CO2与2-丁醇二元系统的高压相平衡模型

采用固定体积可视观察法测定了在323.2~353.2 K温度范围内2-丁醇在CO₂中高压相平衡数据. 运用Peng-Robinson状态方程(PR)和van der Waals-2混合规则建立了相平衡模型, 并运用Chrastil半经验方程建立了溶解度方程. 通过优化计算得到了状态方程中的模型参数, 同时得到的Chrastil溶解度方程为c=ρ^3.3617·exp(-2198.8193/T+6.5545). 二元体系的溶解热为-18.2809 kJ/mol.     

NH2(A2A1,090,423)的电子猝灭和转动态-态传能

在束 气和束 束实验条件下,详细研究了NH2(A1,090,423)自由基分别与Ar,N2,O2和NH3碰撞引起的电子态猝灭和转动态 态传能,获得了总的猝灭截面σQ (分别为≤0.17、0.26、0.30和0.48 nm2),以及相对转动态 态传能截面.利用碰撞络合物模型计算的电子猝灭截面与实验测得的截面具有基本相同的趋势,表明长程吸引势在猝灭过程中起着重要的作用.同时还发现,转动态 态传能中相对截面随着碰撞对的折合质量的减小而下降.由于NH3具有较大的偶极矩以及O2的开壳层电子结构使得猝灭截面增大,而转动态 态传能截面减小.     

阴离子树脂D02吸附2-酮基-L-古龙酸的热力学和动力学研究

应用一种新型的阴离子树脂D02直接吸附发酵液中的2-酮基-L-古龙酸.研究了D02树脂对水溶液中2-酮基-L-古龙酸的吸附热力学和吸附动力学特性.热力学研究表明,2-酮基-L-古龙酸在D02树脂上的吸附平衡数据遵循Langmuir吸附等温方程.吸附过程△G＜0,△S＞0,△H＞0,表明此吸附过程吸热,升高温度有利于吸附反应的发生.动力学研究显示,D02树脂对2-酮基-L-古龙酸的吸附过程主要受内扩散控制.     

NH2(A~2A1, 090,423)的电子猝灭和转动态-态传能

在束-气和束-束实验条件下,详细研究了NH2(A2A1,090,423)自由基分别与Ar,N2,O2和NH3碰撞引起的电子态猝灭和转动态-态传能,获得了总的猝灭截面σQ(分别为≤0.17、0.26、0.30和0.48 nm2),以及相对转动态-态传能截面.利用碰撞络合物模型计算的电子猝灭截面与实验测得的截面具有基本相同的趋势,表明长程吸引势在猝灭过程中起着重要的作用.同时还发现,转动态-态传能中相对截面随着碰撞对的折合质量的减小而下降.由于NH3具有较大的偶极矩以及O2的开壳层电子结构使得猝灭截面增大,而转动态-态传能截面减小.     

NH_2(~2A_1,090,4_(23))的电子猝灭和转动态-态传能

在束-气和束-束实验条件下,详细研究了NH_2(~2A_1,090,4_(23))自由基分别与 Ar,N2,O2和 NH3碰撞引起的电子态猝灭和转动态-态传能,获得了总的猝灭截面σQ (分别为≤ 0.17、 0.26、 0.30和 0.48 nm~2),以及相对转动态-态传能截面 .利用碰撞络合物模型计算的电子猝灭截面与实验测得的截面具有基本相同的趋势,表明长程吸引势在猝灭过程中起着重要的作用 .同时还发现,转动态-态传能中相对截面随着碰撞对的折合质量的减小而下降 .由于 NH_3具有较大的偶极矩以及 O_2的开壳层电子结构使得猝灭截面增大,而转动态-态传能截面减小 .     

La203-Ce02-Zr02热障涂层材料研究

利用DSC测定La2O3-CeO2-ZrO2(简称LCZ)粉的高温相稳定性并与YSZ进行对比,表明LCZ在室温～1300℃内没有相变;采用热膨胀分析仪对粉料的热膨胀性质进行了研究,结果显示氧化铈的添加提高了锆酸镧的热膨胀系数;扫描电镜及能谱分析得出,涂层厚度及元素分布均匀;涂层热循环寿命研究表明LCZ涂层寿命高于LZ涂层.实验结果说明LCZ粉是一种很有应用前景的热障涂层材料.     

