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酰胺与锌盐的准二元水溶液中优先溶剂化作用的超声弛豫研究

Ultrasonic relaxation study of preferential solvation in quasi-two-components aqueous solutions of amides and zinc salts.

作者信息

Miecznik P, Golebiewski Z

机构信息

Institute of Acoustics, Adam Mickiewicz University, Umultowska 85, 61-614 Poznań, Poland.

出版信息

Ultrasonics. 2004 Apr;42(1-9):629-34. doi: 10.1016/j.ultras.2004.01.085.

Abstract

To investigate the effect of preferential solvation the ultrasonic attenuation (2-50 MHz) and velocities (3 MHz) of ZnCl(2) and 2-chloroacetamide (ClCH(2)CONH(2)) in water and its quasi-binary mixtures with the ratio (ZnCl(2)+ClCH(2)CONH(2)):H(2)O=1:55 at 298.15 K have been measured. The creation of specific complexes in the ClCH(2)CONH(2)-H(2)O-ZnCl(2) system have a relaxational character which, within the measurements of ultrasonic absorption in the frequency range 2-50 MHz, have been observed. On the base of these properties the kinetic and dynamic parameters of the observed relaxation have been calculated. To bring into relief the influence of Cl atom in the 2-chloroacetamide molecules for complexation process it has been investigated also the system AA-H(2)O-ZnCl(2). The next step of searching was to investigate the system of CHAA-H(2)O-ZnBr(2), to reduce the influence of Cl atom within ZnCl(2) molecule at the complexation process. The main aim of presented study was to investigate the possibility of complexation in the aqueous solutions of ZnCl(2) with the part of 2-ClCH(2)CONH(2) (CHAA). With regard of big complexing ability of zinc, there exist a theoretical possibility of attachment CHAA to the inner coordination sphere of zinc through chloride atom. There can create here outer-sphere as well as inner-sphere complexes. As a results the observed relaxation processes have been attributed to creation and disintegration the following complexes: Zn(H(2)O)(2)(CHAA)(4)(2+) and Zn(2+)(H(2)O)(3)(CHAA)Cl(2)(-).

摘要

为了研究优先溶剂化的影响,测量了298.15 K下ZnCl₂和2-氯乙酰胺(ClCH₂CONH₂)在水及其与(ZnCl₂ + ClCH₂CONH₂):H₂O = 1:55的准二元混合物中的超声衰减(2 - 50 MHz)和速度(3 MHz)。在ClCH₂CONH₂ - H₂O - ZnCl₂体系中形成的特定络合物具有弛豫特性,这在2 - 50 MHz频率范围内的超声吸收测量中已被观察到。基于这些性质,计算了观察到的弛豫的动力学和动态参数。为了突出2-氯乙酰胺分子中Cl原子对络合过程的影响,还研究了体系AA - H₂O - ZnCl₂。下一步研究是考察CHAA - H₂O - ZnBr₂体系,以减少ZnCl₂分子中Cl原子在络合过程中的影响。本研究的主要目的是研究ZnCl₂水溶液与部分2 - ClCH₂CONH₂(CHAA)络合的可能性。鉴于锌具有很强的络合能力,理论上存在CHAA通过氯原子附着到锌的内配位球上的可能性。这里可以形成外层络合物以及内层络合物。结果,观察到的弛豫过程归因于以下络合物的形成和解离:Zn(H₂O)₂(CHAA)₄²⁺和Zn²⁺(H₂O)₃(CHAA)Cl₂⁻。

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