Robert J. O'Brien

Date of Award


Document Type


Degree Name

Doctor of Philosophy (Ph.D.) in Environmental Sciences and Resources: Chemistry


Environmental Science and Management

Physical Description

2, xiii, 233 leaves: ill. 28 cm.


Tropospheric chemistry -- Mathematical models, Hydroxyl group




Hydroxyl radical HO plays a central role in controlling chemical processes in the troposphere. Current mechanisms are believed to accurately describe its formation, destruction and interaction with other atmospheric trace gases in clean air. Hydroperoxyl radical H0₂ is Iinked to HO in several chain processes and serves among other roles as a reservoir for HO. The relative concentration (H0₂/HO) in clean air is believed to be the order of 10². We here examine the conditions under which steady-state kinetics apply to HO₁ chemistry and derive simple relationships which can be used to predict HO and H0₂ concentration from measurable concentrations of the more stable trace gases. The equations assume a simple form for conditions where the ambient nitrogen oxide concentration is less than 1 ppb. These equations allow closed-form evaluation of the sensitivity of [HO] and [H0₂] to changes in the concentrations of the controlling species and allow assignment of uncertainty limits to the predictions of current tropospheric chemical models. Although most current efforts to test fast tropospheric photochemistry center upon measurements of ambient [HO], our equations indicate that tropospheric [H0₂] determinations may provide a more direct and accurate initial test of our knowledge of HO₁ chemistry in the unpolluted lower atmosphere. Overall the goal of this study is to benefit the experimenter by providing the information of insight and simple but reliable equations and to understand the conditions under which these measurements should be made and how best to interpret their results.


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