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Fischer Veriag, Stuttgart, 1976. (330) Thylstrup, A., et al., Scand. J . Dent Res., 84, 243 (1976). (331) Tomkins, D.W., Coleman, D. S., Powder Metall., 19, 53 (1976) (332) Troyer, F., SfahiEisen, 9, 50 (1975). (333) Tyler, G. A., Thompson, B. J., Opt. Acta, 23, 685 (1976). (334) Tynan, E. E., von Gutfeid, R. J., Rev. Sci. Instrum., 46, 569 (1975). (335) Ueda, R., Mullin, J. B., "Crystal Growth and Characterization Proc, 2nd Int. Spring School on Crystal Growth, Japan 1974", North-Holland, New York. N.Y., 1974. (336) Uhlig, M., Meiliand Texfilber. Int., 56, 578 (1975). (337) Underwood, E. E., Microscope, 24, 45 (1976). (338) Underwood, E. E., Microscope, 24, 49 (1976). (339) van der Kroon, P. H. W., Kicken, J., Microsc. Acta, 77, 445 (1976). (340) Vanderploeg, M., et al., Histochem. J . , 8. 201 (1976). (341) van Toorn, P., Ferwerda. H. A., Opt. Acta, 23, 457 (1976). (342) Van Toorn, P., Ferwerda, H. A,, Opt. Acta, 23, 469 (1976). (343) Verma, R. S.,Dosik, H., J . Microsc. (Oxford), 108, 339 (1976). (344) Veselsky, J. C., Wolfl, A,, Anal. Chim. Acta, 85, 135 (1976). (345) Vialli, D. M., Zanotti, L., Mikroskopie, 32, 305 (1976). (346) Wadaka, S., Sato, T., J . Opt. SOC.Am., 65, 354 (1975). (347) Wade, G., "Acoustic Imagining with Cameras, Microscopes, Phased Arrays and Holographic Systems", Plenum, New York, N.Y., 1976. (348) Walter, F., Textilveredlung, 10, 168 (1975). (349) Walter, F., Schmitt, W., Leitz, Inform., V I , 248 (1976). (350) Wasmund, H., Leifz Inform., V I , 217 (1976). (351) Watts, R. K., "Point Defects in Crystals", Wiley-Interscience, New York, N.Y., 1977. (352) Webb, J., et al., Anal. Chim. Acta, 81, 143 (1976). (353) Wegner, M. W., Christie, J. M., Confrib. Mineral. Petrol., 59, 131 (1976). (354) Weibel, E. R., Beitr. Pathol., 155, 1 (1975). (355) Weibel, E. R., Losa, G., Bolender, R. P., J , Microsc. (Oxford), 107, 255 (1976). (356) Weidmann, G. W., Doll, W., Colloid Polym. Sci., 254, 205 (1976). (357) Weiss, C. H., J . B i d . Photogr. Assoc.. 44, 86 (1976). (358) Welber, B., Rev. Sci. Instrum., 47, 183 (1976). (359) Wells, A. F., "Three Dimensional Nets and Polyhedra", Wiley Interscience. New Vnrk ,._.. - , . ~ , N V ., 1P77 . (360) White, A. D., Appl. Opt., 16, 549 (1977). (361) Whitehouse, W. J., J . Microsc. (Oxford), 107, 183 (1976). (362) Whitman. R. L.. "MultidisciDlinarv Microscoov". Vol. 104 of Proc. of the Sbc. of Photo-Optical 1nstrumentat;on Engineer;, Bellingham, Washington, 1977. (363) Whitman, V. L., Wills, W. F., Jr., Microscope, 25. 1 (1977). (364) Williams, D. F., Adams, D., J . Ciin. Pathoi., 29, 657 (1976). (365) Wilson, Michael B., "The Science and Art of Basic Microscopy", Am. SOC.for Medical Technology, Bellaire, Texas 1976. (366) Wolf, B., Microsc. Acta, 7 8 , 300 (1976). (367) Wong, J., et al., Thin SolidFiims, 33, 341 (1976). (368) Yamamoto, K., Ichioka, Y., Suzuki. T., Opt. Acta, 23, 965, (1976). (369) Yamamoto, K., Ichioka, Y., Suzuki, T., Opt. Acta, 23, 987 (1976). (370) Zemskov, K. L., et al., Kvantovaya Elekfron-(Moscow),3, 35 (1976). (371) Zlegler, L., Schuster, P., Ber. Dfsch. Kerarn. Ges., 5 3 , 257 (1976). (372) Zotikov, A. A., Polyakov, Y. S., Microsc. Acta, 79, 415 (1977).
(287) Schumacher, 8. W., Optik. 45, 355 (1976). (288) Seidl, W., Stain Techno/.,51. 311 (1976). (289) Seifert, H. W., Mikrokosmos, 65, 312 (1976). (290) Selden, M. G., Jr., Microscope, 24, 213 (1976). (291) Selden, M. G., Jr., Microscope, 25, 127 (1977). (292) Shapiro. S.. J . Bioi. Photogr. Assoc.. 44, 29 (1976). (293) Sheftal, N. N., "Growth of Crystals, Vol. 10 (Trans. by J. E. S. Bradley)", Plenum Press, New York, N.Y., 1976. (294) Shelley, David, "Manual of Optical Mineralogy", Elsevier, New York, N.Y., 1975. (295) Sheppard, C. J. R., Optik, 48, 329 (1977). (296) Sheppard, C. J. R., Choudhury, A,, Opt. Acta, 24, 1051 (1977). (297) Short, P. H., Wood Sci., 9, 37 (1976). (298) Singh, J., Singh, K., Opt. Acta, 23, 161 (1976). (299) Singh, K., Singh, J., Microsc. Acta. 78, 149 (1978). (300) Singh. R. N., Opt. Acta, 23, 597 (1976). (301) Sivaram, B. M., et al., Indian J . Phys., 50, 357 (1976). (302) Stater, J., Ralph, B., Microscope, 24, 25 (1976). (303) Slatkine, T., Zeiss Inform., 22, 6 (1976). (304) Smith, A. H. V., J , Microsc. (Oxford), 106, 325 (1976). (305) Smolle, J., Mikrokosmos, 65, 189 (1976). (306) Smutzer, G., Berlin, J., Trans. A m . Microsc. SOC.,95, 109 (1976). (307) Sobott, R. J. G., Mikrokosmos, 65, 281 (1976). (308) Soltzberg. L. J., Athearn. M., Levy, J. E., Simpson. E.L., Appl. Opt., 16, 3206 (1977). (309 Sorgenfrey, W., Mikrokosmos, 65, 179 (1976). (310) Southworth, H. N., "Introduction to Modern Microscopy", Wykeham Publications, (London) Ltd, London, 1975. (31 1) Stach, E., et al., "Stach's Textbook of Coal Petrology, 2nd rev. ed.", Gebr. Borntraeger. Berlin-Stuttgart, 1975. (312) Steele, J. H., Ifju, G., Johnson, J. A,, J . Microsc. (Oxford), 107, 297 (1976). (313) Stewart, W. C., J . Opt. SOC.A m . , 6 6 , 813 (1976). (314) Stroeven, P., J . Microsc. (Oxford).,107, 313 (1976). (315) Takamori, T., Tomazawa, M., J . A m . Cerarn. SOC.,59, 377 (1976). (316) Tarkian, M., et al., Miner. Mag., 40, 97 (1975). (317) Taylor, C. A,, Harburn, G.. Welbemy, T. R., "An Atlas of Optical Transforms", G. Bell & Sons Ltd., London, 1976. (318) Taylor, D. L., et al., Exp. CeiiRes., 101, 127 (1976). (319) Taylor, D. L., "Motile Models of Amoeboid Movement" in "Cell Motility", R. Goldman, T. Pollard, and J. Rosenbaum, Ed., Cold Spring Harbor Press, Cold Spring Harbor. N.Y., 1976, p 797. (320) Taylor, D. L., J . Ceii. B i d . 68. 497 (1976). (321) Taylor, D. L , Rhodes, J. A., Hammond, S. A., J. Cell. Biol., 70, 123 (1976). (322) Taylor, D. L., Zeh, R. M., J . Microsc. (Oxford), 108, 251 (1976). (323) Taylor, M. E., J . Biol. Photogr. Assoc., 44, 26 (1976). (324) Teetsov, A. S., Microscope, 25, 103 (1977). (325) Teicher, G., Bild Ton, 29, 55 (1976). (326) Terrier, P., Ann Mines, 182, 35 (1976). (327) Thaier, H., Mikrokosrnos, 66, 158 (1977). (328) Thaler, H., Mikrokosrnos, 66, 190 (1977). (329) Thiessen, G., Thiessen, H., "Microspectrophotometric Cell Analysis (Vol. 9INo. 4 of the Series "Progress in Histochemistry and Cytochemistry")", Gustav
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Gas Chromatography Stuart P. Cram * Varian Instrument Division, 2700 Mitchell Drive, Walnut Creek, California 94598
Terence H. Risby Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802
INTRODUCTIOK
which had to be searched and reviewed for this paper was larger than for any other biennium, and is reasonably comprehensive in that two different computer library searches, the primary chromatographic literature, and the Preston Technical Abstracts (GC) were used to locate the references cited in this work. It is clear that the ratio of GC applications to fundamental new developments is rapidly increasing. This can be explained in terms of the increasing number of new scientific disciplines and laboratories employing the technique, number and type of analysis which require the resolving power and detection limits of GC, and the maturing of the technique. In the 1977 Directory of Members of the American Chemical Society's Division of Analytical Chemistry ( 4 A ) , more than 21 % of the members listed one of their job spe-
This review surveys the fundamental developments in the field of gas chromatography (GC) during the biennium since the publication of the last review in this series (2A) and covers the years 1976-77. Earlier articles of particular significance appearing in foreign journals and the patent literature which were not available a t the time of the previous review are also included. This review does not represent a comprehensive bibliography or discussion of the literature in GC. Rather. the authors have attempted to be very critical in selecting only the most fundamental developments in theory, methodology, and instrumentation; a few applications are cited only insofar as they advance the state-of-the-art or have particular current relevance to new developments. The number of publications 0003-2700/78/0350-213R$05.00/0
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cialties as “gas chromatography”-second only to those listing their specialty as “general analytical“ (23 7 ~ )When . these numbers are compared to the activity level in other analytical specialties such as UV-visible absorption spectroscopl (1570), high performance liquid chromatography (12 % ’ ), and water pollution analysis ( l o % ) , it may be readily seen why a critical rather than comprehensive literature review was required. Listings of terms, definitions, relationships, and nomenclature for GC have been developed by the IUPAC Committee on Chromatography (1972) and have been published by the American Society for Testing and Materials as standard E 355-77 ( I A ) . Other current sources of definitions and nomenclature have also been published recently ( 3 4 . Therefore a partial listing will not be attempted here because (a) more comprehensive sources are available, and (b) the dichotomy among the choice of symbols used by European and American chromatographers does not need to be propagated further.
BOOKS AND REVIEWS A number of books dealing exclusively with the technique and the applications of gas chromatography have been published since the preparation of the last review in this series. Also reviews on the applications of gas chromatography have increased substantially and most journals have published reviews which have discussed the application of gas chromatography to particular samples. h’hile these reviews are useful to specialists in these areas, they fall outside of the scope of this fundamental review. Therefore, in the interests of brevity. this section will not be exhaustive but will attempt t o discuss those publications which deal with the general technique of gas chromatography. In our aside, it is interesting t o note t h a t this biennium has seen the publication of a number of books on the topic of liquid chromatography which is an area requiring authoritative texts. Ettre (20B) published a review which discussed the development of gas chromatography, second generation gas chromatography, special techniques in gas chromatography, and the future of gas chromatography. Most of the texts which have discussed gas chromatography in general are not published in the English language and these foreign texts are as follows: in Russian, “Guide for Gas Chromatography” (41B), “Handbook of Gas Chromatography” (42%) by Kotsev; “Manual for Gas Chromatography“ by Vyakhirev and Shushunova, “Chromatography, Volume l”, is an unedited book which includes review papers by Soviet specialists in chromatography (68B);“Course in Gas Chromatography” by Golbert and Vigdergauz (28B);in German, the 3rd edition of “Gas Chromatography: Principles, Application. Methods” by Jentzsch (34B) has appeared; in Spanish, “Fundamental5 of Gas Chromatography” by Storch de Garcia (63R);and in Bulgarian, “Gas Chromatography” by Dimitrov and Petsev (16B). These publications show that there is sufficient interest in this field in non-English speaking countries to \$arrant the publication of texts in their native language. T h e latest volume in the ”Advances in Chromatography” has appeared and includes chapters on “Chemically Bonded-Phases in Both Gas and Liquid Chromatography”. “Physicochemical Measurements Using Chromatograph) “, “Gas-Liquid Chromatography in Drug Analysis“, “The Investigations of Complex Association by Gas Chromatography and Related Chromatographic and Electrophoretic Methods”, and “Gas- Liquid-Solid Chromatography” (27B). Perhaps the time has come for the series to consider revision of its publication policy since by the time the authors’ contributions are in print, the text is often already outdated. In the area of columns and columns packing materials the following publications have appeared: texts on “Stationary Phases in Gas Chromatography” by Baiulescu (2%): “Solid Supports in Gas Chromatography” by Benezkin, Pakhomov. and Sakodynskii ( 7 B ) ;reviews on column development and technology in gas chromatography (30B):the use of various vapors as mobile phases in gas chromatography (57B);and on processes In chromatographic columns (36B). Kaiser (35B) and Ettre (19B)published texts on the use of capillary columns in gas chromatography although both books are in German. Two reviews (60R, 74R) discussed this subject and it is expected that by the time the next review in this series appears t h a t capillary columns will receive even greater attention. Berezkin and Fateyeva (5B)and Umbreit (67B)discussed the various parameters which affect the precision of retention data,
and Weiner (71B) discussed the mathematical basis of factor analysis and how it can be used to solve chromatographic problems. Quantitative analysis (40H,X R ) and detectors (11R.X H , 61B) were discussed in various texts although three of them (iiB, 40B, 56B) are written in Russian. Two bvoks in Polish appeared which deal with t h e use of gas chromatography t ( J study adsorption and catalysis (d4B)and to measure various physicochemical parameters (70R). In the area of the applications of gas chromatography to chemical analysis various reports have appeared: Ma et al. (43B) authored a text entitled “Organic Functional Group Analysis by Gas Chromatography”; Peyron ( 5 r j H ) reviewed reaction gas chromatography for the identification of organic compounds; Kashutina et al. (37R) reviewed the silylation procedures used to prepare derivatives of various functional groups suitable for analysis by gas chromatography; and Yevtushenko e t al. (72B) reviewed the use of gas chromatography to determine nitrogen in organic compounds. The to label molecules of interest to allow uses of ‘Hand mechanistic studies to be made in various fields, was reviewed by Blake et al. (9B)and Matucha and Smolkova (46R). The former review was concerned with the use of GC/MS systems whereas the latter reviewed the use of mass spectrometry and various radiochemical detectors. It can be expected that this area will expand even more rapidly in the future, especially with the current interest in G C / M S and the use of stable isotopes. Examples of reports which have reviewed the use of gas chromatography for the analysis of particular sample, are as water (23R, 32R); follows: environmental (29B);air (58B); surface coatings (31B);paints (52B);surfactants (67H);inorganics ( I B , 276’);petroleum (6B,2n‘B);pesticides (IOB,12B. 18B, 22B, 47B, 5 I B , 66B);herbicides (73R);fumigants ( 3 B ) ; insect sex pheromones (8B); foods (14R, 15B, 24B, 38R, 44B, 45B, 59B);polymers and rubbers (4B, 13R, 4YB,5YH. 69H): and biological and clinical (ZB, 33B, 48B, 62R, 64B, 75B, 76”j samples. The “Gas Chromatography Literature Abstracts and Index” (26B) and the “Gas and Liquid Chromatography Abstracts“ (39B) continue to be published periodically and the advent of commercial computerized data systems allows researchers to review the extensive applications of gas chromatography very easily.
C 0 LU MN S Column Theory and Techniques. A detailed treatmcnt of packed columns and the steady-state equations for solute transport in such columns showed how non-uniformities in the packing material make chromatographic peaks more asymmetrical (71C). T h e material and momentum halance equations were solved for the case of single solute a t finite concentration, mobile phase velocity dpperidence on the compound, and finite pressure drop across the column (49C‘). Valentin and Guiochon (67C, 69C1 developed a niodel o f quasi-ideal chromatography to study the effects of large solute concentrations on the deformativn and broadening of GC peaks. T h e model was expanded to include the effects of pressure, pressure gradients, and temperature (t;8C, 6 9 0 . The propagation of large solute band widths was found t o g1~7e Poisson distributions experimentally, as in the case of preparative scale GC (39C). A matheniatical treatment Oi’ nonlinear chromatography linearized the material halance equations according to the first order perturbation theory and from the solution. developed explicit forms for reversible and irreversible chemical changes of solutes i r i the column t 77C’j. From the theory of nonequilibrium stopped-flow GC. the rate constants for desorption and the partition coefhcients a t t ~ o kinds of reactive sites. enthalpies and entropies of adsorption. and the ideal retention times in noneyuilibrium chromatography could be determined (3K‘).The theor)), apparatti-, specifications, and results of the step and pzilsr: method wert developed for the determination of gas -liquid and gas solid equilibrium isotherms (65C, 66C). Because statistical moments of chromatographic peak profiles contain macroscopic information about the kinetics of on-column interactions and mass transpurt phenomena, they have become increasingly important. Simplified equations for the skew and excess were derived on the basis of a hypothetical model in which complexation of the solute
A N A L Y T I C A L CHEMISTRY, VOL 50, NO. 5, APRIL 1978 Stuart P. Cram is Manager of Gas Chromatography Research at Varian Aerograph Walnut Creek, Calif He received his B S from Kansas State Teachers College in 1957, his M S from the Universrty of Wisconsin in 1963, and his Ph D from the University of Illinois in 1966 In 1966 Dr Cram joined the faculty of the University of Florida and later was Chief of the Chromatographic Analysis Section at the National Bureau of Standards before accepting his present position in 1974 He is a memoer of the Editorial Advisory Board of the Journal of Chromatographic Scfence, winner of the Stephen Dal Nogare Chromatography Award, the Distinguished Alumni Award from Kansas State Teachers College, and is a member of the Executive Committee of ASTM E-19 Committee on Gas Chromatography Dr Cram was an invited lecturer at the Purdue University short course on Digital Computers in Chemical Instrumentation' from 1971-74, and is an instructor in the ACS short courses on Modern Techniques in Gas Chromatograph , and 'Capillary Gas Chromatography In 1971 he presented a series of lectures on gas chromatography in Indla under the auspices of NSF His publications and research interests are in the areas of gas and liquid chromatography, mass spectrometry laboratory computers and the development of analytical instrumentation He has authored or cc-authored more than 50 technical publications in these areas He is a member of the American Chemical Society, American Society for Mass Spectrometry, Society for Applied Spectroscopy, Sigma Pi Sigma, Alpha Chi Sigma, and Lambda Delta Lambda
Terence H. Risby is an assistant professor of chemistry and a faculty member of the Center for Air Environment Studies at The Pennsyhank State University. He graduated with a Ph.D. in chemistry from Imperial College of Science and Technology, London University, in 1970. During the academic year 1970-7 1, he was the recipient of a European fellowship from the Royal Society of London at the University of Madrid. His next position, as a research associate, was held at the University of North Carolina at Chapel Hill, and in 1972 he joined The Pennsylvania State University. Dr. Risby's research interests include the significance of metals in biological and environmental systems, elecVica discharges. thermodynamics of gas-liqud chromatography, trace analysis by chemical ionization mass spectrometry, and the use of linear programmed thermal degradation-mass spectrometry to characterize macromolecules. He is on the editorial board of the Journal of Chromatographic Science and is a Chartered Chemist and an Associate of the Royal Institute of Chemistry. He is also a member of the Royal Institution, Chemical Society (London), American Chemical Society, American Society for Mass Spectrometry, Society for Applied Spectroscopy. Chromatography Discussion Group (London), Sigma Xi, and the American Microchemical Society.
molecules with the stationary phase was included (40C). Equations for the first to the fourth cumulant in nonlinear ideal chromatography and for the first moment in nonlinear nonideal chromatography were derived using perturbation theory (76C). Statistical moments were solved for the cases of reaction (75C), nonlinear frontal elution, and elution chromatography (27C). Moment analysis was used to develop a model for instrumental band broadening contributions to capillary G C (RC), and a new method of extracting band broadening parameters from a skewed peak was derived from a n exponentially modified Gaussian peak model (79C). Similar peak models were used to examine the effects of dead volume and flow rate on chromatographic peak shapes ( S I C ) . T h e uncertainty in t h e determination of the statistical moments due to baseline noise was derived, and the influence of all kinds of stationary noise occurring in chromatography was calculated u p to and including the third moment (62C). Methods were published by Lange and Shafranski (32C) for the dptermination of chromatographic peak asymmetry, and by Petitclerc and Guiochon (52C) for the higher order moments of an asymmetrical peak. The latter paper is the first known effort to attempt t h e fourth moment, and illustrates the level of attention and detail required to accurately calculate the contribution of the peak tail to the moments before trying to determine kinetic parameters, for example. Deconvolution of experimental peak profiles n i t h regard to the higher moments showed that the extra column effects due to diffusion, sorption of the solute in connecting tubing, and the
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input peak profile, could be treated by means of the moment vector method (74C). The concept of efficiency in chromatography, expressed in forms other than the plate height or plate number, were treated from a number of points of view (12C, I 5 C , 16C). Contributions to the van Deemter plate height which were examined included: the "B" term. where it was proposed that the need for the rnultipath term, y , could be avoided by an alternative model (IOC); a study of the multipath term showing it is not always flow dependent ( 3 C ) ;the effects of column length by taking into consideration the kinetics of diffusion and column pressure drop (48C);and mass transfer terms, correcting for gas compressibility, in porous layer open tubular columns (22C). In a study of zone dispersion in packings of impermeable spheres, Cluff and Hawkes ( 7 C ) concluded that the reduced plate height and reduced velocity do not adequately represent the effects of column and particle diameters. An equation giving the number of theoretical plates for frontal chromatography was derived on the basis of a semicontinuous column model (57C). Another paper treated the composition of the elution zones in frontal chromatography according to the flow velocities in the zones (47C). An excellent review described the contributions of diffusion and convection on the dispersion of solutes by fluid flow through packed beds ( I I C ) . Gas phase propagation was studied in a column whose cross section varied inversely to the square root of the length (20C), and solute concentration profiles were monitored in a Zeolite column by proton NMR to study transport processes (29C). T h e various types of intermolecular interactions which contribute to solute retention in a GC column were correlated and interpreted in terms of data on the polarizability. dipole moment, and heats of solution for several solute-solvent pairs (13C). Four different mechanisms of separation were identified by experiments showing the dependence of the relative retention and partition coefficient on the amount of stationary phase a t various temperatures and the specific retention volume as a function of temperature ( 4 2 C ) . Factor analysis of solute-stationary phase interactions showed that only two factors had to be introduced to account for 9 2 % of the variance, the main factor (85%) being the polarity of the stationary phase. The maps obtained for solutes and liquid phases are readily usable for selecting a potentially effective stationary phase for a given separation problem (4C). Factor analysis was also applied to determine the principal solute parameters for 18 ethers on 25 stationary phases (59C). Laub et al. (32C, 33C, 36C, 37C) were able to predict and optimize the retention behavior and the separation of complex mixtures with binary stationary phases on the basis of diachoric solutions. This work is fundamentally sound and is particularly impressive and convincing in that a 40-component mixture mas virtually completely separated by the computer-based calculations. This work originated through a series of studies investigating solution and complexation behavior in mixed stationary phase systems (34C, 35C, 53C. 54C). Parcher and Westlake (5OC) introduced the concept of "polarity programming" by using a binary liquid phase where the polarity is changed by controlling the partial pressure of a condensable component in the carrier gas. Experiences with mixed phase columns (41C) showed that the retention index of benzene could be used to measure the extent of liquid phase mixing ( I 9 C ) . The measurement of the association constants of organic molecular complexes was used to determine the effective concentration of a polar stationary phase in mixed systems (9C). Molera e t al. (44C) continued their work on developing computer programs to calculate the optimum mixed phase system, minimum column length, and retention temperatures for programmed temperature analysis. T h e adsorption properties (55C) and interaction factors (64C) on mixed stationary phase columns were calculated from mechanistic studies. Binary mixed phase columns were used successfully for the separation of 15 chlorinated insecticides (63C, 78C). The problem of accurately determining the dead time was discussed and several calculation methods were compared (22C). Graphical solutions ( 7 0 0 and iterative calculation methods (14C) were proposed. From solubility data for methane in stationary phases of different polarity, at different temperatures and pressures, errors in t h e dead volume may
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be estimated (17C). T o overcome some of the inherent problems in calculating or measuring the dead time, accurate calculation of adjusted retention times was proposed (60C). Accurate, precise, and direct measurement of retention volumes used an on-line minicomputer to periodically monitor the column flow, pressure, and temperature (2512). Equations for the retention volume considered nonlinear isotherms, the solute solubility in adsorbed liquid layers (28C), and the amount of stationary phase (6C). Obviously good retention data is essential when trying to predict resolution, and thereby the selection of a column, from Kovats retention indices (73C). T h e work of Huber, Lauer, and Poppe (24C, 38C) will have a long term impact on increasing the efficiency of packed column separations. They demonstrated that small diameter column (0.75-1.5 mm), packed with small diameter particles (230 fim),operated a t inlet pressures to 50 atm, could generate more than 10000 plates/meter. Methods of packing the micropacked columns (0.6-0.8 m m i d . ) for columns up to 15 m long were developed by Rijkes, Cramers, and Bocek (56C). The advantage of these columns is higher permeability so that they can be operated at moderate pressures. Fast analysis times (26C) and multicomponent separations on columns a t pressures u p to 10 a t m were demonstrated (61C). Other developments in column techniques took the form of chromadistillation ( S I C ) , chromareaography in columns with semi-permeable walls (28C),gradient chromatography (46C), a “double pulse” techni ue for measuring the rates of oncolumn reactions induce2 by the overlap of two solute zones with different elution velocities (5SC), and combined partition-chromatographic methods ( 1C, 2C). The properties of packed columns with mono- and bi-molecular layers of stationary phase were characterized in terms of the net retention volume per gram of column packing (72C). An improved device for column packing was reported to give reproducible, high efficiency columns (43C),although for some analyses, an attractive alternative is the in-situ formation of polymer columns such as open pore polyurethane (5C). Column oven temperature and carrier gas flow rates were varied simultaneously in a sequential simplex optimization of a chromatographic separation of isomeric octane mixtures to demonstrate the feasibility of the method (45C). The simplex optimization method was also used to determine the GC conditions which would give an acceptable resolution in minimal time (23C). Liquid Phases. The work of Pesek and Daniels ( 6 1 0 ) on the mechanism for retention in chemically bonded stationary phases compared retention behavior on conventionally coated and chemically bonded columns. A similar comparison with Carbowax 20M showed marked differences between the two coating methods in terms of their chromatographic and thermodynamic behavior (520). Current information on chemically bonded stationary phases for GC and HPLC was reviewed and a large number of applications were summarized (650). T h e surface heterogeneity and sorption properties of bonded phases on glass beads were also investigated ( 1 9 0 ) . Sebestian and Halasz ( 6 9 0 ) bonded monomeric stationary phases with Si-C bonds for GC and HPLC. Thermodynamic data showed that nonpolar solutes interact with nonpolar bonded stationary phases primarily by a n adsorption mechanism rather than solvation with the bonded material behaving as a liquid (620). The mechanism for the separation of enantiomeric amino acid derivatives on chiral stationary phases was found to be predominantly due to the formation of hydrogen bond complexes between the stationary phase and t h e solutes (750). Russian workers characterized stationary phases by concepts such as “comparative statistic polarity” and “characteristic selectivity” ( 7 0 0 ) . A polarity scale for GC stationary phases based on the work of Rohrschneider and McReynolds was derived and 161 phases were tabulated by “retention polarities” ( 7 7 0 ) . Polarity factors, based on Rohrschneider’s method, for a large series of homologous alkyl esters of carboxylic acids ( 5 0 ) and the influence of the stationary phase on retention increments of homologous and isomeric unsaturated esters ( 4 0 ) were reported. T h e principal methods of evaluating the polarity of t h e stationary phase were reviewed and the discrepancies between polarity scales, obtained by different methods, were discussed ( 2 0 ) . Comparing measures of stationary phase polarity was most frequently directed to the question of the choice of column
materials. It is significant that a comparison of seven different methods of calculation used to measure the polarity of liquid phases showed the resulting polarity values to be remarkably similar (500). The nearest neighbor technique was developed as a means of indicating stationary phase selectivity and allows the effect of phase substitution to be calculated (2.50). Computer file search methods were used for column selection even though the data files were limited in the number of solutes and stationary phases ( 4 8 0 ) . Both numerical taxonomy and information theory were studied for their general applicability to selecting phases, and then used to classify 225 liquid phases ( 1 5 0 , 1 7 0 ) . Burns and Hawkes (110) derived and tabulated indices of dispersion, polarity, basicity, and acidity for “preferred” stationary phases and illustrated their use in choosing an appropriate stationary phase. It is hoped that the “Hawkes” committee report (280)regarding preferred stationary phases will be only the first of such actions in this direction and that follow-on studies and programs will be undertaken by appropriate committees, agencies, and organizations. A first set of preferred stationary phases has been established on the basis of the Rohrschneider constants and it was pointed out that intermediate polarities should be realized by using mixed phases ( 8 8 0 ) . Other methods for selecting stationary phases are based on literature references ( 7 9 0 ) ,a linear equation relating GC resolution to Kovats pattern recognition (which reduced retention indices (910), the set of 226 liquid phases t o 16) (9201, and eigenvector projections (490). The latter allows the ten-dimensional data of McReynolds to be reduced to two dimensions so that it is possible to visually choose liquid phases that separate on the basis of polarity and other physical and chemical interactions. A dissenting opinion of the preferred phase concept pointed out that only two of the stationary phases of unique value for the separation of fatty acid esters were included in these lists and that was considered to be inadequate (230). A useful and rational set of criteria for stationary phase properties was given; e.g., thermal-stability given by the maximum temperature limit for a 1-mg loss of phase in 1 L of carrier gas (720). Physicochemical studies are beginning to characterize the common liquid phases extensively so that mass transport, phase selectivity, structural effects. etc., may be understood a t the macroscopic and microscopic levels in chromatographic (dynamic) systems. For example, the additivity principle was applied to the calculation of t h e enthalpic selectivity of GC stationary phases (440),electrolytes were added to stationary phases to show their influence on retention and variability of selectivity (400), and the effects of structure and structural changes of the stationary phase on the retention characteristics of solutes were investigated ( 5 8 0 , 5 9 0 ) . From a mass transfer point of view, fundamental studies included diffusion in silicone stationary phases ( 4 2 0 ) ,measurement of the coefficients of internal diffusion of stationary phases on solid supports (140),and the importance of macropores in polymer packings ( 4 6 0 ) . Fundamental studies of the chemical behavior of stationary phases and solute-solvent interactions were important in developing difficult and complex separations such as the resolution of enantiomers of (i)-oc-aminoacid derivatives on optically active liquid phases ( 7 0 ) . Variation of ring size or incorporation of a heteroatom into the ring of cyclic resolving agents changed retention times and separation factors for diastereomer and enantiomer separations (740). The behavior of oxygenated stationary phases (130),ethylenic unsaturation ( I D ) , and the physical state of the sorption site ( 7 1 0 ) in gas-liquid partition columns were studied. Retention index dispersion values for straight chain solutes were used to obtain relative functional group interaction strengths which are component independent (950). T h e retention behavior and stationary phase selectivity of liquid crystals was investigated for the solid and liquid crystalline states with monolayers and thick films ( 8 7 0 ) , and on silica gel ( 8 7 0 ) and glass beads surfaces ( 3 0 0 ) . Experimental techniques for characterizing the stationary phase in the column or on the solid support included an instrument for determining the density of stationary phases ( 4 7 0 ) ,equations for determining the loss of stationary phase from changes in the retention volume (5701, and a nondestructive temperature programmed technique for determining the amount of stationary phase in the column ( 5 4 0 , 63D).
