Shishkova. L. G . , Dodova. L.. ibid., 24, 1369 (1971) Shmukler. H. W.. J Chromatogr S c i . 10, 137 (19721 -, Shrimai, R. L.. Taianta. 18, 1235 (1971). Singhal. R . P.. Arch. Biochem. Biophys.. 152,800 (1972). Singhal. R . P., Cohn, W E., Anal. Biochem., 45,585 (1972). Singhal, R. P., Cohn. W. E.. Biochim. Biophys. Acta. 262,565 (1972). Sisson. D. H., Mode, V. A,. Campbell, D . O., J . Chromatogr.. 66, 129 (1972) Sitaram. R . , Khopkar, S. M., Chromatographia,,5, 408 (1972) /bid.. 6, 198 (1973). Sixta. V., Suicek, Z., Collect. Czech. Chem. Commun., 37,88,2386 (1972). van Siageren, R., den Boef. G.. van der Linden, W. E.. Talanta, 20, 739 (1973). Smith, D . J., J. Ass. Offic. Anal. Chem., 55, 596 (1972). Smith, J. D.. Anal. Chim. Acta, 57, 371 (1971). Smits, R . . van den Winkel, P., Massart. D . L., Juillard. J.. Morel, J. P., Anai. Chem., 45,339 (1973). Smuts, T. W., Pretorius. V . , ibid., 44, 121 (1972). Snyder, L. R., J . Chromatogr. Sci., 10, 200, 369 (1972). Snyder, R . V.. Angeiici. R. J., Meck, R. B . , J . Amer. Chem. Soc.. 94, 2660 (1972). (493) Stahi, K . W . , Schlimme, E., Bojanowski. D., J . Chromafogr., 83,395 (1973). (494) Starobinets, G. L., Zakhartseva. E. P., Ref. Zh. Khim., 19 GD, No. 10G82 (1971); Anal Abstr., 22,2264 (1972). Steinbach, S., Hering. R., Z. Chem., 11, 350 (1971); ibid., 12,33 (1972). Steinnes, E., Radfochim. Acta, 1 7 , 119 (1972). Stepanov, V. M., Katrukha. S. P., Baratova, L. A . . Belyanova, L. P., Korghenko, V. P., Anal. Biochem., 43,209 (1971). Stevenson, R. L., Burtis, C. A,. Clin. Chem.. 17,774 (1971). Stevenson, R. L., Freiser, H . , Chem. Anal. (Warsaw). 17,675 (1972). Stoehrer, G . , Corbin, E., Brown, G. B.. Anal. Biochem.. 53, 288 (1973). Streiow. F. W. E.. Boshoff, M . P.. Anal. Chim. Acta. 62,351 (1972). Streiow, F. W. E.. Gricius, A. J., Anal. Chem.. 44, 1898 (1972). Strelow. F. W. E., Sondorp. H., Talanta. 19, 1113 (1972). Strelow, F. W. E . , Toerien, F. von S., Weinert. C. H. S. W., Anai. Chim. Acta. 50,399 (1970) Streiow, F W E , Victor, A H., f b l d , 59, 389 (1972) I
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Strelow. F. W. E., Victor, A. H . , Taianta. 19,1019 (1972). Strelow, F. W. E., Weinert, C. H. S. W., Eloff, C.. Anal. Chem.. 44,2352 (1972). Strubert, W., Chromatographia, 6, 51 (1973). Sulcek, 2 . . Sixta, V., Collect. Czech. Cheni. Commun.. 37, 1993 (1972) Sykora, V.. Dubsky, F.. ibid., p 1504. Szczepaniak, W., Chem. Anai. (Warsaw), 16,853 (1971). Tabor. H.. Tabor, C. W., Irreverre, F., Anai. Biochem., 55,457 (1973) Tackett, S. L.. et a/. Anal. Lett., 6, 355 (1973). Takahashi, T., Imamura. T.. Fujimoto. M.. Mikrochim. Acta, 1973,69. Takahashi, Y.. Agr. Biol. Chem., 36, 2575 (1972). Takata. Y., Muto. G.. Anai. Chem.. 45, 1864 (1973). Talasek, V., Eliasek. J., Collect. Czech. Chem. Commun., 37, 2521 (1972). Talasek, V.. Mostecky, J.. Vosta, J . , Eliasek, J., Matejka, Z., Chem. Prum., 22, 69 (1972):Anal. Abstr.. 23,2333 (1972). Tanaka. H., Yamamoto. T., Bunseki Kagaku, 20,784 (1971). Tandon, S. N., Gill, J. S., Talanta 20, 585 (1973). Tanos, F., Tavkozlesi Kut. Kozlem., 18, 109 (1973); Chem. Abstr., 79, 61223c (1973). Tartarini, S., J. Pharm. Sci.. 61, 960 (1972). Tartaru, S., David, B., Filip, G., v. Roum. Chim.. 16,625 (1971). Tatsumoto. M . , Geochim. Cosmochfm. Acta. 37, 1079 (1973). Thompson, G. H., Radiochem. Radioanal. Lett., 10,223 (1972) Todorova, N.. Dodova, L., C. R. Acad. BUig. SCi., 25, 1387 (1972). Tomasz. J., J. Chromatogr., 84, 208 (1973). Tominaga, M., Nakamura. T., Ohashi, S., J . Inorg. Nucl. Chem., 34, 1409 (1972) Torok. G . , Schelenz, R . . Fischer, E., Diehl. J. F . , Fresenius' Z. Anal. Chem., 263, 110 (1973). Tschesche, H., Frank, C.. Ebert, H.. J. Chromatogr.. 85,35 (1973). Tsitovich, I . K., Zh. Anal. Khim., 26, 1908 (1971). Ibid.. 27, 1188 (1972). Tsitovich, I . K . , Sernenova, E. I., ibid., p 763. Tuerler, K., Kaeser, H . , Clin. Chfm. Acta, 32,41 (1971). Ukrainskaya, L. M.. Kuznetsov-Fetisov. L. I . , Ret. Zh. Khim.. 19GD, No. 10G81 (1971); Anal. Abstr., 22,2230 (1972).
