Kinetics of the Catalytic Hydrogen Peroxide Oxidation of Thiodiglycol in Aqueous Solutions
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概要
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The catalytic activities of some inorganic compounds for the hydrogen peroxide oxidation of thiodiglycol (TDG) have been examined in aqueous media at 25°C and at pH 4.7. It has been found that the order of catalytic activities was: Na<SUB>2</SUB>MoO<SUB>4</SUB>, Na<SUB>2</SUB>WO<SUB>4</SUB>>>H<SUB>2</SUB>SeO<SUB>3</SUB>>NH<SUB>4</SUB>VO<SUB>3</SUB>, Na<SUB>2</SUB>TeO<SUB>4</SUB>, UO<SUB>2</SUB>(OAc)<SUB>2</SUB>, Cu(OAc)<SUB>2</SUB>. The rates of oxidation using all these catalysts, except sodium molybdate, may be expressed as <I>v</I>=<I>k</I><SUB>2</SUB>[H<SUB>2</SUB>O<SUB>2</SUB>] [TDG].<BR>The kinetics of this reaction has been studied in detail, especially with the sodium molybdate (SM) catalyst, by means of iodometry. The oxidation in the range [H<SUB>2</SUB>O<SUB>2</SUB>]>2[SM] follows the pseudo-first-order kinetics : <I>v</I>=<I>k</I><SUB>1</SUB><I><SUP>c</SUP></I>[SM] [TDG]. The rate at pH below 2 is several times faster than that at pH 3∼6, the energies of the activation at pH's below 2 and at 3∼6 being 9.21 and 11.2 kcal. mol<SUP>－1</SUP> respectively. The oxidation in the range of [H<SUB>2</SUB>O<SUB>2</SUB>]<2[SM] follows the second-order kinetics : <I>v</I>=<I>k</I><SUB>2</SUB>′[Active oxygen] [TDG]. The values of k<SUB>2</SUB>′ were identical with the second-order rate constants obtained in the oxidation of thiodiglycol by yellow sodium peroxymolybdate. It is probable that dihydroperoxymolybdate, HMoO<SUB>6</SUB><SUP>－</SUP>, produced rapidly from Na<SUB>2</SUB>MoO<SUB>4</SUB> and hydrogen peroxide, oxidizes thiodiglycol The increase in the rate with a decreasing pH may be due to the transformation of HMoO<SUB>6</SUB><SUP>－</SUP> to more active H<SUB>2</SUB>MoO<SUB>6</SUB>, since the Na<SUB>2</SUB>MO<SUB>4</SUB>-hydrogen peroxide system gave two different ultraviolet absorption maxima corresponding to HMoO<SUB>6</SUB><SUP>－</SUP> and H<SUB>2</SUB>MoO<SUB>6</SUB> at pH 4.7 and 0.8 respectively.
- 社団法人 日本化学会の論文
著者
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Sawaki Yasuhiko
Department Of Applied Chemistry Faculty Of Engineering Nagoya University
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Ogata Y.
Department of Nuclear Engineering
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