Steady-state rate of complex reactions under limitation and near equilibrium (one-route mechanism of catalytic reactions)

Explicit equations for the steady-state rate in case when one of the steps is rate-limiting, and in the neighborhood of equilibrium have been derived for a one-route mechanism of a catalytic reaction. Equations have been obtained for a dependence of the observed reaction order and activation energy on the thermodynamic characteristics of the overall reaction.

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Analysis of the stationary kinetic characteristics of an n-stage unbranched catalytic reaction (linear mechanism)

Conclusions We shall discuss what differences the complexity (n-stage character) brings into the kinetic characteristics of the simplest case examined by us: an unbranched cycle, linear with respect to the intermediate substances. In the range in which the reaction proceeds in the forward direction the temperature dependence for an exothermal complex reaction is identical to that for a simple reversible exothermal stage [1]. For a complex endothermal reaction are possible characteristics which are analogous to an elementary endothermal stage: a monotonic dependence, but also a novel property may appear: an extreme (no more than one) due to the strong hidden endothermal character. As was proved in the present study, the action of the partial pressures of the reactants is analogous to their effect on the rate of an elementary reaction: monotonic functions. The difference consists in that here in most cases a limiting rate exists as a result of, for example, the circumstance that the detailed mechanism embraces stages in which no gas phase participates.Consequently, we classified the typical stationary kinetic characteristics of an n-stage unbranched catalytic reaction with a mechanism linear with respect to the intermediate products. The results obtained in our study can be easily extended to other cases, too, when the kinetic equations are of the shape (1), for example, to some empirical equations.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 14, No. 4, pp. 529–533, July–August, 1978.     

Parametric analysis of kinetic models, 8. Two-center catalytic oscillators

The results of parametric analysis for a kinetic model of CO oxidation reaction on two types of active centers of Pt are given. The local bifurcation curves are constructed for every type of center. The regions with self-oscillations are singled out in a plane (p_CO, T). A sum of rate oscillations on every center can have a quasi-chaotic character.     

Parameter sensitivity analysis of stochastic models: Application to catalytic reaction networks

A general numerical methodology for parametric sensitivity analysis is proposed, which allows to determine the parameters exerting the greatest influence on the output of a stochastic computational model, especially when the knowledge about the actual value of a parameter is insufficient. An application of the procedure is performed on a model of protocell, in order to detect the kinetic rates mainly affecting the capability of a catalytic reaction network enclosed in a semi-permeable membrane to retain material from its environment and to generate a variety of molecular species within its boundaries. It is shown that the former capability is scarcely sensitive to variations in the model parameters, whereas a kinetic rate responsible for profound modifications of the latter can be identified and it depends on the specific reaction network. A faster uptaking of limited resources from the environment may have represented a significant advantage from an evolutionary point of view and this result is a first indication in order to decipher which kind of structures are more suitable to achieve a viable evolution.     

甲烷催化燃烧反应机理及催化剂研究进展

在煤矿开采及燃气轮机等工业应用或移动源领域存在甲烷大体量排放,且传统高温焚烧法会导致二次污染,因此,在低温下实现甲烷高效转化成为亟待解决的问题.从能源利用和环境保护角度,催化燃烧技术是实现甲烷废气高效净化的有效措施.本文综述了近年来催化机理和催化剂的研究进展.首先,在实验和理论基础上,总结概括了甲烷氧化机理,其中,重点...     

Kinetic isotope effect and mechanism of catalytic reaction of hydroxybenzenes with epichlorohydrin

Kinetic data are presented for catalytic reactions of 3-nitrophenol and 4,4′-dihydroxydiphenyl sulfone with epichlorohydrin. Magnitudes of the kinetic isotope effects have been determined for these reactions, and a mechanism of catalysis is proposed. Donetsk State University, 24 Universitetskaya ul., Donetsk 340055, Ukraine. Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 34, No. 5, pp. 302–305, September–October, 1998.     

Kinetics and mechanism of the catalytic reaction between alcohols and dimethyl carbonate

The mechanism of the reaction between alcohols and dimethyl carbonate, catalyzed by dicobalt octacarbonyl Co₂(CO)₈, is studied by means of mathematical modeling. Kinetic models for possible schemes of chemical transformations are constructed at different initial concentrations of the catalyst. Based on a comparative analysis of activation energies of possible stages of chemical transformations, possible reaction pathways are determined and an appropriate mechanism is selected.     

