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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 mixturesCanning, R. G. January 1973 (has links)
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.
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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.Canning, R.G. January 1973 (has links)
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. / Bradford University
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