activation parameters with respect to the catalyst have been evaluated. The activation parameters with respect to the slow step of the mechanism are computed and discussed, and thermodynamic quantities are also determined. The active species of catalyst and oxidant have been identified.     

Kinetik und Mechanismus des Ligandentausches zwischen Thallium(III)oxinat und Eisen(III) in Propylencarbonat

The transfer of oxinate ions from thallium (III)oxinate to trivalent Fe(DMF) ₆ ³⁺ in propylenecarbonate takes place via rearrangements within a rapidly formed binuclear thallium(III)—iron(III) complex. In a last rapid step this rearranged complex reacts with excess reactants to the final products whose composition accordingly depends on the ratio of the reactant concentrations.

     

Electron transfer reactions of nickel(III) and nickel(IV) complexes

This review narrates the electron transfer reactions of various nickel(III) and nickel(IV) complexes reported during the period 1981 until today. The reactions have been categorized mainly with respect to the type of nickel complexes. The reactivity of nickel(III) complexes of macrocycles, 2,2′-bipyridyl and 1,10-phenanthroline, peptides and oxime–imine, and of nickel(IV) complexes derived from oxime–imine, oxime and miscellaneous ligands with various organic and inorganic electron donors have been included. Kinetic and mechanistic features associated with such interactions have been duly analyzed. The relevance of Marcus cross-relation equations in the delineation of the electron transfer paths has also been critically discussed.