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Destructive thermal methods were found to be quantitative for determining the amount of stationary phase in the column ( 7 8 0 ) . Similarly. chromatographic methods were given for determining the properties and phase distribution on solid support surfaces for column packings containing very small amounts of stationary phase (890).One method for preparing uniform surface depositions of liquid phases in packed columns makes it possible to predict the weight of the phase deposited by straightforward measurements during the coating process ( 6 7 0 ) . Reaction techniques were used to determine Si-Si bonds in perphenylated oligosilanes ( 3 1 0 ) . A large number of stationark phases were studied for specific separation problems. These included: the maximum operating temperatures (820)and monoterpene hydrocarbon separations ( R I D ) on polyphenylethers; di-n-butyl tetrachlorophthalate for hgdrocarhons ( 6 6 0 ) :Carbowax 20hI on CdC1, for polynuclear aromatic hydrocarbons ( 2 1 0 ) ;seven different polyols for volatiles in alcoholic beverages ( 8 3 0 ) : chiral stationary phases for diastereoisomeric amino acid esters ( 4 3 0 ) :optically active dipeptide carboranes (IOD)!methionine dipeptides ( 3 0 ) , and diamide phases ( 1 2 0 ) for amino acid enantiomers; polysiloxanes with chiral groups for amino acid enantiomers ( 1 8 0 ) ;organic colloids for highly polar compounds ( 4 1 0 , 5 1 0 ) ;the acidic fraction from an esterification product of terephthalic acid and diethylene glycol for the separation of free carboxylic acids (16'0); lanolin for hydrocarbons and oxygenated compounds ( 3 7 0 ) ; calcium complex grease for natural products and methyl esters of fatty acids ( 6 0 ) ; hydrocarbon-formaldehyde resins for polar compounds ( 3 0 0 ) ;silicones with 3-cyanoethyl groups for high boiling compounds (730);Silar lOC, Silar 9CP, SP-2340, and OV-275 for fatty acid methyl esters 1290);polar siloxanes for diacylglycerols ( 6 3 0 ) ;polyphenyl ether sulfones (Poly-S-179) for lubricants, alcohols, triglycerides, cholesteryl. and bile acid esters, and pesticides ( 6 8 0 ) ;fluorinated stationary phases for fluorocarbons ( 8 4 0 . 8 5 0 ) ; polyesters for phenols ( 7 6 0 ) : PdC1,-N-methylacetamide for hexene isomers ( 4 5 0 ) ;organophosphorous liquid phases for hydrocarbons ( 5 6 0 ) and organophosphorous compounds (930); and rubidium henzenesulfonate for isomers of phenols and pyridine bases (8D). Karasek and Hill (38L))reviewed new GC packings, their preparation, and applications. High temperature phases such as polyphenyl ethers demonstrated low bleed performance at 350-400 "C and moderate polarity ( 3 2 0 , 6 8 0 ) . Sovotny et al. (550) evaluated several columns for the analysis of the Martian surface. They included columns such as Dexsil300 with Hi-Eff 8 on Chromosorb W-HP, polymetaphenoxylene on graphitized carbon black, surface bonded polyethylene glycol on Chromosorb R, and Tenax coated with Poly-MPE. Other workers reported primary, secondary, and tertiary surface aminosilanes ( 2 4 0 ) , polytrimethyleneoxide (800), polymerization of melamine ( 2 2 0 ) ,a very nonpolar stationary phase produced by hydrogenation of an Apiezon grease (860)! and tetrachlorodecylcarbazole ( 6 4 0 ) . Liquid crystal columns were characterized in terms of measuring partition coefficients at t h e mesophase-isotropic phase transition point ( 3 9 0 ) and 3 6 0 ) . These columns have by solution thermodynamics (90), most recently found applications in the separation of polycyclic aromatic hydrocarbons (330-350, 900),other heterocyclic compounds ( 2 6 0 , 2 7 0 , 6001, and steroid epimers ( 9 4 0 ) . Solid Supports. The importance of surface homogeneity, pore geometry, and structure was pointed out for solid supports and adsorbents. Some of the problems and sqnthetic methods for inorganic (15E) and macroporous diatomaceous earth ( 7 E ) supports were given. T h e influence of the solid support on the thermodynamics of polymer-solvent interactions (16E) and the chromatographic behavior of liquid crystal stationary phases ( I I E )were investigated as well as methods for silicate solid support modification (LE), the preparation of bonded phases on diatomaceous supports (3Ei, and removal of the microporosity of glass heads ( 8 E ) . Laboratory preparation of 1--40 pm glass beads ( 2 0 E ) solid supports from Bulgarian kieselguhr ( I E , 2 E ) , and modifications of attapulgite as a support (17E) were found to be satisfactory for applications in GC and LC. polar and nonpolar hydrocarbons. and petrochemical products, respectively. A new solid support, Azinchrom-l was developed with a high degree of structural uniformity (6E). Substitution of the Xa+ and Ca2+ cations in ascangel with Li+ and Mg?+ reduced retention volumes and pave better separation efficiencies
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(22E). Three regional supports which were treated or modified for better performance included Korean diatomite ( 1 4 E ) , Belorussian glauconite (ZOE).and carpathian diatomites from Poland (24E). The physical properties of many of the Polish Polisorb supports have been extensively characterized (19E, 24E). Numerous solid supports were tested and evaluated for use in specific applications. These included Porochrom 1 diatomite for chloro-organic compounds (23E),hydrocarbons on organoclays @ E ) ,tertiary aliphatic amines on solid supports modified by Na3P04( 9 E ) ,NaCl as a support for the analysis of water pollutants (21E),and high boiling amines, imidazolines, amides, and aminonitriles (13E),cadmium chloride columns (modified with Carbowaxes) for some polynuclear hydrocarbons (12E),and modified Polisorb for the analysis of vitamin Bs reactants and intermediates (25E). Slattery et al. (18E) pointed out a potential interference in the analysis of the drug iberprofen caused by the solid support itself. Adsorption Columns. A high level of continuing interest in the properties and mechanisms of adsorbents and adsorption columns may be explained by an ever increasing number of areas of applications, on porous polymers and graphitized carbon blacks, and by fundamental studies of the basic sorption-desorption processes. Adsorption effects on solid support surfaces and/or a t stationary phase interfaces are also important in gas-liquid partition chromatography (40F). T h e analogy between gas adsorption and liquid adsorption chromatography made it possible to anticipate adsorption isotherms, energy distribution functions. and other parameters in liquid adsorption chromatography on the basis of the data for gas adsorption chromatography (77F). T h e effects of molecular structure were interpreted in terms of a molecular adsorption model (74F) and showed the importance of hydrogen bonding and steric factors ( I F ) . Similarly, adsorption onto a single type of crystal site was studied on the basis of classical adsorption theory (37E). It was also shown that one can investigate quantitatively the effects of surface heterogeneity in nonlinear and nonequilibrium gas-solid chromatography on the basis of elution theories developed for homogeneous surfaces (35F, 89F). T h e influence of energetic heterogeneity of adsorbents on the separation process in gas-solid chromatography (GSC) was demonstrated (48F) and the adsorbent heterogeneity estimated from the pressure dependence of retention data (67F). Adsorption processes were studied by physical, chemical, and chromatographic methods. For example, Phillips and Burke (61F) used cross correlation chromatography and separated effects caused by nonlinear behavior in the chromatographic system from the major linear correlation peak of the linear behavior. A gradient free pulse method was found to be effective for the study of complex adsorption equilibria (90F). Retention volume measurements were used to determine adsorption isotherms, virial coefficients, and surface energy heterogeneity (76F, 78F) and Lice versa, to predict retention volumes from adsorption isotherms (7o'F). Classification of adsorbents may also be based on retention data of reference compounds on the basis of relative polarity. much like partition GC (62F). Interfacial adsorption (73F),B E T monolayer capacities (84F), and other thermodynamic (29F) and kinetic (91F) studies illustrated that the behavior of fundamental adsorption processes is well understood. Solid state stationary phases acting as adsorbents were discussed from a mechanistic point of view as to whether porous layers or droplets of the same thickness were formed ( S 8 f l . When silanized Chromosorbs were coated with particle fines and covered with a liquid stationary phase, it was found that the silanized Chromosorb was not coated by any film and that its contribution to solute retention was small (42F). Adsorbent reactions for the separation of ortho- and para-hydrogen mixtures ( 1 8 F , 19F) and the catalytic studies of Phillips et al. ( 6 0 0 using differential sample vacancy and stopped-flow GC showed important chemical contributions. New macroporous polymers having specific surface areas up to 500 m2/g and thermal stability u p to 300 "C (52F),a coordination polymer of chromium(II1) h i t h diphenylphosphonic acid which reacts specifically with i7 bond hydrocarbons (80F),and a polar sorbent based on a copolymer containing free hydroxy functional groups (24F) were developed. The importance of the distribution of pores, surface texture parameters (4387, specific surface area, pore size,
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porosity, and thermogravimetric behavior (68F) in porous polymer sorbents was treated. Modification of polymer sorbent surfaces was reported with cellulose to calculate surface areas (55F), colloidal films to get very selective, homogeneous adsorbents ( l o p ) ,monolayer bound cation exchanger (.4g+) for alkene selectivity ( 5 4 F ) , and polymetaphenyl ether to eliminate adsorption on Tenax (5F).The latter column was used for the direct analysis of phenols in water a t the ppm level. The use of porous polymers as adsorbents in sampling columns is well known. A systematic approach for characterizing polymeric adsorbents for sampling was developed and the results of a large number of sorbents were discussed in terms of a variety of sampling experiences (1%'). T h e highest capacity sorbents were found to be Porapak Q and R. The limitations in the specificity of Porapak Q separation columns showed that ethanol and diethyl ether coelute in the analysis of body fluids ( 7 9 9 . However, porous polymers partially separated 32SF6and SF6 with a relative retention of only 1.003 between 35 and -10 "C (5%'). Previous work on the influence of molecular structure on the adsorptivity of silica gels has been extended to show that the elution volumes of parent polynuclear aromatic hydrocarbons may be predicted as well as adsorptivities of alkylaromatic hydrocarbons (64F). Nonlinear temperature behavior of retention indices for various solutes (70F), and adsorption and superficial diffusion of propylene on silica gel were reported (27F). Surface modification of silica gels was reported with Cu2+(17F) and Ag' (15F)salts, LiCl (71F), HF and NH, (69F),alkali and alkali earth metal salts ( 6 F ) , Li, Na, Co, Zn, and Cu derivatives of phthalocyanine (88F), tetrasulfophthalocyanines of Fe, Ni, Co, and Cu (88F),polyarylate (39F),and polymerization of melamine directly on silica adsorbents (33F). The latter columns demonstrated greater specificity than untreated silica or porous polymers, were thermally stable to 600 "C, and the thin films were insoluble in common solvents. In a series of papers, Polish workers extensively studied the physicochemical and chromatographic properties of surface modified silica gel (50F); examples included determining the surface energy balance (47F) and the second and third virial coefficients (46F) on gels modified with aliphatic alcohols (46F. 49F). Although continuing studies were reported for all of the well-known adsorbents, particular emphasis was given t o chemical surface modifications. An example is the retention characterization of the widely studied bentonite clay as an adsorbent and as an adsorbent modified by pyridine and piperidine (8F, 32F). Differences in the adsorption behavior of alumina coated with alkali metal fluorides with respect to saturated and unsaturated hydrocarbons was explained by the preferential interaction of the solute with the alkali metal ion on the surface (57F). Modified alumina demonstrated improved separation of H, and D, at -196 "C (44F). Alkali and alkaline earth rich Zeolites ( 4 F , 86F) and modification of Zeolites by the same ions changed the selectivity significantly (87F),particularly when silver cations were introduced (3F, 87F). Treatment of Molecular Sieve 5A with NO eliminated tailing problems (16F). Illustrative of Zeolite separations were analysis of krypton and nitrogen in gaseous fission products (83F),high purity n-paraffin and alcohols (52F), and a study of the selectivity of different Zeolites toward some nonferous metals (58F). Ion exchangers for GSC may give more selective separations for isomers than GLC, have higher thermal stability, and have negligible bleed (2F). Specific interactions of lightly sulfonated porous polymers (34F, 41F), ion exchanged forms of crystalline zirconium phosphate (25F),and ion exchange forms of montmorillonite clays (85F) were characterized analytically. Graphitized carbon blacks were extensively studied and show real promise in high performance columns because of their well defined properties and versatility by modification. These materials are now commercially available, e.g., Carbopack C. This material was compared to Sterling F T (11F). T h e adsorption/retention behavior of ethers (9F), alkynes (65F),aldehydes, ketones, and alcohols (36F) on graphitized carbon black has been published. Trinitrobenzene (22F) trinitrofluorenone (23F),tetranitrofluorenone (20F),and picric acid (21F)were used as modifiers to evaluate their selectivity to aliphatic and aromatic hydrocarbons (20F) and hydrocarbon isomers (2%'). Glassy carbon columns showed molecular sieving effects and selective adsorption to polar compounds
(81F, 8 2 0 . A cross section of the separations reported using graphitized carbon black includes polynuclear aromatic hydrocarbons (31F , 59F), sulfur compounds in environmental samples (12F),naphthalene homologues (28F),all of the C, isomers (21F), chlorine-, nitrogen-, and phosphorous-containing compounds (63F),acetylene in ethylene ( 1 4 F ) ,and as a trapping material for organic compounds (66F). Charcoal beds were similarly evaluated with respect to adsorpt,ive capacity for sampling atmospheric air samples (26F). It is both interesting and curious that almost all of the literature on graphitized carbon blacks is coming from countries other than the United States. Studies on miscellaneous adsorbents included hydrocracking on Ni-Si02 (720, separations of C,-C7 hydrocarbons on CdO, COO,and NiO (450, measurement of adsorption isotherms on ?JiC12,CoCI2, and BaC1, ( 7 F ) ,and adsorption properties of MoSz (30F) and Sb20, (5383. Capillary Columns. Capillary GC is rapidly developing to meet many of the analytical needs of the 1970's and 1980's such as environmental separations, analyses at trace levels for clinical and biomedical diagnostics, the separation of natural products, and other complex mixtures (48G, 49G). This is nicely shown in the paper by Novotny ( 6 i G ) , entitled "Contemporary Capillary Gas Chromatography". Therefore. this section of the review will stress today's capillary GC capabilities, techniques, and a cross section of some of the analyses for which it is being used routinely; e.g.. analytical and process chromatography (65G). References to new developments in instrumentation, such as multifunctional splitters (29G) and microvolume ECD's (25G),are discussed in t h e Instrumentation section of this review. On the basis of glass capillary columns, Desty (22G) suggested that a sub-picogram, high speed analyzer will be possible in the future in his review of the development and potentialities of the field. In a discussion of the pros and cons of capillary GC, Kaiser (47G) concluded that these columns give excellent analytical separations with retention reproducibility to better than 0.1 retention index unit, are fast, and that two-dimensional GC will be the way of the future. Rijks and Cramers (80G) obtained a relative standard deviation of 0.03 index unit by preparing very reproducible columns with a homogeneous film and negligible wall adsorption. For the most comprehensive discussion of the durability and lifetime of a large number of glass capillary columns, the reader is referred to the article by Grob (36G). The theoretical limits of resolution for such columns can be calculated (28G), although this has to be considered in light of column properties such as adsorption, retention polarity, thermal stability, acidity, and separation efficiency (35G). Therefore Cram, Yang, and Brown (ZOG)proposed that all capillary columns be specified in terms of their separation number, number of theoretical plates per meter, programmed temperature baseline stability, acid-base ratio, and coefficient for skewness using 1-octanol. Questions related to sampling systems, properties, types, and preparation of columns, dead volume effects, useful temperature ranges, etc. were treated in several papers (25G, 41 G , SOG). Schomburg and Husmann (94G) made an excellent case for the use of capillary columns in preference to packed columns and illustrated the power and versatility of many of the capillary techniques. Short columns (10-15 m) often have sufficient resolution for even large ranges of molecular weights (e.g., Cj-CZ7 fatty alcohols) and result in veq- fast analyses (26G). The dependence of capillary column efficiency, elution temperature, and speed of analysis on the temperature, rate of temperature programming, and carrier gas velocity was developed to allow assessment of these variables (46G, IOOG). Rapid separations of ClO-Cl8alkanes were achieved on short (11 m) capillary columns in 2.4 min with an average resolution of 6.5 with gradient temperature programming (28G). Flow programming was found to be a useful complement to temperature programming (72G). Double column systems have been shown to offer the ultimate in designing column selectivity, versatility in sampling and separation techniques, maintaining or re-establishing narrow peak profiles, lend themselves to reproducible retention indices, pre-separation and cumulative trapping (95G),and have been effective in solving difficult analytical separation problems (8G,1OG). A great deal of study has been given to the preparation of high efficiency capillary columns by a surprisingly large
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number of laboratories throughout the world. In fact, this was one of the principal subjects discussed at the first two international symposia on glass capillary chromatography (48G, 49G). In his review of various treatments used in the preparation of glass capillary columns, Roerade (81G ) discussed film formation, addition of surfactants, surface roughening via chemical modification and deposition of solid% and the dynamic and static methods of stationary phase coating methods. Karasek (51G) also gave an excellent perspective on the preparation and coating procedures for glass capillary columns and some examples of their uses. A more basic discussion of glass surfaces, their wettability with organic films, surface roughness, deactivation procedures, and deposition of the stationary phases was given by Novotny and Bartle (68G). They gave special attention to the role of selective surface monolayers in discussing t h e wettability phenomena. T h e theoretical aspects of “tape worm” capillary columns (rectangular cross section) evaluated the potentialities of these columns. Experimental results showed improved performance for a column with a 0.2-mm separation of the walls (75G). The details of preparing, treating, and coating nickel capillary columns showed that surface modification was still recommended, that both SCOT and wall coated columns could be prepared, and that the efficiency of the 0.5-mm i.d. columns was comparable to t h a t of 0.5-mm glass capillary columns (1lG). Methods of preparation of wide bore capillary columns (up to 0.95-nm id.) included etching, carbonization, deposition of layers of silica gel or graphite, deactivation, and coating (3G). PLOT columns of similar diameters were prepared by the dynamic coating procedure and offered the advantages of sample capacity, tolerance to extra column dead volume effects, and a decreased phase ratio so that retention ratios are significantly increased over thin film columns (66G). Bonded phase capillary columns (to borosilicate glass) were shown to be thermally stable a t 300 “C, useful to 325 “C, and particularly well suited for pesticide analyses (24G). Capillary packed columns were reviewed (5G) and their applications (16G)described as complementary alternatives to wall coated capillary columns. High pressure cleaning procedures for stainless steel capillaries were effective in preparing columns for recoating with polyester phases (61G). Various approaches to modifying glass surfaces by chemical and physical means were reviewed and some of the details of the techniques discussed (62G). The effects of surface etching of glass capillary columns gave a 50% increase in the number of effective theoretical plates. Surface hydroxylation prior to silyation also improved the performance of OV-101 columns (98G). Silver coated wall surfaces were deactivated with H2S to form a homogeneous layer for coating and found to be well suited for unstable halogenated compounds, such as chloroterpenes (60G). T h e Ba2C03procedure of Grob and Grob (38G) was developed as a “universal” capillary column preparation procedure and reduced the dependence on the type of glass used. This method was satisfactory for polar phases (37G) and later refined with further development (39G). Columns with surfaces modified by graphitized thermal carbon black were made to behave as adsorption and/or partition columns depending on the amount of liquid phase loading. In the gas-solid chromatography mode, the columns showed high selectivity for geometrical isomers and allowed separations a t lower temperatures than with conventional columns (99G). A procedure for forming the graphitized carbon black layers from a colloidal solution was given (33G). A very promising surface treatment reported was that of forming continuous thin polymeric films on the inside walls, especially if high temperature, thermally stable polymers with the proper surface tension can be found. The only stationary phase studied in these columns was UCON LB 550X (32G). T h e adsorption activity of the insoluble residual stationary phase film in glass capillaries was studied from the point of view of separation on ultra-thin films, a surface deactivation layer, a n interface base for overcoating with other stationary phases, and compared to clean glass surfaces (82G). Other alternatives to surface etching are the controlled deposition of NaCl crystals as described by Watanabe and Tomita (IOlG, 102G) or very thin layers of colloidal silicic acid for the separation of polar compounds (96G). Formation of oxide-type surfaces by dehydration during the drawing operation resulted in surfaces which could be coated satisfactorily with both polar
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and nonpolar stationary phases. Very thin stationary phase films (0.03-0.1 pm) were apparently exceptionally uniform as column efficiencies as high as 3000-10 000 plates per meter were obtained on columns of 0.1-0.15 m m i.d. (97G). This means that these columns are operating a t the theoretical limit of efficiency and approaching the point of being limited by molecular diffusion rather than mass transfer in the gas phase. Characterization of the surface of wall treated and support coated types of capillary columns can be done effectively by observation and analysis by scanning electron microscopy and energy dispersive x-ray (92G, 93G). “Whisker-walled” open tubular (WWOT) capillary columns were formed by silica needle-like whiskers to obtain favorable phase ratios upon coating (85G, 90G). Column efficiencies of 0.25 m m or 70% coating efficiency and capacities u p to 0.5-1.5 pg per component (because of the lower phase ratio) should make these columns particularly promising if surface activity and uniformity of film thickness can be controlled (86G). The details of column preparation (91G),deactivation (87G),chromatographic performance (88G),and applications (89G) have been published. Adsorption activity of stainless steel columns was reduced by cleaning procedures (83G),while deactivation of glass capillaries was performed by silanization (103G),or the Aue method which was satisfactory for both polar and nonpolar phases (13G). Coating procedures for stationary phase deposition are well established, relative to the technology associated with surface treatments and surface properties. Coating procedures for columns with polar phases and Silanox (64G) or cyanopropylsiloxane phases, such as Silar 10C or OV-275, were elaborated (42G). Freeze drying solutions of the stationary phase in-situ avoided the use of wetting agents but was not effective with very viscous phases (40G). The evaluation and characterization of these high performance columns was approached by several workers. Cram, Yang, and Brown (20G) made high accuracy chromatographic measurements using an on-line, real time computer system. Their results showed that meaningful measurements in capillary GC must be made with computer-based systems in order to minimize errors and to characterize the subtle changes and differences which occur. A concept incorporating the effective number of theoretical plates, sample load, and pressure drop was developed by Pauschmann (76G). Jennings (45G) treated film stability and column durability, while Blomberg analyzed the uniformity of stationary phase films (12G)and developed procedures for determining the average thickness of films ( 1 4 3 ) . T h e stationary phase distribution was also studied from photomicrographs and found t o exist as a dense network of small droplets. This stationary phase distribution on the surface was postulated to influence the relative heats of solution and retention indices (43G). The wide diversity of analytical separation problems which are being, and have been, solved by capillary columns may be shown by the following selected examples: steroids (7G, 21G, 23G, 63G, 77G, 84G), fatty acids (27G, 28G, 31G, 57G, 78G),fats and vegetable oils (29G) nitrosamines (34G),amino acids (2G) and amino acid enantiomers (53G),polynuclear aromatic hydrocarbons (73G),PCB’s (58G), polychlorinated dibenzo-p-dioxins and dibenzofurans (17 G ) , chlorinated pesticides (30G), organophosphorous pesticides (n’5G),disaccharides ( I G ) ,barbiturates and other drugs (4G, 104G), petroleum boiling point range ( 4 4 G ) ,petroleum hydrocarbons in marine sediments ( 7 4 G ) , oil spill “fingerprints” (79G), marijuana constituents (69G, 71G),volatile constituents from human serum, urine, and cerebrospinal fluid (4G, 70G),air pollutants (6G),water pollutants (6G),9G), diastereoisomeric amino acids (54G)and isoprenoid acids (52G), chlorophenols (56G),and secondary alcohols (59G).
DETECTORS Introduction. T h e field of detectors for gas chromatography has continued to receive considerable attention in this biennium notably in the area of selective detection systems and, in particular, gas chromatography-mass spectrometry. This continued interest is the result of industry attempting to comply with federal regulations for food, drugs, and the environment by developing ultratrace analysis methods. A number of reviews appeared including one by Adlard which has reviewed both universal (1H) and selective detectors (2H). Other authors discussed selective detectors
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and the roles they play in forensic analysis (19H), pesticide analysis (3H), and in routine analysis (17H). Subsequent parts of this section will consider specific detectors in detail. Quantitation of eluting solutes is as important to the analyst as the identity of the solute and Krzyzanowska (1.2") made a theoretical treatment using 15 equations in an attempt to analyze peak height in terms of detector dynamics. Lovelock (14H) has discussed the use of coherent switching and synchronous demodulation for the identification of weak solute peaks which are present in a noisy or drifting baseline. Often the introduction of novel detectors is the result of the analysis of particular samples; for example, the analysis of trace levels of N-nitrosamines in various samples prompted t h e development of t h e thermal energy analyzer detector (8H-IOM. Nitrosamines have also been analyzed using other detection systems, notably mass spectrometry (26H). Hill and co-workers ( I I H ) considered the design and temperature related characteristics of the piezoelectric detector. This study found that although the relative response changed and the sensitivity decreased with an increase in temperature, the analytical scope of the detector increased. A number of new detectors have been introduced recently. A commercial ultrasonic detector ( 7 H ) was evaluated by monitoring complex gas mixtures which were to be subsequently used to calibrate laboratory gas chromatographs. The design of the detector was discussed together with relative response factors. A neon ionization detector has been de. scribed which uses "Kr as the &emitter. This detector was used for determination of hydrogen (0.5 ppb) and methane (80 ppb) in the presence of nitrogen and oxygen. No attempt was made to analyze solutes other than gases, although the @-emitterwas stable up to 200 "C. Dubowski (6H) developed a solid-state metal-oxide semiconductor detector and demonstrated that it had a linear response for acetone and various alcohols. These solutes were determined using headspace methodology in various biological fluids. Another novel monitor which has recently been developed is the catalytic reaction detector ( 1 5 H ) . T h e basis for this detector is to measure continuously the temperatures in and above a catalytic bed as the column effluent passes through it. When a solute reacts on the bed, a n exothermic or endothermic response is observed. This detector has been used t o monitor unsaturated hydrocarbons with sensitivities comparable to those of a thermal conductivity detector. The response was found to be linear with concentration for 1pentene. Driscoll et al. ( 4 H , 5 H ) described a new design for a photoionization detector which used a very stable sealed ultraviolet lamp (10.2 eV) as its source. This design has comparable response to the flame ionization detector but has increased sensitivity and dynamic range. T h e authors state that this increase in sensitivity is due to the photoionization detector producing ions more efficiently than the flame ionization detector. A Russian research group (13H) described another approach to the detection of ultratrace levels of water, carbon dioxide, oxygen, carbon monoxide, and hydrogen based on chemical amplification by reactions with carbon and cupric oxide. This paper described a procedure which used nine amplification steps and as a result amplified the signal by 464.47 f 0.08. While this approach is not novel, the precision of their design was excellent and the authors investigated all the experimental parameters to observe their effect on the amplification and the reproducibility. Thermal Conductivity Detectors. T h e thermal conductivity detector has continued to receive attention since it is one of the few truly universal detectors. As a result, considerable research has been performed to attempt to predict or measure response factors so that quantitative analysis may be performed. Durbeck and Telin (30 made a study in which five equations were derived which accounted for variations of detector response with respect to bridge current, carrier gas flow-rate, and detector or oven temperature. These correction factors enabled quantitative analysis t o be performed with standard deviations of f270 or less. Janak and co-workers (94 found that the solute peak area was proportional to the absolute column temperature when noctane was used as the solute probe. This effect would be particularly troublesome if the column temperature were programmed during the analysis; however, it appears that this was compensated by the stationary phase bleed. The thermal
conductivity detector has not been more widely used since its sensitivity limits detection to concentrations greater than 0.1 ppm. In order to increase sensitivity and reduce peak broadening due to detector volume ( 6 0 , so that this detector could be used with capillary columns, a systematic study was initiated with the aid of computer data acquisition. T h e results have shown that the peak width and asymmetry were directly related to cell design and volume. Molar response factors were reported for the following groups of compounds; sulfur containing gases ( I I I ) , methyl siloxanes (44, and the higher acetylenes (24. In other studies hydrogen (811,and hydrogen chloride and chlorine ( I Z ) were determined in various gas mixtures. T h e former study used helium as the carrier gas and found that calibration curves for mixtures of hydrogen in helium had a more limited linear range than was expected. There is a controversy in the literature as to whether the gas density balance or the flame ionization detector is better for the quantitative determination of aldehydes and aldehydic esters (51,120, and, at this time, this discussion has not been resolved. A dual gas density balance detector gas chromatograph-mass chromatograph has been used by Uden and co-workers (71) for on-the-fly determination of the molecular weights of long chain alkanes. These researchers used an algorithm to calculate the molecular weights with errors of less than 0.4 amu. Novak and Janak ( I O Z ) discussed the properties and the results obtained with the flow-impedance bridge detector which is one of the few detectors that can be operated a t temperatures in excess of 1000 "C. Flame Ionization Detectors. Blades (35) continued his earlier studies which proposed mechanisms to explain the way that the flame ionization detector responds to various solute molecules by investigating the effect that the carrier gas has on sensitivity. T h e following carrier gases were studied: helium, neon, nitrogen, argon, krypton, and xenon. T h e increased response was attributed to an associative chemiionization reaction between CHO* and the carrier gas and the formation of ions as the result of reactions involving the carrier gas and hydrogen. This mechanism is perhaps supported by an earlier study ( I I4 which showed that the output of the flame ionization detector could be perturbed by the injection of the noble gases onto the column if nitrogen was used as the carrier gas. The author suggested that this could be used for the determination of the column volume and the response was due to perturbation of the production of charge carriers in the flame. Sevcik (94attempted successfully to show that the mechanism of chemiionization in the flame ionization detector occurs by a two-step process. These processes were studied using a furnace reactor and pure nitrogen, with the advantage that the results were not masked by flame reactions. Another study (44reported the design of a device for the rapid optimization of the flow rates of air and hydrogen to the detector. This method is based on feeding an auxiliary gas containing a small concentration of methane into the detector and then optimizing the flow rates by peak height comparison rather than by evaluating signal to noise ratios. Relative molar response factors have been obtained for compounds containing heteroatoms which are known to be detected with lower sensitivity; for example, organosulfur compounds ( 5 4 and aliphatic and aromatic amines (64. Both of these studies showed that there were relationships between the response and the number of carbon atoms. An interesting study was reported using an empty column and a flame ionization detector for the direct determination of hydrocarbons in water ( 1 0 4 . The data collected with this system showed a linear relationship for peak area vs. the total weight of hydrocarbons. Two successful attempts were made to use the flame ionization detector to monitor inorganic gases which normally do not give a detector response. The first used an oxy/hydrogen fuel-rich flame ( 7 4 and observed signals for argon, methane, carbon monoxide, carbon dioxide, helium, hydrogen sulfide, nitric oxide, nitrous oxide, nitrogen dioxide, oxygen, and sulfur dioxide. T h e second ( 8 4 approach employed post-column reactors containing sodium butyrate, or orthophosphoric acid in the presence of oxygen to convert water, hydrogen sulfide, sulfur dioxide, and nitrogen dioxide to species with greater molar response. A novel use of a flame ionization detector is to monitor single aerosol particles ( 1 J ) using a high-speed wave-form electronics.
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T h e flame ionization detector typically uses hydrogen as the fuel gas although the use of gaseous carbon disulfide or formamide as both the carrier gas and the fuel gas for a flame ionization detector was reported ( 2 4 . T h e response of this system was found to be slightly lower for most compounds than if hydrogen was used as the fuel and the authors suggested that the use of these liquids as mobile phases may allow the flame ionization detector to monitor liquid chromatographic effluents. Thermionic Detectors. Publications which discuss thermionic detectors can be divided into three areas: general discussion of this detector vs. other selective detectors for particular applications, the design of new thermionic detectors, and proposed mechanisms which explain the response of thermionic detectors. T h e evaluation and comparison of the various types of thermionic detectors, Coulson electrolytic conductivity detectors, and flame photometric detectors have been reported for various pesticides which contain phosphorus, sulfur, chlorine, or nitrogen heteroatoms (4K). The thermionic and electrical conductivity detectors were observed to have comparable detection limits whereas the conductivity detector was more sensitive to sulfur-containing compounds. Attempts were also made to correlate the responses for these detectors by using chloropyrifos which contain all the heteroatoms of interest. Two reports compared the response of the thermionic detectors for nitrogen, phosphorus, or halogen containing compounds as compared to t h e flame ionization of electron capture detectors. T h e first study (11K) showed that the thermionic detector could be used to assay anticonvulsant drugs on a micro-scale with on-column methylation whereas the second ( 5 K ) showed t h a t pharmaceuticals, amino acids, metabolites, etc. could be analyzed with the thermionic detector. In addition, this latter study attempted to explain the response for nitrogen detection based on the formation of a CN radical. Johnson et al. (8K) and Novak et al. (14mdescribed various methods to improve the fabrication of salt tips for thermionic detectors. The former used a die to press the salt tip whereas the latter used a ceramic cap impregnated with the alkali salt. Burgett e t al. (2K) described a design which used an electrically heated alkali salt and a conventional flame ionization detector and showed that this detector responds to nitrogen or phosphorus compounds. Detectors which are selective for carbon, nitrogen or phosphorus (IOK), or for nitrogen or phosphorus (15M have been reported. Conversion of response was made electronically (IOK) or by changing the electrode design (15K). Mellor (13K) tuned a commercial thermionic detector to respond to sulfur-containing compounds with greater sensitivity than its original response to nitrogencontaining compounds. Two studies described the procedure to be used for the optimization of the response of thermionic detectors towards nitrogen, sulfur, or phosphorus containing compounds (3K, 7K). Hill and Aue (6K) developed a silicon-doped flame ionization detector which enhanced the response of this detector towards organometallic compounds. Three studies continued earlier work which attempt to explain t h e response of thermionic detectors by proposing various mechanisms ( I K , 9K, 12K). Electron Capture Detectors. Electron capture detectors continue to be the most widely used selective detector for gas chromatography. A recent review (6L) discussed the characteristics, properties, theory, and operating conditions of the electron capture detector and summarized its applications. Two other publications compared the flame photometric detector ( 3 L )or the electrolytic conductivity detector ( I 4 L ) with t h e electron capture detector for the analysis of atmospheric (3L)or agricultural samples ( I 4 L ) . Patterson et al. ( 8 L , 9L) described the design and chromatographic characteristics of an asymmetric ECD cell for constant current mode operation. This detector demonstrated a linear dynamic range of greater than lo4,a detection limit of g (0.1 pg), and was specifically designed for use with N2 as a carrier gas. It is unique in that this ECD does not require licensing by the Nuclear Regulatory Commission in the United States. Poole (IOL) suggested reactions whereby electrophoric groups may be introduced into various biological or environmental samples to increase the sensitivity of detection. Also included in this study were references to specific procedures for the formation of various derivatives. Another study by Ross et al. (13L) described methodologies for the
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analysis of nitrates and nitrites in various solutions and for the analysis of the oxides of nitrogen. The basis of the methodology is to convert these compounds into nitrobenzene which is monitored with an electron capture detector after separation. Many studies reported the effects that various parameters have on the response of this detector. Poole ( I I L ) showed that the molar response can vary by three orders of magnitude over a range in temperature of 100 "C. Aue and co-workers have shown how the pressure in the cell ( 5 L ) and the cell potential difference can affect the response of the detector. These same researchers ( I L ) studied the hypercoulometric response for 48 compounds which contain halide or nitro groups. The nonlinearity of constant current electron capture detectors ( I 5 L )was explained by two kinetic models which were derived theoretically and the effect of pulsing the cell potential was discussed in two reports (7L, 8 L ) which attempted to increase the linear dynamic range. Dwight et al. (2L)used j5Fe, an auger electron emitter, to produce a linear response. This source produced better signal-to-noise ratios but had decreased sensitivity. Photoionization was used by Wentworth and co-workers (165) to produce low energy electrons which were captured more readily than thermalized electrons from a 3H source. Rosiek, Sliwka, and Lasa (12L)continued early studies on the mechanisms of electron capture and developed destructive and nondestructive models. T h e latter model could explain the hypercoulometric effect. Flame Photometric Detectors. T h e flame photometric detector has continued to be used for the analysis of sulfuror phosphorus-containing compounds although some selectivity toward halogens was obtained using the Beilstein test. This latter detection mode was studied since a number of compounds such as benzoic acid, N-derivatives of urea, quinoline with ortho substituents, and tartaric acid produced signals which suggested the presence of halogens ( 1 I M ) . Sevcik et al. ( I S M ) measured the selectivity of the response toward sulfur or phosphorus as a function of geometric arrangement and fuel-to-oxidant ratio for various pesticides. They found that interferences due to C2* could be reduced by monitoring phosphorus a t 565 nm but the interference of CN* a t 383 nm for sulfur could not be minimized. Optimization studies for this detector were made by other researchers (7M, 8M) for various sample types. T h e first new flame photometric detector design in more than 10 years was reported by Patterson et al. (12M). Their detector employed a dual flame design in order to minimize the hydrocarbon quenching effect on the sulfur response. The detector achieved a sulfur-to-carbon selectivity greater than lo6 by using the dual flame concept and an optical filter at 365 nm. T h e response of the flame photometric detector toward sulfur is exponential and two reports attempted to correct this nonlinearity through empirically derived curve fits (2M, 5M). When the solvent enters the detector, it can extinguish the flame or cause a change in the baseline and thus interfere with the normal operation of the detector. This problem of baseline changes, which can cause the early initiation of the integrator, can be solved by spiking the sample with volatile compounds (17M). Hasinski (9M) designed a detector which is not easily extinguished by the solvent. Two reports discussed the use of multichannel detection systems which allow the detection of sulfur and phosphorus ( I O M ) or sulfur, phosphorus, and halogens directly (16M). This latter system used indium pellets for the detection of halogens with improved sensitivity and a reduction in interferences. Various approaches were reported which attempted to increase the sensitivity of the flame photometric detector to sulfur-containing compounds. Aavik et al. ( I M ) reduced the sulfur containing compounds to hydrogen sulfide with a post-column reactor and hydrogen whereas Zehner and Simonaitis (181W increased sensitivity by adding traces of sulfur dioxide to the hydrogen. Both methods claimed to have improved detection limits by an order of magnitude. Low-levels of sulfur-containing compounds are often difficult to detect as a result of irreversible adsorption on packed columns. Therefore, the use of capillary columns will probably reduce this problem. Blomberg (3M)described the successful use of a capillary column to separate tobacco smoke. This system is extremely useful for another reason since it IS known that overlapping peaks due to hydrocarbons will produce quenched signals. The use of flame photometric detectors has
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become extremely important with current environmental awareness and the following examples show its application to t h e determination of sulfur containing compounds; total sulfur in gasoline (6W,determination of mercaptans and sulfides in natural gas (13M), and the determination of hydrogen sulfide. carbonyl sulfide, carbon disulfide, and sulfur dioxide in gases and hydrocarbon streams (14M). Spectroscopic Detectors. A large variety of spectrometric detectors have been used as selective detectors for gas chromatography during this biennium. Infrared, fluorescence, and atomic spectrometry have continued to be used with varying degrees of success. I n addition, nuclear magnetic resonance (8h3 was used for the determination of linear formaldehyde oligomers in formalin, ultraviolet photoelectron spectroscopy (ILVfor the determination of nitrosamines, x-ray absorption spectrometry for the detection of sulfur dioxide @ I N ) , colorimetry for the identification of connective tissue hexosamines ( 4 N ) , and chemiluminescence for the determination of vinyl chloride, related compounds ( 17N), and the determination of low molecular weight alkanes and alkenes (511v3. Selective infrared detectors were reviewed by Hausdorff ( I O N ) and the methods for the identification of solute peaks were discussed. Infrared detectors can be used to identify solutes on-the-fly if sufficient sample is eluted. Katlafsky and Dietrich (13?\;)found that if the peak width of the solute was within 20-30 s and if 20-200 Mg of solute was eluted, then a complete infrared spectrum could be obtained in 6 s. Griffiths and co-workers (15M used on-line Fourier transform infrared spectrometry for the successful analysis of the products of combustion or pyrolysis of polymeric substances. Trapping the eluted solutes is another approach to using infrared spectrometry for qualitative and quantitative analysis and three reports have discussed this methodology (SA;,16N, ISM. T h e advantage of this approach is that much lower concentrations of solutes can be detected if a post-column concentration step is performed. Fluorescence spectrometry is much better suited as a selective gas chromatographic detector since it is inherently more sensitive than any absorption technique. However, it is restricted to the detection of compounds which are fluorescent and this has generally limited its use to polynuclear aromatics (13N,19N, 2 4 N . This latter group of compounds is currently very important since they have known carcinogenic properties. Cooney and Winefordner (7N) investigated the limits of detection with various fluorescence instrumental systems. They concluded that t h e optimum systems should have intense UV sources or else have conventional sources with efficient UV excitation monochromators. T h e spectrometric emission from electrical discharges a t reduced or atmospheric pressures in helium or argon has been reported by a number of researchers for the selective detection of various solutes. Talmi and co-workers monitored the atomic emission from a microwave induced atmospheric pressure argon discharge to determine methylmercury ( 2 5 N and a reduced pressure helium discharge to determine various silicon compounds (3N). Black and Sievers (2N) reported a complete methodology for the determination of chromium in blood using a microwave induced atmospheric pressure argon discharge. T h e determination of chromium with a reduced pressure helium discharge was studied by Serravallo and Risby (23N) in an attempt to determine why the introduction of oxygen produced predominantly atomic species. Mechanisms were suggested to explain this effect but the results were not conclusive. Another report (22A9 used a n atmospheric pressure argon discharge to determine selectively aluminum and copper. Hedayati (11N) reported using a 27-MHz source to produce either helium or argon discharges although no comparison may be drawn from this work as compared to previous studies since only carbon was detected. Lantz and Crouch (14rV3 described a spark electrical discharge which was capable of determining the empirical formulas of compounds which contain carbon, phosphorus, nitrogen, hydrogen. sulfur, a c d boron. T h e latter detector is extremely useful since it fragments the solutes completely to the atomic species which by definition produces a selective detection system. Various reports described the use of atomic absorption spectrometry for the selective detection of various volatile metallic and nonmetallic complexes: chromium ( 2 8 N ) ; chromium, copper, cobalt, and iron (27N); tetra alkyl lead
compounds ( 6 M ;and arsenic, selenium, and tin (20N). The use of nondispersive atomic fluorescence spectrometry was recently discussed as a selective chromatographic detector. With exception of one study (6N), the use of these two detectors does not require prior gas chromatographic separation. Electrochemical Detectors. In this biennium there has been a resurgence in the use of electrochemical detectors for gas chromatography. T h e majority of these reports used electrolytic conductivity detectors and the rest used microcoulometry or ion-selective electrodes. Various mercaptans were detected with a selective electrode which measured the mercaptans indirectly by precipitating silver ions. The reduction in silver ions was measured with a silver ion-selective electrode (110).This system can be used to determine other sulfur-containing compounds with the use of a post-column reactor which converts these compounds to hydrogen sulfide. which is then determined in a similar manner to the mercaptans. Hydrogen sulfide was determined a t the ppm and ppb levels by monitoring its electrochemical oxidation (180). A metallized-membrane electrode was used by other workers for the determination of oxygen, carbon monoxide, and hydrogen in respired air in the ppm range with a simple portable gas chromatographic system ( 2 0 ) . Another portable gas chromatographic system monitors carbon monoxide by monitoring the oxidation at a platinum catalyzed electrode (170). Banks et al. (10)used a bromide ion-selective electrode to monitor low levels of methyl bromide in cereals and other foodstuffs. Two reports used microcoulometric detectors for vinyl chloride in water (50),and hydrogen sulfide, mercaptans, sulfides, and disulfides in industrial effluents (190). Both of these approaches used the head-space analytical procedure to obtain samples. Berton ( 3 0 ) described the use of osmotic cells as conductometric detectors for determining traces of alcohols, aromatic hydrocarbons, and chlorine-containing solvents in various samples. T h e response and elemental selectivity toward nitrogen-, chlorine-, and sulfur-containing compounds was studied as a function of gas-phase furnace chemistry reactions, post-furnace reaction or abstraction processes, and solution-phase ionization and neutralization processes occurring in the conductivity cell (140). This study also reviewed the general overall requirements of this detection system. MacDonald and King ( 1 2 0 ) attempted to improve the conductivity detection system by passing the entire effluent through a quartz reaction tube prior to the detector which reduces the solvent interference. In this mode of operation various types of compounds were detected. Lawrence (90) enhanced the sensitivity of a conductivity detector by modifying the conductivity bridge to permit a large dc voltage across the electrodes and thereby increasing sensitivity by three to four orders of magnitude. T h e response of the electrolytic conductivity detector is temperature dependent, although Winnett et al. ( 2 1 0 )described a simple, efficient, and inexpensive way of maintaining a constant temperature in the detector cell. Garwin and Roder (70) described a novel method to monitor hydrogen, hydrogen deuteride, and deuterium impurities in various gases by converting these gases to their chlorides in a reactor containing palladium chloride. This procedure was capable of determining these gases at levels of 0.01%. The following is a list of some of the applications of this detector: determination of various drugs (130, 150, 160),determination of amide residues in proteins ( 4 0 ) , determination of herbicides (80, loo),determination of N-nitrosamines (200), and the determination of vinyl chloride (60). This list is not exhaustive but it is illustrative of the application of the electrolytic conductivity detector. Radiochemical Detectors. Rotin (8P)has written a monograph which discusses the theory and application of radiochemical radioionization detectors to gas chromatography. Other workers (7P) derived theoretical expressions whereby specific activities of delayed peaks could be calculated using the relationship between count rate and count number. An interesting observation of this study was that the activities of narrow and broad gas chromatographic peaks could be evaluated equally well. Braun et al. ( I P ) described a system in which the column effluent is split between a mass spectrometer and a gas proportional counter. This system can determine which solute contains the radioactive tracer which is important for identifying metabolites from metabolism or pharmacokinetic studies. Other studies which use on-the-fly
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radiochemical detectors monitored 14Cor 3H in various labeled gases (3P,5P, 6P, IOP).Radioactive detectors often suffer from contamination from eluting solutes. Therefore, the column effluent is oxidized to I4CO2or 3 H 2 0to minimize this problem (5P,6P). Another approach to this problem is to trap the solutes as they are eluted and then determine the activity 9P). Radiochemical detectors of the collected fractions (4P, were also used for the detection of radioactive rare gas isotopes which are emitted from nuclear fission (2P). Gas Chromatography / Mass Spectrometry. T h e Analytical Chemistry biennial review on “Mass Spectrometry” by Burlingame e t al. ( 6 Q ) also includes a discussion of new G C / M S developments, techniques, and applications. Only selected papers which specifically treat the GC aspects of GC/MS w ill be presented here, such as the paper by Leibrand (45Q)which emphasized the concept of preferred liquid phases for GC/MS in order to minimize stationary phase bleed. Several excellent reviews have been published such as those by Fenselau (19Q), Horning et al. (3IQ),and Smith (56Q).The former discusses the mass spectrometer from the point of view of a GC detector, and illustrates the MS capabilities being used in standard practice today. T h e application of these G C / M S techniques to studies in clinical chemistry was reviewed by Lawson ( 4 I Q ) . Horning et al. ( 3 I Q )discussed the status, design, and operation of GC/MS, HPLC/MS, the characteristics of atmospheric pressure ionization (API) sources, and the potential applications of positive and negative API MS. Other MS sources, such as chemical ionization, spark source, field ionization, field desorption, and photoionization, as well as data handling considerations were reviewed by Smith (56Q). T h e power of using a computer-based MS system as a selective detector for GC was illustrated for environmental analytical measurements by Buddle and Eichelberger (5Q). The advantage of simplicity in using direct coupling of glass capillary columns to the MS by means of Pt-Ir capillary tubing has been described for both E1 (39Q) and CI ( 4 7 4 ) sources. Auxiliary techniques for the open split type of interface such as dilution of high peak concentrations, enrichment by trapping and on-line hydrogenation were described by Henneberg, Henrichs, and Schomburg (29Q, 30Q). This system is especially well suited for glass capillary columns and has the advantages of high yield, flexibility with respect to column parameters, being able to suppress large solvent peaks, and is relatively simple in t h a t no vacuum tight seals of the column to the MS or special geometry at the end of the column is required. Modifications of this design were reported (59Q) as well as the use of divertor values (63Q),devices to “square“ the GC peak profile in order to provide a constant concentration of solute entering the M S (58Q),and a backflush system (20Q) to facilitate the ease and effectiveness of interfacing and decoupling GC‘s and MS‘s. A scheme to quantitatively characterize GC / M S interfaces was reported by Lehman (43Q). Theoretical studies and experimental measurements on the molecular separator showed considerable improvement in the separation efficiency by using low porosity frits, decreasing the cross-sectional area, and increasing the length. Therefore, it may be advantageous to use small bore separators with capillary columns (21Q). Chemical ionization (CI) GC/MS was studied by Hatch and Munson (27Q, 28Q) in a series of papers describing direct coupling into a magnetic sector instrument. Their system showed no loss in chromatographic resolution or MS performance a t flow rates as high as 20 mL/min He (27Q). By continuously recording the ion current of one of the reactant ions, they developed chromatographic traces equivalent to a total ion current monitor. This allows the possibility of using a low energy reactant ion monitoring technique for the selective detection of certain classes of compounds (28Q). Blum and Richter ( 4 Q ) made a case for independently monitoring the GC effluent by FID, because of its relatively universal sensitivity, and supplementing this with the total ion current trace for CI work because of its highly selective response. The ability of negative ion CI to enhance the sensitivity of specific ion currents by a factor of 100-1OOOX was demonstrated in a study of 34 volatile metal chelates by Prescott, Campana, and Risby (5OQ). Various reagent gases were investigated as well as relative sensitivities in the positive and negative ion CI modes. Analyses of the optical isomers of amphetamines in human plasma and saliva (46Q),picomole quantities of
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choline esters (26Q),antiepileptic drugs (44Q),and cyclic boronate derivatives (24Q)typified applications of GC/CIMS. Field ionization MS was shown to give fast, qualitative MS analysis of multicomponent mixtures without preseparation by GC, and was therefore proposed as an alternative to GC/MS. T h e technique was also shown to be quantitative to mol when using stable isotope dilution techniques (37Q). A method was described for continuous mass range specific GC detection using the @-splitof a reverse geometry double focusing MS. The advantages of this scheme include reduction of the background noise due to column bleed, and elimination of the solvent peak (62Q). A combined E I / C I source was designed by Ryhage (53Q) to give optimal sensitivity in both modes. Simple algorithms for improving the efficiency of small data systems in automatic identification of compound classes (13Q), and those designed for handling data from trace levels in environmental samples by reverse searching, linear adjustment of spectra, and spectral abbreviations based on abundance ( I 7Q) enhanced the qualitative-identification capabilities of GC/MS. A microcomputer-based M S designed as a compound selective detector for GC utilized reverse spectral searches and retention time screening to provide a high degree of compound specificity (5763. Rapp et al. (52Q)coupled glass capillary columns directly to high resolution mass spectrometers and made exact mass measurements and computed elemental compositions of components in tobacco smoke condensates a t the 1-2 ng level. This paper represents an outstanding contribution to the analysis of completely unknown samples by using state of the art techniques. Selectivity was investigated with polychlorinated pesticides and PCB’s using chlorine isotope ratios to reconstruct mass chromatograms. This technique offers advantages in resolution and specificity when the chlorine-containing compound is found in a cluster of unresolved chromatographic peaks (9Q). A selected ion monitoring (SIM) system was developed for computer control of the accelerating voltage and magnetic field in order to facilitate this experiment on a magnetic sector instrument and thereby monitor several compounds during a single G C / M S run (64Q). T h e critical experimental parameters for doing GC/MS a t the picomole level were described for using microtechniques and avoiding contamination in the vacuum system (239). Selected ion summation (SIS) analysis is a data processing technique that combines the selectivity of subset masses with t h e sensitivity of ion abundance summations and has been shown to be successful for a wide variety of environmental pollutants (40Q). Decafluorotriphenylphosphine was proposed as a standard reference compound for mass and ion abundance calibration in GC/MS because of its wide and regularly continuous fragmentation pattern ( I S Q ) . Qualitative identification work in GC/MS has been primarily focused on environmental and biomedical/clinical studies. Outstanding environmental examples include the trace analysis of volatile organics in drinking and river water (2Q)and dioxins, such as TCDD (7Q, S Q ) , by capillary GC MS. Toxicological analysis by GC/MS (34Q)was enhanced y the development of a GC/MS system equipped with E1 CI and E I / F I , FD combination sources. These sources lea to rapid assignments to all significant GC peaks and elemental compositions may be determined by a dynamic peak matching technique (65Q). Clinical and pharmacokinetic studies of the ng-pg levels in 0.1-1.0 mL plasma or 1-5 mL urine (32Q),diagnosis of metabolic disorders (33Q),analysis of thyroid hormones at m / e > 700 amu (49Q) represent significant contributions to the technique and the solution of very real, complex, and difficult analytical problems. Foltz (22Q)summarized a discussion of the use of stable isotope labeled internal standards for quantitative GC/MS. The main deterrent to using the technique appears to be lack of availability of the isotope labeled compounds, and isotope memory effects have been noted (15Q). Relative standard deviations of 3% in the peak area ratios with S I M were obtained with internal standards and a &point calibration curve constructed daily (60Q). Single ion monitoring was preferred to multiple ion monitoring for best results (42Q). Klein e t al. (38Q) developed a n inexpensive stable isotope ratio-multiple ion detector. Quantitative comparison of GC/MS profiles of complex mixtures was made by comparing relative concentrations of components, calculated using in-
d
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ternal standards, using the HISLIB method (55Q). Quantitative GC/MS determined volatile nitrosamines ( 1 6 Q ) but only with high resolution MS was agreement obtained with chemiluminescence methods (25Q). Plasma Chromatography (PC) was reviewed from an operational point of view, treated as a gas phase analogue of electrophoresis ( 1 4 Q ) , and evaluated as a separation and identification technique (48Q). Detection of GC effluents was found to be comparable to the FID and ECD using positive and negative modes of operation, and in a single ion mobility mode (analogous to SIM) the PC behaves as a highly sensitive, low resolution detector (35Q). However, the dependence of the plasmagram on sample vapor composition was demonstrated (3Q). Fundamental work dealt with identification of ositive (12Q,36Q) and negative reactant ion ( 1 O Q ) species gy PC/MS. Positive ion spectra of isomeric dihalogenated benzenes illustrated the effect of substitution on the drift time or ion mobility (11Q). T h e analytical capabilities of PC were used for a number of interesting problems such as the separation of mixtures of aromatic ketones in the 0.1-10 ng range (1Q), determination and identification of Ni(C0I4 (62Q), “fingerprint” analysis of heroin and cocaine (34Q), and measurement of the mobility and diffusion coefficients of phosphorous esters and thioesters (51Q). T h e latter study noted asymmetric peaks as being indicative of limited hydration reactions.
