Fluoroalkyl Radical Generation by Homolytic Bond Dissociation in Pentacarbonylmanganese Derivatives

Thermal decarbonylation of the acyl compounds [Mn(CO)₅(COR_F)] (R_F=CF₃, CHF₂, CH₂CF₃, CF₂CH₃) yielded the corresponding alkyl derivatives [Mn(CO)₅(R_F)], some of which have not been previously reported. The compounds were fully characterized by analytical and spectroscopic methods and by several single-crystal X-ray diffraction studies. The solution-phase IR characterization in the CO stretching region, with the assistance of DFT calculations, has allowed the assignment of several weak bands to vibrations of the [Mn(¹²CO)₄(eq-¹³CO)(R_F)] and [Mn(¹²CO)₄(ax-¹³CO)(R_F)] isotopomers and a ranking of the R_F donor power in the order CF₃<CHF₂<CH₂CF₃≈CF₂CH₃. The homolytic Mn−R_F bond cleavage in [Mn(CO)₅(R_F)] at various temperatures under saturation conditions with trapping of the generated R_F radicals by excess tris(trimethylsilyl)silane yielded activation parameters ΔH^≠ and ΔS^≠ that are believed to represent close estimates of the homolytic bond dissociation thermodynamic parameters. These values are in close agreement with those calculated in a recent DFT study (J. Organomet. Chem. 2018 , 864, 12–18). The ability of these complexes to undergo homolytic Mn−R_F bond cleavage was further demonstrated by the observation that [Mn(CO)₅(CF₃)] (the compound with the strongest Mn−R_F bond) initiated the radical polymerization of vinylidene fluoride (CH₂=CF₂) to produce poly(vinylidene fluoride) in good yields by either thermal (100 °C) or photochemical (UV or visible light) activation.     

稀土甘氨酸咪唑配合物[RE(Gly)4(Im)(H2O)](ClO4)3的热化学研究

采用溶解-反应量热法在具有恒温环境的溶解-反应热量计内,测定了[Gd(Gly)4(Im)(H2O)](ClO4)3和[Y(Gly)4(Im)(H2O)](ClO4)3两种稀土甘氨酸咪唑配合物的标准生成焓分别为(-3 461.46 ±0.22) kJ·mol-1 和(-3 926.6±0.90) kJ·mol-1.     

Excess molar enthalpies of binary mixtures of 1-hexene with some cyclic and aromatic hydrocarbons at 298.15 K

Microcalorimetric measurements of excess molar enthalpies, at 298.15 K, are reported for the four binary systems formed by mixing 1-hexene with the cycloalkanes: cyclohexane and methylcyclohexane, and with the aromatic hydrocarcons: benzene and toluene. Smooth Redlich-Kister representations of the results are presented. It was found that the Liebermann-Fried model also provided good representations of the results.     

Effect of core-shell micelle formation on the redox properties of phenothiazine-labeled poly(ethyl glycidy ether)-block-poly(ethylene oxide)

Redox properties of phenothiazine-labeled poly(ethyl glycidy ether)-block-poly(ethylene oxide) (PT-EGE_n-b-EO_m) are reversibly changed by core-shell micelle formation. In the temperature range higher than the critical micellization temperature (cmt), the anodic potential of PT group positively shifts and concomitantly its anodic current decrease, or levels off compared to those of the reference polymer PT-EO_m without the thermo-responsive EGE_n segment. The former alteration is caused by incorporation of hydrophobic PT groups into a core of the micelle and the latter by the decrease in the diffusion coefficient of PT groups due to formation of the core-shell micelles. The cmt value and the temperature-dependent alteration in the redox properties strongly depend on the polymer structure, especially the length of thermo-responsive EGE_n segment. The electrochemically determined hydrodynamic radii of the polymer aggregates seem to be overestimated, compared to the values reported for the aggregates of other thermo-responsive polymers with similar molecular weights, implying the presence of electrochemically inactive PT groups in the copolymers having longer thermo-responsive segments.     

Paradigms and Paradoxes: Energetics of Aqueous Oxyanions of Nonmetals and Metalloids

The enthalpies of formation of simple nonmetal or metalloid oxyanions in aqueous solution are discussed. Archival values are cited and estimates are made. Trends prove evasive.     

Some results from 50 years' research on surface forces

A review is presented about research on surface forces and surface interactions conducted over the past half-century, with some emphasis on the pioneering contributions of the Department of Surface Phenomena at the Institute of Physical Chemistry of the USSR Academy of Sciences.     

Excess enthalpy of ternary mixture for diamine+heptane+cyclohexan

The excess molar enthalpy of ternary mixture for 3-diethylaminopropylamine+heptane+cyclohexane were measured using a Calvet microcalorimeter at 303.15 K. Empirical equations, Redlich-Kister, Tsao-Smith, and Kohler and group contribution models, UNIFAC (modified version) and DISQUAC have been applied. A reasonable representation of ternary data is obtained. This revised version was published online in August 2006 with corrections to the Cover Date.     

考虑材料熔化潜热的高温高压本构

本文在修正的SCG模型基础上，提出了一种考虑了熔化潜热的高温高压本构.该本构所给出的铝的剪切模量的变化分为三个阶段：加工硬化，温度软化和熔化，并在完全熔化点处变为零.并且在前两个阶段，计算的结果与修正的SCG模型所给出的剪切模量的差别不超过4%，这一差别是在动高压实验误差范围之内的，在熔化区所给出的剪切模量与现有的实验数据相符合. 关键词： 剪切模量 熔化潜热 修正的SCG模型 动高压实验     

Physical aging of a polyetherimide: Creep and DSC measurements

Creep and differential scanning calorimetry (DSC) measurements have been used to study the physical aging behavior of a polyetherimide. Isothermal aging temperatures ranged from 160°C to T_g with aging times ranging from 10 min to 8 days. The only measurable effect of physical aging on the short-time creep curves is a shift of the creep compliance to longer times. Andrade plots of the compliance versus the cube root of time are linear at short times with the slope β decreasing with increasing aging time to a constant value once equilibrium is reached. Log β³ is related directly to the degree to which the creep curves shift to longer times with physical aging, and is used in this work as a measure of physical aging. A reduced curve of log β³ versus log aging time is obtained for the aging temperatures investigated by appropriate vertical and horizontal shifts. The enthalpy change during aging increases linearly with the logarithm of the aging time, t_a, leveling off at equilibrium at values which increase with decreasing aging temperature. Hence, both nonequilibrium and equilibrium temperature shift factors can be calculated from the DSC data. Good agreement is observed between the equilibrium temperature shift factors obtained from the creep and DSC data. The temperature dependence of the nonequilibrium temperature shift factors is found to be an order of magnitude smaller than that of the equilibrium shift factors. The time scales to reach equilibrium for enthalpy and for mechanical measurements are found to be the same within experimental error. © 1995 John Wiley & Sons, Inc.     

Enthalpies of sorption of linear hydrocarbons (C2–C8) and chloroderivatives of methane and ethylene on the surface of hydrotalcite

Differential molar adsorption enthalpies (DMAE) were determined by gas chromatographic measurements of specific retention volume of vapors on the surface of two forms of Mg–Al hydrotalcite. A linear dependence of the DMAE on the number of the carbon atoms in hydrocarbons was observed for both form of hydrotalcite. The dependence of the differential molar adsorption enthalpies on the number of chlorine atoms in organic molecules is discussed. A linear dependence of DMAE on the molecular weight of chloroderivatives of methane and ethylene on the basic form in an order monochloromethane < dichloromethane < trichloromethane or vinylidene chloride < 1,1-dichloroethylene < trichloroethylene was found.