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The Effect of Kinetic Energy on the Reactions of Nucleogenic Carbon Atoms with Hydrocarbons; Effet de l'Energie Cinetique sur les Reactions des Atomes de Carbone Nucleogeniques avec des Hydrocarbures; Ehffekt kineticheskoj ehnergii pri reaktsiyakh atomov yadernogenichesko- go ugleroda s uglevodorodami; Efecto de la Energia Cinetica en las Reacciones de Atomos Nucleogenos de Carbono con Hidrocarburos

Conference:

Abstract

The basic technique for studying the effect of kinetic energy on reactions of C atoms produced by nuclear transformation involves the well-known method of moderation with inert gases. However, this can be combined with other techniques such as (1) the use of scavengers to detect processes involving long- lived radicals, (2) degradative studies that serve to fix the position occupied by the labelled atom, (3) double tracer studies in which a reactant is partially labelled with deuterium and the isotopic composition of the labelled products is determined in order to establish the origin of the hydrogen which they contain. In this paper new results on product yields in two systems, neon-ethylene and neon-ethane, will be presented, and the relation of these results to other work involving degradative studies and double tracer experiments will be discussed. The discussion of the neon-ethylene results is in terms of the two previously postulated insertion mechanisms, insertion of the C atom into the C = C and into the C-H bonds to give C-C{sub 2}H{sub 4} adducts, As neon concentration is increased no product is eliminated, but the relative yields of products are altered markedly. Those products such as acetylene and vinyl acetylene which can  More>>
Authors:
Dubrin, J.; Rosenberg, H.; Wolfgang, R.; [1]  MacKay, C. [2] 
  1. Sterling Chemistry Laboratory, Yale University, New Haven, CT (United States)
  2. Haverford College, Haverford, PA (United States)
Publication Date:
Apr 15, 1965
Product Type:
Conference
Report Number:
IAEA-SM-57/70
Resource Relation:
Conference: Symposium on Chemical Effects Associated with Nuclear Reactions and Radioactive Transformations, Vienna (Austria), 7-11 Dec 1964; Other Information: 10 refs., 2 figs., 1 tab.; Related Information: In: Chemical Effects of Nuclear Transformations Vol. I. Proceedings of the Symposium on Chemical Effects Associated with Nuclear Reactions and Radioactive Transformations| 457 p.
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACETYLENE; ALLENE; CARBON 11; CHEMICAL BONDS; DEUTERIUM; ETHANE; ETHYLENE; HYDROGEN; ISOTOPE RATIO; KINETIC ENERGY; MOLECULES; NEON; NUCLEAR REACTIONS; RADICALS
OSTI ID:
22141765
Research Organizations:
International Atomic Energy Agency, Vienna (Austria); Joint Commission on Applied Radioactivity of the International Council of Scientific Unions, Paris (France)
Country of Origin:
IAEA
Language:
English
Other Identifying Numbers:
Other: ISSN 0074-1884; TRN: XA13M3295096366
Submitting Site:
INIS
Size:
page(s) 133-143
Announcement Date:
Oct 24, 2013

Conference:

Citation Formats

Dubrin, J., Rosenberg, H., Wolfgang, R., and MacKay, C. The Effect of Kinetic Energy on the Reactions of Nucleogenic Carbon Atoms with Hydrocarbons; Effet de l'Energie Cinetique sur les Reactions des Atomes de Carbone Nucleogeniques avec des Hydrocarbures; Ehffekt kineticheskoj ehnergii pri reaktsiyakh atomov yadernogenichesko- go ugleroda s uglevodorodami; Efecto de la Energia Cinetica en las Reacciones de Atomos Nucleogenos de Carbono con Hidrocarburos. IAEA: N. p., 1965. Web.
Dubrin, J., Rosenberg, H., Wolfgang, R., & MacKay, C. The Effect of Kinetic Energy on the Reactions of Nucleogenic Carbon Atoms with Hydrocarbons; Effet de l'Energie Cinetique sur les Reactions des Atomes de Carbone Nucleogeniques avec des Hydrocarbures; Ehffekt kineticheskoj ehnergii pri reaktsiyakh atomov yadernogenichesko- go ugleroda s uglevodorodami; Efecto de la Energia Cinetica en las Reacciones de Atomos Nucleogenos de Carbono con Hidrocarburos. IAEA.
