(3F) Brinen. J. S., McClure, J. E.. Anal. Lett.. 5, 737 (1972). (4F) Conway, B E . , Tech. Electrochem.. 1, 389 (1972). (5F) Delahay, P.. Tobias. C. W., Ed , 'Advances in Electrochemistry and Eiectrochemicai Engineering," Wiley-lnterscience, New York. N.Y., Vol. 9, 1973. (6F) Fairless, C., Bard, A. J., Anal. Chem , 45, 2289 (1973). (7F) Fleischmann, M . . Hendra, P. J . . McQuiiian. A. J., J . Chem. Soc.. Chem. Comrnun.. 80 (1973). (8F) ikeshoji, T., Ono. Y., Mizuno, T.. Appi Opt.. 12, 2236 (1973). (9F) Jones, A. H.. France, W. D . , Jr., Ana,. Chem.. 44, 1884 (1972). 1OF) Kim, K. S., O'Leary, T. J.. Winograd, N , /bid.. 45, 2214 (1973). 11F) Krasil'shchik, V. Z . , Yakovleva, A. F . , T r . Vses. Nauch.-lssled. inst. Khim. Reaktiv. Osobo Chist. Khirn. Veshchestv. 134 (1971). 12F) Larsson. R . , Mrha. J,, Blomqvist. J., Acta Chem. Scand., 26, 3386 (1972). (13F) Laser, D., Ariei. M., J . Electroanal Chem.. 41, 381 (1973). (14F) Laser. D., Ariel, M . . Ana/ Chem.. 45, 2141 (1973). (15F) Li, C.-Y..Wilson, G. S . , ;bid.. p 2370. (16F) Marcus. H. L., Waldrop. J. R . Schuler. F. T . , Cain, E F. C., J. Eiectrochem. Soc 119, 1348 (1972). (17F) Matsumoto. T , Sato. M . , Hirayama, S.. Uemura, S., Chem. Lett.. 1077 (1972). (18F) Mattson. J. S., Smith, C. A,. Science. 181, 1055 (1973). (19F) Meyerstein, D . , Hawkridge, F. M.. Kuwana. T., J . Electroana/. Chem.. 40, 377 11972). - -, (2OF) Mclntyre. J. D. E., Surface Sci.. 37, 658 (1973). (21F) Newton. M . P.. Chauvin. J. V.. Davis. D . G., Anal. Lett.. 6,89 (1973). (22F) Petek. M.. Bruckenstein, J., J . Eiectroana/. Chem.. 47, 329 (1973). (23F) Petek. M . . Bruckenstein. S., Feinberg. B., Adams, R. N., ibid.. 42, 397 (1973). (24F) Petek, M . , Neal, T. E., McNeely, R . L.. Spectroscopic Techniques Murray, R. W.. Ana/ Chem.. 45, 32 (1973). (1F) Barnes. I . L., Murphy, T. J.. Gramlich, J. W.. Shields, W. R . . Anal. Chem.. 45, 1881 (25F) Plieth, W. J , , Chem.-lng.-Tech.. 44, 221 (1972). (1973). (2F) Blount, H. N., J . Electroanai Chem.. 42, (26F) Plieth, W. J . , Gruschinske, P.. Ber. Bunseges. fhys. Chern.. 76, 485 (1972). 271 (1973).
