Energetics of formation of alkali and ammonium cobalt and zinc phosphate frameworks

Alkali and ammonium cobalt and zinc phosphates show extensive polymorphism. Thermal behavior, relative stabilities, and enthalpies of formation of KCoPO₄, RbCoPO₄, NH₄CoPO₄, and NH₄ZnPO₄ polymorphs are studied by differential scanning calorimetry, high-temperature oxide melt solution calorimetry, and acid solution calorimetry.α-KCoPO₄ and γ-KCoPO₄ are very similar in enthalpy. γ-KCoPO₄ slowly transforms to α-KCoPO₄ near 673 K. The high-temperature phase, β-KCoPO₄, is 5-7 kJ mol⁻¹ higher in enthalpy than α-KCoPO₄ and γ-KCoPO₄. HEX phases of NH₄CoPO₄ and NH₄ZnPO₄ are about 3 kJ mol⁻¹ lower in enthalpy than the corresponding ABW phases. There is a strong relationship between enthalpy of formation from oxides and acid-base interaction for cobalt and zinc phosphates and also for aluminosilicates with related frameworks. Cobalt and zinc phosphates exhibit similar trends in enthalpies of formation from oxides as aluminosilicates, but their enthalpies of formation from oxides are more exothermic because of their stronger acid-base interactions. Enthalpies of formation from ammonia and oxides of NH₄CoPO₄ and NH₄ZnPO₄ are similar, reflecting the similar basicity of CoO and ZnO.     

Thermodynamics of Binding 2,2′-Bipyridineglycinato Palladium (II) Chloride on Human Serum Albumin

The interaction of human serum albumin (HSA) with 2,2′-bipyridineglycinato palladium (II) chloride was studied by isothermal titration microcalorimetry at 27°C and equilibrium dialysis and UV-Vis. spectrophotometry techniques at temperatures of 27 & 37°C in 2.5 mM phosphate buffer solution at pH = 7.0. The enthalpy of binding was calculated from binding data, which were obtained from equilibrium dialysis in terms of the Wyman binding potential theory related to the van't Hoff relation. The enthalpy of HSA unfolding was determined by subtraction of the microcalorimetric enthalpy (binding and unfolding enthalpies) and the enthalpy of binding. The enthalpy of HSA unfolding, due to the binding of that ligand, was 491.43 kJ mol^?1.     

Gleichgewichtsdruckmessungen im System Se/O/Br

Equilibrium Pressure Measurements in the System Se/O/Br The saturation pressure or saturation decomposition pressure of SeOBr_2,l, Se₂Br_2,l and SeBr_4,s were determined in a membran zero manometer. The decomposition behaviour follows from pressure measurements outside of saturation. From the equilibrium data are derived the Enthalpies of formation: Data see Inhaltsübersicht. Informations about the melting diagrams obtained via the barograms of the condensed compositions SeO₂/SeBr₄ and Se/Br.     

用恒温热重法测定1-己基-3-甲基咪唑苏氨酸离子液体[C6mim][Thr]蒸汽压和蒸发焓

用中和法合成了氨基酸离子液体(AAIL)1-己基-3-甲基苏氨酸盐[C₆mim][Thr],并用核磁共振氢谱(¹H NMR)和核磁共振碳谱(¹³C NMR)进行了表征。以苯甲酸为参考物质,用恒温热重法确定了AAIL[C₆mim][Thr]的蒸汽压和在平均温度下(T_av= 438.15 K)的蒸发焓(Δ^g_lH_m^? (T_av) =128.5 ± 6.0 kJ·mol^-1)。利用Verevkin等人提出的方法计算得到AAIL[C₆mim][Thr]气态和液态的恒压热容差(Δ^g_lC_pm^? = -70.8 J·K^-1·mol^-1),进而计算了不同温度的蒸发焓,其中参考温度(298.15 K)下的蒸发焓Δ^g_lH_m^? (298.15 K) = 138.4 kJ·mol^-1,只比应用我们提出的蒸发焓理论模型估算值大1.6 kJ·mol^-1,小于恒温热重法的实验误差3.0 kJ·mol^-1,说明这个蒸发焓的理论模型有一定的合理性。借助Clausius-Clapeyron方程估算了AAIL[C₆mim][Thr]的假想的正常沸点T_b= 522.07 K,以及沸点的蒸发熵Δ^g_lS_m^? (T_b) = 228.5 J·K^-1·mol^-1,进一步得到了不同温度的蒸发熵和蒸发自由能Δ^g_lG_m^? (T),其结果表明蒸发自由能随着温度的上升而减小,达到沸点温度T_b时变为零,而蒸发熵则随着温度上升而增大,是AAIL[C₆mim][Thr]蒸发过程的驱动力。     