QUALITATIVE AND QUANTITATIVE ANALYSIS Q u a l i t a t i v e Analysis. T h e majority of gas chromatographic qualitative analysis have been via relative retention data or Kovats retention indices. The following reports have been published which contain Kovats retention indices of various compounds: polychlorinated biphenyls on 13 stationary liquid phases ( I R ) ;oxidative products of squalane as a model for t h e oxidation of natural rubber (19R); trimethylsilylated silicates on four stationary liquid phases (253); aliphatic and heterocyclic sulfur containing compounds on three stationary liquid phases (28R);drugs on two stationary liquid phases (an interlaboratory study) (42R);organochlorine pesticides and their photoalteration products on OV-17 (46R); alkylbenzenes on three stationary liquid phases (62R);and alkyl esters, alcohols, and miscellaneous compounds on two stationary liquid phases (these data were then used to identify components in the essence of cantaloupe) (79R). The problems experienced with the use of Kovats retention indices have been t h a t these data have to be determined experimentally. Therefore a number of reports have attemped t o correlate retention index increments with molecular structure for the following compounds: n-alkynes (56R); n-alkenes (52R);monosubstituted cyclopentenes and cyclohexenes (63R);alkylbenzenes (60R);alkenes ( 4 7 R ) ; 2,4-dinitrophenyl hydrazones of carbonyl compounds (50R); nalkynes (54R);alkanes (39R);cyclic alcohols and methylesters (31R);substituted cinnamonitriles (30R);isoalkanes (14R); isoalkanes and cycloalkanes (58R);unsaturated hydrocarbons (69R);hydrocarbons (76R); alkylbenzenes ( 1 7 R ) ; benzene homologues (15R);compounds containing various functional groups (51R);bicycloalkanes (16R);and hydrocarbons (34R). Bellas (5R)developed a program for the calculation of the linear and logarithmic retention indices of various compounds. Takacs and co-workers extended their earlier work on the theory of retention index systems to include expressions for gas chromatographic interactions of solutes on stationary liquid phases (7R)and for the polarity of the stationary liquid phases (70R). Another series of studies by Ashes and Haken (2R,3R) attempted to extend the Rohrschneider prediction scheme to homologous esters. Chretien et al. ( I l l ? , 12R) used topological information in an attempt to explain the Kovats indices of alkenes in terms of physicochemical constants. Similar studies based on intermolecular interactions have developed relationships between molecular structures of various solutes and chromatographic retention data (57R,59R). Empirical quantum chemistry has been used to relate the chemical structure of sterol acetates (26R)and cyclohexane derivatives (24R) to Kovats indices with errors of less than 17‘. Other researchers attempted to correlate the temperature and pressure coefficients of the retention index with the structure of alkylbenzenes (61R) and the variations of retention indices for n-alkynes with temperature ( W R ) . Various
studies considered the accuracy with which Kovats indices can be measured and have discussed the parameters which affect the data (29R, 77R). Takeda (68R) developed a new approach to data compilation and retrieval which used a logarithmic scale to express the retention index data. This procedure can also be used to predict separation. An interesting application of the variation of Kovats indices with molecular structure used gas chromatographic retention data to predict the boiling points of the isodecanes (GI?). Another approach to qualitative analysis by gas chromatography is the use of selective detectors to produce information additional to retention data. T h e most widely used selective detector is the mass spectrometer and many computer algorithms have been written to speed identification of the solute peaks based on mass spectral and Kovats index data (6R, 72R). Nau and Biemann (43R,44R) described an elegant approach to amino acid sequencing which identified peptides by their mass spectra and Kovats indices of the perfluorodideuteroalkylated derivatives. The use of nuclear ma netic resonance spectrometry in addition to Kovats indices a n f mass spectral data was described for the analysis of other complex samples: tobacco and marijuana smoke condensates (37R); airborne particulates (38R);essential oil of Algeria Cypress (67R);and human serum and urine (3%). Other studies used ultraviolet radiation to photodecompose eluting solutes to confirm the presence of polybrominated biphenyl residues in animal feeds and dairy products (18R),or have identified drugs on the basis of their relative retention data and on their responses to thermionic and flame ionization detectors ( 4 R ) . Relative retention data have also been used for qualitative analysis. Relative retention data were reported for 95 pesticides and metabolites relative to aldrin, on nine stationary phases using both flame photometric and electron capture detectors (71R),and for environmentally significant sulfurcontaining compounds (32R). Relative retention data have also been related to the molecular structure for the following solute types: alkylbenzenes (13R);ethers (21R. 22R);methoxy and ethoxyalkanes (23R);and allyloxy and phenoxyalkanes (20R). Thermodynamic parameters, which were calculated from retention data, were also used for qualitative analysis of alkylderivatives of tin, germanium, and silicon (IOR),and the activity coefficients have been related to the structure of branched nonanes ( 8 R ) . The use of derivatization and retention data have been successfully used to identify the structure of the following solutes: position of substitution on the pregnane side chain (74R, 75R);amino acids (78R);phenols and alcohols (73R);unsaturated fatty acids (64R);aldehydes and ketones ( 9 R ) ;and carboxylic acids, amines, and thiols (27R). Multiple column retention data have been used for the identification of Lepidopteran pheromones (40R)and the sterol fraction in 30 vegetable oils ( 4 I R ) . The use of entire chromatograms for fingerprinting complex samples has continued for the identification of anaerobic bacteria (63R), spilled asphalts (36R),and commercial petroleum and synthetic fuels (49R). Guiochon (48R) evaluated the influence of noise on the accuracy and precision with which peak area and retention volume measurements may be made. Two Swedish papers attempted to increase the precision with which retention data can be measured by the use of a differentiating time printer (45R)and an on-line minicomputer (33R). Q u a n t i t a t i v e Analysis. A large number of papers published during the last biennium have shown that (a) the basic principles of quantitation are well established, and (b) that the limitations in quantitating chromatographic results are in sampling, sample preparation, lack of specificity at high sensitivities, and the accuracy and validity of calibration standards. In a collaborative study from the Food and Drug Administration, Margosis (28s) reported excellent interlaboratory agreement between results when certain GC conditions were constrained for the assay. Other interlaboratory studies reported results and limitations for capillary column methods for fats and oils ( I S )and hydrocarbons in tissues and extracts of marine organisms (17s). An innovative calibration scheme for GC analysis using in-situ generation of standards was developed a t Bell Laboratories by Freed and Mujsce (18s).Precolumns containing conversion reagents generate the desired compound from suitable precursors via direct injection. At t h e 5-rig level, a precision of better than 5% was achieved. T h e method is
A N A L Y T I C A L CHEMISTRY, VOL. 50, NO
applicable over a wide dynamic range, is reproducible, facilitates the preparation of standards, and is particularly attractive for analyses involving hazardous or toxic materials. Because of the increasing importance of permeation tubes for calibration of gases and vapors, O'Keefe ( 3 3 s ) treated the details of assembling permeation tubes. An in-depth study of the performance of a NO2 permeation device detailed the conditions which affect the rate of permeation (e.g., temperature, humidity, NOz purity, calibration procedures, memory effects, etc.) and stability (20s). The procedures for standardization of charcoal adsorption tube GC methods for vinyl chloride were given by both an industrial (2s)and a US. federal regulatory agency (8s).Calibration by the continuous mixing of two gas flows via a volumetric gas flow method was shown to be accurate to 1% (relative error) between 100% and 1000vpm ( 7 s ) . Using two precision positive displacement pumps, mixing the two streams, and switching the mixture onto the chromatographic column, Mraw and Kobayashi (30s) prepared calibration curves from 0.02 to 0.997 mol fraction with a n accuracy of 1% in the mole fraction. In a comprehensive treatment of the exponential dilution calibration technique, Ritter and Adams ( 3 5 s )demonstrated that a new, more efficient exponential dilution flask gave detector Calibrations with an uncertainty of fl% over the 3-50 ppm concentration range. Dynamic dilution of organic vapors was reported to give a relative accuracy of better tEan 15% for the concentration range 10 -6-10-3 vol 70 ( 2 4 s ) . Azeotropic mixtures were proposed as standards for detectors, columns, and sampling systems in order to minimize the errors due to composition changes during sampling and injection (21s). T h e sources of error in GC analyses were reviewed and treated by several authors (lOS,15S,43s) while others focused on systematic errors, such as developing calibration coefficients for polar compounds ( 4 0 s ) . Russian workers ( 3 8 s ) applied a scheme of consecutive dispersion analysis to investigate the influence of three variables on the reproducibility of analysis. They reported significant variance due to stationary phase instability and to changes in column packing dennsity. Kugler e t al. (275') averaged data from repeated analyses to improve the reproducibility of retention indices and peak areas and to find an optimum compromise between reproducibility and total analysis time. Peak area, peak height, and noise (or signal-to-noise) measurements were the predominant subject of attention, which is surprising because it is well established that the largest single source of error in the measurement step for GC analyses is the assignment or allocation of the baseline. A rigorous treatment of baseline noise by Smit and Waig (42s) accounted for the effect of time constants, integration time, and analog and digital filters. Peak area measurements using the Monte Carlo method were particularly successful in integrating irregular peak shapes ( 4 7 s ) . Peak height measurements were studied from the point of view of detector dynamics for concentration dependent detectors with significant detector volumes (26s)and for evaluating chromatograms of multicomponent mixtures (e.g., PCB's) superimposed on single components. In the latter case, the apparent concentrations are related to the true concentrations by a set of linear equations which are solved by least squares approximations (16s).Schwartz ( 3 9 s ) addressed the problem of finding the confidence limits for an analysis based on a measurement and read through a nonlinear calibration curve or curve of arbitrary form. A4notherpaper reported sample splitting ahead of the column to relate each sample peak area to the total sample peak area but treated the effects of sample splitting errors, detector response factors, and peak area measurements on the analytical results ( 4 5 s ) . Detector considerations included high specificity by GC-MS for high accuracy analyses using isotope-labeled internal standards in clinical chemistry (4s)and the simultaneous quantitative analysis of 60 compounds in airborne particulate matter by sacrificing detector sensitivity (21s).Errors introduced by the lack of specificity of the Brody-Chaney type of FPD in organophosphorous pesticides were corrected by doping the sample with a low boiling organophosphate to compensate for the nonquantitative detector response during the early part of the chromatogram (51s).By establishing linear relationships between the measured molar response factors a n d the molecular weights of silanes of similar structure, it was possible to predict the relative T C D molar
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response factors for alkoxy silanes which are not readily obtained in pure form ( 1 3 s ) . Procedures for quantitating GC analyses which involve overlapping peaks were suggested using (a) mathematical treatment, (b) more than one column, and/or (c) pure substances to characterize their GC behavior individually (23s). Detection of a second compound in a single peak based on the comparison of two exponentially modified Gaussians was proposed which does not imply knowledge of the time origin or width of either peak ( 3 6 8 . Sample splitting to the reference side of a TCD before the column enabled Butina e t al. (9s) to determine the presence of components in overlapping peaks by absolute calibration. T h e major problem in quantitation was shown to involve the sample itself and the presence of infrequently recognized interferences such as phthalates and plasticizers in biological ( 1 4 s ) and environmental samples (4ZS, 50s). These interferences, their sources, and the errors they introduce were discussed and their importance was emphasized when doing trace analyses. Novak ( 3 2 s )delineated the basic considerations of quantitative chromatographic analysis. It remains that specific column considerations will have to be considered in relation to the sample itself, as Krupcik and Janak (25s) found with column tubing and stationary phase effects in the quantitative analysis of lower fatty acids in metal capillary columns. An unusually large number of papers have appeared comparing GC methods to radioimmunoassay (RIA) (3S,6 S , 22S,34S, 37S, 44S, 46S), enzyme multiplied immunoassay technique (EMIT) (3S, 5S, Z2S,29S,44S, 48S), fluorescence (Z9S, 31S),UV spectrophotometry (44S,49S), TLC (37S,46S), H P L C (IZS),and other methods of analysis, especially for drugs of abuse and anticonvulsants. In all cases cited, the authors reported that either GC was the method of choice or that the other methods correlated well with the GC results. I t was noted that RIA, for example, took nearly twice as long as GC and was more expensive, but offered better sensitivity in that only 10-20 FL of plasma was required (34s). Computerization. The role which computer-based data systems are playing in chromatography continues to expand because of changes in the cost and capabilities of microelectronics, e.g., the microprocessor. T h e status of this field was reviewed and discussed (Z5T) a t the 1976 spring National American Chemical Society's Meeting in a symposium organized by Gill (162') and Dessy. In that symposium, future capabilities and trends were described, both in terms of microcomputer technology and new devices applicable to chromatography (2T,9T). Dessy ( l o r ) and others ( Z I T ) presented the concepts of computer networking, distributed and hierarchical systems to show laboratory data management capability, multichannel instrument operation, sophisticated and flexible data reduction capabilities. and extended calculation and reporting of analytical results. Such system requirements may be seen in laboratories using programmable calculators ( I ZT, 22T, 2773 and magnetic tape systems (24T, Z5T), for example. T h e evolution of large numbers of programmable calculators in the laboratory has made it possible to develop both on- and off-line systems with maximum ease and versatility of program development and laboratory applications a t minimum cost. T h e limitations of data logging on tape are well known, but its use for storing digital data for post-run editing, recalculations, etc., is very cost effective, fast, and versatile. In addition to data acquisition and data reduction, the other domain of computerization is automation. T h e benchmark paper by Baumann e t al. ( 3 T ) on automation in chromatography through microprocessor technology illustrates the improvements in GC system versatility, and emphasizes concepts such as improvement in the credibility of analyses by implementing fault prevention, fault correction, fault detection, and fault location. An excellent example of the power of microprocessors for real-time control and data handling in a system with minimum memory requirements was published from the University of California (127'). These kinds of systems will lead to advanced GC technologies such as the use of cross-correlation techniques to enhance signal to noise, as reported by Annino and Grushka ( I T )for trace analysis and process control. Swedish workers obtained retention volumes with a standard deviation of 0.0270 by continuously monitoring column flow, pressures, and tem-
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perature with a minicomputer in order to calculate the retention volume accurately (19T). The errors produced by the instabilities in inlet pressure and/or column temperature were monitored in order to calculate a correction for the time windows for qualitative identification by workers in Switzerland (29T). Any development effect with laboratory-based data systems requires a careful consideration of programming techniques and requirements. Phillips and Burke ( E T ) treated this subject nicely for the chromatographer and described threaded programming techniques to the development of dedicated language systems. Other examples of enhanced chromatographic performance with software developments included the use of Fast Fourier Transforms for determining retention times and peak areas of overlapping GC peaks. Although the solutions to these calculations are approximations in terms of accuracy, the precision is high (2OT). Statistical criteria for peak sensing with microprocessor systems were compared to off-line data reduction. T h e differences were traceable to truncat,ion errors and errors in the assignment, of the baseline a t t h e peak end (*5T). Digital filters were quantitatively evaluated for their effects on chromatographic data by Cham, Chesler, and Brown (829. Changes in peak shape parameters for Gaussian and asymmetrical chromatographic peaks were described as was an example of implementing digital filters in a microprocessor-based data system which minimized peak distortion, and enhanced peak detection and the signal to noise ratio. Computer-plotting programs were used to correct baseline drift, eliminate the solvent peak, and make threedimensional perspective views of two or more chromatograms ( I 7T). Other chromatographic software packages reported included computer-assisted searches for anomalous compounds in GC-MS ( 1 8 r ) , collecting and processing radio-GC and GC data to measure mass: specific activit,y, and correlate retention times ( 7 T ) ,and calculating boiling point distributions in petroleum fractions (23T). Advancement of GC capabilities, data enhancement, and instrument throughput via computerization are beginning to appear in the analytical literature. Examples include the statistical evaluation of data by calculating regression lines, error estimates, control chart limits, confidence limits on the results ( 6 T ) ,and recursive calculation of the standard deviation (47'). Whether the analyses involve relating the apparent concentrations of PCR's and pesticides to the time concentrations by a set of linear equations solved by a least squares (142'1, water pollution analysis by automated head-space techniques (23T),or the analysis of compounds from the catalytic conversion of methanol to gasoline (2873, accurate and precise quantit,ative measurements and analyses and automated sampling, backflushing, venting, detector switching, and other automatic GC procedures will be required in the future.
METHODOLOGY Instrumentation. An interesting review of American GC instrument companies and their impact on the development of the technique was written by Ettre (2413. Smythe (581;;) treated the impact of microprocessors on modern GC instrumentation, and t h e state of the a r t in process GC was reviewed extensively by Yillalobos (63U). Health and safety considerations have had an impact on the design of all instruments such that neither asbestos nor asbestos block is used for insulation today ( 6 5 l 3 . Instrumental effects on chromatographic resolution, peak shape, and quantitation have generally been assumed to be negligible. However. in an era in which GC is being pushed for higher resolution separations and performance, these effects need to be measured and characterized accurately. Cram and Glenn (19C3 developed a high precision. well defined system t o accurately measure the instrumental contributions to band broadening. They went on to compare their results with those predicted from a theoretical model (18C3 to demonstrate agreement of Contributions as small a!: 5-10 ms2 (e.g., FID). A more empirical approach was developed by Kaiser (.?4C3which was reported to he applicable t.o GC, HPLC. and HPTLC. Instrument contamination and materials questions also become more important at this time for the reasons mentioned above. The excellent treatment of septum, injector, and flow controller bleed by Purcell. Downs, and Ettre (nOl3 is required reading for those doing
trace analysis. high accuracy, high precision, high resolution. and/or good research work in GC. Polyamide-polyimide copolymers were evaluated as ferrules and found to seal glass columns without thermal oxidation to temperatures of 300 "C (23C'). T h e use of glass-lined stainless steel tuhing t o replace metal connecting lines (e.g.. column to detector) was shown to reduce tailing and absorption of small components ( 3('7. Extended instrumental capabilities included a theoretical treatment of hackflushing and programmed longitudinal positive or negative temperature gradients during backflushing. The advantages are decreased retention times and peak skew ( I C , 2LT, 7C, 81'; 22L:; t39C-42C3. T h e three variations of column switching used most frequently include direct and backflushing of columns, subsequent and parallel flushing of columns, and circulation procedures ( 1613. By ling, using a circulating GC, and !or heart cut,ting. Fieid (o21.3 developed peak resolution by essentially programming the column length. The details of such schemes are now readily available, even with continuous feed (60t,?I,and their applications to the separation of benzene and deuterohenzene (2.517 and isomers with a relative retention as low, as 1.035 shows that separation efficiency comparable to capillary columns may be achieved (1413. Use of a variable temperature gradient without carrier gas effected good separations for the case of overloaded columns (5717. Chromathermography was compared to isothermal and linear temperature programming for the analysis of trace levels of impurities in highly volatile solvents. The method uses a negative thermal gradient moving along the column i I I C3. Accessory devices such as effluent splitters designed for micro- and submicrogram work (1713 and a "mercurb- drop bubble flow meter", which claims to have an accuracy of 0.07% (3313, yi11,be useful for improved GC performance, accuracy, and flexibility. A n increasing demand for special purpose GC's such as the "airborne pesticide vapor drift analyzer" rvhich employs a &port sampling valve, 4 w a y switching valve, ECD, and FPD, illustrates this flexibility (231 7 . Instrumental developments unique to capillary GC work focused on pneumatics, inlet systems, and detectors. McGill et al. (461:)pointed out that conversion of packed column GC's for use with glass capillary columns may result in inadequate resolution because of dead voliime and adsorption effects, even when "conversion kits" are iised. They developed a simple method using silanized glass capillary inserts and connecting columns with heat-shrinkable Teflon tubing. For interconnecting tubing, Pt and other noble metals may become active, under certain conditions, and give rise to bandbroadening. tailing, and loss of peaks. Because glass can be permanently deactivated and is not affected by different effluents, it was found to be the material of choice (28C3.Flow programmed separations were effected for capillary-ECD separations of PCB's by programming an exponential flow program in through the splitter outlet needle valve (48l,?. '4 simple design for a flow controlled system for splitless injection was developed CSSC?. .Jennings (3ZC3developed an all glass splitter which was reproducible over split ratios of 100:l to 150:1 and replaceable. Another splitless technique was described which was based on a very rapid evaporation of a solvent free sample by inductively heating a ferromagnetic wire coated with the sample (Curie-point technique) using direct transfer of the sample vapor to the capillary column (2013. Direct injection. especially onto high capacity columns, will be particularly useful in quantitative work (1413. Automated headspace sampling with a capsule injector was used by McConnell and Novotny (-G[Tj for automated analyses o f metabolic profiles. Silyl derivatives were formed on the needle tip in an all glass solids injector designed for capillary work (:38(7,and a Curie-point pyrolyzer was coupled directly to the glass capillary column system (55 13. Packed precolumns may prove to be one of the most useful inlet systems because Ion boiling solvents can be removed. they offer a high injection capacity, and backflushing may he routinely employed ( 3L', 36C3. The resurgence in capillary GC instrumentation flexibility and versatility in solving difficult separation problems has been built on papers such as the one by Weeke, Hastian. and Schomhurg (64I 7 n h o dwcrihed capillary heartcutting. backflushing. trapping. and two-dimensional techniques. all controlled automatically. A low volume micro four-rvay effluent splitter for coupling multichannel detectors
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to capillary columns was designed to include two independent makeup gases (29C3. Details of ECD (53b7 and hlS (26C, 35U) detector systems illustrated advantages with glass capillary columns such as low bleed, high efficiency, enhanced signal-to-noise ratios, and the feasibility of direct coupling. The imDortance and feasibilitv of using. sDectroscoDic detectors with capillaries was demonstrated with vapor phase IR (12C7, G C / M S . F T - N M R . and UV-fluorescence (6C1. Effective removal of oxygen from carrier gases has been achieved a t the level of one part of 1OI6 using the catalysts Pt/y-A1203and Pd/-pAl,O, (49C1.The advantages of using He as a carrier gas for capillary column separations were reexamined and found to include a twofold increase in the number of plates, relative to nitrogen and argon, which is particularly important for isomer separations (43C’). Even H2 was used as a carrier gas for the determination of H2,by first converting the carrier gas all to the ortho form and using a TCD to measure the difference in thermal conductivity with the H2 in the sample (59~53.Pressure programming to change t h e carrier gas velocity is sometimes referred t o as “chromarheography”. Developments in this technique rely on knowing the effect of changes in the inlet pressure, programming rate, column permeability, and carrier gas viscosity (22C3. T h e technique has been applied to peak sharpening concentration profiles (67C1 and preparative-scale GC (66C1. T h e selectivity of t h e mobile phase itself continues as an active area of investigation. By the application of decreased pressure on the column inlet and outlet, it is possible to effect separations of binary mixtures by working on the linear portion of the sorption isotherm (5L3. Inverse GC with an olefinic stationary phase and air as the carrier was found to yield characteristic shifts in retention data so that it is feasible to monitor polymer oxidation reactions (25C3. Advantages of condensable gases and vapors as the mobile phase were shown for the separation of polar compounds. Preparative scale GC with NH,, SO2,freons, and steam as the mobile phase gave reduced retention times and improved peak shapes (54C3. When n-hexane and ethanol were compared to N, as mobile phases, polar components showed longer retention with the polar mobile phase a t temperatures u p to 175 “C. Similar effects were noted with nonpolar solutes and mobile phases (37C3. Japanese workers suggested a displacement mechanism for retention modification behavior in gas-solid chromatography and added polar solutes, such as ethylenediamine, to the carrier gas to obtain good chromatograms of aromatic amines (61C?. Using NH, as a mobile phase in long packed columns made it possible to decrease the pressure gradient and the H E T P . Ammonia has a secondary advantage in t h a t the sensitivity of chlorinated hydrocarbons is increased in the FID (10Cq. Formic acid in the carrier gas is reported to increase the peak area and the number of theoretical plates for barbiturates without changing the retention time. This effect is explained in terms of a reduction of adsorption on the solid support (301/3.This technique also permits on-column injection of the barbiturates as their sodium salts (27C1. Water vapor has also been studied extensively and found to give lower values of H E T P , shorter retention times, and improved peak symmetry (9L7. Because the retention indices of polar compounds are increased and nonpolar compounds decreased with increased water \ apor pressure, chromatographic elution profiles may be changed significantly and require that the inlet pressure be well regulated (51Cr). T h e effective sensitivity of the TCD is also increased with steam by using a precolumn between the analytical column and the TCD to reduce the organic solutes to H2 and light gases (47C3. The pressure and density dependence of the capacity ratios of alkane solutes u p t o squalane were investigated in super-critical fluid chromatography with C 0 2 as a mobile phase (62C1. Using the same mobile phase, Jentoft and Gouw (32C3 showed t h e technique to be useful in isolating specific polynuclear aromatic hydrocarbons IPNAH) from a matrix of predominantly PNAH’s. In fact, by judicious choice of the stationary phase, separations were carried out either on the basis of type selectivity or molecular weight. Quantitation was done by UV and liquid scintillation. Sampling and Sample Preparations. T h e number of basic and fundamentally new developments in sampling, sample preparations, and injection techniques during this biennium was extremely limited. Notable exceptions are the
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papers by Gaspar, Arpino, and Guiochon (38V) and Berezkin and Lipavskii (4V).T h e latter authors investigated sample band broadening processes during transport from the injector to the column as a function of the volume of the sample and volumetric flow rate of carrier gas. However, the importance of developing and characterizing the sampling techniques available has had a great impact on the accuracy, reproducibility, limits of detection, and credibility of analytical results in general. This is illustrated by studies describing the following selected sample preparation methods; vacuum degassing with thin film molecular distillation for isolating ketones and aldehydes from fats and oils (8V), zone melting for concentration of aromatics (59b’); gel permeation chromatography for crude petroleum in water (64V); solvent extraction for isolating polynuclear aromatic hydrocarbons in water or airborne particulate matter ( 1 V, 44v;J E T extraction tubes for drugs in serum and urine (29V);fluorisil and silicic acid for PCB‘s and phthalates in air (28V.4 0 V ; thin-layer chromatography for drug assays (72W; semisolid silicon polymers with centrifugation to separate clotted red cells and serum for drug analysis (fi2V7, aqueous caustic digestion with extraction and column chromatography for aliphatic and aromatic hydrocarbons in marine organisms (106V); ion exchange (5V, or adsorption (83V) chromatography for dioxins, solvent extraction, column chromatography, and gel filtration for polynuclear aromatic hydrocarbons in tobacco smoke (94V),liquid-solid chromatography for monoterpenes in essential oils (91 micro-phase extractions for drugs in biological materials (93l4,and steam distillation for flavor profiling (51V). Fritz (36V) published an excellent and objective review of concentration techniques of solutes from aqueous solutions A general description of the sampling methods used by the USDA a t Gulfport, Miss., for environmental pesticide analysis was published (32V). The increasing requirements for trace organic analysis and characterization of volatiles from small samples has given rise to a large number of papers which developed, studied, and applied preconcentration techniques for GC sampling. These are outlined in Table I to show the types of sampling and sample concentration methods used. These techniques were used at the ppm, ppb, and part per trillion level for primarily environmental, legal. forensic, fingerprint. and diagnostic analyses. A new diaphragm primping system was developed lvhich allows accurate volumetric sampling onto adsorbent concentration traps at flow rates from 1-100 mL/min (74V). The efficiencies of removing organic compounds from aqueous solution by gas stripping, adsorption on Tenax, and thermal desorption were measured for volatile, polar, water soluble compounds (61V). The variables affecting thermal desorption processes were reported to be the desorption volume, desorption efficiency, temperature, vapor concentration, humidity, loading capacity of the adsorbent, and storage characteristics ( I 7V). Detailed procedures were published for stripping or desorption with an inert gas in a closed flow system (42V). The desorption efficiency of CS2 for polar compounds u a s substantially increased by adding 5% methanol (33v). It was pointed out that in-situ decomposition may occur in Tenax while sampling stack gases (77V). The sensitivities obtained using headspace sampling for liquids and solids were discussed by Kolb (57v) who also extended the technique to the thermodg-namic characterization of nonideal solutions (56V). Use of the standard addition method for quantitative trace head space analysis was found to eliminate system matrix effects (26V). Analytical applications of the technique included the determination of monomers in polymers (57V, 9fiV),hydrophilic solutes in solution (26V). halogenated hydrocarbons in water (t54V). organics in water (19V),and volatiles from canned foods (46V). Procedures and methods were described for concentrating volatile trace organic impurities from water and aqueous solutions under dynamic conditions (98V). Theoretical treatments of the technique gave the respective solvent criteria for reaching equilibrium concentrations in terms of their volatilities and distribution coefficients ( 6 V , 105V). T h e method is stated to have analytical advantages over concentration with adsorbents and nonLolatile liquids in the concentration range below 10 70 (10413. Results presented showed the determination of aromatic hydrocarbons, carbonyls, and diethylamine in air a t the 0.1-65 mg/mJ h e 1
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Table I. Summary of Sample Preconcentration Methods Sorbent matrix 1. Tenax
2. Porous polymers
3. Charcoal
4. Polyurethane foam 5. XAD-2
6. 7. 8. 9.
