Comparison of stability constants of alkaline earth chlorides between conductometric and potentiometric studies.
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概要
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The stability constants of alkaline-earth metal chlorides, MCl<SUP>+</SUP> (M<SUP>2+</SUP>=Ca, Sr, Ba), were determined by conductometric and potentiometric measurements in methanol. The conductometric study was made at 5, 15, 25, 35, and 45°C; the potentiometric study was at 25°C. The formation of MCl<SUB>2</SUB> was neglected in the conductometric study, while in the potentiometric study it was taken into account, though it was too slight to determine a reliable value of the stability constant of MCl<SUB>2</SUB>. The stability constants of MCl<SUP>+</SUP>, <I>K</I><SUB>1</SUB>, determined by conductometric measurements were compared with the previous conductometric results of the same metal(II) perchlorates, <I>K</I><SUB>1A</SUB>. The magnitudes of <I>K</I><SUB>1</SUB> and <I>K</I><SUB>1A</SUB> increase in the orders Ca \simeqSr<Ba and Ca<Sr<Ba, respectively. <I>K</I><SUB>1</SUB> is larger than <I>K</I><SUB>1A</SUB> for calcium and strontium, though the <I>K</I><SUB>1</SUB> and <I>K</I><SUB>1A</SUB> values for barium are similar to each other; that is, the degree of such an increase in <I>K</I><SUB>1A</SUB> is larger than that in <I>K</I><SUB>1</SUB>. Both enthalpy and entropy changes determined by conductometric measurements were positive for all the chlorides and perchlorates. However, the enthalpy changes of the chlorides were 1.2–1.4 times as large as those of the perchlorates. On the other hand, the <I>K</I><SUB>1</SUB> from potentiometry was smaller for every chloride and also increased more steeply (in the order Ca<Sr<Ba) than that from conductometry. Therefore, the difference of <I>K</I><SUB>1</SUB> between conductometry and potentiometry decreases in going from Ca to Ba.
- 公益社団法人 日本化学会の論文
著者
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DOE Hidekazu
Department of Chemistry, Faculty of Science, Osaka City University
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Doe Hidekazu
Department Of Chemistry Faculty Of Science Osaka City University
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Kitagawa Toyokichi
Department of Chemistry Faculty of Education Kobe University
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Wakamiya Kenichi
Department of Chemistry, Faculty of Science, Osaka City University
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