氧化层结构对铀在CO/H2气氛中表面反应的影响

用Ｘ射线光电子能谱分析研究了不同氧化层结构的铀金属试样在ＣＯ和Ｈ２氢气保的表面反应。ＣＯ和Ｈ２与铀金属表层反应后，氧化物中氧含量均减少，Ｏ／Ｕ比值随气体乾气量的增加而减少。     

［Ru_6（CO）_（18）］~（2－）在NaX分子筛超笼中的合成和表征

在ＮａＸ分子筛超笼中通过ＲｕⅢ（ＮＨ３）６同ＣＯ＋Ｈ２反应合成了［Ｒｕ６（ＣＯ）１８］２－原子簇阴离子．原子簇阴离子上的羰基配体在氢气存在时具有一定的１３ＣＯ同位素交换活性．ＥＸＡＦＳ的数据表明，８０─９０％的钌原子在ＮａＸ分子筛中以［Ｒｕ６（ＣＯ）１８］２－的方式存在．分子筛笼中的原子簇阴离子在氧化气氛下解离成单核钌羰基物种Ｒｕ１（ＣＯ）２，两者的结构在氧化（Ｏ２）及还原（ＣＯ＋Ｈ２）条件下可以进行可逆转化．     

CO2在受主掺杂CaTiO3体系甲烷氧化偶联反应中的作用

本文采用了ＣＯ２程度升温脱附（ＣＯ２－ＴＰＤ）、ＣＯ２分步热脱附（ＣＯ２－ＳＴＤ）、ＣＯ２气氛中电导测量和ＣＯ２作为甲烷氧化偶联反应（ＯＣＭ）烯释气等方法，研究了在受主掺杂ＣａＴｉＯ３体系的ＯＣＭ反应中ＣＯ２的作用。受主杂质Ｌｉ＾＋，Ｍｇ＾２＋，Ａ＾３＋掺杂的ＣａＴｉＯ３的分压及吸附温度等因素有关。大部分吸附的ＣＯ２与催化剂中的Ｃａ（ＯＨ）２作用形成了ＣＯ３＾－，少部分与催化剂晶格中的活泼氧化物种     

激光促进乙醇氧化偶联反应

用ＸＲＤ、ＩＲ和脉冲ＣＯ２激光，研究了在固体Ｃｕ２（ＰＯ４）（ＯＨ）ｔ Ｐｂ３（ＰＯ４）２表面上激光促进乙醇氧化偶联的反应性能。实验结果表明：乙醇的定位化学吸附态决定着反应产物的选择性，甲基吸附态（〉Ｐ＝０…Ｈ－ＣＨ２ＣＨ２ＯＨ）反应生成１，４－丁二醇，而羟基吸附态（〉Ｐｂ…ＯＨＣＨ２ＣＨ３）则生成乙烯；固体表面构造基元的振动结构是影响激光能量利用率的主要因素，Ｃｕ２（ＰＯ４）（ＯＨ）表面Ｐ＝Ｏ键     

Pd_2X_2（dpm）_2（X＝NCO~－，CH_3CO_2~－，SCN~－，

采用ＮＭＲ方法考察了室温和低温（－７８～－６０℃）下Ｐｄ２Ｘ２（ｄｐｍ）２（Ｘ＝ＮＣＯ－，ＣＨ３ＣＯ，ＳＣＮ－和ＮＯ，ｄｐｍ＝Ｐｈ２ＰＣＨ２ＰＰｈ２）与Ｈ２Ｓ在ＣＤ２Ｃｌ２或ＣＤＣｌ３中的反应。结果表明，在Ｘ＝ＮＣＯ－和ＣＨ３ＣＯ的情况下，Ｈ２Ｓ优先与这些Ｐｄ配合物的阴离子作用生成相应的共轭酸ＨＸ和Ｐｄ２（ＳＨ）２（ｄｐｍ）２，后者在Ｈ２Ｓ存在下又进一步转化为Ｐｄ２（ＳＨ）２（ｄｐｍ）２（μ－Ｓ）；当Ｘ＝ＳＣＮ－和ＮＯ时，反应则生成结构可能为［Ｐｄ２（Ｈ）（ＳＨ）（μ－ＳＨ）（ｄｐｍ）２］＋的双核Ｐｄ配合物。     

