Kinetics and thermodynamics of the electrodeposition of palladium, thallium, and tellurium from different baths

Some kinetic and activation thermodynamic functions for the electrodeposition of palladium, thallium, and tellurium from the best selected baths, viz. niclosamide bath [5-chloro-N-(2-chloro-4-nitrophenyl)-2-hydroxybenzamide] for Pd, alizarin red bath for Tl, and salicylaldehyde bath for Te, are determined. Reaction rate constant (k), half-lifetime (t _1/2), activation energy (E _a), and such activation thermodynamic parameters as entropy change (ΔS*), enthalpy change (ΔH*), and Gibbs free energy (ΔG*) are calculated by applying the rate theory of the first-order reaction and the Eyring theory of the reaction rate. The effect of temperature change in the range of 30–60°C on the above parameters is studied and thoroughly discussed. The effect of metal type on both the reaction rate and the activation energy is also investigated. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 3, pp. 264–271. The text was submitted by the authors in English.     

On the ν-dimensional one-component classical plasma: The thermodynamic limit problem revisited

We prove theH-stability property and the existence of the thermodynamic limit of the free energy density of the two-dimensional, one-component classical plasma. We give lower and upper bounds on the free energy density in any dimensionv and draw some consequences.     

Variational approximations for renormalization group transformations

Approximate recursion relations which give upper and lower bounds on the free energy are described. Optimal calculations of the free energy can then be obtained by treating parameters within the renormalization equations variationally. As an example, a particularly simple lower bound approximation which preserves the symmetry of the Hamiltonian (the one-hypercube approximation) is described. The approximation is applied to both the Ising model and the Wilson-Fisher model. At the fixed point a parameter is set variationally and critical indices are calculated. For the Ising model the agreement with the exact results atd = 2 is surprisingly good, 0.1%, and is good atd=3 and evend=4. For the Wilson-Fisher model the recursion relation is reduced to a one-dimensional integral equation which can be solved numerically givingv=0.652 atd=3, or by expansion in agreement with the results of Wilson and Fisher to leading order in . The method is also used to calculate thermodynamic functions for thed = 2 Ising model; excellent agreement with the Onsager solution is found.Supported in part by the National Science Foundation under Grants Nos. MPS73-04886A01 and GH-41512 and by the Brown University Materials Research Laboratory supported by the National Science Foundation. M.C.Y. was supported by a grant from the Scientific and Technical Research Council of Turkey.     

亚氯酸钠溶液同时脱硫脱硝的热力学研究

在自行设计的小型鼓泡反应器中, 以亚氯酸钠溶液作为吸收剂, 进行了模拟烟气同时脱硫脱硝实验研究, 得到反应的最佳实验条件以及在此条件下同时脱硫脱硝效率. 分析了反应产物, 推导出了亚氯酸钠溶液与硫氧化物、氮氧化物的反应历程以及总化学反应方程式. 利用热力学原理计算出亚氯酸钠溶液同时脱硫脱硝的摩尔反应吉布斯函数、摩尔反应焓变、化学反应平衡常数以及化学反应达到平衡时SO2和NO的分压力. 结果表明: 亚氯酸钠溶液同时脱硫脱硝是可行的, 且可以几乎100%的脱除烟气中的SO2和NO.     

Maximum Profit Output Configuration of Multi-Reservoir Resource Exchange Intermediary

A model of a multi-reservoir resource exchange intermediary also defined as a commercial engine is proposed according to analogies and similarities between thermodynamics and economics. The optimal configuration of a multi-reservoir commercial engine with a maximum profit output objective is determined by applying optimal control theory. The optimal configuration consists of two instantaneous constant commodity flux processes and two constant price processes, and the configuration is independent of a number of economic subsystems and commodity transfer law qualitatively. The maximum profit output needs some economic subsystems to never contact with the commercial engine during commodity transfer processes. Numerical examples are provided for a three-economic-subsystem commercial engine with linear commodity transfer law. The effects of price changes of an intermediate economic subsystem on the optimal configuration of a three-economic-subsystem and the performance of optimal configuration are discussed. The research object is general, and the results can provide some theoretical guidelines for operations of actual economic processes and systems.     

