关于化学反应速率定律与化学平衡的教学法的讨论

Guldberg和Waage两氏在对化学亲和力的研究中,得出化学反应速率与反应物的“活性质量”成正比的关系,他们把这种关系称为质量作用定律,并且很明确地给“活性质量”下个定义,即单位体积内物质的量。由此,他们又明显地另外推导出“平衡条件”,这平衡条件就是平衡常数的传统形式。在用实验方法来验证这     

金属胶束催化体系中经Turing分支形成的空间有序结构与催化活性

摘要基于金属胶束催化反应的三元复合物动力学模型, 分析了金属胶束作为一类特殊的超分子体系, 其参与催化反应的特殊动力学行为与体系中可能出现的自组织结构的关系. 研究结果表明, 在一定的边界条件下, 即使基元反应是线性化学反应步骤, 由于扩散步骤与化学反应的耦合, 以及非理想性的组分热力学行为, 也将不可避免地出现经Turing分支形成的浓度场空间自组织. 计算结果表明, 这种宏观有序结构的形成将使金属胶束催化体系中呈现出以存在反应活性极高的位点为特征的反应活性的空间有序分布; 从自组织理论的角度对这类胶束体系催化活性的时空有序特征给予一定程度的阐释.     

铂电极BZ反应体系的系统动力学分析

在一定的条件下,将铂电极BZ化学反应的六变量高维动力学系约化为三变量体系,同时对该体系进行了全面的系统动力学分析.研究结果表明,通过改变耦合体系的外控参数条件,在将体相保持在均一稳定定态的参数范围内,电极反应相可能进入振荡区,而呈现出电极反应相与体相的动力学行为不一致性.进一步计算出体相处于非振荡状态时,电极反应相产生电化学振荡的外控参数区域.     

化学中的"物理定律"--质量作用定律的创立

质量作用定律 (ｌａｗｏｆｍａｓｓａｃｔｉｏｎ)在现代意义上理解 ,就是在一定温度下 ,一个均匀化学反应 (ｈｏｍｏｇｅ ｎｅｏｕｓｃｈｅｍｉｃａｌｒｅａｃｔｉｏｎ) ,其反应速率与反应物质的浓度成正比。事实上与反应物的质量无关而是与反应物质的浓度有关 ,所以此定律字面的意义是错了 ,但因为习惯也就沿用下来了。在质量作用定律创立的发展史中 ,有 3次比较重大的事件 :一是贝托雷提出质量作用的思想 ;二是威廉米得出第一个物质浓度与反应速率关系的数学表示式 ;三是古德贝格和瓦格比较完整地叙述出质量作用定律。现对该定律创立过程…     

分形介质上的化学动力学

经典的化学反应速率理论，在一定程度上讲只适用于均相反应，非均相反应的化学动力学还很不成熟。最近十几年来，人们开始利用分形的概念来描述非均相反应体系中十分复杂的介质形态，并着手研究分形介质上的化学动力学理论，得到了一些大大不同于经典理论的结果。本文综述了该领域的研究成果与现状。     

动力学方程控制表面反应的模拟模型和方法

提出了动力学方程控制表面反应的模拟模型和方法.该模型从最基本的质量作用定律出发,获得表面反应的动力学方程.而表面反应通过格子模拟反应器进行.通过表面催化样板反应"CO表面催化氧化"检验了该模拟模型和方法,与实验结果吻合.该模型可在其它复杂的表面催化反应体系中推广应用.     

补偿效应：一条化学/化工动力学基本定律的探讨

补偿效应揭示了Arrhenius方程中反应速率常数k的指数项(-E/RgT)与指前因子(k0)项存在着相互补偿关系。不仅存在于催化与非催化,均相与非均相的反应体系及需要克服能垒的物理过程,而且也存在于生命与非生命、能源、环境与材料等许多领域。本文对补偿效应的定位、理论解释及适用范围进行了探讨,指出其在化学/化工动力学中占有重要位置,不仅是一条定律,而且是与质量作用定律、Arrhenius定律并列的又一条基本定律。本文从统计学角度对补偿效应进行了概率分析,试图对其给出更为广义的理论解释,并指出,均相反应体系和非均相反应体系本质上都是不均匀的。中间络合物生成具有耗散结构特征,在近平衡(准平衡)线性区进行,无序度减小伴随着能量及无序度的同向变化,这是补偿效应存在的根本原因。从而提出了反应速率常数中能量分布、无序度分布的概率因子。其对补偿效应的概率解释与能量指数分布说/焓熵补偿关系说是统一的而非对立的。进而还讨论了自然指数律/自然补偿律,指出补偿效应是自然界存在/运动所遵循的自然律在化学反应领域的具体体现。     