La0.8Sr0.2MnO3和La0.8Sr0.2CoO3在γ—Al2O3上的载体效应研究

一般认为Ｌａ０．８Ｓｒ０．２ＭｎＯ３和Ｌａ０．８Ｓｒ０．２ＣｏＯ３两种钱钛矿型复合氧化物是ＣＯ氧化、碳氢（ＨＣ）化合物完全氧化和ＮＯ，还原的良好氧化物催化剂，用复合硝酸功体，制取此类负载型催化剂，负载量１５％，用二甲苯完全氧化反应作为“探针反应”，配合ＸＲＤ分析、ＢＥＴＧ只测定，发现resume     

Pd2X2（dpm）2（X=NCO^—,CH3CO2^—,SCN^—,NO^—3;dpm=Ph2PCH2PPh2）配合…

采用ＮＭＲ方法考察了室温和低温（－７８～－６０℃）下Ｐｄ２Ｘ２（ｄｐｍ）２（Ｘ＝ＮＣＯ＾－，ＣＨ３ＣＯ＾－２，ＳＣＮ＾－和ＮＯ＾－３，ｄｐｍ＝Ｐｈ２ＰＣＨ２ＰＰｈ２）与Ｈ２Ｓ在ＣＤ２Ｃｌ２或ＣＤＣｌ３中的反应。结果表明，在Ｘ＝ＮＣＯ＾－和ＣＨ３ＣＯ＾－２的情况下，Ｈ２Ｓ优先与这些Ｐｄ配合物的阴离子作用生成相应的共轭酸ＨＸ和Ｐｄ２（ＳＨ）２（ｄｐｍ）２，后者在Ｈ２Ｓ存在下又进一步转化为Ｐｄ２（ＳＨ）     

铁基高温变换催化剂制备的穆斯堡尔谱研究Ⅰ.铁氧化物前驱态的相变过程

用穆斯堡尔谱及ＸＲＤ技术对不同铁氧化物前驱态的相变过程进行了，ＦｅＣＯ３沉淀在空气中老化时被氧化分解生成ＦｅＯ（ＯＨ），经干燥、煅烧后合部转化为ａ－Ｆｅ２Ｏ３。（Ｆｅ（ＯＨ）２沉淀物在空气中老化时则转化为Ｆｅ３Ｏ４．２Ｈ２Ｏ和ＦｅＯＯＨ，两者的相对含量受Ｆｅ＾２＋的迁移速率和Ｆｅ（ＯＨ）２的氧化速度的影响。     

甲烷氧化偶联催化反应的特征

应用程序升温反应（ＴＰＲ）及质谱分析表征了ＣａＯ，Ｓｍ２Ｏ３，０．５－１０％Ｓｍ／ＣａＯ催化剂上的甲烷氧化偶联反应特性。谱图分析表明，在４００－１０００℃范围内，甲烷氧化偶联反应产物的变化呈现三个反应温度区域：（１）完全氧化区，反应主要为ＣＨ３·在催化剂表面完全氧化形成ＣＯｘ和Ｈ２：（２）偶联区，主要为ＣＨ３·的氧化和偶联竞争反应，Ｈ２谱线出现明显的低温峰；（３）氧耗尽区，反应为高温气相反应，产物     

