The photochemical decomposition of chlorine dioxide, ClO

CHEMISTRY · Multi-part · AP · Chemistry · Kinetics · Kinetics

Problem

The photochemical decomposition of chlorine dioxide, ClO2_2, in the gas phase is proposed to occur by the following mechanism. Step 1 ClO2+hν→Cl+O2\mathrm{ClO_2 + h\nu \rightarrow Cl + O_2} Step 2 Cl+ClO2→Cl2+O2\mathrm{Cl + ClO_2 \rightarrow Cl_2 + O_2} (fast equilibrium) Step 3 Cl2+hν→2 Cl\mathrm{Cl_2 + h\nu \rightarrow 2\,Cl} Step 4 Cl+O2+M→ClO2+M\mathrm{Cl + O_2 + M \rightarrow ClO_2 + M} (termolecular, slow) The symbol hνh\nu designates a photon of appropriate energy and MM represents any third-body collision partner. (a) Identification of intermediates with justification (b) Derivation of a rate expression containing intermediates (c) Application of the steady-state approximation to obtain an experimentally testable rate law (d) Explanation of the quantum-yield behavior in terms of the intermediate

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