Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH ARTICLE

Oxyhalogen–Sulfur Chemistry: Oxidation of a Thiourea Dimer, Formamidine Disulfide, by Chlorine Dioxide

Bice S. Martincigh A , Morgen Mhike B , Kayode Morakinyo B , Risikat Ajibola Adigun B and Reuben H. Simoyi A B C

A School of Chemistry and Physics, University of KwaZulu-Natal, Westville Campus, Private Bag X54001, Durban 4000, Republic of South Africa.

B Department of Chemistry, Portland State University, Portland, OR 97207-0751, USA.

C Corresponding author. Email: rsimoyi@pdx.edu

Australian Journal of Chemistry 66(3) 362-369 http://dx.doi.org/10.1071/CH12181
Submitted: 5 April 2012  Accepted: 21 November 2012   Published: 11 February 2013

Abstract

The oxidation of formamidine disulfide, FDS, the dimer of thiourea, by aqueous chlorine dioxide has been studied in highly acidic and mildly acidic media. FDS is one of the possible oxidation intermediates formed in the oxidation of thiourea by oxyhalogens to urea and sulfate. The reaction is exceedingly slow, giving urea and sulfate with a stoichiometric ratio of 5 : 14 FDS to chlorine dioxide after an incubation period of up to 72 h and only in highly acidic media which discourages the disproportionation of chlorine dioxide to the oxidatively inert chlorate. Mass spectrometric data suggest that the oxidative pathway proceeds predominantly through the sulfinic acid, proceeding next to the products sulfate and urea, while by-passing the sulfonic acid. Transient formation of the unstable sulfenic acid was also not observed.

Graphical Abstract Image


References

[1]  M. Mrakavova, M. Melichercik, A. Olexova, L. Treindl, Collect. Czech. Chem. Commun. 2003, 68, 23.
         | CrossRef | 1:CAS:528:DC%2BD3sXhtlGjsbY%3D&md5=e2bd641f6590d3cb49a5fed01e6a0096CAS | open url image1

[2]  B. Neumann, S. C. Muller, M. J. B. Hauser, O. Steinbock, R. Simoyi, N. S. Dalal, Abstr. Pap. Am. Chem. Soc. 1995, 209, 234.. open url image1

[3]  M. Kaholek, L. Treindl, React. Kinet. Catal. Lett. 1998, 63, 297.
         | CrossRef | 1:CAS:528:DyaK1cXjsFWgs70%3D&md5=067478e67728f4bcd3411990d2bede73CAS | open url image1

[4]  L. Kolar-Anic, G. Schmitz, J. Chem. Soc., Faraday Trans. 1992, 88, 2343.
         | CrossRef | 1:CAS:528:DyaK38Xltlymurg%3D&md5=ac9e76c6e1032dea36e022f903d8c84dCAS | open url image1

[5]  R. Cervellati, K. Honer, S. D. Furrow, C. Neddens, S. Costa, Helv. Chim. Acta 2001, 84, 3533.
         | CrossRef | 1:CAS:528:DC%2BD38XhtVSisLw%3D&md5=3f6bd32cc9f20533012c0e90e542e611CAS | open url image1

[6]  K. R. Kim, D. J. Lee, K. J. Shin, J. Chem. Phys. 2002, 117, 2710.
         | CrossRef | 1:CAS:528:DC%2BD38Xls1Smu7g%3D&md5=f2d1248754c57ed9b79d3298daaaaaf1CAS | open url image1

[7]  P. V. N. Lalitha, R. Ramaswamy, Collect. Czech. Chem. Commun. 1992, 57, 2235.
         | CrossRef | 1:CAS:528:DyaK3sXhs1ymtrY%3D&md5=ce792636c79286c43b0b0c45c4a01861CAS | open url image1

[8]  L. P. Tikhonova, S. V. Rosokha, E. A. Bakai, Kinet. Catal. 1997, 38, 225.
         | 1:CAS:528:DyaK2sXivV2hsbs%3D&md5=c8bdd562671bb8510cc8d76e0376d1bbCAS | open url image1

[9]  V. Petrov, S. K. Scott, K. Showalter, Philos. Trans. Roy. Soc. A 1994, 347, 631.
         | CrossRef | 1:CAS:528:DyaK2cXmtFCisr8%3D&md5=5317fc5902cdb86b6252cef4f149fee4CAS | open url image1

[10]  C. R. Chinake, R. H. Simoyi, J. Phys. Chem. 1993, 97, 11569.
         | CrossRef | 1:CAS:528:DyaK3sXmslSgurY%3D&md5=dfdbae037f5b3327f7d9e925b67e152dCAS | open url image1