(6E) Copeland, T. R . . Christie, J. H . , Skogerboe. R K.. Osteryoung, R. A., ibid.. p aac, -".I. (7E) Duic, L , Szechter, S . . Srinivasan, S , J . Electroanai. Chem , 41, 89 (1973). (8E) Ellis, W. D., J Chem. E d u c . 50, A131 (1973). (9E) Fiorino, J A,, Moffitt, R . A,. Woodson, A. L.. Gajan. R J . , Huskey, G. E , J. Ass. Offic. Ana/ Chem.. 56, 1246 (1973). 10E) Donadey, G., Rosset, R., Charlot. G . . Chem. Anal.. 17, 575 (1972). (11E) Huderova. L.. Stulik, K.. Talanta 19, 1285 (1972). (12E) Johnson, D . C., Allen, R. E.. /bid.. 20, 305 (1973), f13EI D. R.. Ana/. Lett.. 5, 867 , ~ Kendall. . (1972). (14E) Levit, D . L., Anal. Chem.. 45, 1291 (1973). (15E) Matson, W. R.. Interface Newslett.. January 10, 1974. (16E) Neiman. E. Ya., Brainina, Kh. Z . , Zh. Anal. Khim.. 28, 886 (1973). (17E) Reusmann. G.. Westphalen, J., Fresenius' Z. Anal. Chem.. 259, 127 (1972) (18E) Rotzenblal, E. M., Levchenko. L. F., Veretina. G. N., Zh. Ana/. Khim.. 28, 33 (1973). (19E) Schmid, G. M., Bolger, G. W.. Ciin. Chem.. 19, 1002 (1973). (20E) Searle, B.. Chan. W., Davidow, B . . /bid.. D 76. (21E) Seitz. W. R., Jones, R . . Klatt. L. N.. Mason, W. D.. Anal. Chem.. 45, 840 (1973). (22E) Sieaerrnan. H.. O'Dom. G.. Amer. Lab.. 4 (7)-( 1972). (23E) Sinko. I . , Gomicsek. S., Mikrochim Acta. 3, 163 (1972). (24E) Stulik. K.. Stulikova. M.,Anal. Lett.. 6, 441 11973). (25E) Stulikova,'M., J . Electroanai Chem.. 48, 33 (1973). (26E) Stulikova. M . . Vydra, F., ibid.. 42, 127 (1973). (27E) Kozlovskii, M . T., Zebreva. A. I . , Progr. folarogr.. 3, 157 (1972).
\
(27F) Sato. Y.. Chem L e t t , 1027 (1973) (28F) Strojek. J W., Chem. Anal (Warsaw). 17, 1023 (19721. (29F) Vassos. B. H.,Hirsch, R . F , Letterman. H . ,Ana/. Chem.. 45, 792 (1973) (30F) Wells, E. E., ibid . p 2022 Chromatographic Techniques (1G) Brooks, M . A,, de Silva. J A. F., D'Arconte, L. M I Anal C h e m , 45, 263 (1973). (2G) Brooks, M. A , de Silva. J . A F.. Hackman. M . R . , Anal Chim Acta. 64. 165 (1973) (3G) Davenport, R . J , , Johnson, D. C., Anal. Chem., 45, 1979 (1973) 14GI /bid.. D 1755. i5Gi Dencker, W. D . , Rushneck. D . R.. S h ~ w make, G. R . , Ana/. C h e m , 44, 1753 (1972). (6G) de Silva, J. A. F.. Strolny, N . , Munno. N , Ana/. Chem. Acta. 66, 23 (1973) (7G) Dolan. J. W.. Hall, R C.. Aqal. Chem 45, 2198 (1973) (8G) Farwell, S . 0 . . Beland. F. A,, Geer. R . D , B u / / . Environ. Contam Toxicol. 10, 157 (1973). (9G) Fike. R R , U. S. Patent 3,669.864 (1972) IOG) Gruber, H. L , Huck, H . Journees Int. Etude Piles Combust C. R . 3rd 158 (1969) 11G) Haki. J . , Chromatographia. 5, 357 (1972) 12G) Johnson, D . C , Larochelle, J , Talaflta. 20, 959 (1973) 13G) Kissinger. P. T , Refshauge, C , Dreiling. R . . Adams, R. N . . Ana/ Left.. 6, 465 (1973) (14G) Kojirna, T . , Mitsunolo. I , Seo, Y , Talanta. 19, 539 (1972). (15G) MacDonaid, A,, Duke, P . , J. Chromatogr.. 83, 331 ( 1 973). (16G) Mori, I . , Chikui. S., ] b i d . 64, 390 (1972) (17G) Robertus, R. J.. Schaer, M . J.. Environ. Sci. Techno/.. 7. 849 11973). (18G) Stillman, R . , M a l T. S,, if;krochim. Acta. 4. 491 (19731. (19G) Strohl,'J. H.: Dunlap, K . L , Ana/. Chem 44, 2166 (1972). (20G) Takata. Y.. Muto, G , !bid, 45, 1864 (1973). (21G) Taylor, L. R . , Davenport, R J.. Johnson, D. C.. Talanta. 20, 947 (1973). (22G) Wiiliams, W G.. Carritt, D E.. Anal Chern.. 44, 2119 (1972). ~~
Electroanalysis and Coulometric Analysis Donald G. Davis Department of Chemistry. Louisiana State University of New Orleans. New Orleans. La. 70122
This review covers roughly the period from December 1971 to December 1973. Some earlier papers have been included which were not mentioned previously in this series. Despite continued growth in the field, succinctness is required and thus a higher degree of selectivity has been applied than in the past. Likewise, some of the more obvious points must be left to the readers' basic knowledge.
