To model the temperature-induced partitioning of semivolatile organics in laboratory experiments or atmospheric models, one must know the appropriate heats of vaporization. Current treatments typically assume a constant value of the heat of vaporization or else use specific values from a small set of surrogate compounds. With published experimental vapor-pressure data from over 800 organic Compounds, we have developed a semiempirical correlation between the saturation concentration (C*, mu g m(-3)) and the heat of vaporization (Delta H-VAP, kJ mol(-1)) for organics in the volatility basis set. Near room temperature, Delta H-VAP = -11 log C-10(300)* + 129. Knowledge of the relationship between C* and Delta H-VAP constrains a free parameter in thermodenuder data analysis. A thermodenuder model using our Delta H-VAP values agrees well with thermal behavior observed in laboratory experiments.
%0 Journal Article
%1 Epstein:2010p2678
%A Epstein, Scott A
%A Riipinen, Ilona
%A Donahue, Neil M
%D 2010
%J Environmental Science & Technology
%K Alpha-Pinene, Beta-Pinene Bond-Dissociation Energies, Evaporation Ozonolysis, Parameterization, Particles, Rates, Thermodenuder, Vapor-Pressures, Volatility,
%N 2
%P 743--748
%R 10.1021/es902497z
%T A Semiempirical Correlation between Enthalpy of Vaporization and Saturation Concentration for Organic Aerosol
%U http://pubs.acs.org/doi/abs/10.1021/es902497z
%V 44
%X To model the temperature-induced partitioning of semivolatile organics in laboratory experiments or atmospheric models, one must know the appropriate heats of vaporization. Current treatments typically assume a constant value of the heat of vaporization or else use specific values from a small set of surrogate compounds. With published experimental vapor-pressure data from over 800 organic Compounds, we have developed a semiempirical correlation between the saturation concentration (C*, mu g m(-3)) and the heat of vaporization (Delta H-VAP, kJ mol(-1)) for organics in the volatility basis set. Near room temperature, Delta H-VAP = -11 log C-10(300)* + 129. Knowledge of the relationship between C* and Delta H-VAP constrains a free parameter in thermodenuder data analysis. A thermodenuder model using our Delta H-VAP values agrees well with thermal behavior observed in laboratory experiments.
@article{Epstein:2010p2678,
abstract = {To model the temperature-induced partitioning of semivolatile organics in laboratory experiments or atmospheric models, one must know the appropriate heats of vaporization. Current treatments typically assume a constant value of the heat of vaporization or else use specific values from a small set of surrogate compounds. With published experimental vapor-pressure data from over 800 organic Compounds, we have developed a semiempirical correlation between the saturation concentration (C*, mu g m(-3)) and the heat of vaporization (Delta H-VAP, kJ mol(-1)) for organics in the volatility basis set. Near room temperature, Delta H-VAP = -11 log C-10(300)* + 129. Knowledge of the relationship between C* and Delta H-VAP constrains a free parameter in thermodenuder data analysis. A thermodenuder model using our Delta H-VAP values agrees well with thermal behavior observed in laboratory experiments.},
added-at = {2010-06-22T19:38:37.000+0200},
affiliation = {Carnegie Mellon Univ, Ctr Atmospher Particle Studies, Pittsburgh, PA 15213 USA},
author = {Epstein, Scott A and Riipinen, Ilona and Donahue, Neil M},
biburl = {https://www.bibsonomy.org/bibtex/2c912925892c0fd40ed90abb36a0897f4/gsmith},
date-added = {2010-03-29 14:10:03 -0400},
date-modified = {2010-03-29 14:10:03 -0400},
doi = {10.1021/es902497z},
interhash = {0fd6144bcee08e71fd2b449388507096},
intrahash = {c912925892c0fd40ed90abb36a0897f4},
journal = {Environmental Science {\&} Technology},
keywords = {Alpha-Pinene, Beta-Pinene Bond-Dissociation Energies, Evaporation Ozonolysis, Parameterization, Particles, Rates, Thermodenuder, Vapor-Pressures, Volatility,},
language = {English},
local-url = {file://localhost/Users/geoffreysmith/Documents/Papers/Environmental%20Science%20&%20Technology/2010/Environmental%20Science%20&%20Technology,%2044,%20743-748%202010.pdf},
month = Jan,
number = 2,
pages = {743--748},
pmid = {000273433200033},
rating = {0},
timestamp = {2010-06-22T19:38:44.000+0200},
title = {A Semiempirical Correlation between Enthalpy of Vaporization and Saturation Concentration for Organic Aerosol},
uri = {papers://E88B624E-D406-46FF-9D95-BB9C1AAE3FDC/Paper/p2678},
url = {http://pubs.acs.org/doi/abs/10.1021/es902497z},
volume = 44,
year = 2010
}