(283) Steger, E., Simon, A., Ibid., 294, 1 119.58’1. \----,-
(284) Stekhanov, A. I., Izvest. Akad. S a u k S.S.S.R., Ser. Fiz. 21, 311 (1957). (285) Stekhanov, A. I., Klochikhin, A. A., Fiz. Tuerdogo Tela‘2, 2932 (1960). (286) Stekhanov, A. I., Klockikhin, A. A., Vestnik Leningrad. Univ. 15, KO. 16 (Ser. Fiz. i Khim. No. 3), 145 (1960). (287) Stepanov, B. I., Apanasevich, P. A, Izvest. Akad. Sauk S.S.S.R., Ser. Fiz. 22, 1380 (1958). (288) Sterin, K. E., Trudy Fiz. Inst. n’auk S.S.S.R. 9, 13 (1958). (289) Stoicheff, B. P., “Advances in Spectroscopy,” H. W. Thompson, ed., Vol. 1, p. 91, Interscience, New York, 1959. (290) Stryland, J. C., May, A. D., Rev. Scz. Instr. 31, 414 (1960). (291) Sukhorukov, B. I., Finkel’shtein, A. I., Optika i Spektroskopiya 6,637 (1959). (292) SushchinskiI, M. &I., Izvest. Akad. Xauk S.S.S.R., Ser. Fiz. 22, 1063 (1958). (293) Sbshchinskii, M. M., Issledovaniya Eksptl. Teoret. Fiz., Akad. Nauk S.S.S.R., Fiz. Inst. im. P. N . Lebedeva 1959, 211. (294) SushchinskiI, 51. M.,Spectrochim. Acta 14. 271 (1959’1. (295) Sushchinskii, h1. M., Trudy Fiz. Inst. Akad. Kauk S.S.S.R., Fiz. Inst. am. P. S. Lebedeva 12,54 (1960). (296) Tarte, P., Laurent, P. .4.,Bull. SOC. chim. France 1957,403.
(297) Taurel, L., Delain, C., Compt. rend. 246, 260 (1958). (298) Taylor, R. C., Cluff, C. L., Nature 182, 390 (1958). (299) Taylor, R. C., Schultz, D. R., Emerv. A. R.. J . Am. Chem. SOC.80. 27 (16581. (300) ‘Taylor, R. C., Vidale, G. L., Ibid., 78, 5999 (1956). (301) Titov, E. V., Izmailov, N. A.,
Uchenye Zapiski Khar’kov Gosudarst. L‘niv. im. A . M . Gor’kogo, Trudy Khim.
Fak. i Nauch.-Issledovalel. Inst. Khirn. 82, No. 16, 139 (1957); C. -4. 55,
21799c (1961). (302) Tobin, M. C., J . Opt. SOC.Am. 49, 850 (1959). (303) Tobin, R. .4.,Cohen, L., Saval Research Lab. ReDt. NRL Prom.. 11 iJulv 1959). (304) Toishi,’ K., Niura, S., Sature 175, 81 (1955). (305) Topchiev, A. V., Musaev, I. A., Iskhakova, E. Kh., Kislinskii, A. X.> Gal’pern, G. D., Doklady Akad. ‘%-auk AzerbaZdzhan. S.S.R. 14. 291 11958). (306) Toussaint, A., In;?. chlmisf; 40, 147 (1958). (307) Tramer, A, Mathieu, J. P., Compt. rend. 249, 392 (1959). (308) Treshchova, E. G., Tatevskii, V. M., Daukshas, V. K., Levina, R. Ya., Optika i Spektroskopiya 10,63 (1961). (309) Tsuboi, M., J . Am. Chem. SOC.79, 1351 (1957). (310) Tunnicliff, D. D., Jones, A. C., J . Opt. SOC.Am. 51, 1430 (1961). (311) Ukholin, S. A., Pronina, 11. Z., Issledovaniya Eksptl. Teoret. Fiz. Akad. Sauk S.S.S.R., Fiz. Inst. im. P. -V. Lebedeva 1959, 244. (312) UrazovskiI, S. S., Tomash, N. V., Trudy Khar’kov Politekh. Inst. im. V . I . Lenina, Ser. Khim.-Tekhnol. 13, 9 I
,
ilF)57\.
(313) Valentin, F., Ann. Phys. 4 [13], 1239 (1959). (314) Valentin, F., Compt. rend. 244, 1915 (1957). (315) Venkateswarlu, K., Balasubramanian, C., Proc. Indian Acad. Sci. 51A, 151 (1960). (316) VenkatesR-arlu, K., Ramanswamy K., 2. Physik 163, 457, 463 (1961). (317) Venkateswarlu, K., Thyagarajan, G.. Ibid.. 154. 70 (19591. (318j Vrathy, F., Fischer, R. B., Anal. Chim. Acta 23, 171 (1960). (319) Vratny, F., Fischer, R. B., d p p l . Spectroscopy 14, 76 (1960).
(320) Vratny, F., Fischer, R. B., Talanta 2, 315 (1959). (321) Waters, D. X., Woodward, L. A., Proc. Roy. SOC.(London) 2468, 119 (1958). (322) Weinstock, B., Malm, J. G., J . Am. Chem. SOC.80,4466 (1958). (323) West, R., Niu, H. Y., Powell, D. L., Evans, M. V.,Ibid., 82, 6204 (1960). (324) Whiffen, D. H., J . Opt. SOC.Am. 47, 568 (1957). (325) Whiffen, D. H., Proc. Phys. SOC. (London) 69A, 375 (1956). (326) Wolkenstein, M. W., Doklady Akad. Xauk S.S.S.R. 32, 185 (1941). (327) Woodward, L. rl., Ann. Repts. Progr. Chem. 56, 67 (1959). (328) Woodward, L. A,, Quart. Revs. (London) 10, 185 (1956). (329) Woodward, L. A,, Anderson, L. E., J . Chem. Soc. 1957, 1284. (330) Woodward, L. A., Creighton, J. A., Spectrochim. Acta 17, 594 (1961). (331) Woodward, L. A., Greenwood, N. S., Hall, J. R., Worrall, I. J., J . Chem. SOC.1958, 1505. (332) Woodward, L. .4.,George, J. H. B., ,Vatwe 167, 193 (1951). (333) Woodward, L. A., Long, D. A., Trans. Faraday SOC.45, 1131 (1949). (334) Woodward, L. A,, Owen, H. F., J . Chem. SOC.1959, 1055. (335) Woodward, L. h., Taylor, XI. J., Ibid., 1960, 4473. (336) Yellin, W., Plane, R. A., J . Am. Chem. Soc. 83, 2448 (1961). (337) Yoshino, T., Bernstein, H. J., J . M o l . Spectroscopy 2, 213 (1958). (338) Ibad., p. 241. (339) Yoshino, T., Bernstein, H. J., Spectrochim. Acta 14, 127 (1959). (340) Young, T. F., Xlaranville, L. F., Smith, H. M., “Structure of Electrolytic Solutions,” W. J. Hamer, ed., p. 35, Kiley, Sew York, 1959. (341) Young, T. F., Walrafen, G. E., Trans. Faraday Soc. 57, 34 (1961).
