Atmospheric amines – Part II. Thermodynamic properties and gas/particle partitioning

• Published in: Atmospheric environment (1994) 2011, Vol.45 (3), p.561-577
• Main Authors: Ge, Xinlei, Wexler, Anthony S., Clegg, Simon L.
• Format: Article
• Language: English
• Subjects: Aerosols; Amines; Amino acids; ammonia; Applied sciences; atmospheric chemistry; Atmospheric pollution; Atmospherics; boiling point; chlorides; dissociation; Dissociation constant; Estimates; Exact sciences and technology; Gas/particle partitioning; Liquids; Mathematical models; nitrates; Partitioning; Pollution; prediction; Solubility; surveys; Thermodynamic model; urea; Vapor pressure; water solubility
• ISSN: 1352-2310; 1873-2844
• DOI: 10.1016/j.atmosenv.2010.10.013

Amines enter the atmosphere from a wide range of sources, but relatively little is known about their atmospheric behavior, especially their role in gas/particle partitioning. In Part I of this work ( Ge et al., 2011) a total of 154 amines, 32 amino acids and urea were identified as occurring in the atmosphere, based upon a survey of the literature. In this work we compile data for the thermodynamic properties of the amines which control gas/particle partitioning (Henry’s Law constant, liquid vapor pressure, acid dissociation constant, activity coefficient and solubility in water), and also estimate the solid/gas dissociation constants of their nitrate and chloride salts. Prediction methods for boiling point, liquid vapor pressure, acid dissociation constant and the solubility of the amines in water are evaluated, and used to estimate values of the equilibrium constants where experimental data are lacking. Partitioning of amines into aqueous aerosols is strongly dependent upon pH and is greatest for acidic aerosols. For several common amines the tendency to partition to the particle phase is similar to or greater than that of ammonia. Our results are presented as tables of values of thermodynamic equilibrium constants, which are also incorporated into the Extended Aerosol Inorganics Model ( E-AIM, http://www.aim.env.uea.ac.uk/aim/aim.php) to enable gas/aerosol partitioning and other calculations to be carried out. ► Thermodynamic data of amines that controls gas/particle partitioning are compiled. ► Data includes HLC, vapor pressure, activity coefficient and aqueous solubility. ► Partitioning of amines into aqueous aerosols is strongly dependent upon pH. ► Amines can partition into the aerosol, similar to or greater than that of ammonia.