Measurement of activity coefficients of mixtures by head-space gas chromatography: General procedure

• A general procedure to obtain reliable vapor liquid equilibrium (VLE) data by using HS-GC has been developed.
• A too small or too large liquid fill in the vial may condition the data reliability.
• HS-GC allows obtaining VLE data and activities coefficients in a high throughput scenario.

Head-space gas chromatography (HS-GC) is an applicable method to perform vapor–liquid equilibrium measurements and determine activity coefficients. However, the reproducibility of the data may be conditioned by the experimental procedure concerning to the automated pressure-balanced system. The study developed in this work shows that a minimum volume of liquid in the vial is necessary to ensure the reliability of the activity coefficients since it may become a parameter that influences the magnitude of the peak areas: the helium introduced during the pressurization step may produce significant variations of the results when too small volume of liquid is selected. The minimum volume required should thus be evaluated prior to obtain experimentally the concentration in the vapor phase and the activity coefficients. In this work, the mixture acetonitrile–toluene is taken as example, requiring a sample volume of more than 5 mL (about more than 25% of the vial volume). The vapor–liquid equilibrium and activity coefficients of mixtures at different concentrations (0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 molar fraction) and four temperatures (35, 45, 55 and 70 °C) have been determined. Relative standard deviations (RSD) lower than 5% have been obtained, indicating the good reproducibility of the method when a sample volume larger than 5 mL is used. Finally, a general procedure to measure activity coefficients by means of pressure-balanced head-space gas chromatography is proposed.