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The electron energy distribution function in a mercury‐argon low‐pressure positive column was determined from the second derivative of voltage‐current characteristics of a single probe. The probe signals were analyzed with a digital signal processing technique. The high‐energy tail of the distribution functions ( f∼10-5) was obtained at mercury coldest spot temperature of 20, 42, and 60 °C (mercury density ratio of 4.8×10-4, 2.8×10-3, and 1.0×10-2 ), and discharge current of 0.2, 0.4, and 0.6 A for a 24‐mm‐diam tube. The electron density and electric field strength were measured at the same time, and used as input to a Boltzmann equation analysis code. General agreement was found between the experimental and theoretical results for the distribution function.