对苯二甲酸二丙炔醇酯与C02(CO)8、M02Cp2(CO)4和RuC02(CO)11的反应

室温下,对苯二甲酸二丙炔醇酯分别与Co2(CO)8,Mo2Cp2(CO)4和RuCo2(CO)11反应,得到三个有机金属化合物[C6H4-p-(CO2CH2C2H-μ)2][Co2(CO)6]2(1)、[C6H4-p-(CO2CH2C2H)2][RuCo2(CO)9]2(2)和[(HC2CH2OCO)C6H4-p-(CO2CH2C2H-μ)][Mo2Cp2(CO)4](3).研究发现三种金属核对端炔氢的屏蔽作用依次为RuCo2(CO)9＞Co2(CO)6＞Mo2(CO)4Cp2.化合物1的晶体衍射发现,属三斜晶系,空间群PT,a=8.139(2)A,b=8.808(3)A,c=1 1.343(3)A,β=96.260(6)°,V=773.4(4)A3,Z=1,Dc=1.748g@cm-3,R=0.0513,wR=0.1266.     

[99Tcm(NO)Cl(PL)2]＋类配合物的定量构效关系

用半经验量子化学方法中的ZINDO/1对15种[99Tcm(NO)Cl(PL)2]＋类配合物的结构进行了优化，得到各种物理化学参数和电性参数，并将这些参数对心肌初始摄取值进行多元线性回归分析，得到了4个方程.利用所得方程，提出了该类配合物的心肌摄取机理主要为氧化还原反应机理.     

模拟磷矿脱镁废水中镁离子的交换动力学研究

用动边界模型积分方程描述模拟磷矿脱镁废水中Mg2＋在001×7×7型树脂上的有限浴交换动力学,得到了动力学总方程.Mg2＋的交换过程属颗粒扩散控制,表观活化能为23.45 kJ•mol－1,Mg2＋的表观反应级数为0.68.     

四种深共融溶剂的性质:密度、电导率、动力粘度及折光率

制备了四种四丁基氯化铵类深共融溶剂,包括四丁基氯化铵:丙酸[TBAC:2PA]、四丁基氯化铵:乙二醇[TBAC:2EG]、四丁基氯化铵:聚乙二醇[TBAC:2PEG]、四丁基氯化铵:苯乙酸[TBAC:2PAA].在288.15-338.15 K温度范围内,测定了它们的密度、电导率、动力粘度及折光率.讨论了温度对密度、电导率、动力粘度及折光率等性质的影响.通过经验方程估算了深共融溶剂的热膨胀系数、分子体积、标准摩尔熵及晶格能等热力学性质参数.利用Vogel-Fulcher-Tamman (VFT)方程和Arrhenius方程,将测量的电导率和动力粘度对温度拟合,得到了动力粘度和电导率随温度变化方程式.有关研究对深共融溶剂的工业化应用具有重要意义.     

Sc2MgGa2 and Y2MgGa2

Scandium magnesium gallide, Sc₂MgGa₂, and yttrium magnesium gallide, Y₂MgGa₂, were synthesized from the corresponding elements by heating under an argon atmosphere in an induction furnace. These intermetallic compounds crystallize in the tetragonal Mo₂FeB₂‐type structure. All three crystallographically unique atoms occupy special positions and the site symmetries of (Sc/Y, Ga) and Mg are m2m and 4/m, respectively. The coordinations around Sc/Y, Mg and Ga are pentagonal (Sc/Y), tetragonal (Mg) and triangular (Ga) prisms, with four (Mg) or three (Ga) additional capping atoms leading to the coordination numbers [10], [8+4] and [6+3], respectively. The crystal structure of Sc₂MgGa₂ was determined from single‐crystal diffraction intensities and the isostructural Y₂MgGa₂ was identified from powder diffraction data.     

Electrochemical study of (NEt4)2Cl2FeS2MoS2 and (NEt4)2Cl2FeS2MoS2FeCl2

Summary The ability of [MoS₄]^2–, anions to be used as ligands for transition metal ions has been widely demonstrated, especially with Fe²⁺. The present study has been restricted to linear complexes such as (NEt₄)₂ [Cl₂FeS₂MoS₂] and (NEt₄)₂[Cl₂FeS₂MoS₂FeCl₂]. Their electrochemical properties are described: upon electrochemical reduction, these compounds yield MoS₂, as a black precipitate, and an iron complex in solution, assumed to be [SFeCl₂]^2–. The electrochemical reduction goes through two electron transfers, coupled with the breakdown of the molecular skeleton: a DISPl and an ECE mechanism. Depending on the solvent, the following equilibrium may be observed: [Cl₄Fe₂MoS₄]^2–[Cl₂FeMoS₄]^2–+FeCl₂. The equilibrium constant, K_D, was evaluated by differential pulse polarography. K_D is tightly related to the donor number of the solvent.     

