Abstract
It was first established in 1958 by Abramova, Koeheshkov and Sheverdina that stannous organic compounds could in principle be synthesized by the action of Co{sup 60} gamma irradiation on mixtures of stannous metal and the corresponding alkyl halides. Under the conditions in which the experiments were carried out, in glass equipment without mixing, it was not possible to clarify the kinetic formation-mechanism of this type of organo-metallic compound. The present experiment was carried out in order to discover the effects of a number of factors on the irradiation synthesis velocity of stannous organic compounds in a stannous dibromodibutyl sample. For this purpose a special device with periodic loading of the components and unloading of the reaction products was designed and manufactured. Its excellent features included thermo-setting, effective mixing, and the periodical selection of test-samples for analysis. The main loop - a 2-1 stainless-steel reaction vessel - was provided with a mixer. The device was mounted on a Co{sup 60} gamma irradiation source. Experiments were carried out at a temperature of 80 {+-} 5''S and at atmospheric pressure. The dose intensity amounted to {approx} 50 rad/s (ferrous sulphate dosimeter). Powdered stannous metal and butyl bromide, differing in degree of purity, were
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Citation Formats
Abramova, L. V., Vereshchinskij, I. V., Kocheshkov, K. A., Miretskij, V. Yu., Pozdneev, V. V., Ryabukhin, Yu. S., and Sheverdina, N. I.
Radiation Synthesis of Stannous Dibromodibutyl; Synthese radiochimique de l'etain dibromopibutyle; Radiatsionno-khimicheskij sintez dibromdibutilolova; Sintesis radioquimica del dffiromodibutilestano.
IAEA: N. p.,
1963.
Web.
Abramova, L. V., Vereshchinskij, I. V., Kocheshkov, K. A., Miretskij, V. Yu., Pozdneev, V. V., Ryabukhin, Yu. S., & Sheverdina, N. I.
Radiation Synthesis of Stannous Dibromodibutyl; Synthese radiochimique de l'etain dibromopibutyle; Radiatsionno-khimicheskij sintez dibromdibutilolova; Sintesis radioquimica del dffiromodibutilestano.
IAEA.
Abramova, L. V., Vereshchinskij, I. V., Kocheshkov, K. A., Miretskij, V. Yu., Pozdneev, V. V., Ryabukhin, Yu. S., and Sheverdina, N. I.
1963.
"Radiation Synthesis of Stannous Dibromodibutyl; Synthese radiochimique de l'etain dibromopibutyle; Radiatsionno-khimicheskij sintez dibromdibutilolova; Sintesis radioquimica del dffiromodibutilestano."
IAEA.
@misc{etde_22099284,
title = {Radiation Synthesis of Stannous Dibromodibutyl; Synthese radiochimique de l'etain dibromopibutyle; Radiatsionno-khimicheskij sintez dibromdibutilolova; Sintesis radioquimica del dffiromodibutilestano}
author = {Abramova, L. V., Vereshchinskij, I. V., Kocheshkov, K. A., Miretskij, V. Yu., Pozdneev, V. V., Ryabukhin, Yu. S., and Sheverdina, N. I.}
abstractNote = {It was first established in 1958 by Abramova, Koeheshkov and Sheverdina that stannous organic compounds could in principle be synthesized by the action of Co{sup 60} gamma irradiation on mixtures of stannous metal and the corresponding alkyl halides. Under the conditions in which the experiments were carried out, in glass equipment without mixing, it was not possible to clarify the kinetic formation-mechanism of this type of organo-metallic compound. The present experiment was carried out in order to discover the effects of a number of factors on the irradiation synthesis velocity of stannous organic compounds in a stannous dibromodibutyl sample. For this purpose a special device with periodic loading of the components and unloading of the reaction products was designed and manufactured. Its excellent features included thermo-setting, effective mixing, and the periodical selection of test-samples for analysis. The main loop - a 2-1 stainless-steel reaction vessel - was provided with a mixer. The device was mounted on a Co{sup 60} gamma irradiation source. Experiments were carried out at a temperature of 80 {+-} 5''S and at atmospheric pressure. The dose intensity amounted to {approx} 50 rad/s (ferrous sulphate dosimeter). Powdered stannous metal and butyl bromide, differing in degree of purity, were employed. The reactivity components were applied in different ratios. It was established that under these conditions a controlled radiation-chemistry reaction takes place, the main result of which is a high