Anal. Chem. 1966* 58,264 R-279 R (275) Trautwein, A. X.; Bill, E.; Blaes, R.; Lauer, S.; Winkler, H.; Kostlkas, A. J . Chem. Phys. 1985,8 2 , 3584-3593. (276) Ulirich, H.; Hesse, J. J. Magn. M a p . Mater. 1984, 45, 315-327. (277) Van Burck, U.;Maurus, H. J.; Smirnov, G. V.; Mossbauer, R. L. J . PhyS. C 1984, 17, 2003-2010. (278) Van der Velden, J. W. A.; Stadnik, 2. M. Inorg. Chem. 1984, 2 3 , 2640-2644. (279) Van Rossum, M.; DBzsi, I.; Langouche, G.; Mishra, K. C.; Coker, A,; Das, T. P. "Hyperfine Interactions VI"; Niesen, L., Pleiter, F., de Waard, H., Eds.; J. C. Baltzer AG, Scientific Publishing Company: Basel, Switzerland, 1983; pp 475-478. (280) Van Rossum, M.; Langouche, G.; Mishra, K. C.; Das, T. P. Phys. Rev. B: Condens. Matter 1983,2 8 , 6086-6088. (281) Van Wonterghem, J.; Mmup, S.; Koch, C. J. W. J. Mater. Sci. Lett. 1984, 3, 1080-1082. (282) Vapirev, E. I.; Kamenov, P. S.; Balabanski, D. L.; Ormandjiev, S. I.; Yanakiev, K. J. Phys. (Les Ulis, F r . ) lg83, 44, 675-677. (283) VBrtes, A.; Burger, K.; Takacs, L.; Horvath, I.J. Radioanal. Nucl. Chem. 1984,8 6 , 195-204. (284) Vieira, V. W. A.; Jensen, H. G.; Knudsen, J. M.; Olsen, M. Phys. Scr. 1984,3 0 , 284-288. (285) Vochten, R.; De Grave, E.; Peismaekers, J. Am. Mlneral. 1984, 69, 967-978. (288) Wagner, H. G.; Ackermann, M.; Gonser, U. J. Non-Cryst. SolMs 1984, 847-852. (287) Wagner, H. G.; Ghafari, M.; Klein, H. P.; Gonser, U. J. Non-Cryst. Solids 1984, 6 1 / 6 2 , 427-432. (288) Wallingford, E.; Bordeleau, C. Rev. Sci. Instrum. 1985, 5 6 , 1253- 1256.
(289) Wei, H. H.; Jean, Y. C. Chem. Phys. Lett. 1984, 106, 523-526. (290) Weschenfelder, D.; Schmidt, H.; Oestreich, V.; Czjzek, G. "Hperfine Interactions VI"; Nlesen, L., Pleiter, F., de Waard, H., Eds.; J. C. Baltzer AG, Sclentific Publishing Company: Basel, Switzerland, 1983; pp 1033- 1037. (291) Weyer, G.; Pedersen, F. T.; Grann, H. Nucl. Instrum, Methods Phys. Res. 1985,8718, 103-8. (292) Whittle, G. L.;Calka, A.; Radlinski, A. P.; Luther-Davies, B. J. Magn. Magn. Mater. 1985,5 0 , 278-286. (293) Wlchert, T. "Hyperflne Interactions VI"; Niesen, L., Pleiter, F., de Waard, H., Eds.; J. C. Baltzer AG, Scientific Publishing Company: Basei, Switzerland, 1983; pp 335-355. (294) Willgeroth, S.; Ulirich, H.; Hesse, J. J. Phys. F 1984, 14, 387-397. (295) Winkler, W.; Mehner, H. J. Radioanal. Nucl. Chem. 1984, 8 2 , 15 1-168. (296) Wittmann, F.; Jex, H. Solid State Commun, 1985,5 3 , 407-409. (297) Wu, M. F.; Schroyen, D.; Pattyn, H.; Langouche, G. Nucl. Instrum. Methods Phys. Res. 1983,218, 652-657. (298) Yamada, Y. "Dynamical Properties of Solids, Volume 5: Mossbauer Effect, Structural Phase Transitions"; Horton, G. K., Maradudln, A. A,, Eds.; North-Hoiiand Publishing Co.: Amsterdam, 1984; pp 329-466. (299) Yang, T.; Krishnan, A.; Benczer-Koller, N. Phys. Rev. B : Condens. Matter 1984,3 0 , 2438-2447. (300) Zhang, G. L.; du Marchie van Voorthuysen, E. H.; de Waard, H. Phys. Left l.a-8 -5-, I. I.I..A. , I.A.-L l .f-i l. . (3G)-'Zhang, Y. C.; Li, 2 . L.; Hu, 2. W. Kongjian Kexue Xuebao (Engl. Trans/.)1984,4 , 257-260. (302) Zolotoyabko, E. V.; Iolin, E. M.; Muromtsev, A. V. J . Phys. D 1983, 16, 697-704.
