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Electroanalysis and Coulometric Analysis Allen 1 (3K) Bigeleisen, Jr., J. Cham. Phys. 60, K. G., Muskheleshvili, G. N., Kiladze, i Stabil’n Izotopov i Izluchenii v Nar. 35 (1963). N.Sh., Mikirtumov, V. R., Bakhtadze, Khoz. i Nauke, Moscow (1957). (4K) Boato, G., Casanova, G., Levi, A,, Z. I., At. Energy (U.S.S.R.) 10, 487 (26K) Sakane, R., Isomura, S., Sci. J. Chem. Phys. 37, 201 (1962). (1961)\----I. Papers Inst. Phys. Chem. Res. (Tokyo) (510 Boato, G., Scholes, G., Vallauri, (15K) Jenn, J. T., Aker, P., Energia 56, 164 (1962). M. E., Nuovo Cimento 14, 735 (1959). Nucl. 5, KO.2, 98 (1963). (27K) Palko, A. .4., Drury, J. S., Bull, (6K) Bulatova, R. F., Grigor’ev, V. N., (16K) Johnson, B. S., F. G., U. S. At. W.E., J.Chem. Phys. 35, 103 (1961). Kogan, V. S., At. Energ. (U.S.S.R.)12, Energy Comm. DP-7S2 (1962),36 pp. (28K) Panchenkov, G. M., Timofeev, 428 (1962). (17K) Katal’nikov, S. G., Andreev, B. M., E. M., Tsimmerman, V. D., U.S.S.R. (7K) Casanova, G., Fieschi, R., Terzi, Xi.. At. Energ. (U.S.S.R.)11, 240(1961). Patent 136.630. Nuovo Cimento 18. 837 ( 1960). (18K) Kauder, L. N., Spindel, W., (29K) Proctdr, J. F., Chem. Eng. Progr. (8K) Clusius K., Schleich, K.; Bernstein, Monse, E. U., J. Phys. Chem. 65, 1435 59, So. 3, 47 (1963). R. B., Helv. Chzm. Acta 45, 252 (1962). (1961). (30K) Simon, H., Heubach, G., Z. Satur- (9K) Clusius, K., Schleich, K., End- (19K) Kenion, A. R., Birch, A. J., Brit. forsch. 18b, So.2, 160 (1963). tinger, F., Bernstein, R., Vogelmand, Patent 896,269. (31K) Stouls, L., Fr. Patent 1,271,501. M., J. Chim. Phys. 60, 66 (1963). (20K) Lazard, B., Belg. Patent 611,155. 132K) Uvarov. 0. V.. Sokolov. N. M.. (10K) Clusius, K., Schleich, K., Pies- 121K) Maimoni. A,. A.I.Ch.E. (Am.Inst. Lvaoin. V. v.. Zhavoronov.‘ X. M.: bergen, U., Varde, E., J. Chim. Phys. ~ Chem. Engrs. )’J. i,371 (1961j. Zh.‘Vses. Khim. Obschestva hn. D. I: 60, 48 (1963). (22K) Malyusov, V. A,, Orlov, V. Yu., Mendeleeva 7, 695 (1962). (11K) Devyatykh, G. G., Borisov, G. K., Malafeev, N. A,, Umnik, 5. N., Zhav- (33K) Yarshavskii, Ya. M.) Vaisberg, Pavlov, A. A,, Dokl. Akad. Nauk oronkov. X. M., At. Enera. (Cr.S.S.R.) S. E.. Dokl. Akad. Sauk SSSR 140, SSSR 138, 402 (1961). 11, 435 (1961). 1361 (1961). (12K) Gowland, L., Johns, T. F., At. 123K) Merihis. J.. Bousissineres.,, G.. 134Kl Wetzel.,, K.. Isotonen Tech. 1. 15 Energy Res. Estab. (G.Brzt.) Z/R-2629 ~ Anal. Chim. Acta 25,498 (1961). (1660). (1961),12 pp. (24K) Merlivat, L., Botter, R., Sief, G., (3iK) Itolfsberg, M.>J. Chim. Phys. 60, (13K) Grigor’ev, V. N., Ukr. Fiz. Zh. J. Chim. Phys. 60, (1963). 15 (1963). 6, 472 (1961). (25K) Muehlenpfordt, J., Siewert, G., (36K) Zel’venskii, Ya. D., Efremov, A. (14K) Gverdtsiteli, I. G., Nikolaev, Yu. Gagua, T., Tr. Vses. Nauchn.-Tekhn. A,, Itv. Vysshikh Gchebn. Zavedenii, V., Oziashvili, E. D., Gverdtsiteli, Konj. PO Primeneniyu Radioaktiun. Khim. i Khini. Tekhnol. 5, 727 (1962). Electroanalysis and Coulometric Analysis Allen 1. Bard, Department of Chemistry, The University of Texas, Austin 12, Texas HIS PAPER surveys the literature tails about the experimental conditions, concerned with the effect of surface Tand developments during 1962 and is included. ii book on coulometric oxidation, activation, and adsorption through December 1963, although methods by Abresch and Claassen (5) on the rates of electrode reactions. papers published before 1962 which has also appeared. Oxide Films and Surface Effects. have not appeared in previous reviews An extensive review on the analytical The nature of the surface films on in this series have also been included. applications of mercury electrodes to solid electrodes continues to enjoy electrodepositions, separations, and attention. The mechanism of the formation and reduction of the oxide BOOKS AND REVIEW ARTICLES coulometric methods has appeared (208). This review contains tables film on platinum was discussed by Several books dealing wholly or partly listing the elements determined and Feldberg, Enke, and Bricker (76). The with electroanalytical methods have separated on mercury electrodes and authors used various cyclic techniques appeared. A welcome English trans- the experimental conditions employed to study oxide film effects and con- lation of the book by Charlot, Badoa- in the methods. The literature between cluded that the formation occurs in Lambling, and Tremillon (46) has been 1948 and 1960 is surveyed, and 423 ref- two, one-electron, steps, involving the published. The book is written mainly erences are given. Application of slow formation of Pt(OH),, followed by for analytical chemists and uses current- electrolytic methods to trace analysis a rapid step yielding Pt(O),. On reduc- potential curves and graphical methods has also been reviewed (137, 169). X tion, the reverse steps occur; reduction to treat a variety of electroanalytical general review of electroanalytical of Pt(O), to Pt(OH), is rapid, and of techniques. Xumerous applications are methods appeared in the annual report Pt(OH), to platinum is slow. The given and the book is highly recom- of