Review of Fundamental Developments in Analysis
UItraviolet Spectrometry Robert C. Hirt, Central Research Division, American Cyanamid Co., Stamford, Conn.
T
biennial review of fundamental developments in ultraviolet spectrometry is concerned with the period from the last such review (59) until about October 1961. It is intended, as were previous reviews, to be selective rather than comprehensive. Consequently, many worthwhile papers on analytical ultraviolet spectrometry may not have been mentioned. The uses of spectra in spectra-structure correlations, characterization of compounds, and reaction kinetics are increasingly important, but have generally not been included here. Preference has frankly been given to articles in the English language which are readily available to the analyst. The quantity and quality of papers concerned with ultraviolet spectromHIS
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etry have continued at the high levels of previous years. If any trend can be discerned, it is one of greater sophistication. There are fewer papers reporting on the quantitative determination analysis of a strongly absorbing substance in the presence of weak or nonabsorbers. This type of analysis has contributed to spectrometry being referred to as a “conventional method of analysis.” Ingenious separations or combinations with other techniques are typical of many publications. It is gratifying to see that many analysts are taking advantage of differences in spectra due to changes in solvents and the p H effects. The ability of spectrometry to observe and to measure ionic species has always been a strong point, both for solving interference prob-
lems and for use in spectrometric titrations. Of course, changes upon ionization are useful in spectra-structure studies as well. ORGANIC ELECTRONIC SPECTRAL DATA
The most important event in the field of ultraviolet spectrometry during the past two years was the publication of “Organic Electronic Spectral Data” in two volumes, edited by Kamlet (68) and Ungnade (161). This monumental work had been long awaited and eagerly anticipated by those who knew of this project. Years of labor by over 50 abstracters and a small editorial staff have produced a comprehensive coverage of about 70 journals in the years 1946 through 1955. Subsequent volumes are promised for later years.
Unlike other compilations which present spectral curves or literature references, this book lists a summary of band maxima by wavelength in millimicrons and intensity as log molar absorptivity. Compounds are listed on a molecular formula basis with Chemical Abstracts name. The solvent is included, which is an important feature. References are made t o the original articles. Coverage of the literature appears to be reasonably complete. These volumes are most valuable nhen uhed to answer questions of “&-here does this compound absorb?,” “Has a spectrum of that compound been published, and where?,” and “How intense are the bands?” Although the application of the O.E.S.D. may be termed qualitative rather than (analytically) quantitative, i t is not designed to identify unknown compounds in the manner of the ASTM-IBhI punched cards or other data-retrieval systems. It does, however, bring the world’s electronic spectral data to the spectroscopist’s desk in a compact and remarkably usable form. -4lthough the analyst may not be brave or trusting enough of the intensity data to set up a quantitative analysis, he can make an estimate of concentration that might be good to lo%, and this may suffice until standards may be set up for a rigorous analysis. These volumes have been reviewed (66, 72,156). BOOKS AND REVIEWS
The “Encyclopedia of Spectroscopy” (32) contains a number of articles of interest to ultraviolet spectroscopists. Mellon (91)presents a fine summary on “Analytical Absorption Spectrometry” and Malmstadt (85) describes “Spectrophotometric Titrations.” Analysis of fats and related materials is treated by O’Connor (105) and spectroscopy of fused salts by Clark (33). O’Laughlin and Banks (104) review differential spectrophotometry; Friedel (4.4) describes yapor spectra in the infrared and ultraviolet regions. I n three shorter articles, ultramicrospectrophotometry is discussed by Mason (go), vacuum ultraviolet region instrumentation is summarized by Sherman (130), and longpath ultraviolet absorption spectrophotometry is described by Renzetti (115). Other chapters cover various other fields of spectroscopy. This encyclopedia has been reviewed by Kniseley (74). The second edition of Ewing’s “Instrumental Methods of Chemical Analysis” (@) appeared in 1960. This was rrviewed by Rosenbaum (161). A chapter by TT7alker (158) in “General Cytochemical Methods” (37) is devoted to ultraviolet microspectrophotometry. A general textbook on instrumental analysis by Strobe1 (141) appeared, with the title “Chemical Instrumentation:
A Systematic Approach to Instrumental Analysis,’’ and has been reviewed by Brealey (23). “Advances in Spectroscopy, Vol. 1,” edited by Thompson (146), contained interesting chapters on free radicals (112) and the vacuum ultraviolet (111). It has been reviewed (12s). I n somewhat related fields, books have been published which contain sections of interest to ultraviolet spectroscopists: “Quantitative Molecular Spectroscopy and Gas Emissivities” by Penner (f08), reviewed by Lauer (79), and “Photoconductivity of Solids” by Bube (28), are examples. Cannon (SO) describes the electronics of instrumentation in “Electronics for Spectroscopists,” reviewed by Donner (39) and by the Photoelectrzc Spectrometry Group Bulletan
(105). A rather unique two-volume set by Lang (78) has been published: One part is a text, summarizing the subject field of absorption spectra in the ultraviolet and visible region. The second part is a loose-leaf set of absorption spectral curves, somewhat reminiscent of the classic Friedel and Orchin collection. Tabular data are included as well as plots of log molar absorptivity vs. wavelength. Brode (26) and Roe (120)have published reviews. The “Bibliography of Recent Papers” was continued through 1960 and part of 1961 by Jaycox et al. (65).
