基于知识体系整合的元素无机化学教学改革

元素无机化学是大学化学及相关专业无机化学课程的核心内容。如何教好、学好元素无机化学的知识一直是教学工作者研究的课题。为改变教学现状，提高教学效果，培养学生的逻辑思维和科学创新能力，提出一种整合元素无机化学知识的思路，即：以化合物类型为主线对元素无机化学知识进行系统化整合，并以氧化物部分为例加以说明。     

茂基稀土胺化物与异氰酸正己酯的反应-{(MeC5H4)2Yb[OC(NPh2)N(n-hexyl)]}2的合成及表征

茂基稀土胺化物(MeCp)2YbNPh2(THF)与异氰酸正己酯(n-HexylNCO)按11摩尔比反应, 分离出产物{(MeC5H4)2Yb[OC(NPh2)N(n-hexyl)]}2. 产物经元素分析和核磁共振表征, 并测定了其晶体结构. 配合物属三斜晶系, R-3空间群, 晶胞参数为a=2.9533(11) nm, b=2.9533(11) nm, c=1.5873(6) nm, V=11.9896(80) nm3, Z=9, Dc=1.562 mg·m-3, μ=3.536 mm-1 (Mo Kα), F(000)=5670, R=0.034, Rw=0.064. 该化合物具有二个对称氧桥的双分子结构, 并存在着由氮原子向中心金属镱分子内配位而形成的三环骨架, 中心金属镱的配位数是九, 整个分子呈中心对称.     

“能源化学”本科专业建设建议

"Energy chemistry" was approved as one of the chemistry majors for undergraduate by the Ministry of Education in 2015. Based on the ideas and ways of emerging engineering education, this paper hereby proposed some of constructive suggestions on the training objectives, graduation requirements, curriculum system, teaching contents, teaching staff and conditions for development of "energy chemistry" major.     

面向化妆品产业升级的江南大学应用化学专业建设思考与实践

Based on the development prospect of cosmetics industry, the advantage of light industry characteristic and the foundation of applied chemistry in Jiangnan University, a systematic upgrading of applied chemistry was carried out through "emerging engineering education (3E)" project "upgrade and practice of chemistry-related majors of local and/or trade university responding to the social developments" supported by the Ministry of Education. On the basis of investigation and analysis, the orientation and training goal of applied chemistry were updated first, and then the curriculum system was determined and the curriculum construction is strengthened, so as to achieve more distinctive characteristics, more solid foundation and more comprehensive quality. In view of the new requirements of the 3E for talent training, some practices have been formed in the aspects of multi-disciplinary integration, multi-angle coordination and close integration to industry. Contributing the development of cosmetics industry and seizing the commanding point of science and technology from the perspective of talent training, will play a unique role in human social progress.     

Basicity and structure of 5-hydroxybenzimidazoles in nitromethane

Examination of the acid-base properties of 5-hydroxybenzimidazoles has shown them to exist in nitromethane as the 5-hydroxy-tautomers. Substituents in the 2-position have a predominantly inductive effect on the basicity of the 3-nitrogen, rationalized as in other nitrogen heterocycles by the proximity of the substituents to the reaction center.N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 117977 Moscow. The Research Institute for Intermediates and Dyes, 103787 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 421–425, February, 1992.     

Splitless injection of up to hundreds of microliters of liquid samples in capillary GC: Part II,experimental results

Sample evaporation in splitless injection of large volumes is rapid: depending on the experiment, results indicate that 200 μl of hexane, for instance, evaporates in 2–10 s, producing vapor at a rate of many hundreds of milliliters per minute. A 60 × 4 mm packed bed of 20–35 mesh Tenax TA enabled injection of 200 μl volumes of all solvents tested, and even 1 ml injections were possible provided they were performed over a period of 30 s. Retention of volatile sample components depends on the sample solvent, the injection volume, and the injection speed, but only little on the injector temperature. Losses of n-tridecane varied from hardly 15 % (when dissolved in pentane) to ca 60 % (ethyl acetate); losses of n-heptadecane were usually below 20 %. The column temperature during injection should be at least ca 20–30°C above the standard solvent boiling point.     

Correlation of the position of the bond functions in H-X with electronegativity

S type Gaussian bond functions are optimized for HF, H₂O, NH₃, and CH₄. The optimization is carried out with respect to the exponent and position in the H-X bond. The position is found to correlate well with the electronegativity of Pauling and Allred-Rochow.     

Substituent Effects on the C-C Bond Strength, 15[1] Geminal Substituent Effects, 7[2]. Thermochemistry and Thermal Decomposition of Alkyl-substituted Tricyanomethyl Compounds

The thermolysis reactions of the tricyanomethyl compounds 10a-c were studied in solution. 2,2-Dicyano-3-methyl-3-phenylbutyronitrile ( 10a ) and 2,2-dicyano-3-methyl-3-(4-nitrophenyl)butyronitrile ( 10b ) decomposed heterolytically into carbenium ions and (CN)₃C⁻ anions, while 9-methyl-9-(tricyanomethyl)fluorene ( 10c ) underwent about 11% homolytic C-C bond cleavage into 9-methyl-9-fluorenyl- and tricyanomethyl radicals. The rates of the homolysis were determined by a radical scavenger procedure under conditions of pseudozero order kinetics. From the temperature effect on the rate constants the activation parameters were determined [ΔH ( 10c ) = 155· 2 kJ mol⁻¹, ΔS ( 10c ) = 58· 5 J mol⁻¹ K⁻¹]. Standard enthalpies of formation ΔH (g) were determined for 2,2-dicyanopropionitrile ( 2 ) (422.45 kJ mol⁻¹), 2,2-dicyanohexanenitrile ( 3 ) (349.74 kJ mol⁻¹), 2,2-dicyano-3-phenylpropionitrile ( 4 ) (540.75 kJ mol⁻¹), 2-butyl-2-methylhexanentrile ( 5 ) (-133.20 kJ mol⁻¹), 2,2-dimethylpentanenitrile ( 6 ) (-45.78 kJ mol⁻¹), and 2-methylbutyronitrile ( 7 ) (2.44 kJ mol⁻¹) from the enthalpies of combustion and enthalpies of sublimation/vaporization. From these data and known Δ (g) values for alkanenitriles and -dinitriles, thermochemical increments for ΔH (g) were derived for alkyl groups with one, two, or three cyano groups attached. The comparison of these increments with those of alkanes reveals a strong geminal destabilization, which is interpreted by dipolar repulsions between the cyano groups. - From ΔH (g) of 10c and ΔH of its homolytic decomposition the radical stabilization enthalpy for the tricyanomethyl radical 1 RSE ( 1 ) = -18 kJ mol⁻¹ was determined. Thus, 1 is destabilized, in comparison with the RSEs of tertiary α-cyanalkyl (23 kJ mol⁻¹) and α,α-dicyanoalkyl (27 kJ mol⁻¹) radicals, which were recalculated from bond homolysis measurements^[4] and the new thermochemical data. This change of RSE on increasing the number of α-cyano groups is discussed as the result of the additive contributions by resonance stabilization and increasing destabilization by dipolar repulsion. The amount of the dipolar energies was estimated by molecular mechanics (MM2).