甲烷部分氧化制合成气Ⅱ．镍系催化剂的反应性能

主要用第四周期金属元素的氧化物与Ａｌ２Ｏ３的复合氧化物催化剂上甲烷氧化的结果证实了催化剂设计中的预测：（１）催化剂首先应能解离活化甲烷，（２）催化剂要能较快地活化Ｏ２分子．只有同时满足这两个条件，催化剂才可能有较好的甲烷部分氧化活性．第四周期元素中只有镍具有这样的性质．Ｃｕ，Ｍｎ，Ｃｒ，Ｌａ，Ｃａ，Ｚｎ等氧化物的添加可明显提高Ｎｉ－Ａｌ２Ｏ３催化剂的甲烷部分氧化性能，其中Ｃｕ的助催化性能最好．催化剂ＮｉＯ－ＣｕＯ－Ａｌ２Ｏ３，ＮｉＯ－ＭｎＯ－Ａｌ２Ｏ３，ＮｉＯ－Ｃｒ２Ｏ３－Ａｌ２Ｏ３的反应活性和选择性顺序，与金属Ｃｕ，Ｍｎ，Ｃｒ上ＣＯ和Ｈ２脱附的顺序是一致的     

利用手持技术改进测定乙醇分子结构实验

利用压强传感器代替排水集气法,改进测定乙醇分子结构实验的仪器装置,并探索最佳反应条件。另外,设计两个空白实验,结合压强变化曲线对实验误差进行相关讨论。     

Neutral diterpenoids of oleoresins of five species of conifers of Transcarpathia

The compositions of the neutral diterpenoids of the oleoresins of five species of conifers growing in the Transcarpathia have been studied. It has been found that the oleoresins ofAbies alba M.,Larix decidua M., andPicea excelsa L. contain more than 50% of neutral diterpenoids. The group and qualitative compositions of the oxygen-containing diterpenoids have been determined. In the oleoresins ofAbies alba,Picea excelsa, andPicea abies tertiary alcohols — cis-abienol and isocembrol — predominate, while inLarix decidua the main component is the hydroxy ester larixyl acetate. Primary alcohols related to the resin acids have been found in all the oleoresins investigated. Features of the distribution of diterpenoids according to the species of conifers have been revealed. The results obtained are necessary for the chemotaxonomy of conifers of the family Pinceae.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodynkh Soedinenii, No. 6, pp. 812–816, November–December, 1988.     

光谱仪测试范围的扩展

由于石化行业的生产需要，其材质的使用具有多样性和广泛性，经常会出现顾客委托的测试样品的一个或几个元素跨越光谱仪现有测试程序测量范围的情况。本法通过对光谱仪测试原理的认识，根据光谱仪的测试能力及标样的采集，实现了一个或几个元素测量范围的扩展，并对其测量的影响因素进行了研究。     

Influence of viscosity of medium on processes of oxygen quenching of excited states of mesoporphyrin

The oxygen quenching rate constants for singlet and triplet excited states of the dimethyl ester of mesoporphyrin IX increase with decreasing viscosity of the medium and reach a maximum at a viscosity of approximately 0.4 mPa·sec, after which the rate constants begin to decrease. The drop in rate constant with increasing fluidity of the medium may be related to a nonequilibrium character of the elementary act in the interaction of the reactants in the solvent cage. In viscous media such as isopropyl alcohol, isobutyl alcohol, and isoamyl alcohol, the reaction radius is greater than the sum of the radii of the reacting particles. The long-range character of these processes is due to the relatively weak dependence of the quenching probability on distance.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 2, pp. 161–167, March–April, 1989.     

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.     

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.

     

物质分配系数的测定实验改进

实验教学目的是从解决实际问题出发,以实验技术训练和实验设计思想培养为目标。介绍了将单一的物质分配系数测定实验改进为综合实验,提高了实验效果及实验资源利用率。     

Effect of the Method of Modification of Zeolite X on Selectivity of Catalytic Methylation of Toluene

Theoretical and Experimental Chemistry - The effect of the method of modification of catalysts based on zeolite X by cesium and magnesium cations (ion exchange and impregnation) on the selectivity...