The second literature survey by Hershenson (58) appeared, covering spectra published from 1955 through 1959 [previous volume (57) covered 1930 through 19541. The same format was used. The Hershenson compilations and the Kamlet-Ungnade volumes (68, 151) nicely complement each other, offering the user access to the literature via either the compound name or empirical formula routes. The Hershenson index does not list band positions or intensities, but only the literature reference. An extensive review on “Nolecular Electronic Absorption Spectra” was prepared by Mason (89) containing 483 references in 84 pages of well-written text. Although not primarily concerned with analytical problems, it is useful in the interpretation of spectra. COLLECTIONS OF SPECTRA
I n addition to the literature coverages of Kamlet-Ungna.de and Hershenson, spectral curves have been published in collections, many of which are continuing affairs. The new collection by Lang (78) presented 170 plotted spectra, and promises future editions (one appeared in December 1961 with 178 additional spectra). Project 44 of the ilmerican Petroleum Institute has continued issuing curves, which now total about 880.
A committee of the Manufacturing Chemists’ Association has started issuing spectral curves; this project, as well as API. Project 44, is headed by A. Danti. He has prepared a booklet of “Information for Contributors” (40). The format is the same as that of the API. Ultraviolet spectra are also being issued by Sadtler (12~5);these now total about 1500. The Standard Data Subcommittee of Committee E-13, Absorption Spectroscopy, American Society for Testing RIaterials, has continued issuing ultraviolet and visible spectral data, using IBLI cards. Kame-formula index cards hare been made available for the ultraviolet as well as the infrared region. -\PI, RICA, Sadtler, and Lang collections are being coded, as well as spectra from the literature. Information on this project is available from L. E. Kuentzel, Wyandotte Chemical Corp., Wyandotte, Mich. The activities of the past ten years of Committee E-13 have been summarized by Robey (115). A “Central Library of Spectroscopy” has been announced by the Society for Applied Spectroscopy (16), to publish spectroscopic titles in Interlingua. CELLS AND ACCESSORIES
Interest has always been strong in modifying commercial spectrophotometers and in constructing accessories for handling special samples. A low temperature cell with provision for stirring was described by dloisio ( 1 ) for application to Beckman D K instruments. h high temperature and high pressure device was built by Balchan and Drickamer (10). A Teflon polytetrafluoroethylene and sapphire cell usable to 1000 atm. was described by Gill and Rummel (47). Furnaces for Cary Model 14 spectrophotometers were constructed by Morrey and Madsen (96) for work with fused salts. Clark (33) summarized fused salt spectrosCOPY. The use of KC1 (151)and KHr disks was described (110). X simple thermostatic device for the ubiquitous Beckman DU was built by Martin and Gorin (87). UcCormick and Gorin (82)made an anaerobic cell lvhich permits mixing within the cell proper. An adaptation for the Beckman DU, which permits use of microliter cells, uses a light beam about 0.3 mm. in diameter (49). A simple glass Baly-type cell v a s devised by Breda and Kotkas ($4) for use as a compensator cell in differential photometry. Continuous analysis of column effluents was made possible by quartz flow cells discussed by andemon (6). Riggle (118) prepared a simple test tube holder for the Beckman DU. X letterpen holder has been suggested for use with the Beckman DK-2 ( f 4 3 ) , which ought to be applicable t o other recorders. VOL 34, NO. 5, APRIL 1962
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A semiautomatic plotting attachment for the Beckman D U has been devised by Bowers and Raymond (21). This employs a conventional typewriter with a time drive on the platen and a flexible tape and cam attachment to the transmittance knob. In the trend to make things more automatic, publications should be noted by Kuchler, Strickler, and Grauer (75) for repetitive scanning of spectra in connection with steroid hormone analysis. Mullen and Anton (99) described a multifunction recording photometric titrator, and Olson and Alway (105) modified a Cary Model 11 to the automatic recording of derivative spectra. Tunnicliff and Hawes (160) have attached an absorptivity recorder to a Cary spectrophotometer. The range of wavelength coverage of a General Electric visible spectrophotometer was extended into the ultraviolet by Grum and Scharf (66). The special problems involved in measuring the spectral transmittance of photographic objectives was discussed by Grum and Williams (53), ~ h also o used a Cary instrument. Interest in micro-scale spectrometry was manifested by a review by Strother and Wolken (142) and a short article by Mason (90). Use of a Cary Model 14 spectrophotometer for microspectrophotometry was the subject of a n article by Brown (27). The beam of an Optica CF4 spectrophotometer was reduced in cross section to obtain the spectrum of keratin in a thin section of horse-tail hair (14). Applications of a recording reflectometer were summarized by Anacreon and Noble (4). Smith (133) extended reflectance measurements into the vacuum region. Few previous data seem to have existed on diffusing disks for the ultraviolet; Middleton (94) studied the diffusion of ultraviolet and visible light with ground fused quartz surfaces. Stroboscopic flash as a source for kinetic spectroscopy was used by Current et al. (34). Pulsed electrical discharges in gas tubes were likewise used by Black and Porter (17) in seeking triplet-triplet absorption in connection with flash photolysis studies. The spectral energy distributions of the familiar Beckman and Nester lamps were measured (60) along with other sources of interest with photochemical and photodegradative problems; these sources are compared to natural sunlight. An attempt to simulate sunlight in the laboratory for use with photovoltaic solar energy converters was described (41). The use of Osram lamps for the wavelength calibration of prism spectrometers was described in detail (166). Curve tracings as well as tabular data were presented for these readily available lamps for ultraviolet and visible spectral regions. With suitable filters, some of these lamps make admirable