The alkali hypophosphites KH2PO2, RbH2PO2 and CsH2PO2

The structures of the hypophosphites KH₂PO₂ (potassium hypophosphite), RbH₂PO₂ (rubidium hypophosphite) and CsH₂PO₂ (caesium hypophosphite) have been determined by single‐crystal X‐ray diffraction. The structures consist of layers of alkali cations and hypophosphite anions, with the latter bridging four cations within the same layer. The Rb and Cs hypophosphites are isomorphous.     

Zur Kenntnis der Dialkalimetalldichalkogenide β-Na2S2, K2S2, α-Rb2S2, β-Rb2S2, K2Se2, Rb2Se2, α-K2Te2, β-K2Te2 und Rb2Te2

On Dialkali Metal Dichalcogenides β-Na₂S₂, K₂S₂, α-Rb₂S₂, β-Rb₂S₂, K₂Se₂, Rb₂Se₂, α-K₂Te₂, β-K₂Te₂ and Rb₂Te₂ The first presentation of pure samples of α- and β-Rb₂S₂, α- and β-K₂Te₂, and Rb₂Te₂ is described. Using single crystals of K₂S₂ and K₂Se₂, received by ammonothermal synthesis, the structure of the Na₂O₂ type and by using single crystals of β-Na₂S₂ and β-K₂Te₂ the Li₂O₂ type structure will be refined. By combined investigations with temperature-dependent Guinier-, neutron diffraction-, thermal analysis, and Raman-spectroscopy the nature of the monotropic phase transition from the Na₂O₂ type to the Li₂O₂ type will be explained by means of the examples α-/β-Na₂S₂ and α-/β-K₂Te₂. A further case of dimorphic condition as well as the monotropic phase transition of α- and β-Rb₂S₂ is presented. The existing areas of the structure fields of the dialkali metal dichalcogenides are limited by the model of the polar covalence.     

Formal [(2+2)+2] and [(2+2)+(2+2)] nonconjugated dienediyne cascade cycloadditions

[reaction: see text] Fluoranthene 2 and heptacycle 3 are easily accessible from the reaction of diyne 1 and norbornadiene (NBD) in the presence of the rhodium catalyst. The unusual [(2+2)+(2+2)] adduct 3 was confirmed by the X-ray crystal structure analysis.     

Crystal Structures of [Bu2Sn(O2PPh2)2], [Ph2Sn(O2PPh2)2], and [PhClSn(O2PPh2)OMe]2. Raman Spectra of [Ph2Sn(O2PPh2)2] and [PhClSn(O2PPh2)OMe]2

[(n‐Bu)₂Sn(O₂PPh₂)₂] ( 1 ), and [Ph₂Sn(O₂PPh₂)₂] ( 2 ) have been synthesized by the reactions of R₂SnCl₂ (R=n‐Bu, Ph) with HO₂PPh₂ in Methanol. From the reaction of Ph₂SnCl₂ with diphenylphosphinic acid a third product [PhClSn(O₂PPh₂)OMe]₂ ( 3 ) could be isolated. X‐ray diffraction studies show 1 to crystallize in the monoclinic space group P2₁/c with a = 1303.7(1) pm, b = 2286.9(2) pm, c = 1063.1(1) pm, β = 94.383(6)°, and Z = 4. 2 crystallizes triclinic in the space group , the cell parameters being a = 1293.2(2) pm, b = 1478.5(4) pm, c = 1507.2(3) pm, α = 98.86(3)°, β = 109.63(2)°, γ = 114.88(2)°, and Z = 2. Both compounds form arrays of eight‐membered rings (SnOPO)₂ linked at the tin atoms to form chains of infinite length. The dimer 3 consists of a like ring, in which the tin atoms are bridged by methoxo groups. It crystallizes triclinic in space group with a = 946.4(1) pm, b = 963.7(1) pm, c = 1174.2(1) pm, α = 82.495(6)°, β = 66.451(6)°, γ = 74.922(6)°, and Z = 1 for the dimer. The Raman spectra of 2 and 3 are given and discussed.     

Die Photoionenspektren von SCl2, S2Cl2 und S2Br2

Photoionization Mass Spectra of SCl₂, S₂Cl₂, and S₂Br₂ Photoionization mass spectra of SCl₂, S₂Cl₂, and S₂Br₂ have been measured. Heats of formation, bond energies, and ionization potentials of fragments have been calculated from appearance potentials.