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Chemical Papers

, Volume 73, Issue 4, pp 821–831 | Cite as

Technological condition optimization and kinetic study on the electrochemical soluble manganese(III) production in H2SO4

  • Jinfang Chen
  • Sihao Liu
  • Yan WangEmail author
Original Paper
  • 67 Downloads

Abstract

Soluble trivalent manganese solution can be used as an electrolyte for manganese redox flow battery (MRFB), due to its low cost, environmental friendliness and multiple states of charge. However, poor stability of soluble trivalent manganese solution and low trivalent manganese concentration are the disadvantages of electrolyte. To optimize the stability and conductivity of soluble trivalent manganese solution, the sulfuric acid concentration, one of the major influence factors, should be firstly improved. Two-compartment cell electrolysis technology was successfully used in this work. Moreover, to improve the concentration of Mn3+, some key factors, such as the concentration of MnSO4, current density, electrolysis time and temperature, should be further adjusted. The results demonstrated that the concentration of this produced trivalent manganese (≧ 0.3 M in 6 M H2SO4;≧ 0.4 M in 5 M H2SO4;≧ 0.5 M in 4 M H2SO4) is much higher than that have been reported. Solid product of manganese(III) sulfate was also firstly prepared. For the formation of soluble trivalent manganese, the 5 mol/L H2SO4 is the optimal acidity and 10.9 mA/cm2 is the best current density at 273 K for 3 h. Some electrochemical kinetics parameters had also been calculated (electrolyte is 5 M H2SO4 and 0.4 M MnSO4), e.g., diffusion coefficient of Mn2+ is 5.3057 × 10−6 cm2/s, transfer coefficient of electrode reaction is 0.3782, and exchange current density is 1.5662 × 10−4 A/cm2. The CV results demonstrated that the redox process of Mn(III)/Mn(II) is the quasi-reversible process.

Keywords

Electrochemical synthesis Anodic oxidation Manganese(III) Kinetic study 

Notes

Acknowledgements

The authors gratefully acknowledge the financial support for this research by the Ministry of Education. This work was funded by the National Natural Science Foundation of China.

