In most cases of measuring the HER the electrolyte is saturated with H2. Similarly for the OER it is saturated with O2. But I have also seen papers that saturate the electrolyte with N2 or Ar. Which gives a more accurate assessment of the HER activity? And what are the reasons for saturating the electrolyte with the gas being evolved? My assumption is that it eliminates diffusion gradients.
When you are carrying out the reaction HER or OER, you always have a headspace. If O2/H2 is formed, they are distributed between gas and liquid phases. If the solution is well stirred, you may achieve a thermodynamic equilibrium, described by Henrly law. Thus you will have some gas in a liquid and some in a gas phases. The best way to quantify the total amount of H2/O2 would be to calibrate your reaction vessel The calibration procedure is described in our publications.
Although I don't know the answer to your question, I know that it can be a subject of research. Article Effect of Saturating the Electrolyte with Oxygen on the Acti...
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