Corresponding Author

Jing TANG(jingtang@fzu.edu.cn)


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.

Graphical Abstract


Temperature effect, Cytochrome c, Diffusion coefficients, formal heterogeneous electron-transfer rate constant

Publication Date


Online Available Date


Revised Date


Received Date



[1] Gabrielli C, Keddam M, Lizee J F. Frequency analysis of a temperature perturbation technique in electrochemistry: Part I. Theoretical aspects [J]. Journal of Electroanalytical Chemistry,1993,359(1-2):1-20.

[2] Crooks R M, Fan FRF, Bard A J. Electrochemistry in near-critical and supercritical fluids. 1. Ammonia [J]. Journal of the American Chemical Society,1984,106(22):6851-6852.

[3] Flarsheim W M, Tsou Y M, Trachtenberg I, Johnston K P, Bard A J. Electrochemistry in near-critical and supercritical fluids. 3. Studies of bromide, iodide, and hydroquinone in aqueous solutions [J]. The Journal of Physical Chemistry,1986,90(16):3857-3862.

[4] Crooks R M, Bard A J. Electrochemistry in near-critical and supercritical fluids. 4. Nitrogen heterocycles, nitrobenzene, and solvated electrons in ammonia at temperatures to 150.degree.C [J]. The Journal of Physical Chemistry,1987,91(5):1274-1284.

[5] Peter Grundler, Andreas Kirbs, Dunsch aL. Modern Thermoelectrochemistry [J]. ChemPhysChem,2009,10:1722 – 1746.

[6] Qu Xiao-gang(曲晓刚), Qiao Zhuan-hong(乔专虹),Lu Tian-hong(陆天虹)et al. Study on the Electrochemical Behaviour of Cytochrome C. [J]. Chinese Journal of Analytical Chemistry(分析化学),1994,22(12):1267-1272.

[7] Eddowes M J, Hill HAO. Novel method for the investigation of the electrochemistry of metalloproteins: cytochrome c [J]. Journal of the Chemical Society, Chemical Communications,1977(21):771b-772.

[8] Yeh P K, T. Reversible electrode reaction of cytochrome c. [J]. Chem Lett 1977,10:1145–1148.

[9] Qin Yu-hua(秦玉华), Zhou Li-heng(周立恒), Wang Sheng-tian(王胜天) et al. Direct Electrochemistry of Cytochrome c at Nanoporous Alumina Templates Modified Electrodes . [J]. chem J Chinese Universities(高等学校化学学报),2004,25:636-637.

[10] Qin Yu-hua(秦玉华), Zhang Yuan-jian(张袁健), Xu Xiu-dong(徐修冬) et al. Direct Electrochemistry of Cytochrome c at Hydroxyapatite Modified Glassy Carbon Electrodes. [J]. Acta Chimica Sinica(化学学报),2004,62(9):860-863.

[11] Song Y Y, Jia W Z, Yang C, Xia X H. Template-Synthesized Protein Macroporous Biofilms: Conformational Related Direct Electron Transfer [J]. Advanced Functional Materials,2007,17(14):2377-2384.

[12] Hawkridge* KBKaFM. Temperature and Electrolyte Effects on the Electron-Transfer Reactions of Cytochrome c [J]. J Am Chem Soc,1985, 107( 25): 7412-7417

[13] Dai Y, Zheng Y, Swain G M, Proshlyakov D A. Equilibrium and Kinetic Behavior of Fe(CN)63?/4? and Cytochrome c in Direct Electrochemistry Using a Film Electrode Thin-Layer Transmission Cell [J]. Analytical Chemistry,2010,83(2):542-548.

[14] Bard LRFAJ. Electrochemical Methods Fundamentals and Applications [J]. Chemical Industry Press,1980,62-64.

[15] Zhuang Qian-kun(庄乾坤),Chen Hong-yuan(陈洪渊).The Temperature Effect of Microelectrode and Its Applications to the Determination of Kinetic Parameters .[J]. Chem J Chinese Universities(高等学校化学学报),1996,17(2):224-226.

[16] Nicholson R S. Theory and Application of Cyclic Voltammetry for Measurement of Electrode Reaction Kinetics [J]. Analytical Chemistry,1965,37(11):1351-1355.

[17] Ellis D, Eckhoff M, Neff V D. Electrochromism in the mixed-valence hexacyanides. 1. Voltammetric and spectral studies of the oxidation and reduction of thin films of Prussian blue [J]. The Journal of Physical Chemistry,1981,85(9):1225-1231.

[18] Huang W, McCreery R. Electron transfer kinetics of Fe(CN)6 on laser-activated and CN--modified Pt electrodes [J]. Journal of Electroanalytical Chemistry,1992,326(1-2):1-12.

[19] Taniguchi I, Toyosawa K, Yamaguchi H, Yasukouchi K. Voltammetric response of horse heart cytochrome c at a gold electrode in the presence of sulfur bridged bipyridines [J]. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry,1982,140(1):187-193.

[20] Eddowes M J, Hill HAO. Electrochemistry of horse heart cytochrome c [J]. Journal of the American Chemical Society,1979,101(16):4461-4464.

[21] Cai Chen-xin(蔡称心),Ju Huang-xian(鞠熀先),Chen Hong-yuan(陈洪渊). Studies on Electrode Process Thermodynamics of Cytochrome C at A Microband Gold Electrode Modified with 4,6-Dimethyl-2-mercaptopyrimidine [J]. Chem J Chinese Universities(高等学校化学学报),1995,16(1):31-34.



To view the content in your browser, please download Adobe Reader or, alternately,
you may Download the file to your hard drive.

NOTE: The latest versions of Adobe Reader do not support viewing PDF files within Firefox on Mac OS and if you are using a modern (Intel) Mac, there is no official plugin for viewing PDF files within the browser window.