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The compositions of the vapor‐liquid equilibria have been obtained in a small‐capacity recirculating still for the binary systems comprised of ethanol, propan‐l‐ol and butan‐l‐ol with propyl ethanoate and ethyl propanoate at a constant pressure of 101.32 ± 0.07 kPa. The experimental data were correlated with suitable equations and the azeotropes and their minimum boiling temperatures found were: ethanol + propyl ethanoate (x = y = 0.923; T = 351.5 K), propan‐l‐ol + propyl ethanoate (x = y = 0.610; T = 361.7 K), ethanol + ethyl propanoate (x = y = 0.875; T = 350.9 K) and propan‐l‐ol + ethyl propanoate (x = y = 0.534; T = 366.2 K).