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Title: Predicting the glass transition temperature and viscosity of secondary organic material using molecular composition

Secondary organic aerosol (SOA) accounts for a large fraction of submicron particles in the atmosphere. SOA can occur in amorphous solid or semi-solid phase states depending on chemical composition, relative humidity (RH), and temperature. The phase transition between amorphous solid and semi-solid states occurs at the glass transition temperature (T g). We have recently developed a method to estimate T g of pure compounds containing carbon, hydrogen, and oxygen atoms (CHO compounds) with molar mass less than 450 g mol -1 based on their molar mass and atomic O : C ratio. In this study, we refine and extend this method for CH and CHO compounds with molar mass up to ~ 1100 g mol -1 using the number of carbon, hydrogen, and oxygen atoms. We predict viscosity from the T g-scaled Arrhenius plot of fragility (viscosity vs. T g/T) as a function of the fragility parameter D. We compiled D values of organic compounds from the literature and found that D approaches a lower limit of ~ 10 (±1.7) as the molar mass increases. We estimated the viscosity of α-pinene and isoprene SOA as a function of RH by accounting for the hygroscopic growth of SOA and applying themore » Gordon–Taylor mixing rule, reproducing previously published experimental measurements very well. Sensitivity studies were conducted to evaluate impacts of T g, D, the hygroscopicity parameter (κ), and the Gordon–Taylor constant on viscosity predictions. The viscosity of toluene SOA was predicted using the elemental composition obtained by high-resolution mass spectrometry (HRMS), resulting in a good agreement with the measured viscosity. We also estimated the viscosity of biomass burning particles using the chemical composition measured by HRMS with two different ionization techniques: electrospray ionization (ESI) and atmospheric pressure photoionization (APPI). Due to differences in detected organic compounds and signal intensity, predicted viscosities at low RH based on ESI and APPI measurements differ by 2–5 orders of magnitude. Complementary measurements of viscosity and chemical composition are desired to further constrain RH-dependent viscosity in future studies.« less
Authors:
 [1] ;  [1] ; ORCiD logo [2] ;  [2] ; ORCiD logo [2] ; ORCiD logo [3] ; ORCiD logo [1] ;  [1]
  1. Univ. of California, Irvine, CA (United States). Dept. of Chemistry
  2. Purdue Univ., West Lafayette, IN (United States). Dept. of Chemistry
  3. Univ. of British Columbia, Vancouver, BC (Canada). Dept. of Chemistry
Publication Date:
Grant/Contract Number:
SC0018349; AGS-1654104; NA16OAR4310101; NA16OAR4310102
Type:
Accepted Manuscript
Journal Name:
Atmospheric Chemistry and Physics (Online)
Additional Journal Information:
Journal Name: Atmospheric Chemistry and Physics (Online); Journal Volume: 18; Journal Issue: 9; Journal ID: ISSN 1680-7324
Publisher:
European Geosciences Union
Research Org:
Univ. of California, Irvine, CA (United States); Purdue Univ., West Lafayette, IN (United States)
Sponsoring Org:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23); National Science Foundation (NSF); National Oceanic and Atmospheric Administration (NOAA) (United States)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 54 ENVIRONMENTAL SCIENCES
OSTI Identifier:
1501916

DeRieux, Wing-Sy Wong, Li, Ying, Lin, Peng, Laskin, Julia, Laskin, Alexander, Bertram, Allan K., Nizkorodov, Sergey A., and Shiraiwa, Manabu. Predicting the glass transition temperature and viscosity of secondary organic material using molecular composition. United States: N. p., Web. doi:10.5194/acp-18-6331-2018.
DeRieux, Wing-Sy Wong, Li, Ying, Lin, Peng, Laskin, Julia, Laskin, Alexander, Bertram, Allan K., Nizkorodov, Sergey A., & Shiraiwa, Manabu. Predicting the glass transition temperature and viscosity of secondary organic material using molecular composition. United States. doi:10.5194/acp-18-6331-2018.
DeRieux, Wing-Sy Wong, Li, Ying, Lin, Peng, Laskin, Julia, Laskin, Alexander, Bertram, Allan K., Nizkorodov, Sergey A., and Shiraiwa, Manabu. 2018. "Predicting the glass transition temperature and viscosity of secondary organic material using molecular composition". United States. doi:10.5194/acp-18-6331-2018. https://www.osti.gov/servlets/purl/1501916.
@article{osti_1501916,
title = {Predicting the glass transition temperature and viscosity of secondary organic material using molecular composition},
author = {DeRieux, Wing-Sy Wong and Li, Ying and Lin, Peng and Laskin, Julia and Laskin, Alexander and Bertram, Allan K. and Nizkorodov, Sergey A. and Shiraiwa, Manabu},
abstractNote = {Secondary organic aerosol (SOA) accounts for a large fraction of submicron particles in the atmosphere. SOA can occur in amorphous solid or semi-solid phase states depending on chemical composition, relative humidity (RH), and temperature. The phase transition between amorphous solid and semi-solid states occurs at the glass transition temperature (Tg). We have recently developed a method to estimate Tg of pure compounds containing carbon, hydrogen, and oxygen atoms (CHO compounds) with molar mass less than 450 g mol-1 based on their molar mass and atomic O : C ratio. In this study, we refine and extend this method for CH and CHO compounds with molar mass up to ~ 1100 g mol-1 using the number of carbon, hydrogen, and oxygen atoms. We predict viscosity from the Tg-scaled Arrhenius plot of fragility (viscosity vs. Tg/T) as a function of the fragility parameter D. We compiled D values of organic compounds from the literature and found that D approaches a lower limit of ~ 10 (±1.7) as the molar mass increases. We estimated the viscosity of α-pinene and isoprene SOA as a function of RH by accounting for the hygroscopic growth of SOA and applying the Gordon–Taylor mixing rule, reproducing previously published experimental measurements very well. Sensitivity studies were conducted to evaluate impacts of Tg, D, the hygroscopicity parameter (κ), and the Gordon–Taylor constant on viscosity predictions. The viscosity of toluene SOA was predicted using the elemental composition obtained by high-resolution mass spectrometry (HRMS), resulting in a good agreement with the measured viscosity. We also estimated the viscosity of biomass burning particles using the chemical composition measured by HRMS with two different ionization techniques: electrospray ionization (ESI) and atmospheric pressure photoionization (APPI). Due to differences in detected organic compounds and signal intensity, predicted viscosities at low RH based on ESI and APPI measurements differ by 2–5 orders of magnitude. Complementary measurements of viscosity and chemical composition are desired to further constrain RH-dependent viscosity in future studies.},
doi = {10.5194/acp-18-6331-2018},
journal = {Atmospheric Chemistry and Physics (Online)},
number = 9,
volume = 18,
place = {United States},
year = {2018},
month = {5}
}