Calculation of clustered eigenvalues of large matrices using variance minimization method

The autoadjusting perturbation theory method is presented and developed to calculate eigenpairs of a square matrix. The procedures to simultaneously compute a cluster of eigenpairs by variance minimization are also given. Finally, numerical examples are reported. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 1777–1785, 1998     

玉米芯热解及过程分析

研究了农业废弃物玉米芯热解过程中气、液、固三相产率与裂解温度的关系；气相组成、液相组成与温度的关系，以及热解过程的机理。实验表明，在350℃～400℃，气相成分主要是CO2、CO所占比率为95%;随着温度的升高，H2、C2H4、CH4等气体的比率逐渐增高，CO、CO2的体积分数在逐渐降低。在450℃～500℃，CO、H2所占的比率达50%。GCMS，IR分析表明，裂解过程产生的液体主要是由含氧的化合物酚、呋喃及其衍生物组成；低温有利于酚类质量分数的增加，高温有利于4-乙基-2-甲氧基-苯酚、2-甲基-苯酚的增加；采用TGA分析，建立了热解过程的动力学方程，得到了热解过程的反应机理，即热解过程有两个分解阶段，在不同温度段具有不同的反应规律。在211℃～290℃具有三级反应的特征，其活化能为121.4kJ·mol－1；在290℃～418℃表现为0.5级反应的特征，其活化能为105.7kJ·mol－1。     

Parafac decomposition of three-way kinetic-spectrophotometric spectral matrices corresponding to mixtures of heavy metal ions

Binary and ternary mixtures of some of the following heavy metal ions Zn(II), Ni(II), Pb(II), Co(II) and Cd(II) were analyzed by a ligand substitution kinetic method. Three-way data matrices were generated by acquisition of UV-Vis spectra (332-580 nm) as a function of the time of a substitution reaction observed between the complex of the heavy metal ions with the non selective metallochromic indicator 4-(2-pyridylazo) resorcinol (PAR) and EDTA, and of different relative concentration of the metal ions (1-6 mM). The PARAFAC trilinear model, without restrictions, was used in the data analysis. A full decomposition of the data matrices was obtained (spectra, concentration and time profiles). It was shown that ligand substitution kinetic methods coupled to three-way chemometric analytical methods can be used for the development of robust sensors for the analysis of binary [Zn(II)+Ni(II), Pb(II)+Cd(II), Zn(II)+Pb(II)] or ternary [Zn(II)+Pb(II)+Co(II)] mixtures of metal ions in the micromolar concentration range.     

A study of the reaction mechanism of the catalytic intramolecular conversion of heterocycles

In order to study the reaction mechanism of the catalytic intramolecular conversion of heterocycles [1–3] and to broaden the field of their application, we have studied the dehydration over Al₂O₃ of 1-amino-3-(-tetrahydrofuryl) propane (I), 1-methylamino-1-(-tetrahydrofuryl) propane (II), and 2-(3-hydroxy-1-propyl)-1-methylpyrrolidine (III), leading in all three cases to pyrrolizidine (IV).     

Recent advances on deoximation: From stoichiometric reaction to catalytic reaction

Recent advances on the deoximation reactions are reviewed in this review. It was shown that catalytic deoximation with molecular oxygen as the mild oxidant should be the developing trend of the reaction.     

Brackets to the eigenvalues of the Schrödinger equation,part 1. Tridiagonal matrices

The problem of upper and lower bounds to the first few eigenvalues of a very large or infinite tridiagonal matrix H is studied. Those eigenvalues of a comparison-matrix M _n which are lower than a characteristic limit, together with the corresponding eigenvalues of the variational matrix H _n are shown to bracket exact eigenvalues of H . M _n differs from H _n only in the last off-diagonal element and is easily obtained from H . Sufficient conditions for lower bounds are based on a low estimate of the characteristic limit. For increasing dimensions n, the lower bounds approach the exact eigenvalues from below. As a numerical illustration, brackets to the known eigenvalues of the harmonic oscillator with a linear perturbation are calculated.     

