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Some solvent extraction studies of trivalent metal halides; Quelques etudes sur l'extraction par solvant d'halogenures de metaux trivalents; Izuchenie ehkstraktsii nekotorykh rastvoritelej iz trekhvalentnykh metallicheskikh galoidov; Algunos estudios de la extraccion mediante disolventes de haluros de metales trivalentes

Conference:

Abstract

Radiotracer techniques have made possible physical-chemical studies of the distribution of Ga (III) and In (III) between aqueous HCl and HBr solutions and the organic solvents, bis (2-chloroethyl) ether and nitrobenzene. From measurements of the extraction coefficients over a metal concentration range of greater than 10{sup 10} and under conditions where the coefficient varies by a factor of 10{sup 5}, the empirical behaviour of these systems has been thoroughly explored. The data have been explained in terms of ionization of the complex acid, HMX{sub 4}, in these relatively high dielectric solvents. From the variation of the extraction coefficient with metal concentration the ionization constant has been calculated of the supporting electrolyte, HCl or HBr, in the non-aqueous phase using a method developed by Poskanzer. Variation of the extraction coefficient with HX concentration has been used to calculate stability constants for the complex species MX{sub 3} and MX{sub 4}{sup -}. Since these are aqueous-phase reactions they are independent of the organic solvent used and excellent agreement is obtained for In (III)-HCl, using both bis (2-chloroethyl) ether and nitrobenzene. Attempts to evaluate the formation constants for gallium chloride and bromide complexes failed since the complex formation occurs over a very narrow range  More>>
Authors:
Dietz, Jr, R J; Mendez, J; Irvine, Jr, J W [1] 
  1. Department of Chemistry and Laboratory for Nuclear Science, Massachusetts Institute of Technology, Cambridge, MA (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: 8 figs, 1 tab., 18 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; 07 ISOTOPES AND RADIATION SOURCES; BROMIDES; DIELECTRIC MATERIALS; DISTRIBUTION; ELECTROLYTES; ETHERS; GALLIUM CHLORIDES; HYDROBROMIC ACID; HYDROCHLORIC ACID; ION EXCHANGE; METALS; NITROBENZENE; ORGANIC SOLVENTS; SOLUTIONS; SOLVENT EXTRACTION; STABILITY; TRACER TECHNIQUES
OSTI ID:
22025742
Research Organizations:
International Atomic Energy Agency, Vienna (Austria); United Nations Educational, Scientific and Cultural Organization, Paris (France)
Country of Origin:
IAEA
Language:
English
Other Identifying Numbers:
Other: ISSN 0074-1884; TRN: XA12N1758113035
Submitting Site:
INIS
Size:
page(s) 415-425
Announcement Date:
Jan 16, 2013

Conference:

Citation Formats

Dietz, Jr, R J, Mendez, J, and Irvine, Jr, J W. Some solvent extraction studies of trivalent metal halides; Quelques etudes sur l'extraction par solvant d'halogenures de metaux trivalents; Izuchenie ehkstraktsii nekotorykh rastvoritelej iz trekhvalentnykh metallicheskikh galoidov; Algunos estudios de la extraccion mediante disolventes de haluros de metales trivalentes. IAEA: N. p., 1962. Web.
Dietz, Jr, R J, Mendez, J, & Irvine, Jr, J W. Some solvent extraction studies of trivalent metal halides; Quelques etudes sur l'extraction par solvant d'halogenures de metaux trivalents; Izuchenie ehkstraktsii nekotorykh rastvoritelej iz trekhvalentnykh metallicheskikh galoidov; Algunos estudios de la extraccion mediante disolventes de haluros de metales trivalentes. IAEA.
Dietz, Jr, R J, Mendez, J, and Irvine, Jr, J W. 1962. "Some solvent extraction studies of trivalent metal halides; Quelques etudes sur l'extraction par solvant d'halogenures de metaux trivalents; Izuchenie ehkstraktsii nekotorykh rastvoritelej iz trekhvalentnykh metallicheskikh galoidov; Algunos estudios de la extraccion mediante disolventes de haluros de metales trivalentes." IAEA.
@misc{etde_22025742,
title = {Some solvent extraction studies of trivalent metal halides; Quelques etudes sur l'extraction par solvant d'halogenures de metaux trivalents; Izuchenie ehkstraktsii nekotorykh rastvoritelej iz trekhvalentnykh metallicheskikh galoidov; Algunos estudios de la extraccion mediante disolventes de haluros de metales trivalentes}
author = {Dietz, Jr, R J, Mendez, J, and Irvine, Jr, J W}
abstractNote = {Radiotracer techniques have made possible physical-chemical studies of the distribution of Ga (III) and In (III) between aqueous HCl and HBr solutions and the organic solvents, bis (2-chloroethyl) ether and nitrobenzene. From measurements of the extraction coefficients over a metal concentration range of greater than 10{sup 10} and under conditions where the coefficient varies by a factor of 10{sup 5}, the empirical behaviour of these systems has been thoroughly explored. The data have been explained in terms of ionization of the complex acid, HMX{sub 4}, in these relatively high dielectric solvents. From the variation of the extraction coefficient with metal concentration the ionization constant has been calculated of the supporting electrolyte, HCl or HBr, in the non-aqueous phase using a method developed by Poskanzer. Variation of the extraction coefficient with HX concentration has been used to calculate stability constants for the complex species MX{sub 3} and MX{sub 4}{sup -}. Since these are aqueous-phase reactions they are independent of the organic solvent used and excellent agreement is obtained for In (III)-HCl, using both bis (2-chloroethyl) ether and nitrobenzene. Attempts to evaluate the formation constants for gallium chloride and bromide complexes failed since the complex formation occurs over a very narrow range of acid concentration. Calculation from extraction data of the fraction, (GaCl{sub 4}{sup -})/{Sigma} Ga (III), as a function of HCl concentration gave a quantitative agreement with the data obtained from ion-exchange measurement by Kraus and Nelson. (author) [French] Les techniques utilisant des indicateurs radioactifs ont permis l'etude physico-chimique de la distribution du gallium (II) et de l'indium (III) entre les solutions aqueuses d'HCl et d'HBr et les solvants organiques ether bis (chloro-2-ethylique) et nitrobenzene. On etudie d'une facon empirique et approfondie le comportement de ces systemes, en se fondant sur les mesures des coefficients d'extraction pour une gamme de concentrations du metal superieure a 10{sup 10} et dans des conditions ou le coefficient varie selon un facteur de 10{sup 5}. Les donnees ont ete expliquees en termes d'ionisation de l'acide complexe HMX{sub 4} dans ces solvants a constante dielectrique relativement tres elevee. D'apres la variation du coefficient d'extraction en fonction de la concentration du metal, on a calcule la constante d'ionisation de l'electrolyte de support, HCl ou HBr, dans la phase non aqueuse, en appliquant une methode mise au point par Poskanzer. La variation du coefficient d'extraction en fonction de la concentration d'HX a ete utilisee pour calculer les constantes de stabilite, pour les especes completes MX{sub 3} et MX{sub 4}{sup -}. Etant donne que ces reactions