线性升温条件下纳米ZnSe的生成动力学

用非等温TG-DTG技术,在5.0、10.0、15.0和20.0 K•min－1 4个不同线性升温条件下,研究了从配合物ZnSe(C2H8N2)制备纳米ZnSe的过程动力学.结果表明: 该过程为三维扩散机理；机理函数为反Jander方程, f(α)＝ ，G(α)＝ ；表观活化能E=209.61 kJ•mol－1,指前因子A=1015.7 s－1,动力学方程为 ,并用结果解释了实验现象.初次报导了纳米ZnSe在420 ℃左右氧化为粒度低于40 nm的纳米ZnO.     

水溶性封闭异氰酸酯单体的解封动力学

采用热失重分析(TGA)法研究了水溶性封闭型异佛尔酮二异氰酸酯(IPDI)的热分解过程, 利用傅里叶变换红外光谱法(FTIR)考察了谱图中40 与140 ℃两种温度下的异氰酸酯特征峰. TGA与FTIR的结果表明失重阶段即对应封闭异氰酸酯的解封闭反应. 用Friedman-Reich-Levi (FRL)和Flynn-Wall-Ozawa (FWO)两种动力学模型研究了解封反应的表观活化能E, 所得平均表观活化能分别为125.0和124.5 kJ·mol-1. 采用双等双步法对解封过程进行表观机理函数判断, 结果符合Jander方程, 反应机理为三维扩散, 结合FWO方程确定了反应级数n和指前因子对数lnA的范围.     

EDTA溶液中稀土离子在大孔树脂内的扩散

本文研究了EDTA溶液中稀土在大孔树脂内的扩散,用同位素交换法测定了ce,Tb、Yb的有效粒内自扩散系数(D_e)。D_e值受外部溶液浓度的影响。应用Kataoka双分散大孔扩散方程将D_e值分解为孔道扩散系数D_p和固相扩散系数D_g,表明该方程可用于描述大孔树脂的动力学过程。D_e随树脂粒度增大而增加,D_p远大于D_e,D_g接近于D_e,固相扩散是控制离子在大孔树脂扩散速率的决定步骤。     

室温固-固反应示例

室温固固反应示例陈天牛忻新泉（南京大学配位化学研究所江苏２１００９３）固相反应由于扩散速度的限制，通常认为必须在高温下进行［１］，我们发现某些固相反应不仅在室温或近室温的条件下可以发生［２］，而且可以迅速完成［３］。这里介绍一个在室温（大约２０℃）...     

多孔离子交换树脂内Eu^3＋离子的分步扩散

用同位素交换法研究了Ｅｕ＾３＋离子在Ｄ７２和Ｄ７５１树脂内的扩散过程。应用分步孔道扩方程将粒内有效扩散系数Ｄｃ分解为孔道扩散系数Ｄｐ和固相扩散系数Ｄｇ，表明该方程可用于描述多忆树脂内的动力学过程。实验表明Ｄｃ、Ｄｐ、Ｄｇ均随反应温度的升高而增大。     

固相反应中扩散动力学方程的新探讨

通过对г~NHCTJINHT方程中把э~c/э~r作为产物层增厚速率的基础作出分析,对由扩散控制的固相反应中扩散浓度与时间的关系作了进一步探讨, 提出产物层增厚速率应建立在Fick第二定律的基础上, 并导出了新的扩散动力学方程。     

稀土离子在多孔阳离子交换剂内的扩散动力学

研究了稀土离子在Amberlyst15、D001、XN1010多孔树脂内的自扩散。结果表明,扩散过程遵循二级分散扩散机制。用粒内扩散方程求算了有效粒内扩散系数e,将e分解为树脂孔道扩散系数p及树脂固相扩散系数s,p与该离子在外部溶液中的自扩散系数相近,而s接近于与实验用的多孔树脂交联度相同的凝胶树脂内的自扩散系数值。     

内扩散对煤和石油焦水蒸气气化反应性能的影响

以内蒙褐煤、神府烟煤、遵义无烟煤和石油焦为研究对象,借助热重分析仪,进行了水蒸气气化动力学研究,得到了4种样品焦的本征动力学方程,分析了水蒸气分压和粒径对气化反应的影响。基于幂函数模型得到的动力学参数,结合气固催化理论,提出了计算内扩散效率因子(η)的方法。计算效率因子(ηcal)和实验效率因子(ηexp)的对比结果表明,使用该方法得到的内扩散效率因子可以用于定量评估水蒸气气化反应中内扩散过程的影响程度。     

