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)     

一些烷氯代烃标准蒸发焓的测定

在进行有机氯化物分子内非键合相互作用的热化学研究中, 为了排除分子间的相互作用, 需要准确的标准蒸发焓或升华焓, 以便把凝聚态的标准生成焓转变为气态的数据。文献中多氯代烷烃的蒸发焓数据不多, 其中由直接量热法得到的准确数据更少, 因此我们测量了一些多氯代烷烃的标准蒸发焓, 并对其规律作了一些探讨。     

无穷级亚纯函数的公共值与奇异方向

f（z）为无穷级亚纯函数,且σ（f）〈∞。本文证明了复平内存在奇异方向,f（z）与其k阶导函数f（k）（z）（k≥3）在这方向所对应的任意小角域内至多有两个不同的有穷公‘共值。     

520 mJ langasite electro-optically Q-switched Cr, Tm, Ho:YAG laser

A flash lamp pumped 2.09 μm Cr, Tm, Ho:YAG laser utilizing a self-grown La(3)Ga(5)SiO(14) crystal as the electro-optic Q-switch generator is proposed and demonstrated for the first time. Operating at 3 Hz repetition rate, 520 mJ pulse energy with 35 ns pulse width is achieved by optimizing the Q-switch delay time and compensating for the thermal depolarization with a quarter-wave plate. The corresponding peak power is 14.86 MW, and the Q-switched-to-normal-mode energy extraction efficiency is 66.3%. To our knowledge, this Q-switched giant pulse is the best result reported to date in 2.09 μm laser resonator.     

Determination of combustion energies and the standard enthalpies of formation for the complexes of RE(Et<Subscript>2</Subscript>dtc)<Subscript>3</Subscript>(phen)

Solid complexes, RE(Et₂dtc)₃(phen) (RE=La, Pr, Nd, Sm—Lu), were synthesized with sodium diethyldithiocarbamate (NaEt₂dtc3H₂O), 1,10-phenanthroline (o-phen?H₂O) and hydrated lanthanide chlorides in absolute ethanol. The constant-volume combustion energies of complexes, Δ _C U, were determined by a precise rotating-bomb calorimeter at 298.15 K. The standard enthalpies of combustion, Δ_CH_m ^θ, and standard enthalpies of formation, Δ_fH_m ^θ, were calculated for these complexes, respectively. The experiment results showed the “tripartite effect” of rare earth.     

稀土水杨酸配合物的光谱性质

合成了一系列稀土水杨酸配合物.分别研究了配合物的红外光谱(IR)，紫外(UV)及荧光光谱(FS)性质.红外光谱研究表明,稀土和水杨酸主要通过羧基进行配位，而紫外光谱显示配合物中水杨酸和稀土离子之间的能量传递是主要过程;配合物的荧光性质研究发现水杨酸钆，水杨酸铽，水杨酸镝分子内能量传递效率高，具有很强的荧光性质.     

Thermochemical properties of the rare earth complexes with pyromellitic acid

Fourteen rare earth complexes with pyromellitic acid were synthesized and characterized by means of chemical and elemental analysis, and TG–DTG. The constant-volume combustion energies of complexes, Δ_cU, were measured by a precise rotating-bomb calorimeter (RBC-type II). Their standard molar enthalpies of combustion, , and standard molar enthalpies of formation, , were calculated at T = 298.15 K. The relationship of and with the atomic numbers of the elements in the lanthanide series was examined. The results show that a certain amount of covalence is present in the chemical bond between rare earth cations and the ligand.     

转动弹量热计的建立及对氯苯甲酸热值测定

元素有机物要达到完全的燃烧应当在转动弹量热计中进行,这种量热计与静止弹量热计比较有许多优点。首先,转动的结果起到了对弹液的搅拌作用,使弹内各部分溶液的浓度很快达到平衡。其次,促进了燃烧过程中某些副反应的进行,从而短期获得稳定的反应终态,使燃烧热测量的精度显著提高。     

RE（NO_3）_3·［CH_3CH（NH_2）COOH］_4·H_2O的燃烧热

用转动弹量热计测定了稀土（Ｃｅ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｄｙ、Ｅｒ、Ｙｂ）硝酸盐与ＤＬ－ａ－丙氨酸（１：４）配合物的燃烧热－△_ｃｕ（Ｊ·ｇ￣（－１）），其结果依次为９５９６．１，８８７４．７，８７１０．１，８９３７．３，８９６１．３，８７５１．８，８７００．０和８６５６．４。据此计算的生成焓－△_ｆＨ（ｋＪ·ｍｏｌ￣（－１））分别为３３９３．５３，３６７１．３７，３７４０．８２，３４９５．２１，３４９７．５２，３６２６．７９，３６４１．６４和３５６８．５８。这些结果不但为稀土元素的三分组提供了可靠的实验依据，亦发现了ＲＥ（ＮＯ_３）_３·（ＣＨ_３ＣＨＮＨ_２ＣＯＯＨ）_４·Ｈ_２Ｏ配合物稳定性之变化规律与稀土原子序数的关系。     

硝酸铕与二甲基甲酰胺配合物的研究

一、配合物合成及溶解性 配合物按文献[1]的方法合成,为微红色粉末,易溶于水、DMF、DMSO、乙醚、甲醇、乙醇、丙酮、氯仿,不溶于甲苯、二甲苯、CCl_4。 二、分析方法及实验条件 分析方法和实验条件同文献[1];燃烧能的测定仪器、实验条件,量热计当量计算和热交换校正,燃烧焓的换算和生成热的计算同文献[2]。 结果与讨论 一、配合物的性质 1.组成分析 元素分析实验值(％):Eu27.26,C20.07,H3.76,N14.85;计算值(％):Eu27.27,C19.40,H3.80,N15.08。 2.熔点及X-射线粉末衍射分析 配合物熔点为102.0～102.5℃;配合物及硝酸铕水合物