应用整体升温的方法结合循环伏安和电位阶跃实验技术研究了温度对Fe(CN)63-/4-体系电化学反应的影响，计算不同温度下Fe(CN)63-和Fe(CN)64-的扩散系数D以及异相反应速率常数k0。实验发现，在Fe(CN)63-/4-体系中，Fe(CN)63-的扩散系数随着温度的升高而增大，而Fe(CN)64-的扩散系数则因受到Fe(CN)63-影响而出现相反的趋势。同时，异相反应速率常数也随温度升高而呈现下降趋势，推测这是由于电极表面生成了普鲁士蓝。由于细胞色素c的核心是血红素铁卟啉环，电子的得失都关联铁原子的氧化还原，与Fe(CN)63-/4-体系的电化学反应在一定程度上有其相似性，本文同时应用整体升温的方法研究了温度对细胞色素c电化学反应的影响，计算不同温度下细胞色素c的动力学参数，并与Fe(CN)63-/4-工作比较。
Cyclic voltammetric and chronoamperometric techniques were employed to study the temperature effects on the electrochemical reaction of Fe(CN)63-/4- by self-made thermostatic water bath electrochemical cell. The diffusion coefficient D and the formal heterogeneous electron-transfer rate constant k0 were calculated at different temperatures from 25 °C to 75 °C. In the Fe(CN)63-/4- system, the DO values of Fe(CN)63- were directly proportional to temperature, while DR of Fe(CN)64- inversely proportional to temperature. The values of k0 decreased with the increase of temperature due possibly to the electrode passivation resulted from the decomposition of Fe(CN)63-/4- to a Prussian blue like film. Since the core of Cytochrome c is the heme iron porphyrin, the redox of Cytochrome c reflects that of the iron atoms, which is, in certain degrees, similar to the electrochemical reactions of Fe(CN)63-/4- system. Accordingly, the same techniques were used to study the temperature effects on Cytochrome c. The kinetic parameters of Cytochrome c at different temperature were also calculated and compared with those of Fe(CN)63-/4- system.
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