Vandekerhove, P.. Henderickx. H. K., J. Chromatogr., 82, 379 (1973). Vanheertum, R.. Chromatographia, 6, 217. 390 (1973). Vesilek, J . , Davidek, J.. Fleischwirtschaft. 52,364 (1972). Verdizade, A. A,, Mekhtiev. M. M.. Ret. Zh. Khim., 19GD, No. 10G79 (1971); Anal. Abstr.. 22,2156 (1972). Vernon. F.. Eccles. H.. Anal. Chim. Acta. 63,403 (1973). Vinter. I . K.. Boichinova, E. S., Denisova, N. E., Chetverina, R . E., Zh. Prikl. Khim., 46, 1117, 1471 (1973). Vitek, V., Vitek. K., J. Chromatogr., 60, 381 (1971). Vivilecchia, R., Thiebaud, M . , Frei, R. W., J. Chromatogr. Sci., 10,411 (1972). Vysotskaya, E. S., Mushinskaya. S. K.. Shostenko. Yu. V.. Zh. Fiz. Khim., 47, 1797 (1973). Wald, M., Soyka.'W., Kaysser. E.. Talanta, 20,405 (1973) Warburton, J. A,, Young, L. G.. Anai. Chem., 44,2043 (1972). Wilks, A. D., Pietrzyk, D . J.. ibid., p 676. Williams, A. I . , Analyst (London), 98, 233 (1973). van den Winkei, P.. de Corte, F., Hoste, J.,Anal. Chim. Acta, 56,241 (1971). van den Winkel, P., de Corte. F., Hoste. J., J . Radioanai Chem., 10, 139 (1972). Wodkiewicz, L.. Dybczynski. R., J. Chromatogr., 68,131 (1972). Wolf, F . , Z. Chem. (Leipzig), 12, 184 (1972). Wolf, F.. Schallert, U.. ibid., p 266. Wu, C.. Siggia. S.. Anal. Chem.. 44, 1499 (1972). Yamabe, T., J . Chromatogr., 83, 59 (1973). Yasuda. K., !bid., 72, 413 (1972); ibid., 74, 142 (1972). Yasuienis. R . Yu., Luyanas. V. Yu.. Kekite, V. P., Radiokhimfya, 14, 650 (1972) Yoshida, H., Yonezawa. C.. Bunseki Kagaku, 22,929 (1973). Young, J. L., Yamarnoto, M.. J ChromatOgr., 78,221, 349 (1973). Zagorchev, B . , Chem. Anal. (Warsaw), 17, 973 (1972). Zagorchev. B . , Todorova, N.. Balushev, E.. C. R. Acad. Bulg. Sci., 24, 1063 (1971). Zamorani. A . , Russo. C.. Campisi, S., lnd. Agr., 10, 463 (1972): Anal. Abstr.. 25, 1799 (1973). Zlatkis, A., Bruening, W., Bayer, E., Anal. Chim. Acta, 56,399 (1971). Zukreigelova. M . . Sulcak, Z., Povondra. P., Collect. Czech. Chem. Commun.. 37, 68. 560 (1972). Zweidinger, R . A,, Barnett, L.. Pitt. C. G., Anal. Chem., 45, 1563 (1973).
Kinetic Aspects of Analytical Chemistry Ronald A. Greinke Union Carbide Corporation, Carbon Products Division, Parma Technical Center, 12900 Snow Road, Parma, Ohio 44 130
Harry B. Mark, Jr. Department of Chemistry, University of Cincinnati, Cincinnati, Ohio 45227
This review surveys the literature from December 1971 through November 1973. A few papers published prior to December 1971 have also been included where t h e material discussed is especially relevant for introduction to some of t h e subjects or recent papers reviewed here. Papers pertaining to mechanistic and kinetic studies of reactions were not included unless the results of the study were applied to kinetic analysis. T h e format is similar to the 1972 Annual Review. I t is interesting to note that, although the concept of
using analytical methods based on kinetics or reaction rates goes back 50 or more years to t h e early literature in biochemistry, radiochemistry and gas-phase diffusion (125), and although there has been extensive use of enzymatic and other catalytic type reactions (37,178) in analysis, especially in clinical applications .(57), it was not until the 1950's in the work of Lee and Kolthoff (100) t h a t the broad inherent potentialities and advantages in many chemical situations of kinetic-based analytical methods with respect to conventional equilibrium methods were
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pointed out to chemists. This work stimulated considerable research in the development of general rate-based methods and theory and also resulted in a number of special applications being published during the next 15 years. However, it is somewhat surprising in view of the potentialities of kinetic-based techniques and the large amount of fundamental method development published, that there has not, except for continued massive use in clinical assays, been significant application of these techniques to routine and/or practical analytical problems. On reflection, one reason for this lack of application is relatively obvious. Almost all commercial instrumentation for chemical measurement is designed for equilibrium or steady state measurement and does not perform satisfactorily when used for quantitative time-dependent measurement. Thus, the analytical chemists did not, in general, consider kinetic-based techniques, as both the modification of existing instrumentation was usually impractical from a point of view of cost and impairing the quality of the normal mode of operation of the instrument, and the time and knowledge required to design and build a special instrument was lacking. However, there have been tremendous advances in the past few years in instrument technology, electronic circuitry, and measurement techniques. Furthermore, the costs of integrated circuits and minicomputers have dropped to the point where it is no longer a major investment to design instruments and methods around these devices. Thus, the means of attaining the precision and accuracy necessary to make dynamic reaction systems apdicable to both routine and special analytical problems is available and the number of applications of kinetic methods. as well as further instrument and development, has increased significantly during this past two-year period. Again, as was noted in the previous review two years ago, the most significant advances in kinetic-based analysis are instrumental in nature. One of the major directions in this area of instrument design is in the development of accurate and reliable systems for the measurement of f a s t reaction rates (reactions which have half-lives on the order of milliseconds or less). T h e on-line use of the minicomputer which not only handles the data acquisition and reduction in real-time but also controls and automates the experimental operations has been developed to a very refined state. Furthermore, researchers are also using the computer to analyze the incoming d a t a during the course of an actual experiment and to then adjust automatically, experimental parameters to optimize the specific measurement on that sample. Significant progress in the development of rapid scanning spectrophotometers over the past two years has been a n important development which has permitted one to obtain on a routine basis the complete time-resolved spectra of fairly fast reactions (146). Computer analysis of the total time-resolved spectra of a multicomponent mixture of species reacting simultaneously with a very small differential of rate constants has been shown to be necessary to accurately determine the concentrations of each of the individual components in many situations. It is felt that as these method and instrumental developments are perfected, kinetic-based technique will become as common-place in chemistry as the! now are in clinical assay. This survey classifies the recent literature according to general kinetic papers, catalyzed reaction rate methods, uncatalyzed reaction rate methods, differential reaction rate methods (for mixtures), and computer and instrumental advances.
