Measurements of oxygen diffusion in polystyrene, poly(methyl methacrylate), and poly(vinyl chloride) films varying in thickness from 7 to 57 µm were obtained at 22°C by following the kinetics of quenching of phosphorescence of camphorquinone dissolved in each polymer. Values of diffusion coefficients D were (2.2 ( 0.5) × 10 -7 , (1.4 ( 0.3) × 10 -8 , and (1.3 ( 0.1) × 10 -8 cm 2 s -1 , respectively, in reasonable agreement with literature data. The decreasing trend in D in this series is consistent with increasing polymer properties including cohesive energy density and diffusion activation energy. Comparison of the diffusion-limited rate constant k d , calculated from D, and the bimolecular rate coefficient k q , determined from lifetime and steady state intensity measurements, indicates that triplet CQ immobilized in glassy polymers is quenched with an efficiency k q /k d J 4/9. This result is subject to some uncertainty due to the errors in k q and k d ; however, a value of k q /k d > 4/9 must be considered possible in view of recent reports implying that intersystem crossing between excited complexes of all multiplicity is important in systems where the phosphor is a ketone immobilized in a high-viscosity matrix.
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