ont lieu en phase aqueuse, elles sont independantes du solvant organique et l'on obtient une excellente concordance pour le systeme indium (III)-HCl en employant de l'ether bis (chloro-2-ethylique) et du nitrobenzene. Les efforts en vue d'evaluer les constantes de formation des complexes du chlorure et du bromure de gallium ont echoue, car la formation du complexe ne se produit qu'a l'interieur d'une gamme tres restreinte de concentrations de l'acide. Les resultats des calculs effectues d'apres les donnees d'extraction de la fraction (GaCl{sub 4}{sup -})/{Sigma} Ga(III), en fonction de la concentration d'HCl, correspondent quantitativement aux resultats obtenus par Kraus et Nelson au moyen des echanges d'ions. (author) [Spanish] Las tecnicas que emplean trazadores radiactivos permiten efectuar estudios quimico-fisicos de la distribucion del Ga (III) y del In (III) entre soluciones acuosas del HCl y HBr, y los disolventes organicos eter bis (2-cloroetilico) y nitrobenceno. Los autores han examinado empiricamente el comportamiento de estos sistemas midiendo los coeficientes de extraccion para concentraciones del metal que abarcan un intervalo superior a 10{sup 10} y en condiciones en las que el orden de magnitud del coeficiente varia en un intervalo de 10{sup 5}. Los autores explican los datos obtenidos sobre la base de la ionizacion del acido complejo HMX{sub 4} en estos disolventes, cuyas constantes dielectricas son relativamente elevadas. Empleando un metodo ideado por Poskanzer, han calculado la constante de ionizacion del electrolito soporte, HCl o HBr, en la fase no acuosa a partir de las variaciones que el coeficiente de extraccion experimenta en funcion de las concentraciones del metal. Las variaciones del coeficiente de extraccion con la concentracion de HX han servido para calcular las constantes de estabilidad de las especies complejas MX{sub 3} y MX{sub 4}{sup -}. Como se trata de reacciones en fase acuosa, las constantes son independientes del disolvente organico que se emplee. Para el sistema In (III)-HCl los autores obtuvieron resultados perfectamente concordantes tanto al emplear eter bis (2-cloroetilico) como nitrobenceno. Los autores no consiguieron evaluar las constantes de los complejos de cloruro y bromuro de galio porque dichos compuestos solo se forman en un intervalo de concentraciones de acido muy estrecho. Los valores del cociente (GaCl{sub 4}{sup -})/{Sigma} Ga (III) en funcion de la concentracion de HCl, calculados a partir de los datos de extraccion, concuerdan con los datos que Kraus y Nelson obtuvieron por mediciones del intercambio ionico. (author) [Russian] Metod mechenykh atomov pozvolil provesti izuchenie fiziko-khimicheskogo raspredeleniya Ga (III) i In (III) mezhdu vodnymi rastvorami HCl i HBr i organicheskimi rastvoritelyami, dvojnym ehfirom (2-khloroehtil) i nitrobenzolom. Na osnove izmerenij koehffitsientov ehkstraktsii pri kontsentratsii metalla vyshe 10{sup 10} i pri kolebanii dannogo koehffitsienta v predelakh 10{sup 5} tshchatel'no bylo razrabotano ehmpiricheskoe povedenie dannykh sistem. Rezul'taty vyrazhalis' v stepeni ionizatsii slozhnoj kisloty, HMX{sub 4}, izvestnoj v kachestve rastvoritelya s otnositel'no vysokimi diehlektricheskimi svojstvami. Po kolebaniyam koehffitsienta ehkstraktsii pri razlichnoj kontsentratsii metalla byla poluchena konstanta ionizatsii vspomogatel'nogo ehlektrolita, HCl ili HBr, v nevodnoj faze s ispol'zovaniem metoda, razrabotannogo Poskantserom. Variatsii koehffitsienta ehkstraktsii s kontsentratsiej HX ispol'zovalis' dlya rascheta konstant stabil'nosti dlya slozhnykh obraztsov MX{sub 3} i MX{sub 4}{sup -}. Tak kak oni yavlyayutsya reaktsiyami vodnoj fazy, to ne zavisyat ot ispol'zovannogo organicheskogo rastvoritelya, i poluchena polnaya soglasovannost' dlya In (III)-HCl pri ispol'zovanii dvojnogo ehfira (2-khloroehtil) i nitrobenzola. Popytki provedeniya otsenki obrazovaniya konstant dlya gallievogo khlorida i soedinenij broma okonchilis' neudachej, tak kak slozhnoe obrazovanie proiskhodit v ochen' uzkom diapazone kontsentratsii kisloty. Raschety na osnove rezul'tatov ehkstraktsii fraktsii (GaCl{sub 4}{sup -})/{Sigma} Ga (III) v kachestve funktsii ot kontsentratsii NS1 nakhodyatsya v kolichestvennom sootvetstvii s rezul'tatami, poluchennymi Krausom i Nel'sonom pri izmerenii ionnogo obmena. (author)}
place = {IAEA}
year = {1962}
month = {Mar}
}