Ambient caustic impinger t,raps Carbosieve B Cu2+coated supports Cryogenic traps
10. Dibutyl phthalate w/LN, 11. GC partition columns 1 2 . Glass wool 13. Reverse osmosis 14. Spray vaporization
Analyte sample Pesticides, PCB’s/H,O Industrial pollutants/Air Vinyl chloride/Air Metabolites/Biological fluids Organic pollutants/Air Volatiles/H,O, biological fluids Hazardous pollutants/Air Aromatic amines/Air, solids and dilute solutions Dihydrothiazolesiurine Polynuclear aromatics/Combustion effluents Food volatiles/Foodstuffs Halocarbons/Air Hydrocarbons/Biological containers Industrial pollutants/Air Ethylene/Air Organic pollutants/Air Organic pollutants/H,O Volatilesi Air Volatiles/H,O Food volatilesiFoodstuffs Vinyl chloride/Air DrugsiSerum Fluorocarbon aerosols/Air Organic solvents/Air PCB, pesticides/Air Polychlorinated napthalenes/Air Phthalate esters/H,O Organic pollutants /H,O Pesticides, PCB’s/H,O
( 8 1 v, l O 2 V )
(l02V) ) 7 5V )
( 75 V
Nitrosodimethylamine/Air
Industrial pollutantslAir Amines/H,O Nitrosodime thylamine/Air CHC1,IAir Rice volatiles/Rice Industrial pollutants/Air Metabo’ites/BiologicaI fluids and tissues Organic contaminants/H,O Organics/H,O
(47V). Sampling was done from the equilibrium system without changing the concentration distribution of the two phases (103v). Dissolved gases in water were analyzed by using a precolumn of MgC10, (58V),and from living biological samples with a permeation tube-sampling system (48V). Other gaseous sampling schemes included a 2000-fold concentration of CO (39V), gaseous sample compression (107v), freezing of atmospheric halocarbons (86V),sampling contaminated atmospheres through critical orifices (108V),on-line low pressure sources (34VI, capsule-reactor samples (87V), and septumless headspace sampling without syringes (29V). A method for correcting the volume of gases introduced with a gas-tight syringe was developed mathematically (73V). A high precision automatic sampling system for volatile liquids which requires neither a syringe nor septum was developed a t the University of Lund, Sweden, and employed two flow controllers, two solenoids, an automatic needle valve and a sample chamber (53v). For high-boiling liquid samples, the direct sampler or moving needle system of Cramers and Vermeer (20V) was shown to be applicable to eliminating the solvent and for critical applications such as steroid analysis. Many workers are finding it possible to directly inject large volumes of aqueous samples; e.g., 1000 pL of water to analyze sub-ppb levels of vinyl chloride (37v). Advocates of solid sampling methods have even proposed that liquid samples should be reduced to solids or concentrates to eliminate the solvent peak effects on sampling errors, column perturbations, and detector problems such as nonlinear response or quenching (55’v). However, errors associated with capsule sampling must also be considered such as those due to air drying, adsorption on the capsule walls, creep on the capsule walls, co-distillation with the solvent, and direct volatilization (71 t?. Glass rods were used for introducing low volatility and solid samples, as well as sample concentration (27V). Direct loading of small natural product samples into the injector without instrument modification has
been successful if properly implemented, and the results were compared to those from solvent extraction techniques (92V). Solid sampling gave improved results for the analysis of cannabinoids by volatilizing the plant material in the injector and cold trapping the solutes at the head of the column (30V,
84V). The most innovative sampling system developed during the past several years is the fluidic monostable system of Gaspar, Arpino, and Guiochon (38V). The system can provide variable injection band widths as fast as a few milliseconds and should be particularly applicable to automated high resolution and high speed separations as it has no moving internal parts. Ternary sampling sequences, rather than pseudo-random binary, were studied for the cases of noisy output signals and baseline drift. Applications were suggested for the cases of a wide range of peak sizes on a detector having low signalto-noise ratio (65V). Improved syringe patents were issued for automatic samplers ( 1 0 l V ) and a microsyringe (60V). Modifications to injection ports were proposed for increasing the accuracy of split ratio measurements by interrupting the septum purge during sampling (63V), and for thermal desorption of concentrating traps and in-situ sampling (2V, 70V, 82V, 95V). New methods for the estimation of exposure to CS2during sample handling (43V7 and possible health hazards resulting from the removal of syringes from hot injectors, thereby forming aerosols, were evaluated (90V). Injector innovations ranged from needle guides (99V) to general purpose injection systems designed specifically for biological samples (85V),while special purpose devices were developed for volatile samples (53V),sampling from vacuum systems (18V),automatic sampling of amino acids (76V), injection of volumes less than 0.05 pL (109v), and the generation of nitrosamines via direct injection (35V). Pyrolysis. The use of pyrolysis equipment coupled to gas chromatography for the characterization of high molecular weight materials is an area which has major utility but suffers
A N A L Y T I C A L CHEMISTRY, VOL. 50, NO 5, APRIL 1978
from problems of interlaboratory irreproducibility. These problems have caused researchers to delay acceptance of this analytical methodology. However groups have attempted to assess the problems of correlation of pyrograms with the view to remedying this difficulty. The Pyrolysis Sub-Group of the Chromatography Discussion Group in London (7W) and the American Society for Testing and Materials (Committee E-19) (30W) have made trials in which identical samples were submitted to different laboratories. T h e following pyrolysis units were used in these studies: Curie Point, filament, tantalum boat, and quartz tube pyrolyzers. In each study the pyrolysis temperature and time were specified and so were t h e column and separation conditions. T h e sample used in the British study was an aged styrenated alkyl paint (7W) and t h e American study used polybutadiene and a n isoprenestyrene copolymer. T h e results of these studies showed that a high degree of re roducibility could be achieved if a standard procedure was a&pted. Two reports have described new pyrolyzer units. Tsuge et al. (27W) described a vertical furnace-type continuous mode pyrolyzer, and Schmid e t al. (24") designed a Curie Point pyrolyzer unit which can be coupled to glass capillary columns. This latter design appears t o be promising since the high efficiency of capillary columns may increase the ability of pyrolysis t o differentiate similar samples. T h e major use a n d acceptance of pyrolysis gas chromatography has been for the identification of polymer samples and t h e following samples have been characterized: styrene-methyl methacrylate copolymers ( 2 W ) ; hexafluoropropylenevinylidene fluoride copolymers (3W); silicone rubbers, poly(vinylchlorides), nitrile rubbers, a n d butyl rubbers (5W); methyl methacrylate-divinylstyrene copolymers (16W);sulfonated polystyrene (26W);epoxy polymers (31W); ethylene oxide or propylene oxide copolymers (32"); styrene-a-methylstyrene or divinylstyrene-methylstyrene copolymers (33W) and 179 commercial adhesives (17W). In addition t o the potential use of pyrolysis for identification, these studies have estimated the degree of cross-linking, polydispersity of block copolymers, and the monomer content. T h e analysis of the resulting pyrograms represents a formidable problem to t h e analyst and therefore a number of attempts have used computer data acquisition and various algorithms in attempts to remedy this complexity (1W , 12W). It is expected that future pyrolysis studies will rely more heavily on com uterized automation especially now t h a t the price and availatility of dedicated microprocessors make such systems available t o most laboratories. Other systems which have been subjected to pyrolysis are as follows: quaternary ammonium salts (19W); reaction mechanisms for thermal eliminations and ring closures (15W); anthocyanins ( 1 4 W ) ; thermolysis of butanol isomers ( I O W ) ; aromatic carboxylic acids ( I 1 W); sterols (6W); pyrolysis of methane for the deposition of carbon (18"); alkylbenzenes (25"); generation of alkenes by t h e pyrolysis of alkanes or polyethylene (29W); anthracene and cholesterol (28W); insoluble polymer-like components in airborne particulates (13W);Penicilliun species, A s p e r g i l k niger CM 1 31821 and Neurospora crassa C M 1 75723 (4W);bitumens (22W);coals (9W);oil shales (8W) and saccharin (26"). In other studies, pyrolysis gas chromatography was applied to the analysis of unstable compounds (23W) and to the determination of organic oxygen (21W). C h e m i c a l Reactions. Chemical reactions are another method for solute identification. I n this methodology t h e efficiency of the gas chromatographic column may be increased by selective reactions. These reactions are generally performed prior to the column in separate reaction vessels or in specially designed precolumn reactors. Harris ( 1 6 X ) reviewed this technique in its a p lication to various studies on fatty acids. Dunges ( 9 X )descriged a microreflux system for the alkylation of barbituric acid. Two pulsed microreactors were described ( ] O X ,29x1 and their performance verified by studying t h e hydrogenation of toluene ( 2 9 X ) or the hydrodesulfurization of fuel oils (10x1. McKeag and Hougen ( 3 0 X ) developed a simple microreactor which can be used for subtractive gas chromatography in t h e analysis of alcohols, aldehydes, and ketones. Nigam (33x1 described a dual-channel microreactor which enables subtractive analysis t o be performed in a manner such t h a t t h e resulting chromatograms can be compared directly. This apparatus was subsequently verified
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by studying some hydrogenation reactions. The following reports described the applications of reaction gas chromatography to various studies: hydrocracking of alkanes on a Ni-Si02 catalyst ( 4 0 X ) : oxidation of aromatics on a Pt-SiO, catalyst (2OX); determination of trifunctional impurities in polymethylsiloxanes by reaction to form hydrogen fluoride from sodium fluoride ( 4 1 X ) : polymerization of copolymers of methyl arsenite and methyl siloxanes ( 3 8 X ) ; methylation of urinary organic acids (34x1; silylation of morphine (36X);kinetic studies on the use of labeled silylating agents for steroid hormone analysis by GC/MS (42x1; rearrangement of 3-methoxy-2,5(10)-diene steroids to 3methox 3 5 diene steroids ( 1 4 X ) ; hydro enation of formic acid anchs' derivatives ( 8 X ) ;hexylation of Earbiturates (13X). methylation of phenobarbital (46x1; methylation of synthetil cannabidiol, cannibichromene, and cannabivarin (1X); reaction between sulfur dioxide and carbon in a n attempt to study air pollution in urban areas ( 3 X ) ;hydrolysis of diborane and dichloroborane in the presence of hydrogen, nitrogen, and boron trichloride ( 2 1 X ) ; kinetics of the dissociation of methylc clopentadiene dimers ( 2 7 X ) ; thermooxidation of POlydo&caneamide and polyaromatic imides ( 3 2 X ) ; determination of carbon, hydrogen, nitrogen, and oxygen in silicon by successive oxidative and reductive reactors ( 2 x 1 ; various reactions for the characterization of polymeric materials (44X); cyclotrimerization of ethylene and the cyclodimerization of propylene or propane ( 4 X ) ; the abstraction of amines by cupric salts ( 5 X ) ; hydrogenation of alkylbenzenes to determine the number of C-C bonds ( 1 1 X ) ; esterification of biological trifluoroacetic acid by reaction with phenyldiazomethane ( 2 3 X ) ; oxidation of nitrogen in hydrazine and its derivatives (24X); selective reactions for the determination of alkanes, conjugated dienes and alkynes ( 2 6 X ) ; partial hydrogenation of dimethylene-interrupted methyl cis-octadenynoates ( 2 8 X ) ; the subtraction of aldehydes and ketones by reaction with 3,4,5trimethoxybenzylhydrazine ( 3 1 X ) ; oxidation of organic molecules for the determination of carbon-hydrogen ratios ( 3 7 X ) ; trimethylsilyl derivatives of aqueous phosphates (12X); thermal splitting of alkyltrimethyl ammonium chlorides ( 7 X ) ; abstraction of aldehydes, lactones, and ketones with primary, secondary, and tertiary aminosilanes (15X); determination of sulfhydryl groups by reaction with nitrous acid ( 3 5 X ) ; determination of carbon, hydrogen, and fluorine in fluoro-organics by decomposition t o water, carbon dioxide, and fluorine (analyzed as silicon tetrafluoride) (43X); derivatization of N-methyl and N-aryl carbamates with trimethylanilinium hydroxide ( 4 5 X ) ; derivatization of chloromethylmethyl ether with 2,4,6-trichlorophenol ( 2 2 X ) ; and derivatization of lower aliphatic primary amines with benzaldehyde ( 1 8 X ) ,2-thiophenealdehyde ( 1 9 X ) ,and pentafluorobenzaldehyde ( 17 X ) . Other studies used reaction gas chromatography as a rapid method to estimate reaction parameters for amidations and N-acylations (39x1. Kramer and co-worker ( 6 X ,2 5 X ) , made some theoretical calculations to propose the peak shape for simultaneous first-order reversible reactions for compounds which can interconvert on a gas chromatographic column. The evaluation of this derivation was made with the interconversion of para- and ortho-hydrogen ( 6 X ) . Derivatization. T h e formation of derivatives in quantitative yields for compounds which have either low volatility or thermal stability is an area which has expanded the applications of gas chromatography. Derivatives of inorganic compounds will be discussed in a later section of this review while this section will deal exclusively with organic compounds. Five reviews of this general area appeared in this biennium which discussed derivatization reactions in general ( 1Y , 15Y), procedures for the analysis of fatty acids (24Y),insecticide and herbicide residues ( I I Y ) , and the amine metabolites of pesticides ( 4 Y ) . Without a doubt, the area which received the most attention is the analysis of biologically significant compounds. T h e following is a list of derivatives which were reported for these compounds: pentafluorophenyldimethylsilyl ethers for sterols ( 6 Y ) ;methyl and n-butyl borane derivatives of 3-methoxy4-hydroxyphenylethyleneglycol (major metabolite of brain norepinephrine) (7Y);N-permethyl derivatives of polyamines (found in normal and neoplastic growth of tissues) ( 1 8 Y ) ; N-methyl bis(trifluoroacetamide) derivatives of carbohydrates (44Y); N-heptafluorobutyryl isobutyl esters of amino acids
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ANALYTICAL CHEMISTRY, VOL. 50, NO 5, APRIL 1978
(43Y); N,O-bis(trimethylsilyl)trifluoroacetamide-piperidine derivatives of prostaglandins Ai, B1, BP, El, Ea, F1,, and F2a (41 Y); trimethylsilyl ethers of methylglycosides (37Y); N methyl-bis(trifluoroacetamide) for vitamin Bs (33Y); trimethylsilyl, bis(trimethylsilyl)trifluoroacetamide, trimethylsilylimidazole or bis(trimethylsily1)acetamide derivatives of nucleosides and nucleotides (16Y, 17Y, 32Y); trimethylsilyl derivatives of tryptamines (30Y); 0-w-haloalkyl oxime derivatives of oxosteroids (28Y); O-pentafluorobenzyloxime derivatives of ketosteroids (29Y);trimethyl- or dimethyl-alkylsilyl derivatives of steroids (a mixture of these reagents will distinguish between phenolic and alcoholic hydroxyl groups) (26Y); n-butyl N-trifluoroacetyl esters of protein and nonprotein amino acids (BY); N-permethyl derivatives of pyrimidine and purine nucleosides (12Y); and N(0)-heptafluorobutrylisobutyl esters of protein amino acids (23Y). Donike (13Y)controlled the extent to which organic molecules are derivatized by trimethylsilylation by the addition of methyl orange which turns yellow when the reagent is in excess. This procedure was tested by derivatizing adrenaline and L-tyrosine. Miyazaki et al. (25Y) used trimethylsilyl and other dimethylalkylsilyl ether derivatives to elucidate the structure of steroids according to their hydroxyl content. Drug analysis is another major area where derivatization has allowed gas chromatography to be used for successful analyses. Examples of these derivatization schemes are as follows: the pentafluoropropionic anhydride derivative of metenamic acid (3Y);trimethylsilyl derivatives of piperdine, pyrrolidine, and morphine (35Y);trimethylsilyl derivatives of the cannabinoids (39Y); bis(0-trimethylsilyl) derivative of morphine (40Y);trimethylanilinium hydroxide derivatives of barbituates and hydantoins (42Y); and N-dimethylaminemethylene derivatives of primary sulfonamides (45Y). Wong et al. (47Y) showed t h a t the N-methyl derivatives of certain compounds such as phenobarbital and diphenylhydantoin were found by GC/MS to be artifacts generated after injection. This problem was solved by the use of trimethyl-d9-anilinium hydroxide which appears t o suppress this side reaction. Pesticides and herbicides have been successfully derivatized by t h e use of the following reagents: trimethylphenylammonium hydroxide derivatives of sulfur containing carhamates (5Y); p-bromo-, 2,5-dichloro-, and 3,4-dichlorobenzenesulfonic acid derivatives of carbamates (27Y); pentafluorobenzylderivatives (10Y) or 2-chloroethyl esters (9Y) of herbicidal acids (Dicamba; MCPA; 2,4-DP; 2,4-D; siluex; 2,4; 5-T; 2,4-DB; pichoran; 2,3,6-TBA; and MCPB); silyl, methyl, or alkyl derivatives of hydroxyatrazine and atrazine (221.7; and pentafluorobenzoyl derivative of thiobendazole (31Y). In general applications, derivatives have been suggested for many functional groups: the derivatization of phthalate ester plasticizers by reaction with 2-chloroethylamine hydrochloride (19Y);derivatization of nitrosoproline with 7-chloro-4nitrobenzo-2-0~0-1,3-diazole (46Y); silylation of phenols. phenolcarboxylic acids, hydroxycoumarins, coumarins, catechins, anthoxyanidins, flavonols, flavanones, flavanonols, and anthocyanins (14Y); pentafluorobenzyl carbamates of tertiary amines (20Y); benzaldehyde shift base of lower aliphatic primary amines (21Y); N-methyl-N-trimethylsilylheptafluoramide derivative of butyric acid as a silylating agent for derivatization of p-oxy-ampetamine, caffein. diethylvinylamide, and strychnine (38Y);trimethylsilyl derivatives of hydroxycarboxylic and dicarboxylic acids ( 3 4 8 ; and the use of ,V-trimethylsilylacetanilide and its p-ethoxy derivative to form volatile derivatives with compounds which contain primary, secondary, tertiary, and phenolic hydroxyls, carboxylic, thiophenolic, amine, amide, and imide groups (36Y). Cant and Walker (8Y) described the reverse of derivatization by regenerating monocarbonyls from their 2,4-dinitrophenylhydrazone derivatives on a Celite column impregnated with sulfuric acid. P r e p a r a t i v e S c a l e a n d Trapping. Guidelines to increase t h e Droduction of a Dreparative scale GC by several orders of magitude were given by Roz e t al. (162) s6ch that a 13-cm column could produce 20-220 kg per day under optimum conditions. T h e equation of Conder (52) may be used t o determine the effect of t h e chromatographic design and the optimum for the operating variables (feed band width, column length, degree of band overlap, and column temperature). I t
was pointed out t h a t the carrier velocity and feed concentration should be as high as possible. A method for determining the optimal section height as a function of the resolution and purity desired was based on computer calculations for a model of preparative GC. These calculations determined the relationship between efficacy, resolution, and product purity (82).Pausch (142) described the scale-up of analytical separations to preparative columns by controlling the radial gas flow distribution with special insert baffles. Fogging during peak collection was prevented by the use of small water cooled columns packed with glass beads to maintain the mass transfer rate greater than the heat transfer rate. Hungarian workers packed 17 kg of packing into their 3 m X 10 cm i.d. columns and described their injection pump system and collection efficiency studies (92). A two-section preparative column used a supplementary carrier gas inlet between the sections such that at the time of minimum deflection between two peaks, the carrier gas flow was interrupted. In this manner, components carried by the supplementary flow were separated in the second column. Higher purities of trapped components were reported ( 6 2 ) . An autoclave element for preparing concentrated sample vapors with a high pressure inlet system was patented ( 1 7 2 ) . HETP values of 0.6-0.7 m m were obtained in 86-cm long columns by a novel method of packing preparative columns (52). Long packed columns were compared to circulation schemes experimentally and theoretically. By studying the influences of the particle diameter, separations of isomers with a relative retention of 1.035 were achieved with circulation preparative scale GC ( 4 2 ) . Sequential systems made u p of 1 2 columns were used successfully to separate halocarbon mixtures a t a feed rate of u p to 1 L / h (22). An efficient all-glass splitter and trapping system was designed for samples from nanogram to milligram levels (12). Trapping efficiencies as high as 97% were obtained using glass fiber paper filter disks a t 0 " C (32). Trapping high boilers directly into NMR tubes (122) and freezing out low molecular weight solutes for IR were important for spectroscopic identification (132). For samples in the 1-100 mg range, a trap u i t h longitudinal and radial thermal gradients gave recoveries of 90~95%(122). Silver-oxide packed tubes were used for trapping fatty acids and carrying out methylation reactions directly in the tubes ( 1 0 2 ) . Another example of sequential uses of traps is that of trapping foodstuff volatiles on 120/150 mesh lactose so that they can be added directly to water for odor and taste assessment ( 7 2 ) .
MISCELLANEOUS P h y s i c a l - A n a l y t i c a l M e a s u r e m e n t s . Gas chromatography has continued to be used to determine dynamically various physiocochemical data. T h e usefulness of this information is dependent upon the precision with which the retention data can be measured, and a number of reports have attempted to evaluate the precision of these chromatographic data. Arutjunov et al. (2AA) described a chromatographic instrument to make accurate measurements of retention data and linear gas velocity. Valentin and Guiochon (72AA) developed a general theoretical model which accounts for the sorption, isotherm, and pressure gradient effects, but neglects diffusion and resistance to mass transfer effects. In a companion study, these workers discussed the apparatus, specifications, and results from measurements of solutions and adsorption equilibration isotherms (73AA). Another study attempted to evaluate thermodynamic data which is obtained when nonequilibrium conditions exist, based on the first statistical moment of the elution profile, (37AA). Stewart (70AA) explained the thermodynamics of separation in terms of the entropy changes which accompany the process. T h e following reports measured various solution thermodynamic parameters for different solutes on a series of stationary liquid phases: Flory-Huggins interaction parameters, heats of dilution, and excess heat capacities of normal and branched alkanes on OV-101 (28AA); Flory-Huggins interaction parameters of normal alkanes, aromatic hydrocarbons, and cyclic hydrocarbons in polyisobutylene (43AA); heats of vaporization and vapor pressures of alcohols, halogenated hydrocarbons, and benzene (78AA);solution and adsorption enthalpies of n-nonane, benzene, and cyclohexane in 11 stationary liquid phases (5AA); solution enthalpies and entropies of alkyl derivatives of silicon, germanium, lead, or tin
ANALYTICAL CHEMISTRY, VOL. 50, NO. 5, APRIL 1978
in Apiezon L, polydiethyl bis(glyco1 sebacate), or SKTFT-50 (6AA);partition coefficients and solution enthalpies of acetone and alcohols in squalane, oxydipropionitrile, or polyethylene glycol adipate (these parameters were compared to the same thermodynamic d a t a obtained by static measurements) (23AA);entropies and enthalpies of solution of alkylbenzenes. branched alkanes, and perchlorinated hydrocarbons in squalane (40AA);enthalpies of normal and branched alkanes in Apiezon M, squalane, or OV-101, and the results were discussed in terms of the solution theories of Prigogine and Flory (46AA);enthalpies and entropies of alkanes in n-C36H7, (52AA); entropies and free energies of various functional groups in 75 stationary liquid phases (20AA);free energies of the Rohrschneider solutes in 16 stationary liquid phases (21AA);temperature-dependences of the interaction second virial coefficient of nitrogen with n-alcohols in diisodecylphthalate (57AA);partition coefficients of hydrocarbons, carbonyls, or sulfur-containing compounds in polyethylene glycol adipate ( 7 4 A A ) ;solubility parameters of alkyl derivatives of phenol and resorcinol in Apiezons, phthalates, phosphates, sugars, and alcohols ( 4 4 A A ) ;free energies, enthalpies, and entropies of mixing for heptane or toluene in various polymers and oligomers (58AA);activity coefficients of alcohols, methyl ketones, chlorinated hydrocarbons, aromatic hydrocarbons, and ethers in lignite montan wax or lignite tar ( 3 8 A A ) ;activity coefficients of cyclohexane and n-hexane in n-hexadecane, n-eicosane, or squalane (42AA); activity coefficients of n-heptane, benzene. and substituted benzenes in n-octadecane or n-hexadecylhalide solvents ( 3 3 A A ) ; partition coefficients and activity coefficients of pinenes and halogenated hydrocarbons in polypropylene sebacate or silicone oil MS-200 (71AA); and activity coefficients of various solutes in binary mixtures of squalane and di-n-butyltetrachlorophthalate (19AA). Novakova and Novak (6OAA) described how heats of vaporization of substances with low volatilities can be determined by coating a support with these substances and measuring the temperature dependence of their bleed from the columns. The solubility behavior, surface properties, and ionization constants of the silyl derivative of Prostaglandin F, (Trimethanine salt) have been measured 162AA). Two reports measured the solubility of the following solutes in molten polymers: ethylene, n-hexane, n-octane, benzene, and toluene in low density polyethylene ( 4 5 A A ) .perhalogenated alkanes, n-alkanes, cyclic alkanes, and aromatics in polystyrene (69AA). Other studies concerned the measurement of thermodynamic data and other properties of various adsorbents: heats of adsorption of n-alkanes on lithium stearate or lithium oxystearate (55AA);heats of adsorption of esters, aldehydes, ketones, alcohols, hydrocarbons on e-lactose (51AA); effective diffusivites and heats of adsorption of n-alkanes on a commercial platinum-alumina reforming catalyst ( 7 A A ) ;adsorption energies of aromatic hydrocarbons on graphitized carbon black (29AA); equilibrium solubility and the activation energy of desorption of ethanol and water on polyurethane (32AA);isosteric heat of adsorption of benzene and n-hexane on porous glass beads (25AA); pre-exponential factor of Henry's constant for benzene, n-hexane, and cyclohexane on porous glass beads (26A4): the effect of different isotopes on the adsorption enthalpies and entropies of sulfur hexafluoride on Porapak Q ( j 4 A A ) ; desorption isotherms and pore size distributions for activated carbons using n-butane (67AA); adsorption isotherms for hydrocarbons on alumina (59AA); adsorption isotherms for n-pentane for silica gels ( I A A ) ; sorption isosteres of benzene on Porasil C (17AA); adsorption isotherm for cyclohexane on silica gel (75AA);free energies of adsorption of methylene groups on alumina. Chromosorbs, or Porasil (50AA); and free energies of methylene groups on Amberlite XAD, Chromosorb, Porapaks, Spheron, and Polymer-1 (30AA). In other studies, the surface adsorption characteristics of water and n-propanol on t h e surface of poly(ethy1ene oxide) were measured a t temperatures near the polymer melting point transition (12AA). Hsu et al. (31AA) showed that t h e adsorption energy distribution of heterogeneous surfaces may be measured by gas chromatography. This method has many advantages over other methods of generating similar data. Gearhart and Burke (27AA) measured peak broadening for a number of solute probes to measure the physical and chemical nature of polymeric adsorbants. These workers discussed the results in terms of pore
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size, uniformity, and chemical composition of the polymer. The surface areas of macroporous and mesoporous adsorbents (68AA) and metallic catalysts (22AA) were studied using suitable solutes. T h e diffusion of solutes into the stationary phase has also been reported in the following papers: diffusion coefficients of methane, benzene, and carbon tetrachloride in polyethylene films ( 6 3 A A ) ;diffusion coefficients of long-chain n-alkanes in methyl silicones; phenylmethyl silicones, phenylmethyldiphenyl silicones, trifluoropropylmethyl silicones, and cyanopropyl methylphenyl methyl silicones (39Az4);diffusion coefficients, partition coefficients, and the entropies and enthalpies of evaporation of n-alkanes in polydimethylsilicones (53AA);gaseous diffusion coefficients for ethylene, n-butane, and isobutane in nitrogen (24AA);gaseous diffusion coefficients for methane in helium (77AA); binary diffusion coefficients for use in the calculation of intermolecular forces constants and t h e Lennard-Jones 12-6 potential (11AA); binary diffusion coefficients of aniline and nitrobenzene in hydrogen (8AA); binary gaseous diffusion coefficients of n-alkanes or sulfur hexafluoride in helium, argon, or nitrogen ( 9 A A , IOAA); and t h e gas permeation of helium or argon through polyethylene (34AA, 35AA). Gas chromatography was used t o determine the glass transition temperatures of polystyrene, poly(methy1 methacrylate), styrene-butadiene copolymer, and poly(viny1 chloride) by using n-alkanes or n-alcohols as probe solutes ( 4 A A ) ,and the transition temperatures (melting point) of sodium stearate (76AA). Kelker (36AA) reported a theoretical study which suggests t h a t a linear relationship exists for the logarithm of specific retention volume data for various solutes on different liquid crystals a t the temperature of their isotropic transition when these data are plotted vs. their reciprocal isotropic transition temperatures. Recently there have been a number of novel uses or theories which have measured kinetic data by gas chromatography. Rubinstein and Silchenks (64AA) measured the dynamics of sorption with a reactangular isotherm for kinetics limited by particle diffusion for fulvic acids on activated charcoal. Schulz (66AA)studied the reaction kinetics of two solutes which react irreversibly with each other by consecutive injections onto a gas chromatographic column. Microreactions coupled to gas chromatography have been used to study the kinetics of the oxidation or cracking of hydrocarbons (56AA). The formation of the following complexes was investigated by gas chromatography: antimony trichloride with sodium tetrachloroferrate (65AA);benzene and alkene derivatives with 1-chlorooctadecane (48AA);dodecyllaurate with 1-chlorooctadecane (49AA);substituted alcohols with hexadecyl and dioctyl compounds (18AA); picric acid with napthalenes (16AA);and a theoretical discussion which accounts for the discrepancies between measurements obtained for association constants obtained by gas chromatography and nuclear magnetic resonance spectrometry (47AA). Crow and coworkers (ISAA-ISAA) continued their earlier studies in which the isomerization processes of various carbenes to nitrenes were followed by gas chromatography via isotopic labeling. Gas chromatography continued to be used t o measure the vapor pressure of molecules with low volatilities or substances which are difficult to prepare in ultra-high purity: e.g., 2,4,6-trinitrotoluene (41AA);dibenzothiophene ( 3 A A ) ;and anthracene and triethyleneglycol di-2-ethylbutyrate (61AA). Inorganic GC. T h e use of GC for metals analysis has continued to receive attention by a limited number of laboratories. Burgett (8BB),Komarov (25BB),and Jacquelot and Thomas (20BB)reviewed this field in general and discussed the most recent applications which have used new complexing agents to form volatile metal complexes. Also a general review of t h e properties and applications of fluorinated metal 1,3diketonates has been published (2ZBB). Included in this review is a section devoted to the separation of these chelates by gas chromatography. One problem that has been experienced with metal analysis by gas chromatography is that the detection limits are compound dependent. This has been traditionally attributed to decomposition of t h e metal complexes on t h e column. However a study by Tanikawa (5OBB)showed that the sensitivities of the mass spectrometer, flame ionization detector, and electron capture detector are largely dependent upon the thermal stability and the identity of t h e metal atom.
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T h e successful separation of the rare earth trifluoroacetylacetonates was reported by doping the carrier gas with the ligand (1%)( I 5 B B ) . This had the effect of reducing the decomposition of these chelates on the column and produced the first successful separation of these d-diketonates. Better separations of groups of lanthanide 2,2',6,6'-tetramethyl3,s-heptanedionates have been described on a column packed with coated steel beads (22BB). No mention was made whether any reaction occurred between these chelates and the solid support which was the cause of poor separations in earlier reports. Twenty- five other metal atoms were complexed with this same ligand and the resulting complexes were separated on very short chromatographic columns (37BB). In his doctoral thesis, Leddet (28BB) reported the separation of various pyridine complexes of manganese, magnesium, cobalt, nickel, and copper. T h e gas chromatographic and thermogravimetric analyses of various metal chelates of 2-picolylalkylketones was discussed recently (23BB). This novel ligand complexes the metals through oxygen and nitrogen atoms. Nickel and zinc (33BB),or zinc, nickel, and copper ( 5 I B B ) , or nickel (26BB) bis(N,N-diethyldithiocarbamates) have been prepared and separated. This complexing agent warrants further interest since there are few good ligands for divalent metals. Mangia ( 3 I B B ) repeated other earlier studies and separated the benzoyltrifluoroacetonates of cobalt, nickel, and copper. T h e use of di-n-butyl sulfoxide or tri-n-butyl phosphate adducts with hexafluoroacetylacetone (36BB,38BB) continued to receive attention for the separation of divalent metals (Mn, Fe, Co, and Ni (36BB),and Zn (38BB). Fontaine (14BB),in his doctoral thesis, described a method for the separation of uranium and thorium via complexation and gas chromatography. Makarenko et al. (30BB) reported the separation of trimethylantimony, trimethylarsenic, dimethylselenium, and tetramethyltin. These workers took precautions to remove oxygen and water from the carrier gas and found that, under these conditions, well-shaped elution peaks were obtained. T h e dialkyldithiophosphates of zinc, nickel, palladium, chromium, and rhodium were reported as novel complexes for the analysis of metals by gas chromatography (6BB). These complexes eluted without any evidence of decomposition or tailing. Organolithium compounds were determined by monitoring the reaction products or the decrease in reactants after reaction with allyl bromide or 1,2dibromomethane (44BB). Dilli and Patsalides (13BB) reported. for the first time, the elution behavior of seven tetradentate d-ketoamines of oxovanadium and demonstrated the separation of these complexes from the corresponding nickel and copper complexes. The atmospheric determination of tetraalkyllead compounds continued to receive interest; Chau et al. ( I I B B ) described a complete methodology which includes trapping, separation, and detection by atomic absorption spectrometry. T h e reaction of the following nonmetals with carbon tetrachloride to form volatile halides has been described under various reaction conditions; germanium (18BB,35BB),arsenic (19BB),antimony (42BB,52BB, 58BB), tin (58BB), and silicon ( I B B ,34BB, 39BB). The resulting reaction products Rere then separated by gas chromatography and special care was taken to prevent the hydrolysis of the halide. Many successful attempts have been made to analyze selenium using various substituted amino benzenes (2BB,3BB, 40BB, 45BB-47BB, 57BB). These so called piazselenals are formed quantitatively in the presence of strong acids and can be extracted into toluene and subsequently separated by gas chromatography. This procedure was used for a variety of sample types which range from milk to alloys. T h e formation of hydrides, alkyl or aryl derivatives of arsenic (I6BB,48BB, 49BB),germanium (12BB,53BB),selenium (IOBB),tin (24BB, 32BB, 53BB),and silicon (55BB), have also been reported. These volatile compounds were formed quantitatively, separated with high purity carrier gases, and various detectors were used to monitor the eluted solutes. T h e analysis of chromium in natural water (29BB) and in urine ( 4 I B B ) via chelation with trifluoroacetylacetone was reported. &o, Kutal and Sievers (27BB)made a rate and equilibration study of the cis-trans isomerization of chromium-trwtrifluoroacetylacetonate. Various nickel complexes have been separated by Bruk et al. (7BB) (bis(isopropy1cyclopentadienyl)nickel, (isopropylcyclopentadienyl)nickel, and nickelocene). T h e analysis of inorganic mercury and
organomercurial compounds in water (56BB),biological (9BB, 56BB), and food samples (43BB, 54BB) was reported using alkyl mercury derivatives and forming these compounds by alkylating inorganic mercury. Belcher et al. (5BB)discussed the thermogravimetric and gas chromatographic characteristics of some aryl mercury compounds and suggested that these compounds may be used for the determination of halogens. A new method for the concentration of methyl mercuric chloride was proposed based on foam separation using potassium n-butylxanthate a n d cetyltrimethylammonium bromide ( 17BB). The determination of inorganic phosphates in clinical studies represents a major problem which may be solved by GC/MS, particularly if stable isotopes are used as tracers. Barlthop and Lewis (4BB) described a complete methodology in which the phosphate was precipitated as silver phosphate, then reacted with 1-bromobutane to form tri-n-butylphosphate, and determined gas chromatographically. This methodology was used to analyze phosphates in milk and feces. Novel Applications. Other interesting areas of analysis in which GC has been applied during the past two years have involved numerous areas of national and international importance. These included the search for a possible involvement of a nonbiological toxin in the "Legionnaires Disease" (22CC), studies of schizophrenic humans (15CC), human breast tumors (27CC), anti-convulsant drugs ( I S C C ) , drugs of abuse ( 1 2 0 2 , 23CC), pesticides (25CC) and odors (37CC) in drinking waters, commodity source identification (IOCC),and dibenzofurans (26CC) such as PCDD's and TCDD from the Seveso incident. Examples from the basic sciences are illustrated by the physicochemical and inorganic measurements described elsewhere in this paper, kinetics and mechanisms of organic chemical reactions ( I C C , 1 4 C C ) , and the biochemical behavior of scallops by characterization of their sterol profiles by research groups in the United States and Canada (32CC), Japan (20CC), England (3CC), and Scotland ( I 7 C C ) . T h e isolation of sex pheromones in the grape berry moth (35CC),locust (31CC),cabbage lopper (13CC),and a South African moth (34CC) as well as molting hormones from the tobacco hornworm (19CC),organophosphorous poisoning in the Canadian goose, pigeon, and Japanese quail (18CC), and hepatic metabolism studies in the sheep, cow, pig, guinea pig, rat, turkey, chicken, and duck (24CC)were published. Very interesting results and compounds were separated and identified in the avocado (5CC), deboned chicken ( 2 l C C ) , laboratory monkey chow (38CC), blemished and diseased sweet potatoes (7CC), human urine after eating asparagus (36CC), and inks from XIth to XVIth century manuscripts (2CC). T h e international character of GC may be found in the analysis of DDT in the Australian bent-winged bat ( I I C C ) , cephalic secretions of South African stingless bees ( K C ) , volatiles in Moroccan thyme oil (28CC),pesticides in ant baits in Trinidad (33CC),oils in Lebanese arrack (9CC),essence of Bulgarian roses (39CC),coloring pigments in the wax of the wooly apple aphid in Australia (6CC), and pesticides in pelicans in Idaho (4CC),and the omental fat of Florida racoons (29CC).
ACKNOWLEDGMENT T h e authors acknowledge the assistance in researching, typing, and proofreading this manuscript of Mrs. A. Munro and S.Bird. LITERATURE CITED INTRODUCTION
(1A) "Annual Book of ASTM Standards: Emission, Molecular, and Mass Spectroscopy; Chromatography: Resinography; Microscopy", American Society for Testing and Materials, Philadephia, Pa. 1977, designation E 355-77. (2A) Cram, S. P., Juvet, R. S., Anal. Chem., 48 (5), 411R (1976). (3A) Grob, R. L., Ed., "Modern Practice of Gas Chromatography", Wiley, New York, N.Y., 1977, p 21. (4A) Guthrie, F. A,, "Directory of Members and Divisional History", American Chemical Society, Division of Analytical Chemistry, Washington, D.C.. 1977 BOOKS AND REVIEWS
(le) Anvaer, B. I., Drugov, Y. S., "Gas Chromatography of Inorganic Substance", Khimiya, USSR, 1976.
ANALYTICAL CHEMISTRY, VOL. 50, NO. 5, APRIL 1978 (28)Baiulescu, G. E., "Stationary Phases in Gas Chromatography", Pergamon Press, Rome, 1975. (3B) Berck. B., J . Chromatogr. Sci., 13, 256 (1975). (4B)Berezkin. V G.. Alishoyev. V. R., Nemirovskaya, I. B., "Gas Chromatography of Polymers", Elsevier, Amsterdam, 1977. (56) Berezkin. V. G.. Fateyeva, V. M., Zh. Anal. Khim., 29, 2453 (1974). (6B)Berezkin, V. G.. Gavrichev, V. S., Kolomiets. L. N.. "Gas Chromatography in Petroleum Chemistry", Nauka. USSR, 1976 (78)Berezkin, V. G.. Pakhomov, V. P., Sakodynskii, K. I . , "Solid Supports in Gas Chromatography", Moscow, USSR, 1975 (8B) Beroza, M., J . Chromatogr. Sci., 13, 314 (1975). (9B) Blake, M. I., Crespi, H. L., Katz. J. J.. J . Pbarm. Sci., 64, 367 (1975). (106) Bowman. M. C., J . Chromafogr. Sci., 13, 307 (1975). (11B) Brazhnikov, V. V., "Differenthl Detectors for Gas Chromatography", Nauka. USSR, 1974. (l2B) Burchfield, H. P., Storrs, E. E., J . Chromatogr. Sci.. 13, 202 (1975) (138) Cobler, J. G., Chow, C. D., Anal. Chem., 49 (5), 159R (1977). (148) Conacher, H. 8. S., J . Chrornatogr. Sci., 14, 405 (1976). (158) Dickes, H. J., Nicholas, P. V., "Gas Chromatography in Food Analysis", Halsted Press, New York, N.Y., 1975. (16B)Dimitrov, Kh , Petsev, N., "Gas Chromatography", Nauka Izkustv., Bulgaria 1974. (178) Dinnin, J I., Anal. Chem.. 49 (5),34R (1977). (186) Dorough, H. W., Thorstenson, J. H., J , Chromatogr. Sci., 13, 212 (1975). (19B)Ettre, L. S , "Gas Chromatography Using Capillary Tubes. An Introduction". Vieweg and Sohn, Braunschweig, Germany, 1976. (208) Ettre, L. S.,J . Chromatogr., 112, l(1975). (21B) Evenson, M. A., Anal. Chem , 49 (Si, 16R (1977). (228) Fishbein, L., J . Chromafogr. Sci., 13. 238 (1975). (23B) Fishman, M. J., Erchlmann, D. E., Anal. Chem.. 49 (5).139R (1977). (248)Foltz, A. K., Yeransian. J. A., Sloman. K. G.. Anal. Chem., 49 (5),194R (1977). (258) Fraser, J. M., Anal. Chem., 49 (5), 231R (1977). (268)"Gas Chromatography Literature Abstracts and Index", Preston Technical Abstracts Co., Niles, Ill. (278) Giddings. J. C . . Grushka, E., Cazes, J., Brown, P. R., Ed., "Advances in Chromatography", Vol 14. Marcel Dekker, New York, N.Y., 1977. (288)Golbert, K. A., Vigdergauz, M. S., "Course in Gas Chromatography", 2nd ed., Khimiya, USSR, 1974. (298) Gosink, T. A.. Environ. Sci Technol.. 9, 630 (1975). (308) Grant, D. W., J , Chromatogr., 122, 107 (1976). (31B)Haken, J. K., "Gas Chromatography of Coating Materials", Marcel Dekker, New York, N.Y., 1974. (328) Harrison, R. M., Perry, R . , Wellings, R. A,, Wafer Res., 9. 331 (1975). (338) Husek, P., Macek, K., J . Chromafogr., 113, 139 (1975). (348) Jentzsch. D., "Gas Chromatography: Principles, Application, Methods", 3rd ed., Franckh. Verlagshandlung, Germany, 1975. (358) Kaiser, R., "Gas Phase Chromatography". Vol. 2 : Capillary Chromatography. Thin-Film and Thin-Layer Gas Chromatography, 3rd ed., Bibliogr. Inst., Germany, 1975. (368) KarDov Sci. Res. Phys. Chem. Inst., "Processes in Chromatographic Columns". Moscow, USSR, 1974. (378) Kashutina, M. V., Ioffe, S. L., Tartakovskii, V. A,, UspekhiKhim., 44,
1620 (19751.
(38B)-Khan, M, A., Rao, R. M.. Novak, A. F., Crit. Rev. Food Sci. Nutri., 7 ,
103 (1976). (398) Knapmand, C . E. H., Parris, N. A., Ed., "Gas and Liquid Chromatography Abstrtcts", Appl. Sci. Publ., Essex, England.