GENERAL KINETIC PAPERS Several general kinetic papers were published during the period. Mark (112) outlines the guidelines for carrying out research to develop kinetic-based analytical procedures. T h e recommended areas to consider during method development are the mathematical basis of the method, the reaction mechanism, trace impurities, and instrumental factors. A review of reaction rate methods in analysis was prepared by Mark (113).The review included a summary of the kinetic methods, recent improvements in instrumentation, computer developments, and many applications. Malmstadt, Delaney, and Cordos (106) presented 414R
a review of automated analytical systems for determining a variety of species.
CATALYZED REACTION RATE METHODS As in past years, the application of catalyzed reactions for the determination of a single species in solution is by far the most popular area of kinetic analysis. The main advantages t h a t catalyzed reaction rate methods offer to analysts are the highly sensitive and, in some cases, specific analyses. A review of the use of activators for increasing sensitivity in homogeneous catalytic reaction rate methods was described by Bontchev (12). Several different mechanisms of activation were discussed and used as illustrations of the principles for choice of a n appropriate activator. Gary and Schwing (55) presented a review of the catalytic determination of some elements. A variety of inorganic cations were assayed by catalyzed reaction rate methods. Tabata, Funahashi, and Tanaka (156) reported that ammonia can catalyze the ligand substitution reaction of mercury(I1)-o-cresophthalein complexone complex with trans-1,2-diamino-cyclohexaneN,N,N’,N’-tetraacetic acid. Microgram amounts of a m monia were determined in underground water, rainwater, and an extract of dead pine leaves. A kinetic method for arsenic(III), described by Markova and Maksimenko (116),was based on the enhancing effect of arsenic(II1) on the reduction of silver ions by iron(I1). Dubovenko and Khotinets (46) determined bismuth(II1) by its catalytic effect on the chemiluminescence reaction of lucigenin with hydrogen peroxide. A number of catalytic methods for cobalt have been reported. Costache and coworkers (28-32) have shown t h a t cobalt can catalyze the reaction of hydrogen peroxide with 4-(4-nitrophenylazo)resprcinol (31). tropaeolin ,(32), Ponceau Red (30), 5-(4-[8-arnino-l-hydroxy-7-(4-nitrophenylazo) -3,6-disulfo-2-naphthylazo]phenylazo) -2-hydroxybenzoic acid (29), and direct Brilliant Orange (28). Similarly, Reznik, Chuiko, and Vershinin (140, 167) determined cobalt using the hydrogen peroxide-Alizarin red S reaction. Batley (7) used the oxidation reaction of hydrogen peroxide with Alizarin red S, catalyzed by cobalt, for the assay pg/ml of 6oCo in reactor cooling water circuits. Inof terfering impurities were removed by ion-exchange separation. The catalysis by cobalt of the hydrogen peroxide oxidation of bromopyrogallol red and 4-(4-nitrophenylazo)catechol was studied by Blazys, Paeda, and Jurevicius (11).As low as 0.1 ng of cobalt per ml was determined. Copper was catalytically determined by several procedures. Jankiewicz and Soloniewicz (7930) developed methods for copper based on its enhancing effect on the iron(II1)-thiourea (80) and the iron(III)-l-methyl-2-thiourea (79) reactions. Agents that reduce or coordinate with iron(III), such as Hg(I1) or Au(III), interfere. The copper(11) catalyzed oxidation of quinol by HzOz was the basis for the procedure developed by Orlova (127). Copper was assayed in blood serum by this method. Orav, Kokk, and Suit (126) devised a procedure for the determination of copper which catalyzes the rate of reaction between indigo carmine and HzOz. The sensitivity is 0.18 ng/ml. Two methods were presented for the determination of chromium. Dolmanova et al. (44) based their method on the catalytic effect of chromium(II1) on the oxidation of o-dianisidine by hydrogen peroxide. Kreingol’d e t al. (97) used the chromium catalyzed reaction between l-hydroxy3-methyl-1-phenylurea and potassium bromate for the assay of this cation in high purity salts (of nickel, cobalt, cesium, aluminum, and gallium) and light alloys (of aluminum and magnesium). Zhelyazkova, Bonchev, and Aleksiev (179) described a kinetic method for gold(II1) in iron ores based on its effect on the oxidation of Hg(I1) by Ce(1V). Ir, Pt, Pd, Ru, and Ga interfere. Gold was also determined by Jankiewicz and Soloniewicz (78), who employed the iron(II1) oxidation of thiourea reaction. Tartrate, iodide, fluoride, phosphate, copper(II), and mercury(I1) interfere. Tikhonova, Yatsimirskii, and Svarkovskaya (161) reported that iridium, in concentrations as low as 10 ng/ml, can catalyze the oxidation of diphenylamine with cerium(1V) sulfate. Yatsimirskii et al. (177) devised a procedure for determining iridium, which catalyzes the reaction
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Ronald A. Greinke, Head of Analytical Research and Development of the Carbon Products Division, Parma Technical Center, Union Carbide Corp., received his B.S. degree from the University of Illinois in 1963 and his Ph.D. in analytical chemistry from the University of Michigan in 1967. His interests include kinetic methods of analysis, gas chromatography, and thermal analysis. He has published papers in kinetic analysis, and is a coauthor of the book "Kinetics in Analytical Chemistry." Dr. Greinke is past chairman of the Cleveland Analytical Topics Group. ACS.