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kinson (163) reviewed “AIolecular Spectra in the Vacuum Ultraviolet,” including references. “Solar Spectroscopy in the Vacuum Ultraviolet” was the subject of a review by Tousey ( I @ ) , who NOMENCLATURE A N D METHODS also discussed “Solar Research from The nomenclature situation in ultraRockets” (149). Instrumentation was violet spectrometry appears to have briefly summarized by Sherman (130). reached a stage of maturity. Through Of considerable value in wavelength the devoted efforts of journal editors calibration, as well as identification of and reviewers, nomenclature and usage strange lines, is an extensive tabulation have become fairly uniform, with of emission lines, prepared by Kelly (73). the “absorbance-absorptivity” termiPrice (111) reviewed the vacuum ultranology firmly established. The instruviolet, with 79 references. ment manufacturers have been most COSeya (119) described a concave gratoperative in adopting the recommended ing mounting. Tanaka and Jursa terms and symbols on their instruments (145) proposed a series of continuous and chart papers. A summary of specsources employing rare gases. Warsop trometry nomenclature appeared in the (162) discussed capillary materials for December 1961 issue of ANALYTICAL Lyman discharge tubes. Reflectance ( 5 ) . It generally follows the CHEMISTRY in this difficult spectral region was the nomenclature recommended by ASTM concern of Berning, Hass, and Madden Committee E-13 (128). The only ex(15), Angel et al. ( 7 ) , and Smith (133). ception appears to be defining the rvaveSpecial photomultipliers and their applilength border between the visible and cations have been described by Sommer ultraviolet as 380 mp rather than 400 (134) and Childs (31). Axelrod (9) deniF. I t is gratifying to see “ultraviolet,” vised a split-beam attachment to con“infrared,” “wavelength,” and “wavevert a vacuum spectrometer effectively number” accepted as single words. into a spectrophotometer. The ammoThe Subcommittee on Methods of nia spectrum was re-examined (161). ASTM Committee E-13, under the chairmanship of R. T. O’Connor, pubSPECTROPHOTOMETRIC TITRATIONS lished in 1959: “General Technique of The technique and applications of Ultraviolet Quantitative Analysis.” spectrometric titrations have been This publication has undergone some reviewed by Xalmstadt (85). I t has minor revisions; it is available from appeared logical that these techniques ASTM headquarters. This subcomwould be applied to nonaqueous sysmittee has furnished reviewers for tems, as for phenols (weak acids) in 2spectrometric methods developed by propanol as a solvent (63). Reynolds, other ASTM subcommittees. These Walker, and Cochran (116) titrated activities were included in the review by aromatic amines with acetic anhydride Robey (119). in pyridine. Streuli’s review (139) also contains items of interest. I n instruVACUUM ULTRAVIOLET SPECTROSCOPY mentation, a recording photometric Interest in the ultraviolet region betitration was described (99). Ionizalow 2000 A. has continued to increase tion constants of a number of triazine during the past two years, although the derivatives have been published (61). emphasis has remained on instrumental Naqvi et al. (100) reported the acid disaspects rather than analytical applicasociation constants of pyrazyl methyl tions. The border line between the ketones. “vacuum” or “far”-ultraviolet and the “quartz” or “middle” ultraviolet is not ELEMENTAL ANALYSIS as well defined as previously, when most Determination of elements by use of quartz instruments were only capable of colorimetric methods naturally extends reaching 2100 or 2200 A. Improveitself into the ultraviolet region. This ments in synthetic silica optics and the is partly done to reach absorption bands use of nitrogen-flooded light paths have of systems that are essentially transparpushed the range of instruments which ent in the visible, but perhaps also are not evacuated down to the mercury motivated by the fact that detectability line a t 1849 A., or slightly lower. The (sensitivity) can be improved by using availability of Nester lamps with lithium bands having higher absorptivity values, fluoride windows (G. Faust, Exton, Pa.) and ultraviolet bands are almost always has materially aided in this push to more intense than the longest waveshorter wavelengths. length band falling in the visible. The An extensive review, containing 256 more widespread availability of ultrareferences, on the analytical aspects of violet instruments makes this type of the vacuum ultraviolet region, was pre‘ultraviolet colorimetric analysis” conpared by Kaye (71); part of this also venient to explore. Takahashi and appeared as a special publication of the Robinson (144) presented a table of ASTR‘I (70) which covered the spectrosultraviolet wavelengths for metal checopy conference a t San Francisco, lates, in connection with titration of Calif., October 12 to 15, 1959 Wil-
monochromatic sources for refractive index measurements (notably the thallium green line).
j
divalent metals. Chloranilic acid was used in determination of halides (54). Aluminum 8-quinolinolate in chloroform was discussed by Linnell and Raab (81). Traces of calcium in sodium were determined, using a precipitation as the naphthalhydroxamate followed by solution in EDTA and examination a t 339 mp for high sensitivity (11). Cerium was precisely determined a t micromolar concentrations by Blatz (18). Pearse and Pflaum (107) used oxamidoxime in the determination of cobalt and nickel. Wallace and hlellon (160) used a 3 to 1 tungsten-vanadium complex to measure vanadium as tungstovanadic acid. Mokrasch (96) described the technique for obtaining phosphate in the presence of labile phosphorus compounds, arresting hydrolysis by use of dimethylformamide. Microgram amounts of mercury were separated and determined by use of diethyl dithiocarbamate (55). Kiobium and molybdenum were measured in uranium-base alloys with 8-quinolinol (97‘). A complex absorbing a t 350 mp was utilized by Jacobs (64) for determining rhodium. hleloan, Holkeboer, and Brandt (92) employed benzohydroxamic acid in 1hexanol to measure uranium. This element was also determined using 8quinolinol n ith a detectability of 2 p.p.m. (98). Selenium was found down to 10 p.p.in. in steroids (147). A yellow titanium complex a t pH 3.8 n a s nieasurcd a t 380 mp by Rigg and Wagenbauer (117). The lanthanides wcre studied on a fused LiC1-KC1 eutectic a t 400°C. by Banks, Heusinkveld, and O’Laughlin (12). Dinsel and Sweet (38)used N , N bis(carboxymethy1) anthranilic acid for the determination of iron. An investigation of the spectra of cuprous and cupric salts in concentrated alkali halide solutions %as rrported by Glasner and Avinur (48) Nagnesium complex, measured at 355 mp, was the subject of a study by Cuttitta and White (35). Young and Khite used molten fluoride salts (164) and described their use with rarc earth salts (165). ORGANIC ANALYSIS
