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Electroanalysis and Coulometric Analysis Allen J Subscriber access provided by University of Texas Libraries Electroanalysis and Coulometric Analysis Allen J. Bard Anal. Chem., 1966, 38 (5), 88-98• DOI: 10.1021/ac60237a006 • Publication Date (Web): 01 May 2002 Downloaded from http://pubs.acs.org on February 19, 2009 More About This Article The permalink http://dx.doi.org/10.1021/ac60237a006 provides access to: • Links to articles and content related to this article • Copyright permission to reproduce figures and/or text from this article Analytical Chemistry is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 fractionating columns are few. Van approach to equilibrium. In most (3) Chem. Eng. Xews 43 (26), June 28, 1965. Sway (17) has developed a fraction packed analytical columns, condenser (4) Elliev, Y. E., Devyatykh, G. G., collector for use in vacuum fractiona- holdup is generally very slight, and Dozorov, 5‘. A., Zh. Fiz. Khim. 37,2179 tion. A piston pump ejects the collected should therefore have only a slight (1963). fractions through a relief valve into effect on rate of equilibration. (5) Ellis, S. R. AI., Porter, XI. C., Jones, K. E., Trans. Znst. Chem. Engrs. (Lon- suitable storage vessels at atmospheric Haring and Knol (7) discuss the don) 41, 212 (1963). pressure. Williams (19) has described influence of reflux ratio on the separating (6) Fair, J. R., Ind. Eng. Chem. 56 (lo), an all-glass fraction cutter with a self- effect in a fractionating column. They October 1964. lubricated valve. This unit is suitable distinguish between separating per- (7).. Haring, H. G., Knol, H. W., Rec. Trav. formance as functioning at partial Chim. 83; 645 (1964). for vacuum operation at temperatures (8) Haughton, C. O., Brit. Chem. Eng. 10, as high as 300’ C. reflux and separating power as function- 237 (1965). Little has been added during the past ing under total reflux. Elliev et al. (4) (9) -James, A. T., Martin, A. J. P., Analyst two years to the fund of knowledge deal- developed equations to establish a 77, 915 (1952). (10) &fair,B. J.,Willingham, C. B., J. Res ing with analytical distillation; not similar relationship. Xatl. Bur. Std. 22, 519 (1939). only has distillation equipment been of Finally, a somewhat optimistic role (11) Martin, A. J. P., Synge, L. M., Bao- minor interest, but operating proce- is predicted for distillation by Wilcox chem. J. (London)35, 1358 (1941). dures and improved techniques have (18). He devised special equations to (12) Morton, F., King, P. J., McLaughlin, A., Trans. Inst. Chem. Engrs. (London) been scarcely considered. Pichler and establish conditions for preparing ultra- 42 (8) T-285-T-295, T-296-T-304, NO. Fetterer (13) have confirmed earlier pure materials. These equations are 182 (1964). findings on the consonance between simpler than those for the usual batch (13) Pichler, H., Fetterer, E., Erdoel continuous and intermittent with- distillation, since the quantity of the Kohle 17, 97 (1964). drawal of distillate from a fractionating second component is assumed to be (14) Romani, J. M., Genie Chim. 90, 29 (1963’l\____ column. very small. This approach may be (15) Tiong, Sie Sevan, Waterman, H. I., Barker, Jenson, and Rustin (1) devel- helpful also for the ultimate recovery in Znsenieur (Utrecht) 72. Ch. 71-82 oped equations for predicting the rate of purest form of compounds separated by (1960). (16) Sperando, A., Richard, M., Huber, approach to equilibrium of a batch dis- preparative GLC where some con- M., Chem. Zngr.-Tech. 37, 322 (1965). tillation column. The equations were tamination by eluted fixed phase from (17) Van Sway, &I., Rev. Sci. Znst?. 35, solved by an analog computer. .4c- the GLC column has occurred. 164 (1964). curacy of the equations was tested with (18) Wilcox, W. R., Ind. Eng. Chem. 3, a methylcyclohexane-toluene test mix- LITERATURE CITED Fundamentals 81 (1964). ture in a 4.5-inch diameter bubble tray (19) Williams, F. E., “Techniques of (1) Barker, P. E., Jenson, V. G., Rustin, A., Organic Chemistry,” Vol. IV, 2nd ed., column. For the column studied, J. Znst. Petrol. 49 (478), 316-27 (1963). Wiley, New York (1965). condenser holdup was the most (2) Chanda, SI., Ghosh, K. K., Chem. Age (20) Ziolkowski, Z., Filip, S., Kawaha, important variable affecting the rate of (India)14, 517 (1963). Z., Przemysl Chem. 42, 512 (1963). Electroanalysis and Coulometric Analysis Allen 1. Bard, Department of Chemistry, The University of Texas, Austin, Texas 7871 2 HIS PAPER surveys the literature Table 7 gives the supporting electrolytes detection technique, so valuable in Tand developments during 1964 and for many coulometric titrations. coulometric titrations. An English through December 1965, although The new edition of “Polarographic translation of the book of Abresch papers published before 1964 which have Techniques” by Meites (179) contains and Claassen on ‘[Coulometric Analysis” not appeared in previous reviews in this sections on controlled potential (1) has appeared, as well as a new book series have also been included. electrolysis and coulometry and coulo- on