<rdf:RDF xmlns:rdf="http://www.w3.org/1999/02/22-rdf-syntax-ns#" xmlns:dcterms="http://purl.org/dc/terms/">
<rdf:Description rdf:about="https://riquim.fq.edu.uy/items/show/5819">
    <dcterms:title><![CDATA[<strong>Computational Evidence Suggests That 1-Chloroethanol May Be an Intermediate in the Thermal Decomposition of 2-Chloroethanol into Acetaldehyde and HCl</strong>]]></dcterms:title>
    <dcterms:subject><![CDATA[TERMODINAMICA]]></dcterms:subject>
    <dcterms:subject><![CDATA[ACETALDEHIDO]]></dcterms:subject>
    <dcterms:subject><![CDATA[CLOROETANOL]]></dcterms:subject>
    <dcterms:subject><![CDATA[COMPUTACION-TEORIA]]></dcterms:subject>
    <dcterms:subject><![CDATA[BIBLIOGRAFIA NACIONAL QUIMICA]]></dcterms:subject>
    <dcterms:subject><![CDATA[2019]]></dcterms:subject>
    <dcterms:abstract><![CDATA[The dehalogenation of 2-chloroethanol (2ClEtOH) in the gas phase with and without the participation of catalytic water molecules has been investigated using methods rooted into the density functional theory. The well-known HCl elimination leading to vinyl alcohol (VA) was compared to the alternative elimination route toward oxirane and shown to be kinetically and thermodynamically more favorable. However, the isomerization of VA to acetaldehyde in the gas phase, in the absence of water, was shown to be kinetically and thermodynamically less favorable than the recombination of VA and HCl to form the isomeric 1-chloroethanol (1ClEtOH) species. At the &omega;B97X-D/cc-pVTZ level of calculation, this species is more stable than 2ClEtOH by about 6 kcal mol&ndash;1 at 298 K, and the reaction barrier for VA to 1ClEtOH is 23 kcal mol&ndash;1 versus 55 kcal mol&ndash;1 for the direct transformation of VA to acetaldehyde. In a successive step, 1ClEtOH can decompose directly to acetaldehyde and HCl with a lower barrier (29 kcal mol&ndash;1) than that of VA to the same products (55 kcal mol&ndash;1). The calculations were repeated using a single ancillary water molecule (W) in the complexes 2ClEtOH_W and 1ClEtOH_W. The latter adduct is now more stable than 2ClEtOH_W by about 8 kcal mol&ndash;1 at 298 K, implying that the water molecule increased the already higher stability of 1ClEtOH in the gas phase. However, this catalytic water molecule lowers dramatically the barrier for the interconversion of VA to acetaldehyde (from 55 to 7 kcal mol&ndash;1). This barrier is now smaller than the one for the conversion to 1ClEtOH (which also decreases, but not so much, from 23 to 13 kcal mol&ndash;1). Thus, it is concluded that while 1ClEtOH may be a plausible intermediate in the gas phase dehalogenation of 2ClEtOH, it is unlikely that it plays a major role in water complexes (or, by inference, aqueous solution). It is also shown that neither in the gas phase nor in the cluster with one water molecule, the oxirane path is more favorable than the VA alcohol path. Additionally, a direct conversion of 2ClEtOH to 1ClEtOH through a transition state which resembles a VA molecule in a complex with a chlorine atom and a hydrogen atom on both sides of this planar species was found. This reaction path has also lower activation energy than the conversion to oxirane but not as low as the conversion to VA.]]></dcterms:abstract>
    <dcterms:creator><![CDATA[<strong>Salta, Zoi</strong>]]></dcterms:creator>
    <dcterms:creator><![CDATA[<strong>Kosmas, Agnie Mylona</strong>]]></dcterms:creator>
