Bulletin of the Chemical Society of Japan p. 1395 - 1399 (2004)
Update date:2022-08-24
Topics:
Tokita, Yuichi
Okamoto, Akio
Nishiwaki, Kenichiro
Kobayashi, Mineto
Nakamura, Eiichi
The kinetics of the dimerization and hydration of acetylene in water with a copper(I) catalyst, a so-called Nieuwland catalyst, were investigated. The stationary state kinetics for both reactions could be described assuming that the rate-controlling step is a second-order reaction of an activated catalyst, [H-Cl-Cu-C2H], formed in the reaction mixture, with acetylene or water. The activation energies and activation entropies were 12.4 kcal·mol-1 and -33.3 cal·mol-1·K -1 for the acetylene dimerization, and 17.5 kcal·mol -1 and -34.2 cal·mol-1·K-1 for the acetylene hydration, respectively. The large negative values of activation entropy for these reactions may be accounted for by the role of water as a kind of cocatalyst.
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