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The Quest for the Hydroxyl-Peroxy Radical

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Published/Copyright: August 3, 2010
Zeitschrift für Physikalische Chemie
From the journal Zeitschrift für Physikalische Chemie Volume 224 Issue 7-8

Abstract

The hydroxyl-peroxy radical, HO3, has been the subject of numerous theoretical and experimental studies, not least because of its potential importance in atmospheric chemistry. Nevertheless, it has proved difficult to establish its stability: that is, values of D0(HO-O2), the HO-O2 bond dissociation energy or, equivalently, ΔfHo298(HO3), its standard enthalpy of formation. In this short article, a review is given of the results of experiments and calculations on HO3, culminating in experiments performed at low temperatures (55.9–99.8 K) in a CRESU apparatus, which establish both (i) rate constants for the formation of HO3 in the three-body reaction, OH + O2 + M → HO3 + M, and (ii) equilibrium constants from which values of D0(HO-O2) and ΔfHo298(HO3) can be derived – making use of spectroscopic data for HO3, from which partition functions and standard entropies can be calculated. It is shown that these absolute experimental values for D0(HO-O2) and ΔfHo298(HO3) are: (i) in agreement with the limiting values determined in experiments by Lester and co-workers, and (ii) in fair agreement with the most recent theoretical results. Furthermore, these thermodynamic data make it clear that only very small fractions of OH will be bound with O2 under the conditions found at all levels of the Earth’s atmosphere.

Keywords: Bond Dissociation Energy; Kinetics of Association; Low Temperature Reaction; Atmospheric Chemistry
* Correspondence address: University Chemical Laboratories, Lensfield Road, Cambridge CB2 1EW, Großbritannien,
Published Online: 2010-8-3
Published in Print: 2010-8-1

© by Oldenbourg Wissenschaftsverlag, Cambridge CB2 1EW, Germany

Articles in the same Issue

  1. Physico-Chemical Aspects of Global Atmospheric Change. Dedicated to Reinhard Zellner on the occasion of his 65th birthday
  2. The Quest for the Hydroxyl-Peroxy Radical
  3. Sources and Cycling of Tropospheric Hydroxyl Radicals – An Overview
  4. Kinetics and Products of the Reaction O2(1Σg+) with N2O
  5. An Experimental and Theoretical Study of the Reaction Between NH(X3Σ−) + SO(X3Σ−)
  6. Pressure Dependence of Iso-Propyl Nitrate Formation in the i-C3H7O2 + NO Reaction
  7. Photolysis of Trichloronitromethane (Chloropicrin) under Atmospheric Conditions
  8. The Gas-phase Ozonolysis of 1-Penten-3-ol, (Z)-2-Penten-1-ol and 1-Penten-3-one: Kinetics, Products and Secondary Organic Aerosol Formation
  9. Theoretical Study of the HOCH2OO• + HO2• Reaction: Detailed Molecular Mechanisms of the Three Reaction Channels
  10. Studies of the Formation and Growth of Aerosol from Molecular Iodine Precursor
  11. Heterogeneous Chemistry of Cl2O and HOCl on Frozen Natural Sea Salt, Recrystallized Sea Salt, KCl and NaCl Solutions at 200 and 215 K
  12. Atmospheric Heterogeneous Reactions of Benzo(a)pyrene
  13. Time Resolved Infrared Spectroscopy of Formation and Processing of Secondary Organic Aerosol
  14. Probing the Equilibrium Size and Hydrogen Bonding Structure in Aqueous Aerosol Droplets
  15. Interaction of NO2 with Soot: Oxidation and Gasification at Temperatures Between 300 and 670 K
  16. Uptake of Organic Acids on Ice Surfaces: Evidence for Surface Modification and Hydrate Formation
  17. Aqueous Phase Reactivity of Nitrate Radicals (NO3) Toward Dicarboxylic Acids
  18. Temperature and Ionic Strength Dependence of NO3-radical Reactions with Substituted Phenols in Aqueous Solution
https://doi.org/10.1524/zpch.2010.6135
Keywords for this article
Bond Dissociation Energy; Kinetics of Association; Low Temperature Reaction; Atmospheric Chemistry

Articles in the same Issue

  1. Physico-Chemical Aspects of Global Atmospheric Change. Dedicated to Reinhard Zellner on the occasion of his 65th birthday
  2. The Quest for the Hydroxyl-Peroxy Radical
  3. Sources and Cycling of Tropospheric Hydroxyl Radicals – An Overview
  4. Kinetics and Products of the Reaction O2(1Σg+) with N2O
  5. An Experimental and Theoretical Study of the Reaction Between NH(X3Σ−) + SO(X3Σ−)
  6. Pressure Dependence of Iso-Propyl Nitrate Formation in the i-C3H7O2 + NO Reaction
  7. Photolysis of Trichloronitromethane (Chloropicrin) under Atmospheric Conditions
  8. The Gas-phase Ozonolysis of 1-Penten-3-ol, (Z)-2-Penten-1-ol and 1-Penten-3-one: Kinetics, Products and Secondary Organic Aerosol Formation
  9. Theoretical Study of the HOCH2OO• + HO2• Reaction: Detailed Molecular Mechanisms of the Three Reaction Channels
  10. Studies of the Formation and Growth of Aerosol from Molecular Iodine Precursor
  11. Heterogeneous Chemistry of Cl2O and HOCl on Frozen Natural Sea Salt, Recrystallized Sea Salt, KCl and NaCl Solutions at 200 and 215 K
  12. Atmospheric Heterogeneous Reactions of Benzo(a)pyrene
  13. Time Resolved Infrared Spectroscopy of Formation and Processing of Secondary Organic Aerosol
  14. Probing the Equilibrium Size and Hydrogen Bonding Structure in Aqueous Aerosol Droplets
  15. Interaction of NO2 with Soot: Oxidation and Gasification at Temperatures Between 300 and 670 K
  16. Uptake of Organic Acids on Ice Surfaces: Evidence for Surface Modification and Hydrate Formation
  17. Aqueous Phase Reactivity of Nitrate Radicals (NO3) Toward Dicarboxylic Acids
  18. Temperature and Ionic Strength Dependence of NO3-radical Reactions with Substituted Phenols in Aqueous Solution
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