三分子反应在一维介质上的动力学行为

提出了一种简明的理论分析方法，求出了三分子反应Ａ＋２Ｘ←→３Ｘ在一维介质上的动力学行为的解析解，并成功地解决了该反应动力学行为对初始条件的依赖性问题。还通过数值模拟证实了提出了理论方法的正确性。     

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。     

非线性化学反应在低维介质中的动力学行为

通过数值模拟对３分子自催化反应Ａ＋２Ｘ＝３Ｘ在一维和二维介质中的动力学行为进行了研究。发现在一维和二维情形下，如果施以不同的微观反应规则，该反应的渐近行为既可能偏经典化学反应动力学（平均场理论）所预言的平衡极限行为，也可能与之一致。     

微波干介质反应

微波干介质反应是一门新兴的绿色化学合成技术,已成功地应用于多种有机反应。运用微波干介质反应技术进行一步法或多组分反应研究是当前库合成的研究热点。无溶剂反应具有成本低、操作简便、选择性好等优点,是绿色化学的重要研究方向之一。本文主要介绍了官能团的转化、氧化、还原、杂环化合物的合成、缩合及多组分反应等微波干介质反应。     

氟分子与乙烯反应的直接动力学模拟

Direct dynamics within the framework of DFT was used to study the long-time puzzling mechanism of the reaction between F2 and ethylene. Three types of reactions are widely accepted : F atom elimination reaction, HF elimination reaction and the addition reaction. Several reaction mechanisms have been proposed, but only the radical mechanism can reasonably explain the initial reaction at low temperature. In this article, our calculations support the radical mechanism and the reaction mechanisms of the three reactions, and they are described in detail by trajectory simulation. The reactions in a cryogenic matrix with the reaction mechanism were also discussed.     

关于反应分子数定义的讨论

There are two different views on the definition of reaction molecularity in physical chemistry textbooks and related literatures so far. We give a deep discussion about this conception herein. Starting with the development of chemical kinetics and the definition of elementary reaction and state-state reaction, we clarify that elementary reaction and state-state reaction are the conceptions belonging to macro-and micro-systems, respectively, and reaction molecularity is also belonging to micro-conception. Based on this conclusion, we think that the more reasonable definition of reaction molecularity should be \"the number of chemical particles that take part in a state-state reaction (or an elementary chemi-physical reaction) as a reactant\".     

分子反应动力学在中国的兴起

分子反应动力学是化学学科中一个崭新活跃而重要的分支。虽然其难度很大,可是在短短的20年中,却得到了迅猛的发展。各发达国家都投以巨资,使得这一领域蓬勃地开展。美国著名大学的化学系几乎全都开展这方面的研究,他门推陈出新,竞相开拓出分子反应动力学最新的领域。加州理工学院 A.Zewail 教授就在当年诺贝尔奖获得者 L.Pauling 工作过     

双组份稀土与三溴偶氮胂平行反应的动力学分析

根据三溴偶氮肿(TBA)的离解常数及其稀土配合物的组成比,确定了它与稀土间的总包反应。研究了以La~(3+)、Gd~(3+)、Ho~(3+)为代表的轻、中、重单一稀土与TBA配位反应的经验速率方程、速率常数和实验活化能。研究表明,用TBA对双组份稀土进行速差动力学分析的前提是:应符合准级数的平行反应机理,不形成多核配合物及共显色效应可忽略不计。     

均相化学反应体系的Monte-Carlo计算机模拟

根据反应速率的碰撞理论及反应独立共存原理,对包括振荡反应在内的均相化学反应的计算机模拟进行了探讨,在系统讨论有关Moote-Carlo模拟问题中,着重论述了模拟中分支反应与有效碰撞数的关系及计算机时间与实际反应时间的换算问题。提出了通用于各种均相化学反应的模拟算法,并成功地用于化学振荡反应机理的探讨。     

KIO_3-KSCN-H~+反应体系的非线性动力学研究

研究了 KIO3-KSCN-H+反应体系在连续搅拌流动反应器 ( CSTR)中的非线性动力学行为 .在 CSTR中 ,该反应体系的 Pt电极电位显示出持续振荡现象 ,振荡的浓度范围非常宽 .通过酸度及各种金属离子对体系振荡行为影响的研究发现 ,对振荡体系具有催化作用的可能物种是 H+ 离子而不是金属离子     

3，5-二硝基水杨酸铈的制备﹑热分解机理及非等温反应动力学

用3,5-二硝基水杨酸和硝酸铈为原料,制备了3,5-二硝基水杨酸铈(CeDNS),采用元素分析、X射线荧光光谱和FTIR对其进行了表征。用TG和DSC以及变温固相原位反应池/傅立叶变换红外光谱(RS-FTIR)联用技术研究了3,5-二硝基水杨酸铈的热分解机理,对主放热反应的DSC峰进行了数学处理,计算得到了动力学参数和动力学方程。结果表明,3,5-二硝基水杨酸铈的分解反应共有3个阶段,其中包括一个脱水吸热过程和一个主放热过程,主分解反应发生在第2阶段,主分解反应的表观活化能E_a与指前因子A分别为：159.17 kJ·mol^-1 和10^11.33 s^-1,主分解阶段的反应机理服从Avrami-Erofeev方程(n=1/4),主分解反应的动力学方程为：dα/dt=10^11.33×4(1-α)[-ln(1-α)]^3/4e^-1.92×104/T。     

