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Related Experiment Videos

OH, HO2, and ozone gaseous diffusion coefficients.

Andrey V Ivanov1, Sofia Trakhtenberg, Allan K Bertram

  • 1Department of Chemistry and Biochemistry, University of California-San Diego, La Jolla, CA 92039, USA. avivanov@ucsd.edu

The Journal of Physical Chemistry. A
|February 15, 2007
PubMed
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This study measured diffusion coefficients for hydroxyl (OH), hydroperoxyl (HO2), and ozone (O3) radicals in helium and OH in air. Results align with polar analogues and support Lennard-Jones potential calculations for estimating unknown diffusion data.

Area of Science:

  • Atmospheric Chemistry
  • Chemical Kinetics
  • Physical Chemistry

Background:

  • Accurate diffusion coefficients are crucial for modeling reactive species transport in various environments.
  • Previous data for key atmospheric radicals like hydroxyl (OH), hydroperoxyl (HO2), and ozone (O3) are limited, especially in different gas mixtures.
  • Understanding diffusion behavior aids in predicting atmospheric reaction rates and pollutant dispersion.

Purpose of the Study:

  • To experimentally determine the diffusion coefficients of OH, HO2, and O3 in helium (He) and OH in air at 296 K.
  • To compare experimental diffusion coefficients with theoretical predictions and with diffusion of nonpolar analogues.
  • To validate the use of Lennard-Jones potentials for estimating diffusion coefficients where experimental data is scarce.

Main Methods:

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  • Utilized a coated-wall flow tube reactor coupled with chemical ionization mass spectrometry.
  • Measured the loss rates of reactive species (OH, HO2, O3) to the reactor walls as a function of pressure.
  • Calculated diffusion coefficients from the wall loss measurements.

Main Results:

  • Determined diffusion coefficients: D(OH-He) = 662 ± 33, D(OH-air) = 165 ± 20, D(HO2-He) = 430 ± 30, and D(O3-He) = 410 ± 25 Torr cm² s⁻¹ at 296 K.
  • Observed better agreement between measured diffusion coefficients of OH and HO2 with their polar analogues (H2O, H2O2) than nonpolar ones (O, O2).
  • Found excellent agreement between experimental data and diffusion coefficient calculations based on Lennard-Jones potentials.

Conclusions:

  • Experimental diffusion coefficients for OH, HO2, and O3 were successfully determined.
  • The study highlights the influence of polarity on diffusion behavior of reactive species.
  • Lennard-Jones potential calculations are validated as a reliable method for estimating diffusion coefficients for atmospheric radicals.