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|Title: ||Kinetic analysis of homogeneous catalytic reactions|
|Authors: ||Robb, Lynzi M.|
|Supervisors: ||Cole-Hamilton, David J.|
|Issue Date: ||Nov-2011|
|Abstract: ||Reaction progress kinetic analysis (RPKA) is a powerful tool for determining kinetic
parameters of catalytic reactions. Many of the published articles that have used RPKA have
employed reaction calorimetry for obtaining sufficient data to be reliable. The use of gas
uptake measurements, in place of calorimetry is explored in this Thesis.
Chapter 2 details the use of gas uptake measurements in establishing the order with respect
to substrate and gas for the rhodium catalysed hydrogenation of 1-octene. Previous studies
have used initial rate measurements to establish these orders and the reaction cycle is well
known. The use of RPKA allows the same information to be established in two reactions.
Chapter 3 focuses on the rhodium catalysed hydroformylation of 1-octene as it involves the
reaction of one substrate with two gases. Using RPKA it is possible to determine the order
in substrate and the overall order in gas, but it was found difficult to determine the order
with respect to the individual gases using RPKA alone.
Chapter 4 shows the palladium catalysed methoxycarbonylation of vinyl acetate. The
reaction has two substrate concentrations changing simultaneously as well as a gas. This
chapter shows that by careful design of experiments the orders with respect to each of these
substrates and CO can be determined in minimal numbers of experiments.
Chapter 5 focuses on the methoxycarbonylation of alkynes, which uses RPKA in complex
multistep reactions, to establish if RPKA can be used to determine the kinetics with respect
to the individual reacting components for each step. This study focuses on the
methoxycarbonylation of phenylacetylene to produce methyl cinnamate as well as the
methoxycarbonylation of both terminal and internal linear alkynes. These linear alkynes
carbonylate to produce an α,β-unsaturated ester. The double bond is isomerised from its
conjugated position along the chain to the terminal position where it is trapped and
carbonylated to produce an α,ω-dieter product.|
|Publisher: ||University of St Andrews|
|Appears in Collections:||Chemistry Theses|
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