二氯化氯·五氨合钴(Ⅲ)配合物的热分解动力学机理研究

用非等温热重法研究了二氯化氯·五氨合钴(Ⅲ)配合物[Co(NH3)5Cl]Cl2 的热分解反应机理.非等温热重数据通过ACHAR法和COATS-REDFERN法进行拟合,结果得到第1 步反应的微分动力学函数f(α)= 4α3/4,积分动力学函数g(α)= α1/4, 活化能E1 =132.628 kJ/mol,E2 =24.888 4 kJ/mol;指前因子A1=2.843 9×10-14/s,A2 =2.199 1×10-2/s;动力学补偿效应方程lnA1=4.463 6E1+5.696 4,lnA2=4.516 6E2+38.465.第2步反应的微分动力学函数f(α)=3/2[(1-α)1/3 -1]-1,积分动力学函数g(α)= α+(1-α)ln(1-α), 活化能E1 =137.306 1 kJ/mol,E2=332.607 8 kJ/mol;指前因子A1=2.744 4×1011/s,A2=1.395 8×102 5/s;动力学补偿效应方程lnA1=5.005 8E2+5.617 4,lnA2=5.031 7E1+43.026.

Non-isothermal kinetics of the thermal decomposition of[Co(NH3)5Cl]Cl2

The thermal decomposition kinetic mechanism of [Co(NH_3)_5Cl]Cl_2 has been studied non-isothermally by TG method. The data from non-isothermally experiments were analyzed by ACHAR and COATS-REDFERN method. It was found that the first integral kinetic equation and differential coefficient kinetic eqution for the deamination of [Co(NH_3)_5Cl]Cl_2 are f(α)= 4α 3/4 , g(α)= α 1/4 , activation energy are E _1=132.628 kJ/mol, E _2=24.8884 kJ/mol.Pre-exponential factor A _1=2.8439×10 -14 /s, A _2=2.1991×10 -2 /s, and kinetic compensation effect equation ln A _1=4.4636 E _1+5.6964,ln A _2=4.5166 E _2+38.465. It was found that the second integral kinetic equation and differential coefficient kinetic eqution for the decomposition of [Co(NH_3)_5Cl]Cl_2 are f(α)=3/2[(1-α) 1/3 -1] -1 , g(α)= α+(1-α) ln (1-α) , activation energy are E _1=137.3061 kJ/mol, E _2=332.6078 kJ/mol.Pre-exponential factor A _1=2.7444×10 11 /s, A _2=1.3958×10 25 /s, and kinetic compensation effect equation ln A _1=5.0058 E _2+5.6174,ln A _2=5.0317 E _1+43.026.