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Application of radioisotopes to the investigation of the kinetics and mechanism of reactions of some inorganic complex compounds; Application des radioisotopes a l'etude de la cinetique et du mecanisme des reactions de certains complexes inorganiques; Primenenie radioizotopov k issledovaniyam kinetiki i mekhanizma reaktsij nekotorykh neorganicheskikh slozhnykh soedinenij; Aplicacion de los radioisotopos al estudio de la cinetica y del mecanismo de las reacciones de algunos complejos inorganicos

Conference:

Abstract

Radioisotopes are invaluable tools in the study of many types of inorganic chemical reactions, particularly those involving complex ionic substances in aqueous solution. One important approach is through research on the rates and mechanisms of isotopic exchange processes. For example, a series of studies has been made of the exchange between carbon-14-labelled ''free'' carbonate and the ligand carbonate in octahedral complex ions of the type CoA{sub 2}CO{sub 3}{sup +}, where A = 2 NH{sub 3}, ethylenediamine (en), propylenediamine (pn), or trimethylenediamine (tn). These studies have led to a rather thorough understanding of the nature of this kind of ligand substitution reaction, and of the part played by the non-exchanging amine ligands in the process. Similar studies of oxalate exchange with tris-oxalato complexes of the form M (C{sub 2}O{sub 4}){sub 3}{sup -3}, where M = Co (III), Cr (III), or Rh (III), have been equally fruitful. An alternative technique, applicable only when using low-atomic-weight radioisotopes such as carbon-14, is to observe the equilibrium or kinetic isotope effects in the reaction of interest. I t has, for instance, been possible to interpret differences in the ligand carbonate exchange mechanism of Coen{sub 2}CO{sub 3}{sup +} and Cotn{sub 2}CO{sub 3}{sup +} on the basis  More>>
Authors:
Harris, Gordon M [1] 
  1. Department of Chemistry, University of Buffalo, Buffalo 14, NY (United States)
Publication Date:
Mar 15, 1962
Product Type:
Conference
Resource Relation:
Conference: Conference on the Use of Radioisotopes in the Physical Sciences and Industry, Copenhagen (Denmark), 6-17 Sep 1960; Other Information: 22 refs; Related Information: In: Radioisotopes in the Physical Sciences and Industry. Proceedings of the Conference on the Use of Radioisotopes in the Physical Sciences and Industry. V. III| 652 p.
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AMINES; AMMONIA; AQUEOUS SOLUTIONS; CARBON 14; CARBONATES; COMPLEXES; CYANIDES; HYDROGEN PEROXIDE; IONS; ISOTOPE EFFECTS; ISOTOPIC EXCHANGE; KINETICS; LIGANDS; OXALATES; OXIDATION; THIOCYANATES
Sponsoring Organizations:
University of Buffalo (United States); US Atomic Energy Commission (United States)
OSTI ID:
22025741
Research Organizations:
International Atomic Energy Agency, Vienna (Austria); United Nations Educational, Scientific and Cultural Organization, Paris (France)
Country of Origin:
IAEA
Language:
English
Contract Number:
Contract AT(30-1)-1578
Other Identifying Numbers:
Other: ISSN 0074-1884; TRN: XA12N1757113034
Submitting Site:
INIS
Size:
page(s) 407-414
Announcement Date:
Jan 16, 2013

Conference:

Citation Formats

Harris, Gordon M. Application of radioisotopes to the investigation of the kinetics and mechanism of reactions of some inorganic complex compounds; Application des radioisotopes a l'etude de la cinetique et du mecanisme des reactions de certains complexes inorganiques; Primenenie radioizotopov k issledovaniyam kinetiki i mekhanizma reaktsij nekotorykh neorganicheskikh slozhnykh soedinenij; Aplicacion de los radioisotopos al estudio de la cinetica y del mecanismo de las reacciones de algunos complejos inorganicos. IAEA: N. p., 1962. Web.
