Infrared Absorption Spectra of Solid Metal Sulfites.

Nyberg, Birgit; Larsson, Ragnar; Korppi-Tommola, Jouko; Viitala, Rea; Hyömäki, Jouko; Swahn, Carl‐Gunnar

doi:10.3891/acta.chem.scand.27-0063

Cited by 55 publications

(24 citation statements)

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“…31 Several surface reactions of Chevreul's salt exposed to air, including possible oxidation of S(IV) into S(VI) and Cu(I) to Cu(II), were considered. Since no SO 4 2-was detected by XPS in the final products, the reaction below is most likely to occur: (17) This is consistent with the conclusions of Eatough et al 38 that atmospheric S(IV) species, such sulfites, may have long residence times in the environment.…”

Section: Oxidation By Airsupporting

confidence: 82%

“…4,[10][11][12][13] Although Cu(II) sulfite (CuSO 3 ) seems never to have been isolated, the literature contains references 14 15 The accidental discovery of a Cu, Fe, Mn triple sulfite in the mid 60s, when a hydrometallurgical study was designed to obtain precious metals from deep-sea manganese nodules, gave rise to preliminary studies involving complex sulfites, which resulted in preparation of non-stoichiometric compound mixtures, including the Chevreul's salt. 16 20,21 The vibrational bands of the sulfite group were assigned by comparing them with data reported in the literature.…”

Section: Isomorphic Seriesmentioning

confidence: 99%

“…21 Based on the characterization of solid intermediary products and to TG and DSC curve analyses, Silva et al 21 suggested the thermal decomposition reactions of the double sulfites in air and nitrogen atmospheres presented in Scheme 1: The authors 21 found that the sulfite ion coordination structures strongly influence the course of these salts' thermal decomposition (Figure 8). Sulfite species coordinated to the metal through the oxygen atom (a) are more easily oxidized into sulfate than sulfur coordinated species (b), 7,21 leading to the preferential formation of M II SO 4 and Cu 2 O at the onset of thermal decomposition. 21 The presence of Cu 2 O in the solid residue indicates that the evolution of SO 2 during the first step of thermal decomposition takes place through the break of Cu(I)-S and Cu(I)O-S bonds.…”

Section: Thermal Decompositionmentioning

confidence: 99%

“…The sulfite group can coordinate to the metal as a monodentate sulfur (I) or oxygen (II) donor or, in bidentate form, via oxygen (III) or oxygen and sulfur (IV) (Figure 3). 7 According to Nyberg and Larson, 4 the structure of sulfite compounds can be divided into three groups after coordination of the sulfite ion: (i) compounds without sulfur coordination (under 975 cm -1 ); (ii) compounds with both sulfur and oxygen coordination (over and under 975 cm -1 ); and (iii) compounds with dominant sulfur coordination (over 975 cm -1 ). Chevreul's salt spectrum shows stretching frequencies of high intensity over and under 975 cm -1 , suggesting that the compound belongs to group (ii), with both metal-sulfur bonds and metal-oxygen bonds.…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Isomorphic series of double sulfites of the Cu2SO3.MSO3.2H2O (M = Cu, Fe, Mn, and Cd) Type: a review

Silva¹,

Andrade²

2004

J. Braz. Chem. Soc.

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Embora o primeiro sulfito duplo de valência mista, Cu 2 SO 3 .CuSO 3 .2H 2 O, tenha sido preparado no início do século XIX por M. Chevreul, o interesse por compostos dessa natureza ressurgiu só depois da metade do século XX com a determinação da estrutura cristalina deste composto e a caracterização de seu espectro de absorção na região do infravermelho. Nos últimos anos, os estudos referentes a este tema têm se intensificado, especialmente após a descoberta da possibilidade de substituição isomórfica do Cu(II) no sal de Chevreul por diversos cátions com o mesmo estado de oxidação, gerando uma série de compostos cujas propriedades são fortemente dependentes da natureza do cátion M(II). Devido às suas propriedades interessantes, esses sistemas de valência mista podem ser usados como modelos para identificar intermediários em processos de corrosão atmosférica, bem como para avaliar o papel de metais de transição como catalisadores de autooxidação de S(IV) na conversão do SO 2 na atmosfera.Although the first mixed valence double sulfite, Cu 2 SO 3 .CuSO 3 .2H 2 O, was prepared in the early 19 th century by M. Chevreul, interest in this type of compound was only rekindled in the mid-1960s, when the crystalline structure of Chevreul's salt was determined and its infrared spectrum characterized. Studies of this type of compound have been intensified in recent years, especially after the discovery that the isomorphic Cu(II) in Chrevreul's salt could be replaced by a divalent metal ion, forming an isomorphic series whose properties are strongly dependent on the nature of the M(II) cation. Because of their interesting properties, these mixed valence systems can be used as models to identify intermediates in atmospheric corrosion processes, and to evaluate the role of transition metals as catalysts of S(IV) autoxidation in the conversion of SO 2 in the atmosphere.

