The mechanism of the hydrolysis of polyphosphates. VI. The effect of cations on the hydrolysis of cyclo-tri- and cyclo-tetraphosphates.
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The effect of cations on the rate of the hydrolysis of <I>cyclo</I>-tri- and <I>cyclo</I>-tetraphosphates was studied by adding metal chlorides to aqueous solutions of the ring phosphates. The concentrations of the phosphates and metal chlorides were 0.025 mol dm<SUP>−3</SUP> and 0.1 mol dm<SUP>−3</SUP> respectively. Alkali-metal cations retarded the hydrolysis of both the <I>cyclo</I>-phosphates in acidic media and accelerated it in basic media. The following sequence of efficiency resulted:<BR>Li<SUP>+</SUP>>Na<SUP>+</SUP>>K<SUP>+</SUP>.<BR>Magnesium, calcium, and nickel(II) cations retarded the hydrolysis of the <I>cyclo</I>-phosphates in the pH range of 1.0–2.0 or 1.0–2.7, while they accelerated it in the pH regions higher than 2.7 or 3.5. A copper(II) ion retarded the hydrolysis at pH 1.0, and accelerated it in the pH ranges higher than 2.0. An aluminium ion highly accelerated the hydrolysis of both the ring phosphates at pH 1.0 and 2.0.
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