Entropy measurements and the kinetic method: a statistically meaningful approach

In the literature, data obtained using the kinetic method have been analyzed to provide both ion affinities and relative entropies for the competitive dissociations involved. In this work, the procedure used to extract this information is shown to be statistically flawed. Using more rigorous statistical procedures, we outline alternative methods of acquiring the same information, including straightforward means of analyzing the uncertainties in the thermodynamic quantities obtained. Fortunately, it is expected that the central values reported in previous work need not be changed, but the uncertainties are much larger than has been previously detailed. The validity of the assumptions involved in the extraction of entropy effects is discussed in some detail.