Reaction of Ru(II)-EDTA in sodium formate-formic acid solutions.
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When [Ru<SUP>III</SUP>(Hedta)(H<SUB>2</SUB>O)] was reduced at mercury electrode in sodium formate–formic acid solutions, the reduced species gradually became polarographically inactive. The final product of the deactivation reaction was isolated and identified as Na<SUB>2</SUB>[Ru<SUP>II</SUP>(edta)(CO)]. The kinetics follows the second-order rate equation, −<I>dc</I><SUB>1</SUB>⁄<I>dt</I>=<I>k</I><SUB>obsd</SUB> <I>c</I><SUB>1</SUB> <I>c</I><SUB>2</SUB>, where <I>c</I><SUB>1</SUB>=[[<I>Ru</I><SUP>II</SUP>(Hedta)(H<SUB>2</SUB>O)]<SUP>−</SUP>]+[[Ru<SUP>II</SUP>(edta)(H<SUB>2</SUB>O)]<SUP>2−</SUP>] and <I>c</I><SUB>2</SUB>=[HCOO<SUP>−</SUP>]+[HCOOH]. The <I>k</I><SUB>obsd</SUB> value was found to be expressed by <I>k</I> [H<SUP>+</SUP>]/(<I>K</I><SUB>A</SUB>+[H<SUP>+</SUP>]), where <I>K</I><SUB>A</SUB> (=3.28×10<SUP>−4</SUP> mol dm<SUP>−3</SUP>) and <I>K</I><SUB>R</SUB> (=6.92×10<SUP>−4</SUP> mol dm<SUP>−3</SUP>) are the acid-dissociation constants of formic acid and [Ru<SUP>II</SUP>(Hedta)(H<SUB>2</SUB>O)]<SUP>−</SUP>, respectively, with <I>k</I>=1.01×10<SUP>−5</SUP> s<SUP>−1</SUP> at 25 °C (ionic strength=0.5 mol dm<SUP>−3</SUP>). Several possible mechanisms for the reaction were discussed. Probably the reaction proceeds through the formation of an intermediate involving one formate anion followed by dehydration and rearrangement.
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