Ultraviolet spectromc try has been applied t o 3 varirty of problems, many of them mixturcs that would have caused the analyst considerable hesitation in days of less familiarity with photometric methods. Concrntrated sulfuric acid makes a usrful solvent, and does not dcstroy many organic systems if care is exercised in technique. Olefins are determined in the 300- to 310-mp region in this solvent by Altshuller, Sleva, and Wartburg ( 2 ) . A bathochromic shift in concentrated sulfuric acid (as compared to aqueous systems) permitted 3 rapid assay of a, p-unsaturated acids and 8-hydroxy acids (132). Czech, Fuchs, and Antczak (S6),using
anhydrous carbon tetrachloride as ~01vent, determined mono-, di-, and trichloramines. The microdetermination of methyl chloride was performed by conversion into a material absorbing a t 365 mfi (113). The use of absorption near 300 mp of aliphatic nitro compounds in the presence of a base is described by Gast and Estes (46). A modified absorbance ratio was applied to the system benzonitrile-benzamide by Astle and Pierce (8). Sulfadiazine, sulfamerazine, and sulfathiazole miutures were studied by Marzys (88). Application of ultraviolet spectrometry to chromatographic fractions is useful not only in identification of unknown mixtures, but also in separating the material sought from interfering substances. An example is presented by Parker and Kirk (106) for barbiturates. Phenothiazine in commercial preparations was similarly treated by Brierley and Langbridge (25). A combination of infrared, ultraviolet, and mass spectrometry was used by Helm et al. (56) for studying carbazole in Wilmington, Calif., petroleum. Quaternary nitrogen compounds were determined in the effluent from a chromatographic column by Wall et nl. (159). Extractions are frequently needed to free the sought-after ultraviolet absorbing material from interfering substances. Stevenson (137) has presented a rapid method for salicylate in blood, using extraction by malonic acid in butyl ether with 307 mp as the analytical wavelength. Alternatively, a double extraction n i t h pH 6.86 buffer may be used with observation a t 296 mp. The same author used a butyl ether extract of blood, ~vashed with a borax buffer solution, to find barbiturates in blood (1%). Laurene (80) revien ed nicotine analysis. Studies on protein fractions by Strickland et al. (140) found variations in tyrosine and tryptophan so wide that quantitative estimations may be considered unsafe if these variations are not known in the sample series. GrliE (51) described the analysis of crude vegetable drugs and extracts. Interest in air pollution has increased appreciably. Sawicki et al. (126) describe the separation and characterization of polynuclear aromatic hydrocarbons in urban air-borne particulates, using chromatography combined with ultraviolet, visible, and fluorescence spectroscopy. blader, Schoenemann, and Eye (84) used the high molar absorptivity of free tribromide ion a t 290 mfi in the determination of nonaromatic unsaturates in automobile exhaust; this method used a spectrophotometric titration. Some of the problems of long path length spectrometry were discussed by Renzetti (115). Karr (69) published a list of 204 longest wavelength bands of polynuclear heterocyclic aromatics for analytical use.
Blinn describes the role of ultraviolet spectrometry in determining pesticide residues in foodstuffs (19) in the book by Butz and Noebels (29) on instrumental analysis of food additives. This includes a table summarizing many published methods, and a list of 30 references. Other parts of this book contain useful information on extraction techniques and the role of errors, detectability, specificity, and the concept of “zero tolerance.” Lamb (7‘7) gives a very good description of general colorimetric procedures, much of which is applicable to ultraviolet methods. Because of the more stringent requirements regarding food additives (including packaging components which may migrate into the food), much attention is being given to analytical methods of high sensitivity. Much more acbivity in the development of spectrometric methods for food additives and materials migrating from packaging can be expected in the next few years. The Butz and Noebels book (29) comprises the proceedings of the Symposium and Workshop held a t Michigan State University, hlarch 24 t o 26, 1960. Sawicki, Hauser, and Stanley (127) applied solvent and pH effects to the analysis of aromatic primary amines and ketones. A method of high sensitivity (or detectability) was developed by Belles and Littleman (13) for determining isoniazid and acetylisoniazid in blood, serum, or urine. Both compounds absorb in acid near 265 mp, but shift a t different pH values to maxima a t 300 mp. Bovey and Yanari (20) discuss the effect of solvents on the shifts of ultraviolet bands of aromatic compounds. Polymers and plastics pose a number of analytical problems, many of which can be met by ultraviolet spectrometry. The absorption of the phenyl chromophore in phenyl si1iconc.s has been measured by Uriu and Hakamada (152). Alkylated phenols may be extracted from polyethylene for subsequent spectrometric analysis (136). Tris(nony1ated phenyl) phosphite is determined by use of differences in absorption in iso-octane and in base, in the analysis of styrene-butadiene synthetic polymers (22). The number of sulfide end groups and the number-average molccular weight were determined by measurement a t 308 mp of the complex betneen molecular iodine and sulfide sulfur, by Rosenthal, Frisone, and Coberg (124). Lacoste, Covington, and Frisone (76)FTere able to measure hydroquinone in the presence of its monomethyl ether, ,4reaction with n-butylamine gave a colored product, n-hich, however, was determined a t 345 mp, the band a t this wavelength being 20 times stronger than the visible band a t 540 mp. A bibliography (128) covered papers VOL. 34, NO. 5, APRIL 1962
279 R
concerned with ultraviolet degradation and light stabilization of plastics.
scribed effects of solvents and ionic forms.