Harry 6. Mark, Jr., Professor of Chemistry and Chairman of the Analytical Chemistry Division, Department of Chemistry, University of Cincinnati, received his B.A. degree from the University of Virginia in 1956 and his Ph.D. degree from Duke University in 1960. He was a postdoctoral research associate at the University of North Carolina (with C. N. Reilley) from 1960 to 1962 and at the California Institute of Technology (with F. C. Anson) from 1962 to 1963. He was a member of the staff of the Department of Chemistry at the University of Michigan from 1963 to 1970, Visiting Professor of Chsmistry at the Universite Libre de Bruxelles, 1970, and joined the staff at the University of Cincinnati in 1970. His research interests are in electrochemistry, surface chemistry, kinetic methods of analysis, environmental analytical problems, and instrumentation. In addition to research papers, he is the coauthor of the books "Kinetics in Analytical Chemistry," "Activated Carbon," "Surface Chemistry and Adsorption from Solution," and "Simplified Circuit Analysis; Digital-Analog Logic." He is also a coeditor of the monograph series "Computers in Chemistry and Instrumentation" and a member of the Editorial Board of Analyfical Letters. Chemical Instrumentation. and Taianta. -
of manganese(II1) with mercury(1). They (177) also deduction of AgBr in a photographic plate by p-methylamiscribed a procedure for ruthenium, which enhances the nophenol-quinol developer. reaction of manganese(II1) with p-anisidine. This reaction After extracting ruthenium from a zone on paper chrowith p-anisidine is not catalyzed by any platinum group matograms, Varshal et al. (166) quantitatively determined metals other t h a n ruthenium. ruthenium bv measuring its effect on the rate of formation A kinetic method for lead was proposed by Jasinskiene of t h e benzidine oxidation products. T h e method was used and Kalesnikaite (81). Lead(I1) catalyzes the reaction befor studies on the complex formation between ruthenium tween stilbazo and K2S208. and organic compounds in natural water. T h e rate of oxidation of p-phenetidine by potassium A number of catalytic methods for vanadium were reperiodate is proportional to t h e concentration of mangaported. Welch and Allaway (174) determined as low as 5 nese. Using this reaction, Dolmanova, Poddubienko, and ng of vanadium in biological materials after separation Peshkova (43) determined as low as 0.001 ppm manganese with 8-quinolinol. Its effect on the rate of oxidation of galin nitric acid. Alekseeva and Davydova ( 2 ) determined lic acid by acid-persulfate was followed by a spectrophotomicro amounts of manganese(I1) in clays by a kinetic metric procedure. Zhelyazkova, Tsvetanova, and Yatsimmethod which involved the oxidation of o-dianisidine bv irskii (180) assayed for vanadium(V), which catalyzes the potassium periodate. oxidation of p-phenetidine by BrOs -. The method, actiSeveral papers, presented by Ke and Thibert (88-90) vated by hydroxy-7-iodoquinoline,was used for measuring describe the determination of mercury at the nanogram vanadium in vegetables. Costache a n d Sasu (27,33,34) relevel by use of the reaction between arsenic(II1) and ceriported kinetic vanadium determinations by measuring its um(IV). This a m r o a c h was a m l i e d t o t h e catalytic assay enhancement of the K B r 0 3 oxidation of Solochrome violet of mercury in 'natural w a t e r s and biological materials. RS (27),Eriochrome blue P (34), and indigo carmine (33). Milosz, Majewska, and Krzystek (118) determined mercury Several different inorganic anions, iodide and phosbased on its catalytic effect in t h e reaction of F ~ ( C N ) G ~ -phate, were assayed by catalytic reactions. Funahashi, with 4,4'-bipyridyl. A kinetic method for mercury(I1) was Tabata, and Tanaka (53) described the determination of proposed by Dubovenko and Bogoslovskaya (45). Mercury iodide by its catalytic effect on the substitution reaction of mercury(II)-4-(2-pyridylazo) resorcinol complex with catalyzes t h e chemiluminescence reaction between luminol DCTA (1,2-diaminocyclohexane-N,N,N',N'-tetraacetic and hydrogen peroxide. acid). T h e method was applied to rainwater. Weisz and Klyachko and Petukhova (94) reported a kinetic methZudwig (172,173) designed a continuous catalytic method od for nanogram amounts of molybdenum in t a p water. of analysis using a flow-through cell. A steady slate conMolybdenum catalyzes the oxidation of quinol with iodcentration of product was measured spectrophotometricalate. ly to determine the catalytically active substances. This Alekseeva (3,4) developed several methods for osmium. system was applied to the determination of parts per milOne method ( 4 ) based on the amperometric rate measurement of the reaction between KI a n d Hz02, could detect lion of iodide, mercury(II), manganese. lead, osmium, silver, and l-cystine. Kriss et d . (99) reported a catalytic osmium as low as 0.01 ng/ml. The other method ( 3 ) , a p plied to the evaluation of complex products and minerals method for phosphate based on the reduction of molybfor osmium, utilized the oxidation reaction of arsenite date with tin(I1). Several investigators applied catalyzed reactions for orwith bromate. Filippov, Zyatkovskii, and Yatsimirskii ganic acids. The amino acids, glycine, DL-serine, DL-phe(51) employed the reaction of p-phenedine and bromate nylalanine, m-glutamic acid, and L-arginine inhibit the for trace osmium analysis. Philpenko and Terletskaya rate of t h e copper catalyzed oxidation of catechol violet by (134) applied the osmium-catalyzed oxidation of lucigenin hydrogen peroxide. JanjiC and MilovanoviC (77) report by hydrogen peroxide for measuring osmium. T h e error that the copper-amino acid complexes possess a much was 12% in the 20- t o 50-pg range. lower catalytic activity than free copper. Amino acid conA kinetic method for palladium was devised by Gainulcentrations of 2.0 x 10-6M to 8.0 x 10-6M were deterlina, Ivanov, and Chebotarev (54). Palladium enhances mined with coefficients of variations of 1.8 to 8.1%. Motthe reaction between Ce(1V) and Hg(1). tola and Heath (122) used the modifying effect of nitriloKalinina and Moiseeva (84) used t h e platinum(1V) cattriacetic acid on the oxidation of Malachite Green by peralyzed reaction between iron(II1) and tin(I1) chloride for iodate ion, catalyzed by manganese(II), for the determinathe assay of chloroplatinic acid. T h e authors advise t h a t tion of submicrogram amounts of nitrilotriacetic acid. platinum should first be separated from other metals of the same group, since the method is not very selective. Some organic compounds bond hydrogen ions, and some ligands chelate metal ions in a manner to lower the reducTwo methods were described for determining cobalt. Morozova, Yatsimirskii, and Egorova (121) based their tion potential of the hydrogen ion and metal ion a t a n catalytic method on the reaction of Mn(I1) and BrO- enelectrode surface, which results in a catalytic polarographhanced by rhodium(II1). The method of Pilipenko, Markoic prewave. A large number of papers were published which describe the use of the resulting catalytic current va, and Kaplan (135) used the rhodium(II1) catalyzed reA N A L Y T I C A L C H E M I S T R Y , V O L . 46. NO. 5, A P R I L 1 9 7 4
