## Abstract

Calculations of the size and density of atmospheric aerosols are complicated by the fact that they can exist at concentrations highly supersaturated with respect to dissolved salts and supercooled with respect to ice. Densities and apparent molar volumes of solutes in aqueous solutions containing the solutes H_{2}SO_{4}, HNO_{3}, HCl, Na_{2}SO_{4}, NaNO_{3}, NaCl, (NH_{4}) _{2}SO_{4}, NH_{4}NO_{3}, and NH_{4}Cl have been critically evaluated and represented using fitted equations from 0 to 50 °C or greater and from infinite dilution to concentrations saturated or supersaturated with respect to the dissolved salts. Using extrapolated densities of high-temperature solutions and melts, the relationship between density and concentration is extended to the hypothetical pure liquid solutes. Above a given reference concentration of a few mol kg^{-1}, it is observed that density increases almost linearly with decreasing temperature, and comparisons with available data below 0 °C suggest that the fitted equations for density can be extrapolated to very low temperatures. As concentration is decreased below the reference concentration, the variation of density with temperature tends to that of water (which decreases as temperature is reduced below 3.98 °C). In this region below the reference concentration, and below 0 °C, densities are calculated using extrapolated apparent molar volumes which are constrained to agree at the reference concentrations with an equation for the directly fitted density. Calculated volume properties agree well with available data at low temperatures, for both concentrated and dilute solutions. Comparisons are made with literature data for temperatures of maximum density. Apparent molar volumes at infinite dilution are consistent, on a single ion basis, to better than ±0.1 cm^{3} mol^{-1} from 0 to 50 °C. Volume properties of aqueous NaHSO_{4}, NaOH, and NH_{3} have also been evaluated, at 25 °C only. In part 2 of this work (ref 1) an ion interaction (Pitzer) model has been used to calculate apparent molar volumes of H_{2}SO_{4} in 0-3 mol kg^{-1} aqueous solutions of the pure acid and to represent directly the effect of the HSO_{4} ^{-} ↔ H^{+} + SO_{4}
^{2-} reaction. The results are incorporated into the treatment of aqueous H_{2}SO _{4} density described here. Densities and apparent molar volumes from -20 to 50 °C, and from 0 to 100 wt % of solute, are tabulated for the electrolytes listed in the title and have also been incorporated into the extended aerosol inorganics model (E-AIM, http://www.aim.env.uea.ac.uk/aim/aim. php) together with densities of the solid salts and hydrates.

Original language | English (US) |
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Pages (from-to) | 3393-3460 |

Number of pages | 68 |

Journal | Journal of Physical Chemistry A |

Volume | 115 |

Issue number | 15 |

DOIs | |

State | Published - Apr 21 2011 |

## ASJC Scopus subject areas

- Physical and Theoretical Chemistry

## Fingerprint

Dive into the research topics of 'Densities and apparent molar volumes of atmospherically important electrolyte solutions. 1. the solutes H_{2}SO

_{4}, HNO

_{3}, HCl, Na

_{2}SO

_{4}, NaNO

_{3}, NaCl, (NH

_{4})

_{2}SO

_{4}, NH

_{4}NO

_{3}, and NH

_{4}Cl from 0 to 50 °c'. Together they form a unique fingerprint.