this subject by Patriarche (207). metric titrations. The description of the Several review articles on electro- BOOKS AND REVIEW ARTICLES techniques involved in controlled analysis have been published. Szabad- A number of books dealing with potential electrolysis measurements and vary’s (264) paper gives brief biog- electroanalytical chemistry and electro- the discussion of perturbing effects in raphies for many of the pioneers and chemistry have appeared since the last coulometry are of special interest. An research workers in the field of electro- review. Volume 2a of “Comprehensive introductory book on electroanalytical analysis. Foreign language reviews of Analytical Chemistry” (296) deals with methods has also appeared (161). electroanalysis (191, 198) (Japanese), electrical methods and contains one Other books dealing with electro- electrogravimetric analysis ($1) chapter on an introduction to electro- chemistry which may be of interest to (Dutch), coulometric analysis (5, 182) chemical analysis and another on workers in the field include “The Ency- (Russian), and controlled potential electrodeposition by A. J. Lindsey. clopedia of Electrochemistry” (105), coulometry (257) (French) have also Purdy’s book, “Electroanalytical Conway’s “Electrode Processes” (53), appeared. Methods in Biochemistry” (218) con- Delahay’s “Double Layer and Electrode , NEW TECHNIQUES tains an elementary discussion of con- Kinetics” (62), and Zuman’s “Organic trolled potential coulometry and coulo- Polarographic Analysis” (SIO), which Flow Electrolytic Methods. In- metric titrations, as well as other electro- discuss the fundamental principles and terest has been revived in techniques analytical methods; Table 6 in this electrode reactions which form the based on electrolysis of flowing streams book lists a number of coulometric basis of electroanalytical techniques. of solutions for analysis or separa- titrations that have been performed, the The recent book, “hperometric tions. Sporadic reports in the past limits of concentration for the deter- Titrations,” by Stock (259) contains have been concerned with attempts at minations, and their accuracy; and numerous examples of this end point carrying out the electrolysis of a flowing 88 R ANALYTICAL CHEMISTRY solution on an electrode contained in a in the flowing solution can then be cal- showed that O2 can be separated from column-a marriage of chromatographic culated by equating the current, i, air and other gas mixtures using cata- and electrodeposition techniques- with the rate of flow of solution into the lytic porous oxygen electrodes and the but recent interest in this method, de- column, G, yielding electrolytes and membranes usually scribed as electrolytic chromatography employed in fuel cells. (84,85), potentiostatic chromatography c=-i Thin Layer Electrolysis. Anson (228),or partition chromatography by nFG and co-workers (46, 47, 113, 114) intro- electrodeposition (24, 25) , may signal a duced the technique of electrolyses more widespread application of the where n is the number of electrons trans- carried out in thin layers (0.02 to 0.1 technique. ferred in the electrode reaction and F is mm.) of solution. Christensen and An- For an electrodeposition on a mercury the faraday. son (46) showed that for electrolysis at electrode, the ratio of the concentration Eckfeldt and Shaffer (75) used this a constant current, i, at an electrode of of nietal in the mercury, C,, and in the technique to determine oxygen (and area A, and a cell thickness, I, the solution, Cm+n, is governed by the suggested the term “constant potential following equation holds : usual type of partition or distribution derivative coulometry” for the method), (Equation 1) : nFAlCO l2 employing a flow cell with silver spheres r=--- (3) as the working electrode. The obvious i 30 _-C, -D=- advantage of this method of analysis C, +n compared to galvanic analyzers with for l2 < TO, where D is the diffusion smaller electrodes is that calibration is coefficient of electroactive species, Co is unnecessary (no unknown calibration its concentration, and T is the transition terms appear in Equation 2) and the time. Under conditions where the term except that the distribution coeffi- current is independent of changes in P/3D is negligible, Equation 3 becomes cient, D, is a function of potential, temperature, electrode surface, solution Q = nFA1C” and, if electrochemical equilibrium is viscosity, etc. Oxygen at the 1-p.p.m. (4) attained, can be calculated by the level was determined by this technique the usual coulometric analysis equatioii, Nernst equation, as shown in Equation with a relative error within 1%; at the which holds for both constant current 1. For depositions on a solid electrode, 0.01-p.p.m. level, the error was - 10%. or constant potential analysis. The a similar equation usually holds in Shropshire (245) used a fritted glass advantage of this technique, as with which C, may be taken as 1 for amounts sparger coated with silver or platinum other electrolytic techniques involving of C, greater than a monolayer.
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