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for the sensitive and selective determinations of such ligands, metal ions, and organic compounds. Sinyakova and Milyavskii (151) presented a theoretical paper describing this catalytic phenomenon in the polarography of inorganic compounds. O’Shea and Parker (128) reported the tungsten kinetic wave produced in a hydrogen peroxide and oxalic acid medium. T h e detection limit for tungsten was 5 x 10-6M. Prior separation of the interferences, Cr(VI), Fe(III), Mo(IV), Ti(IV), and V(V), is essential. An electroanalytical study by Taylor, Davenport, and Johnson (157) resulted in a n amperometric method for antimony(II1). T h e anodic wave for bromide was enhanced by antimony. This approach was applied to the determination of antimony in the effluent from a high speed liquid chromatograph. Toropova, Vekslina, and Chovnyk (165) observed t h a t a catalytic wave, proportional to the Ti(1V) concentration, is formed at a stationary graphitedisk electrode in a n acidic solution of K B r 0 3 containing Ti(S04)z. These same authors (164) also reported t h a t a catalytic hydrogen peroxide wave at a rotating graphite electrode, was proportional in height to titanium(1V) concentration. Toropova and Averko-Antonovich (163) polarographically determined as low as 0.1 pg of cyanide per liter from the catalytic wave formed in a nickel(I1) ethylenediamine-cyanide system. Pottkamp, Umland, and Reimann (136) proposed a method for phosphorus based on the catalytic hydrogen wave produced by polarography of molybdophosphoric acid in ethanolic LiCl containing certain carboxylic acids. The cobalt catalytic prewave in the presence of thiamine in its disulfide form, and in a borate medium, was studied by Sanz Pedero and Lopez Fonseca (147). Thiamine analyses in the range of 1 x 10-6 to 10 x 10-6M were performed with a relative error no greater than 1.1%. Thiamine was also determined by Lopez Fonseca (104) by taking advantage of the catalytic wave formed in an ammoniacal medium in the presence of cobalt(I1) or cobalt(II1). Sohr and Weinhold (153) showed t h a t a catalytic current is caused by traces of nucleotides, such as adenosine, guanosine, and cytidine, in the presence of Ca(I1) at a mercury surface completely covered with tributyl phosphate. In favorable cases, 5 x 1 O - I O gram of nucleotide is detectable. T h e catalytic hydrogen wave, observed by Saxena and Chaturvedi (148), of ethylene bis( 3-mercaptopropionate) in the presence of a m moniacal cobaltous chloride, was utilized for the determination of ethylene bis(3-mercaptopropionate). Saksin and Tur’yan (143) applied the polarographic catalytic currents of complexes of titanium(1V) for the determination of the ligands, sulfosalicylic acid, pyrogallol, and catechol. Selenocysteine, formed by reduction of selenocystine a t the dropping mercury electrode in a n ammoniacal buffer, produces a pre-sodium catalytic hydrogen wave. Based on this observation, Voicu and Chlusaru (168) proposed an analytical method for selenocystine in the presence of selenocysteine. The application of catalytic reactions for the indication of the end point in titrimetric analysis has increased in the past years. Weisz and Pantel (169,170) reviewed the principles of applying catalyzed reactions for end-point indication, and presented many new examples of this approach. Weisz, Pantel, and Ludwig (171) used suitable catalytic indicator reactions for the titration of Mn(I1) with EDTA, Hg(I1) with KI, and Cu(I1) with EDTA. Abe and Matsuo (1) determined copper(I1) and manganese(I1) by a reversed titration us. EDTA. T h e oxidation of phenolphthalin by H202, catalyzed by copper(I1) or manganese(II), was the indicator reaction.
UNCATALYZED REACTION RATE METHODS Because of lower accuracy, the use of uncatalyzed reactions for the determination of a single species is not recommended if a suitable equilibrium or non-kinetic method is available. However, when the reaction, employed for the non-kinetic analysis is slow, reversible, or involves a n additional interfering consecutive reaction, an initial reaction rate kinetic method may be advantageous. Owing to the equilibrium-limited slow reaction of carboxylic acid with hydroxylamine in the presence of nickel, Connors and Munson ( 2 4 ) employed a n initial rate assay of some carboxylic acids in the 10-6 to 10-lM range. Kriss, Ru416R
*
denko, and Kurbatova (98) developed a n initial reaction rate method for orthophosphate in the presence of condensed phosphate. Burgess and Ottaway (15) determined arsenic(III), antimony(III), and ascorbic acid by reaction with bromine. T h e bromine was generated at a controlled rate by reaction of bromate with bromide. T h e time required for the bleaching of methyl orange with excess bromine was proportional to the initial concentration of the analyzed species. Crisan et al. (36) determined sodium acetate in solution by a n initial reaction rate method. Carr a n d Jordan (18) presented the mathematical kinetic theory and the method for correcting end-point errors t h a t arise when the kinetics of titration reactions are slow.
DIFFERENTIAL REACTION RATE METHODS A number of differential reaction rate methods were reported for the in situ simultaneous analysis of mixtures with closely related chemical properties. Coetzee, Balya, and Chattopadhyay (21) analyzed nitric oxide and nitrogen dioxide mixtures by reaction with iron(I1) in a sulfolane reaction medium. T h e reaction was run pseudo-first order with respect to the binary mixture. Binary and ternary mixtures of sulfonephthalein dyes were analyzed by Ellis and Mottola (48). The determinations were based on the selective oxidation of the dyes by periodate, catalyzed by manganese(I1). The reactions were run pseudo-first order with respect to the binary or ternary mixture, and the Method of Proportional Equations was employed for the calculations. Hawk et al. (63) determined as many as five organic peroxides in mixtures by reduction with several sulfides. Pseudo-first order kinetics, with respect to the peroxides, were employed. Method of Proportional Equations was used for the analyses. Two- to four-component mixtures of aminopolycarboxylic acids were kinetically analyzed by Coombs, Vasiliades, and Margerum (25). The reaction of cyanide with the nickel(I1) complexes of the acids was employed. On-line regression analysis of stopped-flow spectrophotometric data was used for calculations. Budarin, Yatsimerskii, and Khachatryan (14) determined binary mixtures of rare earth metals by measuring differences in reaction rates of the xylenol orange complexes of the rare earth metals with EDTA. Worthington and Pardue (176) resolved mixtures of La and Nd by means of the ligand-exchange reaction between Cu(I1) and the rare-earth-metal complexes of 1,2-diaminocyclohexane-N,N,N,N’-tetraacetate. They described an analog system for the automated graphical presentation of kinetic data. The technique of pulsed source-time resolved phosphorimetry was reported by Winefordner et al. (60,124) for the kinetic analysis of mixtures of halogenated biphenyls and aryl ketones. Connor e t al. (23) described a solid state signal generator coupled with electronically timed holds for the analysis of mixtures of electroactive species. The technique was applied to the analysis of Cu(I1)-Pb(II), and Tl(1)-Cd(I1) mixtures using stationary electrode voltammetry at a hanging mercury drop electrode.