富钛氧化物体系中TiO1.5的氧化与反应耦合

本文用EMF及化学分析方法研究了富钛（25（wt）％TiO2）氧化物熔渣体系中低价钛氧化的动力学规律,探讨了添加铁氧化物对改善熔渣氧传输动力学条件的机制,及渣中低价钛的氧化与相关耦合反应的关系。     

Imidazole-Catalyzed Henry Reactions in Aqueous Medium

2-Nitroalkanols can be efficiently synthesized using imidazole as a mild Lewis basic catalyst in aqueous medium as well as in organic solvents. The products have been found in good yields without purification (> 95% purity by ¹H NMR) for aromatic aldehydes. Additionally, the very mild reaction conditions prevent the particular side reactions such as aldol condensation, Cannizzaro reaction, or dehydration of the 2-nitro alcohols into nitro alkenes even if aromatic aldehydes are used. This report satisfies the criteria for green synthesis in terms of reaction medium and recycling of the catalyst (imidazole).     

Thermal Behavior,Nonisothermal Decomposition Reaction Kinetics of Mixed Ester Double-base Gun Propellants

The thermal decomposition behavior and nonisothermal reaction kinetics of the double-base gun propellants containing the mixed ester of triethyleneglycol dinitrate（TEGDN） and nitroglycerin（NG） were investigated by thermogravimetry（TG） and differential thermogravimetry（DTG）, and differential scanning calorimetry（DSC） under the high-pressure dynamic ambience. The results show that the thermal decomposition processes of the mixed nitric ester gun propellants have two mass-loss stages. Nitric ester evaporates and decomposes in the first stage, and nitrocellulose and centralite II（C2） decompose in the second stage. The mass loss, the DTG peak points, and the terminated temperatures of the two stages are changeable with the difference of the mass ratio of TEGDN to NG. There is only one obvious exothermic peak in the DSC curves under the different pressures. With the increase in the furnace pressure, the peak temperature decreases, and the decomposition heat increases. With the increase in the content of TEGDN, the decomposition heat decreases at 0.1 MPa and rises at high pressure. The variety of mass ratio of TEGDN to NG makes few effect on the exothermic peak temperatures in the DSC curves at different pressures. The kinetic equation of the main exothermal decomposition reaction of the gun propellant TG0601 was determined as： dα/dt=1021.59（1-α）3e-2.60×104/T. The reaction mechanism of the process can be classified as chemical reaction. The critical temperatures of the thermal explosion（Tbe and Tbp） obtained from the onset temperature（Te） and the peak temperature（Tp） are 456.46 and 473.40 K, respectively. ΔS≠, ΔH≠, and ΔG≠ of the decomposition reaction are 163.57 J·mol^-1·K^-1, 209.54 kJ·mol^-1, and 133.55 kJ·mol^-1, respectively.     

Probing the Limits of Selectivity in a Recognition‐Mediated Reaction Network Embedded within a Dynamic Covalent Library

Two recognition‐mediated reaction processes operating through reactive binary complexes drive resolution of a 24‐component dynamic covalent library, assembled from individual aldehydes and nucleophiles. The effectiveness of the library resolution and selective amplification of one recognition‐enabled species over another is limited by the difference in the rates of the recognition‐mediated reactive processes and the strength of the recognition processes employed in the dynamic system.     

具有1,2-二苯基乙醇结构化合物的异常消除反应研究

报道了4个具有1,2-二苯基乙醇结构的化合物在酸性条件下发生消除反应, 得到未遵循Saytzeff规则的烯烃; 而在SOCl2/DMF条件下, 先氯代再消除则可获得一对双键位置异构的烯烃异构体. 通过计算机模拟, 采用Gaussian 98软件, B3LYP/6-31G方法对两种异构体进行了能量优化, 计算了它们的能量, 推测这类具有1, 2-二苯基乙醇结构化合物在酸性条件下的异常消除反应为动力学主导产物的反应.     

不同离子液体反应介质在生物催化中的应用研究进展

离子液体(ILs)因其独特物理化学性质成为新型反应溶剂和催化剂,在生物催化反应中有着广阔的应用前景。根据不同ILs的水溶性,其与水可形成4种反应介质,即微水ILs单相体系、亲水性ILs-水单相体系、疏水性ILs-水两相体系和ILs微乳液体系。本文分别介绍了不同ILs反应体系中生物催化剂的催化活性、稳定性和选择性,综述了这些体系中的生物催化反应研究进展。