【摘要】 应用Mureinik和Spiro方程到通过外球电子转移的（+）D-Co（phen）₃³⁺外消旋反应,证明了电子转移反应对Co（Ⅲ）和Co（Ⅱ）络离子的浓度是一级的,V=k₂[Co（Ⅲ）][Co（Ⅱ）].测得在水溶液中其活化能Ea为24.5kJ/mol,活化熵ΔS⁺为-151J/mol·K,20℃下的速度常数k₂为3.60 l/mol·S.作者还研究了水溶液中配体为H₂O、py、on、NH₃和bipy的六配位CO（Ⅱ）络离子对（+）D-Co（phen）₃³⁺外消旋速度的影响,得出Co（Ⅱ）络离子同Co（phen）₃³⁺的电子转移反应速度的顺序为: Co（H₂O）₆²⁺<Co（py）₆²⁺<Co（en）₃²⁺<Co（NH₃）₆²⁺<Co（phen）₃²⁺<Co（bipy）₃²⁺更多还原

【Abstract】 Applicaton of Mureinik and Spiro equations to the racemizatlon of (+)D-Co(Phen)33+ in aqueous solution through the outersphere electron transfer reaetion is reported in this paper. The kinetics of the eletron transfer reaction has been found fo be in first order with respect to both Co( Ⅲ ) and Co( Ⅱ ) complex ions, i, ev=k2 [Co (Ⅲ)] [Co( Ⅱ ) ], The activation energy of electron transfer reaction in system Co(phen)33+/2+ is 24.5 kJ/mol, activation entroPy △S+ is-151 J/mol.K, and the rate constant k2 is 3. 60 l/mol · s at 20℃ . The effects of Co(Ⅱ ) complexes coordinated with ligands such as H2O, py, en. NH3 and bipy on racemization of ( + )D-Co(Phen)33+are also studied, and the trend in the rates of electron transfer reactions between Co(phen)33+ and Co( Ⅱ ) complex ionis:Co(H2O)62+<Co(py)62+<Co(en)32+<Co(NH3)62+<Co(phen)32+<Co(ibpy)32+.更多还原