水合醋酸铜热解过程动力学研究

THE KINETIC STUDIES ON THERMAL DECOMPOSITION OF COPPER ACETATE

为了用醋酸铜取代昂贵难求的醋酸铑作原料,合成在太阳能利用方面很有前途的过渡金属双核络合物光敏荆,用热重(TG)法求得了水合醋酸铜热解过程2个步骤的有关动力学参数:第一步骤对应温度为66～140℃;反应级数n=1;表观活化能E=91.7kJ·mol^(-1);指前因子A=6.65×10^(11)min^(-1).第二步骤对应温度为223～295℃;n=1;E=163kJ.mol^(-1);A=7.95×10^(14)min^(-1).确定了2个步骤的速率常数k对温度T的函数关系式.计算了第二步骤的标准活化熵△_r~≠S_m^(?)=34.2J·mol^(-1)·K^(-1),标准活化焓△_r~≠H_m^(?)=162kJ·mol^(-1).评价了醋酸铜的热稳定性,并确定了用其作原料合成双核铜络合物时的适宜反应温度.

Copper acetate is one of reactants for synthesizing dinuclear copper com- plexes.Thermal decomposition of copper acetate is studied by TG.Some kinetic parameters of this thermal decomposition are determined. For the first step of the decomposition, temperature range is 66~140℃, reaction or der n=1, activation energy E=91.7kJ·mol^(-1), preexponential factor A=6.65×10^(11)min^(-1). For the second step, temperature range is 223~295℃, n=1, E=163kJ·mol^(-1), A=7.95×10^(14) min^(-1). entropy of activation and enthalpy of activation of the second step are deter- mined too, △_r~≠S_m^(?)=34.2J·mol^(-1)·K^(-1), △_r~≠H_m^(?)=162kJ·mol^(-1).The thermal stability of copper acetate is evaluated. The temperature range of synthesizing dinudear copper complexes is fixed.