CuSO4-KSCN-H2O2-NaOH反应体系双节律的周期调制

研究了ＣｕＳＯ４－ＫＳＣＮ－Ｈ２Ｏ２－ＮａＯＨ反应体系,新发现了两种双节律现象。继而以流速作为扰动参数,对双节律Ⅱ中两个不同振荡态的不同流速点进行了周期调制,发现在临界区（接近实现ＯＳＳ１→ＯＳＳ２或ＯＳＳ２→ＯＳＳ１的流速点）只能实现单向跃迁;在ＯＳＳ１态的ｋｆ＾０＝４．０ｍＬ／ｍｉｎ和ＯＳＳ２态的ｄｆ＾０＝３．０ｍＬ／ｍｉｎ,能实现在两振荡态间的双向跃迁,而且ＯＳＳ２态比ＯＳＳ１态稳定。     

调制BZ-CSTR反应体系小振荡诱导非平衡相变

以流量为扰动参数,对连续搅拌釜式反应器（ＣＳＴＲ）中的Ｂｅｌｏｕｓｏｖ－Ｚｈａｂｏｔｉｎｄｓｋｙ（ＢＺ）反应体系小振荡进行周期或噪声扰动,改变扰动周期或扰动强度,在某些条件下可以诱导非平衡相变。以ＢＺ反应的四变量Ｍｏｎｔａｎａｔｏｒ模型为基础,对相应流率区进行周期或噪声扰动,计算结果与实验基本定性一致。     

质量作用定律与基元反应概念辨析

质量作用定律适用于所有的基元过程。基元过程是只被一个能峰隔开的两个相邻的有一定稳定性的状态之间的变化。能峰可高可低，最低时为0。基元过程既可以是发生化学变化的基元反应，也可以是简单的物理变化。     

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…     

周期扰动位相对化学振荡的调制效应

由Rossler反应系统的理论模型出发,构造一种具有外部周期扰动的新动力学系统,并采用逆算符法和数值分析法研究该系统的振荡态在周期扰动调制下的动力学行为.结果表明,在周期扰动的调制下,系统的状态由单周期振荡态(1p)变为周期2(2p)、周期4(4p)等多周期振荡态以及混沌态.扰动位相是系统呈现上述多种演化模式的控制参数,在扰动位相不同的数值区间,系统呈现的演化模式不同,而且扰动位相数值的微小改变,还影响每种演化模式的内部结构.     

线性与周期扰动对BZ反应动力学行为的影响

The dynamical behavior taking on single periodic oscillation state in BZ reaction was measured experimentally as the system′s stoichiometric coefficient μ=1. The dynamical behaviors of the system under external linear and periodic perturbation were theoretical investigated. The results show that the system has an unstable region when perturbation varies linearly, and the system only takes on single periodic oscillation state in the region. But the states of the system take on 2np periodic oscillation and chaos under external periodic perturbation, and the dynamical behavior of the system changes from period-doubling into chaos. The theoretical results are also verified by numerical simulation studies.     

非平衡性引起的对质量作用定律的偏离

在化学反应动力学中,质量作用定律占有重要的地位,通常认为,该定律仅适用于理想的反应体系,并假定,一旦反应在平衡条件下遵循质量作用定律,那么在非平衡条件下也应遵循该定律,但根据最近的研究结果,平衡条件下的理想反应体系,在非平衡条件下可能变成非理想体系,换言之,非平衡性可能引起非理想性,这表明,非平衡条件下的(基元)反应并不总是遵守质量作用定律,本文利用文献的一些结果,并结合1个具体反应模型,研究了山非平衡性引起对质量作用定律的偏离,结果表明,非平衡性本身对反应动力学规律有重要影响,对化学反应动力学的研究亦具有一定启发作用。     

卤代羰基叶立德:“推-拉”稳定作用对四苯基环戊二烯酮与卡宾的脱氧反应的影响(英文)

研究了四苯基环戊二烯酮与三溴甲基苯基汞（二溴卡宾的前体化合物）的卡宾反应，发现该反应可给出比通常有立体障碍的酮要高得多的脱氧（以脱CO的形式）产率．本文从羰基叶立德中间体的“推-拉”稳定作用以及该中间体的构象和电子分布的角度出发，并结合产物分析对这一反常现象进行了讨论，发现在潜芳香结构的羰基化合物与二卤卡宾的反应中，有可能由于“推-拉”作用形成具有芳香结构的羰基是中间体，该中间体由于正负电荷及以较好的分散以及其接近0°／90°型的构象，有效地阻碍了分子间环加成和分子内电环化这两个竞争反应的进行，从而使脱氧途径成为该反应的主渠道．本项研究进一步揭示了一些尚未被人了解的反应规律，合理地解释了反应机理．     

Novel variational principles of chemical reaction

Minimum principles of chemical reaction coordinates are established. IRC (intrinsic reaction coordinate) draws the path of minimum distance from reactant to product. The distance is measured in the rigged configuration Riemannian space whose metric is determined by the distribution of the adiabatic potential energy. Moreover, minimum property of the intrinsic principle of least action is established for the intrinsic dynamism of chemical reaction. Minimum principle of the path connecting intercell boundary with cell is also discussed.     

