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首页> 美国政府科技报告 >Reduction of Peroxotitanium(IV) by Sulfur(IV), Iron(II), and Titanium(III) in Acidic Solution
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Reduction of Peroxotitanium(IV) by Sulfur(IV), Iron(II), and Titanium(III) in Acidic Solution

机译：在酸性溶液中通过硫（IV），铁（II）和钛（III）还原过氧钛（IV）

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The net reduction of peroxotitanium(IV) by sulfur(IV) in acidic solution proceeds by a rate-determining dissociation of peroxide from TiO2(2+) followed by the rapid reaction of H2O2 and HSO3(-). The absence of a detectable direct reaction between TiO2(2+) and either SO2 or HSO3(-) is consistent with the previously proposed electrophilic nature of the peroxide moiety when coordinated to a transition-metal ion. The reduction of TiO(2+) with excess iron(II) or titanium(III) was shown to proceed by both a direct reaction and reduction of H2O formed by dissociation of the peroxo complex. The rate expressions for the direct reactions are respectively -d(TiO2(2+))/dt = (k sub a + k sub b/H+))(TiO2(2+) (Fe(II)) and (k sub c/(H(+))(TiO2(2+)(Ti(III)). Values of k sub a = 1.1 + or -0.1/m/s and k sub b = 0.16 + or - 0.01/s at 17/c and k sub c = 11.1 + or - 0.4/s at 25 C were determined at I = 1.0 M (LiClO4). These rate constants are smaller than those reported previously for the corresponding reductions fo H2O2. The results do not allow and assignment of an inner-or outer-sphere mechanism for the direct reactions. The reduced reactivity of the peroxide moiety in TiO2(2+) relative to H2O2 in our system is contrasted with its enhanced reactivity observed in other studies.

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