    <dcterms:creator><![CDATA[<a title="Curriculum Vitae" href="https://www.google.com/url?sa=t&amp;rct=j&amp;q=&amp;esrc=s&amp;source=web&amp;cd=1&amp;ved=2ahUKEwjO5a_q6r_mAhX1IbkGHWsNAxYQFjAAegQIBBAH&amp;url=https%3A%2F%2Fexportcvuy.anii.org.uy%2FCvEstatico%2F%3FurlId%3Da7868d1a46654e7a04ba7167141502086fa0cfad8b13463f75d90af715685994bc8f3eafaad6f6d2f6647277c9782143df93695c8a7d8e14295323ca2e2847d3%26formato%3Dpdf%26convocatoria%3D21&amp;usg=AOvVaw3DgPJlf--GOsjsu4KZ-hpA" target="_self"><strong>Ventura, Oscar N.</strong></a>]]></dcterms:creator>
    <dcterms:creator><![CDATA[<strong>Barone, Vicenzo</strong>]]></dcterms:creator>
    <dcterms:source><![CDATA[Journal of Physical Chemistry A v. 123, no. 10, 2019. -- p. 1983-1998]]></dcterms:source>
    <dcterms:publisher><![CDATA[American Chemical Society]]></dcterms:publisher>
    <dcterms:date><![CDATA[2019]]></dcterms:date>
    <dcterms:rights><![CDATA[<p><strong>Informaci&oacute;n sobre Derechos de Autor</strong></p>
<p>(Por favor lea este aviso antes de abrir los documentos u objetos)</p>
<p><strong>La legislaci&oacute;n uruguaya protege el derecho</strong> de autor sobre toda creaci&oacute;n literaria, cient&iacute;fica o art&iacute;stica, tanto en lo que tiene que ver con sus derechos morales, como en lo referente a los derechos patrimoniales con sujeci&oacute;n a lo establecido por el derecho com&uacute;n y las siguientes leyes (LEY 9.739 DE 17 DE DICIEMBRE DE 1937 SOBRE PROPIEDAD LITERARIA Y ARTISTICA CON LAS MODIFICACIONES INTRODUCIDAS POR LA LEY DE DERECHO DE AUTOR Y DERECHOS CONEXOS No. 17.616 DE 10 DE ENERO DE 2003, LEY 17.805 DE 26 DE AGOSTO DE 2004, LEY 18.046 DE 24 DE OCTUBRE DE 2006)</p>
<p><strong>ADVERTENCIA -</strong> La consulta de este documento queda condicionada a la aceptaci&oacute;n de las siguientes condiciones de uso: Este documento es &uacute;nicamente para usos privados enmarcados en actividades de investigaci&oacute;n y docencia. No se autoriza su reproducci&oacute;n con fines de lucro. Esta reserva de derechos afecta tanto los datos del documento como a sus contenidos. En la utilizaci&oacute;n o cita de partes debe indicarse el nombre de la persona autora.</p>]]></dcterms:rights>
    <dcterms:format><![CDATA[PDF]]></dcterms:format>
    <dcterms:language><![CDATA[Ingl&eacute;s]]></dcterms:language>
    <dcterms:type><![CDATA[Art&iacute;culo]]></dcterms:type>
    <dcterms:identifier><![CDATA[DOI: 10.1021/acs.jpca.8b11966]]></dcterms:identifier>
</rdf:Description><rdf:Description rdf:about="https://riquim.fq.edu.uy/items/show/5817">
    <dcterms:title><![CDATA[<strong>Theoretical study of the microhydration of 1-chloro and 2-chloro ethanol as a clue for their relative propensity toward dehalogenation</strong>]]></dcterms:title>
    <dcterms:subject><![CDATA[TERMODINAMICA]]></dcterms:subject>
    <dcterms:subject><![CDATA[COMPUESTOS ORGANOCLORADOS]]></dcterms:subject>
    <dcterms:subject><![CDATA[CLOROETANOL]]></dcterms:subject>
    <dcterms:subject><![CDATA[BIBLIOGRAFIA NACIONAL QUIMICA 6530 |a 2019]]></dcterms:subject>
    <dcterms:subject><![CDATA[2019]]></dcterms:subject>
