Effect of Fe2+/Fe3+Interconvertion on Reduction Behavior of Fe3+ in Acidic Electrolytes

doi:10.13208/j.electrochem.161129

Abstract

Abstract: The influences of ferrous/ferric (Fe²⁺/Fe³⁺) interconvertion on electrochemical reduction and electrode reaction of Fe³⁺ were investigated by using linear sweep voltammetry, potentiostatic method and cyclic voltammetry (CV) in acidic electrolytes containing chloride ion (Cl^- ) and sulfate ion (SO₄^2-). It was shown that the reduction process of Fe³⁺/Fe²⁺ would take place in two independent stages: (1) the reduction of Fe³⁺ to Fe²⁺ at E=0.35V and (2) the co-precipitation of Fe²⁺ by forming Fe(OH)₂ (E≤-0.3 V) instead of Fe. The major effect of Fe²⁺/Fe³⁺ interconvertion on the reduction is the |ipa/ipc| of quasi-reversible and equilibrium potential in the first stage. Practically speaking, the |ipa/ipc| values increased with the increase of c(Fe³⁺ )/c(Fe²⁺ ), and the values of |ipa/ipc| at fast sweep rates were less strongly affected than those at slow sweep rates. The least variation in |ipa/ipc| (|i_pa/i_pc|≈1.20) with sweep rate was observed in 0.50 mol·L^-1 Fe²⁺ and 0.50 mol·L^-1 Fe³⁺ solutions. Meanwhile, the equilibrium potential was also affected by c(Fe³⁺ )/c(Fe²⁺ ). The equilibrium potential shifted more positively from E₁=0.501 V in No. ① to E₅=0.565 V in No. ⑤ among the five samples studied in this work.

Key words: Fe²⁺/Fe³⁺interconvertion, cyclic voltammetry, polarization curve, reduction behavior

CLC Number:

O646.5

QIN Jian-xin, LIN Feng, LIU Wen-ping, CHEN Chao, REN Meng-de. Effect of Fe²⁺/Fe³⁺Interconvertion on Reduction Behavior of Fe³⁺in Acidic Electrolytes[J]. Journal of Electrochemistry, 2017, 23(6): 702-707.

References

[1] Shi Y H(史艳华). Effect of Fe²⁺ concentration on the electrodeposition Fe-Ni coating on 20 steel[J]. Journal of University of Science and Technology Beijing(北京科技大学学报). 2011, 33(3):313-317

[2] Maria Poroch-Seritan, Lgor Cretescu, Corneliu Cojocaru,et al. Experimental design for modelling and multi-response optimization of Fe–Ni electroplating process[J]. Chemical Engineering Research and Design，2015, 4(96):138-149.

[3] Ju-Hwan Kim, TaiHong Yim, Jae-Ho Lee. Effects of bath and operating conditions on the composition of Ni–Fe alloy electroplating for solar cell substrate[J]. Current Applied Physics, 2013, 13(2):S108-S110.

[4] Mingming Lan, Huiqin Li, Weihua Huang, et al. Effect of cathode vibration and heat treatment on electromagnetic properties of flake-shaped diatomite coated with Ni–Fe alloy by electroplating[J]. Journal of Magnetism and Magnetic Materials, 2015, 377:243-251.

[5] MH Seo, JK Dong, JS Kim. The effects of pH and temperature on Ni–Fe–P alloy electrodeposition from a sulfamate bath and the material properties of the deposits[J]. Thin Solid Films, 2005, 489(1–2):122-129.

[6] Tian H(田华).Study on iron electroplating and Fe-SiC composite electroplating technices[D]. Qingdao: Qingdao University of Science and Technology(青岛科技大学),2009.11-17.

[7] Zhou Y M(周雍茂),LIU M(刘铭). Potential-pH diagrams for the Fe-H₂O system based on the principle of simultaneous equilibrium [J]. Journal of Changsha university of Science and Technology(Natural Science)长沙理工大学学报(自然科学版), 2004, 1(2):89-92.

[8] Caldcron E H, Wuthrich, Mandin P, et al. Estimation of the effectiveness factor of an outer-sphere redox couple (Fe²⁺/Fe³⁺) using rotating disk Ti/IrO₂ electrodes of different loading[J]. Journal of applied electrochemistry, 2009, 39(8):1379-1394.

[9] Derek Pletcher, Helen Saxton. A first course in electrode processes[M]. Royal Society of Chemistry, 2009.

[10] Lu S J(鲁思伽)，Hong J(洪军)，Qi SH L(祁士华), et al. Transform rules between Fe²⁺/Fe³⁺ in the UV/Fenton system[J]. Acta Scientiae Circumstantiae(环境科学学报), 2009, 29(6):1258-1262.

[11] Qin S H, Meng J, Tang X H, et al. Monitoring the inorganic chemical reaction by surface-enhanced Raman spectroscopy: A case of Fe³⁺ to Fe²⁺ conversion[J]. Talanta, 2016, 146:452-456.

[12] Jean Horkans. On the role of buffers and anions in nichel-iron electrodeposition[J]. J. Electrochem. Soc., 1979，126（11）:1861-1867.