the Chemical Society (London), (44). mechanism of surface oxidation of mended as an introduction to this field A number of review articles on coulo- platinum has also recently been dis- for the practicing analyst. Volume 4 of metric methods have appeared. Of cussed by Gilman (89). Part I of the treatise by Kolthoff and special interest to English-speaking, Evidence for a series of platinum ox- Elving (121) is largely devoted to elec- chemists is the review by Kies (115), ides on the electrode surface has been trical methods of analysis. Chapters on with 267 references, on coulometry. presented (133, 168). Mayell and the fundamentals of electrode processes, A brief review of applications of con- Langer (168), by oxidizing platinum electrodeposition, and coulometric trolled potential coulometry to metal potentiostatically or with a constant cur- analysiq are included. Kechnitz’s mono- analysis has appeared (65) as well as rent in acidic solutions, removing any graph, “Controlled Potential Analysis,” other, foreign language, reviews on gaseous oxygen and electrolytically re- (209)has just appeared and is a valuable coulometric methods (1, 2, 178, 250, ducing the surface oxides, showed that addition to the literature of electro 234, 244, 301). the number of coulombs involved in the analytical chemistry. The theory and reduction of the surface depended upon a1)j)aratus of both electrogravimetric ELECTROCHEMICAL THEORY the potential to which the electrode was and coulometrir controlled potential oxidized. Increasing the potential of method. are divuased extensively, and Many of the fundamental electro- preoxidation increased the extent of oxy- an clement-by-element survey of ap- chemical studies most directly ap- gen coverage up to a potential of about plications. in most cases including de- plicable to electroanalysis have been 1.8 volts us. N.H.E. Above this poten- 70 R ANALYTICAL CHEMISTRY tial the number of coulombs decreased to responsible for an increase in reversibil- H&O, and washed) and passive (heated a constant value. The authors propose ity of the electrode reaction (18). in oxygen at 850”, forming a stable a series of platinurn-oxygen couples, Evidence that a fresh layer of finely oxide coating) electrodes and found ending with a “tighi,” platinum oxide divided platinum increases the rate of that the rate of reduction at an active at potentials higher than 1.8 volts. an electrode reaction has been obtained electrode was about double that at a Kozawa (133) found !lumps on current’- in other studies. Shibata (237) passive one. These authors also found potential scans for a platinum electrode examined the effect of preoxidation and that hydrogen oxidation occurs at in strongly alkaline solutions and as- reduction of the electrode on the over- active electrodes but not at passive ones. cribed these to various platinum oxide potential for hydrogen ion reduction These results are in disagreement with and hydroxide couples. and concluded that the beneficial effect those of Sawyer and Seo (228) who Some previous experiments on of this anodization-cathodization pro- found no evidence for hydrogen oxida- platinum oxide formation have been cedure is not due to impurity desorption, tion at gold electrodes. The reduction repeated and reinterpreted. Previous hut, rather to “a freshly electrodeposited of oxygen at palladium electrodes was results indicating preferential oxide platinum. layer which has high studied by Blackburn and Lingane (32). formation at grain boundaries have been activity associated with a small crys- The behavior here was similar to that questioned (181). Breiter (38) has re- tallization rate.” Similar evidence found for the reduction of oxygen at examined the chemic:tl stripping of sur- for active centers on a platinized gold electrodeq. Evidence for two face oxides in chloride media and con- elec7trode has been presented (SI,190). palladium oxides at the electrode sur- cluded that the stririping of the oxide The electroreduction of oxygen at face was presented. occurs by an electrocl- emical mechanism platinum has been investigated further Adsorption Effects. The adsorp- rather than by a direct chemical re- (180, 627) and additional evidence is tion of various components from the action, and that the experiment does not presented for the reduction of oxygen solution, including the electroactive demonstrate a true oxide film as opposed with less overpotential at a freshly species itself or the products of the t,o chemisorbed oxygen. Peters and oxidized electrode. electrode reaction, can also afiect the Lingane (203) examined film formation The oxidation and reduction of H202 rate of electrode reactions. Well in chloride media at several pH’s and at a platinum electrode have been known methods, such as electrocapil- concluded that platinum chloride and studied (146) and both reactions directly larity measurements and analysis of oxychloride films containing both plat- involve participation of the electrode polarographic pre- and postwaves have inum(I1) and platinum(1V) form.
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