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Lookup NU author(s): Professor Katarina NovakovicORCiD, Dr Christophe Grosjean, Dr Mark Willis, Professor Allen Wright
This paper reports on the influence of oscillations on product selectivity as well as the dynamics of product formation during the palladium-catalysed phenylacetylene oxidative carbonylation reaction in a catalytic system (PdI 2, KI, Air, NaOAc in methanol). The occurrence of the pH oscillations is related to PdI2 granularity and the initial pH drop after phenylacetylene addition. To achieve pH and reaction exotherm oscillations regulation of the amount of PdI2 is required, ensuring that the initial pH does not fall significantly below 1 after phenylacetylene addition. Experiments in both oscillatory and non-oscillatory pH regimes were performed in an HEL SIMULAR™ reaction calorimeter with the concentration-time profiles measured using a GC-MS. It is demonstrated that when operating in an oscillatory pH regime product formation may be suppressed until oscillations occur after which there is a steep increase in the formation of Z-2-phenyl-but-2-enedioic acid dimethyl ester. When operating in non-oscillatory pH mode the products are formed steadily over time with the main products being Z-2-phenyl-but-2-enedioic acid dimethyl ester, 2-phenyl-acrylic acid methyl ester and E-3-phenyl-acrylic acid methyl ester. © the Owner Societies.
Author(s): Novakovic K, Grosjean C, Scott SK, Whiting A, Willis MJ, Wright AR
Publication type: Article
Publication status: Published
Journal: Physical Chemistry Chemical Physics
Year: 2008
Volume: 10
Issue: 5
Pages: 749-753
Print publication date: 01/01/2008
Date deposited: 05/07/2010
ISSN (print): 1463-9076
ISSN (electronic): 1463-9084
Publisher: Royal Society of Chemistry
URL: http://dx.doi.org/10.1039/b713906c
DOI: 10.1039/b713906c
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