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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Slowdown of H/D exchange reaction rate and water dynamics in ionic liquids: Deactivation of solitary water solvated by small anions in 1-butyl-3-methyl-imidazolium chloride
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Slowdown of H/D exchange reaction rate and water dynamics in ionic liquids: Deactivation of solitary water solvated by small anions in 1-butyl-3-methyl-imidazolium chloride

机译：离子液体中H / D交换反应速率和水动力学的减慢：氯化1-丁基-3-甲基咪唑鎓中被小阴离子溶解的孤水失活

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The H/D exchange reaction and the rotational dynamics of heavy water (D2O) are studied at 50 degrees C in the ionic liquid, 1-butyl-3-methylimidazolium chloride ([bmim][Cl]), in the [D2O] range of 3-55 M. The initial H/D exchange rates are observed as 1.0 x 10(-7), 4.5 x 10(-6), 1.0 x 10(-5), 4.1 x 10(-5), 1.1 x 10(-4), and 3.7 x 10(-4) s(-1), respectively, at [D2O] of 2.8, 7.1, 8.1, 11, 15, and 25 M. The rate is very slow and less than 10(-5) s(-1) at [ D2O] below similar to 7 M. It steeply increases to the order of 10(-4) s(-1) for 7 M < [D2O] < 10 M, and linearly increases with [D2O] in the more water-rich region. The intercept of the linear region at [D2O] = similar to 9 M is interpreted by considering that each chloride anion deactivates 1.6 equiv water molecules due to the strong solvation. Correspondingly, the rotational correlation time of D2O at [D2O] < 7 M is 1 order of magnitude larger than that in water-rich conditions.
机译：在50°C的离子液体1-丁基-3-甲基咪唑鎓氯化物（[bmim] [Cl]）中，在[D2O]范围内，研究了H / D交换反应和重水（D2O）的旋转动力学。的3-55M。初始H / D汇率观察为1.0 x 10（-7），4.5 x 10（-6），1.0 x 10（-5），4.1 x 10（-5），1.1 x [D2O]分别为2.8、7.1、8.1、11、15和25 M时分别为10（-4）和3.7 x 10（-4）s（-1）。速率非常慢，并且小于10在[D2O]下的（-5）s（-1）类似于7M。对于7 M <[D2O] <10 M，它急剧增加到10（-4）s（-1）的数量级，并且线性增加[D2O]在水更丰富的地区。认为[D2O] = 9 M处的线性区域的截距是通过考虑由于强溶剂化使每个氯阴离子使1.6当量的水分子失活来解释的。相应地，[D2O] <7 M时D2O的旋转相关时间比富水条件下的旋转相关时间大1个数量级。

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