    <dcterms:abstract><![CDATA[This work reports a computational analysis of hydrogen‐bonded clusters of mono‐, di‐, tri‐, and tetrahydrates of the chlorohydrins CH3CHClOH (1ClEtOH) and CH2ClCH2OH (2ClEtOH). The goal of the study is to assess the role of the water solvent into the facilitation of the initial step for dehalogenation of these compounds, a process of interest in several contexts. Molecular orbital methods (MP2), density functional methods (B3LYP, M06, and &omega;B97X‐D), and composite model chemistries (CBS‐QB3, G4) were employed to investigate the structure, electronic distribution, and hydrogen‐bonded structure of seven monohydrates, six dihydrates, five trihydrates, and five tetrahydrates of both species. Standard reaction enthalpy and standard Gibbs free reaction energy (urn:x-wiley:00207608:media:qua25931:qua25931-math-0001) were computed for all aggregates with respect to n independent water molecules and with respect to the dimer, trimer, and tetramer of water, respectively, in order to evaluate stability and hydrogen bonding network. The influence of the water chains on the length and vibrational frequencies, especially of the CCl and OH bonds, was evaluated. Hydrogen bonding in the complexes is discussed at length.]]></dcterms:abstract>
    <dcterms:creator><![CDATA[<strong>Petsis, George</strong>]]></dcterms:creator>
    <dcterms:creator><![CDATA[<strong>Salta, Zoi</strong>]]></dcterms:creator>
    <dcterms:creator><![CDATA[<strong>Kosmas, Agnie Mylona</strong>]]></dcterms:creator>
    <dcterms:creator><![CDATA[<a title="Curriculum Vitae" href="https://www.google.com/url?sa=t&amp;rct=j&amp;q=&amp;esrc=s&amp;source=web&amp;cd=1&amp;ved=2ahUKEwjO5a_q6r_mAhX1IbkGHWsNAxYQFjAAegQIBBAH&amp;url=https%3A%2F%2Fexportcvuy.anii.org.uy%2FCvEstatico%2F%3FurlId%3Da7868d1a46654e7a04ba7167141502086fa0cfad8b13463f75d90af715685994bc8f3eafaad6f6d2f6647277c9782143df93695c8a7d8e14295323ca2e2847d3%26formato%3Dpdf%26convocatoria%3D21&amp;usg=AOvVaw3DgPJlf--GOsjsu4KZ-hpA" target="_self"><strong>Ventura, Oscar N.</strong></a>]]></dcterms:creator>
    <dcterms:source><![CDATA[International Journal of Quantum Chemistry v. 119, no. 17, 2019. -- 15p.--e25931]]></dcterms:source>
    <dcterms:publisher><![CDATA[Wiley]]></dcterms:publisher>
    <dcterms:date><![CDATA[2019]]></dcterms:date>
    <dcterms:rights><![CDATA[<p><strong>Informaci&oacute;n sobre Derechos de Autor</strong></p>
<p>(Por favor lea este aviso antes de abrir los documentos u objetos)</p>
<p><strong>La legislaci&oacute;n uruguaya protege el derecho</strong> de autor sobre toda creaci&oacute;n literaria, cient&iacute;fica o art&iacute;stica, tanto en lo que tiene que ver con sus derechos morales, como en lo referente a los derechos patrimoniales con sujeci&oacute;n a lo establecido por el derecho com&uacute;n y las siguientes leyes (LEY 9.739 DE 17 DE DICIEMBRE DE 1937 SOBRE PROPIEDAD LITERARIA Y ARTISTICA CON LAS MODIFICACIONES INTRODUCIDAS POR LA LEY DE DERECHO DE AUTOR Y DERECHOS CONEXOS No. 17.616 DE 10 DE ENERO DE 2003, LEY 17.805 DE 26 DE AGOSTO DE 2004, LEY 18.046 DE 24 DE OCTUBRE DE 2006)</p>
<p><strong>ADVERTENCIA -</strong> La consulta de este documento queda condicionada a la aceptaci&oacute;n de las siguientes condiciones de uso: Este documento es &uacute;nicamente para usos privados enmarcados en actividades de investigaci&oacute;n y docencia. No se autoriza su reproducci&oacute;n con fines de lucro. Esta reserva de derechos afecta tanto los datos del documento como a sus contenidos. En la utilizaci&oacute;n o cita de partes debe indicarse el nombre de la persona autora.</p>]]></dcterms:rights>
    <dcterms:format><![CDATA[PDF]]></dcterms:format>
    <dcterms:language><![CDATA[Ingl&eacute;s]]></dcterms:language>
    <dcterms:type><![CDATA[Art&iacute;culo]]></dcterms:type>
    <dcterms:identifier><![CDATA[DOI: 10.1002/qua.25931]]></dcterms:identifier>
</rdf:Description></rdf:RDF>