REVIEW ARTICLES An extensive review covering electrochemical analysis (108) has appeared, as well as several emphasizing the revival of coulometry (254) and the present state of the art (64, 82). A manual of controlled potential coulometry (103) .promises to be helpful, as does a discussion of coulometry in organic synthesis (231). A summary of the work a t the National Bureau of Standards (77) including some excellent coulometric studies (many of which will be referred to later) has become available. Coulometry in gas
analysis (196), water quality control (249), pollution monitoring (266), gas chromatography detectors (200), and sulfur in pharmaceuticals (227) have been reviewed. Heviews on coulometric instrumentation (8, 70), uranium and tranuranium elements (236), and a comparison of end-point techniques have been published (255).
RECENT T R E N D S A N D SOME BASIC STUDIES Previous reported trends in the field continue. Only a little work on electrogravimetry has been done in the past two years, although coulometric methods of all types enjoy ever-increasing popularity. Interest remains high in the use of controlled potential coulometry in organic and biochemistry chemistry for synthesis and fundamental studies. Much work continues in the area of gas analysis (chromographic detectors, analysis of combustion products, and the like) often using variable current. Potential scanning coulometry and other variations of potential or A N A L Y T I C A L C H E M I S T R Y , VOL. 46,
NO. 5, APRIL 1974
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Table I. Controlled Potential Coulometric Determinations Method
Substance determined
Cd, T1, P b , Cu
Cu, Fe, Au
Cu, F e
Fe Hz, HzO? Pu, u Pu Pu Pu P u and U
U
u (VI) U
V
Zn
Two-step flow, carbon electrode. All deposited, 0.5M HClO, ( - 1.40 V us. HgSO,). Each oxidized and coulometrically reduced in 2nd column in turn I n slags and Cu-Au alloys, potentiostatically Z r matrix, Cu to metal, F e t o F e z +0.5M H2S04-0.5M Na3 citrate, H g electrode. Cu re-oxidized often complexing FelII) with 1,lO-phenanthroline. Fe3+ in oxides, 1M H2SOd 0.03 V us. SCE (Ar passed). Also in presences of Mg and M n Radiolysis products-pH studied Column coulometry-carbon electrode Two-step flow, 0.5M HzSO, Pu t o PulIII) $0.1 V us. AgC1. Coulometric oxidation +0.75 V Reduced PuIIII) P b reductor, oxidized to Pu(1V) at +0.9 V us. SCE, 1M HCl, Pt electrode Potential scanning coulometry. Various acids, interference study Oxidation at 0 73 V bs. AgCl of Pu(II1) and UIIV); reduction at 0.33 V. PuUV) t o Pu(II1). Mixed H?SO, and "03, TilIII) prior reducing agent, Au electrode 10-mg range, 1 M HZSO, Nitrate present iNzHd added),
Reference
128)
(
100)
1213) 1214) (221) (132) ,130, 131) (256) f166)
1237) (80)
(158) (238)
0.5M H,SOI
Stoichiometry of UOZ+X precision coulometry Reduction V 1V) to V (IV). Media effects and interferences studied New atomic weight 165.377 =k 0.0031
1218) 39)
(
1 70)
Organic Substances
Uric acid Oxalate
I n serum Two-step flow-to avoid interferences, 0.5M H?SOI coulometric oxidation a t +1.60 V us. AgCl
1207) 1129)
-
current are continually being investiagated, but the use of constant current, especially for titrations, continues to be the most popular approach, with standard controlled potential coulometry with current integration a reasonably close second. Some fundamental studies which have appeared are of importance to workers in the field. Of special note are two series by Bishop and his coworkers. One deals with the precise coulometric determination of acids in cells without liquid junction (40-43), and the other continues their work on mass and charge transfer kinetics and coulometric current efficiencies (36-38). Diffusional titration errors with cells containing noninteracting membranes (63)have also been considered. Naturally coulometry has been combined with other techniques especially for end-point detection and sample pretreatment. Of a more unusual nature has been the combination of ellipsometry and coulometry to investigate electrode surface phenomena (46, 272), and the coulometric calibration of ion selective electrodes ( 2 5 ) . ELECTROSEPARATIONS AND ELECTROGRAVIMETRY Although the practice of these methods undoubtedly continues, publications in this area continue to decrease to the point of near extinction. Lead has gravimetrically been determined as Pb02 from an HEDTA solution (33) 22R
A N A L Y T I C A L CHEMISTRY, V O L . 46, N O . 5, APRIL 1974
as have Hg and Sn by internal electrolysis (269). A substantial decrease in electrolysis time has been achieved for the analysis of Cu, Bi, Pb, and S b by the use of a vibrating electrode (147). A mechanistic study of the deposition of copper has been reported (76). CONTROLLED POTENTIAL COULOiMETRY Controlled potential coulometric determinations are listed in Table I. Since there is an ever-increasing tendency to use more complex chemical treatments, double-step electrolysis with intermediate chemical treatment and column (single and double) electrolysis, it has not always been possible to include complete conditions in the table, so the original papers should be consulted in most cases. One interesting development has been the simultaneous determination of n and D by making use of the transition time from linear to cylindrical diffusion at a thin wire electrode ( 5 3 ) . Electrode Mechanisms. There continues to be much interest in the use of controlled potential electrolysis in mechanistic studies, both inorganic and organic, often leading to new synthetic routes. Some of these papers are considered here. On the inorganic front, the electrofluorination of urea to NFB has been studied (2,59), as have the reactions of COz in molten nitrates (281). It has been reported that three electrons are involved in the reduction of 12-molybdoarsenic acid (164), and the numbers of elec-
Donald 0 . Davis was born in Stoneham, Mass., and received his education at Wesleyan University (EA, 1954) and Harvard University (PhD, 1957). He joined the faculty of Georgia Tech in 1957 and moved to the Chemistry Department at Louisiana State University in New Orleans in 1959. Formerly, he was department chairman and dean of the Graduate School and is now professor of chemistry. He is a former Science Advisor to the Food and Drug Administration and has authored several chapters in advanced monographs. His current research interests include coulometric and cyclic voltammetric methods. especially as applied to biologically interesting compounds, especially metalloporphyrins and quinones, investigation of the kinetics and mechanisms of electrode reactions, and the analysis of trace metals by flameless atomic absorption.
