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Comparative study by infrared spectrometry of the behaviour of Y-H and Y-D groups. Valencies frequency and molecular association constants; Etude comparee par spectrometrie infrarouge du comportement de groupements YH et YD. Frequences de valence et constantes d'association moleculaires

Abstract

In the first part of the report a comparison is made of the relative lowering of the frequencies determined using homologous hydrogenated and deuterated vibrators dissolved in various solvents, with the gaseous state as reference. It is confirmed that one always has ({delta}{nu}/{nu}{sub g}){sub YH} {>=} ({delta}{nu}/{nu}{sub g}){sub YD}. Certain results suggest the existence of interactions between vibrational and electronic states, but the different behaviours of OH and OD molecules and of NH and deuterated-N compounds show that the phenomenon is complex. In the second part of the report a quantitative examination is made of about a hundred molecular associations which are formed in solution in an inert solvent by means of hydrogen or deuterium bridges. The proton and deuton donor auto-associations are studied first of all, the association constants K{sub H} are then determined for the proton donors with various acceptors, as are the K{sub D}/K{sub H} ratios obtained after partial substitution in these donors of the hydrogen by deuterium. The results show that it is necessary to distinguish thermo-dynamic effects (which can be calculated when all frequencies of the free dynamic and complexed molecules, are known) and chemical effects connected with the nature of the donors and acceptors;  More>>
Authors:
Leicknam, J P [1] 
  1. Commissariat a l'Energie Atomique, Saclay (France). Centre d'Etudes Nucleaires
Publication Date:
Feb 01, 1966
Product Type:
Thesis/Dissertation
Report Number:
CEA-R-2924
Resource Relation:
Other Information: TH: These ES sciences physiques; 273 refs; PBD: Feb 1966
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTROSCOPY; ACETIC ACID; CARBAZOLES; CHEMICAL BONDS; DEUTERIUM COMPOUNDS; FERMI RESONANCE; HEPTANOIC ACID; HYDROCHLORIC ACID; HYDROGEN COMPLEXES; INDOLES; INFRARED SPECTRA; ION PAIRS; ISOTOPE EFFECTS; ISOTOPIC EXCHANGE; OPACITY; PHENOLS; PYRROLES; SOLVENTS; VALENCE; VIBRATIONAL STATES
OSTI ID:
20598747
Research Organizations:
CEA Saclay, 91 - Gif-sur-Yvette (France); Faculte des Sciences de l'Universite de Paris, 75 (France)
Country of Origin:
France
Language:
French
Other Identifying Numbers:
TRN: FR05R2924045259
Availability:
Available from INIS in electronic form
Submitting Site:
FRN
Size:
[108] pages
Announcement Date:

Citation Formats

Leicknam, J P. Comparative study by infrared spectrometry of the behaviour of Y-H and Y-D groups. Valencies frequency and molecular association constants; Etude comparee par spectrometrie infrarouge du comportement de groupements YH et YD. Frequences de valence et constantes d'association moleculaires. France: N. p., 1966. Web.
Leicknam, J P. Comparative study by infrared spectrometry of the behaviour of Y-H and Y-D groups. Valencies frequency and molecular association constants; Etude comparee par spectrometrie infrarouge du comportement de groupements YH et YD. Frequences de valence et constantes d'association moleculaires. France.
Leicknam, J P. 1966. "Comparative study by infrared spectrometry of the behaviour of Y-H and Y-D groups. Valencies frequency and molecular association constants; Etude comparee par spectrometrie infrarouge du comportement de groupements YH et YD. Frequences de valence et constantes d'association moleculaires." France.
@misc{etde_20598747,
title = {Comparative study by infrared spectrometry of the behaviour of Y-H and Y-D groups. Valencies frequency and molecular association constants; Etude comparee par spectrometrie infrarouge du comportement de groupements YH et YD. Frequences de valence et constantes d'association moleculaires}
author = {Leicknam, J P}
abstractNote = {In the first part of the report a comparison is made of the relative lowering of the frequencies determined using homologous hydrogenated and deuterated vibrators dissolved in various solvents, with the gaseous state as reference. It is confirmed that one always has ({delta}{nu}/{nu}{sub g}){sub YH} {>=} ({delta}{nu}/{nu}{sub g}){sub YD}. Certain results suggest the existence of interactions between vibrational and electronic states, but the different behaviours of OH and OD molecules and of NH and deuterated-N compounds show that the phenomenon is complex. In the second part of the report a quantitative examination is made of about a hundred molecular associations which are formed in solution in an inert solvent by means of hydrogen or deuterium bridges. The proton and deuton donor auto-associations are studied first of all, the association constants K{sub H} are then determined for the proton donors with various acceptors, as are the K{sub D}/K{sub H} ratios obtained after partial substitution in these donors of the hydrogen by deuterium. The results show that it is necessary to distinguish thermo-dynamic effects (which can be calculated when all frequencies of the free dynamic and complexed molecules, are known) and chemical effects connected with the nature of the donors and acceptors; among these latter, the possible formation of 'ionic pairs' has without doubt a great influence on the direction of the isotopic effect. (author) [French] Dans une prerrere partie, en prenant l'etat gazeux comme reference, on compare les abaissements relatifs de frequence determinee avec des vibrateurs hydrogenes et deuteries homologues dissous dans divers solvants. On confirme que l'on a toujours ({delta}{nu}/{nu}{sub g}){sub YH} {>=} ({delta}{nu}/{nu}{sub g}){sub YD}. Certains resultats conduisent a envisager l'existence d'interactions entre etats vibratoires et electroniques, mais le comportement different des molecules OH et OD et des composes NH et N-deuteries montre que le phenomene est complexe. Dans une seconde partie, on examine quantitativement une centaine d'associations moleculaires formees en solution dans un solvant inerte par pont hydrogene et pont deuterium. Les auto-associations des donneurs de proton et de deuton sont tout d'obord etudiees, puis on determine les constantes d'association K{sub H} des donneurs de proton avec divers accepteurs et les rapports K{sub D}/K{sub R} obtenus apres substitution partielle du deuterium a l'hydrogene dans ces donneurs. Les resultats montrent qu'il faut distinguer des effets thermodynamiques (qui seront calculables lorsque toutes les frequences des molecules libres et complexees seront connues) et des effets chimiques lies a la nature des donneurs et des accepteurs; parmi ces derniers, la formation eventuelle de 'paires ioniques' a, sans doute, une grande importance sur le sens de l'effet isotopique. (auteur)}
place = {France}
year = {1966}
month = {Feb}
}