Kinetics and Mechanisms of the Reactions of Ce(IV) and Co(III) with Variamine Blue, [<I>N</I>-(<I>p</I>-Methoxyphenyl)phenylenediamine], in Aqueous Perchlorate Media
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The kinetics of the non-complementary reactions of Ce(IV) and Co(III) with Variamine Blue perchlorate were studied under nitrogen atmosphere in aqueous perchlorate media of ionic strength μ=2.0 M. The iminoquinone form of Variamine Blue was spectrophotometrically followed at 550 nm by stopped-flow technique. The rate constants of the stepwise reaction, M<SUP><I>n</I>+</SUP>+(V.B.)\overset<I>k</I><SUB>α</SUB>\underset<I>k</I><SUB>γ</SUB>\rightleftharpoonsM<SUP>(<I>n</I>−1)+</SUP>+(V.B.)<SUB>sox</SUB>,M<SUP><I>n</I>+</SUP>+(V.B.)<SUB>sox</SUB>\xrightarrow<I>k</I><SUB>β</SUB>M<SUP>(<I>n</I>−1)+</SUP>+(V.B.)<SUB>ox</SUB>+2H<SUP>+</SUP> were evaluated at 25°C to be <I>k</I><SUB>α</SUB>=1.7×10<SUP>5</SUP> and <I>k</I><SUB>β</SUB>=2.4×10<SUP>5</SUP> M<SUP>−1</SUP> sec<SUP>−1</SUP> for Ce<SUP>4+</SUP> and <I>k</I><SUB>α</SUB>=1.35×10<SUP>4</SUP> and <I>k</I><SUB>β</SUB>=1.53×10<SUP>4</SUP> M<SUP>−1</SUP>sec<SUP>−1</SUP> at [H]=1.0 M for Co<SUP>3+</SUP>. The rates of Ce<SUP>4+</SUP> were not affected by [H]. The [H]-dependece of <I>k</I><SUB>α</SUB> and <I>k</I><SUB>β</SUB> for Co<SUP>3+</SUP> gives the mechanism Co<SUB>aq</SUB><SUP>3+</SUP>+B\overset<I>k</I><SUB>1</SUB>\rightleftharpoons product, CoOH<SUB>aq</SUB><SUP>2+</SUP>+B\overset<I>k</I><SUB>2</SUB>\rightleftharpoons product, Co<SUB>aq</SUB><SUP>3+</SUP>\overset<I>K</I><SUB>h</SUB>\rightleftharpoonsCoOH<SUB>aq</SUB><SUP>2+</SUP>+H<SUP>+</SUP>, with <I>K</I><SUB>2</SUB>\simeq10<SUP>7</SUP> M<SUP>−1</SUP>sec<SUP>−1</SUP>, suggesting an outer-sohere mechanism for the electron transfer with CoOH<SUP>2+</SUP>.
- 公益社団法人 日本化学会の論文
著者
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Imamura Taira
Department Of Chemistry Faculty Of Science Hokkaido University
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FUJIMOTO Masatoshi
Department of Chemistry, Faculty of Science, Hokkaido University
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