trons involved in the reduction of Ti(1V) and W(VI) in phosphoric acids have been determined (149). A study of the Ag/AgCl system in methanol (233) and one of the reduction of actinide(1V) halides in DMSO (19) have been published. The use of nonaqueous solvents in coulometry of all sorts seems to be growing in popularity. Controlled potential coulometry has been applied (usually as a subsidiary technique to cyclic voltammetry, polarography, and spectroscopy) to the study metal complexes with organic ligands. This area cannot be completely covered here, but includes such studies as that of the reduction of zinc tetraphenylporphyrin (157), uranium( VI)-diethylenetriarninepentaacetic acid (110) and the o-ethyl thioacetothioaceto and similar complexes of Zn, Cd, and Hg (47, 48). Extensive work has also been accomplished in the organic area such as studies of carbonium, carbanions, and radicals in the triphenylmethane series (143), the anodic fluorination of halobenzenes (224), the trifluoroacetoxylation of methylbenzenes (251), and the oxidation of 1,2-dithiol-3-thiones (211 ) . Studies on electrohydrodimerization (219), continue (dimethyl fumarate). Aromatic nitro compounds have been reduced in a variety of organic solvents and the products characterized (270, 271) as have substituted nitronaphthalenes in aqueous media (114, 115). The reduction of 3-iminoindolenine derivatives has been shown to yield the 3-aminoindoles (11) and isatin-3-oxime has been similarly considered (IO). Monitoring by IR during electrolysis has identified cyclopropones as intermediates in the reduction of qa-dibromoketones (90). The mechanism of the reduction of naphthastyril and its monohalo derivatives has been reported (78), as has the formation and stability of halogenated benzonitrile anion radicals ( 2 7 ) . The reduction of the following compounds has also been studied: 1,4-diphosphonicyclohexa-2,5-diene(243); a$ unsaturated esters (134); acetylacetone (262); neutral red (250); and tosyl esters (267). Controlled potential electrolysis has also been applied in the preparation of tetramethylammonium hydroxide (146) and in peptide synthesis ( 5 5 ) . CONTROLLED CURRENT COULOMETRY-COULOMETRIC TITRATIONS Table I1 lists many of the coulometric titrations reported in the past two years. There is a t r m d toward micro methods and, more important, an increasing application of coulometric titrations to clinical analysis. This is exemplified by the recent report of the determination of iron in serum (176). Two new titrants have appeared-a rare event these days. Both are reductants, one being U(III), the strongest reducing agent successfully used so far ( 8 1 ) ; and the other, the blue reduction product of 18tungsto-2-arsenic acid (49). Very high precision work continues including the assay of potassium dichromate (280) and a new determination of the faraday via iodine with a precision of about 14 ppm (50). Coulometric thickness determinations have also been reported, including measurements of sulfide tarnish (278), silver coatings (123), and electrodeposits (135). Chemical oxygen demand determi-
nation (84) on an automated basis has been accomplished, as well as the analysis of petroleum for neutralization value, bromine number and moisture in nonaqueous solution (189). Novel methods include the determination of hypochlorite and hydrogen peroxide based on the liberation of OXYgen coulometrically determined at a porous silver electrode (85), and the ultramicro determination of Mn oxidized in a capillary and color matched with a larger anodically oxidized solution (253). A series of papers has appeared on analyses by the “substoichiometric coulometric method” first reported in the last review. In this approach, metals, sometimes in mixtures, are deposited on an electrode using a specific current for a specific time, and then stripped at another constant current as the electrode potential is recorded. The more usual approach is, of course, to deposit at constant potential and then strip in one of several ways. In this manner determinations of Bi (126), Cu-Ag-Bi alloys (125), Se (127), Ag-Bi (124), Zn (51, and Zn-Cu alloys ( 4 ) have been accomplished. A detaded study of the deposition and dissolution of Ag on Pt has also been reported (175). Here, as expected, the old problem, the oxidation of Pt, again produces problems. Some work in solid state coulometric titrations continues (258, 267). Gaseous Samples. There appears to be an ever-increasing use of coulometric titrations with controlled current that involve the introduction of a gaseous sample into the electrochemical cell. Frequently, the gas sample is produced by combustion of materials of interest in an appropriate flowing atmosphere. However, a number of methods involve direct air pollution analysis or on-line determination of gaseous reactants or products. These methods can be catagorized into those using discrete samples, continuous monitors (with or without combustion or pyrolysis), and those associated with or used as detectors for gas chromatographs. Often these methods are based on automatic apparatus that generates a titrant at a rate proportional to the value of an indicator signal, rather than making use of constant current. The area under the “current-time’’ curve is integrated. The indicator signal may be potentiometric, amperometric, or colorimetric in nature. Table nI summarizes recent applications of this approach. APPARATUS A considerable number of new or improved instruments have been reported. These will be considered under the heading “electrodes and cells,” “coulometric titration apparatus,” and “potentiostats and coulometers.” Clearly perfect classification is not possible, and it is hoped that this somewhat arbitrary division will not unduly confuse the reader. Electrodes a n d Cells. As many practitioners are aware, carbon electrodes are becoming more popular because of the development of nonporous forms of this material. Vitreous carbon has been recommended as a working electrode for redox titrations (112) and acid-base work (113) and impregnated graphite for coulometry (174). Various electrodes have been considered for the generation of halogens. Pt and Au are useful but not C, W, or T a (220). New cell designs abound. Two suitable for various types of work, make use of high speed solution circulation (95, 226) and can be used for spectrophotometry as well. A vacuum-line cell for electrosynthesis has been designed (225) as well as cells for micro (162) and ultramicro analysis (6). A new coulometric oxygen analyzer having a carbon cathode and a cadmium anode has been reported (65). For gas analysis, improved cell designs (234, 241) have also been published. Of special interest has been the construction of flow-thru cells as detectors for the increasingly important field of high pressure liquid chromatography (133, 257). Detection limits in the nanogram range are possible, and improvements remain to be made. An extensive study of cells as components of control systems has been reported (217) and also the effects of cell design on coupled chemical reactions (193). Apparatus for regenerating coulometric cells has been constructed (32) as have a detector for gas analysis (150), a coulometric calibrator for GC detectors (276), and a device to study surface reaction rates (248).