MISCELLANEOUS
(1) Aloisio, C. J., Rev. Sci. Znstr. 32, 452 (1961). (2) Altshuller, A. P., Sleva, S. F., Wartburg, A. F., ANAL. CHEM. 32, 946 (1960). (3) Altshuller, A. P., Wartburg, A. F., Zbid., 32, 174 (1960). (4) Anacreon, R. E., Noble, R. H., AppE. Spectrosco y 14,29 (1960). (5) ANAL. &EM. 33, 1968 (1961). (6) Anderson, N. G., Zbid., 33, 790 (1961). (7) Angel, D. W., Hunter, W.R., Tousey, R., Hass, G., J . Opt. SOC.Am. 51, 913
LITERATURE CITED
Articles of interest to analytical spectroscopists which were not readily placed in the previous categories are included in this section. Treatment of data has been the subject of several articles. The actual utility of these procedures must be determined in practice; so these are presented without comment, for the exploratory use of the reader. A f1961). \----, least squares method in matrix n-as de(8) Astle, M. J., Pierce, J. B., ANBL. scribed for analysis of multicomponent CHEM.32,1322 (1960). (9) Axelrod, N. N.. J . O p t . SOC.Am. 51. systems, using the ergosterol system as ‘ 898 (1961). a n example (1%). The use of multiple (10) Balchan, A. S., Drickamer, H. G., regression for assays of more than one Rev. Sci. Inst?. 31, 511 (1960). component was the subject of a note (ll).Banerjee, D. K., Budke, C. C., Miller, F. D., ANAL.CHEM. 33, 418 (103). The “curvature inversion tech(1961j. nique” was presented (62) with illustra(12) Banks, C. V., Heusinkveld, M. R., tive typical problems. O’Laughlin, J. W., Zbid., 33, 1235 An article by Reid (114) on “quantum (1961). (13) Belles, Q. C., Littleman, M. L., phenomena in biology” and a summary Zbid., 32,720 (1960). of “n-to-pi” transitions in nitrogen (14) Bendit, E. G., Ross, D., Appl. heterocyclics by Goodman (50) offer inSpectroscopy 15,103 (1961). formation of interest. Marcus (86) pre(15) Berning, P. H., Hass, G., Madden, R. P., J . Opt. SOC.Am. 50,586 (1960). sented a survey on electron transfer Bibliotheca Central de Spectroscopia, spectra of inorganic ions. Ergun, &IC- (16) Appl. Spectroscopy 15, 56 (1961). Cartney, and Ralline (43) described (17) Black, G., Porter, G., Spectrochim. absorption of thin sections of coal. Acta 16. 1442 (1960). (18) Blatz, L. Ad.,ANAL.CHEM.33, 249 Friedel and Queiser (46) discuss the (1961). measurement of the aromaticity of car(19) Blinn, R. C., “Utility of Ultraviolet bonaceous materials, pointing out errors Spectrophotometry in Determining Pesarising from scattering and fluorescence. ticide Residues in Foodstuffs,’’ Chap. IX, pp. 125-36, W. H. Butz, H. J. Traces of hydrogen peroxide were Koebels, eds., “Instrumental Methods measured by Xleloan, Mauck, and Hufffor the Analysis of Food Additives,” man (93), using the decrease in absorpInterscience, New York, 1961. tion of the benzohydroxamic acid che(20) Bovey, F. A,, Yanari, S. S., Xature 186, 1042 (1960). late of uranium a t p H 6 and 380 mp. (21) Bowers, G. X., Jr., Raymond, S., Kauman et al. (101) studied the Schiff ANAL.CHEM.32,1901 (1960). reaction and its analytical application to (22) Brandt, H. J., Zbid., 33, 1390 (1961). sulfur dioxide. Kitrogen dioxide was (23) Brealey, L., Analyst 86,273 (1961). (24) Breda, E. J., Kotkas, E. V., ANAL. converted to nitrite ion in alkaline soluCHEM.33,816 (1961). tion and measured at 355 mp by Altshul(25) Brierley, A., Langbridge, D. M., ler and Wartburg (3); better sensitivity Analyst 86,709 (1961). was obtainable by using 211 rng as the (26) Brode, W.R., J . Opt. SOC.Am. 50, 742 (1960). analytical wavelength. Johnson (67) (27) Brorn, P. K., Zbid., 51, 1000 (1961). described purification of hydrocarbon 28) Bube, R. A., “Photoconductivity of solvents. Sclids,” Wiley, New York, 1960.‘( Vandenbelt (154) presented an inter(29) Butz, W.H., Xoebels, H. J., Instrumental Methods for the Analysis of laboratory comparison of Cary spectroFood Additivies,” Interscience, New photometers, showing very good agreeYork, 1961; especially Chap. IX, pp. ment in wavelength and photometric 125-36. accuracy. A hollliium filter was pro(30) Cannon, C. G., “Electronics for Spectroscopists,” Hilger and Watts, posed (166) as an ultraviolet wavelength London, 1960. standard; these are obtainable as Corn(31) Childs, C. B., J . Opt. SOC.Am. 51, ing N o . 3130. A note on “quality” by 583 (1961). Vandenbelt (163) offers sage advice for (32) Clark, G. k., ed., “Encyclopedia of Spectroscopy, Reinhold, New York, analysts. 1960; especially pp. 1-79. McDonald and Cook (83) present a (33) Clark, G. L., “Fused Salts Spectronovel “solvent” for high molecular photometry,” “Encyclopedia of Specweight materials-polyethylene. The troscopy,” pp. 48-57, Reinhold, New York, 1960. sample is stirred into melted polyethyl(34) Current, J. H., Raper, 0. F., Kramer, ene, which is then pressed to form a film, H. H., Bair, E. J., J . Opt. SOC.Am. 50, which is mounted in the beam of the 668 (1960). spectrophotometer. Transmission to (35) Cuttitta, F., White, C. E., ANAL. CHEM.31,2087 (1959). 220 mp is obtained. Van Duuren (157) (36) Czech, F. W., Fuchs, R. J., Antczak, studied the absorption and fluorescence H. F., Ibid., 33, 705 (1961). excitation spectra of aromatic hydrocar(37) Danielli, J. F., ed., “General Cytobons and heterocyclic aromatics, and dechemical Methods,” Vol. 1, Academic I-- - - I
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ANALYTICAL CHEMISTRY
