Document Type


Date of Award


Degree Name

Master of Science in Chemical Engineering - (M.S.)


Chemical Engineering and Chemistry

First Advisor

Richard B. Trattner

Second Advisor

Howard S. Kimmel

Third Advisor

Angelo J. Perna


Chlorobenzene was chosen as a model system for the study of photochemically induced reactions in an aqueous environment. It was the goal of this research to achieve a reaction system which best approximates conditions existing in the environment. To do this, a basic model system was established, and then the effect on the rate by various parameters was studied. These parameters, which included the presence of oxygen and such inorganic compounds as might be present in receiving waters, (e.g. nitrate, sulfate, and phosphate), were chosen so as to meet the goal of this research.

Kinetic data was obtained for seven different systems. A value of 0.0319 min.-1 was found when chlorobenzene was irradiated in the basic model system of helium and water. When oxygen was substituted for helium, the rate decreased to 0.0224 min.-1. The presence of inorganic compounds resulted in both increases and decreases from the basic model system. When chlorobenzene was irradiated in solutions of 0.1M NaNO3 and 0.01M Na3PO4, the rates decreased to 0.0193 min.-1 and 0.0225 min.-1 respectively. The increase in the rate to 0.0440 min.-1 when chlorobenzene was photolyzed in a 0.00328M Fe2(SO4)3 solution prompted us to look for a possible explanation for this increase. The systems of 0.111 NaNO3 and 0.00323M Fe2(SO4)3 were rerun using a pyrex filter which would insure that the energy absorbed by the chlorobenzene was through energy transfer from the inorganic compounds rather than by diredt absorption of light. It was found that chlorobenzene did react in these systems which would indicate photosensitized reactions.



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