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Evidence of quasi-intramolecular redox reactions during thermal decomposition of ammonium hydroxodisulfitoferriate(III), (NH4)2[Fe(OH)(SO3)2]·H2O

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Abstract

Synthesis of ammonium hydroxodisulfitoferriate(III), (diammonium catena-{bis(μ 2-sulfito-κO,κO)-μ 2-hydroxo-κ2O}ferrate(III) monohydrate) (NH4)2[Fe(OH)(SO3)2]·H2O (compound 1) and its thermal behavior is reported. The compound is stable in air. Its thermal decomposition proceeds without the expected quasi-intramolecular oxidation of sulfite ion with ferric ions. The disproportionation reaction of the ammonium sulfite, formed from the evolved NH3, SO2 and H2O in the main decomposition stage of 1, results in the formation of ammonium sulfate and ammonium sulfide. The ammonium sulfide is unstable at the decomposition temperature of 1 (150 °C) and transforms into NH3 and H2S which immediately forms elementary sulfur by reaction with SO2. The formation and decomposition of other intermediate compounds like (NH4)2SnOx (n = 2, x = 3 and n = 3, x = 6) results in the same decomposition products (S, SO2 and NH3). Two basic iron sulfates, formed in different ratios during synthesizing experiments performed under N2 or in the presence of air, have been detected as solid intermediates which contain ammonium ions. The final decomposition product was proved to be α-Fe2O3 (mineral name hematite).

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Acknowledgements

J. Magyari thanks for supporting the research by Ministry of Education, Science and Technological Development of the Republic of Serbia (Grant No. 172014). I. M. Szilágyi thanks for a János Bolyai Research Fellowship of the Hungarian Academy of Sciences and an ÚNKP-17-4-IV-BME-188 Grant. An OTKA PD-109129 Grant, a VEKOP-2.3.2.-16-2017-00013 and a K 124212 Grant are acknowledged.

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Authors and Affiliations

  1. Research Centre for Natural Sciences, Hungarian Academy of Sciences, Magyar Tudósok krt. 2, Budapest, 1519, Hungary

    Tünde Kocsis, Zoltán May & László Kótai

  2. Department of Chemistry, Biochemistry and Environmental Protection, Faculty of Sciences, University of Novi Sad, Trg Dositeja Obradovića 3, Novi Sad, 21000, Serbia

    József Magyari

  3. János Szentágothai Research Centre, University of Pécs, Ifjúság útja 20, Pecs, 7624, Hungary

    István E. Sajó

  4. Institute of Chemistry, ELTE Eötvös Lorand University, Pázmány Péter sétány 1/A, Budapest, 1117, Hungary

    Tibor Pasinszki & Zoltán Homonnay

  5. Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, Műegyetem rakpart 3, Budapest, 1111, Hungary

    Imre M. Szilágyi

  6. Department of Organic Chemistry and Technology, Budapest University of Technology and Economics, Budafoki út 8, Budapest, 1111, Hungary

    Attila Farkas

  7. Institute of Mineralogy and Crystallography, Universitat Wien, Althanstraße 14 (UZA 2), 1090, Vienna, Austria

    Herta Effenberger

  8. Faculty of Earth Science and Engineering, The University of Miskolc, Miskolc-Egyetemváros, 3515, Hungary

    Sándor Szakáll

  9. Department of Chemistry, Deogiri College, Station Road, Aurangabad, MS, 431 005, India

    Rajendra P. Pawar

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  1. Tünde Kocsis
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Correspondence to László Kótai.

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Kocsis, T., Magyari, J., Sajó, I.E. et al. Evidence of quasi-intramolecular redox reactions during thermal decomposition of ammonium hydroxodisulfitoferriate(III), (NH4)2[Fe(OH)(SO3)2]·H2O. J Therm Anal Calorim 132, 493–502 (2018). https://doi.org/10.1007/s10973-017-6901-4

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