慢对峙反应的热动力学对比参量法

根据热动力学基本理论,推导了对峙反应的热动力学对比参量方程,建立了对峙反应对比参量法的数学模型。该法利用特征时间t~m和2t~m时对应的热谱数据计算反应的对比参量,进而解析出较慢对峙反应的速率常数和平衡常数。利用该法分别研究了硝基乙烷与氨和三(羟甲基)氨基甲烷质子转移反应的热动力学,实验结果表明了较慢对峙反应对比参量法的正确性。     

时间参量法(Ⅳ)──对峙反应的热动力学研究

根据热动力学基本理论和对峙反应的通用微分动力学方程,将时间作为已知参量,建立了对峙反应热动力学时间参量法的数学模型,并利用该法分别研究了硝基乙烷与氨和三(羟甲基)氨基甲烷反应的热动力学.     

Thermokinetic Research Method for Simple-order Reactions. Double-thermoanalytical curve method

A novel thermokinetic research method for determination of the rate constant of a reaction taking place in a batch conduction calorimeter under isothermal conditions is proposed: the double-thermoanalytical curve method. The method needs only the characteristic time parameter t _m, the peak height Δ_m at time t _m and the peak area a*_m after time t _m for two thermoanalytical curves measured with different initial concentrations of the reactants: it conveniently calculates the rate constants. The thermokinetics of four reaction systems were studied with this method, and its validity was verified by the experimental results. This revised version was published online in July 2006 with corrections to the Cover Date.     

特征参量法 2: 可逆反应

根据几类可逆反应通用的微分动力学方程和热动力学变换方程,本文建立了可逆反应的特征参量研究法。应用该法在两个温度下研究了硝基乙烷分别与氨和Tris反应的热动力学, 实验结果验证了可逆反应特征参量法的正确性。     

Characteristic parameter method for studying chemical kinetics in calorimeter

A novel thermokinetic research method for determination of rate constants of simple-order reaction in batch conduction calorimeter under isothermal condition, the characteristic parameter method, is proposed in this paper. Only needing the characteristic time parameter tm obtained from the measured thermoanalytical curve, the kinetic parameters of reactions studied can be calculated conveniently with this method. The saponifications of ethyl propionate and ethyl acetate in aqueous ethanol solvent, the polymerization of acrylamide in aqueous solution, the ring opening reaction of epichlorohydrin with hydrobromic acid have been studied. The experimental results indicate that the characteristic parameter method for simple-order reaction is correct. This revised version was published online in August 2006 with corrections to the Cover Date.     

绝热式热动力学的研究4: 可逆反应的热谱解析

本文建立了可逆反应在绝热系统中的热动力学研究法, 并用自制的绝热式自动热量计, 研究了三个可逆反应体系的热动力学, 验证了本文方法的正确性。     

特征参量法1: 简单级数反应的热动力学研究法

建立了测定热动力学体系冷却常数的线性拟合法和简单级数反应通用的热动力学研究法---特征参量法。导出了简单级数反应的动力学参数Kn和速率常数kn的通用计算式。应用冷却常数的线性拟合法在不同温度下测定了两个反应体系的冷却常数, 探讨了温度、浓度、介质及装样方式对冷却常数的影响。应用简单级数反应的特征参量法研究了一级、二级、三级和分数级反应的热动力学, 结果文献值吻合。讨论了热动力学体系的冷却常数对速率常数计算结果的影响。     

热动力学特征对比参量法及其应用研究

基于简单级数反应的积分和微分热动力学方程，建立了热动力学特征对比参量 法的数学模型，提出了一种由特征时间参量计算特征对比参量的方法，通过几种不 同级数模型反应的热动力学研究证明了方法的正确性，并利用该法研究了过氧化氢 在磷酸盐缓冲液中氧化对苯醌反应的动力学特征，实验结果表明该反应动力学方程 可以表示为：dC(醌)/dt=kC(醌)C(H_2O_2)~0.5C(H~+)~(-0.5)     

HEH[EHP]从硫酸介质中萃取钴的反应热测定和热动力学性质

热动力学函数;微量量热法;HEH[EHP]从硫酸介质中萃取钴的反应热测定和热动力学性质     

绝热式热动力学的研究III:二级反应的热谱解析

本文建立了二级发应在绝热系统中的热动力学研究, 并用自制的绝热式自动量热计, 研究了几个放热反应体系的热动力学, 而且对吸热反应体系的热动力学研究进行了探索。     

热动力学对比参量法 --简单级数反应

根据化学反应动力学和热动力学基本理论, 建立了简单级数反应的热动力学对比参量方程, 提出了一种新的热动力学研究法--对比参量法. 利用该法可以从一张热谱图上同时解析出化学反应的速率常数、半衰期和热动力学体系的冷却常数. 实验结果验证了方法的正确性.     

