Determinations of combustion and formation enthalpies of C60 and C70

By using a micro-bomb calorimeter, the standard enthalpies of combustion of C₆₀ and C₇₀ have been determined to be - (25 947.1±8.5) and - (29 956.1 ± 8.9) kJ/mol respectively. A g. 1. c. analysis indicated that the amounts of residual organic solvents in the samples were very small, and their effects on the final results were negligible. The energy of combustion ofC60 determined in this work is in agreement in the uncertainty interval with that determined by means of traditional calorimeter using macro amount of sample. The enthalpies of formation of these two substances have been derived. The strain energies in the molecules of C₆₀ and C₇₀ were estimated by a bond energy scheme and by using corannulene as the model compound, the results estimated from different methods are very close. Project supported by the National Natural Science Foundation of China (Grant No. 29473143)     

Sedimentation and drying dissipative structures of colloidal silica (1.2 μm in diameter) suspensions in a glass dish and a polystyrene dish

Sedimentation and drying dissipative structural patterns formed in the course of drying colloidal silica spheres (1.2 μm in diameter) in aqueous suspension have been studied in a glass dish and a polystyrene dish. The broad ring patterns are formed within a short time in suspension state by the convection flow of water and colloidal spheres. The broad ring patterns are not formed when a dish is covered with a cap, which demonstrates the important role of the convectional flow of silica spheres and water accompanied with the evaporation of water on the air-suspension interface. The sedimentary spheres always move by the convectional flow of water, and the broad ring patterns became sharp with time. Broad ring and microscopic fine structures are formed in the solidification processes on the bases of the convectional and sedimentation patterns. Drying patterns of the colloidal suspensions containing sodium chloride are star-like ones, which strongly supports the synchronous cooperative interactions between the salt and colloidal spheres.     

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).     

Thermochemical study of aliphatic and phenyl-substituted geminal diacetates

The standard enthalpies of combustion _c H ^o of aliphatic diacetates1 and aromatic diacetates2 were measured calorimetrically. The enthalpies of vaporization _vap H ^o or sublimation _sub H ^o of1 and2 were obtained from the temperature function of the vapor pressure measured in a flow system. From _f H ^o(g) of1 and2 new values of group increments for the estimation of standard enthalpies of formation of these classes of compounds were derived. The geminal interaction energy between the geminal acyloxy groups shows no anomeric stabilization.Geminal Substituent Effects, Part 12, for part 11 see Ref. 7.     

不同添加物对表面活性剂溶液预胶束形成的影响

关于表面活性剂溶液中预胶束的形成问题已有不少报道［’－‘］．预胶束是表面活性剂溶液在浓度很稀时（远小于其临界胶束浓度（CMC》、表面活性分子所形成的一种集合体·由于一般的物理化学方法对其难于捡出，因此常被研究者忽略．文献间曾指出：预胶束形成的驱动力与胶束一样，也是疏水作用所致．因此表面活性分子的链长、头部极性、溶剂性质以及添加物的引入等因素必然会影响预胶束的形成．本工作是对添加物的引入问题所作的初步研究·。作中所研究的阴离子表面活性剂有十二烷基硫酸钠（sss）·＋”烷基；Iv酸钠（5％）和十六烷基硫酸…     

Delphinidin–Aluminum(III) Complexes in Aqueous and Non-Aqueous Media: Spectroscopic Characterization and Theoretical Study

Summary. The study of delphinidin complexation with trivalent aluminum in acidic aqueous buffered (pH 3.0 and 3.8) and methanolic solutions was performed utilizing electronic absorption spectroscopy and quantum chemical calculations. In its structure delphinidin possesses several chelating sites in competition towards aluminum(III). Molar ratio plots denoted the formation of only one aluminum(III):delphinidin complex of stoichiometry of 1:1 in both investigated media. Semiempirical calculations, performed at the restricted HF AM1 level, enabled the determination of the structural features of free delphinidin and structural modifications caused by chelation of aluminum(III). Considering the pigment molecular structure and the results of the theoretical calculations it is possible to equally implicate C3′–C4′ and C4′–C5′ hydroxyl groups as those with the predominant chelating power.     