References

  1. Alsheyab M, Jiang JQ, Stanford C (2009) On-line production of ferrate with an electrochemical method and its potential application for wastewater treatment—a review. J Environ Manag 90(3):1350–1356CrossRefGoogle Scholar
  2. Aslan Hakan, Öktemer Atilla, Dal Hakan, Hökelek Tuncer (2017) Synthesis of ferrocene substituted dihydrofuran derivatives via manganese(III) acetate mediated radical addition-cyclization reactions. Tetrahedron 73:7223–7232CrossRefGoogle Scholar
  3. Barek J, Berka A, Steyermark A (1980) The use of trivalent manganese compounds in titrimetr. Crit Rev Anal Chem 9:55–95CrossRefGoogle Scholar
  4. Barnet NW, Hindson BJ, Jones P, Smith TA (2002) Chemically induced phosphorescence from manganese(III)during the oxidation of various compounds by manganese(III), (IV)break and (VII)in acidic aqueous solutions. Anal Chim Acta 451:181–188CrossRefGoogle Scholar
  5. Bhaskar A, Liu C-J, Yuan JJ (2013) Thermoelectric properties of Ca(1-x)Gd(x)MnO(3-δ) (0.00, 0.02, and 0.05) systems. J Electroceram 31:124–128CrossRefGoogle Scholar
  6. Buch JJU, Pathak TK, Lakhani VK, Vasoya NH, Modi KB (2007) High temperature thermoelectric power study on calcium substituted lanthanum manganites. J Phys D Appl Phys 40(17):5306CrossRefGoogle Scholar
  7. Cao XZ, Wang XQ, Song TY (1994) Activity on the oxidation of styrene with manganese benzolporphyrins as the catalysts under mild conditions. Inorg Chem 2:91–95Google Scholar
  8. Chao Y, Xie L, Cao W (2013) Chemiluminescence enhancement effect for the determination of acetaminophen with the catalysis of manganese deuteroporphyrin (Mn(III)DP). Key Eng Mater 575:249–252CrossRefGoogle Scholar
  9. Chuang C, Chen Y (2016) Manganese(III) acetate mediated oxidative radical cyclizations of α-substituted N-[2-(phenylethynyl)phenyl]acetamides. Tetrahedron 72:1911–1918CrossRefGoogle Scholar
  10. Goncharik VP, Tikhonova LP, Yatsimirskii KB (1973) State of manganese (III) in solutions of perchlorate and sulfuric acids. Zh Inorg Khim 18:1248–1254Google Scholar
  11. Gorni-Pinkesfeld O, Hasson D, Semiat R, Shemer H (2017) Hybrid electrolysis–crystallization system for silica removal from aqueous solutions. Desalination 407:41–45CrossRefGoogle Scholar
  12. Gritzner, G (1977) Operation of a diaphragm electrolylytic cell for producing chlorine including feeding an oxidizing gas having a regulated moisture content to the cathode. US, US4035255Google Scholar
  13. Jin M (2009) Electrochemical properties of Mn3+/Mn2+couple at spectroscopic graphite. Meeting Abstract No. 186, 215th ECS Meeting, The electrochemical Society, San Francisco,24–29 May 2009Google Scholar
  14. Kirby F, Burnea B, Shi H, Ko KC, Lee JY (2017) Reduction potential tuning of first row transition metal MIII/MII (M = Cr, Mn, Fe Co, Ni) hexadentate complexes for viable aqueous redox flow battery catholytes: a DFT study. Electrochim Acta 246:156–164CrossRefGoogle Scholar
  15. Kong Y, Chen X, Ni J, Yao S, Wang W, Luo Z et al (2010) Palygorskite–expanded graphite electrodes for catalytic electro-oxidation of phenol. Appl Clay Sci 49(1–2):64–68CrossRefGoogle Scholar
  16. Kuhn AT, Randle TH (1983) Kinetic study of the electrolytic oxidation of manganese(II) to manganese(III) in sulphuric acid. J. Chem. Soc. Faraday Trans 79:417–430CrossRefGoogle Scholar
  17. Laviron E (1979) General expression of the linear potential sweep voltammogram in the case of diffusionless electrochemical systems. J Electroanal Chem Interfacial Electrochem 101:19–28CrossRefGoogle Scholar
  18. Lim Keun Hong, Park Seung, Yun Jong-Il (2015) Study on exchange current density and transfer coefficient of uranium in LiCl-KCl molten salt. J Electrochem Soc 162:E334–E337CrossRefGoogle Scholar
  19. Liu Y, Lin Q, Li L, Fu J, Zhu Z, Wang C, Qian D (2014) Study on hydrometallurgical process and kinetics of manganese extraction from low-grade manganese carbonate ores. Int J Min Sci Technol 24:567–571CrossRefGoogle Scholar
  20. Mahadevaiah AG, Kumar MSY, Sathisha MS, Suresh MAMS, Gowtham MD (2007) Exploitation of simple redox reaction between manganese(III) and o-tolidine for a highly sensitive spectrophotometric determination of ascorbic acid. Anal Chem Indian J 6:70–74Google Scholar
  21. Otamonga J-P, Abdel-Mageed A, Agater IB, Jewsbury RA (2015) A kinetic study of the enhancement of solution chemiluminescence of glyoxylic acid oxidation by manganese species. Luminescence 30:507–511CrossRefGoogle Scholar
  22. Pastor TJ, Pastor FT (2000) The role of manganese(IV) compounds as oxidants—a review. Talanta 52:959–970CrossRefGoogle Scholar
  23.  Rajesh B, Ravindranathan Thampi K, Bonard JM, Xanthopoulos N, Mathieu HJ et al (2003) Carbon nanotubes generated from template carbonization of polyphenyl acetylene as the support for electrooxidation of methanol. J Phys Chem B 107:2701–2708CrossRefGoogle Scholar
  24. Selim RG, Lingane JJ (1959) Coulometric titration with higher oxidation states of manganese: electrolytic generation and stability of manganese(III) in sulfuric acid media. Anal Chim Acta 21:536–544CrossRefGoogle Scholar
  25. Shyla B, Nagendrappa G (2013) Redox spectrophotometric method involving electrolytically generated manganese(III) sulphate with diphenylamine for the determination of ascorbic acid present in the samples of various fruits, commercial juices and sprouted food grains. Food Chem 138:2036–2042CrossRefGoogle Scholar
  26. Soloveichik GL (2015) Flow batteries: current status and trends. Chem Rev 115:11533–11551CrossRefGoogle Scholar
  27. Tripathy S, Vanjari SRK, Singh V, Swaminathan S, Singh SG (2016) Electrospun manganese (III) oxide nanofiber based electrochemical DNA-nanobiosensor for zeptomolar detection of dengue consensus primer. Biosens Bioelectron 90:378–387CrossRefGoogle Scholar
  28. Vogel AI (1961) A text-book of quantitative inorganic analysis. Longmans 26(2):130–143Google Scholar
  29. Wan M, Yuan H, Ma YC, Zhang WH (2018) Determination of optimal geometrical parameters of peripheral mills to achieve good process stability. Adv Manuf 6(61006):1–13Google Scholar
  30. Wang XM, Nishina T, Uchida I (1997) Application of the microelectrode technique to the kinetic study of lithium deposition/dissolution and alloying in organic solutions. J Power Sources 68:483–486CrossRefGoogle Scholar
  31. Wang J, Wang C, Huo Y, Nie Y, Li L (2010) Preparing of Mn(III) solution used for chemiluminescence detection. Chinese J Anal Chem 27:32–34Google Scholar
  32. Xue FQ, Wang YL, Wang WH, Wang XD (2008) Investigation on the electrode process of the mn(ii)/mn(iii) couple in redox flow battery. Electrochim Acta 53(22):6636–6642CrossRefGoogle Scholar
  33. Yang E, Shi J, Liang H (2012) On-line electrochemical production of ferrate (VI) for odor control. Electrochim Acta 63:369–374CrossRefGoogle Scholar
  34. Zhang Y, Zhang Z, Qi G, Sun Y, Wei Y, Ma H (2007) Detection of indomethacin by high-performance liquid chromatography with in situ electrogenerated Mn(III) chemiluminescence detection. Anal Chim Acta 582:229–234CrossRefGoogle Scholar

Copyright information

© Institute of Chemistry, Slovak Academy of Sciences 2018

Authors and Affiliations

  1. 1.School of Chemical Engineering and PharmacyWuhan Institute of TechnologyWuhanPeople’s Republic of China

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