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Effect of the C-alpha substitution on the ketonic decarboxylation of carboxylic acids over m-ZrO2: the role of entropy

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Effect of the C-alpha substitution on the ketonic decarboxylation of carboxylic acids over m-ZrO2: the role of entropy

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dc.contributor.author Oliver-Tomás, Borja es_ES
dc.contributor.author Gonell-Gómez, Francisco es_ES
dc.contributor.author Pulido, Angeles es_ES
dc.contributor.author Renz, Michael es_ES
dc.contributor.author Boronat Zaragoza, Mercedes es_ES
dc.date.accessioned 2017-05-26T10:44:59Z
dc.date.available 2017-05-26T10:44:59Z
dc.date.issued 2016
dc.identifier.issn 2044-4753
dc.identifier.uri http://hdl.handle.net/10251/81820
dc.description.abstract [EN] The kinetics of the ketonic decarboxylation of linear and branched carboxylic acids over m-ZrO2 as a catalyst has been investigated. The same apparent activation energy is experimentally determined for the ketonic decarboxylation of both linear pentanoic and branched 2-methyl butanoic acids, while the change in entropy for the rate-determining step differs by nearly 50 kJ mol(-1). These results show that the difference in reactivity between linear and branched acids is due to entropic effects, and is related to the probability of finding the reactant molecules adsorbed and activated in a suitable way on the catalyst surface. es_ES
dc.description.sponsorship The authors thank MINECO (Consolider Ingenio 2010-MULTICAT, CSD2009-00050 and Severo Ochoa program, SEV-2012-0267), Generalitat Valenciana (PROMETEOII/2013/011 Project), and the Spanish National Research Council (CSIC, Es 2010RU0108) for financial support. Red Espanola de Supercomputacion (RES) and Centre de Calcul de la Universitat de Valencia are gratefully acknowledged for computational facilities and technical assistance. A. P., F. G. and B. O.-T. thank MINECO (Juan de la Cierva and FPU Programme) and CSIC (JAE Programme) for their fellowships, respectively. M. R. is grateful to the Generalitat Valenciana for a BEST 2015 fellowship. en_EN
dc.language Inglés es_ES
dc.publisher Royal Society of Chemistry es_ES
dc.relation.ispartof Catalysis Science and Technology es_ES
dc.rights Reserva de todos los derechos es_ES
dc.subject Catalytic ketonization es_ES
dc.subject Acetic-acid es_ES
dc.subject Chemical es_ES
dc.subject Biomass es_ES
dc.subject Condensation es_ES
dc.subject Mechanism es_ES
dc.subject Zirconia es_ES
dc.subject Oxides es_ES
dc.subject Fuels es_ES
dc.subject.classification QUIMICA INORGANICA es_ES
dc.subject.classification QUIMICA ANALITICA es_ES
dc.title Effect of the C-alpha substitution on the ketonic decarboxylation of carboxylic acids over m-ZrO2: the role of entropy es_ES
dc.type Artículo es_ES
dc.identifier.doi 10.1039/c6cy00395h
dc.relation.projectID info:eu-repo/grantAgreement/MICINN//CSD2009-00050/ES/Desarrollo de catalizadores más eficientes para el diseño de procesos químicos sostenibles y produccion limpia de energia/ es_ES
dc.relation.projectID info:eu-repo/grantAgreement/MINECO//SEV-2012-0267/ es_ES
dc.relation.projectID info:eu-repo/grantAgreement/GVA//PROMETEOII%2F2013%2F011/ES/Catalizadores moleculares y supramoleculares altamente selectivos, estables y energéticamente eficientes en reacciones químicas (PROMETEO)/ es_ES
dc.relation.projectID info:eu-repo/grantAgreement/CSIC//2010RU0108/ es_ES
dc.rights.accessRights Abierto es_ES
dc.contributor.affiliation Universitat Politècnica de València. Instituto Universitario Mixto de Tecnología Química - Institut Universitari Mixt de Tecnologia Química es_ES
dc.description.bibliographicCitation Oliver-Tomás, B.; Gonell-Gómez, F.; Pulido, A.; Renz, M.; Boronat Zaragoza, M. (2016). Effect of the C-alpha substitution on the ketonic decarboxylation of carboxylic acids over m-ZrO2: the role of entropy. Catalysis Science and Technology. 6(14):5561-5566. https://doi.org/10.1039/c6cy00395h es_ES
dc.description.accrualMethod S es_ES
dc.relation.publisherversion http://dx.doi.org/10.1039/c6cy00395h es_ES
dc.description.upvformatpinicio 5561 es_ES
dc.description.upvformatpfin 5566 es_ES
dc.type.version info:eu-repo/semantics/publishedVersion es_ES
dc.description.volume 6 es_ES
dc.description.issue 14 es_ES
dc.relation.senia 328380 es_ES
dc.identifier.eissn 2044-4761
dc.contributor.funder Ministerio de Economía y Competitividad
dc.contributor.funder Generalitat Valenciana
dc.contributor.funder Consejo Superior de Investigaciones Científicas
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