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

Citation
J. Polster et H. Dithmar, Spectroscopic-kinetic analysis of first and second order reactions on the basis of multidimensional absorbance (A) diagrams, PHYS CHEM P, 3(6), 2001, pp. 993-999
Citations number
41
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
ISSN journal
14639076 → ACNP
Volume
3
Issue
6
Year of publication
2001
Pages
993 - 999
Database
ISI
SICI code
1463-9076(2001)3:6<993:SAOFAS>2.0.ZU;2-P
Abstract
The absorbance (A), absorbance difference (AD) and absorbance difference qu otient (ADQ) diagrams are called Mauser diagrams. Typically, these diagrams represent two-dimensional plots. The so-called Mauser space is multidimens ional (n greater than or equal to2). 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) l eads 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 ly ing in the Mauser space (n >s). The distances of the individual measured po ints with regard to the origin of the (one-dimensional) coordinate system c an 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 w hich 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 kin etically. The procedure is shown by evaluating reactions of first and secon d order (s=2; n=3 and 4). The advantages of geometric analysis of Mauser sp ace are discussed.