一种确定煤基吸附剂内各扩散系数的简易方法

多孔介质内的扩散有分子扩散和表面扩散两种。在吸附温度较高时 ,表面扩散可忽略 ,而在温度较低的吸附过程中 ,两种扩散均须考虑。Ｓｃｈｎｅｉｄｅｒ和Ｓｍｉｔｈ[1 ] 曾用色谱法探讨了一种计算扩散系数的方法。他们认为等温吸附呈线性变化 ,引入了曲折系数 ,计算出分子扩散系数 (下称气相扩散系数 ) ,表面扩散系数 (下称吸附相扩散系数 )则由综合扩散系数减去分子扩散系数得到。文献 [2 ]则认为吸附过程非线性变化 ,服从Ｆｒｕｎｄｌｉｃｈ方程或Ｌａｎｇｍｕｉｒ方程。从质量平衡方程得出相对吸附量方程 ,再求出各扩散系数。前一种方法将…     

D-101大孔吸附树脂对黄花蒿黄酮的吸附热力学和动力学研究

通过静态吸附实验,研究了D-101大孔吸附树脂对黄花蒿黄酮的吸附热力学和动力学过程。结果表明,当温度在298~318K和在实验研究浓度范围内,D-101大孔吸附树脂对黄花蒿黄酮的吸附符合Freundlich等温吸附方程;ΔG0,吸附过程能自发进行;ΔH0,为放热过程;ΔS0,D-101大孔吸附树脂吸附黄花蒿黄酮的作用大于水的解吸过程,导致熵减。分别采用准一级动力学方程、准二级动力学方程和粒内扩散动力学模型探讨其吸附特性,研究结果表明,吸附过程符合准二级动力学方程,粒内扩散与膜扩散交互控制黄花蒿黄酮在D-101大孔吸附树脂上的吸附。     

A simulation of the mass‐transfer effects on the kinetics of solid–gas reactions

A theoretical analysis of the influence of mass‐transfer effect on the kinetic of solid–gas reactions has been carried out by assuming that the partial pressures of the gases generated in the reaction are proportional to the reaction rate. The influence of mass‐transfer phenomena on the apparent activation energy, calculated by the isoconversional methods of Friedman, and on the reaction model is discussed. In the present study, simulated nonisotherm, isotherm, and controlled rate thermal analysis (CRTA) data have been used. Master plots based on the differential forms of the kinetic equations describing solid‐state reactions have been employed by using the concept of the generalized time (θ), introduced by Ozawa; this permits the application of these master plots to the kinetic analysis of reactions whatever the type of temperature program used for recording the experimental data. It has been shown that when the simulated mass‐transfer effect is present the variable effective activation energy E remains nearly constant while the reaction model approaches zero order. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 217–222, 2008     

The effect of external and internal diffusion on the sorption of radioactive ions by reactive cloth filter: Part I

In this study, a new mathematical model was suggested to account for the effect of internal and external diffusion on fluid–solid noncatalytic reactions. The special features of this model are the combination of the transport processes and the chemical reaction kinetics with the added factor due to the structural properties of the solid reactant. The model was examined theoretically and experimentally. A reactive cloth filter that separates radionuclides from radioactive waste solutions is used as a practical application for the model. Analyses of the respective rate data in accordance with another two theoretical models showed that process is controlled by the rate of the diffusion step. The external and internal mass transfer constants across the liquid film and the resin matrix were determined from the graphical representation of the proposed model. The practical validation with the theoretical results offered satisfactory agreement at most of the process stages.     

Some aspects of diffusion: fluctuations in reaction diffusion,and geometric influences in nonuniform media

Summary We deal with two diffusion problems: Space-integrated conserved entities characterizing very fast - diffusion - controlled reactions, such as time lags, etc. are universal. They are given by relationships which do not reflect the failure of the mean field hydrodynamic equations. We present another application which does not reflect this failure, for determining the surface flux via a diffusion controlled reaction producing a colored product. Another anomalous diffusion process we considered is transport through cellular materials whose cell sizes are highly nonuniform. We have analyzed the effects of extreme nonuniformity by considering fractal-like models of cellular solids. The diffusion current through these models can exhibit anomalous time-dependencies which are not predicted by the diffusion equation. In particular, it is shown that the initial diffusion current can be characterized by a power-law dependence on the time. Furthermore, the exponent of the power law is given in terms of the distribution of cell sizes in the fractal-like cellular solid.     