A study of heat and mass transfer of Non-Newtonian fluid with surface chemical reaction

Considering the significance of non-Newtonian fluid usage in manufacturing such as molten plastics, polymeric materials, pulps, and so on, significant efforts have been made to investigate the phenomenon of non-Newtonian fluids. In this article the influences of heat and mass transfer on non-Newtonian Walter's B fluid flow over uppermost catalytic surface of a paraboloid is encountered. An elasticity of the fluid layer is considered in the freestream together with heat source/sink and has the tendency to cause heat flow in the fluid saturated domain. The flow problem of two-dimensional Walter's B fluid is represented using Law of conservation of mass, momentum, heat, and concentration along with thermal and solutal chemical reactive boundary conditions. The governing equations are non-linear partial differential equation and are non-dimensionalized by employing stream function and similarity transformation. The final dimensionless equations yielded are coupled non-linear ordinary differential equations. Furthermore, shooting technique along with RK-4th order method is used to get the numerical results. Graphs and tables are modeled by using MATLAB software to check the effects of Walter's B parameter, Chemical reaction parameter and Thickness parameter on temperature, velocity, and concentration profiles. Tabular analysis shows the results of some physical parameters like skin friction coefficient, Nusselt number and Sherwood number due to the variation of Walter's B parameter, thickness parameter and chemical reactive parameter.     

Mean spherical approximation-mass action law theory of equilibrium and conductance in ionic solutions

An improved Bjerrum theory obtained by combining the mean spherical approximation with the mass action law (MSA&MAL) is used to calculate the fraction of ions unpaired over the full range of states of a primitive model electrolyte. It is combined with a new theory for the electrical conductance of the primitive model under the MSA to yield the conductance of an electrolyte over a wide range of concentrations and Bjerrum parameters with only two parameters A_o and R, the distance of closest approach, adjusted to fit the conductivity data. The theory fits the data for aqueous alkali halides over a wide concentration range with A_o values in good agreement with those deduced by more conventional theories and with reasonable small ion pairing constants deduced from the data. It fits the data for LiBr in octanol without the need for invoking triple ion formation. It leads to reasonable predictions for the conductance curves for 1:1 electrolytes even up to the molar region for solvents with dielectric constant from 10 to 80.     

Some solved problems of the periodic system of chemical elements

Basic questions on the periodic system (PS) of chemical elements are still under discussion. Several common misconceptions will be resolved. The word “chemical element” comprises more than two concepts. The PS can be rationalized on a quantum chemical basis, namely with the aid of four concepts: (1) electron configurations of bonded atoms, (2) realistic sequences of orbital energies, (3) spatial extension of valence and Rydberg orbitals, and (4) energy gaps above the closed 1s² and np⁶ shells (n = 2–6). The PS of known elements cannot be naively extrapolated. The common discussion of the PS in textbooks of general, inorganic, and physical chemistry needs revision. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

Rayleigh's distillation law and linear hypothesis of isotope fractionation in thermal ionization mass spectrometry

The relationship which exists between Rayleigh's distillation law and linear models of instrumental isotopic fractionation in thermal ionization mass spectrometry is shown. If the process of isotope fractionation in the mass spectrometer source occurs in terms of a Rayleigh's distillation, and, within the range of mass of isotopes of the element, the vapor/residue distribution coefficient is a linear function of mass with a slope which is sufficiently small in absolute value, then the linear hypothesis of isotope fractionation is fulfilled.The model shows that the fractionation factor per amu, defined as the instantaneous difference between the measured and true values of the isotope ratio, per unit of measured/true value and per unit of mass difference between the two isotopes which define the ratio, can be interpreted as a function of two parameters: the residual mass fraction of the sample on the filament, and the rate of change of the distribution coefficient with mass. These two parameters can be calculated and, in particular, the value of the residual mass fraction of the sample when the measured values of the isotopic ratios coincide with the actual values can be calculated as a function of the rate of change with mass of the distribution coefficient.A linear model of instrumental isotopic fractionation can be derived from the exponential hypothesis of fractionation, which can be also interpreted in terms of a Rayleigh's distillation process, but where mass is an exponential function of the distribution coefficient.Experimental results of instrumental isotopic fractionation (up to 1% amu⁻¹) of strontium in NIST standard reference material 987, loaded as a nitrate on a single tungsten filament, can be interpreted in terms of the linear models of isotope fractionation (and therefore of Rayleigh's distillation law) within experimental error. They show: (i) changes in the vapor/residue distribution coefficient with mass in the range −0.006 to −0.004 amu⁻¹; (ii) approximately constant rates of sample consumption in the range of residual mass fraction from 1 to 0.3–0.25, which are between 0.05 and 0.13% min⁻¹; (iii) values of the residual mass fraction of the sample, when the measured values of the isotopic ratios coincide with the true ones, between 0.3668 and 0.3671, which correspond to sample consumption of 63.3%.Since the linear hypothesis of fractionation is fulfilled, the values of isotopic ratios of strontium in the standard material can be determined. The global weighted averages of the weighted averages of the results obtained in eleven runs in which ⁸⁶Sr, ⁸⁷Sr and ⁸⁸Sr peaks were sampled are as follows: ⁸⁶Sr/⁸⁸Sr = 0.119445 ± 0.000053, ⁸⁷Sr/⁸⁶Sr = 0.71016 ± 0.00019, and ⁸⁷Sr/⁸⁸Sr = 0.084826 ± 0.000040.     

