非等温反应过程中新的动力学方程

对于非等温过程中的动力学方程，正确的Arrhenius方程的温度积分应该是从T₂到T₁，但是许多动力学方程中的温度积分是从T到0 K，例如Ozawa等方程。我们的研究指出对于某些反应，这些方程中的活化能存在较大的误差，因此我们提出了一个新的动力学方程。凭借等转化率法，应用新的方程可以精确求解线性或非线性加热过程中化学反应的活化能。用新方程对2个经典反应（聚酰胺的热裂解和一水草酸钙的热分解）的研究表明：Ozawa方程的活化能有时是精确的，有时偏差太大。     

含醇溶液的热力学研究I.超额焓模型

提出了一个醇与烃混合的热力学模型，据此，得到了一个简单的超额焓方程， 它由物理和化学贡献两部分组成。这个方程具有一定的通用性，能够推广到其它含 醇溶液。方程不仅能满意地用来描述超额焓与组成间的关系，而且还能显示组分间 的相互作用。     

修正的Mark—Houwink方程及其应用

介绍了由Ｐ．Ｍａｎａｒｅｓｉ等人提出的修正的Ｍａｒｋ—Ｈｏｕｗｉｎｋ方程，该方程的新颖之处在于把特性粘数［η］与多分散性聚合物的Ｍｎ，Ｍｗ，和Ｍｚ相联系。方程中的参数不受分子量分布的影响，方程的有效性不仅经过大量具有连续性和不连续性的分子量分布的聚合物实例的检验，而且通过具体实验，指出了该方程应用于确定Ｍｎ、Ｍｗ、Ｍｚ，以及Ｍａｒｋ—Ｈｏｕｗｉｎｋ方程中Ｋ．α常数时的成功与不足之处。     

线性柱色谱分离过程的递推方程

依据非平衡热力学分离理论中的局域平衡假设和流体力学的Lagrangian描述方 法，首次提出了线性柱色谱分离过程中溶质带迁移和扩散的状态递推方程，克服了 以经典动力学为基础的塔板理论不能准确预测时变控制条件下溶质扩散的局限性。 反相色谱梯度洗脱的实验数据支持递推方程的理论预测，与基于塔板理论的预测方 法比较，状态递推方程法更具优越性。状态递推方程还为采用动态优化控制柱分离 过程奠定了基础。     

低浓度三分子双曲型反应-扩散方程的非线性理论

建立了低浓度三分子模型双曲型反应-扩散的波动方程，研究了定态的稳定性，重点研究了Turing不稳定问题，指出双曲型方程的Turing不稳定不受扩散系数不相等（Dx≠Dy）这一条件的约束，进而对方程作近似的分支分析，讨论了出现极限环的条件，最后对极限环和定态不稳定作了数值研究．     

线粒体体外代谢热动力学模型及其演化优化研究

导出了线粒体体外代谢的热动力学方程，探讨了它和指数模型的关系，将演化计算技术引入生物热化学领域，用ＭＴＤ方程和演化计算技术，对文献报导的八种鱼肝线粒体体外代谢的热动力学参数进行了全局优化。     

三组分共聚酯数均聚合度和数均分子量的计算方程

为便于生产控制以制得预定分子量的产物，根据直接酯化法合成聚对苯二甲酯乙二酯（ＰＥＴ）共聚酯的特点，综合考虑各种主、副反应，从统计观点出发，对三组分ＰＥＴ共聚酯体系的齐聚物和缩聚物，分别建立了其数均聚合度Ｘｎ和数均分子量Ｍｎ的简化和非简化计算方程．将简化Ｘｎ方程与Ｃａｒｏｔｈｅｒｓ方程进行计算比较，其结果完全相同；将简化Ｘｎ方程应用于二组分聚酯体系，其形式与传统的二组分线型缩聚物Ｘｎ方程形式相同，各Ｘｎ和Ｍｎ方程可推广应用于二组分聚酯体系和三组分以上的多组分共聚酯体系．     

静止化学反应界面：理论和验证

在静止中和反应界面的基础上，提出了静止化学反应界面的概念，导出了一些静止化学反应界面方程。这些方程显示：为了建立稳定的静止化学反应界面，正、负反应离子（比如氢离子和氢氧根离子）的迁移数必须相等。分析表明，方程的理论预测与下列事实定量吻合：（１）已建立的静止中和反应界面的实验，（２）基于Ｋｏｈｌｒａｕｓｃｈ′ｓ调整函数的计算机模拟。     

含时间变量的凝胶溶胶分配方程及其应用

在Ａａ－Ｂｂ型综聚反应的凝胶溶胶分配（ＧＳＤ）方程中引入相应的聚合反应动力学方程．模拟计算的溶胶分数（Ｓ）对反应程度（Ｐ_Ｂ，Ｐ_Ｂ＇）的关系曲线与实验结果基本吻合．利用含时间的ＧＳＤ方程，解决了非线型缩聚反应交联网络的模拟计算，给出了交联度随时间的变化曲线，也为凝胶点的计算提供了一种方法．     

原子簇离子产生的动力学方程与分布函数

由激光等离子体反应产生的原子簇分子与离子，经历了分子-离子反应的过程．本文尝试将Smoluchowski方程加以扩展，用于描述原子簇离子的生成过程．通过应用解析方法，求解不可逆聚合过程的动力学方程，推导出了原子簇离子统计分布的函数关系式，证实了实验中观察到的原子簇的统计分布规律．     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

恶臭嗅辨实验室建设探讨

针对恶臭测试的环境影响问题,提出了解决的实例方案,并对方案的要点及优缺点进行讨论,此方案在实际操作中具有较好的效果。     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。     

Summary of development of the theory of stability of colloids and thin films

In this review, the research of the author in the field of colloidal systems is summarized. The factors influencing colloidal stability are systematized and analyzed. Examples are presented to illustrate the practical utilization of the theory of stability of colloids and thin films.This review was prepared on the basis of the works of the author, which were awarded the State Premium for 1991 in the field of science and technology, chemistry section.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1708–1717, August, 1992.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

解决能源问题的新途径--光解水制氢的研究

面对日益枯竭的能源危机,氢能是一种洁净、最有前景的替代能源。目前在各种制氢的方法中光催化分解水制氢的研究最多,光解水过程中催化剂最关键,本文对利用太阳能光解水的途径、提高光催化反应效率以及光催化剂的开发研究进行了综述。