yield of stannous dibromodibutyl. It was shown that the process has an induction period whose duration depends upon the purity of the initial butyl bromide; this has a notable effect on the formation velocity of the end product. It was found that the tin, not used up in the reaction, can be repeatedly used for the purpose of obtaining stannous dibromodibutyl and the induction period entirely eliminated. The features described provide the pre- requisites for an uninterrupted process. A reaction mechanism is proposed to explain the principles of the process which give a substantial irradiation yield. (author) [French] Le fait qu'il est, en principe, possible de realiser la synthese de composes organiques de l'etain en soumettant un melange d'etain metallique et d'halogenures appropries a l'action des rayons gamma du {sup 60}Co a ete etabli pour la premiere fois par Abramova, Kotchechkov et Cheverdina en 1958. Les conditions des experiences, qui etaient executees a l'aide d'un appareillage en vene depourvu de melangeur, ne permettait pas de determiner les lois cinetiques qui president a la formation des composes organometalliques de cette categorie. L'etude consideree a ete entreprise pour elucider l'influence qu'exercent plusieurs facteurs sur la vitesse a laquelle se produit la synthese radiochimique des composes organiques de l'etain, en prenant comme exemple l'etain dibromodibutyle. A cette fin, les auteurs ont concu et construit une installation speciale assurant le chargement periodique des composants et l'evacuation des produits de la reaction. Cette installation permettait de maintenir une temperature constante, d'assurer une agitation efficace et de prelever periodiquement des echantillons aux fins d'analyse. Son element essentiel - un recipient en acier inoxydable d'une contenance de deux litres ou se produisait la reaction - etait equipe d'un melangeur. Elle comprenait une source de rayons y{gamma} au {sup 60}Co. Les experiences ont eu lieu a une temperature de 80 {+-} 5{sup o}C, sous pression atmospherique. Le debit de dose, mesure a l'aide d'un dosimetre au sulfate ferreux, etait d'environ 50 rad/s. On a utilise de la poudre d'etain metallique et du bromure de butyle de puretes differentes. Les substances entrant dans la reaction ont ete employees en proportions diverses. On a constate qu'il se produisait, dans ces conditions, une reaction radiochimique orientee au cours de laquelle se formait essentiellement de l'etain dibromodibutyle en grande quantite. Les auteurs montrent que le processus comporte une periode d'amorcage dont la duree depend du degre de purete du bromure de butyle initial. Ce facteur exerce en outre une influence sensible sur la vitesse, de formation du produit final. On a constate que l'etain qui n'est pas entre dans la reaction peut etre utilise de nouveau pour la production d'etain dibromodibutyle, mais que dans ce cas la periode d'amorcage est totalement inexistante. Les particularites mentionnees creent les conditions necessaires pour la realisation d'un processus continu. Les auteurs proposent un mecanisme reactionnel pour expliquer la regularite du processus dont le rendement radiochimique est eleve. (author) [Spanish] La posibilidad de efectuar la sintesis de compuestos organicos del estafio por irradiacion con los rayos gamma del {sup 60}Co de mezclas de estano y de los respectivos haluros alquilicos fue establecida por primera vez en 1958 por Abramova, Kocheshkovy Sheverdina. Las condiciones en que se realizaron los experimentos, en aparatos de vidrio, sin agitadores, no permitieron determinar las leyes cineticas de la formacion de ese tipo de compuestos organo-metalicos. El presente trabajo sirvio para aclarar la influencia de una serie de factores sobre la velocidad de la sintesis radioquimica de los compuestos organicos del estafio tomando como ejemplo el dibromodibutilestaflo. Con ese objeto, se construyo un aparato especial que facilita la carga periodica de los reactivos y la descarga de los productos de reaccion. Dicho aparato permite estabilizar la temperatura, agitar eficazmente los reactivos y extraer periodicamente muestras para analisis. El elemento esencial es el recipiente de reaccion, de acero inoxidable, de 2-1 de capacidad, provisto de un agitador. El aparato se coloca sobre una fuente gamma de {sup 60}Co. Los experimentos se efectuaron a