A N A L Y T I C A L C H E M I S T R Y , V O L . 46, NO. 5, APRIL 1974
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Table 11. Electrogenerated Titrants and S u b s t a n c e s Determined by Coulometric T i t r a t i o n Substance determined
Electrogenerated titrant
Reference
Oxidants
Bromine
Chromium(V1) Ferricyanide Iodine
Manganese (111) Oxygen Vanadium (IV) Vanadium (V)
Be as 2-methyl-8-quinoline Primary carbamates CN - free and coordinated Cyclamates Gold Phenol Acid or alkaline phosphatase Platinum(I1) and (IV); Sn(I1) as reductant Salicylates in serum Fe(II), M n ( I I ) , V(IV), CefIII) Cr(II1) As, Sb, Cu Ge(I1) HgfII), C N - form thru ligand exchange N-Isopropyl-CY- (2-methyl-hydrazine)-ptoluamide HCl Polythionates Se in Urine SO, in sulfite liquor Thionalide Various-titrant stabilized by F Vanadium Redox enzymes-methylviologen reductant Pyrocatechol Uranium
1140) (98)
Reductants
Chromium (11) Iron(I1)
Iron(I1) Manganese(1) and Molybdate (V) Tin 111) Titanium (111)
18-Tungsto-2-arsenic acid reduction product Uranium(II1) Vanadium (IV)
Traces of V 0 2 + ,Sb, Sn, etc. AgW Cr in A1 Cr and Ce Cr in catalytic oxides Cr and V in alloys Ethanol and ethoxydiethyl-aluminum after excess Cr(V1) Glycerol after excess Cr (VI) Mn and Cr in organics v (V) Fe(CN)s4- etc. in C N - media Se(IV), Fe(III), Mo(VI), CuiII) FE(III), CR(VI), V(V) On P b cathode-oxidants Ce and F e in alloys F e and Cr in alloys Fe and Ti (excess Ce (IV)) Mo (VI) Nitrates Fe(II1)
(141) (139) (188) (185) 1183) (154) 1186) ( 72)
134)
1240) (106) (138)
(28) (142) (190) (187) (184) (62, 94) (60, 61) (49)
U Fe(CN)bSPrecipitating and complexing agents
(246) .