1-乙基-3-甲基咪唑丙氨酸离子液体热力学性质的研究

用中和法合成了氨基酸离子液体1-乙基-3-甲基咪唑丙氨酸([C₂mim][Ala]),并利用恒温环境的溶解反应热量计,在(288.15±0.01) K-(308.15±0.01) K温度范围内每隔5 K,测定不同质量摩尔浓度离子液体在水中的溶解焓(Δ_solH_m^θ).根据Archer的方法,通过线性拟合得到了该离子液体的标准摩尔溶解焓(Δ_sol),并计算了其相对表观摩尔溶解焓(^ΦL).在298.15 K下,根据Glasser经验方法得到了格子能U_POT = 566 kJ·mol^-1,并计算了其阴阳离子水化焓值(ΔH⁺ + ΔH^-) = -620 kJ·mol^-1及阴离子水化焓ΔH^-([Ala]^-) = -387 kJ·mol^-1.此外,估算了[C₂mim][Ala]水溶液的热容(C_p(sol))和表观摩尔热容(^ΦC_p).     

结晶型聚合物注塑过程冷却模型的数值模拟

对HDPE平板状注塑件的冷却过程进行了数值模拟 .基于小分子结晶性物质的冷却模型 ,建立了固相、液相及固液相界面的控制方程 ,方程中引入热焓E和参数T 后 ,将带耦合条件的热传导方程转变为非线性抛物型方程 ,按控制容积法将其离散后 ,用数学软件Matlab获得了PE的三维温度场 ,这为探讨带相转变的热传导问题提供了一种有效的数值方法 .通过对制件芯层温度变化的模拟值与实验值的比较 ,比较了不同相变温度下理论结果的准确性 ,结果表明 ,在引入一定过冷度后 ,将相变温度定义在低于平衡熔点以下时 ,该方法的模拟值具有更好的准确性 .同时 ,模型分析了不同工艺条件对制件芯层冷却过程的影响 ,通过相变平台出现的先后以及终止时间的不同 ,说明充模温度主要影响熔体阶段的冷却以及相变出现的先后 ,而模具温度主要影响固体阶段的冷却以及相变平台终止的先后 .     

A method for the estimation of the enthalpy of formation of mixed oxides in Al2O3-Ln2O3 systems

A new method is proposed for the estimation of the enthalpy of formation (Δ_oxH) of various Al₂O₃-Ln₂O₃ mixed oxides from the constituent binary oxides. Our method is based on Pauling's concept of electronegativity and, in particular, on the relation between the enthalpy of formation of a binary oxide and the difference between the electronegativities of the oxide-forming element and oxygen. This relation is extended to mixed oxides with a simple formula given for the calculation of Δ_oxH. The parameters of this equation were fitted using published experimental values of Δ_oxH derived from high-temperature oxide melt solution calorimetry. Using our proposed method, we obtained a standard deviation (σ) of 4.87 kJ mol⁻¹ for this data set. Taking into account regularities within the lanthanide series, we then estimated the Δ_oxH values for Al₂O₃-Ln₂O₃ mixed oxides. The values estimated using our method were compared with those obtained by Aronson's and Zhuang's empirical methods, both of which give significantly poorer results.     

Structural studies of cyclic ureas: 3. Enthalpy of formation of barbital

A thermochemical and thermophysical study has been carried out for crystalline barbital [5,5′-diethylbarbituric acid]. The thermochemical study was made by static bomb combustion calorimetry, from which the standard () molar enthalpy of formation of the crystalline barbital, at T = 298.15 K, was derived as −(753.0 ± 1.8) kJ · mol⁻¹. The thermophysical study was made by differential scanning calorimetry over the temperature interval (265 to 470) K. A solid–solid phase transition was found at T = 413.3 K. The vapour pressures of the crystalline barbital were measured at several temperatures between T = (355 and 377) K, by the Knudsen mass-loss effusion technique, from which the standard molar enthalpy of sublimation, at T = 298.15 K was derived as (117.3 ± 0.6) kJ · mol⁻¹. The combination of the experimental results yielded the standard molar enthalpy of formation of barbital in the gaseous phase, at T = 298.15 K, as −(635.8 ± 1.9) kJ · mol⁻¹. This value is compared and discussed with our theoretical calculations by several methods (Gaussian-n theories G2 and G3, complete basis set CBS-QB3, density functional B3P86 and B3LYP) by means of atomization and isodesmic reaction schemes.