INSTRUMENTAL, COMPUTER, AND OTHER KINETIC METHODS In this two-year period, extensive and critical review articles and monograph chapters covering instrumental and computer aspects of kinetic methods of analysis have been written by Malmstadt et al. (106), Crouch (37), J a n bta (76),and Mark (113). Recently, Malmstadt et al. have written a comprehensive article on developments in instrumentation designed specifically for rate determination (107). They classify rate determination techniques as derivatiue, fixed-time, and variable-time methods. T h e general principles and applicability of these methods are discussed. With respect to instrumental measurement, they then briefly describe the various classical circuits or methods of measurement in rate determination and also describe the various types of experimental output and signals obtained using the usual experimental methods (automatic titration, spectrophotometry, atomic absorption, flame emission methods, etc.). The major topic of this paper is to point out the effect and limitations imposed by noise on rate measure-
A N A L Y T I C A L CHEMISTRY, VOL. 46, NO. 5, A P R I L 1974
ment. A detailed discussion of t h e effects of noise on the various electronic and instrumental techniques employed in the Integration (fixed-time) method is given. Techniques covered are analog integration, t h e so-called modified analog integration, digital integration, and minicomputer implementation of t h e integration technique. Techniques employed in the variable-time and derivative methods are also discussed briefly. They concluded t h a t the most practical, versatile, and useful rate-determining instrumentation would be designed around the minicomputer. An example block diagram of such an instrument is given in a second paper by t h e same authors (108). The computer acts to control all experimental settings, sample and reagent handling operations, a n d all d a t a smoothing, manipulation, and conversion to output or readout. Crouch has written, in a monograph chapter, a n excellent and comprehensive description of the applications of computer circuitry and techniques to kinetic methods of analysis (37). H e has shown t h a t it is very important to consider the nature of t h e transducer signal output in choosing the type of method employed to determine the analytical results from the rate d a t a . He also discusses why the computing system used must be specified by the type of analytical and/or chemical problems t h a t are to be solved. This is a n important point t h a t is often neglected in the design of computerized instrumentation in all areas. T h e mathematical basis for the various kinetic methods of analysis are discussed in detail to point out how they affect instrument design. Parker and Pardue (130) have designed a n inexpensive miniature on-line digital computer system (MOLD) specifically for multipurpose kinetic analysis. This MOLD computer system employs stored programs suitable for a variety of kinetic methods. I t is a hybrid system which includes analog circuitry for preconditioning of t h e analog signals, a memory bank for storing data, and a digital output of t h e analytical results. Its low cost enable t h e investigator to be able to dedicate this device to a single instrument or experiment. However, it is versatile enough so that only small interface modification and simple operating program changes are all t h a t is necessary to use it with different instruments. This is a n attractive feature as it enables one to use existing instrumentation for accurate rate measurement. Similarly, for those laboratories which have the necessary commercial instruments and access to a computer but do not have expertise in interfacing the two, Iracki a n d Malmstadt (106) have designed a n improved ratemeter interface which solves this type of problem. Worthington and Pardue (176) have developed a simple analog system for the automatic graphical presentation of simultaneous kinetic analysis d a t a . T h e system uses the graphical extrapolation method (115) for the determination of the concentrations of a two-component mixture. General discussions of total computer automation of reaction-rate methods of analysis have been discussed by Malmstadt et al. (108) and Crouch (37). Scott and Burtis (150) have written a review concerning a totally automated miniature analyzer system based on a multiple-cuvet assembly mounted on a rotor system which is rotated through a stationary photometric system (5,6,17,83,160). Called t h e GeMSAEC fast analyzer, this system is designed to increase the time efficiency of clinical assays, many of which are rate-based techniques. Rotation rates as high as 5000 rpm can be used. There has been considerable research over the past two-year period on the computer automation of stopped-flow kinetic measurement instrumentation and its application to analytical problems (9,25,37,38,144). Sanderson, Bittikofer and Pardue (144) have designed a very sophisticated fully automated instrument which employs a computer-controlled sample preparation unit, a new type sampling system, and realtime d a t a collection and treatment. Bechwith and Crouch ( 9 ) have also developed a fully automated stopped-flow system featuring a vertical flow system to minimize air bubble problems, pneumatically actuated valves, and a spring-loaded stopping syringe. T h e entire operating cycle is controlled by a digital sequencing system. T h e dead time of the flow system and mixing time were on the order of 5 msec and approximately 1000 samples per hour can be analyzed. A variable-ratio stopped-flow mixing de-
vice has been developed by Harvey and Borcherdt (62). T h e problem of effective temperature as a potential source of error with certain instruments for stopped-flow measurements has been analyzed by Chattopadhyay and Coetzee (20). As mentioned in the introduction of this review, perhaps one of t h e most useful a n d significant advances in instrumentation for kinetic measurement has been the rapid development of practical designs and optical transducers for rapid scanning spectrophotometric (RSS) measurements. T h e analytical potentialities of a n instrument capable of obtaining complete spectra every msec or less are tremendous and have been discussed by a number of authors (52,114,146). Santini, Milano, and Pardue (146) have given an excellent and informative discussion of the field. They have classified RSS instruments as either dispersion or multiplex spectrometers. There are two basic approaches to multiplex scanning spectrometers: the Fourier (105) and Hadamard (41) transform methods. There are also two basic approaches t o dispersion scanning RSS instruments: the scanned spectrum systems and the recently developed array detector systems. T h e applicabilities, limitations, and potentialities of these are discussed. They also cover the recent developments and advances in analog and digital electronics, computer technology, and opto-electronic transducer systems as they pertain to RSS instrumentation. Special emphasis is placed on the potentials of the Vidicon tube (essentially a T V camera tube) (I6,39,47,86,120,139,145,162), solid state array detectors (69,72,82), the acousto-optic filter, and electronically controlled refracting elements. Santini et al. have published a preliminary report of the design of a Vidicon tube S S R instrument used for fast kinetic measurements (145). Mark et al. (114) have presented the design of a computer-controlled laser excitation source instrument employed to