过渡状态理论的发展及应用综述

过渡状态理论是化学动力学上继碰撞理论的又一理论,是20世纪30年代由埃林等人在量子力学和统计力学发展的基础上提出的。理论的形成过程中曾引入一些假设和模型,意思是化学反应不是只通过简单碰撞就形成产物,而是经过一个以一定构型存在的过渡态。理论中势能面概念的提出引导人们从分子间作用的微观层次来考察化学反应的机理。这个理论的提出解决了该阶段上碰撞理论解决不了的问题。     

THERMODYNAMIC STUDY ON THE ADSORPTION OF SOME ORGANIC ACIDS FROM AQUEOUS SOLUTIONS BY UNMODIFIED AND MODIFIED MONTMORILLONITE CLAYS

In this study, the adsorption of some organic acids from aqueous solutions on modified and unmodified montmorillonite clays was carried out as a function of temperature and initial concentration of the adsorbate, through adsorption isotherms and their thermodynamic parameters (ΔS, ΔH, and ΔG). The results showed that the adsorption capacity of the adsorbents increased with the concentration, at constant temperature, and decreased with the increase of temperature, at constant concentration. The negative values of ΔG and ΔH showed that the adsorption was a spontaneous and exothermic process. In general the experimental data were well represented by the Langmuir and Freundlich isotherms models.     

Thermodynamics of ion conductivity of alkali halides across a polystyrene-based titanium arsenate membrane

The electric conductance of ion across titanium arsenate membrane has been recorded. Aqueous solutions of KCl, NaCl and LiCl were used. The conductance values of titanium arsenate membrane have been found to increase with increase in concentrations as well as temperature (10-50 °C) in these cases. The conductance values of electrolytes follow the sequence for the cations: K⁺ > Na⁺ > Li⁺. Negative ΔS values are considered to indicate formation of bond between the permeating species and the membrane material. The physico-chemical characterization of the hybrid material was established by XRD, TGA and simultaneous SEM studies.     

Temperature effects on the determination of oxidative stability with the metrohm rancimat

Reproducibility of Oil Stability Index (OSI) values determined on the Metrohm Rancimat was measured with a single run and between experimental runs. Within a single experiment, a range of 0.13 h and a standard deviation of 0.066 h were determined. For multiple experiments, standard deviations of 0.24 and 0.26 were obtained for soybean and low-erucic rapeseed oil, respectively. The effect of temperature was determined for safflower, soybean, lowerucic rapeseed, corn, peanut and olive oils. A linear relationship was established between log (OSI) and temperature. The linear equation obtained for soybean oil was utilized to calculate variability of the OSI due to temperature differences in the heating block.     

三元硝酸熔盐高温热稳定性实验研究与机理分析

通过熔盐质量损失率和试样中NO2-含量变化状况,以及熔盐材料的热重(TG)曲线,研究了三元硝酸熔盐(53%KNO3-40%NaNO2-7%NaNO3)在空气和氮气气氛中高温条件下的热稳定性性能。结果表明,三元硝酸熔盐空气中的上限使用温度为773K,高温时存在劣化现象;而在氮气气氛中三元熔盐的热分解温度为723K。同时,从热力学和动力学角度分析得到,三元硝酸熔盐在773K以下空气中发生的反应为亚硝酸钠的分解和氧化;而在氮气气氛中三元熔盐723K以下时主要发生的是亚硝酸钠的分解反应。在氧气含量一定的情况下,氧气的扩散和亚硝酸盐的分解反应符合一级反应动力学模型。     

Thermodynamics of dissolution of glassy polymers

A parametric semi-empirical thermodynamic theory for the dissolution of glassy polymers in liquids is formulated based on the experimental results on Gibbs energy, enthalpy and entropy of mixing in isothermal conditions for a large number of systems. The values of these thermodynamic functions include the contribution from the glassy structure of the polymer, which depends on the volume fraction of metastable voids, the cohesion energy of polymer, and the entropy depression parameter. The glassy-state contribution to the enthalpy and entropy of mixing is large and negative, which provides sufficient difference from the same functions for the elastic polymers. However, this also leads to the enthalpy/entropy compensation, and the values of Gibbs energy of mixing only weakly depend on the glassy nature of the polymer. The theory is shown to provide adequate explanation for all specific features of the concentration dependences of different thermodynamic functions found in experiment at constant temperature. The parameters of the model are tabulated for a large variety of solutions of polymer glasses.     

Influence of Process Variables on the Reactivity of Low Formaldehyde Emission Urea-Formaldehyde Resin

One of the important characteristics of the thermosetting resins such as urea-formaldehyde resin is the cure property. This is an invaluable characteristic for determining the processing capabilities of the resin. Differential scanning calorimetry (DSC) measurements are ideally suited to achieve this end. This paper presents the results of the effect of process variables on the enthalpy of cure of a low formaldehyde emission UF resin prepared by a four-stage process as described in the text. Response surface methodology (RSM) was used to design and the analyze the experiments. Urea (U) was added to the reaction mixture according to a pre-determined program of varying the number of additions and the duration between the additions during the second stage of the process. A mathematical relationship between the process variables and enthalpy of cure was established. The urea-formaldehyde (UF) resin was prepared under optimum conditions. Experiments were performed with the resin so prepared to determine the energy of activation of the curing reaction catalyzed by ammonium chloride.     

