Abstract
A stirred-flask ebulliometer was used to measure total vapor-pressure (PTx) data on nine mixtures of water + acrylic acid (and the pure components) between 45 and 112 °C and pressures from 10.00 to 101.325 kPa. These PTx data and the derived vapor-liquid equilibrium data show no azeotropic behavior. To verify that water + acrylic acid is a zeotrope at 101.325 kPa, dilute-solution AT data at 101.325 kPa were measured in a twin-arm Cottrell-lift-pump ebulliometer. Data on water + propanoic acid, with a known azeotrope at 101.325 kPa, were measured to test the experimental method. These dilute-solution measurements confirmed the known azeotrope for water + propanoic acid and conclusively demonstrated zeotropy for water + acrylic acid at 101.325 kPa. The system exhibits large positive deviations from ideality (derived γ ∞ = 2.5-5.7) that decrease with increasing temperature. Equimolar G E /T derived from fitted isothermal activity coefficient parameters decreases with increasing temperature, which predicts a positive HE. The excess function data show that the system water + acrylic acid belongs to the class of mixtures where G E > 0 and H E > 0 (this includes other water + organic acid mixtures); TS E shows a crossover from TS E > 0 to TS E < 0.
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