[13] Bard A J, Faulkner L R.. Electrochemical Methods-Fundamentals and Applications[M]. New York: John Wiley&Sons,INC, 1980. 237.

[14] Z.-W. Tian（田昭武）. Electrochemical Research Methods(电化学研究方法) [M]. Beijin：Science Press (科学出版社)，1984,3:4-7.

[15] Allen J. Bard, Larry R. Faulkner. Electrochemical Methods Fundamentals and Applications[M]. New York: John Wiley&Sons,INC, 1980. 51-53.

Effect of Fe²⁺/Fe³⁺Interconvertion on Reduction Behavior of Fe³⁺in Acidic Electrolytes

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Xue-Fan Cai, Sheng Sun. Cyclic Voltammetric Simulations on Batteries with Porous Electrodes [J]. Journal of Electrochemistry, 2021, 27(6): 646-657.
[2]	XING Yi-fei, LI Na, WEN Xiao-fang, HAN Hong-yan, CUI Min, ZHANG Cong, REN Ju-jie, JI Xue-ping. Electrochemical Determination of Dopamine Based on Metal-Substituted Polyoxometalates Composites [J]. Journal of Electrochemistry, 2020, 26(6): 890-899.
[3]	HAN Ping, FENG Hai-tao, DONG Ya-ping, TIAN Sen, ZHANG Bo, LI Wu. Electrochemical Oxidation of Metal Chromium in odium Hydroxide Aqueous Solution [J]. Journal of Electrochemistry, 2020, 26(3): 413-421.
[4]	GUO Jia-yao, CHEN Duan, ZHANG Jie, ZHAN Dong-ping. Cyclic Voltammetry Coupled with Faradic Adsorption/Desorption Processes: A Finite Element Simulation [J]. Journal of Electrochemistry, 2020, 26(2): 281-288.
[5]	LING Yun, TANG Jing, LIU Guo-kun, ZONG Cheng. Transient Electrochemical Surface-Enhanced Raman Spectroscopic Study in Electrochemical Reduction of P-Nitrothiophenol [J]. Journal of Electrochemistry, 2019, 25(6): 731-739.
[6]	LI Ming-xue, SHI Hang, LIU Jia, ZHANG Meng, ZHOU Jian-zhang, WU De-yin, TIAN Zhong-qun. Electrochemical Behaviors of Azopurine on Gold Electrodes [J]. Journal of Electrochemistry, 2019, 25(6): 651-659.
[7]	M. Rostom Ali, S Sankar Saha, Md Ziaur Rahman. Electrodeposition of Cobalt from Eutectic-Based Ionic Liquid [J]. Journal of Electrochemistry, 2018, 24(5): 546-554.
[8]	DONG Peng-fei, LI Na, ZHAO Hai-yan, CUI Min, ZHANG Cong, REN Ju-jie，JI Xue-ping. Synthesis of Keggin Polyoxometalates Modified Carbon Paste Electrode as A Sensor for Dopamine Detection [J]. Journal of Electrochemistry, 2018, 24(5): 555-562.
[9]	HUANG Shuai-shuai, LIU Cheng, JIN Lei, YANG Fang-zu, TIAN Zhong-qun, ZHOU Shao-min. Complex Coordination Silver Electrocrystallization Mechanism on Glassy Carbon Electrode Surface [J]. Journal of Electrochemistry, 2018, 24(4): 344-350.
[10]	M. Rostom Ali, R. K. Biswas, Md. Golam Zakaria. An electrochemical dissolution study of ilmenite fraction of beach sand in sulphuric acid solution [J]. Journal of Electrochemistry, 2017, 23(4): 420-428.
[11]	HUANG Xian-jie, YAN Hui, HUANG Shuai-shuai, YANG Fang-zu*, TIAN Zhong-qun, ZHOU Shao-min. Electrochemical Nucleation of Invar Alloy on Glassy Carbon Electrode [J]. Journal of Electrochemistry, 2017, 23(1): 7-12.
[12]	ZHENG Yan-jie, YAO Hong, WENG Shao-huang, PENG Hua-ping,GONG Shi-wen, HUANG Li, DAI Qiang, LIN Xin-hua. Electrochemical Behaviors and Determinations of Terbutaline Sulfate at Poly Eriochrome Black T Modified Electrode [J]. Journal of Electrochemistry, 2016, 22(6): 617-623.
[13]	YANG Xing，CHEN Ping*. An Electrochemical Investigation of p-sulfophenylazo Calix[4]arene in a Buffer Solution [J]. Journal of Electrochemistry, 2016, 22(1): 37-42.
[14]	SONG Xiu-li, JIA Rui-long, DONG Wen-yan, LIANG Zhen-hai*. Mechanism Study on the Electrocatalytic Oxidation of Acetylene to Oxalic Acid [J]. Journal of Electrochemistry, 2015, 21(4): 353-361.
[15]	ZOU Xian-ping, KANG Zong-xuan, HUANG Yu-lan, SHU Dong*, ZHONG Ya-yun, HAO Jun-nan, LIAO Yu-qing. Reaction Mechanisms Study of Pb Electrodes in Sulfuric Acid and Sodium Sulfate Solutions by EQCM [J]. Journal of Electrochemistry, 2015, 21(4): 362-367.