Press, New York, 1958; especially Chap. 3, pp. 164-219. (38) Dinsel, D. L., Sweet, T. R., ANAL. CHEM.33.1078 f 1961’1. (39) Donne;, W.,‘ Spectrochim. Acta 17, 579 (1961). (40) Danti, A., “Information for Contributors to the Catalogs of Ultraviolet Spectra Data,” Dept. Chemistry, Agricultural and Mechanical College of Texas, College Station, Tex., 1961. (41) Elliott, J. F., Hysell, R. E , Meikleham, V., J . Opt. SOC.Am. 50,713 (1960). (42) Ergun, S., McCartney J. T., Walline, R. E., Fuel 40, 109 (1961). (43) Ea-ing, G. W.,“Instrumental Methods of Chemical Analysis,” 2nd ed., McGraw-Hill, New York, 1960; espe cially pp. 15-74. (44) Friedel, R. A., “Vapor Spectra (Infrared and Ultraviolet),” pp. 577-82, G. L. Clark, ed., “Encyclopedia of Spectroscopy,” Reinhold, New York, 1960. (45) Friedel, R. A., Queiser, J. A., Am. SOC. Testing Materials, Spec. Tech. Publ. NO. 269,218-26 (1960). (46) Gast, J. H., Estes, F. L., ANAL. CHEM.32.1712 (1960). (47) Gill, S:J., Rumrnel, W.D., Rev. Sci. Znstr. 32,752 (1961). (48) Glasner, A., Avinur,. P.,. A N ~ L . CHEM.33,’1122 (1961). 149) Glick. D.. Greenburn. L. J.. Zbid.. . 32. 736 (1960’1. (50) ’Goodman,’ L., M o l . Spectroscopy 6, 109 (1961). (51) GrliC, L., J. pharm. Belg. 14, 45 (1959). 152) Grum. F.. Scharf. P. T.. J . O p t . ’ doc. Am.’50,816 (1960). (53) Grum, F., Williams, F. C., Zbzd., 50, 675 (1960). (54) Hadjiioannou, T., “Sulfate, Chloride, and Fluoride Determinations with Chloranilic Acid,” pp. 70-1, G. L. Clark, ed., “Encyclopedia of Spectroscopy,” Reinhold, New York, 1960. (55) Hakkila, E. A., Waterbury, G. R., ANAL.CHEM.32,1340 (1960). (56) Helm, R. V., Latham, D. R., Ferrin, C. R., Ball, J. S., Ibid., 32, 1765 (1960). (57) Hershenson, H. M., “Ultraviolet and Visible Absorption Spectra. Index for 1930-1954,” Academic Press, New York, 1956. (58) Zbid., “Index for 1955-1959,” 1961. (59) Hirt, R. C., ANAL. CHEM.32, 2254 (1960). (60) Hirt, R. C., Schmitt, R. G., Searle, N. D., Sullivan, A. P., J . Opt. Soe. -4m. 50,706 (1960). (61) Hirt, R. C., Schmitt, R. G., Straws, H. L., Koren, J. G., J . Chem. Eng. Data 6, 610 (1961). (62) Hiskey, C. F., ANAL.CHEJI.33, 927 (1961). (63) Hunimelstedt, L. E. I., Hume, D. N., Zbid., 32, 1792 (1960). (64) Jacobs, W. D., Zbid., 32, 514 (1960). (65) Jaycox, E. K., Siomkajlo, J. M., Xash, D. L., eds., Appl. Spectroscopy 14, No. 1, 19A, No. 2, 15A, No. 3, 23A, No. 4, 19A, No. 5, 20.4 (1960); 15, No. 1,17A (1961). (66) Johnson, E. -4.,Brit. Bull. Spectroscopu, KO.40, 174 (1961). (67) Johnson, G. D., Spectrochim. Acta 16, 1489 (1960). (68) Kamlet, M. J., Ed .,,, “Organic Electronic Spectral Data, Vol. 1, 1946-1952, Interscience, New York, 1960. (69) Karr, C., Jr., A p p l . Spectroscopy 14, 146 (1960). (70) Kaye, W Am. SOC.Testing Materials, Spec& Tech. Publ. No. 269, 63-72 (1960). (71) Kaye, W., A p p l . Spectroscopy 15, 89, 130 (1961).
(72) Kellett, E. G., Nature 191, 107 (1961). (73) Kelly, R. L., “Vacuum Ultraviolet Emission Lines (below 2000 Angstroms),” Office of Technical Services, OTS UCRL 5612 (1959). (74) Kniseley, R. N., Spectrochim. Acta 17,904 (1961). (75) Kuchler, R. J., Strickler, H. S., Grauer, 1%.C., ANAL.CHEM.33, 1048 (1961). (76) Lacoste, R. J., Covington, J. R., Frisone, G. J., Ibid., 32, 990 (1960). (77) Lamb, F. C., “Colorimetric Procedures for the Determination of Food Additives,” Chap. VIII, pp. 109-24, ITr.H. Butz, H. J. Noebels, eds., “Instrumental Methods for the Analysis of Food Additives,” Interscience, New York, 1961. (78) Lang, L., “Absorption Spectra in the Ultraviolet and Visible Region,” Academic Press, Budapest, Hungary, 1959, Xew York, 1961. (79) Lauer, J. L., A p p l . Spectroscopy 14, 57 (1960). (80) Laurene, 8.H., “Nicotine Analysis,” pp. 68-70, G. L Clark, ed., “Encyclopedia of Spectroscopy,” Reinhold, New York, 1960. (81) Linnell, R. H., Raab, F. H., AKAL. CHEW33, 154 (1961). (82) McCormick, R. J., Gorin, G., Ibid., 33, 157 (1961). (83) McDonald, F. R., Cook, G. L., Appl. Spect)oscopy 15, 110 (1961). (84) blader, P. P., Schoenemann, K., Eye, M., ~ ~ X A CHEW L . 33, 733 (1961). (85) Malmstadt, H V., “Spectrophotometric Titration,” pp. 71-6, G. L. Clark, ed., “Encyclopedia of Spectroscopy,” Reinhold, Kew York, 1960. (86) Marcus, R. J., J Solar Energy Sci. and Eng. 4, No. 4, 20 (1960). (87) Martin, H. J., Gorin, G., ANAL. CHEM.32,892 (1960). (88) Marzys, A. E. O., Analyst 86, 460 (1961). (89) Mason, S. F., Quart R e m 15, 287 (1961). (90) Mason, .J :! B., “Ultramicrospectrophotometry, pp. 76-7, G. L. Clark, ed., “Encyclopedia of Spectroscopy,” Reinhold, New York, 1960. (91) Mellon, hl. G., “Analytical Absorption Spectrometry,” pp. 1-12, “Encyclopedia of Spectroscopy,” Reinhold, Sew York. 1960. (92) Rfeloan, C. E., Holkeboer, P., Brandt, IT. W.,ANAL.CHEW 32, 791 (1960). (93) Meloan, C. E., Mauck, hl , Huffman, C., Ibzd., 33, 104 (1961). (94) Middleton, W. E. K., J . Opt. SOC. Am. 50,757 (1960). (95) Mokrasch, L. C., ANAL.CHEM.33, 432 (1961). (96) Morrey, J. R., Madsen, ,4. W., Rev. Sci. Insty. 32, 799 (1961). 197) Rlotoiima. K.. Hashitani., H.., ASAL. CHEM.33,48 (1961). (98) Motojirna, K., Yoshida, H., Izawa, K., Ibid., 32, 1083 (1960). (99) hlullen, P. W.,Anton, A., Zbid., 32, 103 (1960). (100) h’aqvi, N., Amma, E. L., Fernando, Q., Levine, R , J . Phys. Chem. 65, 218 (1961). (101) Nauman, R. V., West, P. W., Tron, F., Gaeke, G. C., ANAL.CHEM. 32, 1307 (1960). ~
(102) Niebergall, P. J., Mattocks, A. M., DmLg Standards 28, No. 3, 61 (1960). (103) O’Connor, R. T., “Fats, Oils, Fatty Acids and Glycerides (Ultraviolet Spectrophotometry),” p. 33-47, G. L. Clark, ed., “Encycfopedia of Spectroscopy,” Reinhold, New York, 1960. (104) O’Laughlin, J. W., Banks, C. V., “Differential Spectrophotometry,” pq; 19-32, “Encyclo edia of Spectroscopy, Reinhold, New j o r k , 1960. (105) Olson, E. C., Alway, C. D., ASAL. CHEM.32,370 (1960). (106) Parker, K. D., Kirk, P. L., Ibid., 33.1378 (1961). (107) Pearse, G.’ A., Jr., Pflaum, R. T., Ibid., 32,213 (1960). (108) Penner, S. S., “Quantitative Molecular Spectroscopy and Gas Emissivities,” Addison-Wesley Pub. Co., Reading. Mass.. 1959.
