Partial molal heat capacities of aqueous tetraalkylammonium bromides as functions of temperature

Enthalpies of solution have been measured from 5 to 85°C for aqueous tetraethyl- and tetrapropylammonium bromides, and the integral heat method is employed to evaluate for these electrolytes over a wide temperature range. Data taken from the literature have been used to evaluate for aqueous Bu₄NBr over a similar temperature range. These data, along with similar data for Me₄NBr, previously reported, have been used to evaluate absolute ionic heat capacities. While the absolute values agree only qualitatively with two other methods of division, the temperature dependences of the three methods essentially agree up to 65°C. Heat capacities due to structural effects on the solvent, obtained by subtracting the inherent heat capacities of the ions, are extraordinarily positive for all four tetraalkylammonium ions and have negative temperature coefficients, indicating that all four ions, including the tetramethylammonium ion, are structure-making ions.     

Zircon SHRIMP age of Mesoarchaean meta-argilloarenaceous rock in the Anshan area and its geological significance

In order to better understand the early continental evolution of the Anshan area, one ofthe typical Precambrian distribution areas of the North China Craton, the geochronology and REEcomposition of the zircons from the meta-argillo-arenaceous rock occurred as enclave in 3.1 GaLishan trondhjemite are studied by using SHRIMP ll ion microprobe. It is indicated that the Pa-leoarchaean is a very important continental formation period in the Anshan area and 3.2 Ga can beregarded as the boundary between the Paleoarchaean and Mesoarchaean.     

Photochemical properties and structures ofN-amino andN-azomethine derivatives of 2,4,6-triphenylpyridinium perchlorates

The molecular structures of the initial compounds and the products of photocyclization involving amino and azomethine groups in perchlorates ofN-amino (1) andN-azomethine (2) derivatives of 2,4,6-triphenylpyridinium cations were studied. Cations1 and2 have an essentially non-coplanar arrangement of the -Ph rings, and the product of photocyclization of2, cation3, is characterized by a flattened structure. It was found that the orientation of the lone electron pair of the N atom with respect to one of the planes of the -Ph rings in molecule1 is more favorable for monocyclization involving the amino group. The structure of molecule2 allows two routes of the photoreaction,viz., O N proton transfer and monocyclization with an -Ph ring. However, the structural features of molecule2 are more favorable for photocyclization.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 296–301, February, 1995.     

Thermodynamic properties of organic compounds in aqueous solution. II. Apparent molal heat capacities of piperidines,morpholines, and piperazines

Apparent molal heat capacities of some piperidine, morpholine, and piperazine derivatives in aqueous solution have been determined by adiabatic calorimetry in the temperature range 20–55°C and in the molality range 0.2–1m. Comparison of experimental values with those calculated through group contributions, found for monofunctional compounds, indicates strong interactions between the hydrophilic centers. An interpretation is given of the possible mechanism of this interaction. Also, values of ΔC _p for the addition reaction of proton to nitrogen centers of mono- and bifunctional organic compounds are examined.     

The convergence properties of direct methods of energy minimization with respect to linear coefficients in the LCAO-MO-SCF approach

It is shown that in the LCAO-MO-SCF problem, if the molecular orbital orthonormality constraints are introduced in the manner first suggested by Fletcher, then the Hessian of the problem is singular. It is suggested that this singularity may well account for the slow convergence observed using direct energy minimization methods to solve the SCF problem. Ways of avoiding the consequences of this singularity are discussed.     

Determination of enthalpies of formation of organic free radicals from bond dissociation energies 2. Halosubstituted radicals

The enthalpies of formation (ΔH _f ^o) for 23 halosubstituted radicals were determined from the published data on bond dissociation energies. The ΔH _f ^o values of the corresponding molecules necessary for the calculation of ΔH _f ^o of the radicals were taken from handbooks or calculated by the additive-group method. The conjugation energies of the radicals are calculated, and the effect of substituents at the π-system on these values was shown. Errors of determination of the ΔH _f ^o values of the radicals were estimated. For Part 1, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 643–646, April, 1998.     

Conformational energies of cyclenes

An universal function for non-bonded interactions, which takes into account the relative orientation of the bonds is considered in calculating the conformational energies of cycloalkenes and cycloalkadienes. A comparison is made with previous results obtained by using usual 6-exp functions for non-bonded interactions.     

锰（Ⅱ）—邻菲口罗啉配合物极谱吸附波及其应用

在ｐＨ９．５ＮＨ３ＮＨ４Ｃｌ缓冲溶液中，Ｍｎ（Ⅱ）与邻菲口罗啉形成的配合物在－１．３６Ｖ（ｖｓ．ＳＣＥ）处产生一灵敏的吸附波，一阶导数峰电流与Ｍｎ（Ⅱ）浓度在５×１０－８５×１０－６ｍｏｌ／Ｌ范围内呈线性关系，检出限为２×１０－８ｍｏｌ／Ｌ对极谱性质及反应机理进行了研究，用该法测定了大豆和茶叶中的微量锰，结果满意     

Reaction paths of some open-shell reactive intermediates

The intermolecular interaction energy for reacting systems in singlet, triplet and doublet states was partitioned by the perturbation expansion method into the chemically meaningful five interaction terms: the Coulomb, exchange-repulsion, induction, dispersion, and charge-transfer energies. In the local ZDO approximation, these energy terms were evaluated for the dimerization of methylenes (^1,3CH₂), the additions of carbenes (^1,3CH₂ and^1,3CF₂) as well as amino radicals (²NH₂ and²NF₂) toward ethylene, and the hydrogen abstractions by methylenes (^1,3CH₂), nitrene (³NH), and hydroxyl radical (²OH) from methane. It has been found that the reaction path is much influenced by the spinmultiplicity, and that the charge-transfer and exchange-repulsion terms play a dominant role in determining the course of reactions.