某些含氮有机碱在水-乙醇和水-丙酮介质中的电离

A. Chebotarev, E. M. Rakhlytskaya, D. Snigur, T. M. Scherbakova, K. Bevziuk, K. Snihur
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摘要

本文用电位滴定法测定了体系中不同浓度的有机溶剂在水-乙醇和水-丙酮介质中的一些含氮有机碱(morfoline、哌啶和苄胺)的电离常数(pKa)。结果表明,有机水介质中含氮有机碱的pKa值随体系中有机溶剂含量的增加而自然降低。结果表明,所研究的含氮有机碱的性质(芳香族或杂环族)和介质的物理化学性质受其电子给体能力的性质和变化程度的显著影响。值得注意的是,所研究的含氮有机碱(morfoline,哌啶和苄胺)从水介质过渡到有机介质(乙醇或丙酮)时,随着体系中有机溶剂含量的增加,pKa值自然降低。一般来说,在从水介质到有机介质(乙醇或丙酮)的转变过程中,pKa的变化可达2.43个单位。结果表明,电位滴定法测定的含氮有机碱的pKa值与水-乙醇和水-丙酮溶液介电常数的反比呈线性关系,符合伊兹梅洛夫理论。因此,我们可以得出结论,混合溶剂组分比例的变化以及介质的介电渗透率一般不会导致所研究的含氮有机碱的溶剂化特性发生显著变化。
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IONIZATION OF SOME NITROGEN-CONTAINING ORGANIC BASES IN WATER-ETHANOL AND WATER-ACETONE MEDIA
In this paper, the ionization constants (pKa) of some nitrogen-containing organic bases (morfoline, piperidine and benzylamine) in water-ethanol and water-acetone media at various concentrations of organic solvent in the system has been determined by the potentiometric titration method. It was established that the value of pKa of nitrogen-containing organic bases in aqueous-organic media naturally decreases with increasing content of organic solvent in the system. It was shown that their nature (aromatic or heterocyclic) and the physico-chemical properties of the medium are significantly influenced by the nature and degree of change in the electron donor ability of the nitrogen-containing organic bases studied It should be noted that for the studied nitrogen-containing organic bases (morfoline, piperidine and benzylamine), when passing from an aqueous medium to an organic one (ethanol or acetone), the pKa values naturally decrease with an increase in the content of the organic solvent in the system. In general, in the transition from an aqueous medium to an organic one (ethanol or acetone), a change in pKa can reach 2.43 units. It was established that the dependence of the values of pKa of nitrogen-containing organic bases which were determinate via potentiometric titration method on the inverse of the dielectric constant of water-ethanol and water-acetone solutions tends to be linear, consistent with Izmailov’s theory. Thus, we can conclude that the change in the ratio of the mixed solvent components and, as a result, in general, dielectric permeability of the medium does not lead to a significant change in the solvation characteristics of the nitrogen-containing organic bases studied.
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