measure the time resolved phosphorescence decay spectra of multicomponent mixtures and/or mixed excited state emission decay systems. T h e potentialities of the use of phosphorescent decay rates in analysis and software development problems are discussed. Kanzig and coworkers have also developed a computerized phosphorescence decay system (85). An instrument for time-resolved phosphorimetry using a n electronically gated photomultiplier has been described by Hamilton and Naqui (59). Wells (175) and Mark et al. (114) have developed computer automated software and interfaces for scanned spectrum type dispersion RSS spectrophotometers. Malmstadt et al. (109) have published a n extensive discussion of the circuitry, instrumentation, a n d applications of photoncounting techniques in spectrophotometry. They discuss briefly t h e applications to luminescence decay-time measurements which could have analytical application, as has also been discussed by Mark et al. (114). They point out t h a t techniques have been developed which can measure decay-times as short as a few nanoseconds (8). Kirschner and Perone have published a new experimental design for electroanalytical measurement of the rates of flash photolysis processes (93). A compact scanning photomultiplier system for chemiluminescence reaction studies has been designed by Kava11 et al. (87). Although usually not related to analytical methods based on reaction rate determination or even kinetic measurements directly, there have been a number of papers published recently which are concerned with problems related to t h e computer data acquisition of transient signals and/or data reduction or manipulation of information related to transient signals. These papers are cited here as they could be useful to researchers working on kinetic methods and/or instrumentation for rate measurements. A monograph on the subject of the fundamentals of computers written for chemists which covers software, hardware, interfacing, and application has been recently published (22). Kelley and Horlick (92) have discussed the practical considerations for digitizing analog signals. They show t h a t quantitative measures for the quality of digital d a t a can be obtained by regenerating a n analog signal from t h e digital data. This resulting signal can then be compared to the original analog signal. T h e regeneration is carried out by simple operations on the Fourier transform of a continuous representation of the digital d a t a .
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The effects of sampling interval, sampling duration, quantization, digitization time, aperture time, and random variations of sampling interval are discussed. Hieftje ( 6 5 6 6 ) has written a n excellent two-part article on signalto-noise enhancement through instrumental techniques. Part I discusses the basics of signals, noise, and signal-tonoise (S/N)enhancement in the frequency domain. He shows how simple techniques improve signal collection but also carefully points out t h a t this is often accompanied by increases in measurement times and/or loss of resolution. Thus, selected trade-off or compromise must be made in applying these techniques. Part I1 is more relevant to those interested in kinetic measurement as it discusses techniques such as signal averaging, boxcar integration, and correlation techniques which are applicable to nonperiodic or irregular waveforms or for signals which have no synchronizing or reference wave. Horlick (20) has pointed out t h a t by utilizing t h e information available on Fourier transformation of a signal ( a spectrum in this case), several data-handling operations such as smoothing, differentiation, and resolution enhancement can be conveniently carried out with effective results in maximizing the S / N ratio of the measurement. Hayes et al. (64) have presented a very detailed analysis and evaluation of the application of digital smoothing by Fourier transformation on various types of periodic and transient signals. A comparison is made with the more common floating least squares techniques, and the advantages and pitfalls are discussed. T h e detection of spectral information using cross-correlation techniques and an analog cross-correlation readout system have been published by Horlick (70) and Horlick and Codding ( 7 1 ) , respectively. Smith (152), Reilley (138),and Minami (119),Ingle and Crouch (73-75) and Crouch (37) have published very comprehensive studies of signal-to-noise ratio theory as applied to spectrophotometric measurement and reaction rate determinations. Steinier and coworkers (154) have published some general comments on smoothing and differentiation of data by a simplified least square procedure. There are a number of papers in the area of computer based instrumentation which also are worth mention here, although they are not directly related to kinetic methods of analysis. The circuitry and measurement techniques given could have application in rate measurement problems. Hahn and Enke (58)have discussed real-time clocks for laboratory-oriented computers and have given criteria for the selection and/or construction of the optimum clock system for specific applications. Dessy and Titus ( 4 2 ) have written a very useful introductory article on computer interfacing. A systematic approach, called MIRACL, for software development on small laboratory computers has been given by Keller and coworkers ( 9 1 ) . Creason, Loyd. and Smith (35) have designed a computerized sampling technique for digital d a t a acquision of high-speed transient measurement. The common problem with digital data acquisition systems is the bandpass limitation imposed by the finite time required to digitize and store a data point. T h e sampling technique described here is capable of enhancing by a t least three orders-of-magnitude the effective bandpass of a computerized data acquisition system. Perone (131,132) has pointed out the tremendous potentialities of real-time computer control of experimental parameters and the interactive approach to computerized experimentation. Liston (101) has constructed a useful digital chemical analyzer system. Davis and Schmidlin (39) have designed a generalized interface system for 16bit computers. Computer simulation of kinetic mechanisms has also LITERATURE CITED
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become widespread in various 'areas of reaction rate studies and has been applied to analysis problems in a few cases. J a n a t a (76) has recently reviewed the. application of analog computer simulation of kinetic reaction models with emphasis on biochemical applications. A recent paper by Nakanishi (123) also covers analog simulation, Manock ( 1 1 1 ) has developed the use of the Monte Carlo method to kinetic reaction simulation in general, and Feldberg (50), Malov (110) and Prater (137) have reviewed the applications of digital simulation techniques to electrochemical kinetic studies. Peterson and Butcher (133) have examined the use of integration of complex rate equations using a n infinite series approach. There have been a variety of other instrumental a d vances directed toward kinetic measurement or techniques that would be useful to rate determination. A programmable monochromater system for accurate high speed wavelength isolation has been develo ed by Cordos and Malmstadt ( 2 6 ) . O'Haver et al. (&5) have described a wavelengtli-programmed luminescence spectrometer. T h e inexpensive nature and high speed of a digital transient recorder has been shown by