(408) Kogan, L. A,, "Quantitative Gas Chromatography". Khimiya, Moscow, USSR, 1975. (418)Kotsev, N., "Guide for Gas Chromatography", Yir, Moscow, USSR. 1976. (428)Kotsev, N., "Handbook of Gas Chromatography", Mir. Rub, USSR, 1976. (43B) Ma, T. S., Ladas, A. S., "Organic Functional Group Analysis by Gas Chromatography", Academic Press, New York, N.Y., 1976. (44B) Maga, J. A,, Crit. Rev. food Sci. Nutr.. 6, 241 (1975). (458)Masada, Y., "Analysis of Essential Oils by Gas Chromatography and Mass Spectrometry". Wiley, New York, N.Y.. 1976. (46B) Matucha, M., Smolkova. E.. J . Chromatogr., 127, 163 (1976). (478) McLeod, H. A,, J . Chromatogr. ,Sci., 13, 302 (1975). (488) Melville, R . S..Dobson, V. F., Selected Approaches to Gas Chromatography-Mass Spectrometry in Laboratory Medicine", U.S.Dept. Health, Education, and Welfare, National Institutes of Health, Bethesda, Md., 1975. (498) Nesterov, A. E., Lipatov, Yu. S., "Inverse Gas Chromatography in the Thermodynamics of Polymers". Naukova Dumka, USSR, 1976. (50B) Novak, J., "Quantitative Anatysis by Gas Chromatography", Marcel Dekker. New York, N.Y., 1975. (518) Oller, W. L., Cranmer, M. F., J , Chromatogr. Sci., 13, 296 (1975). (52B) O'Neili, L. A., Proc. Anal. Div. Chem. Soc., 12, 233 (1975). (538)Pankov, A. G., Khripin, E. G., "Quantitative Gas Chromatography in the Production of Monomers for Synthetic Rubber", Neftepererab. Neftekhim. Prom. Rub, USSR, 1977. (548)Paryjczak, T., "Gas Chromatography in Studies of Adsorption and Catalysis", Panst. Wyd. Nauk., Poland, 1975. (55B) Peyron, L., Spectra 2000, 3. 31 (1975). (568)Rotin. V. A. "Radioionization Detection in Gas Chromatography", Atomizdat. Ruble B., USSR, 1974. (57B)Rudenko. B. A., Baidarovstseva, M. A,, Agayeva, M. S., Zh. Anal. Khim., 30, 1191 (1975). (588) Saltzman. 8. E., Burg, W. R., Anal. Chem., 49 (5),1R (1977). (59B) Scanlon, R. A., Crit. Rev. Food Technol., 5, 357 (1975). (60B) Schomburg, G., Dielmann, R., Husmann, H., Weeke, F., J , Chromatogr., 122. 55 (1976). (61B) Sevcik. J.. "Detectors in Gas Chromatography", Elsevier, Amsterdam,
1976. (628)Stepovaya. L. P.. Kholkin, Yu. I., "GLC of Monosaccharides as Trirnethylsilyl Derivatives". Khromatog. Anal. Khim. Drevesiny, Riga, USSR, 1975.
233R
(63B)Storch de Garcia, J. M.. "Fundamentals of Gas Chromatography", Alhambra, Spain, 1975. (64B)Sunozova, E. V., Trubnikov, V. I., Sakcdynskii, K. I., "Gas Chromatography of Amino Acids", Nauka, USSR, 1975. (658)Tekhniki, I. N., "Chromatography", Vol. 1. Viniti. Acad. Sci., USSR, 1974. (66B) Thornburg, W.. Anal. Chem., 49 (5),98R (1977). (67B) Umbreit, G. R., Chemtech, 7, 101 (1977). (68B)Vyakhirev, D. A,, Shushunova, A. F., "Manual for Gas Chromatography", Vysshaya Shkola, Moscow, USSR.
(69B) Wadelin, C . W., Morris, M. C . , Anal. Chem., 49 (5), 133R (1977). (708) Waksmundzki, A,, "Use of Gas Chromatography in Physicochemical Studies", Zakl. Nor. I m . Pssolinskich, Poland, 1974 (718)Weiner, P. H., Chemtech. 7 , 321 (1977). (72B)Yevtushenko, N. S.,Yaskina, D. Z., Chumachenko, M. N.. Treshunova, T. S., farmafsiya. 23, 74 (1974). (73B) Yip, G., J , Chromatogr. Sci., 13, 225 (1975). (748) Zabkiewic, J. A,, Chem., N . Z . , 38. 73 (1974) (758) Zak, B., Clin. Chem., (Winsfon-Salem, N . C . ) , 23, 1201 (1977). (768) Zavattini, G., Boll. Chim. Farm., 115, 65 (1976). (778) Zeman, I."Chromatographic Separations Separations in Surfactant Analyses". Olomouc, Czechoslovakia. 1976. COLUMNS
Column Theory and Techniques
(1C) Berezkin, V. G., Loschilova. V. D., Pankov, A. G., J . Chromatogr., 112, 353 (1975). (2C) Berezkin, V. G., Pankov, A. G., Loshchilova, V. D., Chromatographia. 9,
490 (1976). (3C) Bowers, W., Hawkes, S.. J . Chrornatogr., 134, 166 (1977). (4C) Chastrette, M., J , Chromafogr. Sci., 14, 357 (1976). (5C) Chen, T. M., Hess, G. G., Severs, R. E., J . Chromatogr.. 134, 170 (1977). (6C) Chupanova. A. V., Aivazov, B. V., T r . Khim. Tekhnol., 1974 (3),79. (7C) Cluff, J. R., Hawkes, S. J., J . Chromatogr. Sci., 14, 248 (1976). (8C)Cram. S. P., Glenn, T. H., Jr.. J . Chromatogr., 112, 329 (1975). (9C) Czajkowska, T., Waksmundzki. A,, J . Chromatogr., 119. 91 (1976). (1OC) Deininger, G., Chromatographia, 9, 251 (1976). (11C) De Ligny, C . L., Hammers, W. E , J . Chromafogr., 141, 91 (1977). (12C) Delley, R., Chromatographia, 9, 10 (1976). (13C) Dwyer, J., Karim. K. A., Ind. Eng. Chem.. Fundam., 14, 196 (1975). (14C) Ebel, S.,Kaiser, R. E., Chromatographia, 7,696 (1974). (15C) Ettre, L. S..Chrornatographia, 8 , 291 (1975). (16C) Ettre, L. S., Chromatographia. 8 , 355 (1975). (17C) Ezrets, V. A., Vigdergauz, M. S., Chromatographla, 9, 205 (1976). (18C)Filonenko, G. V., Dovbush, T. I., Korol, A . N., Chromatographia, 7. 293 (1974). (19c)FitzgeraM, P. L., Gallaher, T. N., Palocsay, F. A., Leary, J. J., J. Chromatogr. Sci., 15, 119 (1977). 12Oc) Granaer. R.. Veranaud. J.-M.. C . R . Hebd. Seances Acad. Sci.. Ser. C 2 8 2 , 5 5 9 (1976)" (21C) Haken, J K , Wainwright, M S I Smith, R J J Chromatogr , 133, 1 (1977) (22C) Hawkes, S. J.. J . Chromatogr., 124, 359 (1976). (23C) Holderith, J., Toth, T., Varadi, A., J . Chromatogr., 119, 215 (1976). (24C)Huber, J. F. K., Lauer, H. H., Poppe, H., J. Chromatogr., 112, 377 (1975). (25C)Jonsson, J. A., Jonsson, R., Malm, K., J . Chromatogr., 115,57 (1975). (26C) Kaiser, R. E., J . Chromatogr., 112, 455 (1975). (27C) Kalinichev, A. I., Pronin. A. Ya., Zolotarev, P. P., Goryacheva. N. A,, Chmutov, K. V., Filimonov, V. Ya., J , Chromafogr., 120, 249 (1976). \
. I
(28C) Kanunnikova, Ye. V., Gryaznov, V. M., Yanovskii, C M., Pavlova, L. F.. Zhukhovitskii, A. A,, Zavod. Lab., 42, 15 (1976). (29C) Karger, J., Renner, E., Schollner, R., Seifert, H.-G., Chem. Technol., 27, 38 (1975). (30C) Lange, P. K., Shafranski, I.V., Avtomatiz. Kontrol. izmerif. Prib.. 1974 (6),9. (310 Katsanos, N. A.. Karaiskakis. G., Karabasis. I Z., J Chromatogr., 130. 3 (1977). (32C) Laub, R. J.. Purneii, J. H., Anal. Chem., 48, 799 (1976). (3%) Laub, R. J., Purnell, J. H., Anal. Chem., 48, 1720 (1976). (34C) Laub, R. J., Purnell, J. H., J . A m . Chem. Soc., 98, 30 (1976). (35C) Laub, R. J.. Purnell, J. H., J , A m . Chem. Soc., 98, 35 (1976). (36C) Laub, R. J., Purnell, J. H., J . Chromatogr., 112. 71 (1975). (37C)h u b , R. J., Purnell, J. H., Williams, P. S., J . Chromatogr., 134, 249 (1977). (38C)Lauer. H. H., Poppe, H., Huber. J. F. K., J . Chromatogr., 132, 1 (1977). (39C)Le Parlouer, P., Boinon, B., Vergnaud, J.-M., C. R . Hebd. Seances Acad. Sci., Ser. C , 280, 933 (1975). (40C) Li, K.-P., Li, Y.-Y. H., Anal. Chem., 48, 737 (1976). (41C)Lynch, D. F., Palocsay, F. A,, Leary, J. J., J Chromatogr. Sci., 13. 533 (1975). (42C) 2112Mariich. (1975). L. I., Lenkevich, Zh. J.. Ganzha, L. M., Zb. Anal. Khim., 30,
(43C) McKeag, R. G., Hougen, F. W., Anal. Chem., 49, 684 (1977). (44C)Molera. M. J.. Dominguez. J A G., Biarge. J F., J Chromafogr. Sci., 14, 299 (1976). (45C) Morgan, S.L., Deming. S. N., J . Chromatogr.. 112, 267 (1975). (46C)Myagkov, Ye. A., Guglia. V. G I Okhotnikov. B. P., Zhukhovitskii, A. A,, Zavod. Lab., 40, 1183 (1974). (47C) Myagkov, Ye. A., Zhukhovitskii, A. A., Zavod. Lab., 41, 783 (1975). (48C)Ohzeki, K., Kambara, T., Kodama, K., J . Chromatogr., 121, 199 (1976). (49C) Parcher, J. F., Ho. T. H., Haynes, M. W., Jr., J . Phys. Chem., 80, 2656 (1976). (50C) Parcher, J. F.. Westlake. T. N.. J . Chromatogr., Sci., 14,343 (1976). (51C) Pauls, R. E., Rogers, L. B., Anal. Chem., 49, 625 (1977). (52C) Petitclerc, T., Guiochon, G., J . Chromatogr. Sci.. 14, 531 (1976). (53C)Purnell, J. H.. Vargas de Andrade, J. M., J . Am. Chem. Soc.. 97, 3585
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(1975). (54C) Purnell, J. H., Vargas de Andrade. J. M., J . Am. Chem. Soc., 97, 3590 (1975). (5%) Rayss, J.. Waksmundzki, A . Chem. Anal. (Warsaw),21, 1045 (1976). (56C) Rijks, J. A.. Cramers, C. A,, Bocek, P., Chromatographia. 8, 482 (1975). (57Cl Rozhenko, I.N., Zyskin, A . G., Zelvenskii, V. Yu., Sakodynskii. K. I . , Chromatographia. 10, 25 (1977). (58C) Schulz, P., Anal. Chem., 47, 1979 (1975). (59C) Selzer, R. B , Howery, D. G.. J . Chromafogr.. 115, 139 (1975) (60C) Sevcik. J., J . Chromatogr.. 135, 183 (1977). (61C) Shkolina, L. A., Kugucheva, Ye. Ye., Berezkin. V. G.. Artemova, 0. A , Zavod. Lab., 41, 787 (1975). (62C) Smit, H. C., Walg. H. L., Chromatographia, 9, 483 (1976). (63Cl Suzuki, M.. Yamato. Y., Watanabe, T., J . Assoc. Off. Anal. Chem.. 58, 297 (1975) (64Cl Szentirmay, Zs., Tarjan, G., Bekesi. L., Gajari, J.. Takacs, J. M., J . Chromatogr., 119, 333 (1976). (6%) Valentin, P., Guiochon, G.. J . Chromatogr. Sci., 14, 56 (1976). (66Cl Valentin, P., Guiochon, G.. J . Chromatogr. Sci., 14, 132 (1976). (67C) Valentin, P., Guiochon, G., Sep Sci., 10, 245 (1975). (68C) Valentin, P , Guiochon, G., Sep Sci., 10, 271 (1975). (69C) Valentin. P.. Guiochon, G., Sep. S o . , 10, 289 (1975). (7OC) Vigdergauz, M. S., Zh. Anal. Khim.. 30, 2035 (1975). (71C) Vink, H., J . Chromatogr., 135, 1 (1977). (72C) Waksmundzki, A., Rayss. J., J . Chromatogr., 119, 557 (1976). (73C) West, S. D., Hall, R. C.. J . Chromatogr Sci., 14, 339 (1976). (74C) Yamaoka. K.. Nakagawa. T., Anal. Chem., 47, 2050 (1975). (7%) Yamaoka, K.. Nakagawa. T , J . Chromatogr., 117, 1 (1976). (76C) Yamaoka, K., Nakagawa. T., J . Phys. Chem., 79, 522 (1975). (77Cl Yamaoka, K., Nakagawa, T., J . Phys. Chem., 79, 2515 (1975) (78C) Yamato, Y., Susuki, M., Watanabe, T., J . Assoc. Off. Anal. Chem., 59, 1180 (1976). (7%) Yau. W. W., Anal. C h e m , 49, 395 (1977). (80C) Zhukhovitskii, A. A,, Kanunnikova, Ye. V.. Novikova, L. G., Sazonov, M. L., Shvartsman, V. P., Yanovskii, M. S., Zavod. Lab.. 40, 1179 (1974). (8lC) Zhukovitskii, A. A., Yanovskii, S. M.. Shavrzman, V. P., J . Chromatogr , 119. 591 (1976). Liquid Phases (1D) Ackman, R. G., Eaton, C. A., J Chromatogr. Sci.. 13, 509 (1975). (2Dl Alessi, P., Kikic, I . , Papo. A., J . Chromatogr , 131, 31 (1977). (3D) Andrawes, F.. Brazell, R., Parr, W., Zlatkis, A,, J . Chromatogr., 112, 197 (1975). (4D) Ashes, J. R., Haken, J. K., J . Chromafogr.. 111, 171 (1975). (5D) Ashes, J. R.. Haken, J. K., .I Chromatogr., 118. 183 (1976). (6Dl Badoni, R. P.. Bhagat, S. D., Indian J , Chem., 14A, 905 (1976). (7D) Beitler, U., Feibush, B.. J . Chromatogr., 123, 149 (1976). (8D) Bhattacharjee, A.. Bhaumik, A , J . Chromatogr.. 115, 250 (1975). (9D) Bocquet, J. F , Pommier, C., J . Chromatogr.. 117. 315 (1976). (lOD) Brazell, R.. Parr, W., Andrawes, F., Zlatkis, A,, Chromatographia, 9, 57 (1976). (11D) Burns, W., Hawkes, S. J., J , Chromatogr. Sci., 15, 185 (1977). (12171 Charles, R., Beitler, U., Feibush. B., Gil-Av, E., J . Chromatogr., 112, 121 ( 1975). (13Dl Chastrette, M., Tagand, G., Chromatographia, 7, 176 (1974). (14D) Chupanova, L. V., Zhukhovitskii, A. A,. Aivazov, B. V., Zavod. Lab., 41, 538 (1975). (15D) De Clercq, H., Massart, D. L., Van Oudheusden, D.. Analusis, 3, 527 (1975). (16D) Drahokoupilova, M., Matousek, P., Horska, J., Chem. Prumysl. 26, 638 ( 1976). (17D) Eskes, A., Dupuis, F., Dijkstra, A , . de Clerq, H., Massart. D. L.. Anal. Chem., 47, 2168 (1975). (18D) Frank, H., Nicholson, G. J., Bayer, E., J. Chromatogr. Sci.. 15, 174 (1977). (19D) Gawdzik, J., Suprynowicz, 2.. Jaroniec, M.. J , Chromatogr., 131, 7 (1977). (20D) Grushka, E , Solsky, J. F , J Chromatogr , 112, 145 (1975). (21D) Guha, 0 . K., Bhaumik. A.. J . Chromatogr., 119, 181 (1976). (22D) Gvozdovich, T. N., Kiselev, A. V., Yashin. Ya. I., J . Chromatogr , 116, 63 (1976). (23D) Haken, J. K., J . Chromatogr. Sci.. 13, 430 (1975). (24Dl Haken, J. K., Ho, D. K. M., J . Chromatogr., 112, 135 (1975) (25D) Haken, J K.. Wainwright, M. S., Do Phuong, N., J . Chromatogr., 117, 23 (1976). (26D) Hall, M., Mallen, D. N B.. J . Chromatogr. Sci , 14, 451 (1976). (27D) Hall, M., Mallen, D. N. B., J Chrornatogr., 118, 268 (1976). (28D) Hawkes, S . , Grossman. D.. Hattkopf. A,, Isenhour. T.. Leary. J., Parcher, J., J . Chromatogr. Sci.. 13. 115 (1975). (29D) Heckers, H.. Dittmar, K., Melcher, F. W.. Kalinowski, H. 0.. J . Chromatwr., 135 93(1977) (30D) Hetper, J , Zasz Nauk Inst Giezk Synt Org Blachowni Slask , 4, 70 119741 (31D) Hillerova, E., Sir, Z . , Collect. Czech. Chem. Commun., 40, 1341 (1975). (32D) Itskikson, L. E., Shulgaitser, L. A,, J Chromatogr., 108, 358 (1975). (33D) Janini. G. M., Muschik, G. M.. Zielinski, W. L., Jr., Anal. Chem., 48, 809 (1976) (34Dl Janini. G. M., Shaikh, B., Zielinski, W. L., Jr., J . Chromatogr.. 132, 136 11977) I._..,.
(35Dl Janini, G. M.. Muschik, G. M., Schroer, J. A., Zielinski, W. L.. Jr., Anal. Chem.. 48. 1879 119761. (36D) Jeknavorian. A. A,: Barrett, P.. Watterson, A. C., Barrv. E. F., J . Chromatogr , 107, 317 (1975) (37D) Kapoor, V B , Rawat, B S I Nigam, R N , Indfan J Technol, 14, 306 11976) (38D) Karasek, F. W., Hill. H. H., Jr., Res lDev., 26 (12), 30 (1975) (39Dl Kelker. H., J . Chromatogr , 112, 165 (1975).
(40D) King, J. W.. Anal. Chem., 47, 1414 (1975). (41D) Kirsh, S. I.. Karabanov, N. T., Vigdergauz, M. S., Chromatographia. I O , 188 (1977). (42D) Kong, J. M., Hawkes. S. J., J . Chromatogr. S o , 14, 279 (1976) (43D) Konig, W. A , Chromatographia. 9, 72 (1976). (44Dl Korol, A. N., Chromatographia. 8, 335 (1975). (45D) Kraitr, M., Komers, R., Cuta, F.. Collect. Czech. Chem. Commun.,39, 1440 (1974). (460) Kraus, M., Kopecka. H.. J . Chromatogr., 124, 360 (1976). (47Dl Laub, R., Pecsok, R. L., G - I - T , 19, 202 (1975). (48D) Lekova, K., Gerasimoff, M., Chromatographla, 7, 595 (1974). (49Dl Lowry, S. R., Woodruff, H. B., Isenhour, T. L., J . Chromatogr. Sci.. 14, 129 (1976). (50Dl Lowrv. S R., Ritter. G L., Woodruff. H. B., Isenhour, T. L.. J , Chromatogr Sci., 14; 126 (1976). (51Dl Martynyuk, R . N. Vigdergauz, M. S.. Chromatographia, 9. 454 (1976). (52D) Mori, S., J . Chromatogr., 135, 261 (1977). (53D) Myher, J. J., Kuksls, A,, J . Chromatogr. Sci.. 13, 138 (1975). I 1 97RI Nikolov. R. N., Petsev. N. D., Stefanova, A. D., Chromatographia, 9, 81 (54Dl
,, " .
").
(55D) Novotny, M., Hayes, J. M., Bruner, F., Simmonds, P G., Science, 189 (4198), 215 (1975) (56D) Nurtdinov, S. Kh, Novikov, V. F., "Osnonvn. Organ. Sintez Neftekhim.". Vol. 3, Yaroslavl. USSR, 1975, pp 139-42. (570) Olsson, A -M.. Mathiasson, L., Jonsson, J. A,, Haraklson. L., J. Chromtogr , 128, 35 (1976) (58D) Pacakova, V.. Ullmannova, t i , Chromatographia, 7, 175 (1974) (59D) Packova, V , Ullmannova, H Smolkova, E , Chromatographia, 7, 171 119741 (60D) Pailer, M., Hlozek, V., J . Chromatogr., 128, 163 (1976). (61D) Pesek, J. J., Graham, J. A,. Anal. Chem., 49, 133 (1977). (62D) Pesek, J. J., Daniels, J. E., J . Chromatogr. Sci., 14, 288 (1976). (63D) Petsev, N. D.. Petkov, V. H., Dimitrov, Chr., J . Chromatogr., 114, 204 (1975). (64D) Pielichowski, J., Hetper, J.. Kyziol, J. 6..Chem. Anal. (Warsaw),21, 1191 (1976). (65D) Rehak, V., Smolkova, E.. Chromatographia, 9, 219 (1976). (66D) Ryba, M., J . Chromatogr., 123, 327 (1976). (67Dl Sannier, H., Renon, H., Bull. SOC.Chim. Fr., Part I, No. 1-2, 85 (1976). (88D) Schwartz, R. D., Mathews, R. G., Ramachandran, S., Henly, R. S., Doyle, J. E., J . Chromatogr., 112 111 (1975). (69D) Sebestian, I.,Halasz, I . , Chromatographia, 7, 371 (1974). (70D) Semenchenko, L. V., Vigderguaz, M. S., Zh. Anal. Khim.. 30, 883 (1975). (71D) Serpinet, J., Chromatographia, 8, 18 (1975). (72D) Shnol, V. Ya.. Fridman, V. A,, Gelshtein, R. M.. Khim. from., 1975, 898. (73D) Sobolevskii. M. V., Nazarova, D. V., Stegalkina, V. V., Luskina, B. M., Konovalova, L. V., Turkeltaub. G. N., USSR Patent No. 397 842 (March 2. 1974). (74D) Souter, R. W , J Chromatogr.. 114, 307 (1975). (75D) Stolting. K , Konig, W. A., Chromatographia, 9, 331 (1976). 176D) Stvskin, Ye. L.,Tarabai, Ye. P., Chikishev, Yu. G., Lukoyanova, L. V., Zavod. L a b , 41, 667 (1975). (77D) Tarjan, G.. Kiss, A,, Kocsis, G.. Meszaros, S., Takacs, J. M., J. Chromtogr., 119. . ... 327 .- 119761. -, (78D) Tesarik, K., Borkovcova. I.. Chromatographia, 8, 286 (1975). (79Dj Trommsdorff, H., G - I - T , 18. 764 (1974). (80D) Tsuge, S., Fujimoto, T.. Miyahara, N , Kobayashi. T., Takeuchi. T., J . Chromafogr. Sci., 15, 73 (1977). (81D) Tyson, B. J., J . Chromatogr.. 111, 419 (1975). (82Dl Utkin, V. A., Kobrina, V. N., Khmelnitskii, A. G.. Izv. Sibir. Otd. Akad. NaUk, SSSR 1975; Ser Khlm. Nauk, No. 2 , 154 (1975). (83Dl Verachtert, H., Van Oevelen, D., Bevers, J., J , Chromatogr., 117, 295 (1976). (84D) Vernon, F.. Edwards, G. T., J . Chromatogr., 110, 73 (1975). (85D) Vernon. F., Edwards, G. T., J . Chrornatogr.. 114, 87 (1975). (86Dl Vernon, F., Ogundipe, C. 0. E., J . Chromatogr., 132, 181 (1977). (87Dl Vetrova, 2 . P., Vyakhirev. D. A.. Karabanov, N. T., Maidatsenko, G. G., Jashin, Ja. I., Chrohatographia, 8, 643 (1975). (88Dl Vigdergauz, M. S., Bankovskaya, T. R., Chromatographia, 9, 548 (1976). (89Dl Waksmundzki, A,, Rayss, J., J . Chromatogr., 119, 557 (1976). (90D) Wasik, S., Chesier, S.. J . Chromatogr., 122, 451 (1976). (91D) West, S D., Hall, R. C., J . Chromatogr. Sci., 14, 339 (1976). (92D) Wold, S., J . Chromatogr. Sci., 13, 525 (1975). (93Dl Zerba, E. N., Ruveda. M. A., Libertella, R., J . Chromatogr., 108, 380 (1975). (94Dl Zielinski. W. L., Martire, D. E., Anal. Chem.. 48. 11 11 (1976). (95D) Zielinski. W. L., Jr., Johnston. K.. Muschik, G. M., Anal. Chem., 48, 907 (1976). \
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Solid Supports (1E) Atanasova, A., Nauchn. T r . Plovdlv. Univ., (Bulgaria),12 (31, 67/75 (1974). (2E) Atanasov, A., Shever, G. I., Khim. Ind. (Bulgaria),47 (21, 89 (1975). (3E) Aue, W. A.. Daniewski, M. M., Picket E. E., J. Chromatogr., 111, 37 (1975). (4E) Bebris, N. K.. Berezkin, V. G., Kiselev, A. V.. Nikitin, Yu. S., Pakhomov. V. P., Zavod. L a b , 41, 785 (1975) (5E) Berezkin, V. G.. Gavrichev, V. S., J . Chromatogr., 116, 9 (1976). (6E) Fisher, S. I., Aliev, M. I., Alkhazov, T. G., Vagdasaryan, 8 . V.. Sultanov, N. T., Shirinbekova, F. I., Shapovalov, L. A., Khim. Technol. Topliv. Masel, 1975 (41, 53. 17E1 . , Gavrilova. T. B., Issled. Sintetich. Prirod. Mineral. Adsorb., State Univ.. Sarafov. USSR. 1974, 59. (8El Gawdzik, J.. Suprynowicz, Z.,Jaroniec, M., Chromatographia, 10, 191 119771. , - , (9E) Golovnya, R. V., Zhuravleva. I . L., Kapustin, Yu P., Zh. Anal. Khim., 30, 2241 (1975).
ANALYTICAL CHEMISTRY, VOL. 50, NO. 5, APRIL 1978 (10E) Gornak, A. I., Komarov. V. S., Issled Sintetich. Prircd. Mineral. Adsorb., State UdV.. Saratov, USSR, 1974, 109. (11E) Grushka, E.. Solsky. J. F.. J . Chromatogr., 112, 145 (1975). (12E) Guha, 0. K., Goswami, T. K., J . Chromatogr , 135, 359 (1977). (13Ej Kazinik, Ye. M., Petrishcheva, G S., Batukova. G. I . , Moiseyeva, A. F., Zh Anal Khim.. 29, 2232 (1974). (14E) Li. J W., Kim. H. S.. Kim, J H.. Punsok Huahak, 12 (2), 79 (1974). (15E) Mokeyev, V. Ya., Gulova V. M I Surova, V V., Nitechim Cherkassy, USSR, 1974. (16E) Nesterov. A. Ye., Lipatov, Yu. S., L'ysokomol. Soyedin.. 17, 671 (1975). (17E) Res Ind, 19 (3). 111 (1974). (18E) Slattery, J. T.. Yavobi, A., Levy, G., Kaiser, D. G., J . Pharm Sci., 65, 1710 (1976). (19E) Suprynowicz, Z., Tracz. E., Chem. Anal. (Warsaw), 21. 1089 (1976). (20E) Tesarik. K., Kalab. P., Siavik. V I Chem Lisry. 69, 758 (1975). (21E) Tomi, P., Iuonas, E., Pop, F., Rev. Chim.. 25, 761 (1974). (22E) Tsitsishviii, G. V., Dolidze, L. Sh., Sabelashvili. Sh. D., Soobshch. Akad. Nauk Gruz. SSR, 75. 609 (1974). (23E) Vlasenko, Ye. V.. Gavrilova, T. B., Kiseiev, A. B., Sb. Nauchn. T r . Gazov. Khromatogr , 21, 30 (1974) (24E) Waksmundzki, A . Suprynowicz, Z.. Gawdzik, J , Trocewicz, J., Chem. Anal. (Warsaw), 20. 135 (1975). (25E) Zakharova, T. K.. Novikova, N I.. Trubnikov. V. 1.. Korolev. A A , , Berezkin. V. G I Sakosynskii. K . I . , Rubtsov, I . A., Fatayeva, V I., Sb. Nauchn. T r . Gazov. Khrornatogr.. 23, 29 (1974). Adsorption Columns (1F) AI-Bahrani, K. S., Martin, R . J., Water Res., 10, 731 (1976). (2F) Allulli. S.. Tomassini, N , Bertoni. G., Bruner, F.. Anal. Chem., 48. 1259 (1976). (3F) Andronikashvili, T. G., Banakh, 0. S., Soobshch. Akad. Nauk Gruz. SSR, 76, 365 (1974). (4F) Andronikashvili. T. G.. Tsltsishvili. G. V.. Laperashvili, L. Ya.. Chromatographb, 8 , 223 (1975). (5F) Bartle, K . 0.. Elstub. J., Novotny. M., Robinson. R J., J Chromatogr., 135, 351 (1977). (6F) Bebris. N. K., Bruk, A. I . , Vetrova, Z. P., Vyakhirev, D A,, Nikitin, Yu. S.. Kolloid 3 . .37. 627 119751. (7F) -Eelyakova: D:. Kalpakyan, A. M , Issled. Sintetich. Prirod. Mineral. Adsorb., State U n w Saratov, USSR, 1974, 120. (8F) Berezkin. V. G.. Gavrichev, V S., J . Chromatogr., 116, 9 (1976) (9FI Bezus, A. G., Kiselev. A. V., Makogon, A. M., Model, E. I.. Shcherbakova, K. D., Chromatographia. 7 , 246 (1974) (1OF) Bruk. A. I . , Vetrova. Z P . Vyakhirev. D. A . KaraDanov, N T., Yashin, Ya. I., Kolloid. Z h , 37, 118 (1975). (11F) Bruner, F., Bertoni. G.. Ciccioli. P.. J . Chromatogr., 120, 307 (1976). (12F) Bruner. F., Ciccioii. P , Bertoni. G.. J . Cbromatogr.. 120. 200 (1976). (13F) Butler, L. D.. Burke. M. F., J , Chromatogr. S c i , 14, 117 (1976). (14F) Carson, J. W., Lege, G.. Irizarry. J., J . Chromatogr. Sci.. 13, 168 (1975). (15F) Chen. S. L., Stein, R. A., Mead. J. F., Chem Phys. Lipids. 16, 161 (1976). (16F) Ciay. D. T.. Lynn, S., Anal. Chem , 47, 1207 (1975). (17F) Datar, A. G., Ramanathan, P. S., J . Chromatogr, 114, 29 (1975). (18F) Dericbourg. J., Chromatographia, 9, 333 (1976). (19F) Dericbourg, J., J , Chromatogr., 123, 405 (1976). (20F) DiCorcia, A., Liberti, A . , Sarnperi, R., J . Chromatogr , 122. 459 (1976). (21F) DiCorcia. A , Sarnperi, R., Anal. Chem , 47, 1853 (1975). (22Fj DiCorcia, A., Samperi, R . , J . Chromatogr.. 117, 199 (1976). (23F) DiCorcia, A., Samperi, R., Capponi, G., J . Chromatogr., 121, 370 (1976). (24F) Dufka, O.,Malinsky. J., 4th Natl Makrofest Conf Proc., P a r t I . 1976, 123. (25F) Dyer, A., Leigh, D.. Sharpies. W. E., J . Chromatogr., 118, 319 (1976). (26F) Eaton, H. G.. Thompson, J. K., Carhart. H. W., J Chrornatogr Sci.. 15. 36 (1977). (27F) Fortina, L.,Marani, A., Pinna, F., Traverso, P., Chim. Ind.. 57, 520 (1975). (28F) Frycka. J., Chromatographia, 8 , 413 (1975). (29F) Gavrichev. V. S., Berezkin, V. G., Zh. Fiz. Khim., 1974, 30. (30F) Gavrilova, T. B.. Kiselev, A. V., Storozhenko, T. M.. Kolloid Zh., 38, 1070 (1976) (31F) Gold, A.. Anal. Chem.. 47, 1469 (1975). 132F) Guseva, N. I.. Alekperova, S. A,, Dzhavadov, S. P . , Dzhafarly, S 2 . . Azerbaid. Khim Zh.. i 9 7 4 (4), 90. (33F) Gvozdovich, T. N.. Kiselev, A. V., Yashin, Ya. I . , J . Chromatogr., 116, 63 11976). (34Fj 'Hirsch, R. F.. Phillips, C. S. G.. Anal. Chem.. 49, 1549 (1977). (35F) Hsu. C. C.. Rudzinski, W., Wojciechowski. B. W., Chromatographia, 8 , 633 (1975). (36Fj Kalashnikova, E V., Kiselev, A. V.. Makogon, A M., Shchervakova, K D., Chromatographia, 8 , 399 (1975). (37F) Kawasaki, T., J . Chromatogr , 120, 271 (1976). (38F) Khobotova. T P., Yanovskii, S. M., Zhukhovitskii, A . A,, Sb. Nauch. T r . Gazov. Khromatogr., 23, 16 (1974). (39F) Kiselev, A. V., Zung, L., Nikitin. Yu. S.. Kolloid Zh., 34, 64 (1972). (40F) Komaita, T., Naito. K., Takei, S., J , Chromatogr., 114, 1 (1975). (41F) Komers. R., Collect. Czech. Chem. Commun.. 41. 1500 (1976). (42F) Kourini. A., Meicot, B., Serpinet, J., Chrornatographia, 9 , 523 (1976). (43F) Kraus, M., Kopecka, H.. J . Chromatogr , 124. 360 (1976). (44F) Krishnan, M S.. Ramanathan. P S.. Indian J . Technol., 14, 246 (1976). (45F) Kuchkayeva, I. K., Yegorova, S. A,, Bolotina, N. E., Kurnikova, N. R., Issled. Obl. flektrokhim. Fiz. Khim. Polimerov. Saratov, USSR, 1975, 35 (46F) Leboda, R., Chem. Anal (Warsaw), 21. 1001 (1976). (47F) Leboda, R.. Suprynowicz. Z., Waksmundzka-Hajnos, M.. Chem. Anal. (Warsaw), 21, 437 (1976). (48Fj Leboda. R.. Waksmundzki. A,, Sokolowski. S.. J . Chromatogr., 124, 60 (1976). (49F) Leboda. R.. Waksmundzki. A , Suprynowicz. Z., Raszewski. T . Chem. Anal. (Warsaw), 21, 831 (1976)
i.
