Summary
The kinetics of the reaction of phenylisocyanate with 1-butanol have been studied at low concentrations in carbon tetrachloride solution at three temperatures. The present paper describes the relation between the reaction rate and the concentration of the alcohol dimer and the 1:1 alcoholurethane associate. Therefrom we conclude that the monomeric alcohol does not play any significant part in the reaction. We explain the observed rate equation with the second-order term of the reactants with the equality of the productsk AA K AA andk AU K AU (rate constant and association constant of alcohol dimer and 1:1 alcohol-urethane associate).
For the reaction of alcohol dimer ΔH ≠=45.4 kJ mol−1 and ΔS ≠=− 142J mol−1K−1. We interpret this result in terms of a six-cyclic transition state.
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Thiele, L. Kinetik der unkatalysierten Urethanbildung. Monatsh Chem 123, 865–874 (1992). https://doi.org/10.1007/BF00811541
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DOI: https://doi.org/10.1007/BF00811541