[11]  I. R. Epstein, K. Kustin, P. Dekepper, M. Orban, Sci. Am. 1983, 248, 112.
         | CrossRef | 1:CAS:528:DyaL3sXhtlartbY%3D&md5=8578122d0bc3d78ce9ad0aa23e3f31c3CAS | open url image1

[12]  C. J. Doona, S. I. Doumbouya, J. Phys. Chem. 1994, 98, 513.
         | CrossRef | 1:CAS:528:DyaK2cXmtlCgtg%3D%3D&md5=0c2276aa0f4d22b1ef21820e728fc6aaCAS | open url image1

[13]  C. J. Doona, R. Blittersdorf, F. W. Schneider, J. Phys. Chem. 1993, 97, 7258.
         | CrossRef | 1:CAS:528:DyaK3sXkvVWit7k%3D&md5=16b9434149a0f2428e9f0d98da07cefaCAS | open url image1

[14]  S. I. Doumbouya, A. F. Munster, C. J. Doona, F. W. Schneider, J. Phys. Chem. 1993, 97, 1025.
         | CrossRef | 1:CAS:528:DyaK3sXmslKktQ%3D%3D&md5=c72a96ee2964ced7a3e4ed741f097be9CAS | open url image1

[15]  C. R. Chinake, R. H. Simoyi, J. Phys. Chem. 1994, 98, 4012.
         | CrossRef | 1:CAS:528:DyaK2cXit1yns7o%3D&md5=9f852d57f5c4ab234cd48ccd12d25969CAS | open url image1

[16]  C. R. Chinake, R. H. Simoyi, J. Chem. Soc., Faraday Trans. 1997, 93, 1345.
         | CrossRef | 1:CAS:528:DyaK2sXislGnt7c%3D&md5=a907ea03e844c8e74d9e4ca099c21263CAS | open url image1

[17]  M. Alamgir, I. R. Epstein, Int. J. Chem. Kinet. 1985, 17, 429.
         | CrossRef | 1:CAS:528:DyaL2MXhvFaju74%3D&md5=ab4318f1c91fad715bbab0af4a300776CAS | open url image1

[18]  R. M. Noyes, J. Am. Chem. Soc. 1980, 102, 4644.
         | CrossRef | 1:CAS:528:DyaL3cXksFCkuro%3D&md5=64c5670ab60f86cfac234302b330f8acCAS | open url image1

[19]  G. Rabai, M. Orban, J. Phys. Chem. 1993, 97, 5935.
         | CrossRef | 1:CAS:528:DyaK3sXis1WlsbY%3D&md5=6d5be1e263d82307c4eca753dc96bbd5CAS | open url image1

[20]  G. Peintler, I. Nagypal, I. R. Epstein, J. Phys. Chem. 1990, 94, 2954.
         | CrossRef | 1:CAS:528:DyaK3cXhs1Kjs7c%3D&md5=d2d8d8c58ae11d8b4759d137bebc3761CAS | open url image1

[21]  T. R. Chigwada, E. Chikwana, R. H. Simoyi, J. Phys. Chem. A 2005, 109, 1081.
         | CrossRef | 1:CAS:528:DC%2BD2MXmslKktg%3D%3D&md5=4e144e2940dcf0d43e5f5eccbe7aafe5CAS | open url image1

[22]  T. C. Bruice, A. B. Sayigh, J. Am. Chem. Soc. 1959, 81, 3416.
         | CrossRef | 1:CAS:528:DyaF3cXntFSq&md5=e9f3ac59ec91933614705b0567e60833CAS | open url image1

[23]  T. C. Bruice, R. T. Markiw, J. Am. Chem. Soc. 1957, 79, 3150.
         | CrossRef | 1:CAS:528:DyaG2sXosFKmtg%3D%3D&md5=38562922ef2302a9090b64759b1cdc40CAS | open url image1

[24]  M. A. Salem, C. R. Chinake, R. H. Simoyi, J. Phys. Chem. 1996, 100, 9377.
         | CrossRef | 1:CAS:528:DyaK28XivVClu7w%3D&md5=406e5914f37067fc7ca69b9ce56eac7aCAS | open url image1

[25]  S. V. Makarov, C. Mundoma, J. H. Penn, S. A. Svarovsky, R. H. Simoyi, J. Phys. Chem. A 1998, 102, 6786.
         | CrossRef | 1:CAS:528:DyaK1cXkslGqtL4%3D&md5=e03d1142890fad01b0de21ca380c90d8CAS | open url image1

[26]  S. A. Svarovsky, R. H. Simoyi, S. V. Makarov, J. Chem. Soc. Dalton Trans. 2000, 511.
         | 1:CAS:528:DC%2BD3cXhtVKjur0%3D&md5=ce708e259939390fa9bf9238d9b5d7c8CAS | open url image1