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(5OF) Leboda, R., Waksmundzki, A., Suprynowicz, Z., Waksmundzka-Hajnos, M., Chem. Anal. (Warsaw), 21, 165 (1976). (51F) Long, M., Raverdino, V.. DiTuilio, G.. Tomarchio, L., J . Chromatogr., 117, 305 (1976). (52F) Lukas, J., Hradil, J., Krivakova. M., Coupek, J., J Chromatogr., 114, 335 (1975). (53F) Lykourghiotis, A . , Hadzistelios. I , Katsanos. N. A,, J . Chromatogr.. 110, 287 (1975) (54Fj Magidman, P., Barford, R. A,. Saunders. D H , Rothbart. H L , Anal Chem, 48 44 (1976). (55F) Mohlin, U-B.. Gray, D. G., J . Colloid Interface Sci., 47, 747 (1974). (56F) Molseyev, N., Platzner, I . , J . Chromatogr. Sci., 14, 143 (1976) (57F) Moriguchi. S., Naito, K.. Takei, S.. J . Chromatogr., 131, 19 (1977). (58F) Nikashina. V. A . , Zvereva, L. I., Olshanova, K. M., Potapova. M. A,, J . Chromatogr . 120, 155 (1976). (59F) Payrau, G I Chromatographia, 10, 17 (1977). (60F) Phillips, C . S G.. McIlwrick, C. R., Mackenzie, R. E., Chromatographia, 7 , 357 (1974). (61F) Phillips, J. B.. Burke, M. F.. J . Chromatogr. Sci., 14, 495 (1976). (62F) Podyacheva, G. M., Mokeyev. V. Ya., Barannik. I . D., Vigdergauz, M. S.. Zh. Anal Khim , 30, 1080 (1975). (63F) Pcdyacheva. G. M , Vigdergauz, M. S., Zh. Anal Khim., 30, 1903 (1975). (64F) Popl. M.. Dolansky, V , Mostecky, J., J . Chromatogr., 117, 117 (1976). (65F) Rang, S. A., Eisen, 0 . G., Kiselev. A. V., Meister, A. E.,Schcherbakova, K. D., Chromatographia, 8 , 327 (1975). (66F) Raymond, A,. Guiochon, G., J . Chromatogr. Sci., 13, 173 (1975). (67F) Rdzinski, W , Waksmundzki, A,, Lebcda. R.. Jaroniec. M.. Chromatograph!k. 7 , 663 (1974). (68F) Sakodynskii, K Panina, L.. Klinskaya. k., Chromatographb. 7, 339 (1974). (69F) Sarkar, H. S., Ghosh. S. K., Sinha, A,, Technol., 11. 400 (1974). (70F) Sarkar, H. S., Ghosh, S. K., Sinha. A,, Techno/., 11. 405 (1974). (71F) Sawatzky, H., George, A. E.,Smiley, G. T.. Montgomery. D. S., Fuel. 55, 329 (1976). (72Fj Scott, K. F.. Phillips, C. S. G., J . Chromatogr.. 112, 61 (1975). (73F) Serpinet, J., Anal. Chem.. 48, 2264 (1976). (74F) Soczewinski, E., Dzido. T., Golkiewicz, W., Chromatographia. 10, 298 (1977). (75F) Sokoiowski, S.. Lebcda. R.. Waksmundzki, A . J . Chromatogr., 128, 180 (1976). (76F) Suprynowicz, Z., Gawdzik, J., Jaroniec, M., J . Chromatogr., 133. 349 (1977). (77F) Suprynowicz. Z., Jaroniec, M.. J . Chromatogr., 117, 11 (1976). (78F) Suprynowicz. Z.. Jaroniec. M , Gawdzik J.. Chromatographia, 9. 161 (1976) (79F) Swallow, W H., Hentschel. P. R., J . Chromatogr., 130, 403 (1977). (80F) Szcepaniak. W.. Nawrocki. J.. J , Chromatogr., 138, 337 (1977) (81F) Tanaka, K., Ishizuka, T., Sunahara. H.. BunsekiKagaku. 25, 183 (1976). (82F) Tanaka, K., Ishizuka. T.. Sunahara. H., Yamada, S.. Bunseki Kagaku, 25, 187 (1978). (83F) Thouzeau. F , Chromatographia, 9. 506 (1976) (84F) Tremaine, P. R., Gray, D. G., Anal. Chem.. 48, 380 (1976). (85F) Tsitsishvili, G. V., Issled Sintet Prird'. Mineral. Adsorb . Saratov. USSR, 1974. 67 (86F) Tsitsishvili, G. V.. Andronikashvili, T. G.. Banakh. 0. S.. Soobshch. Akad. Nauk Gruz. SSR. 74. 345 (19741. (87Fj Tsitsishvili, G. V., Andronikashviii. T. G., Sabelashvili, Sh. D., Osipova, N. A., J . Chromatogr., 130, 13 (1977). (88F) Vetrova, Z P., Karabanov, N. T., Yashin, Ya. I..Kolloid. Zh., 37, 946 (1975). (89F) Wojciechowski, B. W., Rudzinski, W., J . Chromatogr., 137, 1 (1977). (9OF) Yelinek. A. V , Berman. A D.. Kholdyakov. N. I.. Yanovskii, M. I.,Franck, Yu. A., Kinet. Katal., 16, 992 (1975). (91F) Yevseev, L. N., Plachenov, T. G., Seballo, A. A , , Kinet. Katal., 16, 538 (1975). Capillary Columns
(1G) Adam, S., Jennings, W. G., J . Chromatogr., 115, 218 (1975) ( 2 G ) Adams, R. F., Vandemark. F. L., Schmidt, G. T., J . Chromatogr. Sci., 15, 63 (1977). (3Gj Badings, H: T., vand der Pol. J J. G I Wassink. J. G I Chromatographia, 8 , 440 (1975). (4G) Bailey, E., Fenoughty M.. Richardson, L.. J . Chromatogr.. 131. 347 (1977). (5G) Berezkin, V. G., Shkolina. L A., Lipavsky, V. N.. Serdan, A A.. Barnov, V. A , J Chromatogr., 141, (197 (1977). (6G) Bergert, K. H., Betz, V., Pruggmayer, D., Chromatographia. 7. 115 (1974). (7Gi Berthou. F . Picart. D.. Bardou. L Floch. H. ti..J . Chromatogr., 118, 135 (1976). (8Gj Bertsch, W., Anderson, E., Holzer, G., Chromatographia, 10, 449 (1977). (9G) Bertsch, W., Anderson, E., Holzer, G.. J . Chromatogr.. 112, 701 (1975). (10G) Bertsch, W., Hsu, F., Zlatkis, A., Anal. Chem.. 48. 928 (1976). (11G) Bertsch, W.. Shunbo, F.. Chang, R. C.. Zlatkis. A,, Chromatograohia. 7 , 128 (1974). (12G) Blomberg, L., Chromatographia, 8 , 324 (1975) (13G) Blomberg, L., J . Chromatogr., 115, 365 (1975). (14G) Blomberg, L., J . Chromatogr., 138, 7 (1977). (15G) Brechbuhler, B.. Gay, L.. Jaeger, H., Chromatographia, 10. 478 (1977) (16G) Bruner, F., Ciccioli, P., Brancaleoni, E., Longo. A,, Chromatographia, 8. 503 (1975). (17G) Buser, H. R.. Anal Chem.. 48, 1553 (1976). (18G) Buys, T. S., Smuts, T. W , de Clerk. K., First Natl. Symp. Chromatogr., Pretoria, South Africa, 1976. (19G) Cram, S. P., McCoy, R. N., Howe, R. L.. Iwao. K . R., Varian Instrum. Div. Tech. Bull., 1977. (20G) Cram, S P., Yang, F J.. Brown, A. C., 111. Chromatographia, 10. 397 (1977). ~
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ANALYTICAL CHEMISTRY, VOL. 50, NO. 5, APRIL 1978
(21G) Deelder. R. S., Ramaekers, J. J. M., Van den Berg, J. H. M., Wetzels, M. L., J . Chromatogr.. 119, 99 (1976). (22G) Desty, D. H., Chromatographia, 8, 452 (1975). (23G) Edmonds, C . G., Smith, A. G., Brooks, C. J. W., J . Chromatogr , 133, 372 (1977). (24G) Einig, R. G., MacDonald, J. L., Anal. Chem.. 48. 2281 (1976). (25G) Ettre, L. S., J . Chromatogr. Sci., 13, 354 (1975). (26G) Fedyanin, A. A., Zh. Anal. Khim., 30, 200 (1975). (27G) Fedyanin. A. A,, Prikhodko, A. A,, Kukushkina, N. A , Zavod. Lab., 40, 1066 (1974) (28G) Fenimore, D. C.. J . Chromatogr., 112, 219 (1975). (29G) Flanzy, J., Boudon, M., Leger. C., Pihet, J.. J . Chromatogr. Sci., 14, 17 (1976). (30G) Franken, J. J., Luyten, B. J. M., J . Assoc. O f f . Anal. Chem., 59, 1279 (1976). (31G) Gloor, R., Leidner, H., Chromatographia, 9, 616 (1976). (32G) Gordon, A. L., Taylor, P. J., Harris, F. W., J . Chromatogr. Sci.. 14, 428 (1976). (33G) Goretti, G. C., Liberti, A., Nota, G., Chromatographia, 8, 486 (1975). (34G) Gough, T. A,, Sugden, K., J . Chromatogr., 109, 265 (1975). (35G) Grob. K., Chromatographia, 7, 94 (1974). (36G) Grob, K., Chromatographia, 8, 423 (1975). (37G) Grob, K., Grob, G., Chimia, 31, 175 (1977). (38G) Grob, K., Grob, G.. J . Chromatogr., 125, 471 (1976). (39G) Grob, K., Grob, G., Grob, K., Jr., Chromatographia, 10, 161 (1977). (40G) Harrison, I.T., Anal. Chem., 47, 121 1 (1975). (41G) Hartigan, M. J., Ettre, L. S., J . Chromatogr., 119. 187 (1976). (42G) Heckers, H., Melcher, F. W., Schloeder. U., J . Chromatog., 136, 311 (1977). (43G) Hoch, K.. Pacakova. V.. Collect. Czech. Chem. Commun.,40, 519 (1975). (44G) Jackson, B. W., Judges. R. W., Powell, J. L., J . Chromatogr. Sci., 14, 49 (1976). (45G) Jennings, W.G., Chromatographia, 8. 690 (1975). (46G) Jennings, W. G., Adam, S., Anal. Biochem., 69, 61 (1975). (47G) Kaiser, R. E., Chromatographla, 7, 92 (1974). (48G) Kaiser, R . E., Proc. First Int. Symp. Glass Cap. Chromatogr. Incl. Glass Micropack Col., Inst. Chromatogr., Bad Durkheim, Germany, 1975. (49G) Kaiser, R. E., Proc. Second Int'l. Symp. Glass Cap. Chromatogr., Inst. Chromatogr., Bad Durkheim, Germany, 1977. (50G) Kaiser, R. E., Rieder, R., Chromatographia, 8, 491 (1975). 151GI Karasek. F. W.. Res./Dev..26 (111. 40 119751. i52Gj Katesl M., Hancockl A. J., Ackman, d. G.. Chiomatogr. Sci.. 15, 177 (1977). (53G) Koenig, W. A., Nicholson. G. J., Anal. Chem., 47, 951 (1975). (54G) Konig, W. A., Rahn, W., Eyem, J., J . Chromatogr.. 133, 141 (1977). (55G) Krijgsman, W., Van De Kamp, C. G., J . Chromatogr., 117, 201 (1976). (56G) Krijgsman, W., Van De Kamp, C. G., J . Chromatogr., 131, 412 (1977). (57G) Krupcik, J., Hrivnak, J.. Janak, J.. J . Chromatogr. Sci., 14, 4 (1976). (58G) Krupcik, J., Leclercq, P. A., Simova, A.. Suchanek, P., Collak, M., Hrivnak, J., J . Chromatogr., 119, 271 (1976). (59G) Krupcik, J.. Tesarik. K., Hrivnak, J., Chromatographia, 8, 553 (1975). (60G) Leets, K. V., E m , A. Yu., USSR Patent 416610 (Jan. 7, 1974). (61G) Lowry, R. R., Tinsley, I.J.. J . A m . Oil Chem. Soc., 52, 298 (1975). (62G) Marshall, J. L., Parker, D. A., J . Chromatogr., 122, 425 (1976). (63G) Matthiesen, U., Staib, W., Chromatographia, 10, 70 (1977). (64G) McKeag. R. G., Hougen, F. W., J . Chromatogr., 136, 308 (1977). (65G) Muller, F., Oreans, M., Chromatographia. 10, 473 (1977). (66G) Nikelly, J. G., Anal. Chem., 48, 987 (1976). (67G) Novotny, M., Anal. Chem., 50, 16A (1978). (68G) Novotny, M., Bartle, K. D.,Chromatographla, 7, 122 (1974). (69G) Novotny, M., Lee, M. L., Low, C.-E., Raymond, A., Anal. Chem., 48, 24 (1976). (70G) Novotny, M., McConnell, M. L., Lee, M. L., Farlow, R., Clin. Chem., ( Winston-Salem, N . C . ) ,20, 1105 (1974). (71G) Novotny, M., Lee, M. L., Low, C. -E,, Maskarinec, M. P., Steroids. 27, 665 (1976). (72G) Nygren, S., Mattsson, P. E., J . Chromatogr., 123, 101 (1976). (73G) Onuska, F. I . , Wolkoff, A. W., Combra, M. E., Larose, R . H., Anal. Len., 9, 451 (1976). (74G) Overton, E. B., Bracken, J.. Laseter, J. L., J . Chromatogr. Sci., 15, 169 (1977). (75G) Papendick, H. D.. Baudisch, J., J . Chromatogr., 122, 443 (1976). (76G) Pauschmann. H., Chromatographia, 9, 517 (1976). (77G) Pfaffenberger, C. D., Horning, E. C., J . Chromatogr., 112, 581 (1975). (78G) Pullarkat, R . K., Reha, H., J . Chromatogr. Sci., 14, 25 (1976). (79G) Rasmussen, D. V., Anal. Chem., 48, 1562 (1976). (BOG) Rijks. J. A., Cramers, C. A., Chromatographia, 7. 99 (1974). (81G) Roeraade, J., Chromatographia, 8, 511 (1975). (82G) Ryba, M., Chromatographia, 9, 105 (1976). (83G) Ryba, M., J . Chromatogr., 123, 317 (1976). (84G) Sandra, P., Verzele, M., Vanluchene, E., Chromatographia,8 , 499 (1975). (85G) Schieke, J. D., Doctoral Dissertation, Univ. of Pretoria, Pretoria, South Africa, 1975. (86G) Schieke, J. D..First Natl. Symp. Chromatogr., Pretoria, South Africa, 1976. (87G) Schieke, J. D.. Pretorius, V., J . Chromafogr., 132. 217 (1977). (88G) Schieke, J. D., Pretorius, V., J . Chromatogr., 132. 223 (1977). (89G) Schieke, J. D.. Pretorius, V., J . Chromatogr., 132. 231 (1977). (90G) Schieke, J. D., Comins, N. R., Pretorius, V., Chromatographia, 8, 354 (1975). (91G) Schieke, J. D., Comins, N. R., Pretorius. V., J . Chromatogr, 112, 97 119751. (92G) Schieke, J. D., Cornins, N. R . , Pretorius, V., J . Chromatogr., 114, 190 (1975). (93G) Schieke, J. D . Cornins, N. R., Pretorius, V., J . Chromatogr., 115, 373 (1975).
i,
(94G) Schornburg, G.. Husmann, H., Chromatographia. 8, 517 (1975) (95G) Schomburg, G., Husmann. H., Weeke, F.. J. Chromatcgr.. 112, 205 (1975). (96G) Schulte, E., Chromatographia, 9, 315 (1976). (97G) Simon, J., Szepesy, L., J . Chromatogr.. 119, 495 (1976). (98G) van Rijswick, M. H. J., Tesarik, K., Chromatographia, 7, 135 (1974). (99G) VidaCMadjar. C., Bekassy, S.. Gonnord, M. F., Arpino, P I Guiochon, G.. Anal. Chem., 49, 768 (1977). (100G) Vlodavets, M. L., Perovskyay, N. V., Sb. Nauchn Tr. Gazov. Kromatogr., 21, 11 (1974). (101G) Watanabe, C., Tomita, H., J . Chromatogr. Sci., 13, 123 (1975). (102G) Watanabe, C., Tomita, H.. J . Chromatogr., 121, 1 (1976). (103G) Welsch, Th.. Engewald, W., Klaucke. Ch., Chromatographia, 10, 22 (1977). (104G) Wu, A., Pearson, M. A,, Anal. Lett., 10, 381 (1977). DETECTORS Introductlon (1H) Adlard, E. R . . Crit. Rev. Anal. Chem., 5, 1 (1975). (2H) Adlard. E. R., Crit. Rev. Anal. Chem., 5, 13 (1975) (3H) Aue, W. A , J . Chromatogr. S o . , 13, 329 (1975). (4H) Driscoll, J. N., Chromatographia, 9, 567 (1976). (5H) Driscoll, J. N., J . Chromatogr., 134, 49 (1977). (6H) Dubowski, K . M., Clin. Chem. (Winston-Salem, N . C . ) ,22, 863 (1976). Grishin, A. P., (7H) Dyadyunov, V. A., Vyskrebentsev, V. P., Arutyunov, Yu. I.. Avfomatiz. Kook-Izmer. Prib., Nauchn., Tekhn. SB., 1975, 29. (8H) Fine. D. H., Lieb, D.. Rufeh, F., J . Chroma!ogr., 107, 351 (1975). (9H) Fine. D. H.. Rounbehler, D.P.. Anal. Lett., 9, 595 (1975). (10H) Fine, D. H., Rounbehler, D. P., J . Chromatogr., 109, 271 (1975). (11H) Karasek, F. W., Guy, P., Hill, H. H., Tiernay, J. M.. J . Chromatogr., 124, 179 (1976). (12H) Krzyzanowska, H., J . Chromatogr., 114, 179 (1975). (13H) Larin. N. V., Revin, Yu. V.. Balabanov, V. V.. Panukhnik. 1. I . , Zh. Anal. Khim., 30, 976 (1975). (14H) Lovelock. J. E., J . Chromatogr., 112, 29 (1975). (15H) Nakajima, F., Sakai, K., Bunseki Kagaku, 25, 378 (1976). (16H) Pellizzari, E. D., Bunch, J. E., Bursey, J. T., Berkeley, R. E., Anal. Lett., 9, 579 (1976). (17H) Pialiucci. R.. Averill. W.. Purcell. J. E.,Ettre. L. S.. ChromatoaraDhia, 8. 165 (7975). (18H) Popp. P., Oppermann, G., Chem. Technol., 28, 95 (1976). (19H) Taylor, J. F., Proc. Anal. Div. Chem. Soc.. 13, 168 (1976). Thermal Conductivity Detectors (11) Amouroux, J., Foll, J. P.. Bull. SOC. Chim. h..Part I, 1975, 1049. (21) Carson, J. W.. Lege, G.. J . Chromatogr. Sci., 13, 109 (1975). (31) Durbeck, H. W., Telin, B., Chromatographia, 8. 180 (1975). (41) Kowalski, J., Scibiorek, M., Chojnowski, J., J. Chromatcgr., 130, 351 (1977). (51) Lanser, A C., Johnston, A. E.,Dutton, H J.. J . Am. Oil Chem. Soc., 52, 274 (1974). (61) . , Lochmuller. C. H.. Gordon. B. M.. Lawson. A. E.. Mathieu. R. J.. J. Chromatwr. Sci., 15, 285 (1977). (71) Loyd. R. J., Henderson, D. E , Uden. P. C., Anal. Chem., 48, 1645 (1976). (81) Lvova, T. M.. Tsebukhovskaya, L. Ye., Bondareva, L. T., Degtyareva, 0. F., Zh. Anal. Khim., 30, 1697 (1975). (91) Novak. J.. Guha. 0. K.. Janak. J.. J . Chromatoar.. 112. 365 (1975). , , { l o r ) Novak, J., Janak, J., J . Chromatogr., 138, 1 (1577). (111) Skorik, L. D., Zalkin, V. S.. Sb. Nauchn. Tr. Gazov. Khromatogr.. 21, 51 (1974). (121) Van Der Plank, P.,J , A m . Oil Chem. Soc.. 52, 424 (1975). Flame Ionization Detectors (1J) Akpeter, L. L., Jr.. Hermann. T. S., Pilney. J. P., Senechal, A . J , Overland, D. L , €nviron. Sci. Technol., 10, 997 (1976). (2J) Berezkin, V. G., Rudenko, B. A. Popova, T. P., Agayeva, M. N., Lipavsky, V. N., Sokoiin, G. F., Zabokritsky, M. P.. J . Chromatogr., 130, 318 (1977). (3J) Blades, A. T., J . Chromatogr. Sci., 14, 45 (1976). (AI) Buser, H.U., Friedrich, K., Grolimund, K., Chromatographia,9, 641 (1976). (5J) Filby, W. G., Gunther, K., Penzhorn. R. D.,Anal. Chem., 47, 2283 (1975). (6J) Linder, W., J . Chromatogr., 111, 331 (1975). (7J) Russev, P., Gough, T. A., Wollam, C. J., J . Chromatogr., 119, 461 (1976). (8J) Sakharov, V. M., Beskova, G. S., Butusoava, A. I., Zh. Anal. Khim., 31, 250 (1976). (9J) Sevcik. J.. Klima, M., Chromatographia. 9 , 69 (1976). (1OJ) Takeda, T.. Umino, M., BunsekiKagaku, 26, 357 (1977). (11J) Thombs, D. A,, Chromatographia. 6 , 111 (1973) Therrnionlc Detectors (1K) Brazhnikov, V V., Shumidel, E. 6.. J . Chromatogr., 122, 527 (1976). (2K) Burgett. C. A., Smith, D. H., Bente, H. 6.. J . Chromatogr., 134, 57 (1977). (3K) Chamberlain, A. T., J . Chromatogr., 116, 180 (1976) (4K) Cochrane, W. P., Greenhalgh, R., Chromatographia, 9, 255 (1976). (5K) Hein, H.. Chem. Lab. U . Betr., 25, 352 (1974). (6K) Hill, H. H.. Jr., Aue, W. A., J . Chromatogr., 122, 515 (1976). (7K) Hoodless, R . A., Sargent, M., Treble, R . D.. J . Chromatogr., 136, 199 ( 1977). (8K) Johnson, E. M.. Kaiman, B. D., Lambrecht. R. W., Anal. Chem.. 48, 1271 (1976). (9K) Kolb, B., Auer, M., Pospisil, P., J . Chromatogr. Sci.. 15, 53 (1977). (10K) Kolb, B., Auer, M., Pospisil, P., J Chromatogr.. 134, 65 (1977). (11K) Least, C. J., Johnson, G. F., Solomon, H. M., Clin. Chem. ( Winston-Salem, N . C . ) , 23, 593 (1977).
ANALYTICAL CHEMISTRY, VOL. 50, NO. 5, APRIL 1978 (12K) Lubkowitz, J. A., Glajch. J. L., Semonian, B. P., Rogers, L, B., J . Chromatogr., 133, 37 (1977). (13K) Mellor, N., J . Chromatogr., 123 396 (1976). (14K) Novak, J., Dressler, M., Czech. Patent 149796 (1973). (15K) Verga, G. R., Poy, F., J . Chromatogr.. 116. 17 (1976). Electron Capture Detectors (1L) Aue. W. A . , Kapila, S., J . Chromatogr., 112. 247 (1975). (2L) Dwight, D. J., Lorch, E. A., Lovelock. J. E., J . Chromatogr.. 116, 257 (1976) 13L) Farwell, S. O., Rasmussen, R. A., J , Chromatogr. S o . , 14, 224 (1976). (4L) Kapila, A.. Aue, W. A.. J . Chromatogr., 108, 13 (1975). (5L) Kapila, A., Aue. W. A , J Chromafogr , 118, 233 (1976). (6L) Krausova, J., f r u m . Potravin, 27, 47 (1976). (7L) Lasa, J.. Rosiek. J.. Chem. Anal.. 21. 201 (1976). (8L) Patterson, P. L., J . Chromatogr., 134, 25 (1977). (9L) Patterson, P. L., Felton, J.. Freitas, E., Howe, R., Varian Insfrum. Div.. Tech Bull., (1976). (1OL) Poole, C. F., Chem. Ind., 11, 479 (1976). ( l l L ) Poole, C. F., J . Chromatogr., 118, 280 (1976). (12L) Rostek, J., Sliwka. I., Lasa, J., J . Chromatogr., 137, 245 (1977). (13L) Ross, W. D.. Buttler, G. W., Duffy. T. G., Rehg, W. R . . Wininger, M. T., Sievers. R . E., J Chromafogr., 112. 719 (1975). (141) Ryan, J. J., Lawrence, J. F.. J . Chromatogr.. 135, 117 (1977). (15L) Sullivan. J. J., Burgett, C. A , Chromatographia, 8 , 176 (1975). (16L) Wentworth, W. E , Tishbee, A , , Batten, C. F., Zlatkis, A,, J . Chromatogr.. 112, 229 (1975). Flame Photometric Detectors (1M) Aavik, Kh. E.. Ioonson, V. A., Kallasorg, R A,, Karavayeva, V. G.. Loog, E P.. Novikov, Yu N.. Revelskii, I . A,, Sirota, T. S.. USSR Patent 397840 (1974). (2Ml Attar. A.. Foraev. R.. Horn. J.. Corcoran. W. H.. J . Chromatoar. Sci.. ' 15, 222 (1977). (3M) Blomberg, L.. J . Chromatogr , 125, 389 (1976). (4M) Bruner, F., Ciccioli, P., Bertoni, G.. J . Chromatogr., 120, 200 (1976). (5M) Burnett. C H.. Adams, D. G . . Farwell, S. 0.. J . Chromatogr. Sci., 15, 230 (1977). (6M) Clay, D.'A., Rogers, C H., Jungers, R. H., Anal. Chem., 49, 126 (1977). (7M) Eckhardt, J G., Denton. M. B., Moyers, J. L., J . Chromatogr. Sci., 13, 133 (1975). (8M) Greenhalgh, R., Wilson, M. A., J . Chromatogr., 128. 157 (1976). (9M) Hasinski, S., J . Chromatogr.. 119. 207 (1976). (10M) Joonson, V A.. Loog, E. P., J . Chromatogr., 120, 285 (1976). (11M) Moore, C. E., Hara, D., Marks, G. E., Appl. Spectrosc.. 29, 531 (1975). (12M) Patterson, P. L., Howe, R., Hornung, V., Abu-Shumays. A,. Vari3n Instrum. Div.. Tech Bull., (1977). (13M) Pearson, C. D , J . Chromatogr Sci.. 14, 154 (1976). (14M) Pearson, C D , Hines, W. J., Anal. Chem., 49, 123 (1977). (15M) Sevcik. J . Thao. N T. P I Chromafographia, 8, 559 (1975). (16M) Versino, B., Vissers, H.. Chromatographia, 8 , 5 (1975). (17M) Zehner. J M., Simonaitis, R . A,. Anal. Chem., 47, 2485 (1975) (18M) Zehner, J. M.. Simonaitis, R . A., J . Chromatogr. S c i , 14, 348 (1976). 1
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Spectroscopic Detectors (1N) Betteridge, D., Hasanuddin, S. K.. Rees, D 1.. Anal. Chem., 48. 1078 (1976) (2N) Black, M. S., Sievers, R. E., Anal. Chem., 48, 1872 (1976). (3N) Bostick, D. T., Talmi. Y., J . Chromafogr. Sci.. 15, 164 (1977). (4N) Braund, K. G . , Ghosh, P , Taylor, T. K. F., Larsen, L. H., Anal. Biochem., 64, 10 (1975). (5N) Bruening, W., Concha, F. J. M., J . Chromatogr., 112, 253 (1975). (6N) Chau. Y K , Wong, P. T. S.. Saitoh, H., J Chromatogr. Sci., 14, 162 (1976). (7N) Cooney, R . P., Winefordner, J. D , Anal. Chem., 49, 1057 (1977). (8N) Dankelman, W.. Daemen, J. M . H., Anal. Chem.. 48, 401 (1976). (9Nl Esposito, G. G.. Lillian. D , Podolak, G. E., Tuggle, R. M., Anal. Chem., 49, 1774 (1977) (10N) Hausdorff, H H , J Chromatogr., 134. 131 (1977). (1 1N) Hedayati, M. A.. Bull. Iranian Pet. Inst., 1975, 5. (12N) John, E. D., Nickless, G., J , Chromatogr., 138, 399 (1977). (13N) Katlafsky, B , Dietrich, M. W.. Appl. Spectrosc., 29, 24 (1975). (14Nl Lantz, R. K., Crouch, S. R.. Clin. Chem. (Winston-Salem, N.C.), 21. 1032 (1975). (15N) Ltebman, S. A., Alstrom, D. H., Griffiths, P. R., Appl. Spectrosc., 30. 355 (1976) (16N) Louw, C. W., Richards, J. F., Appl. Spectrosc., 29, 15 (1975). (17N) McClenny. W. A.. Martin. B. E., Baumgardner, R. E., Jr., Stevens, R. K., O'Keeffe, A. E.. Environ, Sci. Techno/.. 10, 810 (1976). (18N) Mercaldo, D. F.. I n t . Lab., 1974, 75. (19N) Mulik. J., Cooke, M , Guyer. M F., Semenink, G. M., Sawicki, E., Anal. Lett., 8 . 51 1 (1975). (20N) Parris, G E.. Blair, W. R., Brinckman, F. E.. Anal. Chem., 49, 378 (1977). (21N) Rudnichenko, V Y e , Dobrochiver, I . G., Zavod. Lab., 42, 282 (1976). (22N) Sakamoto, T., Kawaguchi, H , Mizuike, A,, J . Chromatogr., 121, 383 (1976). (23N) Serravallo, F. A.. Risby, T. H., Anal. Chem.. 47, 2141 (1975). (24N) Siegfried, R.. J Chromatogr.. 118, 270 (1976). (25N) Talmt. Y., Mesmer. R. E., Water Res., 9 , 547 (1975). (26N) Van Loon. J. C., Lichwa. J., Radzutk, B., J . Chromafogr.,136, 301 (1977). (27N) Wolf, W. R., J . Chromatogr.. 134, 159 (1977). (28N) Wolf, W. R . Anal Chem.. 48. 1717 (1976).
237R
Electrochemical Detectors Banks, H. J., Desmarchelier, J. M., Elek, J. A., festic. Sci., 7, 595 (1976). Bergman, I., Coleman, J. E., Evans, D., Chromatographia. 6, 581 (1975). Berton, A., Off. Emball., 1974, 82. Davy, K. W. M., Morris, C. J. 0. R., J . Chromatogr., 136, 361 (1977). (50) Dressman, R. C., McFarren, E. F , J . Chromatogr Sci., 15, 69 (1977). ( 6 0 ) Ernst! G. F., Van Lierop, J. B. H., J . Chromatogr., 109. 439 (1975). (701 Garwin, E. L., Roder, A,, J . Chromatogr. Sci., 14, 541 (1976). ( 8 0 ) Lawrence. J. F., J . Chromafogr., 121, 85 (1976). ( 9 0 ) Lawrence, J. F., J . Chromatogr., 128, 154 (1976). (100) Lawrence, J. F., Ryan, J. J., J , Chromatogr., 130, 97 (1977). (110) Kojima, T., Seo, Y., Sato, J., BunsekiKagaku, 24, 772 (1975). (120) MacDonald, J., King, J. W., J . Chromatogr., 124, 364 (1976). (130) Pape, B. E., Clin. Chem. (Winston-Salem, N.C.), 22, 739 (1976). (140) Pape, B. E., J . Chromatogr., 134, 1 (1977). (150) Pape, B . E., Ribick. M. A.. J . Chromatogr., 136, 127 (1977). 11601 Risk. C. A,. Hall. R. C.. J . Chromafoor.., Sci.. 15. 156 11977) i 1 7 0 j Stetter, J. R u t D. d.,Blurton, K. F., Anal. Chem.. 46, 924(1976). (180) Stetter, J. R., Sediak, J. M., Biurton, K. F., J . Chromatogr. Sci., 15, 125 (1977). (190) Vitenberg, A. G., Kuznetsova, L. M.. Butaeva, I. L., Inshakov, M. D., Anal. Chem., 49, 128 (1977). (200) Von Rappard, E., Eisenbrand, G., Preussman, R., J . Chromatogr., 124, 247 (1976). (210) Winnett, G.. Illlngsworth, W. L., J . Chromatogr. Sci., 14, 255 (1976).
(10) (20) (30) (40)
d.,
~-
~
Radiochemical Detectors (1P) Braun, W. H., Madrid, E. O., Karbowski, R. J., Anal. Chem., 48, 2284 (1976). (2P) Charrier, G., Malherbe, P., Bull. Info. Sci. Tech. 1975, 59. (3P) Czerkawski, J. W., Breckenridge, G., Anal. Blochem., 67, 476 (1975). (4P) Derks, J. H. G. M., Muskiet, F. A. J., Wolthers, B. G.. Thijssen, J. H. H., Drayer. N. M., Clin. Chem. (Winsfon-Salem, N . C . ) ,23, 518 (1977). (5P) Fock. H.. Chromatographla. 9, 99 (1976). (6P) Karmen, A., Longo, N. S.,J . Chromatogr., 112, 637 (1975). (7P) Kiricsi, I., Varga, K., Fejes, P., J . Chromatogr., 123, 279 (1976). (8P) Rotin, V. A., "Radioionization Detection in Gas Chromatography", USSR, 1975. (9P) Tukva, R., Seda, J., J . Chromatogr., 108, 37 (1975). (1OP) Volpe, P., Catiglioni, M., J . Chromafogr.. 114, 23 (1975). Gas Chromatography/Mass Spectrometry ( 1 0 ) Benezra, S. A., J . Chromatogr. Sci., 14, 122 (1976). (20) Bertsch, W , Anderson, E., Holzer, G.. J . Chromafogr., 112, 701 (1975). ( 3 0 ) Bird, G. M., Keller, R. A,, J . Chromatogr. Sci.. 14, 574 (1976). ( 4 0 ) Blum, W., Richter, W. J., J , Chromatogr., 132, 249 (1977). ( 5 0 ) Budde, W. L., Eichelberger, J. W., J . Chromafogr., 134, 147 (1977). ( 6 0 ) Burlingame, A. L., et al., Anal. Chem., this issue. ( 7 0 ) Buser, H.-R., Anal. Chem., 49, 918 (1977). (80) Buser, H.-R., J . Chromafogr., 114, 95 (1975). ( 9 0 ) Canada, D. C., Regnier, F E , J . Chromatogr. Sci., 14, 149 (1976). ( 1 0 0 ) Carr, T. W., Anal. Chem.. 49, 828 (1977). (110) Carr, T. W., J . Chromatogr. Sci., 15, 85 (1977). (120) Carroll, D. I.. Dztdic, I.. Stillwell. R. N., Horning. E. C., Anal. Chem.. 47, 1956 (1975). (130) ClerC, J. T., Kutter, M., Reinhard, M., Schwarzenbach, R., J. Chromafogr., 123, 271 (1976). (140) Cohen, M. J., Wernlund, R. F., Ind. Res., 17 (e), 58 (1975). (150) Corina, D. L., Harper, K. E., J . Chromatogr. Sci.. 15, 317 (1977) (160) Crathorne, B., Edwards, M. W., Jones, N. R., Walters, C. L., Woolford, G., J . Chromatogr., 115, 213 (1975). (170) Davidson, W. C., Smith, M. J.. Schaefer, D. J., Anal. Len.. 10, 309 (1977). (180) Eichelberger, J. W., Harris, L. E., Budde, W. L., Anal Chem., 47, 995 (1975). (190) Fenselau, C., Anal. Chem., 49, 563A (1977). (200) Fluckiger, R., Chromatographia, 8, 434 (1975). (210) Fock, W., Anal. Chem., 47, 2447 (1975). (220) Foltz, R. L., Biomed. Specfrom.. 2, 227 (1975). (230) Frick, W., Chang, D., Folkers, K., Daves, G. D., Jr., Anal. Chem.. 49, 1241 (1977). 1240) Gaskel, S.J., Edwards, C. G., Brooks, C. J. W., Anal. Lett., 9. 325 (1976). (250) Gough, T. A.. Webb, K. S., Pringuer, M. A., Wood, B. J.. J . Agric. Food Chem., 25, 663 (1977). (260) Hanin, I., Skinner, R. F., Anal. Biochem., 66, 568 (1975). ( 2 7 0 ) Hatch, F., Munson, E., Anal. Chem., 49, 169 (1977). (280) Hatch, F., Munson, B., Anal. Chem., 49, 731 (1977). (290) Henneberg, D., Hendrichs, U., Schomburg, G., Chromatographia, 6, 449 (1975). (300) Henneberg, D., Henrichs, U., Schomburg, G., J , Chromatogr., 112, 343 (1975). (310) Horning, E. C., Carroll, D. I., Dzidic, I . , Haegele, K. D.. Lin, S . 4 , Oertli, C. U.. Stillwell, R. N., Clln. Chem. (Winston-Salem, N . C . ) ,23, 13 (1977). (320) Horning, M. G.. Nowlin, J., Butler, C. M., Lertratanangkoon, K., Sommer, K., Hill, R. M., Clin. Chem. (Winston-Salem, N . C.), 21, 1282 (1975). (330) Jellum, E., Stokke, O., Eldjarn, L., Clin. Chem. ( Winston-Salem, N.C.), 16, 800 (1972). (34Q) Karasek, F. W.. Hill, H. H., Jr., Kim, S. H., J Chromatogr., 117, 327 (1976). 1350) Karasek. F. W.. Hill. H. H.. Jr.. Kim. S. H.. Rokushika. S.. J . Chromatoor.. ' 135, 329 (1'977). (360) Karasek, F. W., Kim, S. H., Hill, H. H., Jr.. Anal. Chem.,48, 1133 (1976). (370) Kempster, E. J., First Nat'l. Symp. Chromatogr., Pretoria, So. Africa, 1976. 13801 Klein. P. D.. Haumann. J. R.. Hachev. D. L.. Clin. Chem. iWinston-Salem. N C ), 21, 1253 (1975) (390) Kohler, M , Hohn, M , Chromafographm 9 61 1 (1976)
238R
A N A L Y T I C A L CHEMISTRY, VOL. 50, NO. 5, APRIL 1 9 7 8
(40Q) Kuehl, D. W., Anal. Chem., 49, 521 (1977) (4101 Lawson, A. M., Clin. Chem. (Winston-Salem, N . C . ) , 21, 803 (1975) (42Q) Lee, M. G., Millard, B. J., Biomed. Mass. Spectrom., 2, 76 (1975). (4301 Lehman, J. P., Anal. Chem.. 49, 518 (1977). (44Q) Lehrer, M., Karmen, A,, Clin. Chem. ( Winston-Salem. N C.), 22, 1207 (1976). ( 4 5 0 ) Leibrand, R. J.. J . Chromatogr Scl., 13, 556 (1975). (46Q) Matin. S. B., Wan, S. H., Knight, J. B., Biomed. Mass Spectrom , 4 , 118 (1977). ( 4 7 0 ) Matthiesen, U.. Kump. B., Staib, W., Chromatographia. 10, 303 (1977). ( 4 8 0 ) Metro. M. M., Keller, R . A,, Sep Sci.. 9 , 521 (1974). ( 4 9 0 ) Petersen, B. A., Vouros, P , Anal. Chem., 49, 1304 (1977). (50Q) Prescott, S. R.. Campana, J. E., Risby. T. H., Anal. Chem., 49, 1501 (1977). (5lQ) Preston, J. M., Karasek, F. W., Kim, S. H., Anal Chem., 49, 1746 (1977). (52Q) R a w , U.. Schroder, U., Meier, S., Elmenhorst, H., Chromatographia, 8, 474 (1975). (53Q) Ryhage. R . , Anal. Chem., 48, 1829 (1976). ( 5 4 0 ) Shipe, J. R., Savory, J., Clin. Chem. ( Winston-Salem, N.C.), 22, 1198 (1976). (550) Smith, D. H . , Achenbach, M., Yeager, W. J., Anderson, P J., Fitch, W. L., Rindfleisch, T. C., Anal. Chem., 49, 1623 (1977). ( 5 6 0 ) Smith. S. R., Crit. Rev. Anal. Chem., 5 , 243 (1975). (57Q) Strauss. P. A., Hertel. R. H., J . Chromatogr.. 134, 39 (1977). (580) Thomas, B . R., J . Chromatogr., 109, 168 (1975) ( 5 9 0 ) Thome, F. A., Young, G. W., Anal. Chem., 48, 1423 (1976). ( 6 0 0 ) Van Vaeck, L., Van Cauwenberghe, K.. Anal. Lett., 10. 467 (1977). ( 6 1 0 ) Wernlund. R. F., Cohen, M. J., Res.lDev., 26 (71, 32 (1975). (62Q) Wilson. B., Snedden. W., Biomed. Mass Spectrom., 2 , 131 (1975). (63Q) Wolen. R. L., Pierson, H. E . Anal. Chem.. 47, 2068 (1975). (64Q) Young, N. D., Holland, J. F., Gerber, J. N., Sweeley, C. C.. Anal. Chem., 47, 2373 (1975). (65Q) Zune, A., Dobberstein, P.. Maurer, K. H., Rapp, U. J . Chromatogr., 122, 365 (1976). QUALITATIVE AND QUANTITATIVE ANALYSIS Qualitative Analysls
(1R) Albro, W.. Haseman, J. K., Clernmer. T. A,, Corbett, J., J , Chromatogr , 136, 147 (1977). (2R) Ashes, J. R., Haken. J. K., J . Chromatogr, 135. 61 (1977). (3R) Ashes. J. R . , Haken. J. K., J . Chromatogr , 135, 67 (1977). (4R) Baker. J. K., Anal. Chem., 49, 906 (1977). (5R) Bellas, T E., Chromatographia, 8, 38 (1975) (6R) Blaisdell, B. E., Anal. Chem., 49, 180 (1977) (7R) Bojti, E.. Mihok. M., Borbely, I . , Barkai. J., Takacs. J. M., J , Chromatogr . 119, 321 (1976). (8R) Castello, G., D'Amato, G., J . Chromatogr., 116, 249 (1976). (9Rl Cerda, V., Mongay, C., Analusis, 4 , 94 (1976) (10R) Chernoplekova, V. A., Korol, A. N., Sakodynskii, K . I , Lopatina, V. S., Kocheshkov, K. A.. Zh. Anal. Khim.. 30, 1285 (1975). (11R) Chretien, J. R., C . R . Hebd. Seances Acad. Sci., 281. 151 (1975). (12R) Chretien, J. R., Dubois. J. E., Anal. Chem.. 49, 747 11977). (13R) Cno, A,, J , Chromatogr., 110. 233 (1975). (14R) Dimov, N., J . Chromatogr., 119, 109 (1976) (15R) Dimov, N., J . Chromatogr., 137, 265 (1977). (16R) Engewald, W., Epsch, K., Welsch, Th., Graefe, J., J . Chromatogr., 119, 119 (1976). (17R) Engewald, W.. Wennrich, L., Chromatographia, 9 , 540 (1976). (18R) Erney, D. R., J . Assoc. Off. Anal Chem.. 58. 1202 (1975). (19R) Evans, M. B., Newton, R., Chromatographia. 9 , 561 (1976). (20R) Fellous, R., Lizzani-Culvelier, L., Luft R., Rabine, J. P.. Chromatographla, 8, 629 (1975). (21R) Fellous, R , Lizzani-Culvelier, L., Luft, R., Rabine, J. P., J . Chromatogr , 110, 7 (1975). (22R) Fellous, R.. Lizzani-Culvelier. L., Luft., R.. Rabine, J. P.. J . Chromatogr , 110, 1 3 (1975). (23R) Fellous, R.. Lizzani-Culvelier. L., Luft, R , Rabine. J. P.,J . Chromatoqr., 110, 19 (1975). (24R) Firpo, G., Gassiot, M., Martin, M.. Carbo, R., Guardino. X., Aibaiges, J., J . Chromatoor. 117. 105 119761. (25R) Garzo, G: Hoebbel. D . , ~ J Chromatogr., . 119, 173 (1976). (26Rl Gassiot, M., Fernandez. E., Firpo, G., J . Chromatogr., 108, 337 (1975). (27R) Gine. M.. Cerda. V., Analusis, 3 , 580 (1975). (28R) Golovnya. R. V.. Garbuzov. V. G., Chromatographia. 8. 265 (1975). (29R) Guardino. X., Aibaiges, J , J Chromatogr., 118. 13 (1976) (30Ri Heintz, M., Druilhe, A , Lefebvre, G., Seyden. J , Lefort, D., Chromatcgraphia, 8, 378 (1975). (31R) Heintz, M., Gruselle. M., Druilhe, A.. Lefort, D.. Chromatographia. 9 , 367 (1978). (32R) Hoshika, Y . , Kojima, I., Koike, K., Yoshimoto, K., Bunseki Kogaku, 24, 400 (1975). (33Rl Johnsson, J. A . Jonsson. R.. Malm, K., J . Chromatogr.. 115. 57 (1975). (34R) Kalashnikova, E. V . , Kiselev, A. V., Poshkus, D. P., Shcherbakova, K. D., J . Chromatogr., 119. 233 (1976). (35Rl Kamerling. J. P., Gerwig, G. J., Vliegenthart, J. F . G., J . Chromatogr., 143, 117 (1977). (36R) Kawahara, F. K.. Environ. Sci. Technol, 10, 761 (1976). (37R) Lee, M. L., Novotny. M., Bartle, K. D., Anal. Chem., 48, 405 (1976). (38R) Lee. M. L., Novotny, M., Bartle. K. D.. Anal. Chem., 48, 1566 (1976). (39R) Lombosi, T. S., Lombosi, E. R., Bernat, I.. Bernat, Zs. S z . , Takacs, E. C., Takacs, J. M., J . Chromatogr., 119. 307 (1976). (40R) Macdonald, L. M., Weatherston. J., J . Chromatogr , 118, 195 (1976). (41R) Mannino, S., Amelotti, G.. Riv. Ital. Sostanze Grasse, 52. 79 (1975) (42R) Moller, M. R.. Chromatographia, 9 . 311 (1976).