Kinetic Determinations and Some Kinetic Aspects of Analytical Chemistry Horacio A. Mottola Department of Chemistry, Oklahoma State University, Stillwater, Oklahoma 74078
Harry B. Mark, Jr.* Department of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221
The organizational structure of previous reviews (1) has been, basically, retained in the preparation of this report. The papers reviewed have been selected from those that appeared since November 1983 and were received for the authors' consideration through approximately November 15, 1985. Highlights of the First International Symposium on Kinetics in Analytical Chemistry have been covered in a previous review (1) and it is rewarding to report here the anticipation of a second international gathering in September 1986. This Second Symposium on Kinetics in Analytical Chemistry is under organization with the support of the University of Ionnina (Ionnina, Greece), the Greek Chemists Association, and the Ministry of Culture and Science of Greece. It is scheduled to take place from September 9 through September 12, 1986, in Preveza, Greece. The symposium will consist of five plenary lectures, contributed papers, and poster sections on a variety of kinetic topics of interest to analytical chemists. Although catalytic methods continue their dominance in the number of methods published, a noticeable decrease in the use of inhibition and activation of catalytic systems has been observed in the past 2 years. Worth noting also is the increased use of electrochemical techniques in general and in flow systems in particular. Differential procedures have shown an increase in the number of papers dedicated to them in the past 2 years.
BOOKS AND REVIEWS Volume 16 of a series of monographs and textbooks on Clinical and Biochemical Analysis, entitled "Chemi- and 264 R
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Bioluminescence", contains material of interest to kinetic methods, particularly its Chapters 11 (Analytical Applications of Gas Phase Chemiluminescence, by D. H. Stedman and M. E. Fraser) and 12 (Chemiluminescence Analysis in Solution, by M. L. Grayeski) (2). Kricka and Thorpe (3) reviewed chemiluminescent and bioluminescent methods in chemical analysis. Their review, after discussion of the most useful types of chemiluminescent and bioluminescent reactions, considers measurement of peak light intensity (differential kinetic measurements) or area under the light-emission-time curve (integral kinetic methods) and closes with a review of applications mainly in the bioanalytical area. The mechanism of electrochemiluminescent reactions in solution as well as their use for the determination of low concentrations of organic and inorganic species has been reviewed by Herejk and Holzbecher ( 4 ) . In an extra issue of the second volume of the publication Quimica Analitica (Spanish Society of Analytical Chemistry) have appeared the five plenary lectures presented at the First Symposium on Kinetics in Analytical Chemistry. They were: an overview presentation of the impact that kinetics has had in the development of analytical chemistry (5), a holistic view of chemical analysis with emphasis on kinetic methods (6), a discussion of kinetics and mechanism of metal chelation processes in solvent extraction (7), temperature, solvent, and salt effects in analytical applications of kinetics (8), and selectivity in catalytic methods (9). Historical accounts of the evolution of a given branch of chemistry are welcome contributions; they account for the present status of such a branch by recalling its roots and 0 1986 American Chemical Society
KINETIC ASPECTS OF ANALYTICAL CHEMISTRY
data aimed at predicting the value of the analytical signal at equilibrium, to increase the reliability of the determination, have been reviewed by Harris and Hultman (17). Reviews on differential reaction rate methods are not commonly found in the literature dedicated to kinetic determinations; an exception is a recent review hy PCra-Bendito (18) on the determination of inorganic species. Chihisov (19) has reviewed analytical applications of fast reaction kinetics, and Ezerskaya and Kiseleva discussed catalytic polarographic currents of platinum metal complexes and their analytical applications (20). Ion exchange kinetics in some selective systems has been reviewed by Liherti and Passino (21). K I N E T I C M E T H O D S FOR THE D E T E R M I N A T I O N O F CATALYSTS
