Spectroscopic-kinetic analysis of first and second order reactions on the basis of multidimensional absorbance (A) diagrams

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Abstract

The absorbance (A), absorbance difference (AD) and absorbance difference quotient (ADQ) diagrams are called Mauser diagrams. Typically, these diagrams represent two-dimensional plots. The so-called Mauser space is multidimensional (n ≥ 2). The axes of this space are established by the absorbances or absorbance differences of n wavelengths. A reaction system that consists only of one linearly independent reaction step (s = 1) leads to a straight line in Mauser space. This line is obtained independent of the reaction order of the system. A one-dimensional coordinate axis can be established which is orientated in the direction of the straight line lying in the Mauser space (n > s). The distances of the individual measured points with regard to the origin of the (one-dimensional) coordinate system can be evaluated kinetically. The procedure is demonstrated using reactions of first and second order (s = 1; n = 4 and 6). A reaction system described by two linearly independent steps (s = 2) leads to a curve in the Mauser space which lies on a plane. A two-dimensional coordinate system can be introduced which lies in this plane. The coordinates of the Mauser curve with regard to the established (two-dimensional) coordinate system can be evaluated kinetically. The procedure is shown by evaluating reactions of first and second order (s = 2; n = 3 and 4). The advantages of geometric analysis of Mauser space are discussed.

Original languageEnglish
Pages (from-to)993-999
Number of pages7
JournalPhysical Chemistry Chemical Physics
Volume3
Issue number6
DOIs
StatePublished - 2001

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