THERMAL DECOMPOSITION REACTION IN ETHANOL SOLUTION OF DEUTERATED ACETONE CYCLIC DIPEROXIDE AND ACETONE DIPEROXIDE. SECONDARY INVERSE ISOTOPIC EFFECT

Detalhes bibliográficos
Autor(a) principal: Nesprias,Karina
Data de Publicação: 2017
Outros Autores: Eyler,Gladys, Cañizo,Adriana, Barreto,Gastón
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Química Nova (Online)
Texto Completo: http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422017000400388
Resumo: The characterization by mass spectrometry and the kinetic study of the thermal decomposition reaction of deuterated acetone diperoxide (dACDP) was studied in ethanol in the 140-165 ºC temperature range. The comparison with the non deuterated species (ACDP) was also made. The kinetic behavior observed for both compounds follows a pseudo first order kinetic law up to at least 86 % peroxide conversions. It could be observed that under the established experimental conditions, the dACDP decomposes ca. 1.2 times faster than the ACDP. The activation parameters were calculated for both peroxides and allowed to postulate a single process initial step, the unimolecular thermal decomposition through the O-O bond cleavage to form an intermediate biradical. The products of the acetone derived peroxides thermal decomposition support a radical-based decomposition mechanism. The changes in kinetic parameters between dACDP and ACDP were justified attending to differences in ring substituents sizes. A secondary inverse kinetic isotope effect is observed (kH/kD <1).
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spelling THERMAL DECOMPOSITION REACTION IN ETHANOL SOLUTION OF DEUTERATED ACETONE CYCLIC DIPEROXIDE AND ACETONE DIPEROXIDE. SECONDARY INVERSE ISOTOPIC EFFECTisotopic secondary inverse effectacetone diperoxidedeuterated acetone diperoxidethermolysisThe characterization by mass spectrometry and the kinetic study of the thermal decomposition reaction of deuterated acetone diperoxide (dACDP) was studied in ethanol in the 140-165 ºC temperature range. The comparison with the non deuterated species (ACDP) was also made. The kinetic behavior observed for both compounds follows a pseudo first order kinetic law up to at least 86 % peroxide conversions. It could be observed that under the established experimental conditions, the dACDP decomposes ca. 1.2 times faster than the ACDP. The activation parameters were calculated for both peroxides and allowed to postulate a single process initial step, the unimolecular thermal decomposition through the O-O bond cleavage to form an intermediate biradical. The products of the acetone derived peroxides thermal decomposition support a radical-based decomposition mechanism. The changes in kinetic parameters between dACDP and ACDP were justified attending to differences in ring substituents sizes. A secondary inverse kinetic isotope effect is observed (kH/kD <1).Sociedade Brasileira de Química2017-05-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersiontext/htmlhttp://old.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422017000400388Química Nova v.40 n.4 2017reponame:Química Nova (Online)instname:Sociedade Brasileira de Química (SBQ)instacron:SBQ10.21577/0100-4042.20170037info:eu-repo/semantics/openAccessNesprias,KarinaEyler,GladysCañizo,AdrianaBarreto,Gastóneng2017-06-07T00:00:00Zoai:scielo:S0100-40422017000400388Revistahttps://www.scielo.br/j/qn/ONGhttps://old.scielo.br/oai/scielo-oai.phpquimicanova@sbq.org.br1678-70640100-4042opendoar:2017-06-07T00:00Química Nova (Online) - Sociedade Brasileira de Química (SBQ)false
dc.title.none.fl_str_mv THERMAL DECOMPOSITION REACTION IN ETHANOL SOLUTION OF DEUTERATED ACETONE CYCLIC DIPEROXIDE AND ACETONE DIPEROXIDE. SECONDARY INVERSE ISOTOPIC EFFECT
title THERMAL DECOMPOSITION REACTION IN ETHANOL SOLUTION OF DEUTERATED ACETONE CYCLIC DIPEROXIDE AND ACETONE DIPEROXIDE. SECONDARY INVERSE ISOTOPIC EFFECT
