The pinhole discharge using a novel electrode configuration was generated in various water–ethanol mixtures. Proton transfer reaction time-of-flight mass spectrometry was used for the diagnostics of stable discharge products. The sampling was realized by nitrogen constant flow over the liquid surface. Mostly, aliphatic hydrocarbons were detected. The number of products and their concentrations was observed in the dependence on the changing experimental conditions: alcohol concentration in the solution, the electrodes polarity, and the discharge duration. More compounds were detected with the increasing alcohol concentration and in the case of the positive polarity of the pinhole electrode.

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