Catalytic activity of silica in ozone formation in electrical discharges

The catalytic action of granular silica packing on ozone formation has been observed under discharge conditions. Using a glass ozonizer with a metal high-voltage electrode, at a frequency of 400 Hz it was possible to obtain much higher ozone concentrations in the presence q( silica than without packing, with the same total energy consumption. The dependence between ozone production and energy efficiency is considered, and conditions of the optimum ozonizer run are discussed. It is shown that in the all-glass ozonizer with a narrow discharge gap, the ozone concentration may be as high as 6.5% (ca. 130g O₃/m³) when silica packing is applied.     

稀土高氯酸盐-谷氨酸配合物[Pr2(L-α-Glu)2(ClO4)(H2O)7](ClO4)3•4H2O的低温热容和热化学研究

合成了一种稀土高氯酸盐-谷氨酸配合物. 经TG/DTG、化学和元素分析、FTIR及与相关文献对比, 确定其组成为[Pr₂(L-α-Glu)₂(ClO₄)(H₂O)₇](ClO₄)₃•4H₂O, 纯度为99.0%以上. 利用显微熔点仪分析发现其没有熔点. 在78～370 K温区, 用精密绝热量热仪测量其低温热容, 在285～306 K温区发现一明显吸热峰, 归结为固-固相变过程. 通过相变温区三次重复热容测量, 得到相变温度T_tr、相变焓Δ_trH_m和相变熵Δ_trS_m分别为(297.158±0.280) K, (12.338±0.016) kJ•mol^－1和(41.520±0.156) J•K^－1•mol^－1. 用最小二乘法将非相变温区的热容对温度进行拟合, 得到了热容随温度变化的两个多项式方程. 用此方程进行数值积分, 得到每隔5 K的舒平热容值和相对于273.15 K的热力学函数值. 根据TG/DTG结果, 推测了该配合物的热分解机理. 依据Hess定律, 选择1 mol•dm^－3盐酸为量热溶剂, 利用等温环境溶解-反应量热计, 测定了该配合物的标准摩尔生成焓为: Δ_fH_m⁰＝－(7223.1±2.4) kJ•mol^－1.     

STUDIES OF THE HOMOLOGATION OF METHANE ONSUPPORTED TRANSITION METAL CATALYSTS

Introduction0ncofthcintriguingpr0blcmsinhctcrogcncouscatal}'sisisthcactit'ationanddircctconversionofmcthancintoliquidfucIanduscful.h..i..l,lllMcthancactivationisvcry'difficultbccauscn1cthancisathcrmod}'namicalI}'stablccompoundt`ithanoblcgas-likcconfigurati0nThcvcry'strongtctrahcdralC-Hbonds(435kJ/mol)offcrnofiJnctionalgroups,magncticm0mcnts'orpolardistortionstofacilitatcchcmicalattackThismakcsmcthanelcssrcactivcthanncarl}'allitsconvcrsionproducts.Rccentl}'oxidativccouplinghasbecnconsidcrcda…     

Hydrogen Effect on Coke Removal and Catalytic Performance in Pre-Carburization and Methane Dehydro-Aromatization Reaction on Mo/HZSM-5

1. Introduction As an effective utilization of methane, the methane dehydro-aromatization was focused in the last decade [1-28]. Over the Mo/HZSM-5 bi- functional catalyst at high reaction temperature, methane can be converted into light aromatics (ben- zene and naphthalene) and hydrogen. Mo active species can activate the C—H bond of methane; and HZSM-5 supplies the acid sites for the oligomeriza- tion and cyclization of hydrocarbons to form aromat- ics, and suppresses the deeper condens…