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Section: Oxidation By Airsupporting

confidence: 82%

Section: Isomorphic Seriesmentioning

confidence: 99%

Section: Thermal Decompositionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Isomorphic series of double sulfites of the Cu2SO3.MSO3.2H2O (M = Cu, Fe, Mn, and Cd) Type: a review

Silva¹,

Andrade²

2004

J. Braz. Chem. Soc.

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“…The sulfur-bound structure is supported by the Raman spectrum. The assignments in Table 3 are straightforward and closely follow the known frequencies of the CH3Hg(II) species in other complexes, the isoelectronic molecule NH3HgS03 (16) and the free and complexed S032-anion (28,29). The mercury-carbon stretching frequency of 541 cm-l is, as shown in Table 4, typical for complexes with a sulfur atom bound to mercury.…”

Section: Sulfitementioning

confidence: 74%

Proton magnetic resonance and Raman spectroscopic studies of methylmercury (II) complexes of inorganic anions

Rabenstein¹,

Tourangeau²,

Evans³

1976

Can. J. Chem.

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. Conlplexation of methylmercury(I1) by sulfate, selenate, carbonate, sulfite, selenite, thiocyanate, selenocyanate, sulfide, and selenide in aqueous solution has been studied by proton magnetic resonance and Raman spectroscopy. Formation constants were determined for the SO$, Se042-, C032-, S032-, Se032-, Se03H-, SCN-, and SeCN-complexes from the p H dependence of the chemical shift and the 199Hg-IH spin-spin coupling constant of the methyl group of CH3Hg(II) in solutions containing both CH3Hg(II) and ligand. The chemical shift and the 199Hg-lH spin-spin coupling constant of the CH3Hg(II) in each of the complexes were also obtained from the same measurements. Proton magnetic resonance parameters were measured for several complexes with sulfide and selenide. The ligand donor atom in each of the complexes was identified using the formation constants, the I99Hg-lH spin-spin coupling constant of the complexed methylmercury and the Raman spectral data. It is of particular interest that, in the selenite complex, the methylmercury is bonded to an oxygen atom whereas sulfur is the donor atom in the sulfite complex. Chem. 54,2517Chem. 54, (1976.On a CtudiC, par rmn et par spectroscopie Raman, la complexation du mCthylmercure(l1) par les ions sulfate, sCl6nate, carbonate, sulfite, sClCnite, thiocyanate, sClCnocyanate, sulfure et s6lCnure en solution aqueuse. On a dCterminC les constantes de formation des complexes du S0,2-, Se042-, C032-, S032-, Se032-, Se03H-, SCN-et SeCN-B partir de la d6pendance des dkplacenlents chimiques sur le pH et des constantes de couplage spin-spin 199Hg-lH des groupes mkthyles du CH3Hg(II) dans des solutions contenant B la fois du CH3Hg(II) et du ligand. On a aussi obtenu, B partir des mCmes mesures, les dCplacements chimiques et les constantes de couplage spin-spin 199Hg-lH du CH3Hg(II) dans chacun des complexes. On a mesurC les paramktres rmp de plusieurs complexes avec le sulfure et le selenure. On a identifie, dans chaque complexe, l'atome agissant comnle ligand donneur en faisant appel aux constantes de formation, aux constantes de couplage spin-spin 199Hg-HI du mCthylmercure complex6 et aux donnks des spectres Raman. I1 est important de noter que dans le complexe sClCnite, le mCthylmercure est liC L l'atome d'oxygkne alors que le soufre est l'atome donneur dans le complexe sulfite.[Traduit par le journal]

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Reactivity of sulphur dioxide with Cu(100) surface investigated by infrared reflection absorption spectroscopy: role of structure and oxidation level

Dubot

Jacqueson

Pradier

2000

Surf. Interface Anal.

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Infrared Absorption Spectra of Solid Metal Sulfites.

Cited by 55 publications

References 0 publications

Isomorphic series of double sulfites of the Cu2SO3.MSO3.2H2O (M = Cu, Fe, Mn, and Cd) Type: a review

Isomorphic series of double sulfites of the Cu2SO3.MSO3.2H2O (M = Cu, Fe, Mn, and Cd) Type: a review

Proton magnetic resonance and Raman spectroscopic studies of methylmercury (II) complexes of inorganic anions

Reactivity of sulphur dioxide with Cu(100) surface investigated by infrared reflection absorption spectroscopy: role of structure and oxidation level

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