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首页> 外文期刊>Journal of Physical Organic Chemistry >Solvent effect on the heat of solution and partial molar volume of magnesium perchlorate
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Solvent effect on the heat of solution and partial molar volume of magnesium perchlorate

机译:溶剂对溶液热和高氯酸镁部分摩尔体积的影响

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摘要

For magnesium perchlorate (MP), the solvent effect on the heat of solution and partial molar volumes (PMV) at 25 °C was studied. Since the complete dissociation of magnesium perchlorate is more difficult to achieve as compared with lithium perchlorate (LP), the concentration dependence of the values of the heat of solution and partial molar volume were noted. Only in highly polar solvents with large donor numbers (DN), such as water, dimethyl sulfoxide, N,N-dimethyl formamide, and formamide, the differential and integral values of the enthalpies of solution were the same in the range of concentrations studied. In all solvents studied, the values of the heat of solution of MP were highly exothermic and exceed that of LP by more than 30 kcal mol~(-1). The values of the partial molar volume of MP were changed from 82.3 cm~3 mol~(-1) in formamide to -2.4 cm~3 mol~(-1) in acetone, and correlate linearly with that of LP (R=0.975). Taking into account the significant change in the properties of molecules in the solvate shell of cation Mg~(2+), the large increase in the reactivity of reactants, activated by such interaction with Mg~(2+) cation is expected.
机译:对于高氯酸镁(MP),研究了在25°C时溶剂对溶液热和部分摩尔体积(PMV)的影响。由于与高氯酸锂(LP)相比,高氯酸镁的完全解离更困难,因此注意到溶液热值和部分摩尔体积的浓度依赖性。仅在水,二甲基亚砜,N,N-二甲基甲酰胺和甲酰胺等具有较大供体数(DN)的高极性溶剂中,溶液焓的微分和积分值在所研究的浓度范围内相同。在所有研究的溶剂中,MP溶液的热值都非常放热,比LP高30 kcal mol〜(-1)。 MP的部分摩尔体积的值从甲酰胺中的82.3 cm〜3 mol〜(-1)变为丙酮中的-2.4 cm〜3 mol〜(-1),与LP线性相关(R = 0.975) )。考虑到阳离子Mg〜(2+)的溶剂化物壳中分子性质的显着变化,可以预期通过与Mg〜(2+)阳离子的这种相互作用而活化的反应物的反应性将大大提高。

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