The Effect of Water on the Quantification of Volatile Species by Differential Electrochemical Mass Spectrometry.

Differential electrochemical mass spectrometry (DEMS) is one of the most powerful online techniques for quantitative determination of volatile species from electrochemical reactions. The products distribution as well as the respective production rate derived from DEMS measurements shed important light on the mechanisms and kinetics of complex reactions. In real measurements, the background mass signal of species to be detected changes with the reaction and the measurement conditions, which interferes the quantification of DEMS analysis. In this study, we analyzed systematically how the background mass signals of species change with the amount of water enters into the vacuum chamber from the electrolytic cell, since water is the dominant species in the cell with aqueous electrolyte. Our results reveal that during DEMS measurement, (1) there is a rather long time(>30 min) for the mass signals of volatile species to reach steady values after the filament for electronic ionization is turned on due to large sampling of water from the aqueous electrolyte; (2) the reaction of water with the hot filament changes the latter's surface state, it also produces H and O, which can interfere the quantification of H and O produced by electrode reactions; (3) the ionization probabilities of other species are also affected by the change of the filament's surface state, the competition for ionization of water as well as the reaction between ionized water fragments with related species in the ionization chamber. Strategies on how to obtain reliable mass signals purely related to electrocatalytic reactions are provided.