Dubrin, J., Rosenberg, H., Wolfgang, R., and MacKay, C. 1965. "The Effect of Kinetic Energy on the Reactions of Nucleogenic Carbon Atoms with Hydrocarbons; Effet de l'Energie Cinetique sur les Reactions des Atomes de Carbone Nucleogeniques avec des Hydrocarbures; Ehffekt kineticheskoj ehnergii pri reaktsiyakh atomov yadernogenichesko- go ugleroda s uglevodorodami; Efecto de la Energia Cinetica en las Reacciones de Atomos Nucleogenos de Carbono con Hidrocarburos." IAEA.
@misc{etde_22141765,
title = {The Effect of Kinetic Energy on the Reactions of Nucleogenic Carbon Atoms with Hydrocarbons; Effet de l'Energie Cinetique sur les Reactions des Atomes de Carbone Nucleogeniques avec des Hydrocarbures; Ehffekt kineticheskoj ehnergii pri reaktsiyakh atomov yadernogenichesko- go ugleroda s uglevodorodami; Efecto de la Energia Cinetica en las Reacciones de Atomos Nucleogenos de Carbono con Hidrocarburos}
author = {Dubrin, J., Rosenberg, H., Wolfgang, R., and MacKay, C.}
abstractNote = {The basic technique for studying the effect of kinetic energy on reactions of C atoms produced by nuclear transformation involves the well-known method of moderation with inert gases. However, this can be combined with other techniques such as (1) the use of scavengers to detect processes involving long- lived radicals, (2) degradative studies that serve to fix the position occupied by the labelled atom, (3) double tracer studies in which a reactant is partially labelled with deuterium and the isotopic composition of the labelled products is determined in order to establish the origin of the hydrogen which they contain. In this paper new results on product yields in two systems, neon-ethylene and neon-ethane, will be presented, and the relation of these results to other work involving degradative studies and double tracer experiments will be discussed. The discussion of the neon-ethylene results is in terms of the two previously postulated insertion mechanisms, insertion of the C atom into the C = C and into the C-H bonds to give C-C{sub 2}H{sub 4} adducts, As neon concentration is increased no product is eliminated, but the relative yields of products are altered markedly. Those products such as acetylene and vinyl acetylene which can be formed from the initial C-C{sub 2}H{sub 4} adducts via processes with a high energy requirement decrease in importance, and the yields of products formed in low energy processes, such as C{sub 5} compounds, increase. The ethane pattern is similar. Degradative studies have already shown that the intramolecular C{sup 11} distribution in allene and methyl- acetylene formed from ethylene is affected by neon moderation. These results imply both participation of the C = C and C-H bonds in formation of these products, and a dependence of the ratio of attack at the two bond types on the kinetic energy of the reacting C atom. Other work involving double tracer studies on acetylene formation from single molecules such as CH{sub 2}CD{sub 2}, CH{sub 3}CH{sub 2}D, CD{sub 9}CDH{sub 2} and from various mixtures of other labelled alkanes and alkenes indicates that the removal of kinetic energy from, the C atom has little effect on the relative rate of attack at various types of C-H bonds. (author) [French] Le procede fondamental permettant d'etudier l'effet de l'energie cinetique sur les reactions des atomes de carbone produits par transformation nucleaire se fonde sur la methode bien connue du ralentissement 5 l'aide de gaz inertes. Toutefois, il peut etre combine I d'autres procedes: 1. emploi d'agents de balayage pour deceler les processus dans lesquels interviennent des radicaux de longue periode; 2, etudes de degradation qui servent a determiner la position occupee par l'atome actif; 3, etudes a l'aide d'un double