Stepwise Formation of Proton Hydrates H+ · NH2O · pTBP · Cl- in Tributyl Phosphate Solutions of HCL: Composition, Structure and Peculiarities of IR Spectra Full article
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PCCP: Physical Chemistry Chemical Physics
ISSN: 1463-9076 , E-ISSN: 1463-9084 |
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Output data | Year: 1999, Volume: 1, Number: 12, Pages: 2961-2966 Pages count : 6 DOI: 10.1039/a901176e | ||
Tags | chloride ion; hydrochloric acid; proton; tributyl phosphate | ||
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Abstract:
Stepwise formation of several H+·NH2O·pTBP proton hydrates in tributyl phosphate (TBP) solutions of HCl has been studied by IR spectroscopy. As the water content in solutions increases, sequential formation of four compounds (H3O+–Cl-·TBP)n (I), (H5O2+·Cl-·TBP)m (II), (H5O2+·Cl-·H2O·TBP)p (III) and [H5O2+·Cl-·2H2O·TBP] (IV) has been found. A generic connection between the structures of I–IV and particular features of their IR spectra has been established. The proton monohydrate in I should not be considered as a hydroxonium ion H3O+, but rather as a molecular fragment of a proton disolvate of the B1–H+–B2 type, where B1=H2O and B2=Cl-. As a stronger proton acceptor in comparison with FeCl4- and ClO4- ions, the Cl- anion has a direct contact with the H5O2+ cation in II–IV. As a result, only H2O molecules of the first co-ordination sphere of the H5O2+ distributed cation are spectroscopically distinguishable from more distant H2O molecules of the surroundings. It has been shown that the main features of the IR spectra of the H5O2+ cation, including the so-called continuous background absorption (CBA), are due to its intrinsic properties and to the influence of molecules of the first co-ordination sphere that are bound to it. Water molecules of the second and following hydration spheres of the contact ion pair H5O2+·Cl- do not feel the proton charge and do not affect CBA to a noticeable extent.
Cite:
Stoyanov E.S.
Stepwise Formation of Proton Hydrates H+ · NH2O · pTBP · Cl- in Tributyl Phosphate Solutions of HCL: Composition, Structure and Peculiarities of IR Spectra
PCCP: Physical Chemistry Chemical Physics. 1999. V.1. N12. P.2961-2966. DOI: 10.1039/a901176e WOS Scopus РИНЦ
Stepwise Formation of Proton Hydrates H+ · NH2O · pTBP · Cl- in Tributyl Phosphate Solutions of HCL: Composition, Structure and Peculiarities of IR Spectra
PCCP: Physical Chemistry Chemical Physics. 1999. V.1. N12. P.2961-2966. DOI: 10.1039/a901176e WOS Scopus РИНЦ
Dates:
Submitted: | Feb 11, 1999 |
Accepted: | Mar 19, 1999 |
Published print: | Jun 1, 1999 |
Identifiers:
Web of science | WOS:000082188600012 |
Scopus | 2-s2.0-0033564552 |
Elibrary | 13328238 |
Chemical Abstracts | 1999:353741 |
Chemical Abstracts (print) | 131:175748 |
OpenAlex | W2027137422 |