CAJ | 학술논문

用磷钼酸与咪唑合成了一种新的杂多酸-有机电荷转移盐(C_3H_5N_2H)_3[PMo_(12)O_(40)].通过元素分析、红外光谱、固体漫反射光谱、电子自旋共振及热分析等测试技术对其进行了表征,用单扫描法(Achar法和Coats-Redfern法)对合成化合物的TG分析结果进行了非等温热分解动力学研究.推断结果表明,合成化合物的第1步热分解为球对称的三维扩散机理(n=2),其动力学方程为dα/dt=1.58×10~8[1-(1-α)~(1/3)]~(-1)(1-α)~(2/3)exp(-40 931.0/T),求得分解反应的表观活化能E=340.30 kJ/mol,指前因子A=1.05×10~8 s~(-1).标题化合物对紫外光具有光致变色性质,用固体漫反射光谱研究了其光致变色反应动力学.结果显示,其光致变色反应表现为一级或准一级动力学,速率常数k=9.80×10~(-5) s~(-1).
용린목산여미서합성료일충신적잡다산-유궤전하전이염(C_3H_5N_2H)_3[PMo_(12)O_(40)].통과원소분석、홍외광보、고체만반사광보、전자자선공진급열분석등측시기술대기진행료표정,용단소묘법(Achar법화Coats-Redfern법)대합성화합물적TG분석결과진행료비등온열분해동역학연구.추단결과표명,합성화합물적제1보열분해위구대칭적삼유확산궤리(n=2),기동역학방정위dα/dt=1.58×10~8[1-(1-α)~(1/3)]~(-1)(1-α)~(2/3)exp(-40 931.0/T),구득분해반응적표관활화능E=340.30 kJ/mol,지전인자A=1.05×10~8 s~(-1).표제화합물대자외광구유광치변색성질,용고체만반사광보연구료기광치변색반응동역학.결과현시,기광치변색반응표현위일급혹준일급동역학,속솔상수k=9.80×10~(-5) s~(-1).
A new heteropolyacid-organic charge transfer salt (C_3H_5N_2H)_3[PMo_(12)O_(40)] was synthesized from phosphomolybdic acid and imidazole, and characterized by means of elemental analysis, infrared spectrum(IR), diffuse reflectance spectrum(DRS), electron spin resonance(ESR) and thermal analysis techniques(TG). The decomposition mechanism and nonisothermal kinetic parameters of the salt were obtained from an analysis of the TG-DTG curves obtained by means of the single scanning methods(the Achar method and Coats-Redfern method). For the first step of the thermal decomposition reaction, the possible reaction mechanism was suggested to be a three-dimensional diffusion. Its kinetic equation with parameters is dα/dt=1.58×10~8[1-(1-α)~(1/3)]~(-1)(1-α)~(2/3) exp(-40 931.0/T) with E=340.30 kJ/mol and A=1.05×10~8 s~(-1). The salt shows photochromism under ultraviolet light, and its photochromic reaction was studied with solid diffuse reflectance spectra and found to exhibit first-order or pseudo-first-order kinetics with a rate constant k=9.80×10~(-5) s~(-1).