Deuterium exchange in the systems of H2O+/H2O and H3O+/H2O

The reactions of H2O+, H3O+, D2O+, and D3O+ with neutral H2O and D2O were studied by tandem mass spectrometry. The H2O+ and D2O+ ion reactions exhibited multiple channels, including charge transfer, proton transfer (or hydrogen atom abstraction), and isotopic exchange. The H3O+ and D3O+ ion reactions exhibited only isotope exchange. The variation in the abundances of all ions involved in the reactions was measured over a neutral pressure range from 0 to 2 x 10(-5) Ton. A reaction scheme was chosen, which consisted of a sequence of charge transfer, proton transfer, and isotopic exchange reactions, Exact solutions to two groups of simultaneous differential equations were determined; one group started with the reaction of ionized water, and the other group started with the reactions of protonated water. A nonlinear least-squares regression technique was used to determine the rate coefficients of the individual reactions in the schemes from the ion abundance data. Branching ratios and relative rate coefficients were also determined in this manner. A delta chi-squared analysis of the results of the model fitted to the experimental data indicated that the kinetic information about the primary isotopic exchange processes is statistically the most significant, The errors in the derived values of the kinetic information of subsequent channels increased rapidly, Data from previously published selected ion flow tube (SIFT) study were analyzed in the same manner, Rigorous statistical analysis showed that the statistical isotope scrambling model was unable to explain either the SIFT or the tandem mass spectrometry data. This study shows that statistical analysis can be utilized to assess the validity of possible models in explaining experimentally observed kinetic behaviors. Published by Elsevier Science B,V.