Harris, Gordon M. Application of radioisotopes to the investigation of the kinetics and mechanism of reactions of some inorganic complex compounds; Application des radioisotopes a l'etude de la cinetique et du mecanisme des reactions de certains complexes inorganiques; Primenenie radioizotopov k issledovaniyam kinetiki i mekhanizma reaktsij nekotorykh neorganicheskikh slozhnykh soedinenij; Aplicacion de los radioisotopos al estudio de la cinetica y del mecanismo de las reacciones de algunos complejos inorganicos. IAEA.
Harris, Gordon M. 1962. "Application of radioisotopes to the investigation of the kinetics and mechanism of reactions of some inorganic complex compounds; Application des radioisotopes a l'etude de la cinetique et du mecanisme des reactions de certains complexes inorganiques; Primenenie radioizotopov k issledovaniyam kinetiki i mekhanizma reaktsij nekotorykh neorganicheskikh slozhnykh soedinenij; Aplicacion de los radioisotopos al estudio de la cinetica y del mecanismo de las reacciones de algunos complejos inorganicos." IAEA.
@misc{etde_22025741,
title = {Application of radioisotopes to the investigation of the kinetics and mechanism of reactions of some inorganic complex compounds; Application des radioisotopes a l'etude de la cinetique et du mecanisme des reactions de certains complexes inorganiques; Primenenie radioizotopov k issledovaniyam kinetiki i mekhanizma reaktsij nekotorykh neorganicheskikh slozhnykh soedinenij; Aplicacion de los radioisotopos al estudio de la cinetica y del mecanismo de las reacciones de algunos complejos inorganicos}
author = {Harris, Gordon M}
abstractNote = {Radioisotopes are invaluable tools in the study of many types of inorganic chemical reactions, particularly those involving complex ionic substances in aqueous solution. One important approach is through research on the rates and mechanisms of isotopic exchange processes. For example, a series of studies has been made of the exchange between carbon-14-labelled ''free'' carbonate and the ligand carbonate in octahedral complex ions of the type CoA{sub 2}CO{sub 3}{sup +}, where A = 2 NH{sub 3}, ethylenediamine (en), propylenediamine (pn), or trimethylenediamine (tn). These studies have led to a rather thorough understanding of the nature of this kind of ligand substitution reaction, and of the part played by the non-exchanging amine ligands in the process. Similar studies of oxalate exchange with tris-oxalato complexes of the form M (C{sub 2}O{sub 4}){sub 3}{sup -3}, where M = Co (III), Cr (III), or Rh (III), have been equally fruitful. An alternative technique, applicable only when using low-atomic-weight radioisotopes such as carbon-14, is to observe the equilibrium or kinetic isotope effects in the reaction of interest. I t has, for instance, been possible to interpret differences in the ligand carbonate exchange mechanism of Coen{sub 2}CO{sub 3}{sup +} and Cotn{sub 2}CO{sub 3}{sup +} on the basis of equilibrium isotope-effect measurements made on the carbonate exchange reaction. Similarly, data on the kinetic isotope effect in the acid-catalysed aquation of the Co (NH{sub 3}){sub 4}CO{sub 3}{sup +} ion has supported deductions as to the nature of the rate-determining bond-breakage step in such reactions. Finally, the mechanistic path of certain atoms or radicals in inorganic reactions, where a choice between alternative explanations must be made, is frequently facilitated by a radioactive tracer experiment. An example is the proof that cyanide does not appear as a rapidly exchanging intermediate in the oxidation of thiocyanate ion by hydrogen