temperaturas de 80 {+-}5{sup o}C y a presion atmosferica. La intensidad de dosis medida con ayuda de un dosimetro de sulfato de hierro es de {approx}50 rad/s. Se utilizaron diversas proporciones de estafio metalico en polvo y bromuro de butilo de distintos grados de pureza. Se comprobo que en tales condiciones se desarrolla una reaccion radioquimica orientada en virtud de la cual se produce basicamente dibromodibutilestaflo con elevado rendimiento. Se demostro que el proceso tiene un periodo de induccion cuya duracion depende de la pureza del bromuro de butilo inicial. Este mismo factor influye tambien notablemente en la velocidad de formacion del producto final. Se comprobo que el estafio que no interviene en la reaccion puede volver a utilizarse para obtener dibromodibutilestaflo, pero en ese caso se anula por completo el periodo de induccion. Estas propiedades satisfacen los requisitos para la realizacion de un proceso continuo. Los autores proponen un mecanismo de reaccion, para explicar las leyes de este proceso que se desarrolla con un elevado rendimiento radioquimico. (author) [Russian] Printsipial'naya vozmozhnost' sinteza olovoorganicheskikh soedinenij pri dejstvii {gamma}-izlucheniya Co{sup 60} na smesi metallicheskogo olova i sootvetstvuyushchikh galoidalkilov vpervye byla ustanovlena Abramovoj, Kocheshkovym i SHeverdinoj v 1956 g. Usloviya provedeniya opytov v steklyannoj apparature bez peremeshivaniya ne pozvolyali vyyavit' kineticheskie zakonomernosti obrazovaniya ehtogo klassa metalloorganicheskikh soedinenij. Nastoyashchaya rabota byla postavlena dlya vyyasneniya vliyaniya ryada faktorov na skorost' radiatsionno-khimicheskogo sinteza olovoorganicheskikh soedinenij na primere dibromdibutilolova. S ehtoj tsel'yu byla skonstruirovana i izgotovlena spetsial'naya ustanovka s periodicheskoj zagruzkoj komponentov i vygruzkoj produktov reaktsii. Otlichitel'nymi osobennostyami ustanovki yavlyalis' vozmozhnost' ee termostatirovaniya, osushchestvlenie ehffektivnogo peremeshivaniya i periodicheskogo otbora prob dlya analizov. Osnovnoj uzel ustanovki (reaktsionnyj sosud iz nerzhaveyushchej stali ob''emom 2-1) byl snabzhen meshalkoj. Ustanovka montirovalas' na istochnike {gamma}-izlucheniya Co{sup 60}. Opyty provodilis' pri temperature 80 {+-} 5{sup o}C i atmosfernom davlenii. Moshchnost' dozy sostavlyala {approx}50 rad/sek (po ferrosul'fatnomu dozimetru). Primenyalos' metallicheskoe poroshkoobraznoe olovo i bromistyj butil raznoj stepeni ochistki. Komponenty reaktsii bralis' v razlichnykh sootnosheniyakh. Ustanovlennoe chto v dannykh usloviyakh protekaet napravlennaya radiatsionnokhimicheskaya reaktsiya, v rezul'tate kotoroj v osnovnom obrazuetsya dibromdibutilolovo s vysokim kolichestvennym vykhodom. Pokazano, chto protsess protekaet s induktsionnym periodom, dlitel'nost' kotorogo zavisit ot chistoty iskhodnogo bromistogo butila. EHtot zhe faktor zametno vliyaet ne skorost' obrazovaniya tselevogo produkta. Najdeno, chto olovo, ne voshedshee v reaktsiyu, mozhet povtorno ispol'zovat'sya dlya polucheniya dibromdibutilolova. Pri ehtom polnost'yu ustranyaetsya induktsionnyj period. Otmechennye osobennosti sozdayut predposylki dlya provedeniya nepreryvnogo protsessa. Predlozhen mekhanizm reaktsij dlya ob{sup y}asneniya zakonomernostej protsessa, protekayushchego so znachitel'nym radiatsionno-khimicheskim vykhodom. (author)}
place = {IAEA}
year = {1963}
month = {Nov}
}
title = {Radiation Synthesis of Stannous Dibromodibutyl; Synthese radiochimique de l'etain dibromopibutyle; Radiatsionno-khimicheskij sintez dibromdibutilolova; Sintesis radioquimica del dffiromodibutilestano}
author = {Abramova, L. V., Vereshchinskij, I. V., Kocheshkov, K. A., Miretskij, V. Yu., Pozdneev, V. V., Ryabukhin, Yu. S., and Sheverdina, N. I.}
