The homogeneous unimolecular decomposition of gaseous alkyl nitrites - IV—The decomposition of Iso -propyl nitrite

Abstract

It has already been shown that the first three straight chain members of the nitrite homologous series, i. e ., methyl, ethyl, and n -propyl nitrites, have exhibited in their thermal decomposition the characteristics pertaining to homogeneous unimolecular reactions. This paper deals with the investigation carried out on iso -propyl nitrite decomposition. This member of the series is particularly interesting as it allows comparison to be made between a straight-chain and a branched-chain isomer. The effect of these chemical configurations on the activation energy and the decomposition rates can be very effectively studies as no complications enter into the reactions to confuse measurements. Experimental Reaction velocities were measured as before by observing the rate of pressure change in a system at constant volume. The reaction vessels were Pyrex glass bulbs with a capacity of about 125 cc. The apparatus was similar to that used in previous experiments. The connecting tubing was heated to 105° C to prevent any of the products of the reaction condensing out. Control and measurement of the temperature was carried out as before. The temperature could be maintained constant to within 0·25° C.