非高斯噪声增强纳米尺度钯粒子表面一氧化碳氧化反应随机速率振荡

过去的几十年里,人们对噪声的积极作用进行了广泛研究,其中,化学反应体系中噪声的作用引起人们的很大兴趣.人们研究了单晶表面和纳米粒子表面催化体系中内、外噪声对反应振荡的影响,发现了随机共振和相干共振现象.然而,在以往的研究中,人们总是用高斯噪声代替实际噪声.但实验研究表明,神经元和自催化反应等生物化学反应体系中可能存在非高斯噪声.本文研究非高斯噪声对纳米尺度钯粒子表面一氧化碳催化氧化反应速率振荡的影响.我们首先给出了不存在外噪声时体系振荡随粒子尺度的变化情况,得到了内噪声相干共振行为.其次,我们重点研究了在非高斯噪声作用下体系反应速率的振荡.发现,随着非高斯噪声与高斯噪声的偏离q的增大,振荡规律性经历了由差变好到再变差的演化,而且在某个最佳的q值,振荡变得最有规律性.我们分别给出了振荡时间序列、功率谱和信噪比随q值的变化,充分反映了上述振荡的演化情况.这个结果表明,适当的外噪声能够增强纳米尺度钯粒子表面一氧化碳氧化反应随机速率振荡,而且存在某个最佳的外噪声,使速率振荡得到最大程度的增强.同时表明,非高斯噪声可能比高斯噪声起到更大的增强作用.最后,我们对非高斯噪声增强一氧化碳反应速率振荡这一现象的物理机制作了简单...     

BZ反应系非理想性对化学振荡动力学区域的影响

基于Debye-Huckel强电解质溶液活度系数理论、反应速度的活化络合物理论以及三变量微分方程奇点理论,探讨了非理想性对BZ反应体系振荡动力学区域的影响。以Oregonator为模型建立了均匀体系非理想BZ反应的系统动力学方程,计算并绘制了化学振荡的临界"溴酸钠浓度-离子强度"阈值图谱,划分了不同的动力学区域,并进行了一系列实验研究,得到了与理论分析一致的结论.     

基于Monte Carlo模拟的化学反应动力学参数估算

提出并采用基于MonteCarlo模拟与动力学实验相结合的化学反应动力学参数估算方法,由基元反应确定MonteCarlo模拟具体做法,将MonteCarlo模拟结果与动力学实验结果相比较,根据比较结果自动调整和优化动力学参数,从而无需事先确定动力学方程即可有效估算各种化学反应的动力学参数值.采用该方法估算了丙烯氨氧化反应动力学参数,并对估算结果进行了分析与讨论.     

Numerical Modeling of an Ar–H<Subscript>2</Subscript> Radio-Frequency Plasma Reactor under Thermal and Chemical Nonequilibrium Conditions

The species densities and the thermal and chemical nonequilibrium phenomena in an Ar–H₂ radio frequency inductively coupled plasma reactor used for hydrogenation of materials have been investigated through numerical simulation. The mathematical model consists of a two-temperature fluid dynamics model and a chemical kinetics model that takes into account the effect of local chemical nonequilibrium. Computations are carried out for the rf plasma running at 11.7 kW and 27 kPa for different Ar–H₂ mixtures and for pure argon. Predicted results for the electron and heavy-species temperatures, the species densities, as well as the degree of thermal and chemical nonequilibrium, are presented in detail. It is found that the electron and hydrogen atom densities in the reactor and in the near-wall region of the torch are strongly altered by nonequilibrium effects. The hydrogen atom density remains high in the reactor zone, and peaks in a region that has been found to be attractive for material processing. Deviations from thermal and chemical equilibrium are greatly reduced by the addition of hydrogen to an argon plasma.     

