Solution

ID: past-exam-of-the-chemistry-course-of-the-year-3-of-the-natural-sciences-course-of-the-university-of-cambridge/2022/paper-2a/section-a/16/b/solution

Rearrangement gives the Stern-Volmer equation
Thus a straight-line plot against has unit intercept and slope . Determine using an independently measured unquenched lifetime, or use known in the restricted model. Yield measurements alone do not separate two unknown rate constants. Equivalently the slope of is .
Use the absorbed intensity rather than incident intensity to normalize samples, and correct solvent/background signals, quencher absorption and fluorescence reabsorption. Under dynamic fluorescence quenching the lifetime ratio should follow the same straight line as the yield ratio. A reduced intensity without the corresponding lifetime change suggests static fluorescence quenching or an optical artefact; curvature can also indicate multiple populations or more complicated kinetics.

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