Studies on the Ruthenium Complexes. IX. Kinetic Studies on the Deaquation-anation Reaction of Aquapentaammineruthenium(III) Complexes
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概要
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The deaquation-anation reaction of [Ru(OH<SUB>2</SUB>)(NH<SUB>3</SUB>)<SUB>5</SUB>]X<SUB>3</SUB>-type complexes in the solid state, as shown by the [Ru(OH<SUB>2</SUB>)(NH<SUB>3</SUB>)<SUB>5</SUB>]X<SUB>3</SUB>(s)→[RuX(NH<SUB>3</SUB>)<SUB>5</SUB>]X<SUB>2</SUB>(s)+H<SUB>2</SUB>O(g) equation, where X is Cl, Br, I, and NO<SUB>3</SUB> respectively, was kinetically studied by means of thermogravimetry (TG) along with differential thermal analysis (DTA). The activation energy and entropy in the reaction process (<I>E</I><SUB>a</SUB> kcal/mol, <I>ΔS</I><SUP>\neweq</SUP> e.u.) are, respectively, found by isothermal kinetic study to be (22.7, −7.1) for the chloride, (23.4, −5.2) for the bromide, (26.7, 5.8) for the iodide, and (19.3, −15.9) for the nitrate. The reaction seems to proceed through the following two steps, except in the case of the iodide: [Ru(OH<SUB>2</SUB>)(NH<SUB>3</SUB>)<SUB>5</SUB>]X<SUB>3</SUB>→[RuX(OH<SUB>2</SUB>)(NH<SUB>3</SUB>)<SUB>5</SUB>]X<SUB>2</SUB>→[RuX(NH<SUB>3</SUB>)<SUB>5</SUB>]X<SUB>2</SUB>+H<SUB>2</SUB>O. The first step is regarded as the rate-determining one.
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