(131) Shlyapochnikov V. A., Slovetskii, V. I., Optics and Spectroscopy 10, 132 (1961). (132) Slepecky, R. A., Law, J. H., ANAL. CHEM.32, 1695 (1960). (133) Smith, A., J . Opt. SOC.Am. 50, 862 (1960). (134) Sommer, A. H., Rev. Sci. Znstr. 32,356 (i96i). (135) Spell, H. L., Eddy, R. D., ANAL. CHEM.32,1811 (1961). (136) Sternberg, J. C., Stillo, H. S., Schwendeman, R. H., Ibid., 32, 84 (1960). (137) Stevenson. G. R..Ibid...~32, 1522 ‘ (1960). (138) Zbid., 33, 1374 (1961). (139) Streuli, C. il., Ibid., 34,302R (1962). (140) Strickland, R. D., Mack, P. A., Podleski, T. R., Childs, W. A,, Zbid., 32, 199 (1960). (141) Strobel, H. A., “Chemical Instrumentation: A Systematic Approach to Instrumental Analysis,” AddisonWesley Pub. Co., Reading, Mass., 1960. (142) Strother, G. K., Wolken, J. J., “hlicrospectrophotometer of Simplified Design,” pp. 62-8, G. L. Clark, ed., “Encyclopedia of Spectroscopy,” Reinhold, New York, 1960. (143) Sunshine, I., Cordek, L., ChemistAnalyst 49,118 (1960). (144) Takahashi, I. T., Robinson, R. J., A N ~ LCHEM. . 32, 1350 (1960). (145) Tanaka, Y., Jursa, A. S., ,J. Opt. SOC.Am. 50,1118 (1960). (146) Thompson, H. W., Ed., “Advances in Spectroscopy,” Vol. 1, pp. 56-75, Interscience, New York, 1959. (147) Throop, L. J., ANAL. CHEM. 32, 1807 (1960). (148) Tbusei, R., J . Opt. SOC.Am. 51, 2x4 (1961). \----,-
(149) Tousey, R., Science 134,441 (1961).
(150) Tunnicliff, D. D., Hawes, R. C., J . Opt. SOC.A h . 50, 1039 (1960). (151) Ungnade, H. E., “Organic Electronic Roectral Data.” Vol. 2. 19531955, Interscience, Xiw York, isso. 52) Uriu, T., Hakamada, T., J . Chem. SOC.Japan 62, 1421 (1959). 53) Vandenbelt, J. hl., A p p l . Spectroscopy 14, 110 (1960). 54) Vandenbelt, J. M., J . Opt. SOC.Am. sn. _ _ 24 - - i 1 w,n\ (155) Ibid., 51, 802 (1961). (156) Vandenbelt, J. M., Record Chem. Progr. 22, 188 (1961). 1157) Van Duuren. B. L.. ANAL.CHEM. 32, 1436 (1960). (158) Walker, P. M. B.,,, “Ultraviolet Microspectrophotometry, Chap. 3, pp. 164-219, J. F. Danielli, ed., “General Cytochemical Methods,” Vol. 1, Academic Press, Sew York, 1958. (159) Wall, J. S., Christianson, D. D., Dimler, R. J., Senti, F. R.,ANAL. CHEM.32,870 (1960). (160) Wallace, G. W.,Mellon, M. G., Ibzd., 32, 204 (1960). (161) Walsh, A. D., Warsop, P. A., Trans. Faraday SOC.57, 345 (1961). (162) Warsop, P. A., Spectrochim. Acta 16, 575 (1960). (163) Wilkinson, P. G., J . Mol. Spectroacopy 6 , 1 (1961). (164) Young, J. P., White, J. C., ANAL. CHEY.32,799 (1960). (165) Ibid., p. 1658. (166) Zwerdling, S., Theriault, J. P., Spectrochim. Acta 17, 819 (1961). I
(1960)l’ 25) Sadtler Research Laboratories, Samuel P. Sadtler and Sons, 1517 Vine St., Philadelphia 2, Pa., Ultraviolet O..^,.+””
upb”,
a.
26) Sawicki, E., Elbert, W., Stanley, T. W., Hauser, T. R., Fox,. F. T., ANAL.CHEM.32; 810 (1960). 27) Sawicki, E., Hauser, T. R., Stanley, T. W., Ibid., 31,3063 (1959). (128) Searle, E. Z., Hirt R. C., SOC. Plastics Eng. Trans. 2 , 36 (1962). (129) Seya, M., J . Opt. SOC.Am. 49, 724 (1959). (130) Sherman, E. O., Jr., “Vacuum Ultraviolet Region Instrumentation,” pp. 77-9, G. L. Clark, ed., “Encyclopedia of Spectroscopy,” Reinhold, Yew York, 1960.
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