The use of gas uptake measurements, in place of calorimetry is explored in this Thesis.
- Gaseous mercury oxidation behavior in homogeneous reaction with chlorine compounds | SpringerLink;
- Homogeneous reaction?
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.
- Catalyzed Reaction Definition.
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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.
Heterogeneous catalysis - Wikipedia
Collections Chemistry Theses. Journal of Material Cycles and Waste Management. Homogeneous oxidation reactions of gaseous elemental mercury were experimentally tested to study the behavior of mercury compounds that contribute to toxic emissions in combustion flue gas. Chemical equilibrium calculations and reaction kinetics analysis were also carried out to help explain the experimental results. In particular, the chemical forms of oxidized mercury and their reaction paths were verified in detail. Among the experimental results, molecular chlorine was confirmed to have a higher oxidizing ability toward elemental mercury than hydrogen chloride does.
From the chemical equilibrium calculation, the final product of mercury compounds oxidized by chlorine was confirmed to be mercury chloride HgCl 2. Numerical analyses of reaction kinetics were mostly consistent with the experimental results and the chemical equilibrium calculations.
The ratio of mercury oxidization by chlorine increases with temperature from K to K, although it decreases at temperatures higher than K. Sensitivity analysis revealed the dominant reaction path of the mercury oxidation by chlorine.
First, elemental mercury reacts with Cl radicals to form HgCl. Unable to display preview. Download preview PDF.