Comparison between 1,2-Dihydropyridine and 1,4-Dihydropyridine on Hydride-Donating Ability and Activity

In this paper, detailed comparisons of the driving force in thermodynamics and intrinsic force in the kinetics of 1,2-dihydropyridine and 1,4-dihydropyridine isomers of PNAH, HEH, and PYH in hydride transfer reactions are made. For 1,2-PNAH and 1,4-PNAH, the values of the thermodynamic driving forces, kinetic intrinsic barriers, and thermo-kinetic parameters are 60.50 and 61.90 kcal/mol, 27.92 and 26.34 kcal/mol, and 44.21 and 44.12 kcal/mol, respectively. For 1,2-HEH and 1,4-HEH, the values of the thermodynamic driving forces, kinetic intrinsic barriers, and thermo-kinetic parameters are 63.40 and 65.00 kcal/mol, 31.68 and 34.96 kcal/mol, and 47.54 and 49.98 kcal/mol, respectively. For 1,2-PYH and 1,4-PYH, the order of thermodynamic driving forces, kinetic intrinsic barriers, and thermo-kinetic parameters are 69.90 and 72.60 kcal/mol, 33.06 and 25.74 kcal/mol, and 51.48 and 49.17 kcal/mol, respectively. It is not difficult to find that thermodynamically favorable structures are not necessarily kinetically favorable. In addition, according to the analysis of thermo-kinetic parameters, 1,4-PNAH, 1,2-HEH, and 1,4-PYH have a strong hydride-donating ability in actual chemical reactions.     

Conductometric Studies of Formation the Inclusion Complexes of Phenolic Acids with β-Cyclodextrin and 2-HP-β-Cyclodextrin in Aqueous Solutions

An attempt was made to evaluate the possibility of creating and assessing the stability of inclusion complexes of selected phenolic acids [trans-4-hydroxycinnamic acid (trans-p-coumaric acid), trans-3,4-dihydroxycinnamic acid (trans-caffeic acid), trans-4-hydroxy-3-methoxycinnamic acid, (trans-ferulic acid) and trans-3-phenylacrylic acid (trans-cinnamic acid)] with β-cyclodextrin and 2-HP-β-cyclodextrin in aqueous solutions in a wide temperature range 283.15 K–313.15 K. On the basis of the values of the limiting molar conductivity (Λ_CDNaDod), calculated from the experimental data, the values of the formation constants and the thermodynamic functions of formation (standard enthalpy, entropy, and Gibs standard enthalpy) of the studied complexes were determined. It has been found that the stability of the studied complexes increases with lowering of the molar mass of cyclodextrin and lowering of the temperature.     

二次有机气溶胶的气体/粒子分配理论

本文重点评述了二次有机气溶胶形成的气体/粒子分配理论,简要介绍了它的发展和可能的应用.在大气中,气体有机物种的氧化可以产生半挥发性的有机化合物,二次有机气溶胶的形成可以用气体/粒子分配的吸收模型来评估.气体/粒子分配过程决定于半挥发性化合物的成分、浓度和蒸气压,以及吸收性材料的浓度和成分.在气体/粒子分配理论的基础上,人们又研究和开发出二次有机气溶胶的分子组分的气体/粒子分配的热力学模型,它可以用来预估气溶胶中液态水的含量、无机物的分布、亲水性和疏水性有机物的分布.二次有机气溶胶形成的化学机理和气体/粒子分配的热力学模型与加利福尼亚工学院三维都市/区域性大气模型相结合,可以用于气相和气溶胶相模拟.     

荧光淬灭和加强理论公式合理性的热力学分析

通过荧光法在不同温度下研究了3种第三代头孢新药: 盐酸头孢吡肟、头孢匹胺和头孢唑肟钠与人血清白蛋白(HSA)和牛血清白蛋白(BSA)的作用, 分别应用荧光淬灭和荧光加强理论公式计算了它们的结合常数等, 进而分别计算了它们的热力学函数. 因对应于不同的理论公式得出的K_A值并不完全相同, 由此得到它们相应的热力学参数也有所不同. 本文对这些热力学数据的差异进行了分析比较, 结果表明: 基于荧光加强理论公式(4)获得的热力学数据显示更为合理. 因而我们建议, 即使在研究受体-底物的荧光淬灭反应时, 采用荧光加强理论公式(4)可以获得更符合实际的结果.     

锰基液流电池电解液的体积性质研究

体积性质是锰基液流电池电解液的重要热力学性质,常用于解释溶液中复杂的离子间相互作用关系。本文在283.15-318.15 K温度范围内,测定了浓度为0.5-3.0 mol/kg的MnSO₄水溶液的密度值,得到了MnSO₄溶液的几个热力学参数和弱分子间的相互作用关系。结合Pitzer电解液表观摩尔体积热力学模型,得到了体积参数β(0)V MX,β(1)V MX和CV MX,而且计算值与实验值的相关系数能够达到0.988。这一研究可以更好地理解锰电解液中离子相互作用机制,为优化电解液成分和提高电池性能提供理论支撑。