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硫酸存在时N-溴代苯二甲酰亚胺对甘露糖的胶束催化氧化(英文)

Micelle Catalyzed Oxidation of Mannose by N-Bromophthalimide in the Presence of Sulfuric Acid
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摘要 The kinetics of micellar-catalyzed oxidation of mannose by N-bromophthalimide was studied in the presence of sulfuric acid at 313 K. The orders of reaction with respect to [mannose], [oxidant], and [H+] were found to be fractional, first, and negative fractional order, respectively. Anionic micelles of sodium dodecyl sulfate showed a partial inhibitory effect, while cationic micelles of cetyltrimethylammonium bromide increased the reaction rate with the same kinetic behavior. The reaction was catalyzed by cationic micelles, because of favorable electrostatic/thermodynamic/ hydrophobic/hydrogen bonding between reactants and cationic micelles. Their catalytic roles are best explained by Berezin′s model. A variation of [phthalimide] showed that the rate of reaction decreased with increasing [phthalimide]. It was observed that, an increase of [mercuric acetate] had no effect on reaction velocity. The influence of salts on the reaction rate was also studied. The rate constant (kW), binding constants (KS+KO), and corresponding activation parameters (Ea, △H#, △S#, and △G#) were determined. A detailed mechanism with associated reaction kinetics is presented and discussed. The kinetics of micellar-catalyzed oxidation of mannose by N-bromophthalimide was studied in the presence of sulfuric acid at 313 K. The orders of reaction with respect to [mannose], [oxidant], and [H^+] were found to be fractional, first, and negative fractional order, respectively. Anionic micelles of sodium dodecyl sulfate showed a partial inhibitory effect, while cationic micelles of cetyltrimethylammonium bromide increased the reaction rate with the same kinetic behavior. The reaction was catalyzed by cationic micelles, because of favorable electrostatic/thermodynamic/ hydrophobic/hydrogen bonding between reactants and cationic micelles. Their catalytic roles are best explained by Berezin's model. A variation of [phthalimide] showed that the rate of reaction decreased with increasing [phthalimide]. It was observed that, an increase of [mercuric acetate] had no effect on reaction velocity. The influence of salts on the reaction rate was also studied. The rate constant (kw), binding constants (Ks+Ko), and corresponding activation parameters (Ea, △H^#, △S^#, and △G^#) were determined. A detailed mechanism with associated reaction kinetics is presented and discussed.
出处 《物理化学学报》 SCIE CAS CSCD 北大核心 2009年第2期319-326,共8页 Acta Physico-Chimica Sinica
基金 The project was supported by the Found of Chhattisgarh Council of Science and Technology (CGCOST), Raipur, (Chhattisgarh), India (621/CCOST/MRP/07)
关键词 胶枣催化 氧化 动力学 甘露糖 Micellar catalysis Oxidation Kinetics Mannose Berezin's model
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参考文献56

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