spellingShingle THERMAL DECOMPOSITION REACTION IN ETHANOL SOLUTION OF DEUTERATED ACETONE CYCLIC DIPEROXIDE AND ACETONE DIPEROXIDE. SECONDARY INVERSE ISOTOPIC EFFECT
Nesprias,Karina
isotopic secondary inverse effect
acetone diperoxide
deuterated acetone diperoxide
thermolysis
title_short THERMAL DECOMPOSITION REACTION IN ETHANOL SOLUTION OF DEUTERATED ACETONE CYCLIC DIPEROXIDE AND ACETONE DIPEROXIDE. SECONDARY INVERSE ISOTOPIC EFFECT
title_full THERMAL DECOMPOSITION REACTION IN ETHANOL SOLUTION OF DEUTERATED ACETONE CYCLIC DIPEROXIDE AND ACETONE DIPEROXIDE. SECONDARY INVERSE ISOTOPIC EFFECT
title_fullStr THERMAL DECOMPOSITION REACTION IN ETHANOL SOLUTION OF DEUTERATED ACETONE CYCLIC DIPEROXIDE AND ACETONE DIPEROXIDE. SECONDARY INVERSE ISOTOPIC EFFECT
title_full_unstemmed THERMAL DECOMPOSITION REACTION IN ETHANOL SOLUTION OF DEUTERATED ACETONE CYCLIC DIPEROXIDE AND ACETONE DIPEROXIDE. SECONDARY INVERSE ISOTOPIC EFFECT
title_sort THERMAL DECOMPOSITION REACTION IN ETHANOL SOLUTION OF DEUTERATED ACETONE CYCLIC DIPEROXIDE AND ACETONE DIPEROXIDE. SECONDARY INVERSE ISOTOPIC EFFECT
author Nesprias,Karina
author_facet Nesprias,Karina
Eyler,Gladys
Cañizo,Adriana
Barreto,Gastón
author_role author
author2 Eyler,Gladys
Cañizo,Adriana
Barreto,Gastón
author2_role author
author
author
dc.contributor.author.fl_str_mv Nesprias,Karina
Eyler,Gladys
Cañizo,Adriana
Barreto,Gastón
dc.subject.por.fl_str_mv isotopic secondary inverse effect
acetone diperoxide
deuterated acetone diperoxide
thermolysis
topic isotopic secondary inverse effect
acetone diperoxide
deuterated acetone diperoxide
thermolysis
description The characterization by mass spectrometry and the kinetic study of the thermal decomposition reaction of deuterated acetone diperoxide (dACDP) was studied in ethanol in the 140-165 ºC temperature range. The comparison with the non deuterated species (ACDP) was also made. The kinetic behavior observed for both compounds follows a pseudo first order kinetic law up to at least 86 % peroxide conversions. It could be observed that under the established experimental conditions, the dACDP decomposes ca. 1.2 times faster than the ACDP. The activation parameters were calculated for both peroxides and allowed to postulate a single process initial step, the unimolecular thermal decomposition through the O-O bond cleavage to form an intermediate biradical. The products of the acetone derived peroxides thermal decomposition support a radical-based decomposition mechanism. The changes in kinetic parameters between dACDP and ACDP were justified attending to differences in ring substituents sizes. A secondary inverse kinetic isotope effect is observed (kH/kD <1).
publishDate 2017
dc.date.none.fl_str_mv 2017-05-01
dc.type.driver.fl_str_mv info:eu-repo/semantics/article
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.uri.fl_str_mv http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422017000400388
url http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422017000400388
dc.language.iso.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv 10.21577/0100-4042.20170037
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv text/html
dc.publisher.none.fl_str_mv Sociedade Brasileira de Química
publisher.none.fl_str_mv Sociedade Brasileira de Química
dc.source.none.fl_str_mv Química Nova v.40 n.4 2017
reponame:Química Nova (Online)
instname:Sociedade Brasileira de Química (SBQ)
instacron:SBQ
instname_str Sociedade Brasileira de Química (SBQ)
instacron_str SBQ
institution SBQ
reponame_str Química Nova (Online)
collection Química Nova (Online)
repository.name.fl_str_mv Química Nova (Online) - Sociedade Brasileira de Química (SBQ)
repository.mail.fl_str_mv quimicanova@sbq.org.br
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