Spectroscopic and Photochemical Research on the Diazo-Compounds etc.

Abstract

(1) The photochemical absorption spectra of the diazo-compounds were measured, and the rays which act chemically were elucidated. (2) The photolysis of D. N. S. and D. B. S.-solutions was observed quantitatively by employing the light-thermostat. (Concentration of the solution was mol/200.) It was observed that the decomposition proceeds with the constant velocity independent of the concentration. It was shown theoretically that the influence of the decomposition product of D. N. S. upon the photolysis is negligible. (3) The influence of quinine sulphate upon the decomposition velocity of D. N. S. was observed. By adding quinine sulphate the decomposition velocity of D. N. S. was reduced. And the more quinine sulphate was added, the slower became the velocity. The result was compared with those from the kinetic equation which was derived by applying Langendyk-Weigert's distribution theory. The experimental values of _x/a were rather larger than those obtained from the equation ; and the result was discussed. (4) The influence of temperature upon the photolysis of D. N. S. and D. B. S. was studied, and the nature of the decomposition was made clear. (I) Temperature influence upon D. N. S. is negligible. The photolysis is practically a pure photochemical reaction. (II) Temperature influence upon D. B. S.-photolysis is also negligible in the region of 2°C and 22°C. The results obtained at 45°C and 60°C showed some complexity. In order to make clear the nature of this photolysis, the thermal decomposition of the solution was thoroughly studied. From the theoretical point of view, it was shown numerically how the pure photo-reaction of D. B. S. is disturbed by the thermal reaction, and how the decomposition is accelerated, together with its practical meaning. (5) It was found by measurement that the quantumefficiency of the photolysis of D. N. S.-solution at λ = 366 mμ was 0.16.