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doctoral thesis
Kinetika dimerizacije C-nitrozo spojeva u čvrstom stanju
Zagreb: University of Zagreb, Faculty of Science, 2015. urn:nbn:hr:217:325405
Varga, Katarina
University of Zagreb
Faculty of Science
Department of Chemistry

Institutional repository: Repository of the Faculty of Science

Cite this document

Varga, K. (2015). Kinetika dimerizacije C-nitrozo spojeva u čvrstom stanju (Doctoral thesis). Zagreb: University of Zagreb, Faculty of Science. Retrieved from https://urn.nsk.hr/urn:nbn:hr:217:325405

Varga, Katarina. "Kinetika dimerizacije C-nitrozo spojeva u čvrstom stanju." Doctoral thesis, University of Zagreb, Faculty of Science, 2015. https://urn.nsk.hr/urn:nbn:hr:217:325405

Varga, Katarina. "Kinetika dimerizacije C-nitrozo spojeva u čvrstom stanju." Doctoral thesis, University of Zagreb, Faculty of Science, 2015. https://urn.nsk.hr/urn:nbn:hr:217:325405

Varga, K. (2015). 'Kinetika dimerizacije C-nitrozo spojeva u čvrstom stanju', Doctoral thesis, University of Zagreb, Faculty of Science, accessed 18 December 2024, https://urn.nsk.hr/urn:nbn:hr:217:325405

Varga K. Kinetika dimerizacije C-nitrozo spojeva u čvrstom stanju [Doctoral thesis]. Zagreb: University of Zagreb, Faculty of Science; 2015 [cited 2024 December 18] Available at: https://urn.nsk.hr/urn:nbn:hr:217:325405

K. Varga, "Kinetika dimerizacije C-nitrozo spojeva u čvrstom stanju", Doctoral thesis, University of Zagreb, Faculty of Science, Zagreb, 2015. Available at: https://urn.nsk.hr/urn:nbn:hr:217:325405

Metadata
TitleKinetika dimerizacije C-nitrozo spojeva u čvrstom stanju
Title (english)Kinetics of dimerization of C- nitroso compounds in solid state
AuthorKatarina Varga
MentorHrvoj Vančik (mentor)
Committee memberVladislav Tomišić (predsjednik povjerenstva)
Committee memberHrvoj Vančik (član povjerenstva)
Committee memberDavor Margetić (član povjerenstva)
GranterUniversity of Zagreb
Faculty of Science
(Department of Chemistry)
Zagreb
Defense date and country2015-06-08, Croatia
Scientific / art field,
discipline and subdiscipline		NATURAL SCIENCES
Chemistry
Universal decimal classification
(UDC)		54 - Chemistry. Crystallography. Mineralogy
Abstract
Kao prikladan model za proučavanje kinetike i mehanizama reakcija organskih molekula u kristalima odabrana je jednostavna reakcija dimerizacije C-nitrozo spojeva. Kako defekti nastali sublimacijom i uređenost molekula u kristalnoj rešetci utječe na konstantu brzine dimerizacije 4-brom (1) i 4-jodnitrozobenzena (4) istraženo je u različitim topokemijskim okolinama: od molekula monomera koji se nalaze u rešetci dimera nakon fotolize, molekula monomera u vlastitoj kristalnoj rešetci do nasumično orijentiranih molekula monomera u tankom sloju. Iz temperaturne ovisnosti konstante brzine reakcije procijenjena je energija aktivacije za dimerizaciju 1 u čvrstom stanju. Iako se danas vrlo malo pažnje posvećuje proučavanju mehanizama termalno potpomognutih reakcija izomerizacije u čvrstom stanju, a mnogo fotokemijskim reakcijama, u ovom radu detaljno je istražena termalno potpomognuta izomerizacija E-3-halogennitrozobenzena u Z-dimerne analoge. Pošto direktna „unimolekularna“ E-Z izomerizacija do sada još nije opažena, pokazano je da se Z-E izomerizacija azodioksida u čvrstom stanju može odvijati bez stvaranja slobodnih nitrozo molekula. Praćena je kinetika dimerizacije u različitim topokemijskim okolinama, kao i izomerizacija E-3-klor (2) i E-3-bromnitrozobenzena (3) u Z-dimerne analoge pri različitim temperaturama, na temelju kojih su određeni odgovarajući parametri aktivacije za dimerizaciju i izomerizaciju u čvrstom stanju.
Abstract (english)
Dimerization of nitroso compounds has been used as a suitable model for kinetic studies of organic reactions in crystals. The influence of the surface defects caused by sublimation of molecules on the dimerization rates of 4-bromo (1) and 4-iodonitrosobenzene (4) has been investigated in various topochemical environments: from monomer molecules in the crystal lattice prepared by photolysis to the randomly oriented monomer molecules in a thin layer. The activation energy for the dimerization of 1 has been estimated from the temperature dependence of the reaction rate. Most of the literature on the isomerisation in the solid state is focused on the photochemical reactions and very little attention is paid to the thermally induced reactions. In this work we have been investigated the solid state thermal isomerization of the E-3-halogenonitrosobenzenes in their Z-dimeric analogues. It has been shown that azodioxide Z-E isomerization in the solid state could occur without the formation of the free nitroso molecules. Such „unimolecular” isomerization has not yet been observed. The reaction has been studied by measuring the reaction rate of dimerization in different topochemical conditions by exploring the isomerization of E-3-chloro (2) and E-3-bromonitrosobenzene (3) at different temperatures and also by analyzing activation parameters for the solid state dimerization and isomerization.
Keywords
Keywords (english)
Languagecroatian
URN:NBNurn:nbn:hr:217:325405
Study programmeTitle: Doctoral study in chemistry
Study programme type: university
Study level: postgraduate
Academic / professional title: doktor/doktorica znanosti, područje prirodnih znanosti, polje kemija (doktor/doktorica znanosti, područje prirodnih znanosti, polje kemija)
Type of resourceText
Extent139 str. ; 30 cm
File originBorn digital
Access conditionsClosed access
Terms of useLicence In copyright icon
Created on2018-08-31 08:51:52