Stewart (155) and Harvey et al. (61) to be a very valuable tool for analog computation in fast chemical kinetics studies. Megargle and Marshall (117) have developed a new volumetric and sampling system for use with a time-shared computer. Giannovario and Spritzer have built a low cost attachment for digital plotting with a conventional X-Y recorder ( 5 6 ) . Korte and Denton ( 9 6 ) have discussed the chemical applications of a digital time domain conversion system which can interconvert slow and fast d a t a and, hence, increase the flexibility of conventional recorders. Dawson et al. have devised a simple slopetrace reader for conventional recorders ( 4 0 ) . The use of printing calculators with the LKB Reaction Rate Analyzer has been evaluated by Brown and Smith ( 1 3 ) . Ion-selective electrodes have also been applied as transducers in kinetic studies and analytical methods. Thompson and Rechnitz have described the construction and properties of ion-selective flowthrough electrodes for use as heavy metal detectors (158) and have also applied crystal-membrane ion-selective electrodes to fast reaction (rate constants u p to l@M-lsec-l) flow systems (159). Llenado and Rechnitz (102,103) have developed ion-electrode based automatic analysis systems for enzymatic reactions. Knevel and Kehr ( 9 5 ) have employed chloride ion-selective electrodes in a study of the initial cyclization of methyl-bis(/3-chloroethy1)amine hydrochloride. Other papers on continuous flow instrumentation techniques that are of interest or use in rate measurement have also been published recently by Hollowell e t al. ( 6 8 ) , Schwartz (149), Bethune and coworkers ( I O ) , and Ostling (129). Mottola and Heath (122) have published a modification of a flow-photometric system employed for variable-time kinetic determinations and Himoe et al. (67) have described an automated flow system employing a substrate gradient technique used for enzyme assay. Rogers and Daub (141) have employed a scanning calorimetric system (142) in the determination of vapor-phase kinetic data and Evans and coworkers (49) have described a simple means of semiautomation of kinetic studies by conduction calorimetry. The problem of kinetically slow reactions in automated linear titrations has been discussed theoretically by Carr and Jordan ( 1 8 ) . The instrumentation for automatic theormometric titrations (29) and the effects of slow kinetics on the resulting titration curves have been demonstrated (18).
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Chemical Microscopy George G . Cocks Cornel/ University, Ithaca, N. Y. 74850
T h e previous review in this series ( 4 5 ) covered the twoyear period from January 1970 through December 1971. This review covers the period from January 1972 through December 1973. However, a number of references are included here which were omitted from the previous review. In this review, a n attempt has been made to include articles and books of potential interest to those who use the microscope to solve chemical problems. However, no a t tempt has been made to report publications in the fields of biochemistry, petrography, metallography, or ceramography unless these appeared to be of direct interest to chemists or chemical engineers. The chemical applications of electron microscopy are also omitted. References t o publications in the fields of optics and crystallography are included if they appear to be of direct interest to chemists or chemical engineers. The great diversity and number of publications of interest to chemical microscopists make it nearly impossible to find and review all of them. Therefore, we would appreciate comments or suggestions, particularly with regard to the omission of important published articles. I also appreciate the kindness of those who pointed out omissions from the 1970-71 review, and those who sent reprints of papers for inclusion in this review. In preparing this review, many references to the literature were first found in bibliographic sections of several journals, notably Microscopica Acta and Mikroskopie. The Microscope too has started a bibliography in the form of perforated pages, printed on one side only, which can be easily converted into a personal bibliography.
BOOKS OF GENERAL INTEREST A small book illustrating some of the microscopes in t h e collection of the Science Museum in South Kensington, London, entitled “Microscopes to the E n d of the 19th Century,” has been published by Palmer and Sahiar ( 2 3 1 ) . T h e first book in a series planned to cover much of the field of microscopy has been written by the late Wolfgang Zieler (332). This book, entitled “The Optical Performance of the Light Microscope: Part 1,” deals with the geometrical optical aspects of image formation. We understand t h a t another book by Mr. Zieler dealing with physical optics will be published in the same series. In his “Basic Microscope Techniques” (236), Perlman discusses various types of microscopes and microscopical 420R
techniques. Skvortsov et al. (280) have described (in Russian) Russian microscopical equipment as well as the theory of image formation. Brian Ford has written a nontechnical handbook (82). I t includes a history of the microscope as well as “do it yourself” instructions on microscopy and microscopical techniques particularly applied to medical and biological specimens. Another guide to microscopical methods for zoologists and botanists has been written by Grimstone and Skaer ( 2 12). TWOmore volumes in the familiar series “Advances in Optical and Electron Microscopy” have been published. Volume 4 ( 1 2 ) contains two chapters of interest to light microscopists: The “Quantimet Image Analysing Computer” and “Photomicrography and its Automation.” T h e rest of the chapters deal with electron microscopy. Volume 5 (12) contains chapters on remote control microscopy, automated microscopy for cytological analysis, a method for measuring and processing the characteristic geometrical and optical magnitudes of microscopic objects, instruments for stereometric analysis, and first and second order theory of image formation. A supplement to the “Atlas of Optical Phenomena” has been published by the same authors (36).I t shows 15 optical phenomena (in color) including interference colors, diffraction by a circular aperture, interference of parallel and convergent polarized light, polarization interference contrast. interference microscopy, holography, and interferometry by holography. Francon and Mallick (84) have written a book entitled “Polarization Interferometers: Applications in Microscopy and Macroscopy.” This book gives the basic principles with a minimum of mathematics. Francon has written still another book (83), this one in French, on optics and the formation and treatment of images. It includes material on the formation if images by holography and by other optical instruments as well as optical theory. Two books dealing with other aspects of optics are, “Polarized Light and Optical Measurement” (43) and “Optical Production Technology” (135). McCrone and Delly have revised “The Particle Atlas.” This revised 2nd edition (199) consists of four volumes. Vol. 1 is devoted to instruments and techniques. Vol. 2 is a light microscopy atlas, Vol. 3 is an electron microscopy atlas, and Vol. 4 is a handbook for analysts consisting primarily of tables and charts. The atlas portions of this work present 2700 light and electron micrographs. These micrographs combined with the descriptions of instru-
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