Temperature-resolved X-ray diffractometry as a thermoanalytical method

Development and experimental setup of the time-, and temperature -resolved X-ray powder diffractometry are described. This method allows far deeper insight into solid state reactions than conventional thermoanalytical methods like differential scanning calorimetry (DSC) or thermogravimetry. As an example, the dehydration of caffeine hydrate was investigated. We found that in earlier stages the reaction is nucleation controlled, whereas for higher extent of reaction diffusion limitation becomes rate-controlling.     

氧化锌颗粒脱硫中固体扩散的动力学分析

用电子探针显微分析 (EPMA)对ZnO基脱硫剂的脱硫颗粒径向硫分布行为进行了考查 ,对颗粒最外层粒子的实验结果分别用未反应收缩核模型及改良收缩核模型进行了动力学处理 ,给出了固体扩散活化能的参数估值。通过与热重研究的比较 ,进一步证实了固体粒子扩散的作用。     

Numerical solution of nonlinear and non-isothermal general rate model of reactive liquid chromatography

Abstract

A nonlinear general rate model (GRM) of liquid chromatography is formulated to analyze the influence of temperature variations on the dynamics of multi-component mixtures in a thermally insulated liquid chromatographic reactor. The mathematical model is formed by a system of nonlinear convection–diffusion reaction partial differential equations (PDEs) coupled with nonlinear algebraic equations for reactions and isotherms. The model equations are solved numerically by applying a semi-discrete high-resolution finite volume scheme (HR-FVS). Several numerical case studies are conducted for two different types of reactions to demonstrate the influence of heat transfer on the retention time, separation, and reaction. It was found that the enthalpies of adsorption and reaction significantly influence the reactor performance. The ratio of density time heat capacity of solid and liquid phases significantly influences the magnitude and velocity of concentration and thermal waves. The results obtained could be very helpful for further developments in non-isothermal reactive chromatography and provide a deeper insight into the sensitivity of chromatographic reactor operating under non-isothermal conditions.     

XRD谱研究扩散控制的固-固相反应

很多分子固体和低维固体在室温或低热温度条件下可发生固相反应^[1,2],甚至可以在短时间内完成^[3,4].我们已成功地用低热固相合成法合成了200多个化合物,其中大多数为结构新颖的原子簇化合物^[5～7].     

A model for the propagation of a redox reaction through microcrystals

Chronoamperometry of reversible redox reactions with the insertion of cations into solid particles immobilised at an electrode surface is analysed theoretically using a semiinfinite planar diffusion model. A coupled diffusion of electrons and ions within the crystal lattice is separated in two differential equations. The redox reaction is initiated by the polarisation of the three-phase boundary, where the crystal is in contact with both the electrode and the solution. From this contact line the redox reaction advances on the surface and into the crystal body by the diffusion of ions and conductance of electrons. The effects of the geometry and conductivity of the particles on the current are discussed. Received: 28 December 1996 / Accepted: 17 February 1997     

A modified model of diffusion-controlled reactions

The treatment used for diffusion-controlled reactions is extended to the case when the final jumplike step of the reagent approach differs essentially from the preceding diffusion. In terms of the model proposed it is possible to take into account, in a simple way, chemical inhomogeneity of the reagents when the in-cage reaction rate depends on the pair state (for example, on the molecular orientation). In this connection the reaction can be controlled either by the reagent intrusion into the solvation shell of the partner, or by the in-cage relaxation.     

Leaching of El-Missikat low-grade fluoritized uranium ore by sulfuric acid: mechanism and kinetic

A well-characterized low-grade fluoritized uranium samples from new occurrence in Gabal El-Missikat prospect, Eastern Desert, Egypt was subjected to sulfuric acid leaching. The effects of leaching parameters on uranium dissolution mechanism were investigated. The shrinking core model was used to model leaching reactions. The kinetics equations indicates that the reactions appear to be controlled by layer diffusion process. The activation energy for uranium dissolution was evaluated. Low activation energy value (2.54 kJ mol⁻¹) confirm the diffusion layer mechanism. The presence of fluoride ions in the solution increases the dissolution of uranium. The optimum process operating parameters were: sulfuric acid concentration: 1.5 M, solid–liquid ratio: 1:3, contact time 8 h; agitation speed rate 200 rpm; and ore particle size − 75 µm at temperature 60 °C, in the absence of an external oxidant. Under these experimental conditions, the extraction efficiency of uranium was about 91%.