appraising landmark8 in such development. A very readable gem in this line of contributions has been given hy Laidler, who reviewed the impact that chemical kinetics, especially through the outstanding contributions of Jacobus H. van't Hoff and F. Wilhelm Ostwald, had on the origins of physical chemistry (10). Analytical chemists interested in kinetics should benefit from its reading. A wealth of fundamental information on the interfacial kinetics in solution of interest to analytical chemists can be found in a publication of the Royal Society of Chemistry (22). The hook resulted from a general discussion meeting of the Faraday Division (University of Hull, April Sll, 1984) and opens with an introductory lecture on mass transfer and reactions at interfaces by P. Meares. It includes several papers of interest on interfacial kinetics in liquid-liquid distribution, transport across membranes, electrochemical kinetics, ion exchange, dissolution rates, and linear freeenergy relationships in heterogeneous catalyzed reactions. A short review of kinetic methods with emphasis on recent trends has recently been published in the French language (12). Uskakova and Dolmanova (13) have reviewed kinetic methods for the determination of nonmetallic species. Two hundred fifty seven literature citations are included, with emphasis on Russian contributions. Freiser (14) has reviewed the use of solvent extraction techniques for the study of the kinetics and mechanisms of metal chelate formation. As is usual in Accounts of Chemical Research, Freiser's review is mainly concerned with work performed in his lahoratory. In this instance, however, the situation is plainly justified hecause, as pointed out by Freiser, the approach has not attracted many users and the bulk of the contributions are derived form the studies of himself and eo-workers. In a review on analytical applications of 1,2- and 1.3cyclohexanedione bis(2-hydroxybenzoylhydrmnes),Gallego et al. (15)have included their use in kinetic methods. Raman and Sastru (16) have reviewed trace metal determinations by kinetic methods. Procedures for utilization of reaction rate
Again the determination of catalysts single8 itself out as the most prolifc area within kinetic methods of determination. It would seem that the fraction of such contributions in the total count of material reviewed in theae reviews has stabilized, with catalytic determinations accounting for more than 40% of the material reviewed in 1982, 1984, and herein. Their highest percentage occurred in 1972 when catalytic determinations accounted for 68% of the total reviewed material (5). Table I summarizes methods proposed for the determination of catalysts. Transition-metal ions continue to he the most commonly determined species, and Contributions from Japanese and Spanish sources are challenging the dominance that Russian workers have enjoyed through the years. Manganese determinations also have made a strong showing in the past 2 years, paralleling the relatively large number of papers dedicated to catalytic determinations of copper. The chemistry of transition-metal complexes with uncommon oxidation states is relevant to the mechanistic aspects of catalytic determinations. Stabilization, by complexation. of intermediate or higher oxidation states for the catalytic species may play an important role in the catalytic action as well as in the activation of catalysis. Number 2 of volume 25 (1985) of the Israel Journal for Chemistry (D. Meyerstein, guest editor) assembles papers discussing different kinetic aspects involving, for instance, metal complexes of Ni(I), Ni(III), Cu(III), Pt(IV), Ag(III), Mn(III),and Mo(IV). Kinetic considerations also of interest to analytical chemists involved with catnlytic methods are presented hy Okamoto and Hayashi (68). With focus on the amplification of substrate cycle system in enzymecatalyzed reactions, a discussion on several kinetic characteristics of hiochemical cyclic reaction systems is presented. Commonly, catalytic reactions are used for the