Browsing by Author "Smith, D."

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    Kinetics and Thermodynamics of the Formation of the Donor Acceptor Complex of Tetracyanoethylene with Hexamethyl benzene in Solution, by a Microwave Temperature-jump method
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1972, 68 (5), 1972) Caldin, E. F.; Crooks, J. E.; O’Donnell, D.; Smith, D.; Toner, S.
    The rate of formation of the donor-acceptor complex between tetracyanoethylene and hexamethylbenzene, in 1-chlorobutane as solvent, has been measured at –83°C by a temperature-jump method using microwave heating. Equilibrium constants have also been determined over a range of temperature. The rate constant is (1.45 ± 0.3)× 108 l. mol–1 s–1(the uncertainty referring to the estimated limits of error). This is smaller by an order of magnitude than the calculated value for a diffusion-controlled reaction. The reason for this is discussed and it is concluded that there is possibly an energy barrier due to solvation changes. The rate constant in a solvent consisting of chlorobenzene + n-heptane (40–60 v-v) has also been determined, allowance being made for the parallel complex-formation between chlorobenzene and tetracyanoethylene; at –60°C, it was found to be (8 ± 3)× 108 l. mol–1 s–1.