Copper(I1) Fluoride Ferrocyanide Mercury(I1) Silver (I)
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A N A L Y T I C A L C H E M I S T R Y , VOL. 46,
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Neodynium (feed-back controlled current) Zn Methionine La Zn (ultramicro) Thiols and disulfides C1- (Actinometry using trichloroacetic acid)
NO. 5,
A P R I L 1974
1247) (178) (136) (228) ( I 59) (212) (168) 183)
Table 11. (Continued) Reference
Substance determined
Electrogenerated titrant
Precipitating and complexing agents
C1- in serum Ferro and ferricyanide Glutathione, cysteine, thiourea(micr0) Proteins (SH) Water analysis (C1-) Acids and bases
Acids
Amines in acetonitrile Amines (biogenic)-low water solvent Amines etc.-Bi electrode pair detector Cd and Ni (ppt a t cathode); H at anode determined Mixed bases-nonaqueous Acidity in rain water Weak acids in tetrahydrofuran Acids in isopropanol Organophosphorous compounds icombusted-H2POI - titrated) Nicotine-nonaqueous +
Bases
Water determination
Karl Fischer reagent
Water in silicone compounds Water (micro) New reagent composition-multititration
Table 111. Coulometric Titrations Using Gaseous Samples Substance determined
Carbon
Carbon and hydrogen Chlorine Chloride
Hydrogen Nitrogen
Type of sample
Reference
Metals Steel-collaborative study Organics Organics in sea water Steel-CO, as acid in isopropanol Organics-pg range Organics Organics-automatic titrations C1, gas-on-line Dichloroacetylene and contaminants GLC Micro Organics-nanoequivalents C1 Organics Organics-also determines N N 02-continuous NOn
Oxygen
Phosphorous Sulfur
Water
Total N in petroleum In Ti Organics-titrate I? vaporized from anhydroiodic acid Water and gases; viologen radical cation titrant I n gases, porous catalytic electrode Organophosphorous compounds Organics Steel Instrumentation Organics HLSand total S, organics pollutants etc. H,S in gases Petroleum products SO: in atmosphere SO,(continuous) SO,, instrumentation I n gases Industrial olefins Minerals (micro)
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(206) (119)
(268) (260) (2) (86) (117) 1201) 158) (20) (91j (54, 56, 57, 75) (194) 1153) (17, 241 (197, 235) (277) (68)
46, NO. 5, A P R I L 1974.
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Coulometric Titration Apparatus. Among the new instruments in this catagory are a coulometric moisture monitor ( 1 8 ) , a high quality coulometric titration featuring feedback current control (177, 179), mercaptan titrators (74, 93), a water titrator (160), a continuous Fe(I1) mopitor (73), and a pulsed coulometer for gas analysis (156). A novel coulometric device for determining Ag in photographic solutions has been patented (93, as have coulometric titrators and indicator systems (239, 273). A universial coulometric analysis apparatus has been tested (70, 71), a simple end-point detection