Anal. Chem. 1994,66, 131R-162R
Kinetic Determinations and Some Kinetic Aspects of Analytical Chemistry Horacio A. Mottola’ Department of Chemistry, Oklahoma State University, Stillwater, Oklahoma 74078-0447
Dolores P6rez-Bendito Department of Analytical Chemistry, University of Cbrdoba, 1407 1 Cbrdoba, Spain Review Contents Books and Reviews Kinetic Methods for Determination of Catalysts Kinetic Methods Based on Activation or Inhibition of Catalysis Titrimetric Methods with Catalytic End-Point Indication Kinetics and Mechanisms of Some Catalyzed Reactions of Analytical Interest Kinetic Determinations Based on Electrode Reactions and Processes and Associated Kinetic Aspects Applications of Luminescence and Associated Kinetic Aspects Single-Reactant Determination by Kinetic Methods Based on Uncatalyzed Reactions Differential Rate Methods Miscellaneous Kinetic Aspects of Analytical Chemistry Kinetics in Some Separation and Ion-Exchange Processes Computation and Modeling Instrumentation General Miscellanea
131R 137R 141R 142R 143R 145R 146R 147R 150R 151R 151R 152R 154R 155R
Basically, this review retains the organizational structure of the previous one in this series ( I ) . The papers reviewed have been selected from those that appeared since November 1991 and that were available for the authors’ consideration through approximately November 1, 1993. The Fourth International Symposium on Kinetics in Analytical Chemistry took place in Erlangen (Germany), near Nuremberg, with the participation of 125 scientists from 20 different countries. The program of the meeting comprised 30 oral presentations and 55 posters; some of these have appeared in a special issue of The AnaZyst (London),including an account of how kinetics has maintained its vitality in analytical chemistry and how the field has evolved from the First to the Fourth International Symposium (2). It is of interest to note that the general trends disclosed in such an overview can be found in this review. The Fifth International Symposium of this series is scheduled to take place at Lomonosov Moscow University, Moscow, Russia, in 1995.
BOOKS AND REVIEWS A review on kinetic determinations of reactants utilizing uncatalyzed reactions (3) is justified by the following: (1) recent advances in instrumentation and data manipulation that provide competitive alternatives to nonkinetic-based methods and (2) the scarcity of reviews on the topic. A brief 0003-2700/94/0366-0131$14.00/0 0 1994 American Chemical Society
Horacio A. Mottola is Professor and Head of the Chemistry Department, Oklahoma State University. He was born in Buenos Aires, Argentina, and received his undergraduate and graduate education at the University of Buenos Aires. He earned Licenciate and Doctoral degrees from the University of Buenos Aires and did predoctoral work with Professor Ernest B. Sandell at the University of Minnesota (Minneapolis). He spent 2 years at the University of Arizona (Tucson) as a postdoctoral research associate in Professor Henry Freiser’s research group. After teaching for 2 years at the University of the Pacific (Stockton, CA), he joined OSU in the fall of 1967. His research interests include studies on the role of kinetics in analytical chemistry (including reaction rate methods), chemical immobilization of enzymes and chelating agents for use in reactors in continuous-flow systems, chemically modified electrodes for sensing in flow systems, analytical separations, and photochromism of metal chelates. He is the author of a monographon “Kinetic Aspects of Analytical chemistry”. Dolores P6rez-BendHo is Professor and Head of the Analytical Chemistry Department of the University of Cbdoba, Spain. She was awarded a PhD. degree in chemistry from the University of Seville (Spain) in 1968. After 7 yearsas Assistant Professor at that university, she joined the Faculty of Sciences of the University of C&doba, where she has been full professor at the Analytical Chemistry Department since 1980. Professor P6rez-Bendito’s research interests include trace analysis, molecular spectroscopy, kinetic methods of analysis with special emphasis on differential reaction-rate methods, stoppedflow methodology, automated kinetic analysis, chemometrics, chemiluminescence spectroscopy, immunoassays and micellar catalysis. She has published extensively on these topics and is the coauthor of several textbooks and a monograph on Kinetic Methods in Analytical Chemistry, which has been translated to Russian. She is a member of the Editorial Board of Anal’ica Chimica Acta.
and selected account of chemi- and bioluminescencetechniques in clinical chemistry covers both direct determinations and determinations based on coupled enzymatic reactions ( 4 ) . Practical examples focus on fertility tests and chemosensitivity, both topics of contemporary interest. A short account of Robert Boyle’s contributions to early investigations of luminescence is of academic interest in consideration of the transient nature of the luminescence phenomenon (5). The application of luminescence techniques in general, and fluorescence and chemiluminescence in particular, in biochemical analysis is covered in a recent book ( 6 ) . Spectrofluorometry with time selection has been included in a review of new approaches in luminescence determinations by Romanovskaya (7). Analytical Chemktry, Vol. 66,No. 12,June 15, 1994 131R
Table 1. Determination of Dlfferent Catalytic Species by Kinetic Methods Based on Prlmary Effects
species
indicator reaction
+ K104
antimony
Neutral Red
chromium
azomethine (salicylal-H-acid + H202
dynamic range or detection limit, ng/mL 0-8
photodecolorization of Methyl Red photooxidation of rivanol
50 1-200
cerium
2- [8-hydroxy-5-sulfo-7-quinolyl)azo]- 0-600 1,8-dihydroxy-3,6-naphthalene-3,6disulfonic acid decomposition
cobalt
Cr(V1)
+ I-
24
phenylfluorone + H202
0-0.8
aminobenzenesulfonic acid + H202 gallic acid + 0 2 sulfite + 0
0-0.8
Alizarin Red Alizarin tiron
2
+ H202
+ H202
0-4
+ H202
3,4-dihydroxybenzoic acid + H202 copper
diphenylcarbazide
+0 2
+ Fe3+
photometric monitoring at 440 nm for 2-3 min
0.2-2.0
flow injection spectrometry; RSD
