Gas/Particle Partitioning Constants of Nicotine, Selected Toxicants, and Flavor Chemicals in Solutions of 50/50 Propylene Glycol/Glycerol As Used in Electronic Cigarettes.

Abstract

For an electronic cigarette (e-cigarette) aerosol with known total particulate matter concentration (TPM, μg/m3), predictions of the fractions of some compound i in the gas and particle phases ( fg, i and fp, i) at equilibrium can be made based on Kp, i (m3/μg), the compound-dependent gas/particle partitioning equilibrium constant. fg, i and fp, i affect the modes and locations of deposition in the respiratory tract. Kp, i depends inversely on (1) the pure compound liquid vapor pressure ( pL, io), (2) mole fraction activity coefficient (ζ i) in the absorbing liquid, and (3) mean molecular weight of the absorbing liquid (MW). Kp, i values were measured at 20 °C for 32 compounds as spiked into simulated e-cigarette liquids prepared as 50/50 mixtures (by weight) of propylene glycol (PG) and glycerol (GL). Kp, i values at 37 °C were estimated. The 32 compounds were nicotine (in free-base form), seven toxicants (propanal, acetone, hydroxyacetone, benzene, toluene, p-xylene, and ethylbenzene), and 24 flavor chemicals (2,3-pentanedione ("acetyl propionyl"), isobutyl acetate, ethyl butyrate, butyl butyrate, isoamyl acetate, 2,3-dimethylpyrazine, 3-methyl-1-butanol, limonene, 2,3,5-trimethylpyrazine, p-cymene, benzaldehyde, ( Z)-3-hexen-1-ol, menthol, 2-acetylpyrrole, benzyl alcohol, methyl salicylate, cinnamaldehyde, methyl anthranilate, (+)-aromadendrene, cinnamyl alcohol, methyl cinnamate, maltol, ethyl maltol, and coumarin). The measured log Kp, i values were found to be generally correlated with literature values of log pL, io; the scatter is caused by variation in ζ i between ∼1 and ∼1000. Kp measurements were attempted, but values were not reported for acetaldehyde, 2,3-butanedione (diacetyl), vanillin, and ethyl vanillin. Acetaldehyde was found to form significant amounts of its cyclic trimer and cyclic tetramer; for diacetyl, the evidence suggested significant amounts of reaction products, possibly hemiketals and ketals with PG/GL, and for vanillin and ethyl vanillin, the Kp values are large and accordingly more difficult to measure. fg values are calculated using a range of Kp and TPM values.