determination of the catalyst and only seldom for reactant. Recently, however, Grases and March (69)reported the determination of technetium(VI1) by means of the oxidation of Variamine Blue by Tc(VI1) that is catalyzed by copper(I1). The concentration of Tc(VI1) amenable to determination is 0.2-2.4 tq/mL. The data are treated by either the method of tangents or a fixed-time approach; the method has been applied to the analysis of synthetic nuclear fuels. An approach to catal ic determinations by continuous addition of catalyst has een described hy Weisz e t al. (70). The time needed to reach a prechosen level change in the system is the basis for measurement. The advantage of the approach seems to reside in competitive limits of detection. A unique sample processing configuration by which to perform on-line simultaneous determinations of two catalytic species in the same sample has been presented by Lazar0 et al. (71). It uses two indicator reactions yielding fluorescent products of the eame characteristics (h,= 350 nm, X., = 430 nm). Different residence times in a two-channel flow injector system provide temporal separation of the signals corresponding to the two catalyzed reactions. The configuration is used to determine copper(I1) and mercury(I1) using 2,2'dipyridyl ketone hydrazone in basic medium for mercury and dipyridyl ketone phenylhydrazone (with H2,02.HCI) for copper. The flow injection system was operated in an intermittent stopped flow fashion. Kinetic determinations based on estimating reaction rates from temperature-time plots, and from induction times recedii heat evolution, in nonaqueous catalytic systems have een recently considered (72). Alekseeva et al. (73)investigated the effect of perchloric
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KINETIC ASPECTS OF ANALYTICAL CHEMISTRY
Table I. Determination of Different Catalytic Species by Kinetic Methods Based on Primary Catalytic Effects. element
indicator reaction
comments
ref
cadmium complexation of M(I1) by a$,Y,B-tetra(p-sulfonatopheny1)porphine
22
cobalt
23
copper
gold
iodine
iron
lead
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fixed-time procedure (absorbance change after 20 or 30 min reaction); photometric monitoring, a t 413 nm, of ligand disappearance; ionic strength kept at 0.01 (NaNO,) to prevent ligand dimerization; cadmium determined down to M; interfering lead separated-by coprecipitation with manganese(1V) oxide in presence of sulfate4,5-dihydroxy-1,3-benzene- sample processed by a flow injection technique; absorptiometric monitoring of color formation at 440 nm; temperature, 40 “ C ; peak height linear with cobalt concentration in sulfonic acid (Tiron) the range of 5-200 pg/mL; processing rate, about 7 samples/h HzOz protocatechic acid + HzOz flow injection system affording a limit of detection of 0.2 ppb and 50 determinations/h with a relative standard deviation of about 1.5%; good selectivity [only Ni(II), Mn(II), and Fe(II1) interfere if present in 50-, 50-, and 100-fold excess, respectively] aerial oxidation of sulfite selective determination with thermometric monitoring in the 5-30 ng/mL range; initial rate (method of tangents) used for preparation of calibration graphs; optimum pH 9 direct blue 6B (C.I. 24410) application to cobalt determination in zinc and cadmium selenides a t pH 10.8, using Titron as activator; sample pretreatment by ion exchange separation needed + HqOz coloration of potassium fixed-time determination; color developed for 1 h, in the dark, at 40 O C and pH 12; trithiocarbonate absorbance measured at 395 nm against reagent blank; approximate limit of detection (from calibration curve), 0.1 ng/mL under similar experimental conditions manganese(I1) accelerates the color development and manganese can be determined a t ng/mL levels; interference by Bi(III), Cu(II), iron(I1 and III), and “1) is eliminated by masking with citrate and cyanide aerial oxidation of ascorbic reaction rate monitored thermometrically; copper determined in the 0.1-2 pg/mL range; few acid interferences application: determination of copper in nickel-base alloys reduction of dithiophosphinate complexes of iron(II1) oxidative coupling of N,N- three different procedures presented; limit of detection,