(43R) Nau. H., Biemann, K., Anal. Biochem., 73. 139 (1976). (44R) Nau, H.. Biemann, K., Anal. Biochem., 73, 154 (1976). (45R) Nilsson, O., Chromatographia, 10, 5 (1977). (46R) Onuska, F. I., Comba, M. E., J , Chromatogr., 119, 385 (1976). (47R) Papazova, D., Dimov, N., d . Chromatogr., 137, 259 (1977). (48R) Petitclerc, T.. Guiochon, G., Chromatographia. 8 185 (1975). (49R) Petrovic, K., Vitorovic, D., J . Chromafogr., 119, 413 (1976). (50Rl Pias, J. B., Gasco, L., Chromatographia. 8 , 270 (19751. (51Rl Piringer, 0 , Jaiobeanu, M., Stanescu. U., J , Chromatcgr., 119, 423 (1976). (52R) Pang, S., Kuningas, K., Orav, A,. Eisen, O., Chromatographia, 10. 5 5 (1977). (53R) Rang, S , Kuningas, K , Orav. A , Eisen, 0.. Chromatographia, 10, 115 (1977). (54R) Rang, S , Kuningas. K., Orav A., Eisen, O., J Chromatogr., 119. 451 (1976). (5%) Rang, S., Kuningas, K., Orav, A,, Eisen, 0 . . J . Chromafogr., 128, 53 ( 1976). (56R) Rang, S , Kuningas. K., Orav. A , , Eisen, 0 , J . Chromatogr., 128. 59 (1976). (57Rl Senenchenko, L. V., Brezhnieva, V. G., Zh. Anal. Khlm..30, 2076 (1975). (58R) Sidorov, R. I., Khovostikova, A. A,, Zh. Anal. Khim., 30, 340 (1975). (59R) Soczewinski, E., Matysik, G.. Dumkiewicz, W., J . Chromatogr., 132, 379 (1977). (60Rl Sojak, L., Janak. J., Rijks, J. A., J . Chromatogr.. 135, 71 (1977). (61R) Sojak, L., Janak, J., Rijks, J. A,, J . Chromatogr., 138. 119 (1977). (62R) Sojak, L., Rijks, J. A,, J . Chromatogr., 119. 505 (1976). (63R) Smalls, U., Myhill. M. K.. Nipper, H. C.. Clin. Chem. ( Winston-Salem. N . C . ) , 22, 1169 (1976). (64Rl Strocchi, A.. Bonaga, G.. Riv. Ital. Sestanze Grasse. 52, 84 (19751. (65R) Sultanov. N. T., Arustamova. L. G.. J . Chromatogr., 115, 553 (1975). (66R) Szentirmay, Zs., Tarjan, G., Bekesi, L., Gajari, J.. Takacs, J. M., J . Chromatogr., 119, 333 (1976). (67R) Tabacchi. R., Garnero, J., Buil. P., Riv. Ita/ Essenze Profumi. 57, 221 (1975). (68R) Takeda, I., Bunseki Kagaku. 24, 686 (1975) (69R) Tarjan, G., J . Chromatogr. Sci.. 14, 309 (1976). (70R) Tarjan, G., Kiss, A., Kocsis, G., Meszaros. S., Takacs, J. M., J , Chromatogr, 119, 327 (1976). (71R) Thompson, J. F.. Mann, J. 8.. Apodaca, A. O . , Kantor. E. J., J . Assoc Off. Anal. Chem., 58, 1037 (1975). (723) Tsuchiya, Y.. Boulanger. J., Sumi. K.. Chromatographia, 10, 154 (1977). (73R) Tullberg, L., Peeve, I. E.. Smith, B. E. F.. J . Chromatogr , 120, 102 (1976). (74R) Vandenheuvel, F. A,, J . Chromatogr., 115, 161 (1975) (75R) Vandenheuvel. F. A.. J . Chromafogr , 133, 107 (1977). (76R) Vanheertum, R., J Chromatogr. Sci.. 13. 150 (1975). (77R) Wasserfallen, K., Rinderknecht, F., Baumgartner, E., Chromatographia, 10, 176 (1977). (78R) Whelan, J. K., J Chromatogr., 111. 337 (1975). (79R) Yabumoto, K.. Jennings, W. G., Yamaguchi, M., Anal. Biochem., 78. 244 (1977). Quantitative Analysis
( 1 s ) Ackman, R. G.. Bariow, S. M., Duthie, I . F.. J . Chromatogr. Sci., 15, 290 (1977). (2s) Bankovich, P W., Modrell, R. W., Am. Ind. Hyg. Assoc. J . , 37, 640 (19761. (3s)Batra, K. K., Parnell, P., Clin Chem ( Winston-Salem. N . C . ) .22. 1207 (1976). ( 4 s ) Bjorkhem, 1.. Blomstrand. R., Lantto. O., Svensson. L., Ohrnan, G.. Clin. Chem. ( Winston-Salem. N . C . ) , 22, 1789 (1976). (5s) Booker. H. E.. Darcey, B. A., Clin. Chem. (Winston-Salem. Y.C.), 21. 1766 (19751. ( 6 s ) Bost, R. O . , Sutheimer, C. A., Sunshine, I . , Ciin. Chem (Winston-Salem. N.C.). 22, 689 (1976). (75) Brassens, A.. Analusis, 3 , 576 (1975). (8s) Burg, W. R., Birch, S. R., Cuddeback, J. E., Saitzman, B E.,Envron. Sci. Technol., 10, 1233 (1976). ( 9 s ) Butina, I. V , Kogan. L. A., Burdin, G. A., Zh Anal Khim., 30, 389 (1975). ( 1 0 s ) Butlin, A. G., Proc. Anal. Div. Chem Soc., 14 (5). 109 (1977). i l l s ) Cautreels, W., Van Cauwenberghe. K., J . Chromalogr., 131, 253 (1977) ( 1 2 s ) Chamberlain. R. T.. Stafford, D. T., Maijub, G.. McNatt, B.. Clin. Chem (Winston-Salem, N . C . ) , 22, 1207 (1976). ( 1 3 s ) Dearlove, T. J , Kaas. R L., Atkins, R P A , , J . Chromatogr S c i , 14, 448 (1976). (145) de Zeeuw. R. A,. Jonkmn, J. H. G., van Mansvett, F. J W., Anal. Biochem , 67, 339 (1975). ( 1 5 s ) Dupis, M - C , Charrier, G., Luta, M I Analusis, 3, 191 (1975) ( 1 6 s ) Eder, G., J . Chromatogr., 121. 269 (1976). ( 1 7 s ) Farrington. J W., Teal, J. M., Medeiros. G C , Burns, K. A . , Robinson, E. A., Jr.. Quinn, J G.. Wade. T. L , Anal. Chem . 48, 1711 (1976). ( 1 8 s ) Freed. D. J . Mujsce. A M.. Anal. Chem , 49. 139 (1977) ( 1 9 s ) Huffman. D H.. Hignite, C. E., Clin. Chem (Winston-Salem, N C ). 22. 810 (1976). ( 2 0 s ) Hughes, E. E., Rook, H.L., Deardorff. E. R.. Margeson, J H., Fuerst. R. G., Anal. Chem.. 49, 1823 (1977). ( 2 1 s ) Ioffe, B. V.. Vitenberg. A. G., Marinichev, A . N., Kuznetsova, L. M I Chrornatographia. 9 , 502-(1976) (225) Jain, N. C., Sneath, T. C., Leung, W J , Budd, R. D.. J . Pharm. S o . , 66, 66 (19771. (235) Janik, A,, Chromatographia. 8, 563 (1975) ( 2 4 s ) Kozlov, S. T., Povolotskaya, M. I . , Tantsyrev. G. D., Zh Anal. Khiin.. 30, 197 (1975). 125s) Krupcik, J., Hrivnak. J,, Janak, J., J . Chromatogr Sci.. 14, 4 (1976). (265) Krzyzanowska, H., J . Chromatogr.. 114. 179 (1975). (275) Kugler. E.. Langlais, R., Halang, W., Hufschmidt, M , Chromatographia, 8. 468 (1975).
ANALYTICAL CHEMISTRY, VOL. 50, NO. 5, APRIL 1978 (285) Margosis, M., J . Pharm. Sci.. 64, 1020 (1975). (29s) M e l e a n , S . W., Young, D. S., Yonekawa, W., Clin. Chem. ( Winston-Sakm, N.C.I. 23. 116 11977). (30s) Mraw, S . C',, Kobayashi, R., J . Chromatogr. Sci., 15, 191 (1977). (315) Mroszczak, E. J., Riegelman. S . , Clin. Chem. ( Winston-Salem, N . C . ) , 18, 987 (1972). (32s) Novak, J.. Proc. 4th Natl. Makrotest Conf., Part I. 1976,39. (33s) O'Keefe, A. E.. Anal. Chem., 49, 1278 (1977). (345) Orme, M. L., Borga, O., Cook, C. E., Sjoqvist, F., Clin. Chem. (Winston-Salem, N . C . ) ,22, 246 (1976). (35s) Ritter, J. J., Adams, N. K., Anal. Chem., 48,612 (1976). (365) Rix, H., Malenge, J. P., Chromatographia, 9, 554 (1976). (37s) Roerig, D. L., Wang. R. I.H., Mueller, M. M., Lewand. D. L.. Adams, S . M., Clin. Chem. (Winston-Salem, N . C . ) ,22, 1915 (1976) (38s) Sarylov, V. N., Ogloblina, I. P., Ulyanova, V. I., Rudenko. V. N., Adler, Y. P., T r . Vsyes. Nauchn. Issled. Inst. Khim. Reaktivov Osobo Chist. Vyeshch., 36, 232 (1974). (39s) Schwartz, L. M., Anal. Chem.. 49, 2062 (1977). (40s) Semenchenko, L. V., Mashukova, G. A., Laptieva, F. I., Rezinkina, Ye. N., Zavod. Lab., 42,281 (1976). (415) Singmaster, J. A., 111, Crosby, D. G., Bull. Environ. Contam. Toxicol., 16. 291 (1976). (425) Smit, H. C., Waig, H. L., Chromatographia, 8,311 (1975). (43s) S&n. D., Simon, J., C h Chem. (Winston-Salem,N.C.),22, 1216 (1976). (44s) Spiehler, V.. Sun, L., Miyada, D. S., Sarandis, S.G., Walwick, E. R., Klein, M. W., Jordan, D. B., Jessen, B.. Clin. Chem. ( Winston-Salem, N . C . ) ,22, 749 (1976). (45s) Stolyarov, B. V., Vitenberg, A. G., Kuznetsova, L. M., Ogongo, L. N.. Smirnova, S. A., Chromatographia, 9, 3 (1976). (46s) Treiber, L. R., Clin. Chem. (Winston-Salem, N . C . ) ,21, 1847 (1975). (47s) Turina, S . . Klasinc, L., Jamnicki, V., Chromatographia, 7, 203 (1974). (48s) van der Slooten, E. P. J., van der Helm, H. J., Clin. Chem. ( Winston-Salem, N . C . ) ,22, 1110 (1976). (49s) Watts, R., Carter, T., Taylor, S . , Clin. Chem. ( Winston-Salem, N . C . ) , 22. 1692 (1976). (50s) Webster, R . D. J., Nickless, G., R o c . Anal. Div. Chem. Soc., 13,333 (1976). (51s) Zehner, J. M., Simonaitis. R. A., Anal. Chem., 47, 2485 (1975).
Computerization (1T) Annino, R., J . Chrornatogr. Sci., 14,265 (1976). (2T) Bass, J. E., J . Chromatogr. Sci., 14, 173 (1976). 13T) Baumann, F., Brown, A. C., 111, Cram, S. P., Hartmann, C. H., Hendrickson, J., J . Chromatogr. Sci.. 14, 177 (1976) (4T) Biesel, H. R., Chromatographia, IO, 173 (1977). (5T) Bobba. G. M., Donaghey, L. F.. J . Chromatogr., Sci., 15. 47 (1977). 16Tl, Bovden. - - , ~ . G.- R.. Johnson. M. C.. Johnson. R. N.. Kho. B. T.. Warner. C. R., J . chroma tog;.^ SGl,15, 278 i1977). (7T) Campbell, I . M., Doerfler, D. L.. Donahey, S. A,, Kadlec, R., McGandy, E. L. Naworal. J. D., Nulton. C. P., Venza-Raczka, M., Wimberly, F., Anal. Chem., 49, 1726 (1977). (8T) Cram, S. P.. Chesler. S. N., Brown, A. C., 111, J . Chromatogr.. 126. 279 (1976). (9T) Crockett, 1. L.. Mikkelsen, L.. J . Chromatogr. Sci., 14, 169 (1976). (10T) Dessy, R . E., Anal. Chem., 49, 1100A (1977). (11T) Dobbs, C. R., McGinnis, C. M.. Peddie, J. G.. In?. Lab., 1974, 19. (12T) Donaghey, L. F., Bobba, G. M., Jacobs, D.. J . Chromatogr. Sci., 14, 274 (1976). (13Ti Dowty, B.. Green, L.. Laseter, J. L., J . Chromatogr. Sci., 14. 187 (1976). (14T) Eder, G., J . Chromatogr., 121, 269 (1976). (15T) Emery, E. M.. J . Chromatogr. Sci., 14,261 (1976). (16T) Gill, J: M., J . Chromatogr. S c i . , 14, 165 (1976). (17Ti Glaser, E. R., Silver, B., Suffet, I. H., J . Chromatogr. Sci., 15.22 (1977) 118TI Jellum. E.. Helland. P.. Eldiarn. L.. Markwardt. U.. Marhofer, J.. J , Chromatogr, 573 (1975).' (19T) Jonsson, J. A,, J . Chromatogr., 1 1 1 , 265 (1975). (20T) Kullik, E., Kaljurand. M., Ess, L.. J . Chromatogr.. 118. 313 (1976). (21T) Leung, A. T., Hubbard. J. R.. Miller, L. A,, J . Chromatogr. Sci., 14,166 (1976). (22T) McWilliam, I.G., 3rd Aust. Symp. Anal. Chem., Melbourne, 1975. (23T) Mikkelsen. L., Green, L. E., J . Chromatogr. Sci., 14, 190 (1976). (24T) Norman, P, W.. Fells, I., J . Chromatogr., 132, 533 (1977). (25T) Owen, J. M., J . Chromatogr., 109, 395 (1975). (26T) Phillips, J. B., Burke, M. F.. J . Chromatogr. Sci., 14, 270 (1976). (27T) Robinson, P. G.. 3rd Aust. Symp. Anal. Chem.. Melbourne, 1975. (28T) Stockinger. J. H., J . Chromatogr. Sci., 15, 198 (1977). (29T) Wasserfallen. K., Rinderknecht, F., Baumgartner, E., Chromatographia, 10. 176 (1977). ~
ii2,
METHODOLOGY
Instrurnentatlon (1U) Abdeddaim, K.. Belabbes, R., Vergnaud, J.-M., J . Chromatogr., 1 1 1 , 253 (1975) (2U) Abdeddaim, K., Vergnaud, J.-M., C . R. Hebd. Seances Acad. Sci., Ser. C . , 280,981 (1975). (3U) Ackman, R. G . . Sipos, J. C.. J . Chromatogr. Sci., 14, 568 (1976). 14U1 Anisimov. A. F.. Berezkin. V. G.. Zhuravleva. M. A,. LiDaVskv. V. N.. Markelov, V. F., Shkolina, L. A., J . Chromatogr., 1 1 1 , 409 (i975): (5U) Arenkova, G. G.. Zavod. Lab.. 41, 665 (1975). (6U) Bartle. K . D., Lee. M. L., Novotny, M., Proc. Anal. Div. Chem. Soc., 13, 304 (1976). (7U) Belabbes. R , LeParlouer, P., Vergnaud. J.-M.. J . Chromatogr., 120,81 (1976). (8U) Belabbes, R., Vergnaud, J.-M.. C . R . Hebd. Seances Acad. Sci., Ser.
239R
C . , 280. 1497 (1975). (9U) Berezkin. V. G., Rudenko, B. A.. Kyazimov, E. A,, Agayeva, M. N.. Rcdionov, A. A., Serdan, A. A., I z v . Akad. Nauk. SSR, Ser. Khim., 1975, 2352 (IOU) Berezkin, V. G.. Shkolina, L. A,, J . Chromatogr., 119. 33 (1976). (11U) Berezkin, V. G., Starostina, N. G., Chromatographia, 8. 395 (1975) (12U) Brady. R. F., Jr., Anal. Chem., 47, 1425 (1975). (13U) Buser. H.. Friedrich, K., Grolimund, K.. J . Chromatogr., 108, 181 (1975) (14U) Chlzhkov, V. P., Rudenko, B. A.. Sinitsyna, L. A.. Yushina, G. A . f r v Akad. Nauk. SSSR, Ser. Khim., 1975, 1207. (15U) Chizhkov, V. P., Sinicyna, L. A,, Zh. Fiz. Khim., 48, 142 (19741 (16U) Chizhkov. V. P., Yushina, G. A,. Zh. Anal. Khim., 31, 16 (19761. (17U) Coduti. P. L., J . Chrornatogr. Sci., 14,423 (1976). (18U) Cram. S. P.. Glenn, T. H.. Jr., J . Chromatogr , 112. 329 (1975). (19U) Cram. S . P., Glenn, T. H., Jr., J , Chromatogr., 119. 55 (1976). (2ou) de Leeuw, J. W.. Maters, W. L., Meent, D. V. D., Boon, J. J., Anai Chem., 49, 1881 (1977). (21U) Devallez. B., Abdeddaim, K.. Granger. R., Vergnaud. J-M.. C R . Hebl. Seances Acad. Sci., Ser C..280, 1073 (1975). (22U) Devallez, 8.. Cognet. G., Vergnaud. J.-M., J . Chromatogr.. 109, 1 (1975). (23Ui Ellis, L.. J . Chromatogr. Sci.. 13, 178 (1975). (24U) Ettre, L. S . , J . Chromatogr. Sci., 15,90 (1977). (25U) Evans, M. B., Newton, R., Chromatographia, 9. 561 (1976). (26U) Eyem, J.. Chromatographia. 8,456 (1975). (27U) Greenwood, N. D., Guppy, I . W., Simmons, H. P., J . Chromatogr SCL. 13. 349 (1975). (28U) Grob, K., Chromatographia, 9, 509 (1976). (29U) Hrivnac, M., Frischknecht, W., Cechova. L., Anai. Chem., 48.937 (1978). (30U) Ioannides, C., Chakraborty, J., Parke, D. V., Chromatographia, 7,351 (1974). (31Ui Jennings, W. G., J Chromatogr. Sci.. 13, 185 (1975). (32U) Jentoft. R. E., Gouw, T. H., Anal. Chem., 48,2195 (1976). (33U) Jonsson, J. A,, J . Chromatogr., I l l . 271 (1975). (34U) Kaiser, R. E., Chromatographia, 9,463 (1976). (35U) Kazyak. L.. Anal. Chem.. 48, 1826 (1976). (36U) Kirsten. W. J., Mattsson. P. E., Alfons, H., Anal. Chem.. 47. 1974 ( f37UI Kvazimov. E. A,, Aaaveva, M. N.. Dokl. Akad. Nauk Azerbaid SSR, 30 ' ( E ) , 38 (1974). (38U) Lauwereys, M., Vercruysse, A,, Chromatographia. 9. 520 (1976). (39U) Le Parlouer, P., Boinon, B., Vergnaud, J -M., C. R. Hebd. Seances Acad Sci., Ser C , 282,495 (1976). (40U) Le Parlouer, P., Boinon, B., Vergnaud. J.-M.. C . R . Hebd. Seances Acad. Sci.. Ser. C . 282. 655 119761. (41U) Le Parlouer, P., Boinon, B.. Vergnaud. J -M.. C . R . Hebd. Seances Acad. Sci.. Ser. C . , 282,717 (1976). (42U) Le Parlouer, P., Boinon, B.. Vergnaud, J.-M., J . Chromatogr., 133,253 (1977). (43U) Mayzaud, P., Ackman. R . G., Chromatographia, 9. 321 (1976). (44U) McCallum, N. K.. Cairns, E. R., J . ?harm. Sci., 66, 114 (1977) (45U) McConnell, M. L., Novotny, M., J . Chromatogr., 112. 559 (1975). (46U) McGill, A. S.. Parsons, E.. Smith A,. Chem. Ind. (London),11, 456 (1977) (47U) Nonaka, A,, Anal. Chem., 48, 383 (1976). (48U) Nygren, S . , Mattsson. P. E.,J . Chromatogr.. 123, 101 (1976) (49U) Paryjczak. T., Jozwiak, W., Goralski, J.. J . Chromatogr , 120,291 11976). (50U) Purcell, J. E., Downs, H. D., Ettre. L. S., Chromatographia. 8.605 (1975). 151U) Rakhmankulov. Sh. M.. Vidqderqauz. M. S., Izv. Akad. Nauk SSSP. Ssr. - Khim., 1975, 587. (52U) Reid, A. M., J . Chromatogr Sci.. 14. 203 (1976). (53U) Rejthar, L., Tesarik. K., J . Chromatogr., 131,404 (1977). (54U) Rudenko, B. A,, Baydarovtseva, M. A,. Kusovkin, V. A,. J , Chromatogr.. 112.373 119751. 155U) Schmid J D Schmid P P Simon W Chromatographia 9 59711976) (56U) Schulte. E.. Chromatographia, 7, 138 (1974). (57U) Silayeva, I. A,. Yanovskii, S . M.. Zh. Anal. Chem., 30. 387 (1975). (58U) Smythe. L. E., ?roc. R Aust. Chem. Inst,. 44 ( 5 ) . 121 (1977) 159UI V. Ye,. Golovina. 2. M.. Zavod. Lab., 41, 670 ,1975) ,~ - , Steoanienki. -r (60U) Sussman. M. V., Chemfech. 6, 260 (1976) (61U) Tsuda. T., Ichiba, T.. Muramatsu, H., Ishii, D.. J . Chromatogr, 130,87 (1977). (62U) van Wasen, U., Schneider. G. M., Chromatographia. 8. 274 (1975! (63U) Villalobos, R . , Anal. Chem., 47. 983A (1975). (64U) Weeke. F.. Bastian, E.. Schomburg. G.. Chromatographia, 7. 163 ( 1 9 ? 4 (65U) Wolff, M. S., Langer, A. M., Shirey, S. B., Science. 191 (4225). 333 (19761 (66U) Yefimov, V. D , Sb Nauchn. Tr Gazov. Khrornatogr.. 21.35 11974) (67U) Zhukhovitskii. A. A,, Kanunnikova, E. V., Novikova. L . G , Sazonov, M L., Shavartzman, V. P.. Yanovskii, S . M., Chromatographia, 8,369 (19751 I
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Sampling and Sample Preparation (1V) Acheson, M A , . Harrison, R . M.. Perry. R., Wellings. R . A , . Water Res.. 10. 207 (1976) (2V) Aue, W. A., Hastings-Vogt. C.R.. Younker, D. R.. J Chromatogr . 114. 184 (1975). (3V) Becka. J., Feltl, L., J Chromatogr., 131, 179 (1977). ( 4 V ) Berezkin. V. G., Lipavskii, V. N., Zavod. Lab., 40. 1185 (19741. (5V) Blaser, W. W., Bredeweg, H. A . , Shadoff, L. A,, Stehl. R. H., Ana/. C h e m 48,984 (1976). (6V) Borisov. V. N., Ioffe. B. V.. Vitenberg, A . G., Zh. Anal. Khim., 30, 128'3 (1975). (7V) Bowen, B. E., Anal. Chem.. 48, 1584 (1976) (8V) Brandt. P. E., Jensen. B. H.. J . A m . Oil Chem. Soc.. 52, 278 ( 1 9 7 5 ~ . (9V) Brown, H. H., Meoia, J M.. Clin. Chem. (Winston-Salem,N.C.), 21.37' ( 1975). (1OV) Bullard, R. W , Holguin, G., J . Agric. Food Chem., 25, 99 (1977: (11V) Burnett, R . D.. A m . Ind. Hyg. Assoc. J , , 37, 37 (1976). (12V) Butler. T. J., Clin. Chem. (Winston-Salem, N . C . ) . 20. 866 (13741 (13V) Chang, K., Chiou, W. L.. J . Pharm. S c i , 65, 56 (1976). (14V) Chriswell. C. D.. J . Chromatogr.. 132,537 (1977).
ANALYTICAL CHEMISTRY, VOL. 50, NO. 5, APRIL 1978
240R
(15V) Chriswell, C. D., Fritz, J. S.. J . Chromatogr., 136, 371 (1977). (16V) Coburn, J. A., Valdmanis, I . A., Chau. A. S. Y . , J . Assoc. Off. Anal. Chem., 60, 224 (1977). (17V) Coker, D. T.. f r o c . Anal. Div. Chem. Soc., 14 (5), 108 (1977). (18V) Cosgrove, B. A., Gay, I. D., J . Chromatogr., 136, 306 (1977). (19V) Cowen, W. F., Cooper, W. J., Highfill, J. W., Anal. Chem., 47, 2483 (1975). (2OV) Cramers, C. A., Vermeer, E. A., Chromatographia, 8. 479 (1975). (21V) Cronn, D. R.. Harsch, D. E., Anal. Lett., 9 . 1015 (1976). (22V) Cuddeback, J. E., Burg, W. R., Birch, S. R., Environ. Sci. Technol., 9 , 1168 (1975). (23V) De Greef, J.. De Proft, M., De Winter, F.. Anal. Chem., 48. 38 (1976). (24V) Deinzer, M., Melton, R., Mitchell, D., Water Res., 9 . 799 (1975). (25V) Dowty, B. J., Green, L. E., Laseter, J. L., Anal. Chem.. 48, 946 (1976). (26V) Drozd, J., Novak. J., J . Chromatogr., 136, 37 (1977). (27V) Dubsky, H., Hana, K., Pestalova, M., Samkova, H., Chem. Listy. 70, 750 (1976). (28V) Edwards, R., Pestic. Sci., 5 , 293 (1974). (29V) Eisenberg, R. B., Barney, I., Lantz, R. K., Clin. Chem. ( Winston-Salem, N . C . ) . 23, 1130 (1977). (30V) Fairiie, K.. Fox, B. L., J . Chromatogr. Sci., 14, 334 (1976). (31V) Fisher, R. L.. Relser, R. W., Lasoskl, B. A., Anal. Chem., 49, 1621 (1977). (32V) Ford, J. H., McDaniei, C. A., White, F. C., Vest, R. E., Roberts, R. E., J . Chromafogr. Sci., 13. 291 (1975). (33V) Fracchia, M., Pierce, L., Graul, R., Stanley, R., A m . Ind. Hyg. Assoc. J . , 38, 144 (1977). (34V) Frankiewicz, T. C.. Williams, F. W., J . Chromatogr. Sci., 14, 63 (1976). (35V) Freed, D. J., Mujsce, A. M., Anal. Chem., 49, 1544 (1977). (36V) Fritz, J. S., Acct. Chem. Res., 10, 67 (1977). (37V) Fujii. T., Anal. Chem., 49, 1985 (1977). (36V) Gaspar, G., Arpino, P., Guiochon, G., J. Chromatogr. Sci., 15, 256 (1977). (39V) Ghosh, A. K., Rajwar. D. P., Bandyopadhyay, P. K., Ghosh, S. K., J , Chromatogr., 117, 29 (1976). (40V) Giam, C. S.,Chan, H. S.,Neff, G. S.,Anal. Chem., 47, 2319 (1975). (41V) Gough, K . M., Gesser, H. C.,J . Chromatogr., 115, 383 (1975). (42V) Grob, K., Zurcher, F., J . Chrornatogr.. 117, 285 (1976). (43V) Herber, R. F. M., Poppe, H., J . Chromatogr., 118, 23 (1976). (44V) Hill, H. H., Jr., Chan, K. W., Karasek, F. W., J . Chromatogr., 131, 245 (1977). (45V) Hill, R. H., Jr., McCammon, C. S., Saalwaechter, A T.. Teass, A . W., Woodfin, W. J., Anal. Chem., 48, 1395 (1976). (46V) Hurst, R. E., Anal. Chem., 47, 1221 (1975). (47V) Ioffe. B. V.. Vitenbera. A. G..Borisov. V. N.. Kuznetsov. M. A,. J . Chromatogr., 112, 311 (1975). (48V) Ishii, M.,Otaka, H., Katume, T., Bunseki Kagaku, 25, 561 (1976). 149V) Ives. F. F.. J , Assoc. Off. Anal. Chem.. 58. 457 (19751. ~, (50V) Jenn'ings, W.G., Filsoof, M., J . Agric. FoodChem., 25, 440 (1977). (51V) Jeon, I . J., Reineccius G. A., Thomas. E. L., J . Agric. FoodChem.. 24, 433 11976) \ ' - ' - I ' (52V) Jones, P. W., Glammer, R. D., Strup, P. E., Stanford, T. B., Enwiron Sci. Technol.. i o . 806 11976). (53V) Jonsson, R., Jonsson, J. A., J . Chromatogr., 120, 197 (1976). (54V) Kaiser, K . L. E.. Oliver, B. G.. Anal. Chem., 48, 2207 (1976) (55V) Karlsen, J., Rasmussen. K. E.. Meed. Norsk, Farm. Selsk., 37, 51 (1975). (56V) Kolb, B., J . Chromatogr., 112, 287 (1975). (57V) Kolb, B., J . Chromatogr., 122, 553 (1976). (58V) Kollig, H. P., Falco, J. W., Stancil, F. W., Jr., Environ. Sci Technol., 9, 957 (1975). (59V) Korbina, V. N., Krualik, G. Z., Utkin, V. A., Izv. Sibir. Otdei. Akad. Nauk SSSR. Ser. Khim. N i u k , 5 , 115 (1974). (60V) Korotkevich, Yu. N., Tsarkov, M. S.,USSR Patent 407233 (July 23, 1974). (61V) Kuo, P. P. K., Chian, E. S. K., DeWalle, F. B., Kim, J. H., Anal. Chem., 49. 1023 (1977). (62V) Laessig, R., Westgard. J., Carey, N., Hassemer, D., Schwartz. T., Clin. Chem. (Winston-Salem. N . C . ) , 21, 971 (1975). (63V) Langlais, R. Schlenkermann, R., Weinberg. W., Chromatographia. 9, 601 (1976). (64V) Larson, R. A,, Weston, J. C., Bull. Environ. Contam. Toxicol., 16, 44 (1976). (65V) Laurgeau, C., Barras, F., Chromatographia, 8. 373 (1975) (66V) Leoni, V., Puccetti, G., Colombo, R. J., D'Ovidio, A . M.,J . Chromatogr.. 125, 399 (1976). (67V) Levadie, B., MacAskill, S. M., Anal. Chem., 48, 76 (1976). (68V) Lewis, R. G., Brown, A. R., Jackson, M. D., Anal. Chem.. 49, 1668 (1977). (69V) Liebich, H. M., Zlatkis. A., Bertsch, W.. Van Dahm, R., Whitten, W. K., Biomed. Mass Spectrom., 4 , 69 (1977) (70V) Ligon, W. V., Jr., Johnson. R. L.. Jr., Anal. Chem., 46, 481 (1976). (71V) Lines, C.S., Brain, K. R., Ross, M. S. F., J . Chromatogr.. 117, 59 (1976). (72V) Madarash. G. R.. Larsen. J. W.. Clin. Chem. (Winston-Salem. N . C . ) . ' 20, 861 (1974). (73V) Mohnke, M., Hofling, R.. Chromatographia, 6, 345 (1975). (74V) Moore, G., Steinle, S., LeFebre, H., Am. Ind. Hyg, ASSOC.J . , 38, 195 (1977). (75V) Murray, K. E., J . Chromatogr., 135, 49 (1977). (76V) Nair, B. M., Appelqvist, L.-A., J . Chromatogr., 133, 203 (1977). (77V) Neher, M. B., Jones, P. W., Anal. Chem., 49, 512 (1977). (78V) Nelms, L H., Reiszner, K. D , West, P. W., Anal. Chem., 49, 994 (1977). (79V) Parsons, J. S., Mitzner, S., Environ. Sci. Technol., 9, 1053 (1975). (80V) Pellizzari, E. D., Bunch, J. E., Berkley, R. E., McRae, J., Anal. Chem., 48. ., 803 ... (19761 (81'4 Pellizzari, E. D Bunch, J. E., Carpenter, B. H., Sawicki, E., Environ. Scl. Technol., 9 , 552 (1975). (82V) Pellizzari, E. D..' Carpenter, B. H., Bunch, J. E., Sawicki, E.. Environ. Sci. Technol., 9 , 556 (1975). (83V) Ramstad, T., Mahle, N. H.. Matalon, R., Anal. Chem., 49, 386 (1977). (84V) Rasmussen, K. E., J . Chromatogr., 109, 175 (1975). (85V) Rasmussen, K. E., Karlsen, J., J . Chromatogr. Sci., 14, 67 (1976). I
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- I
I
~
(86V) Rasmussen, R. A , Harsch, D. E., Sweany, P. H.. Krasnec, J. P , Cronn, D. R., J . Air Pollut. Contr. Assoc.. 27, 579 (1977). (87V) Robertson, T. J., Gottschall, W. C., Anal. Lett., 10, 183 (1977). (88V) Russell, J. W.. Environ. Sci. Technol., 9 . 1175 (1975). (89V) Russell, J. W.. Shadoff. L. A.. J . Chromatogr., 134, 375 (1977). (9OV) Sansone, E. B., Wolochow, H.. Chatigny, M. A,, Anal. Chem., 49, 670 (1977). (91V) Scheffer, J. J. C., Svendsen. A. B , J . Chromatogr., 115, 607 (1975). (92V) Senanayake, U. M., Edwards, R. A., Lee, T. H., J . Chromatogr , 116, 468 (1976). (93V) Serfontein, W. J., Botha, D.. De Villiers, L. S., J . Chromatogr.. 115. 507 (1975) (94V) Severson, R. F., Snook, M. E., Arrendale, R. F., Chortyk, 0. T.. Anal. Chem., 48, 1866 (1976). (95V) Shen, J., Anal. Chem.. 49, 886 (1977). (96V) Steichen, R . J., Anal. Chem.. 48. 1398 (1976) (97V) Stepan, S. F., Smith, J. F., Water Res . 11, 339 (1977). (98V) Stepanenko. V. Ye., Goiovina, Z. M.. Zh. Anal. K h m , 30, 890 (1975). (99V) Tishbee, A.. Anal. Chem., 49, 1267 (1977). (1OOV) Turner, 8. C., Glotfelty, D. E., Anal. Chem., 49, 7 (1977). (101V) Varian Assoc., Australian Patent 481 977 (April 7, 1977). (102V) Versino, B., Knoppei, H., DeGrwt, M., Peil, A., Poelman, J., Schauenburg. H., Vissers, H., Geiss. F., J . Chromatogr., 122, 373 (1976). (103V) Vitenberg, A. G., Butaeva. I . L., Dimitrova, Z. St., Chromatographia. 8 , 693 (1975). (104") Vitenberg, A. G., Ioffe, B. V.. Borisov, V. N., Zh. Anal. Khim.. 29, 1795 (1974). ( l 0 5 V ) Vitenberg, A. G., Kuzentsov, M. A., loffe, B. V, Zh. Anal. Khim , 30, 1051 (1975). (106V) Warner, J. S., Anal. Chem., 48, 578 (1976). (107V) Wel, L., Kaufman, M., Anal. Chem., 48, 2029 (1976). (108V) Williams, F. W., Stone, J. P., Eaton, H. G., Anal. Chem., 48, 442 (1976). (109V) Zhukov, A. V., Pchelkin, V. P., J . Chromatogr., 132, 543 (1977), (1lOV) Zlatkis, A.. Andrawes, F., J . Chromatogr.. 112, 533 (1975). (1 11") Zlatkis, A.. Lieblich, H. M.. Clin. Chem. ( Winston-Sakm, N C ), 21. 1001 (1975). Pyrolysis (1W) Allshoyev, V. P., Berezkin, V. G., Viktorova, E. N , J Chromatogr., 108, 275 (1975). (2W) Beienkii. B. G., Gankina, E. S.. Nefedov, P. P., Lazareva, M. A,. Savitskaya, T. S., Voichikhina, M. D., J . Chrornatogr., 108, 61 (1975). (3W) Blackwell, J. T., Anal. Chem., 48, 1883 (1976). (4W) Burns. D. T., Stretton, R. J., Jayatilake. S. D. A. K., J . Chromatogr , 116. 107 (1976). (5W) Chi-An Hu, J.. Anal. Chem.. 49, 537 (1977). (6W) Gassiot-Matas, M., Danes, E., Chromatograph/a, 9 , 151 (1976). (7W) Gough, T. A., Jones, C. E. R.. Chromatographia, 8, 696 (1975) (8W) Hanson, R. L., Brookins, D.. Vanderborgh, N E., Anal. Chem , 48, 2210 (1976). (9W) Hanson, R. L., Vanderborgh. N. E.. Brookins, D G., Anal. Chem.. 49, 390 (1977). ( l o w ) Ingram, G., Rizvi, S M. H. Microchem. J . , 20. 324 (1975) (11W) Kojima. T., Morishita, F., Lkano. T.. BunsekiKagaku, 26, 67 (1977). (12W) Kullik, E , Kaljurand, M.. Koel, M., J . Chromafogr., 112, 297 (1975) (13W) Kunen. S. M., Burke, M. F.. Bandurskii, E. L., Nagy, B., Atmos Environ , 10, 913 (1976). (14W) Lanzarini. G., Morselli, L., Pifferi, P. G., Giomanini. A . G , J . Chromatogr , 130, 261 (1977). (15W) Merritt, C. Jr., DiPietro, C., Hand, C. W., Cornell, J. H., Remy. C.E., J Chromatogr., 112. 301 (1975). (16W) Milina, R . , Pankova, M., Plast. Massy, 1. 59 (1976). (17W) Noble, W., Wheals, B. B.. Whitehouse, M.J., Forensic Sci., 3 , 163 (19751 (18W) Noles, G. T., Lieberman, M L., J . Chromatogr., 114, 211 (1975). (19W) Ono. Y Hayama. Y., Tanaka, S., Bunseki Kagaku, 25, 736 (1976) (20W) Parrish. J. R., Anal. Chem., 47, 1999 (1975). (21W) Pella, E., Andreoni, R., Mikrochim. Acta, 11, 175 (1976). (22W) Ramljak, Z.. Deur-Siftar, D., Solc., A., J . Chromatogr., 119, 445 (1976) (23W) Schaden, G., J . Chromatogr., 136, 420 (1977). (24W) Schmd, J. P I Schmid, P. P., Simon, W., Chromatographia. 9 , 597 (1976) (25W) Svob, V., Deur-Siftar, D , J Chromatogr., 135, 85 (1977). (26W) Szinai, S. S.. Roy, T. A., J . Chromatogr. Sci.. 14, 327 (1976) (27W) Tsuge, S., Takeuchi, T., Anal. Chem.. 49, 348 (1977). (28W) Vanderborgh, N. E.. Hanson, R. L., Brower, C . . Anal. Chem., 47, 2277 (1975). (29W) Voorhees, K. J., Hileman, F. D., Einhorm, I . N , Anal Chem., 47, 2385 (1975). (30W) Walker, J Q.. J , Chromatogr. Sci., 15, 267 (1977). (31W) Waysman, C., Matelin, D., Duc, C. L., J . Chromatogr. 118, 115 (1976) (32W) Zeman, I., Novak, L., Miner. L.. Stekla, J., Holendova, 0.. J , Chromatogr., 119, 581 (1976). (33W) Zizin, V. G., Grigorieva. L. A., Berdina, L Kh.. Plast Massy, 1, 55 (1976)
.
