Abstract

We have systematically studied a kinetic scheme of consecutive reactions by using generalized two-dimensional (2D) correlation analysis as reported by Noda. The correlations between reactant-intermediate, intermediate-product, and reactant-product pairs are analyzed with the related rate constants and absorption coefficients. When the reference spectrum is set at zero, the synchronous and asynchronous correlation spectra for the kinetic model are almost free from the influence of poor quality signals. If an appropriate reference spectrum is selected, the intermediate can be feasibly distinguished from other species involved in the reaction. A ratio of asynchronous to synchronous correlation intensity yields a coherence spectrum, which is characterized by different plateau-type peak intensities. When a steady-state condition fits the kinetic model, the peak summation of reactant-intermediate and intermediate-product correlation will approach the intensity of the reactant-product correlation. The coherence spectrum is useful for pattern recognition of the reaction scheme and also provides an effective way to identify the location and the extent of spectral overlap between two peaks.

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