Evaluation of Thermodynamic Parameters for Separation of Hexavalent Chromium by Fly Ash

Abstract

Kinetics and thermodynamic parameters of Cr⁶⁺ separation by fly ash from aqueous solution has been evaluated. It was found that the separation process is partly diffusion controlled and endothermic in nature. The mass transfer coefficient increases with an increase in temperature. The activation energy and change of enthalpy were also evaluated and found to be 17.5 kJ/mol and 14.47 kcal/mol, respectively. The free energy of the process was small but positive, and it decreases with an increase of temperature. The change of entropy was found to be small and remains unchanged over the 30 to 50°C temperature range. This process follows the Langmuir isotherm model where Q _o and b were also determined at different temperatures.     

新型硬质聚氨酯泡沫的热分解行为及动力学

利用热重分析法比较研究了新型硬质聚氨酯泡沫[超支化聚氨酯多元醇型（HBPU型）]和硬质聚氨酯泡沫（RPUF）在氮气中的热分解行为,探讨了HBPU型RPUF在不同升温速率下的热分解动力学,运用Kissinger最大失重率法和Flynn-Wall-Ozawa等失重百分率法计算获得了其热分解过程的活化能。研究结果表明,HBPU型RPUF的初始分解温度(T_5%)为205℃,半寿温度(T_50%)为361℃,略低于传统的RPUF。Kissinger法得到的HBPU型RPUF的热分解表观活化能为159.8 kJ/mol;Flynn-Wall-Ozawa法得到的热分解过程分为三个阶段:第一阶段的平均活化能为82.8 kJ/mol,第二阶段的平均活化能为140.7 kJ/mol,第三阶段的平均活化能为111.3 kJ/mol,HBPU型RPUF具有较好的热稳定性。     

阻聚剂的存在对碳氢燃料热分解动力学的影响

利用含阻聚剂和不含阻聚剂的DSC曲线,分别确定其热分解反应的动力学参数,经此来研究阻聚剂的存在对于碳氢燃料的性能的影响。     

Brazilian encapsulated fish oils: Oxidative stability and fatty acid composition

Encapsulated fish oils are extensively commercialized in Brazil. These products could have an effect in the reduction of heart diseases because of their high content of polyunsaturated fatty acids. However, information about their composition and quality are still lacking. Fatty acid composition, oxidative stability (Rancimat, 80°C, 2.5 g sample and 8.3 L/h air), peroxide value (PV), and polar compound content were determined in sixteen trademarked encapsulated fish and cod-liver oils, purchased from Brazilian markets. The highly polyunsaturated fatty acid (eicosapentaenoic acid+docosahexaenoic acid) level appear to be typical of marine oils (16.2 and 32.1%). The PV ranged from 2.1 to 20.3 meq/kg, which is considered high, whereas the Rancimat induction periods varied from 1.95 to 8.45 h. The samples analyzed contained from 0.1 to 8.3% polar components. In some cases, both composition and quality were inadequate for this kind of product. One of the samples did not contain cod-liver oil, it appears that it contained soybean oil. Presented at the 6th Latin American Congress and Exhibit on Fats and Oil Processing, LA-AOCS, Campinas, SP, Brazil, Sept. 1995.     

On the information and methods for computing phase equilibria and thermodynamic properties

The Helmholtz free energy or an equation of state relating temperature, pressure, volume and composition plays a key role in the calculation of phase equilibria and thermodynamic properties. Such information is usually available for vapor, partially available for liquids, and rarely available for solids. Depending on the information available, different methods are used for properties calculation. In this study, various methods were systematically presented and their relations with available information were comprehensively discussed.     

An empirical approach for predicting kinematic viscosities of biodiesel blends

Kinematic viscosity (η) is an important property of diesel fuels, including biodiesels, which are marketed mostly as the blends in many countries around the world. In this study, the free energy of viscous flow (ΔG_vis) for a non-associated liquid mixture is assumed to be the summed of ΔG_vis of individual components. Hence, the Eyring’s equation, η = Ae(−ΔG_vis/RT), is transformed to ln η_blend = a + bn₁ + c/T + dn₁/T (where, a, b, c and d, T and n₁ are thermodynamically related constants, absolute temperature and mole fraction of biodiesel, respectively). The transformed equation is used to predict kinematic viscosity of biodiesel blends (η_blend) of different degree of blending at any temperatures from pour point to 100 °C. The predicted kinematic viscosities are in good agreement with those reported in literatures at all temperatures. The highest deviation is ±5.4% and the average absolute deviation (AAD) is less than 2.86%. The transformed equation can also be used to predict kinematic viscosities of pure fatty acid methyl esters in diesel fuel. Methyl ricinoleate is an exception. The AAD is 4.50% and the deviation is as high as 12.80%. The high deviation suggests that molecular interactions between methyl ricinoleate and diesel fuel is high and cannot be ignored.     

PMDA-ODA型聚酰亚胺纤维的热稳定性研究

通过干法纺丝制备了聚酰亚胺(PI)纤维,采用热失重(TGA)测试分析了其热稳定性能.TGA测试表明,均苯四甲酸酐-4,4.二氨基二苯醚(PMDA-ODA)型PI纤维500℃之前不发生分解,其热分解稳定性要优于P84纤维.并利用Kissinger和Flynn-Wall-Ozawa方法计算并比较了PI和P84纤维在空气中热...     

CSM对EPDM硫化胶耐热氧稳定性的影响

用热空气老化试验、差示扫描量热法和热重分析法研究添加少量氯磺化聚乙烯（ＣＳＭ）的ＥＰＤＭ硫化胶的热氧稳定性。结果表明：添加ＣＳＭ的ＥＰＤＭ硫化胶第一分解阶段的活化能低于未添加ＣＳＭ硫化胶的,而第二分解阶段的活化能却高于未添加ＣＳＭ硫化胶的。这说明,添加ＣＳＭ能提高ＥＰＤＭ硫化胶耐长期热氧老化性能,但对硫化胶早期的热分解起加速作用