Proton affinities of primary alkanols: An appraisal of the kinetic method

The kinetic method is a now well-established technique for determining ther mochemical properties such as acidities and proton affinities. We present h ere a study of the application of the kinetic method to the proton affiniti es (PA) of a series of homologous primary alkanols, namely ethanol through n-octanol. Both metastable and collisionally activated dissociations of pro ton-bound alkanol pairs were studied, the latter as a function of the targe t gas and its pressure. Plots of ln([R1OH2+]/[R2OH2+]) VS PA for both exper iments were obtained to determine new PA values and investigate the signifi cance of the "effective temperature" term. When the experiments are conside red in detail, it is apparent that the kinetic method is essentially a semi empirical relationship, without a sound physicochemical basis.