III International Conference

PP-I-24REACTION OF PHENYLACETYLENE CARBONYLATION TO ANHYDRIDE OFPHENYLMALEIC ACID ON OSCILLATING REGIMEGorodsky S.N., Kasatkina O.V., Bruk L.G., Temkin O.N.M.V. Lomonosov State Academy of Fine Chemical Technology, Moscow, RussiaE-mail: Gorodsky@yandex.ruIn the field of the catalytic reactions with metal complexes new oscillatory process -reaction of phenylacetylene oxidative carbonylation to anhydride of phenylmaleic acid in thesystem LiBr-PdBr 2 -CO-O 2 -(CH 3 ) 2 CO is found. Independence of an oscillatory mode of agases mixture composition is shown at the percentage of CO no more than 50 %. Thepreliminary mechanism of process was proposed.At study of catalytic reactions kinetics not trivial dynamic behavior of reaction inhomogeneous and heterogeneous systems (the critical phenomena) is even more oftenobserved - occurrence of oscillations of intermediates concentrations, oscillations of reactionrates, polystationary, the hysteresis, chaotic behavior [1, 2]. In this article we should like toreport about a new oscillatory system which is found out in our laboratory in typical processcatalyzed by metal complexes - reaction of phenylacetylene oxidative carbonylation toanhydride of phenylmaleic acid proceeding in palladium complexes solutions.Experiments on phenylacetylene oxidative carbonylation (PhA) (1) were carried out inthe closed system.In researched system oscillations of values of platinum electrode potential (E Pt )(fig. 1), pH, and also the characteristic step form of a curve of gas mixture absorption (CO,О 2 ) have been found.EPt,mV4003503002502001500 20 40 60 80 100 120 T,minFig. 1. The oxidative carbonylation of PhA in system LiBr-PdBr 2 -H 2 O-acetone.[LiBr] 0 =0,2М; [PdBr 2 ] 0 =0,01М; [PhA] 0 =0,1М; [Н 2 О] 0 = 0,75М;V (CH3) 2СO=10mL; [CO] 0 : [O 2 ] 0 = 1:150