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Lookup NU author(s): Dr Julie Parker,
Dr Katarina Novakovic
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The oscillatory nature of the palladium catalysed phenylacetylene oxidative carbonylation (PCPOC) reaction was first reported by Temkin and colleagues1-4. It was demonstrated that the PCPOC reaction in a catalytic system (PdI2, KI, O2, NaOAc in methanol) exhibits oscillations in redox potential, pH and the rate of CO/O2 gas mixture consumption. Later on, Novakovic and colleagues5-8 investigated the characteristics of the PCPOC reaction and carried out this reaction in a calorimeter for the first time. They reported simultaneous oscillations in pH and rate of heat evolution (Qr)5, the influence of oscillations on product selectivity as well as the dynamics of product formation6 and the influence of the reaction temperature on the period and amplitude of oscillations7. In addition, the products resulting from this reaction have been reported.8 To make use of all observations the reaction mechanism responsible for the oscillations needs to be understood. In this quest, the reaction network responsible for the initial reactions of PdI2 in this system were studied.9 Subsequently, the role of water in this oscillatory system, as well as the importance of the order of reactant addition and its effect on product formation have been reported.10 This recent study enabled the proposal of a prospective theory to describe the oscillatory behaviour. In this work the existence of oscillatory behaviour in the concentration of phenylacetylene and carbonylation products (E-3-phenylacrylic acid methyl ester, Z-2-phenylbut-2-enedioic acid dimethyl ester, E-2-phenylbut-2-enedioic acid dimethyl ester, 5,5-dimethoxy-3-phenylfuran-2(5H)-one and 3-phenylfuran-2,5-dione) is uncovered. The amplitude of the oscillations in phenylacetylene was as high as 34% relative to the initial amount of phenylacetylene added to the system. 1. A.V. Malashkevich, L.G. Bruk and O.N. Temkin, J. Phys. Chem. A, 1997, 101 (51), 9825-9827; 2. S.N. Gorodskii, A.N. Zakharov, A.V. Kulik, L.G. Bruk and O.N. Temkin, Kinet. Cat., 2001, 42 (2), 251-263; 3. S.N. Gorodskii, E.S. Kalenova, L.G. Bruk and O.N. Temkin, Russ. Chem. Bull., 2003, 52 (7), 1524-1543; 4. O.N. Temkin and L.G. Bruk, Kinet. Cat., 2003, 44 (5), 601-617; 5. K. Novakovic, C. Grosjean, S.K. Scott, A. Whiting, M.J. Willis and A.R. Wright, Chem. Phys. Lett., 2007, 435, 142–147; 6. K. Novakovic, C. Grosjean, S.K. Scott, A. Whiting, M.J. Willis and A.R. Wright, Phys. Chem. Chem. Phys., 2008, 10, 749-753; 7. K. Novakovic, A. Mukherjee, M. Willis, A. Wright and S. Scott, Phys. Chem. Chem. Phys., 2009, 11, 9044-9049; 8. C. Grosjean, K. Novakovic, S.K. Scott, A. Whiting, M.J. Willis and A.R. Wright, J. Mol. Cat. A, 2008, 284, 33-39; 9. K. Novakovic, J. Parker, Int. J. Chem. Eng, 2011; 10. K. Novakovic, J. Parker, Submitted.
Author(s): Novakovic K; Parker J
Publication type: Conference Proceedings (inc. Abstract)
Publication status: Published
Conference Name: Gordon Research Conference on Oscillations and Dynamic Instabilities in Chemical Systems
Year of Conference: 2012