abstractNote = {It was first established in 1958 by Abramova, Koeheshkov and Sheverdina that stannous organic compounds could in principle be synthesized by the action of Co{sup 60} gamma irradiation on mixtures of stannous metal and the corresponding alkyl halides. Under the conditions in which the experiments were carried out, in glass equipment without mixing, it was not possible to clarify the kinetic formation-mechanism of this type of organo-metallic compound. The present experiment was carried out in order to discover the effects of a number of factors on the irradiation synthesis velocity of stannous organic compounds in a stannous dibromodibutyl sample. For this purpose a special device with periodic loading of the components and unloading of the reaction products was designed and manufactured. Its excellent features included thermo-setting, effective mixing, and the periodical selection of test-samples for analysis. The main loop - a 2-1 stainless-steel reaction vessel - was provided with a mixer. The device was mounted on a Co{sup 60} gamma irradiation source. Experiments were carried out at a temperature of 80 {+-} 5''S and at atmospheric pressure. The dose intensity amounted to {approx} 50 rad/s (ferrous sulphate dosimeter). Powdered stannous metal and butyl bromide, differing in degree of purity, were employed. The reactivity components were applied in different ratios. It was established that under these conditions a controlled radiation-chemistry reaction takes place, the main result of which is a high yield of stannous dibromodibutyl. It was shown that the process has an induction period whose duration depends upon the purity of the initial butyl bromide; this has a notable effect on the formation velocity of the end product. It was found that the tin, not used up in the reaction, can be repeatedly used for the purpose of obtaining stannous dibromodibutyl and the induction period entirely eliminated. The features described provide the pre- requisites for an uninterrupted process. A reaction mechanism is proposed to explain the principles of the process which give a substantial irradiation yield. (author) [French] Le fait qu'il est, en principe, possible de realiser la synthese de composes organiques de l'etain en soumettant un melange d'etain metallique et d'halogenures appropries a l'action des rayons gamma du {sup 60}Co a ete etabli pour la premiere fois par Abramova, Kotchechkov et Cheverdina en 1958. Les conditions des experiences, qui etaient executees a l'aide d'un appareillage en vene depourvu de melangeur, ne permettait pas de determiner les lois cinetiques qui president a la formation des composes organometalliques de cette categorie. L'etude consideree a ete entreprise pour elucider l'influence qu'exercent plusieurs facteurs sur la vitesse a laquelle se produit la synthese radiochimique des composes organiques de l'etain, en prenant comme exemple l'etain dibromodibutyle. A cette fin, les auteurs ont concu et construit une installation speciale assurant le chargement periodique des composants et l'evacuation des produits de la reaction. Cette installation permettait de maintenir une temperature constante, d'assurer une agitation efficace et de prelever periodiquement des echantillons aux fins d'analyse. Son element essentiel - un recipient en acier inoxydable d'une contenance de deux litres ou se produisait la reaction - etait equipe d'un melangeur. Elle comprenait une source de rayons y{gamma} au {sup 60}Co. Les experiences ont eu lieu a une temperature de 80 {+-} 5{sup o}C, sous pression atmospherique. Le debit de dose, mesure a l'aide d'un dosimetre au sulfate ferreux, etait d'environ 50 rad/s. On a utilise de la poudre d'etain metallique et du bromure de butyle de puretes differentes. Les substances entrant dans la reaction ont ete employees en proportions diverses. On a constate qu'il se produisait, dans ces conditions, une reaction radiochimique orientee au cours de laquelle se formait essentiellement de l'etain dibromodibutyle en grande quantite. Les auteurs montrent que le processus comporte une periode d'amorcage dont la duree depend du degre de purete du bromure de butyle initial. Ce facteur exerce en outre une influence sensible sur la vitesse, de formation du produit final. On a constate que l'etain qui n'est pas entre dans la reaction peut etre utilise de nouveau pour la production d'etain dibromodibutyle, mais que dans ce cas la periode d'amorcage est totalement inexistante. Les particularites mentionnees creent les conditions necessaires pour la realisation d'un processus continu. Les auteurs proposent un mecanisme reactionnel pour expliquer la regularite du processus dont le rendement radiochimique est eleve. (author) [Spanish] La posibilidad de efectuar la sintesis de compuestos organicos del estafio por irradiacion con los rayos gamma del {sup 60}Co de mezclas de estano y de los respectivos haluros alquilicos fue establecida por primera