Christophe Grosjean - Achieving pH and Qr oscillations in a palladium-catalysed phenylacetylene oxidative carbonylation reaction using an automated reactor system

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      Publication Details (including relevant citation   information):

      Novakovic, K.; Grosjean, C.; Scott, S. K.; Whiting, A.; Willis,   M. J.; Wright, A. R. Chem. Phys. Lett.,   2007, 435, 142‐147


      This Letter reports an experimental study which achieves   reproducible oscillations in both pH and heat output (Qr) during   a palladium-

      catalysed phenylacetylene oxidative carbonylation reaction in an   homogeneous catalytic system (PdI2–KI–Air–NaOAc in methanol

      solution). Experiments were performed in an HEL SIMULAR reaction   calorimeter with precise control of temperature and gas

      flow rates. Under certain experimental conditions a second set of   oscillations was observed. Oscillations in Qr were exothermic   with

      no corresponding endotherm. Total energy released during   oscillations followed a staircase function with a maximum of 600   J/oscillation.

      Heat release was in phase with pH fall, and decreased as pH   increased.

      Address (URL): 24739&_coverDate=02%2F12%2F2007&_alid=1743128999&_rdoc=1&_fmt=high&_orig=search& _origin=search&_zone=rslt_list_item&_cdi=5231&_sort=r&_st=13&_docanchor=&view=c& _ct=1&_acct=C000014659&_version=1&_urlVersion=0&_userid=224739&md5=9a5362a30bca7 596c5e2b8ff52d3d72f&searchtype=a