Temperature-Dependent Phase Transitions of Aqueous Aerosol Droplet Systems in Microfluidic Traps

Priyatanu Roy; Liora E. Mael; Iaroslav Makhnenko; Robert Martz; Vicki H. Grassian; Cari S. Dutcher

doi:10.1021/acsearthspacechem.0c00114

Temperature-Dependent Phase Transitions of Aqueous Aerosol Droplet Systems in Microfluidic Traps

Priyatanu Roy, Liora E. Mael, Iaroslav Makhnenko, Robert Martz, Vicki H. Grassian, Cari S. Dutcher

Research output: Contribution to journal › Article › peer-review

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Abstract

Well-mixed atmospheric aqueous aerosol droplets containing multiple chemical species can undergo processes such as liquid-liquid phase separation (LLPS) and crystallization depending on the ambient temperature and relative humidity (RH). So far, only a handful of single droplet studies have examined the effect of temperature in conjunction with the organic to inorganic ratio (OIR) on the separation RH for LLPS. In this work, we present a temperature-controlled microfluidic static trap approach to study the LLPS and efflorescence phenomenon in multiple ternary systems in a quasi-equilibrium manner. Ammonium sulfate or sodium chloride is used as the inorganic phase and 3-methylglutaric acid (3-MGA), poly(ethylene glycol), poly(propylene glycol), or poly(ethylene glycol) diacrylate is used as the organic phase. Results show a clear trend in droplets containing 3-MGA with either salt of the initial LLPS and efflorescence events occurring at higher RH at lower temperatures, while this trend is less obvious for the other organics. The organic to inorganic ratio (OIR) of the system also affected the type of first phase transition, which can be either LLPS or efflorescence. Finally, the rate of RH change also had an impact on the temperature dependence of the formation of either anhydrous or dihydrous crystals of sodium chloride upon efflorescence. These results help inform the effects of temperature, OIR, and rate of RH change on the phase state of aqueous aerosol droplets containing multiple species.

Original language	English (US)
Pages (from-to)	1527-1539
Number of pages	13
Journal	ACS Earth and Space Chemistry
Volume	4
Issue number	9
DOIs	https://doi.org/10.1021/acsearthspacechem.0c00114
State	Published - Sep 17 2020
Externally published	Yes

Bibliographical note

Funding Information:
This work was supported by NSF through the NSF Center for Aerosol Impacts on Chemistry of the Environment (CAICE), an NSF Funded Center for Chemical Innovation (CHE-1801971), including support for P.R., NSF Graduate Research Fellowship Program (DGE-1650112) for support of L.M., and the NSF CAREER (AGS-1554936), including support of I.M. Portions of this work were conducted in the Minnesota Nano Center, which is supported by the National Science Foundation through the National Nano Coordinated Infrastructure Network (NNCI) under Award Number ECCS-2025124. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the National Science Foundation. Finally, the authors would like to thank Shweta Narayan and Shihao Liu for their advice on microfluidic fabrication and experimental methods.

Publisher Copyright:
Copyright © 2020 American Chemical Society.

Keywords

dehydration rate
liquid-liquid phase separation
microfluidics
model aerosols
organic to inorganic ratio
separation relative humidity
temperature-dependent

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title = "Temperature-Dependent Phase Transitions of Aqueous Aerosol Droplet Systems in Microfluidic Traps",

abstract = "Well-mixed atmospheric aqueous aerosol droplets containing multiple chemical species can undergo processes such as liquid-liquid phase separation (LLPS) and crystallization depending on the ambient temperature and relative humidity (RH). So far, only a handful of single droplet studies have examined the effect of temperature in conjunction with the organic to inorganic ratio (OIR) on the separation RH for LLPS. In this work, we present a temperature-controlled microfluidic static trap approach to study the LLPS and efflorescence phenomenon in multiple ternary systems in a quasi-equilibrium manner. Ammonium sulfate or sodium chloride is used as the inorganic phase and 3-methylglutaric acid (3-MGA), poly(ethylene glycol), poly(propylene glycol), or poly(ethylene glycol) diacrylate is used as the organic phase. Results show a clear trend in droplets containing 3-MGA with either salt of the initial LLPS and efflorescence events occurring at higher RH at lower temperatures, while this trend is less obvious for the other organics. The organic to inorganic ratio (OIR) of the system also affected the type of first phase transition, which can be either LLPS or efflorescence. Finally, the rate of RH change also had an impact on the temperature dependence of the formation of either anhydrous or dihydrous crystals of sodium chloride upon efflorescence. These results help inform the effects of temperature, OIR, and rate of RH change on the phase state of aqueous aerosol droplets containing multiple species. ",

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Temperature-Dependent Phase Transitions of Aqueous Aerosol Droplet Systems in Microfluidic Traps

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