indicateur, dans lesquelles un coips en reaction est partiellement marque par le deuterium et la composition isotopique des produits marques est determinee en vue d'etablir l'origine de l'hydrogene que ces produits contiennent. Les auteurs presentent des resultats nouveaux sur les rendements dans les deux systemes neon-ethylene et neon-ethane, et discutent la relation entre ces resultats et ceux d'autres travaux fondes sur des etudes de degradation et des experiences a l'aide d'un double indicateur. Pour ce qui est des resultats relatifs au systeme neon-ethylene, la discussion se fonde sur les deux mecanismes d'insertion anterieurement admis, a savoir insertion de l'atome de carbone dans la double liaison C = C et dans la liaison C-H, de maniere a donner des produits d'addition C-C{sub 2}H{sub 4}. Lorsque la concentration en neon augmente, on retrouve tous les produits, mais les rendements relatifs varient sensiblement. Des produits tels que l'acetylene proprement dit et le vinyl-acetylene, qui peuvent se former a partir des produits d'addition initiaux C-C{sub 2}H{sub 4} par des processus exigeant une forte energie, perdent de leur importance, tandis que le rendement en produits formes a basse energie, tels que les composes de C{sub 5}, accusent une augmentation. L'ethane suit un processus similaire. Les etudes de degradation ont deja montre que la distribution de {sup 11}C intramoleculaire dans l'aliene et le methylacetylene formes a partir de l'ethylene est influencee par le ralentissement du au neon. Ces resultats impliquent a la fois la participation de la double liaison C = C et de la liaison C-H a la formation des produits et le fait que le rapport d'attaque aux deux types de liaisons depend de l'energie cinetique de de l'atome de carbone en reaction. D'autres travaux fondes sur des etudes a l'aide d'un double indicateur, sur la formation d'acetylene a partir de molecules isolees, telles que CH{sub 2}CD{sub 2}, CH{sub 3}CH{sub 2}D, CD{sub 3}CDH{sub 2}, et a partir de divers melanges d'autres alcanes et alcenes marques indiquent que la perte d'energie cinetique par l'atome de carbone exerce peu d'effet sur la vitesse d'attaque relative aux diverses liaisons C-H. (author) [Spanish] La tecnica basica para estudiar la influencia ejercida por la energia cinetica en las reacciones de atomos de carbono producidos por transformacion nuclear recurre al metodo bien conocido de moderacion con gases inertes. Ahora bien, este puede combinarse con otras tecnicas tales como; 1) empleo de depuradores para detectar procesos en que intervengan radicales de periodo largo; 2) estudios por degradacion para determinar la posicion ocupada por el atomo marcado; 3) estudios con indicadores dobles, en los que un reactivo se marca parcialmente con deuterio y se determina la composicion isotopica de los productos marcados con miras a establecer el origen del hidrogeno que contienen. En la memoria se exponen nuevos resultados sobre el rendimiento en productos de dos sistemas, neon-etileno y neon-etano, y se estudia la relacion de estos resultados con otros trabajos que comprenden estudios por degradacion y experimentos con indicadores dobles. Los resultados referentes al sistema neon-etileno se discuten en funcion de dos mecanismos de insercion previamente propuestos, a saber, la insercion del atomo de carbono en los enlaces C = C y C-H para formar compuestos de adicion C-C{sub 2}H{sub 4}. Al aumentar la concentracion de neon no desaparece ningun producto, pero los rendimientos relativos sufren modificaciones considerables. Los productos tales como el acetileno y el vinil-acetileno que pueden formarse a partir de los compuestos iniciales de adicion C-C{sub 2}H{sub 4}, en virtud de procesos que requieren gran cantidad de energia, disminuyen