Parametric uniqueness of deficiency zero reaction networks

In this paper it is shown that deficiency zero mass action reaction networks containing one terminal linkage class are parametrically and therefore structurally unique with a fixed complex set. Clearly, weakly reversible deficiency zero networks with one linkage class belong to this class. However, it is shown through an illustrative example that deficiency zero networks with several linkage classes can have multiple dynamically equivalent realizations, even if the individual linkage classes are weakly reversible.     

Quantum-chemical study of the mechanism of the growth reaction in the catalytic polymerization of alkenes

Conclusion The present review examines only some of the problems of the mechanism of the growth reaction in the catalytic polymerization of alkenes, which have been the subject of quantum-chemical studies by a number of workers. The number of theoretical papers in this field is small. Nevertheless, the results obtained make it possible to understand various important characteristic features of not only the polymerization reaction but also other interesting reactions involving the participation of organometallic compounds.Institute of Catalysis, Academy of Sciences of the USSR, Siberian Branch. Translated from Zhurnal Strukturnoi Khimii, Vol. 18, No. 3, pp. 525–545, May–June, 1977.     

低温等离子体场内复合不同晶型氧化锰催化降解甲苯性能和机理

作为典型的挥发性有机化合物,甲苯通常来源于建筑涂料、交通运输和各种工业生产过程,是PM2.5、臭氧和光化学烟雾的重要前驱体,对环境和人类健康造成巨大影响.近年来,低温等离子体技术因具有在常温常压下就能通过高能电子、活性氧物种和羟基等活性粒子有效降解挥发性有机物的优点而受到广泛关注.然而,高能耗和大量副产物的产生是等离子体技术工业化应用的巨大障碍.当前最有效的策略之一是将等离体技术与催化技术结合,从而加快反应速率,提高产品的选择性和能源利用率.在所应用的催化剂中,MnO2因具有较好的O3分解效率而成为最有潜力的催化剂之一.但是MnO2具有不同的晶型结构、隧道结构和形貌,这些均会显著影响MnO2的催化活性.本文通过一步水热法制备了α-,β-,γ-和δ-MnO2四种MnO2催化剂,并将其用于等离子体催化降解甲苯研究,在此基础上系统考察了等离子体催化降解性能和MnO2不同晶型之间的关系.结果表明,当能量密度为160 J/L时,等离子体单独降解甲苯去除效率为32.5%.引入催化剂能够显著提高甲苯的降解效率,其中α-MnO2效果最显著,甲苯降解效率能够提升至78.1%,β-,γ-和δ-MnO2能够相应提升至47.4%,66.1%和50.0%.采用X射线衍射、拉曼光谱、扫面电子显微镜、透射电子显微镜、比表面积-孔结构分析、氢气程序升温还原和X射线光电子能谱等手段研究了催化剂的理化特性.结果表明,隧道结构、催化剂在等离子体中的稳定性、Mn–O键能和催化剂表面吸附氧均在等离子体催化降解甲苯中发挥了重要作用.在此基础上,通过GC-MS分析降解产生的气相副产物推断甲苯在等离子体和等离子体催化体系中的降解机理.在等离子体催化体系中,通过Mn4+,Mn3+和Mn2+价态的变化,等离子体产生的O3,O2*和其他活性自由基会被吸附到催化剂表面,随后与催化剂吸附的甲苯或中间副产物发生氧化还原反应,将甲苯氧化为CO2等小分子物质.此外,MnO2作为分解O3最有效的催化剂,可以吸附O3并将其分解为O?或者与H2O生成?OH参与到反应中,从而提高甲苯的降解效率.     

Molecular insights of nanozymes from design to catalytic mechanism

Emerging as cost-effective potential alternatives to natural enzymes, nanozymes have attracted increasing interest in broad fields. To exploit the in-depth potential of nanozymes, rational structural engineering and explicit catalytic mechanisms at the molecular scale are required. Recently, impressive progress has been made in mimicking the characteristics of natural enzymes by constructing metal active sites, binding pockets, scaffolds, and delicate allosteric regulation. Ingenious in-depth st...     

A direct catalytic asymmetric mannich-type reaction to syn-amino alcohols

The Mannich reaction is one of the most widely utilized chemical transformations for the construction of nitrogen-containing compounds. With the increasing occurrence of nitrogen in drugs and natural products, highly asymmetric variants of the Mannich reaction are desirable. In this communication, we report the application of our dinuclear zinc catalyst to a highly asymmetric Mannich-type reaction to generate syn 1,2-amino alcohols.