[27]  G. Rabai, R. T. Wang, K. Kustin, Int. J. Chem. Kinet. 1993, 25, 53.
         | CrossRef | 1:CAS:528:DyaK3sXht1eqsr0%3D&md5=ff0bf34c646ca4f8616df13243dc8cb2CAS | open url image1

[28]  G. Gordon, J. Am. Water Works Assoc. 2001, 93, 163.
         | 1:CAS:528:DC%2BD3MXislGisL4%3D&md5=49f692c38eb79e4097c473772098012dCAS | open url image1

[29]  O. Olagunju, P. D. Siegel, R. Olojo, R. H. Simoyi, J. Phys. Chem. A 2006, 110, 2396.
         | CrossRef | 1:CAS:528:DC%2BD28XptFSitw%3D%3D&md5=3108c08a2991033eea51c16088361411CAS | open url image1

[30]  L. Wang, D. W. Margerum, Inorg. Chem. 2002, 41, 6099.
         | CrossRef | 1:CAS:528:DC%2BD38XotVOks78%3D&md5=4846ab86e5a15c98209393dd69d92452CAS | open url image1

[31]  J. F. Ojo, J. L. Petersen, A. Otoikhian, R. H. Simoyi, Can. J. Chem. 2006, 84, 825.
         | CrossRef | 1:CAS:528:DC%2BD28XkvVyks7g%3D&md5=4e70066e82b78fffd00b2b23907c8442CAS | open url image1

[32]  J. L. Petersen, A. A. Otoikhian, M. K. Morakinyo, R. H. Simoyi, Can. J. Chem. 2010, 88, 1247.
         | CrossRef | 1:CAS:528:DC%2BC3cXhsFGgtr3J&md5=23526a5bd57e0ef12c01122e2338e28dCAS | open url image1

[33]  S. V. Makarov, C. Mundoma, J. H. Penn, J. L. Petersen, S. A. Svarovsky, R. H. Simoyi, Inorg. Chim. Acta 1999, 286, 149.
         | CrossRef | 1:CAS:528:DyaK1MXhvFKmu70%3D&md5=4e5cd4ad42705381b5e83338112ec66aCAS | open url image1

[34]  O. Olagunju, P. A. Siegel, R. Olojo, R. H. Simoyi, J. Phys. Chem. A 2006, 110, 2396.
         | CrossRef | 1:CAS:528:DC%2BD28XptFSitw%3D%3D&md5=3108c08a2991033eea51c16088361411CAS | open url image1

[35]  O. Olagunju, P. A. Siegel, R. Olojo, R. H. Simoyi, J. Phys. Chem. A 2006, 110, 2396.
         | CrossRef | 1:CAS:528:DC%2BD28XptFSitw%3D%3D&md5=3108c08a2991033eea51c16088361411CAS | open url image1

[36]  T. R. Chigwada, R. H. Simoyi, J. Phys. Chem. A 2005, 109, 1094.
         | CrossRef | 1:CAS:528:DC%2BD2MXms12rsQ%3D%3D&md5=81e13710830ad39fb02eff68dd58a70cCAS | open url image1

[37]  S. Carballal, B. Alvarez, L. Turell, H. Botti, B. A. Freeman, R. Radi, Amino Acids 2007, 32, 543.
         | CrossRef | 1:CAS:528:DC%2BD2sXlsVGnsbo%3D&md5=da8fc968a48d180ea5cd2892935eca2aCAS | open url image1

[38]  S. A. Koksharov, G. V. Chistyakova, O. N. Murav’ev, S. V. Makarov, Russ. J. Appl. Chem. 1999, 72, 1225. open url image1

[39]  S. V. Makarov, Y. V. Polenov, A. N. Aleksandrova, V. V. Budanov, Izv. Vuz. Khim. Kh. Tekh. 1983, 26, 1231.
         | 1:CAS:528:DyaL2cXntVaquw%3D%3D&md5=cdece7d5648e4106c62cfdb4d0307e13CAS | open url image1

[40]  S. V. Makarov, C. Mundoma, S. A. Svarovsky, X. Shi, P. M. Gannett, R. H. Simoyi, Arch. Biochem. Biophys. 1999, 367, 289.
         | CrossRef | 1:CAS:528:DyaK1MXkt1Ghtr8%3D&md5=1ebbd150d503d31849238acd3c710e88CAS | open url image1

[41]  S. V. Makarov, E. V. Kudrik, R. van Eldik, E. V. Naidenko, J. Chem. Soc. Dalton Trans. 2002, 4074.
         | 1:CAS:528:DC%2BD38Xos1eksr0%3D&md5=56bbf46a7f00dc71d760e00fb6e0f7e3CAS | open url image1



Export Citation