peroxide, although cyanide is an important end-product. (author) [French] Les radioisotopes sont particulierement precieux dans l'etude de nombreux types de reactions de chimie minerale, notamment de reactions ou interviennent des ions complexes en solution aqueuse. Les recherches sur la vitesse et le mecanisme des echanges isotopiques constituent un aspect important de ces applications. C'est ainsi qu'on a fait une serie d'etudes sur l'echange entre du carbonate ''libre'' marque au carbone-14 et le carbonate qui joue le role de coordinafc dans les ions complexes octaedriques du type CoA{sub 2}CO{sub 3}{sup +}, ou A represente le 2NH{sub 3}, ou l'ethylene-diamine (en), ou la propylene-diamine (pn) ou la trimethylene-diamine (tn). Grace aux etudes ainsi effectuees, on connait assez exactement la nature de ces reactions par substitution de coordinate, ainsi que le role joue par les coordinais amines qui ne participent pas a l'echange. Des etudes analogues sur l'echange entre oxalates dans les complexes tri-oxaliques de forme M (C{sub 2}O{sub 4}){sub 3}{sup 3-}, ou M=Co (III), Cr (III), ou Rh (III), n'ont pas ete moins fecondes en resultats. Une autre technique, applicable seulement lorsqu'on utilise des radioisotopes de faible poids atomique comme le carbone-14, consiste a observer les effets d'equilibre ou les effets cinetiques que les isotopes exercent sur la reaction etudiee. C'est ainsi qu'il a ete possible d'interpreter des differences dans le mecanisme d'echange du coordinat carbonate dans le Coen{sub 2}CO{sub 3}{sup +} et le Cotn{sub 2}CO{sub 3}{sup +}, par mesure de l'effet isotopique a l'etat d'equilibre dans la reaction d'echange des carbonates. De meme, des donnees sur l'effet isotopique cinetique dans l'hydratation avec catalyseur acide de l'ion Co(NH{sub 3}){sub 4}CO{sub 3}{sup +} ont confirme les deductions faites en ce qui concerne l'etape a laquelle se rompt la liaison, etape qui determine la vitesse de ces reactions. Enfin, la determination des positions successives de certains atomes ou radicaux, dans des reactions inorganiques pour lesquelles il faut choisir entre differentes explications, est souvent facilitee par l'emploi d'indicateurs radioactifs. C'est ainsi qu'on a pu prouver que le cyanure n'est pas un produit intermediaire qui subit un echange rapide dans l'oxydation de l'ion thiocyanate par le peroxyde d'hydrogene, quoique le cyanure soit un produit final important de la reaction. (author) [Spanish] Los radioisotopos constituyen medios auxiliares de incalculable valor para el estudio de muchos tipos de reacciones de la quimica inorganica, especialmente de aquellas en que intervienen iones complejos en solucion acuosa. Uno de sus aspectos mas importantes es la determinacion de las velocidades de reaccion y del mecanismo de los intercambios isotopicos. Por ejemplo, el autor ha realizado una serie de estudios sobre el intercambio entre carbonato ''libre'' marcado con carbono-14 y carbonato ligante en iones complejos octaedricos del tipo CoA{sub 2}CO{sub 3}{sup +}, donde A = 2NH{sub 3}, etilendiamina (en), propilendiamina (pn) o trimetilendiamina (tn). Estos estudios han permitido comprender a fondo la naturaleza de las reacciones de sustitucion de ligantes de este tipo y del papel que desempenan en el proceso los ligantes amino que no experimentan intercambio. Igualmente fructiferos han sido unos estudios analogos del intercambio de restos oxalato en complejos trioxalicos de formula M (C{sub 2}O{sub 4}){sub 3}{sup 3-}, en la que M = Co (III), Cr (III) o Rh (III). Otra tecnica, que puede aplicarse solamente cuando se emplean radioisotopos de