vez en 1958 por Abramova, Kocheshkovy Sheverdina. Las condiciones en que se realizaron los experimentos, en aparatos de vidrio, sin agitadores, no permitieron determinar las leyes cineticas de la formacion de ese tipo de compuestos organo-metalicos. El presente trabajo sirvio para aclarar la influencia de una serie de factores sobre la velocidad de la sintesis radioquimica de los compuestos organicos del estafio tomando como ejemplo el dibromodibutilestaflo. Con ese objeto, se construyo un aparato especial que facilita la carga periodica de los reactivos y la descarga de los productos de reaccion. Dicho aparato permite estabilizar la temperatura, agitar eficazmente los reactivos y extraer periodicamente muestras para analisis. El elemento esencial es el recipiente de reaccion, de acero inoxidable, de 2-1 de capacidad, provisto de un agitador. El aparato se coloca sobre una fuente gamma de {sup 60}Co. Los experimentos se efectuaron a temperaturas de 80 {+-}5{sup o}C y a presion atmosferica. La intensidad de dosis medida con ayuda de un dosimetro de sulfato de hierro es de {approx}50 rad/s. Se utilizaron diversas proporciones de estafio metalico en polvo y bromuro de butilo de distintos grados de pureza. Se comprobo que en tales condiciones se desarrolla una reaccion radioquimica orientada en virtud de la cual se produce basicamente dibromodibutilestaflo con elevado rendimiento. Se demostro que el proceso tiene un periodo de induccion cuya duracion depende de la pureza del bromuro de butilo inicial. Este mismo factor influye tambien notablemente en la velocidad de formacion del producto final. Se comprobo que el estafio que no interviene en la reaccion puede volver a utilizarse para obtener dibromodibutilestaflo, pero en ese caso se anula por completo el periodo de induccion. Estas propiedades satisfacen los requisitos para la realizacion de un proceso continuo. Los autores proponen un mecanismo de reaccion, para explicar las leyes de este proceso que se desarrolla con un elevado rendimiento radioquimico. (author) [Russian] Printsipial'naya vozmozhnost' sinteza olovoorganicheskikh soedinenij pri dejstvii {gamma}-izlucheniya Co{sup 60} na smesi metallicheskogo olova i sootvetstvuyushchikh galoidalkilov vpervye byla ustanovlena Abramovoj, Kocheshkovym i SHeverdinoj v 1956 g. Usloviya provedeniya opytov v steklyannoj apparature bez peremeshivaniya ne pozvolyali vyyavit' kineticheskie zakonomernosti obrazovaniya ehtogo klassa metalloorganicheskikh soedinenij. Nastoyashchaya rabota byla postavlena dlya vyyasneniya vliyaniya ryada faktorov na skorost' radiatsionno-khimicheskogo sinteza olovoorganicheskikh soedinenij na primere dibromdibutilolova. S ehtoj tsel'yu byla skonstruirovana i izgotovlena spetsial'naya ustanovka s periodicheskoj zagruzkoj komponentov i vygruzkoj produktov reaktsii. Otlichitel'nymi osobennostyami ustanovki yavlyalis' vozmozhnost' ee termostatirovaniya, osushchestvlenie ehffektivnogo peremeshivaniya i periodicheskogo otbora prob dlya analizov. Osnovnoj uzel ustanovki (reaktsionnyj sosud iz nerzhaveyushchej stali ob''emom 2-1) byl snabzhen meshalkoj. Ustanovka montirovalas' na istochnike {gamma}-izlucheniya Co{sup 60}. Opyty provodilis' pri temperature 80 {+-} 5{sup o}C i atmosfernom davlenii. Moshchnost' dozy sostavlyala {approx}50 rad/sek (po ferrosul'fatnomu dozimetru). Primenyalos' metallicheskoe poroshkoobraznoe olovo i bromistyj butil raznoj stepeni ochistki. Komponenty reaktsii bralis' v razlichnykh sootnosheniyakh. Ustanovlennoe chto v dannykh usloviyakh protekaet napravlennaya radiatsionnokhimicheskaya reaktsiya, v rezul'tate kotoroj v osnovnom obrazuetsya dibromdibutilolovo s vysokim kolichestvennym vykhodom. Pokazano, chto protsess protekaet s induktsionnym periodom, dlitel'nost' kotorogo zavisit ot chistoty iskhodnogo bromistogo butila. EHtot zhe faktor zametno vliyaet ne skorost' obrazovaniya tselevogo produkta. Najdeno, chto olovo, ne voshedshee v reaktsiyu, mozhet povtorno ispol'zovat'sya dlya polucheniya dibromdibutilolova. Pri ehtom polnost'yu ustranyaetsya induktsionnyj period. Otmechennye osobennosti sozdayut predposylki dlya provedeniya nepreryvnogo protsessa. Predlozhen mekhanizm reaktsij dlya ob{sup y}asneniya zakonomernostej protsessa, protekayushchego so znachitel'nym radiatsionno-khimicheskim vykhodom. (author)}
place = {IAEA}
year = {1963}
month = {Nov}
}