device described (229), and various methods for the electrochemical studies of ionic melts have been compared (99). Potentiostats and Coulometers. New fast response potentiostats have been reported (148, 195), one including a specialized cell (195).Other new potentiostats include one designed especially for U and Pu in nuclear fuels (202) and a low cost, general purpose instrument (67). New approaches include the “couloximeter” for 0 2 analysis (107) and “coulopotentiography” developed for complete coulometry of a solution flowing thru a column (91). LITERATURE CITED
( 1 ) Aavik. H. E., Kabun, A. V., Kallasorg, R.. Revel’skii, I . A,. Tr. Vses. lssled. Soveshch. Ostatkov Pestits. Protil. Zagryazneniya / m i Prod. Pitan., Kormov Vnesh. Sredy. 2nd, 16 (1971). (2) Aavik, H., Kallasorg, R.. Revei’skii, I. A,. Tr. Vses. Soveshch. lssled. Ostatkov Pestits. Profil. Zagryazneniya / m i Prod. Pitan., Kormov Vnesh. Sredy, 2nd, 23. (1971). (3) Agasyan, P. K.. Basov, V. N., Kostromin. A. i., Vestn. Mosk. Univ.. Khim. 13, 353 ( 1972) . (4) Agasyan. P. K., Smyshlyaeva, L. N. Zavod. Lab., 38, 1326 (1972). (5) Agasyan. P. K.. Smyshlyaeva, L. N., Kharmrakulov. T. K., Zh. Anal. Khim., 27, 257 (1972) ( 6 ) Alimarin. I . P.. Petrikova. M. N., Kokina, T. A,, Ocherki Sovrem. Goekhim. Anal. Khim., 540 (1972). (7) Al’perin, V . Z.,Khamrakulov, T. K., Il’yasov, D. A.. Pepeiyaeva, 2 . A,, Chernyakov, V. V., Zavod. Lab., 38, 643 (1972). (8) Al’perin, V. Z., Ii’yasov, D . A,, Nezhinskii. V. V.. Rylov, V. A.. Prib. Sist. Upr., 7, 41 (1972). (9) Altman, Roger L.. Anal. Chim. Acta, 63, 129 (1973). (10) Andruzzi, Romano, Cardinali. Mario E., Carelli. itala, Trazza. Antonio, Ann. Chim.. 61, 415 (1971). i l l ) Andruzri, Romano, Cardinali, Mario E., Careili, Italo, Trazza, Antonio, J. Electroanal. Chem. lnterfacial Electrochem.. 36, 147 (1972). (12) Anisimova. G. F.. l z v . Akad. Nauk SSSR. Ser. Khim., 669 (1972) (13) Anisimova. G. F., Klimova, V. A., ibid., p 581
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26R
As usual, the number of new coulometers is substantial, considering the number in existence already. These include an iodine (micro) coulometer (22), an electrolytic coulometer (215), a colorimetric (12) model (79), a redox coulometer (274), a mercury coulometer 1230). and a coulometer and timing apparatus (263). An electrolytic coulometer cell electrode has been described (44). A simple device for DME millicoulometry has been reported (292). Solid electrolyte coulometers are also still being developed (109, 122, 163). Several studies on the effect of ac current on errors in different mercury coulometers have appeared (121, 216, 232), as well as consideration of an electrolytic coulometer as a component of electronic circuits (282). In general, electronic coulometers will probably continue to be most useful for chemical studies and analysis.
