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    Reaction calorimetry applied to kinetic problems. The design and construction of an isothermal calorimeter with heat compensation by the Peltier effect, and the application of the calorimeter in the study of reaction kinetics in solvent/water mixtures.

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    Canning.pdf (9.174Mb)
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    Publication date
    2010-02-11T16:32:59Z
    Author
    Canning, R.G.
    Supervisor
    Diaper, John
    Keyword
    Reaction calorimetry
    Kinetic problems
    Isothermal calorimeter
    Peltier effect
    Reaction kinetics
    Solvent / water mixtures
    Rights
    Creative Commons License
    The University of Bradford theses are licenced under a Creative Commons Licence.
    Institution
    University of Bradford
    Department
    Not given
    Awarded
    1973
    
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    Abstract
    An isothermal calorimeter controlled by the Peltier effect has been designed and constructed in order to investigate reaction rates in solventwater mixtures. Because a thermal method was used a constant temperature environment was essential and this was achieved by using a water bath controlled to + 0.0010C. This callorinieter has been used to study the alkaline hydrolysis of methyl acetate in dimethylsulphoxide, and tetrahydrofuran - water mixtures at 15, 25 and 35 [degrees]C. The results of other investigations on similar reactions have been reviewed and an attempt has been made to correlate the electrostatic theories of Laidler and Eyring, and Amis and jaffe with these results. Finally, because it appears that specific solvent interactions play a major part in the reaction rates the role of water in the reaction mechanism has been examined. A mechanistic explanation has been proposed in order to correlate the rate of reaction with the composition of water-solvent mixtures which justifies the Laidler and Eyring treatment of solvent effects on ion-molecule reactions.
    URI
    http://hdl.handle.net/10454/4227
    Type
    Thesis
    Qualification name
    PhD
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    Theses

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