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Reevaluation of Donor Number Using Titration Calorimetry

机译:用滴定量热法重新评估供体数

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摘要

Many empirical parameters have been suggested to measure solvent effects in chemical reactions. Gutmann’s donor number has been a successful parameter to quantify the electron-donating property of the solvent molecule; it is defined as the enthalpy change of the addition reaction of solvent molecule to SbCl5 in 1,2-dichloroethane. Calorimetric measurements can be applied to determine the quantity. Because the existence of water is critical for reactions in organic solvents, we have analyzed the enthalpy change using the titration calorimetry while considering the complexation with water. The determined donor numbers of formamide, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and 1,1,3,3-tetramethylurea (TMU) are 22.4, 26.5, 30.0, and 40.4, respectively. The values of DMF and DMSO are in perfect agreement with those of Gutmann. A reliable value for TMU is obtained for the first time on the basis of the enthalpy change for the addition reaction.
机译:已经提出了许多经验参数来测量化学反应中的溶剂作用。古特曼的供体数是量化溶剂分子的电子给体性质的成功参数。它定义为1,2-二氯乙烷中溶剂分子与SbCl5的加成反应的焓变。量热测量可以用于确定数量。由于水的存在对于有机溶剂中的反应至关重要,因此我们在考虑与水络合的同时,使用滴定量热法分析了焓变。确定的甲酰胺,N,N-二甲基甲酰胺(DMF),二甲基亚砜(DMSO)和1,1,3,3-四甲基脲(TMU)的供体数分别为22.4、26.5、30.0和40.4。 DMF和DMSO的值与Gutmann的值完全一致。首次基于加成反应的焓变获得可靠的TMU值。

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