bajo peso atomico, tales como el carbono-14, consiste en observar los efectos de equilibrio o los efectos cineticos que los isotopos ejercen sobre la reaccion. Como ejemplo, el autor ha logrado interpretar diferencias entre los mecanismos de intercambio de los restos carbonato ligantes entre el Coen{sub 2}CO{sub 3}{sup +} y el Cotn{sub 2}CO{sub 3}{sup +} por medicion del efecto isotopico, en estado de equilibrio, efectuada en la reaccion de intercambio de carbonatos. De la misma manera, los datos relativos al efecto cinetico de los isotopos en la hidratacion del ion Co(NH{sub 3}){sub 4}CO{sub 3}{sup +} catalizada por acidos han corroborado las teorias sobre el caracter de la fase de ruptura de enlaces, que determina la velocidad de estas reacciones. Por ultimo, los experimentos con trazadores radiactivos facilitan frecuentemente el estudio de las posiciones sucesivas de ciertos atomos o radicales en las reacciones inorganicas para las que existen diversas explicaciones teoricamente posibles. Como ejemplo puede citarse la demostracion de que en la oxidacion del ion tiocianato por peroxido de hidrogeno, el cianuro no es un producto intermedio que sufre un intercambio rapido a pesar de que constituye uno de los principales productos finales. (author) [Russian] Ispol'zovanie radioizotopov okazyvaet neotsenimye uslugi pri issledovanii khimicheskikh neorganicheskikh reaktsij samykh raznoobraznykh vidov i, v chastnosti, reaktsij so slozhnymi ionizirovannymi veshchestvami v vodnykh rastvorakh. Odnim iz vazhnykh metodov sluzhit izuchenie skorosti i mekhanizma protsessov izotopnogo obmena. Tak, naprimer, byl proveden ryad issledovanij obmen a mezhdu t.n. ''svobodnym'' karbonatom, mechennym uglerodom-14, i svyazyvayushchim karbonatom oktaehdral'nykh slozhnykh ionov tipa CoA{sub 2}CO{sub 3}{sup +}, gde A = 2 NH{sub 3}, ehtilendiamin (en), propilendiamin (pn) ili trimetilendiamin (tn). EHti issledovaniya priveli k dovol'no tochnomu ponimaniyu kharaktera reaktsij ehtogo roda po zamene svyazi, a takzhe roli v ehtoj reaktsii neuchastvuyushchikh v obmene svyazyvayushchikh aminovykh zven'ev. Analogichnye issledovaniya obmena oksalatov, provedennye so slozhnymi trioaksalatami tipa M (C{sub 2}O{sub 4}){sub 3}{sup -3}, gde M=Co (III), Cr (III) ili Br (III), dali stol' zhe plodotvornye rezul'taty. Drugim metodom, primenimym tol'ko v sluchae ispol'zovaniya radioizotopov s malym atomnym vesom, kak naprimer ugleroda-14, mozhet sluzhit' izuchenie v sootvetstvuyushchikh reaktsiyakh ravnovesiya ili kineticheskogo izotopnogo vozdejstviya. Tak, naprimer, na osnovanii izmereniya ravnovesiya vozdejstviya izotopov v reaktsiyakh obmena karbonatov predstavilos' vozmozhnym istolkovat' razlichie v mekhanizme obmena svyazyvayushchikh karbonatov Coen{sub 2}CO{sub 3}{sup +} i Cotn{sub 2}CO{sub 3}{sup +}. Podobnym zhe obrazom dannye o kineticheskom vozdejstvii izotopov pri kislotno-katalizirovannoj gidratatsii ionov Co (NH{sub 3}){sub 4}CO{sub 3}{sup +} podtverdili vyvody otnositel'no kharaktera ehtikh reaktsij v stadii razryva svyazi, opredelyayushchej skorost' reaktsij. Nakonets, opyty s primeneniem radioaktivnykh indikatorov chasto oblegchayut izuchenie traektorii nekotorykh atomov ili radikalov v neorganicheskikh reaktsiyakh, pri kotorykh prikhoditsya delat' vybor mezhdu dvumya vozmozhnymi ob{sup y}asneniyami. Primerom ehtogo mozhet sluzhit' dokazatel'stvo togo, chto, po-vidimomu, pri okislenii tiotsionatovykh ionov perekis'yu vodoroda tsianidy ne yavlyayutsya sredoj bystrogo obmena, khotya oni i yavlyayutsya vazhnym konechnym produktom. (author)}
place = {IAEA}
year = {1962}
month = {Mar}
}