Chemical Reactions (1x1 Bailey, K.. Gagne, D.. J Pharm. S o . , 64. 1719 (1975) (2x1 Balabanov, V. V., Larin. N. V.. Zorin, A. D., Revin, Yu. V., foluch. Anal. Veshchestv Osoboi Chist. Gurki. 1974, 153. (3X) Balckwood, J. D., McCarthy, D. J.. Proc. Chem Eng., 28. 25 (1975). (4XI , , Braahin. 0. V.. Preobrazhenskii. A. V.. Liberman. A. L , I z v . Akad. Nauk SSSR: Ser. Khlm., 1974, 2751. (5X) Chriswell, C. D., Kissinger. L. D.. Fritz, J S . Anal Chem , 48, 1123 (1976). (6x1 Cremer. E., Kramer, R., J . Chromatogr.. 107, 253 (1975) (7X) Degtyarev, V. A., Pisarev, V. T., Gaibova, N. D , Sb. Tr Byrov Khim , 3 , 115 (1975).
ANALYTICAL CHEMISTRY, VOL. 50, NO. 5, APRIL 1978 (8x1 Dorinq, C. E., Stevenz. D., Geyer, R., Hopfner, J., Acta Chim. Acad. Sci. Hung., 8 5 , 47 (1975). (9X) Dunges, W., Chromatographia, 9, 571 (1976). ( l o x ) Fazli-Khosrochani, R., Kieffer, R., Deluzarche, A,, Tanielian, C., Bull. SOC. Chim. F r . . Part 111. 1975. 719. (11X) Franc, J., Pour, J.. J. Chromatogr., 131, 291 (1977). (12X) Getty. R. H., Stone, J., Hanson, R. H., Anal. Chem., 49, 1086 (1977). (13X) Giovanniello, T. J.. Pecci, J., Clin. Chem. ( Winston-Salem, N . C . ) ,22, 1208 (1976). (14X) Gorog, S., Lauko, A,, J. Chromatogr.. 118, 411 (1976). (15X) Haken, J. K., Ho, D. K. M., 3rd Aust. Symp. on Anal. Chem., Melbourne, Mav 1975. (16X) 'Harris, W. E., J. Chromafogr. Sci., 13, 514 (1975). (17X) Hoshika, Y., Anal. Chem., 49, 541 (1977). (lax) Hoshika, Y., J. Chromatogr., 115, 596 (1975). (19X) Hoshika, Y.. J. Chromatogr., 136, 253 (1977). (2OX) Ivanov, A. N., Yagomyagi, A. E., Eizen, 0. G., Kinet. Katal.. 15, 1029 (1974). (21x1 Ivanova, N. T., Wiozhine, L. D., Syavtsilb, S. V., Avdonin, G. V., Franguiyan, L. A,, Cherkassy, USSR, 1974. (22x1 Kallos, G. J., Albe. W. R., Solomon, R. A,, Anal. Chem., 49, 1817 (1977). (23X) Karashlma, D.. Shigematsu, A.. Furukawa, T., Nagayoshi. T., Matsumoto. I . , J . Chrornatogr., 130, 77 (1977). (24X) Komarkova, H., Churacek, J., Komarek, K., Krizek, F., J. Chromatogr., 119, 243 (1976). (25X) Kramer, R., J. Chrornatogr., 107, 241 (1975). (26x1 Kugucheva. Ye. Ye., Aiekseyeva, A. V., S b . Tr. Nauchn. Issled. Inst. Sintet. Spirtov Organ Prod., 5 , 165 (1974). (27x1 Langer, S. H., Melton. H. R., Griffith, T. D., J . Chromatogr., 122, 487 (1976). (28x1 Lie Ken Jie, M. S. F., J. Chromatogr.. 131, 239 (1977). (29X) Maiorov, D. M., Dydykina, G. V., Dementeva, M. I., Sergienko, I.F., Kinet. Katal., 16, 266 (1975). (30X) McKeag, R. G., Hougen, F. W., Anal. Chem.. 49, 1078 (1977) (31x1 Moore, B. P., Brown, W. V., J. Chromatogr.. 121, 279 (1976). 132X) . . Nemirovskava. I . B.. Berezkin. V. G., Kovarskava. B. M., Vvsokomol. Soedin., 17, 675 (1975). (33X) Nigam, R. N., J . Chromatogr.. 119, 620 (1976). (34x1 Oakes, T. R., Willis, C. E., Clin. Chem. ( Winston-Salem, N . C . ) ,18, 690 (19721. (35X) Palvanova, M. V.. Tatarinskti. V. S.. Fedvachkin. I . M.. Zavod. Lab., 41, 930 (1975). (36x1 Rasmussen, K. E., J. Chrornatogr., 120, 491 (1976). (37X) Scheil, G. W., Harris, W. E., J. Chromatogr. Sci., 14, 412 (1976). (38x1 Schep, R. A.. J. So. Afr. Chem Inst., 28, 33 (1975). (39X) Schindlbauer, H.. Gruber, H., Biller, E., J . Chromatogr., 115, 311 (1975). (40x1 Scott. K. F., PhilliDs. C. S. G., J. Chromatoor., 112, 61 (1975). (41X) Starodubtseva, I V , Ezerets, M A , Bulycheva, A. S I Zh Anal Khim , 31, 586 (1976). (42X) Struckmeyer, H. F., Ckn. Chem. ( Winston-Salem. N.C.),23, 1136 (1977). (43X) Tkacheva, V. N.. Bukina, V. K.. Dokl. Akad. Nauk Uzb. SSR., 1975, 31. (44X) West, J C., J. Polym. Sci., 49, 141 (1975). (45X) Wien, R. G., Tanaka, F. S., J. Chromatogr., 130, 55 (1977). (46X) Wu, A,, Clin. Chem., (Winston-Salem, N . C . ) , 20, 630 (1974) Derlvatization (1Y) Ahuja, S., J. Pharm. Sci., 65, 163 (1976). (2Y) Amico, V., Oriente. G.. Tringali, C., J. Chromatogr., 131, 233 (1977). f3Y) Bland. S. A,. Blake, J. W.. Rav. R. S.. J. Chromatoar. Sci.. 14. 201 (1976). , , (4Y) Bradway, D. E., Shafik, T.,'J. Chromatogr. Scr. 15, 322 (1977). (5Y) Bromilow, R. H., Lord, K . A., J . Chromatogr., 125, 495 (1976). (6Y) Burkinshaw, P. M., Morgan, E. D., Poole, C. F., J . Chromatogr., 132, 548 (1977). (7Y) Cagnasso, M., Biondi, P. A., Anal. Biochem., 71, 597 (1976). (8Y) Cant, P. A. E., Walker, N. J., J . Chromatogr,, 130, 267 (1977). (9Y) Chau, A. S. Y.. Terry, K., J. Assoc. Off. Anal. Chem.. 5 8 , 1294 (1975). (1OY) Chau, A S. Y., Tarry. K., J, Assoc. Off. Anal. Chem., 59, 633 (1976). I l l y ) Cochrane, W. P., J. Chromatogr. Sci., 13, 246 (1975). (12Y) De Leenheer, A. P.. Gelijkens, C. F., Anal. Chem., 48. 2203 (1976). (13Y) Donike, M., J. Chromatogr., 115, 591 (1975). (14Y) Drawert, F., Leupold, G., Chromatographia, 9, 605 (1976). (15Y) Drozd, J., Chem. Listy. 70, 268 (1976). (16Y) Gehrke. C. W.. Patel, A. B., J. Chromatogr., 123, 335 (1976). (17Y) Gehrke, C. W., Patel, A. B.. J . Chromatogr., 130, 103 (1977). (18Y) Giumanini, A. G., Chiavari, G., Scarponi, F. L., Anal. Chem., 48, 484 (1976). (19Y) Glam, C. S., Chan, H. S., Hammargren, T. F., Neff, G. S., Anal. Chem., 48, 76 (1976). (20Y) Hartvig, P., Handl, W., Vessman, J., Svahn, C. M., Anal. Chem., 48, 390 (1976). (21Y) Hoshika, Y., J. Chromatogr., 115, 596 (1975). (22Y) Khan, S. U., Greenhalgh, R.. Cochrane, W. P., J. Agric. FoodChem., 23, 430 (1975). (23Y) MacKenzie, S. L., Hogge, L. R., J . Chromatogr., 132, 485 (1977). (24Y) Metcalfe, L D., J. Chromatogr. Scl., 13, 516 (1975). (25Y) Miyazaki, H., Ishibashi, M., Itoh, M., Nambara. T.. B/omed. Mass Speckom., 4, 23 (1977). (26'0 Miyazaki, H., Ishibashi, M., Itoh, M., Yamashita, K., Nambara, T . , J. Chromatogr., 133, 311 (1977). (27Y) Moye, H. A., J, Agric. Food Chem., 23, 415 (1975). (28Y) Nambara, T., Iwata, T., Kigasawa, K., J. Chromafogr., 118, 127 (1976). (29Y) Nambara, T., Kigasawa, K., Iwata, T., Ibuke, M., J. Chromatogr., 114, 81 (1975). (30Y) Narasimhachari, N., Leiner, K., J. Chromatogr. Sci., 15, 181 (1977). (31Y) Nose, N., Kobayashi, S . , Tanaka. A., Hirose, A., Watanabe, A,, J .
241 R
Chromatogr., 130, 410 (1977). (32Y) Patel, A. B., Gehrke, C. W., J. Chromatogr., 130, 115 (1977). (33Y) Patzer, E. M., Hilker, D. M., J. Chromatogr., 135, 489 (1977). (34Y) Petersson, G., J, Chromatogr. Sci.. 15, 245 (1977). (35Y) Piekos, R., Osmklowski, K., Kobylczyk, K., Grzybowski, J., J. Chromatogr., 116, 315 (1976). (36Y) Piekos, R., Teodorczyk, J., Grzybowski, J., Kobylczyk. K., Osmialowskt. K., J, Chromatogr., 117, 431 (1976). (37'0 Pritchard, D. G.. Todd, C. W.. J . Chromatogr.. 133, 133 (1977) (38Y) Radmacher, A., Fed. Rep. Germany Patent 2 262 842 (1975). (39Y) Rasmussen, K. E., J. Chrornatogr., 114, 250 (1975). (40Y) Rasmussen, K. E., J. Chromatogr., 120, 491 (1976). (41Y) Rosello, J., Tusell, J., Gelpi, E., J . Chromatogr., 130, 65 (1977). (42Y) Serfontein, W. J.. De Villiers, L. S., J. Chromatogr., 130, 342 (1977). (43Y) Siezen, R. J., Mague, T. H., J. Chromatogr., 130, 151 (1977). (44Y) Sullivan, J. E., Schewe, L. R., J , Chromatogr. Sci., 15, 196 (1977). (45Y) Vandenheuvel, W. J. A., Gruber, V. F.. J . Chromatogr., 112, 513 (1975). (46Y) Wolfam, J. H., Feinberg, J. I., Doerr, R. C., Fiddler, W., J. Chromatogr., 132, 37 (1977). (47Y) Wong, L. K., Costello, C. E., Biemann, K., J. Chromatcgr., 116, 321 (1976). Preparatlve Scale and Trapping (12) Baker. R., Bradshaw, J. W. S.. Evans, D. A., Higgs, M. D., Wadhams, L. J., J . Chrornatogr. Sci., 14, 425 (1976). (22) Barker, P. E., Deeble, R. E., Chromatographia, 8, 67 (1975). (32) Carnes, M. G., Brenner, M. L., Anal. Biochem., 64, 5 (1975). (42) Chizhkov, V. P., Yushina, G. A.. Sinitzina, L. A., Rudenko, B. A,, J . Chromatogr., 120, 35 (1976). (52) Conder, J. R.. Chromatographia. 8, 60 (1975). (6Z) Galperin, G. D., Shifman, V. S.. Zhestkov, D. K., Gordadze, G. N., Leontieva, S. A., Lulova, N. I., Grinberg, A. A., Kondakova. N. F., Kvasova, V. A,, Khim. Tekhnol. Topliv Masel, 1975 (3), 59. (72) Gramshaw, J. W., Chem. Ind. (London). 24, 1072 (1976). (82) Grenier-Loustalot, M. F.. Metras, F., Campillo, J. P., Bonastre, J.. Grenier, P., J. Chromatogr., 118, 1 (1976). (92) Gyimesi, J., Szepesy, L., Chromatographia, 9, 195 (1976). (102) Johnson, C. B., Wong, E., J . Chromatogr., 109, 403 (1975) (112) Kindsvater, J. H., Rietz. R . R., J. Chromatogr. Sci., 13, 149 (1975). (122) Magnusson, G., J . Chromafogr., 109, 393 (1975). (132) Norin, K. H., Analyst(London), 99, 717 (1974). (142) Pausch, J. B., Chromatographia, 8, 80 (1975). (152) Reese, C. E., Grushka, E., Chromatographia, 8 , 85 (1975). (162) Roz, B., Bonmati, R.. Hagenbach. G.. Valentin, P.. J. Chromatogr. Sci., 14, 367 (1976). (172) Sakodynskii, K. I., Volkov, S. A.. Zelvenskit, V. Yu., USSR Patent 409 129 (December 7, 1974). MISCELLANEOUS
Physical-Analytical Measurements (1AA) Alksnis, 0. N., Yanovskii, S. M., Zavod. Lab., 41, 976 (1975). (2AA) Arutjunov, Yu. I., Geller, Z. I.. Korlyakov, G. A., Karanov, Ye. M., Avtom. Neftedob. Prom., 4, 246 (1974). (3AA) Aubry, M., Mayoral, M. N., Villardry, P.. Bull. SOC.Chim. F r . , Part 1, 1975, 200. (4AA) Braun, J. M., Lavoie, A., Guillet, J. E., Macromolecules, 8, 31 1 (1975). (5AA) Castells, R . C., J. Chromatogr., 111, 1 (1976) (6AA) Chernoplekova. V. A., Korol, A. N., Sakodynskii, K. I., Kocheshkov, K. A., I z v . Akad. Nauk SSSR, Ser. Khim.. 4, 834 (1975). (7AA) Choudhary, V. R., Menon, P. G., J. Chromatogr., 116, 431 (1976). (BAA) Choudhary, V. R., Parande, M. G., J . Chromatogr., 132, 344 (1977). (9AA) Cloete, C. E., Smuts, T. W., De Clerk, K., J. Chromatogr., 120, 1 (1976). (10AA) Cloete, C. E., Smuts, T. W., De Clerk, K., J . Chromatogr., 120, 17 (1976). (11AA) Cloete, C. E., Smuts, T. W., De Clerk, K., J. Chromatogr., 120, 29 (1976). (12AA) Courval, G., Gray, D. G., Macromolecules, 8, 326 (1975). (13AA) Crow, W. D., Khan, A. N., Paddon-Row, M. N., Aust. J. Chem., 28, 1741 (1975). (14AA) Crow, W. D., Khan, A. N., Paddon-Row, M. N., Sutherland, D. S.,Aust. J. Chem., 28, 1763 (1975). (15AA) Crow, W. D., Paddon-Row, M. N., Aust. J. Chem., 28. 1755 (1975). (16AA) Crowne, C. W. P., Harper, M. F., J. Chromatogr. Sci., 14, 201 (1976). (17AA) Deininger, G., Asshauer, J., Halasz, I., Chromatographia, 8, 143 (1975). (18AA) De Ligny, C. L.. Koole, N. J.. Nelson, H. D.. Nieuwdorp, G. H. E., J . Chromatogr., 114, 63 (1975). (19AA) Eon. C., Pommier, C., Guiochon, G., Bull. SOC.Chim. Fr., 1974, 1277. (20AA) Figgins, C. E., Reinbold, B. L., Risby, T. H., J . Chromatogr. Sci., 15, 208 (1977). (21AA) Figgins, C . E., Risby, T. H., Jurs, P. C., J. Chromatogr. Sci., 14, 453 (1976). (22AA) Figueras, F., Mencier, B , De Mourgues, L., Perrin, M., Chromatographia, 8, 203 (1975). (23AA) Filonenko, G. V.. Korol, A. N., J . Chromatogr., 119, 157 (1976). (24AA) Garusov, A. V., Vigdergauz. M. S., Zasvod. Lab.. 41, 1481 (1975). (25AA) Gawdzik, J., Jaroniec, M., J. Chromatogr., 131, 1 (1977). (26AA) Gawdzik. J., Suprynowicz, Z., Jaroniec, M., J. Chromatogr., 121, 185 (1976). (27AA) Gearhart, H. L., Burke, M. F., J. Chromatogr. Sci., 15, 1 (1977). (28AA) Hammers, W. E., De Ligny, C. L., J. Polym. Sci., Polym. Phys. Ed., 12, 2065 (1974). (29AA) Hofmann, H. J., Engewald, W., Heidrich, D., Porschmann, J., Thieroff, K., Uhlmann, P., J. Chromatogr.. 115, 299 (1975). (30AA) Hradil, J., Stamberg, J., 4th Natl. Conf., Pardubice, Part 1 , 1976, 115. (31AA) Hsu, C. C.. Rukzinski. W.. Wojciechowski, B. W., Chromatographia,
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ANALYTICAL CHEMISTRY, VOL. 50, NO. 5, APRIL 1978
8, 633 (1975). (32AA) Hung, C. W., Nunez, L. J., Autian, J., J . Pharm. Sci., 62, 1308 (1973). (33AA) Janini, G. M., Martire, D. E., J . Phys. Chem., 78, 1644 (1974). (34AA) Kapanin, V. V., Lemanik, 0. B., Vysokomol. Soedin., 17, 2354 (1975). (35AA) Kapanin, V. V., Priiipov, V. V., Vysokomoi. Soedin., 18, 718 (1976). (36AA) Kelker, H., J . Chromatogr., 112, 165 (1975). (37AA) Kocirik, M., Zikanova, A,, Chem. Zvesti, 29, 361 (1975). (38AA) Koloskov, 0 S.. Navokovskii, Ye. M., Belkyevich, P. I . , Vestn. Akad. Nauk Belorusk. SSR, Ser. Khim. Nauk, 6, 43 (1975). (39AA) Kong, J. M., Hawkes, S. J., J . Chromatogr. Sci., 14, 279 (1976). (40AA) Korol, A. N., Chromatographia, 8, 385 (1975). (41AA) Leggett, D. C., J . Chromatogr., 133, 83 (1977). (42AA) Letcher, T. M., Netherton. G., J . Chem. Thermodyn., 7, 353 (1975). (43AA) Leung, Y., Eichinger, B. E., J . Phys. Chem., 78, 60 (1974). (44AA) Lille, U., Kundel. H., Eisen, O., J . Chromatogr., 116, 1 (1976). (45AA) Maloney, D. P., PrausnRz, J. M., Am. Inst. Chem. Eng. J., 22, 74 (1976). (46AA) Manners, W. E., Bos, B. C., Vaas, L. H., Loomans, Y. J. W. A,, De Ligny, C. L., J . Polym. Sci., Polym. Phys. Ed., 13, 401 (1975). (47AA) Martire, D. E., Anal. Chem., 48, 398 (1976). (48AA) Mathiasson, L.. J . Chromatogr., 114, 39 (1975). (49AA) Mathiasson, L., J . Chromatogr., 114, 47 (1975). (50AA) Mathur, D. S., Saha, N. C . , J . Chromatogr., 138, 33 (1977). (5 I A A ) McMullin, S. L.. Bernhard, R. A., Nickerson. R. A., J . Agric. Focd Chem., 23, 452 (1975). (52AA) Meyer, E. F., Baiocchi, F. A,, Anal. Chem., 49, 1029 (1977). (53AAl Millen, W., Hawkes, S., J . Chromatogr. Sci., 15, 148 (1977). (54AA) Moiseyev, N., Platzner, I., J . Chromatogr. Sci., 14, 143 (1976). (55AA) Mysak, A. E., Nikitina, N. S.,Mankovskaya, N. K., Ermolenko, I.V., Kolloid. Z h . , 36, 1175 (1974). (56AA) Nand, S., Desai, B. K., Sarkar, M. K., J . Chromatogr., 133, 359 (1977). (57AA) Neogi, P., Kudchadker, A. P., J . Chem. Soc., Faraday Trans. 7 . 73, 385 (1977). (58AA) Nesterov, A. Ye., Lipatov, Yu. S., Vysokomol. Soedin., 16, 1919 (1974). (59AA) Neumann, M. G., J . Chem. Educ.. 53, 708 (1976) (60AA) Novakova, N., Novak, J., J . Chrornatogr., 135, 13 (1977). (61AA) Power, W. H., Woodworth, C . L., Loughary, W. G., J . Chromatogr. Sci., 15, 203 (1977). (62AA) Roseman, T J., Yalkowsky. S. H., J . Pharm. Sci., 62, 1680 (1973). (63AA) Rosolovskaya, Ye. N., Salvinski, Ya.. Vysokomol. Soedin. 18. 1428 (1976). (64AA) Rubinstein. R. N., Silchenko. S. A., J . Chromatogr.. 123, 251 (1976). (65AA) Saleem, M., Khan, M. A.. Shahid, M., Igbal, K., Chromatographia, 8, 699 (1975). (66AA) Schulz, P.. Anal. Chem.. 47, 1979 (1975). (67AA) Semonian, 8. P., Manes, M., Anal. Chem., 49, 991 (1977). (68AA) Serpinet, J., J . Chromatogr., 119, 483 (1976). (69AAl Steel, L. I., Harnish, D. G., Am. Inst. Chem. Eng. J . , 22, 117 (1976). (70AA) Stewart, G. H., J . Chromatogr. Sci., 14, 69 (1976). (71AA) Sunal, A. B., Barker, P. E., J . Chromatogr. Sci.. 13, 541 (1975). (72AA) Valentin, P., Guiochon, G., J . Chromatogr. Sci., 14. 56 (1976). (73AA) Valentin, P., Guiochon, G., J . Chromatogr. Sci., 14, 132 (1976). (74AA) Vitenberg. A. G., Ioffe, B. V., Dimitrova, 2 . St., Butaeva, I.L., J . Chromatogr., 112, 319 (1975). (75AA) Waksmundzki. A., Jaroniec, M., Suprynowicz, Z., J . Chromatogr., 110, 381 (1975). (76AA) Wasik, S. P., J . Chromatogr. Sci., 14, 516 (1976). (77AA) Yang, F., Hawkes, S., Lindstron, F. T., J . Am. Chem. Soc., 98, 5101 (1976). (78AA) Yoshikawa, Y., Shinozaki, A , Arita, K., EunsekiKagaku, 25, 341 (1976). Inorganic GC (1BB) Agliulov, N. Kh., Zuyeva, M. V., Feshchenko, I. A., Fayerman, V. I . , Zh. Anal. Khim., 30, 1733 (1975). (2BB) Akiba, M., Shimoishi, Y., Toei, K., Analyst(London) 100, 648 (1975). (388) Akiba, M., Shimoishi, Y., Toei, K., Analyst(London), 101, 644 (1976). (488) Barlthop. D.. Lewis, P. A., Analyst(London), 100, 862 (1975). (588) Belcher, R., Rodriquez-Vazquez, J. A,, Stephen, W. I., Uden. P. C., Chromatographia, 9, 201 (1976) (6BB) Brockway, D , Cardwell T J , 3rd Aust Symp Anal Chem , Melbourne, Mav 1975 (7BB) 'Bruk, A. I., Vetrova, Z. P., Vyakhirev, D. A,, Karabanov, N. T., Yashin, Ya. I., T r . Khim. Khim. Tekhnoi., 1974, 139. (8BB) Burgett, C . A., Sep. Purif. Methods, 5 , 1 (1976). (9BB) Cappon, C. J., Smith, J. C., Anal. Chem., 49, 365 (1977). (1OBB) Chau. Y. K., Wong, P. T. S., Goulden, P. D., Anal. Chem., 47, 2279 (1975). ( I l B B ) Chau, Y. K., Wong, P. T. S., Saitoh, H., J . Chromatogr. Sci., 14, 162 (1976). (1288) Devyatykh, G. G., Balabanov, V. V., Gusev, A. V., Karatayev, Ye. N., Agliulov, N. Kh., Zh. Anal. Khim , 30, 1630 (1975). (13BB) Dilli, S., Patsalides, E., J . Chromatogr., 130, 251 (1977). (14881 Fontaine, R., Doctoral Dissertation, Univ. of Paris, France, 1972. (15BB) Fujinaga, T., Kuwamoto, T., Kimoto, T., Talanta, 23, 753 (1976). (16BB) Gavriiov, V. I., Khlebnikov, V. N., Komleva, A. A., Chernokalskii, B. D., Zh. Obshch. Khim.. 44, 2506 (1974). (17BB) Hobo. T., Ogura, T., Suzuki, S., Araki, S., Eunseki Kagaku, 24, 288 (1975). (18BB) latridis. B., Parissakis, G., Anal. Chem., 49, 909 (1977). (19BB) Iatridis, B., Parissakis, G., J . Chromatogr., 122, 505 (1976). (20BB) Jacquelot, P., Thomas, G., Bull. Soc. Chim., F r . , 1973, 1261. (21BB) Joshi, K. C . . Pathak, V. N., Coord. Chem. Rev., 22, 37 (1977). (2288) Kito, A., Miyake, Y., Bull. God. Ind. Res. Inst., Osaka, 25, 93 (1974). (2388) Kito. A., Nakane. M., Miyake, Y . , Bunseki Kagaku, 26, 19 (1977). (24BB) Koch, J., Figge, K., J , Chromatogr., 109, 89 (1975). (2588) Komarov, V. A., Zh. Anal. Khim., 31, 366 (1976). (26BB) Krupcik, J., Garaj, J., Holotok, S., Oktave, D., Kosik, M., J . Chromatogr.,
112, 189 (1975). (2788) Kutal, C., Sievers, R. E., Inorg. Chem., 13, 897 (1974). (28BB) Leddet, M., Doctoral Dissertation, Univ. of Paris, France, 1974 (2988) Lovett, R. J., Lee, G. F., Environ. Sci. Techno/., 10, 67 (1976). (30BB) Makarenko, V. G., Fedorov, V. A., Yefrenov, Ye. A,, O r b V. Yu., FiliDDov, E. P., Zh. Anal. Khim.. 30, 1183 (1975). (31BB) Mangia, A., Chim. Ind., 5 7 , 48 (1975). (3288) Manoia. _ ~ A,. . , Chim. Ind.. 5 7 . 49 119751. Masaryk, J.. Krupcik. JI, i;araj, J..'Kosik: M , J Chromatogr., 115. 256 (1975). (3488) Michael, G.. Danne, U., Fischer, G., J . Chromatogr., 118, 104 (1976). (3588) Mironov, V. F., Gar, T. K., Z h . Obshch. Khim., 45, 103 (1975). (36BB) O'Brien, T. P., O'Laughlin, J. W., Talanta, 23, 805 (1976). (37BB) Okubo, T., Aoki, F., J . Natl. Chem. Lab , 69, 44 (1974). (3888) O'Laughlin, J. W., O'Brien, T. P.. Talanta. 22, 587 (1975). (3988) Parissakis, G., Iatridis, B., Chromatographia, 10, 37 (1977). (4088) Poole, C. F.. Evans, N. J., Wibberley, D. G., J . Chromatogr., 136, 73 (1977). (4188) Ryan, T. R., Vogt, C. R. H., J . Chromatogr., 130, 346 (1976). (42BB) Saleem, M., Khan, M. A., Shahid, M.. Iqbal, K., Chromafographia. 6, 699 (1975). (4388) Schafer, M. L., Rhea, U., Peeler, J. T., Hamilton, C.H., Campbell, J. E., J . Agric. Food Chem.. 23, 1079 (1975). (44BB) Schnecko, H., Eisenbach, C. D.. Kearn, W., J . Chromatogr. Sci., 14, 219 (1976). (45BB) Shimoishi, Y., Analyst(London), 101, 298 (1976). (46BB) Shimoishi, Y., Bull. Chem. SOC.Jpn.. 48, 2797 (1975). (47BB) Shimoishi, Y., J . Chromatogr., 136, 85 (1977). (48BB) Talmi, Y., Bostick, D. T., Anal. Chem., 47. 2145 (1975). (4988) Taimi, Y., Bostick, D. T., J Chromatogr. Sci., 13, 231 (1975). (50BB) Tanikawa, K., Eunseki Kagaku, 25, 721 (1976). (51BB) Tavlaridis, A., Neeb, R., Naturwissenschaften, 63, 146 (1976). (5288) Trotter, W . J , Young, S. J. V., J . Assoc. Off. Anal Chem., 5 8 , 466 (1975). (5388) Voronmov, M. G.. Mirskov, R . G.. Ishchenko, 0. S., Sttnikova, S. P.. Z h . Obshch. Khim., 44, 2462 (1974). (5488) Watts, J. O., Boyer, K. W., Cortez, A., Elkins, E. R., Jr., J . Assoc. Off. Anal. Chem., 5 9 , 1226 (1976). (55BB) Yablokov, V. A.. Sunin, A. N., Yablokova, N. V., Ganyushkin, A. V., Zh. Obshch. Khim., 44, 2446 (1974). (56BB) Zarnegar, P., Mushak, P., Anal. Chim. Acta, 6 9 , 389 (1974). (57BB) Zuyeva, M. V., Dudorov, V. Ya.. Agliulov, N. Kh., Salganskli, Yu. M., J . Chromatogr.. 109, 239 (1975). (58BB) Zuyeva, M. V., Dudorov, V. Ya.. Agliulov, N. Kh., Salganskii. Yu M , Zh. Anal. Khim., 31, 185 (1976). ~
Novel Applications (1CC) Akimoto, M., Echigoya, E., J . Chem. Soc., Faraday Trans. 7 , 73, 193 (1977). (2cC) Arpino, P., Moreau, J.-P., Oruezabal, C., Flieder, F.. J . Chromatogr , 134, 433 (1977). (3CC) Ballantine, J. A., Roberts, J. C . . Morris, R. J., Eiomed. Mass Spectrom., 3, 14 (1976). (4CC) Benson, W. W., Brock, D W., Gabica, J.. Loomis, M., Bull. Environ. Contam. roxicoi., 15, 543 (1976). (5CC) Brown, B. I., Aust. Hod. Res. News/.. 34 (4), 41 (1973). (6CC) Cameron, D. W., Drake, C. 6..Aust. J . Chem., 29, 2713 (1976). (7CC) Catalano. E. A., Hasling, V. C., Dupuy, H. P., Constantin, R. J.. J . Agric. Food Chem., 25, 94 (1977). (8CC) Crewe, R. M., Fletcher, D. J. C., S . Afr. J . Sci., 72, 119 (1976). (9CC) Dagher, S. M.. Ruhayyim, 1. G., J . Food Sci., 40, 917 (1975). (IOCC) Davies, A. M. C . . J . Chromatogr., 115, 293 (1975). (1lCC) Dunsmore, J. D., Hall, L. S., Kotteh, K. H., Search, 5 (3). 110 (1974). (12CC) Dvorchik, 8. H., Miller, S . H., Graham, W. P., J . Chromatogr., 135, I, d. 1. 11977) j
(13CC) Ferkovich, S. M., Mayer. M. S., Rutter, R. R., J , Insect Physioi., 19, 2231 (1973). (14CC) Frey, H. M.. Kennedy, G. J., J . Chem. Soc., Faraday Trans. 7 . 7 3 , 164 (1977). (15CC) Gordon, S. G., Smith, K., Rabinowitz, J. L., Vagelos. P. R., J LipdRes , 14, 495 (1973). (16CC) Hill, R. E., Latham, A. N., J . Chromatogr., 131, 341 (1977) (17CC) Idler, D. R., Khalil, M. W., Gilbert, J. D., Brooks, C.J. W., Steroids, 27, 155 (1976). (18CC) Jennings, D. M., Bunyan, P. J.. Brown, P. M., Stanley, P. I., Jones, F. J. S., Pestic. Sci., 6. 245 (1975). (19CC) Kaplanis, J. N., Robbins, W. E., Thompson, M. J.. Dutky, S. R.,Stero!ds, 27. 675 (1976). (20CC) Kobayashi. M., Mitsuhashi. H., Steroids, 26, 605 (1975). (21CC) Lee, Y. B.. Hargus, G. L., Kirkpatrick, J. A,. Berner, D. L.. Forsythe, R. H., J , Food Sci., 40, 964 (1975). (22CC) Liddle, J. A,. Needham. L. L., Kimbrough, R. D.. Bayse, D. D., Clin. Chem (Winston-Salem. N . C . ) ,23, 1159 (1977). (23CC) Lynn, R. K., Leger, R. M., Gordon, W. P., Olsen, G. D., Gerber. N.. J . Chromatogr., 131, 329 (1977). (24CC) Machin, A. F., Rogers, H., Cross, A . J., Quick, M. P., Howells L C., James, N F., Pestic Sci.. 6 , 461 (1975). (25CC) NcNeil. E. E.,Gtson. R., Miles, W. F., Rajabalee, F J. M.. J . Chromatcgr., 132, 277 (1977). (26CC) Mieure, J. P., Hicks, O., Kaley, R. G.. Michael, P. R., J . Chromatogr. Sci., 15, 275 (1977). (27CC) Millinaton, D., Jenner, D. A,, Jones, T., Griffiths, K., Biochem. J . , 139, 473 (1974. (28CC) Miquel, J. D., Richard, H. M. J., Sandret, F. G., J . Agric. FoodChem., 24, 833 (1976).
ANALYTICAL CHEMISTRY, VOL. 50, NO. 5, APRIL 1978 (29CC) Nalley, L., Hoff, G.. Bigler, W., Hull, W., Bull. Environ. Contam. Toxicol., 13. 741 (1975). (30CC) Nicolov, N., Tsuotsourlova, A.. Nenov. N., Riv. Ifal. Essenze Profumi, 58. 349 (1975). (31CC) None, D. J., Eggers, S. H., May, I. R., J. InsectPhysiol., 19, 1547 (1973). (32CC) Patterson, G. W., Khalil, M. W., Idler, D. R . , J . Chromatogr., 115, 153 (1975). (33CC) Phillips, F. T., Pesfic. Sci., 5, 147 (1974).
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(34CC) Read, J. S., Hewitt, P. H., Warren, F. L., Myberg. A. C., J . InsectPhysiol., 20, 441 (1974). (35CC) Roelofs, W. L., Tette, J. P., Taschenberg, E. F., Comeau, A,, J , Insect Physiol., 17, 2235 (1971). (36CC) White, R . H., Science, 189 (4205), 810 (1975). (37CC) Wood. N. F., Snoeyink, V. L., J . Chromatogr., 132, 405 (1977). (38CC) Yang, R . S. H., Mueller, W. F., Grace, H. K., Gilberg. L., Coulston, F., J . Agric. Food Chem., 24, 563 (1976).
Ultraviolet and Light Absorption Spectrometry J. A. Howell” Western Michigan University, Kalamazoo, Michigan 49008
L. G. Hargis University of New Orleans, New Orleans, Louisiana 70722
At the request of ANALYTICAL CHEMISTRY, the topics of Light Absorption and Ultraviolet Absorption Spectrometry, which have previously been reviewed separately, have been combined. This review reports t h e developments in these fields from December 1975 through November 1977, primarily as documented in Chemical Abstracts, and extends the series of reviews sponsored by ANALYTICAL CHEMISTRY beginning in 1945 for Light Absorption Spectrometry (62,323,324)and 1949 for Ultraviolet Absorption Spectrometry (101, 102,210, 211, 216, 462). T h e subject matter has been divided into sections on Chemistry, Physics, and Applications, as was done with previous reviews on Light Absorption Spectrometry. T h e citations in this review represent a n effort on t h e authors‘ part to select from the very extensive literature those developments which are of most probable interest to analytical chemists. T h e authors apologize in advance for any error of judgment in omitting certain references. IUPAC has formulated provisional recommendations for publication of papers on molecular absorption spectrophotometry between 200 and 800 n m (224)and two other reports dealing with problems in nomenclature have appeared (218, 326). Readers should consult the January issue of ANALYTICAL CHEMISTRY, page 191, for guidelines to be used when publishing in this journal. Several reviews regarding reagents or specific constituents have been published. T h e use of 2-nitroso-5-dimethylaminophenol and 2-nitroso-5-diethylaminophenol for determining cobalt has been reviewed (575). T h e applications of pyrimidine derivatives to the determination of various metal ions have been summarized and their sensitivity and selectivity toward the platinum metals noted (388). Organic dyes (186) and general spectrophotometric reagents (411,540)used for trace metal determinations have been surveyed. Several reviews of methods for particular substances or classes of substances have appeared including those for lithium and sodium (641),titanium (640),the platinum metals (4401,and amines (79, 80). Methods for phosphorus and arsenic as reduced heteropolymolybdates have been reviewed (400). The use of ultraviolet spectrometry in the functional group analysis of organic compounds has been discussed (405) and photochemical methods in chemical analysis have been reviewed (408). Several reviews of new or specialized instrumental techniques have appeared, including optoacoustic spectrophotometry (10, 1421, dual wavelength spectrophotometry (213), and dual wavelength and derivative absorption spectrophotometric determination of inorganic and organic substances (501). T h e use of standards for qualitative and quantitative analysis in spectrophotometry has been discussed (601, 621)
along with t h e uses and limitations of the standard addition technique (270). An extensive review of photomultiplier detectors has appeared (639). An article on how spectrophotometric methods involving solvent extraction steps should be developed and reported contains some excellent suggestions (303). Books related to ultraviolet and light absorption spectrometry are: “Methods of Absorption Spectroscopy in Analytical Chemistry” (407);“Practical Manual for Photometric and Spectrophotometric Methods of Analysis”, 4th ed. (74);“Determination of Elements” (304);“Spectrophotometric Analysis in Organic Chemistry“ (53);“Photometric Analysis: Methods for Determination of Nonmetals” (33);“The Analysis of Organic Materials, No. 9: Aldehydes-Photometric Analysis” (477);“Colorimetric and Fluorometric Analysis of Organic Compounds and Drugs” (406);“Colorimetric and Fluorometric Analysis of Steroids” (47);“Organic Electronic Spectral Data”, Vol. 19 (144);“Absorption Spectra in the Ultraviolet and Visible Region”, Vol. 20 (284);“Absorption Spectra in t h e Ultraviolet and Visible Region: Cumulative Index (16-20)” (285);“Standard Reference Materials: Glass F i l t e r s a s a S t a n d a r d Reference M a t e r i a l for Spectrophotometry” (317 ) ;“Color-Universal Language and Dictionary of Names’‘ (257). This last book is also available as part of a National Bureau of Standards color kit (No. 2107) which includes color name charts illustrated with centroid colors.
CHEMISTRY T h e use of mixed ligand and extractable ternary ion-association complexes continues to increase in popularity. The ready availability of dual wavelength and derivative spectrometers has led to numerous applications especially in the analysis of drugs and pharmaceutical samples. This part of t h e review deals with the chemistry involved in t h e development of suitable reagents, absorbing systems, and methods. Metals. T h e complexing ability of 1,2,5,8-tetrahydroxyanthraquinone-3-methylamine-N,N-diacetic acid and its use for determining boron, group 2a metals, and fluoride (via its lanthanum or cobalt complex) has been studied (20). Twenty-nine derivatives of quinoline-2-thiol have been synthesized and their color reactions with various metal ions investigated (353). Several new ligands have been synthesized a n d evaluated as reagents for metals including salicylaldehyde-4-phenyl-3-thiosemicarbazone for copper(II),nickel, cobalt(II), a n d vanadium(I1) (396), di-2-pyridyl ketone thiosemicarbazone for iron(II), nickel, and cobalt(I1) (3091, a n d pyridylazo a n d quinolylazo derivatives of 4,5-di-
