The absorption spectrum of SO and the flash photolysis of sulphur dioxide and sulphur trioxide

Abstract

The flash photolysis of sulphur dioxide under adiabatic conditions results in the complete temporary disappearance of its spectrum , which then slowly regains its original intensity over a period of several milliseconds. Simultaneously with the disappearance of the sulphur dioxide spectrum a continuous absorption appears in the far ultra-violet and fades slowly as the sulphur dioxide reappears. It is shown that the effect of the flash is thermal rather than photochemical, and the possibility of the existence of an isomer of sulphur dioxide at high temperatures is discussed; the disappearance of the normal spectrum on flashing is explained in this way. Several previously unrecorded bands of SO observed in the photolysis indicate that the vibrational numbering of its spectrum should be revised by the addition of 2 to the present values of v' . This leads to a value of the dissociation energy of 123.5 kcal. In formation about the levels v' = 4, 5 and 6 has also been obtained. The isothermal flash photolysis of sulphur trioxide results in the appearance of vibrationally excited SO, and the primary photochemical step in this reaction is discussed.