浆态搅拌釜中FT合成的动力学研究

在自制的５００ｍｌ浆态搅拌器采用模试鼓泡浆反应器无载体沉淀Ｆｅ－Ｃｕ－Ｋ催化剂进行了ＦＴ合成动力学研究。在２５０－２８０℃，１．５ＭＰａ，１－２．５１／ｇｌａｔ．ｈ和Ｈ２／ＣＯ＝１．０９范围内，排除传质效应的条件下，得到了本征动力学数据，实验结果用线性参数估计方法按照速率常数ｋ，活化能Ｆ     

Fe－Mn－K催化剂FT合成反应的研究

研究了Ｆｅ－Ｍｎ－Ｋ催化剂ＦＴ合成动力学及产物分布规律，并探讨了反应条件对（ＣＯ＋Ｈ＿２）转化率及α－己烯／正己烷比的影响。结果表明，该催化剂的产物分布需用两个α才能较好地描述；反应温度及反应气氛下Ｈ＿２／ＣＯ比对α－己烯／正己烷比具有较大影响：最后获得的动力学方程为：－ｒ＿（Ｈ＿２＋ＣＯ）＝ａＰ＿（ＣＯ）Ｐ＿（Ｈ＿２）／（Ｐ＿（ＣＯ）＋ｂＰ＿（Ｈ＿２Ｏ）），从活化能的角度看，该粒度催化剂存在着内扩散效应。     

催化动力学光度法测定微量钴的研究

在ｐＨ＝４．０的ＨＡｃ－ＮａＡｃ介质中，在避光条件下，钴对无色的Ｆｅ（Ⅲ）－联吡啶配合物还原成红色的Ｆｅ（Ⅱ）－联吡啶配合物有较强的催化作用。据此本文建立了微量钴的新催化动力学光度法，对钴的线性范围为０～１．０μｇ／ｍＬ Ｃｏ，检测限为０．０１８μｇ／ｍＬ。本法选择性较好，多数离子均允许大量存在。本法测定了维生素Ｂ１２及分子筛中的钴，获得满意的分析结果。并对钴的催化机理作了初步探讨。     

合成CFC-12替代物HFC-134a的CrF3/AlF3催化剂的研究

考察了不同反应条件下ＨＣＦＣ－１３３ａ与ＨＦ在ＣｒＦ３／ＡｌＦ３催化剂作用下生成ＨＦＣ－１３４ａ的反应性能。需用ＧＣ－ＦＴＩＲ方法鉴定了产物的组成，探讨了副产物形成的原因，并进行了催化剂的稳定性试验。结果表明在ＨＦ／ＨＣＦＣ－１３３ａ流量比为１０和３５０℃和条件下，得到了较高的转化率和选择性。     

催化动力学光度法测定水中微量锰

１引言研究了锰（Ⅱ）催化亮绿ＳＦ褪色反应的动力学特性。在ＮａＡｃ－ＨＡｃ介质中，锰（Ⅱ）对高碘酸钾氧化该试剂的褪色反应具有强烈催化作用，其褪色反应速率与锰（Ⅱ）的浓度在一定范围内呈良好的线性关系。详细研究了亮绿ＳＦ催化动力学光度法测定微量锰（Ⅱ）的条件，建立了测定微量锰（Ⅱ）的新方法。有关文献中催化动力学光度法测定锰（Ⅱ）的检出限大多为１０－１０ｇ／ｍＬ，本方法的检出限为６．０×１０－１１ｇ／ｍＬ，选择性较好，方法相对标准偏差２．５％，用于测定水样中的锰，结果满意。２实验部分２．１主要试剂和仪器…     

本体溶液法合成超高分子量聚苯乙烯

对２，３－二氰基－２，３－二苯基丁二酸二乙酯引发苯乙烯本体溶液聚合，合成超高分子量聚苯乙烯的宏观动力学进行了研究。结果表明，这种引发剂在苯乙烯中引发聚合性能温和，在一定条件下，随反应时间的增长，聚合产物的分子量不断增高，可形成超高分子量聚合物。     

食品中微量铁的催化动力学光度分析法

在酸性条件下，氯酸钾能氧化二甲基黄使之褪色，Ｆｅ３＋能催化该反应，且含Ｆｅ３＋量与△Ａ（△Ａ＝Ａ０－Ａ，Ａ０、Ａ分别为非催化反应与催化反应溶液的吸光度）在一定范围内呈良好的线性关系，以此为指示反应建立了一种新的测定微量Ｆｅ３＋的催化动力学光度分析法。本法具有灵敏度高、专属性强、操作简便等特点。其含Ｆｅ３＋量的测定范围为４×１０－６～１．２×１０－３ｇ／Ｌ。     

新型Mn—Fe／γ—Al2O3高温脱除H2S的研究（Ⅰ）

本文将Ｍｎ－Ｆｅ担载在γ－Ａｌ２Ｏ３上，在７７３－９８３Ｋ条件下进行了脱除Ｈ２Ｓ的研究，结果表明，此种新型的高温脱硫剂对Ｈ２Ｓ有很好的脱除效果，且有较好的再生能力。     

新催化动力学光度法测定痕量钯

在磷酸－邻苯二甲酸氢钾缓冲溶液（ｐＨ２．０）中,利用钯（Ⅱ）对次磷酸钠还原二甲苯蓝ＦＦ褪色的催化作用,建立了用斜率法测定痕量钯的新动力学分光光度法。在加入金（Ⅲ）的条件下,钯（Ⅱ）的检测下限为２．７×１０－１１ｇ／ｍＬ,线性范围为０．０４～６．０ｎｇ／ｍＬ。该法已应用于测定二次阳极泥中钯的含量。     

F－T法合成烃进展

介绍了Ｆ－Ｔ合成的发展史以及当今世界Ｆ－Ｔ合成的发展趋势。对Ｆ－Ｔ合成反应动力学和可能机理、传统的Ｆ－Ｔ合成催化剂以及现代超细粒于型（ＵＦＰ）Ｆ－Ｔ合成铁催化剂、产物分布等进行了综述。参考文献２８篇。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

关于"对‘燃料电池物理及化学性能的有限时间热力学分析方法'的讨论”答复

把有限时间热力学理论用于化学过程的研究,将会得到一系列新的结论,开展这方面的研究是很有意义的.文献[1]以燃料电池为例,在同时考虑化学反应及传热不可逆性的情况下,研究了燃料电池的性能界限,文献[2]指出了文献[1]计算化学反应及传热不可逆性而引起系统与有关环境的总熵产生率的错误以及由此而导致的结论所存在的问题,并进行了富有启发性的分析与讨论.但文献[2]对于系统与有关环境的总熵产生率的计算也是不正确的,由此得到的其它结论自然不能成立.本文将就此情况下系统与有关环境的总熵产生率的计算再次进行讨论,并给出电池功率和效率的有限时间热力学性能界限.