en importancia, mientras que aumenta el rendimiento de los productos formados por procesos que exigen poca energia, tales como los compuestos C{sub 5}. Algo semejante sucede con el etano. Los estudios por degradacion han mostrado que la distribucion intramolecular de {sup 11}C en el aleno y el metilacetileno formados a partir de etileno es afectada por el efecto moderador del neon. Ello implica la participacion de los enlaces C = C y C-H en la formacion de estos productos, asi como una relacion de dependencia entre la razon de ataque en esos dos tipos de enlace y la energia cinetica del atomo de carbono que interviene en la reaccion. Otros estudios con indicadores dobles acerca de la formacion de acetileno a partir de moleculas sencillas tales como CH{sub 2}CD{sub 2}, CH{sub 3}CH{sub 2}D, CD{sub 3}CDH{sub 2} y a partir de varias mezclas de otros alcanos y alquenos marcados indican que la perdida de energia cinetica por el atomo de carbono ejerce escaso efecto en el indice relativo de ataque en varios tipos de enlace C-H. (author) [Russian] Osnovnaja metodika izuchenija jeffekta kineticheskoj jenergii pri reakcijah atomov ugleroda, obrazuemyh v rezul'tate jadernyh preobrazovanij, svjazana s ispol'zovaniem horosho izvestnogo metoda zamedlenija s pomoshh'ju inertnyh gazov. Odnako jetot metod mozhet sochetat'sja s drugoj metodikoj, kak, naprimer, 1) ispol'zovanie akceptorov radikalov dlja obnaruzhenija processov, svjazannyh s dolgozhivushhimi radikalami; 2) issledovanija javlenij degradacii dlja ustanovlenija polozhenija, zanimaemogo mechenym atomom; 3) issledovanija s ispol'zovaniem dvojnyh indikatorov, v kotoryh reagirujushhee veshhestvo chastichno metitsja dejteriem, i izotopnyj sostav mechenyh produktov opredeljaetsja s cel'ju ustanovlenija proishozhdenija vodoroda, kotoryj v nih soderzhitsja. V doklade predstavleny novye rezul'taty otnositel'no vyhodov produktov v dvuh sistemah, neon- jetilen i neon -jetan, i obsuzhdaetsja vopros o vzaimosvjazi jetih rezul'tatov s dannymi drugoj raboty, svjazannoj s issledovanijami javlenij degradacii i provedeniem opytov s ispol'zovaniem dvojnyh indikatorov. Obsuzhdenie rezul'tatov izuchenija sistemy neon -jetilen proishodit v ramkah dvuh ranee opredelennyh mehanizmov vvedenija atomov ugleroda v svjazi C-C i C-H s cel'ju poluchenija proizvodnyh C-C{sub 2}H{sub 4} . Po mere uvelichenija koncentracii neona ne ustranjaetsja nikakogo poolukta. olnako zametno menjajutsja otnositel'nye vyhody produktov. Takie produkty, kak acetilen i vinilacetilen, kotorye mogut byt' obrazovany iz pervonachal'nyh proizvodnyh C-C{sub 2}H{sub 4} v rezul'tate osushhestvlenija processov s bol'shim rashodom jenergii, terjajut svoe znachenie, v to vremja kak uvelichivajutsja vyhody produktov, obrazuemyh v hode processov nizkoj jenergii, kak naprimer, C{sub 5} soedinenija. Shema jetana javljaetsja analogichnoj. Issledovanija javlenij degradacii uzhe pokazali, chto na vnutrimolekuljarnoe raspredelenie C{sup 11} v allene i metilacetilene, obrazuemom iz jetilena, okazyvaet vlijanie zamedlenie neona. Jeti rezul'taty podrazumevajut kak uchastie svjazej C-C i C-H v obrazovanii jetih produktov, tak i zavisimost' velichiny vozdejstvija na oba tipa svjazi ot kineticheskoj jenergii reagirujushhego atoma ugleroda. Rezul'taty drugoj raboty, svjazannoj s issledovanijami ispol'zovanija dvojnyh indikatorov, po problemam obrazovanija acetilena iz edinichnyh molekul, kak naprimer, CH{sub 2}CD{sub 2}, CH{sub 3}CH{sub 2}D, CD{sub 3}CDH{sub 2} i iz razlichnyh smesej drugih mechenyh alkanov i alkenov, pokazyvajut, chto snjatie kineticheskoj jenergii s atoma ugleroda okazyvaet nebol'shoe vlijanie na otnositel'nuju skorost' vozdejstvija pri razlichnyh tipah svjazej C-H. (author)}
place = {IAEA}
year = {1965}
month = {Apr}
}