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
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.