Tropospheric ozone and photochemical processing of hydrocarbons; laboratory based kinetic and product studies.

  • Kimberley Leather

Student thesis: Phd


Laboratory based temperature-dependent kinetics and product yields for alkene ozonolysis and the reaction of CH3O2 with ClO and BrO have been measured via chamber studies and a turbulent flow tube coupled to CIMS (Chemical Ionisation Mass Spectrometry). In order to gain a better understanding of the fate of the products formed during hydrocarbon oxidation and their subsequent impact on the ozone budget (and so the oxidising capacity of the atmosphere) it is imperative to know the rate at which these reactions proceed and to identify their product yields.As tropospheric temperature varies, Arrhenius parameters were determined during the ozonolysis of selected alkenes. The temperature dependent kinetic database was extended and the activation energies for the ozonolysis of selected alkenes were correlated with an existing SAR (Structure Activity Relationship). Given the myriad organic species in the atmosphere, SARs are useful tools for the prediction of rate coefficients. Inclusion of Arrhenius parameters into the SAR allows for prediction over a range of temperatures, improving the conditions reflected in models. Achieving mass balance for alkene ozonolysis has proven to be a difficult challenge considering the numerous pathways of the Criegee Intermediate (CI). The product yield of formic acid - an organic acid with significant atmospheric implications which is under predicted by models - was determined as a function of relative humidity during ethene ozonolysis. This reaction exhibited a strong water dependence which lead to the prediction of the reaction rate of the CI with water which ranges between 1 × 10-12 - 1 × 10-15 cm3 molecule-1 s-1 and will therefore dominate its loss with respect to bimolecular processes in the atmosphere.Peroxy radicals, strongly influence the total oxidising capacity of the troposphere. The reaction of peroxy radicals with halogen oxides is recognised to be responsible for considerable ozone depletion in the atmosphere, exacerbated by reactive halogens (X, XO) taking part in catalytic cycles. Arrhenius parameters were determined for ClO + CH3O2 and BrO + CH3O2. Temperature is an important parameter affecting rate, exemplified here as the reaction involving ClO exhibited a positive temperature dependence whereas for BrO a negative temperature dependence was evident. As a consequence, the impact of ClO + CH3O2 with respect to ozone loss is diminished. Global modelling predicts a reduction in ozone loss by a factor of around 1.5 and implicates regions such as clean marine environments rather than the polar stratosphere. Conversely, a more pronounced temperature dependence for the reaction of BrO with CH3O2 placed particular importance on lower stratospheric chemistry where the modelled CH3O2 oxidation is doubled. The main products for this reaction were identified to be HOBr and CH2O2. The decomposition of CH2O2 could enhance HOx in the lower and middle stratosphere and contribute to a significant source of HOx in the upper troposphere. Bimolecular reaction of CH2O2 with water could also provide a none negligible source HC(O)OH in the upper troposphere. Alkenes and peroxy radicals undergo chemical processing in the atmosphere whilst acting as a source and sink of ozone and thus can impose detrimental effects on the biosphere, climate and air quality of the Earth.
Date of Award31 Dec 2012
Original languageEnglish
Awarding Institution
  • The University of Manchester
SupervisorC J Percival (Supervisor) & Andrew Horn (Supervisor)


  • flow-tube
  • peroxy radical
  • chamber studies
  • tropospheric
  • CH3O2
  • chemistry
  • atmospheric science
  • ClO
  • Criegee
  • halogen oxide
  • CIMS (Chemical Ionisation Mass Spectrometry)
  • kinetics
  • ozonolysis
  • BrO
  • ozone
  • organic acid
  • formic acid
  • alkene

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