自函数回归法: 连续一级反应的热动力学研究

根据热动力学基本原理,推导出了连续一级反应热动力学自函数递推方程,从而建立了一种新的连续一级反应的热动力学研究法---自函数回归法.应用该法分别研究了丁二酸二乙酯和邻苯二甲酸二乙酯皂化反应的热动力学。     

热动力学的研究(XXlV)——等浓度三级反应的热动力学

本文根据热动力学的基础理论,建立了等浓度三级反应的无量纲参数法,并用此法研究了甲醛与氨反应的热动力学.实验测得的速率常数与文献值吻合.     

Calorimetric Reaction Rate Determination with the Characteristic Kinetic Parameter Method

On the basis of the theory of thermokinetics proposed in the literature, a novel thermokinetic method for determination of the reaction rate, the characteristic parameter method, is proposed in this paper. Mathematical models were established to determine the kinetic parameters and rate constants. In order to test the validity of this method, the saponifications of ethyl benzoate, ethyl acetate and ethyl propionate, and the formation of hexamethylenetetramine were studied with this method. The rate constants calculated with this method are in agreement with those in the literature, and the characteristic parameter method is therefore believed to be correct.In the light of the characteristic parameter method, we have developed further two thermo-kinetic methods, the thermoanalytical single and multi-curve methods, which are convenient for simultaneous determination of the reaction order and the rate constant. The reaction orders and rate constants of the saponifications of ethyl acetate and ethyl butyrate and the ring-opening reaction of epichlorohydrin with hydrobromic acid were determined with these methods, and their validity was verified by the experimental results.This revised version was published online in November 2005 with corrections to the Cover Date.     

绝热式热动力学的研究II: 一级反应的热谱解析

本文采用自制的绝热式自动量热计,对两个反应体系进行了一级反应的绝热式热动力学研究.速率常数的计算结果在误差范围内,与文献值符合均好.本文还在实验数据处理中提出了局外过程热效应的线性校正法.     

连续一级反应的热动力学研究法: 自函数回归法

根据热动力学基本理论,推导出了热导式量热计测量的连续一级反应的热谱曲线的动力学解析方程,并推出了连续一级反应热动力学的自函数递推方程,由此建立了一种研究连续一级反应的热动力学新方法-自函数回归法。通过对丁二酸二乙酯和邻苯二甲酸二乙酯的皂化反应的热谱曲线分析,验证了自函数回归法的正确性。     

时间参量法4: 简单级数反应的双谱法

根据简单级数反应的热动力学方程,提出了一种新的热谱曲线解析方法---简单级数反应的双谱法。该法利用两张热谱曲线的特征热谱数据α~m^*,Δ~m,和t~m,便能以简单的数学形式计算出化学反应的速率常数。实验结果验证了方法的正确性。     

Bestimmung der Extraktionskonstanten der Tellur-Pyrasolindithiocarbaminate

Abstract

In this work the exchange reactions between the ion Te(IV) in the aqueous phase and the aryl substituted pyrasolindithiocarbaminates of zinc into chloroform have been investigated. The equilibrium (exchange) constants of these reactions have been determined experi mentally. The extraction constants and two-phase stability constants of Te(PDTC)₄ have been calculated.     

Complex Formation of Crown Ethers with Cations in Water–Organic Solvent Mixtures. III. Thermodynamics of Interaction Between Na+ Ion with 15-Crown-5 Ether in Water–Acetonitrile Mixtures at 25°C

Enthalpies of solution of 15-crown-5 ether in the acetonitrile–water–sodium iodide system have been measured at 25°C. The equilibrium constants of complex formation of 15C5 with sodium iodide have been determined by molar conductance at various mole ratios 15C5 to sodium iodide in mixtures of water with acetonitrile at 25°C. The thermodynamic functions for complexation of the crown ether with Na⁺ were calculated. From the result, the standard Gibbs energies of complex formation as a function of the normalized Lewis acidity parameters E ^N _T and enthalpy of solvation of 15C5 in the mixtures of water with acetonitrile have been analyzed. The enthalpies of transfer of the 15C5 complex with sodium iodide from pure acetonitrile to the mixtures studied were calculated and discussed.     

热动力学时间变量法——简单级数化学反应

在热动力学理论基础上提出了一种新的热动力学研究法--时间变量法.该法无须将反应进行到底,只需知道一张热谱图上的3个时间点t,t时刻峰高△和t前峰面积a,就可用计算机数值方法求算反应的速率常数.应用该法研究了一级反应、等浓度二级反应、不等浓度二级反应、三级反应和1.5级反应的热动力学.