Influence of Ions on the Size Dependent Morphology of Aerosol Particles

Ott, Emily-Jean E.; Freedman, Miriam Arak

doi:10.1021/acsearthspacechem.1c00210

Title: Influence of Ions on the Size Dependent Morphology of Aerosol Particles

Journal Article · 01 September 2021 · ACS Earth and Space Chemistry

DOI: https://doi.org/10.1021/acsearthspacechem.1c00210 · OSTI ID:1836820

Ott, Emily-Jean E. ^[1];

^[2]

Pennsylvania State Univ., University Park, PA (United States); The Pennsylvania State University
Pennsylvania State Univ., University Park, PA (United States)

The study of aerosol particles composed of mixtures of organic and inorganic compounds provides insights for understanding chemistry in the atmosphere as well as information about phase transitions of systems under confinement. In the submicron size regime, we have previously found that liquid-liquid phase separation can be inhibited at sufficiently small particle diameters leading to phase separated particles at larger sizes and homogeneous particles below a threshold diameter. In this paper, we have investigated the influence of cations and anions in the inorganic compound (NH₄⁺, Na⁺, SO₄^2-, HSO₄^-, and Cl-) on the phase separation of submicron aerosol particles. Each of five salts were studied with two different organic compounds. Surprisingly, a strong dependence on the identity of the cation is evident in the size dependence of the particle morphology and no dependence on the anion was found. Sodium containing samples exhibit phase separation in particles below 20 nm in diameter whereas ammonium containing samples cease to undergo phase separation in particles between 45 and 65 nm in diameter. The separation relative humidity for supermicron droplets also depends on the identity of the cation in the inorganic component if the anion is the same across the salts compared. In addition, the correlation between the separation relative humidity and size dependence was investigated and displays a trend, but is not a dominant feature of the data. We explain the results in terms of hard and soft ions, where the harder cation (Na⁺) leads to phase separation down to smaller sizes while the softer cation (NH₄⁺) prevents phase separation and causes particles up to a larger diameter to remain homogenous. This study has implications for atmospheric chemistry in regions dominated by sea spray aerosol, which contains sodium as the primary cation, when compared to continental aerosol, where ammonium is an abundant cation. Additionally, these findings can be used to understand the influence of cations on the phase transitions of confined materials.

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Research Organization:: Pennsylvania State Univ., University Park, PA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0018032

OSTI ID:: 1836820

Journal Information:: ACS Earth and Space Chemistry, Journal Name: ACS Earth and Space Chemistry Journal Issue: 9 Vol. 5; ISSN 2472-3452

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Title: Influence of Ions on the Size Dependent Morphology of Aerosol Particles

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