ACKNOWLEDGMENT Support of the National Science Foundation (GP-19749) is gratefully acknowledged, as is the assistance of Mrs. Marie Cole and Mrs. Carolyn Newton.
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(1972).
Ion Selective Electrodes, Potentiometry, and Potentiometric Titrations Richaid P. Buck William Rand Kenan J r . Laboratories of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, N.C. 27574
The literature compiled for this review includes developments in the general areas of fundamental and applied potentiometry published since the last review (168). The final issue of Chemical Abstracts consulted was Vol. 79, No. 23, December 10, 1973. Again I have emphasized ion selective electrodes and their applications in all fields of applied science. To achieve a review of practical length, nonaqueous titrimetry, potentiometry in molten salts, electrodes and systems pertaining primarily to batteries, fuel cells, and electrochemical synthesis have been omitted. Nearly 300 references to complex ion equilibria and acid-base equilibria, followed potentiometrically, have been deleted. More tables and less discussion characterize this review over those in the past because the literature in the field continues to increase. Ion selective electrodes in particular find applications in biology, medicine, natural water, and air chemistry and even solid state physics. Conversely, fundamental literature in these diverse fields has an impact on the development of improved electrodes. Important fundamental papers are included where they are immediately pertinent.
BOOKS, REVIEWS, AND SURVEYS Only two books have appeared (183, 795) which are exclusively concerned with ion selective electrodes (ISE’s). However, others are in preparation. Geddes’ book on elec28R
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trodes (346) is aimed a t applications in biophysics while edited volumes by Eisenman (290), the Specialist Reports of the Chemical Society (201), and Vijh’s volume on semiconductor electrochemistry (1207) provide important background reviews on materials and transport properties as well as potentiometric results on systems closely related to ISE’s. A further supplement of “Stability Constants of Metal-Ion Complexes” has been issued (1068) and a new volume on interfacial electrochemistry which bridges the gap between electrodics and colloid science has appeared (879). A full review of the theory and application of ISE’s including literature through the end of 1971 is by Koryta (588). Other reviews of general nature in English, except as noted, are by Baumung, Ger. (99), Clerc and Pretsch, Ger. (212), Clerc, Kahr, Pretsch, Scholer and Wuhrmann, Ger. (213), Fiori and Formaro, Ital. (316), Hozumi, Jap. (464), Hulanicki, Pol (467), Ijsseling, Neth. (475), Oehme, Ger. (866), Omang, Norweg. (874), Pretsch, Scholer, Kahr, and Wuhrmann, Ger. (935), Sapio and Braun (1014), and Wilson (1244). Reviews emphasizing heterogeneous membranes of the Pungor type are by Pungor and/ or Toth (940) Serb. (943, 945, 948, 949, 1162, 1164). The latter four emphasize selectivities, mechanisms, and time responses. Klara Toth has also described potentiometric research in Hungary (1163). The Matrafured (Hungary) Conference on ISE’s produced a number of important pa-