Calculation of the mass transfer coefficient with a chemical reaction in a gas-liquid system

A solution of the problem of mass transfer in a turbulent boundary layer has been obtained with a first-order chemical reaction occurring in the liquid phase. The dependence of the enhancement factor for absorption and of the mass transfer coefficient on the model parameters can be used for building up a hierarchic model of the gas-liquid reactor.

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稳定图的测定与矩形离子阱质谱性能分析

从理论上讲, 离子阱质谱仪的性能是由阱内电场分布决定的,而电场分布又是由组成离子阱的电极几何结构和离子阱工作电压决定的. 对于矩形离子阱, 即使不考虑其几何结构的偏差, 其阱内的电场分布一般也很复杂. 在矩形离子阱内, 除四极电场外, 还包含多种成分的其他各种高阶场, 它们直接影响离子在阱内的运动轨迹和离子阱质谱的性能. 由于各种电场成分对离子阱内离子运动的影响非常复杂, 还很难从数学上给出精确的解析解, 使得目前从理论上还无法预测高阶场成分对质谱性能的影响. 本工作通过测定不同几何结构的矩形离子阱的稳定图, 从实验上比较了不同场半径, 即不同电场分布条件下的离子阱质谱性能的差别. 实验中, 通过改变离子阱的几何比例结构, 详细测定了不同结构的矩形离子阱的稳定图特征, 并与实验测得的质谱分析结果进行比较. 同时, 我们还详细介绍了矩形离子阱质谱的稳定图的测定方法, 并根据得到的不同情况下的稳定图结构分析了离子阱的质谱性能. 研究结果表明： 可以通过比较试验得到的稳定图结构来判断其离子阱质谱仪的性能如质量分辨能力等. 此外, 实验结果还发现： 对于y方向拉伸结构的矩形离子阱, 其实验绘制得到的是不完整的稳定图. 但根据稳定图边界的特点, 通过采用四极直流电压调制的方法, 可以对y方向拉伸结构的矩形离子阱的性能进行改善, 极大地提高了阱的质量分辨能力.     

响应性凝胶与非线性化学反应相互作用研究进展

本文综述了响应性凝胶与非线性反应动力学相互作用的研究进展,从实验及理论方面评述了pH振荡器中响应胶的振荡行为、P(NIPAAm-co-Ru(bpy)3)共聚凝胶中Belousov-Zhabotinsky(BZ)化学反应引起的膨胀-收缩振荡、行波和纳米制动器的制备及生理条件下凝胶自振荡行为,成为化学能向机械能转化的智能材料领域中活跃的研究方向; 同时凝胶的响应性作用于非线性化学反应可控制反应动力学的分岔行为.最后对该研究领域的发展方向和应用前景进行了展望.     

Group of symmetry of the periodic system of chemical elements

The concurrence of the group of symmetry of the periodic system of elements with the group of dynamical symmetry of a hydrogenlike atom is employed in the theoretical investigation of atoms. The character of the degeneracy of the eigenvalues of a hydrogenlike atom Hamiltonian, without changing its eigenfunctions, was changed by introducing into this Hamiltonian a term which violates the symmetry in relation to transformations from the subgroup O(4) of the group SO(4, 2). In consequence, it was realized that such “reorganization” of the states of a hydrogenlike atom, which form a representation of the group SO(4, 2), effects the splitting of this representation into finite‐dimensional multiplets, first of which are in full agreement with the experimentally observable composition of electron shells of atoms, and retains the physical meaning of quantum numbers that define electron states. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 72: 499–508, 1999