非平衡非线性化学

概述了非平衡非线性化学的主要研究内容和最新进展,着重介绍了各种非平衡非线性化学现象以及与之有关的非平衡态热力学理论和非线性化学动力理论;介绍一些典型的理论方法和实验手段以及涨落化学的概念;讨论了非平衡非线性化学研究的意义以及与其它科学尤其是生物学的联系。     

A microscopic model of chemical reactions with reorganization. High-energy approximation

A dynamical model of a chemical reaction, accompanied by reorganization of the immediate environment of the isolated chemical subsystem, is proposed. The model enables studying the emergence of nonequilibrium distribution functions as a combined result of the interaction within the dynamical subsystem and the energy exchange with a subsystem of inactive degrees of freedom (thermal bath). The study is based on the quasiclassical high-energy approximation for nonadiabatic effects in the energy exchange within the dynamical subsystem, for strong and weak coupling of the oscillator mode with the thermal bath. Such an approximation allows for the important statement that nonequilibrium effects in thermal reactions are absent if the initial translational distribution along the reaction coordinate and the initial vibrational distribution in transversal degrees of freedom are Boltzmann-like with the same temperature. The results obtained in the absence of the initial equilibrium distribution have been used for interpreting the kinetics of endothermic plasmochemical reactions proceeding under nonequilibrium conditions.     

Open-system nonequilibrium steady state: statistical thermodynamics, fluctuations, and chemical oscillations

Gibbsian equilibrium statistical thermodynamics is the theoretical foundation for isothermal, closed chemical, and biochemical reaction systems. This theory, however, is not applicable to most biochemical reactions in living cells, which exhibit a range of interesting phenomena such as free energy transduction, temporal and spatial complexity, and kinetic proofreading. In this article, a nonequilibrium statistical thermodynamic theory based on stochastic kinetics is introduced, mainly through a series of examples: single-molecule enzyme kinetics, nonlinear chemical oscillation, molecular motor, biochemical switch, and specificity amplification. The case studies illustrate an emerging theory for the isothermal nonequilibrium steady state of open systems.     

形成晶体条纹的一个界面反应-扩散模型

基于晶体生长动力学的非平衡非线性特性和耗散结构的概念,提出了一个非理想的界面反应一扩散模型,其中界面动力学引起的晶面多重态现象和扩散过程的耦合可导致滞后现象。它可以解释某些晶体中有序条纹的形成。     

Thermodynamic derivations of conditions for chemical equilibrium and of Onsager reciprocal relations for chemical reactors

For an isolated chemical reactor, we derive the conditions for chemical equilibrium in terms of either energy, volume, and amounts of constituents or temperature, pressure, and composition, with special emphasis on what is meant by temperature and chemical potentials as the system proceeds through nonequilibrium states towards stable chemical equilibrium. For nonequilibrium states, we give both analytical expressions and pictorial representations of the assumptions and implications underlying chemical dynamics models. In the vicinity of the chemical equilibrium state, we express the affinities of the chemical reactions, the reaction rates, and the rate of entropy generation as functions of the reaction coordinates and derive Onsager reciprocal relations without recourse to statistical fluctuations, time reversal, and the principle of microscopic reversibility.     

A self-consistent one-dimensional model for He nonequilibrium kinetics in RF discharges

A self-consistent one-dimensional model for nonequilibrium kinetics in RF discharges has been elaborated it which connects two different RF discharge modeling viewpoints: a microscopic vienpoint (Boltzmann equation for the electron energy distribution function, master equation for the electronic states of He) and a macroscopic one (fluid model). Ac results show the role of excited states in affecting the macroscopic properties (electron density, electron temperature. electric field) of the system. The reliability of the model is assessed by comparing the results obtained by it with existing experimental results. In general. a satisfactory agreement is obtained.     

Thermal and Chemical Nonequilibrium Effects in Free-Burning Arcs

Effects caused by thermal and chemical nonequilibrium in free-burning arcs in argon are presented and discussed. The results cover a range of arc currents between 100 and 200 A, interelectrode distance of 5–10 mm, and a variation of the electrode material and the shape of the cathode tip. The results obtained show that nonequilibrium in the near-electrode regions has a strong impact on the distributions of temperatures, electric conductivity and current density, and the arc voltage. Departure from chemical nonequilibrium in the vicinity of the cathode as a result of transport processes is indicated. Moreover, overpopulation of the atomic ground state close to the arc axis, under population of the excited states in the arc periphery with respect to the equilibrium values, axial dependence of the off-axis maximum of the radial emission coefficient of Ar I at 696.5 nm, and enhanced population of the Ar (1s₄) resonance level due to trapping of resonance radiation in the arc periphery are considered.     

Mechanisms of charge separation in bacterial photosynthesis

The physical aspects of the primary charge separation processes in bacterial photosynthesis are discussed. The donor-acceptor model of electron transfer due to participation of protein current states is used. The kinetics of photosynthetic reaction center (PRC ) processes is investigated and the PRC energetic scheme is constructed using the nonequilibrium density matrix method. It is shown that with allowance for the effect of vibrational sublevels of states participating in transitions the theory describes well experimental data.