3rd Annual
Review of Analytical Chemistry FOR
the third time a group of outstanding analysts have prepared reviews of recent developments in the various fields of analytical chemistry. The articles covering the theoretical or fundamental material appear on the following pages. In the February issue eight articles will review the applications of new developments i n a number of industries and fields of specialization.
As in previous years, these review articles will be combined in a single reprint for those who require i t as a ready reference. Copies will be available at 81.50 each from the Reprint Department, AMERICAN CHEMICAL SOCIETY.
-The
Editors
LIGHT ABSORPTION SPECTROMETRY M. G. MELLON Purdue University, Lafayette, Znd.
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HIS review follows the general viewpoint adopted for prior surveys by the author (135). The past year yielded another large number of relevant publications. From the list examples were selected to represent the various categories of the subject. Four reviews relating to this topic have appeared in foreign periodicals (31, 46, 50, 133). I t seems worth mentioning once more that light, as defined in the famous report of the Colorimetry Committee of the Optical Society of America (92), is a term limited to the range of wave lengths of radiant energy which give rise t o the sensation of vision in the normal human eye. The sensation is one of color for particular spectral' distributions of the light. Without light, then, there is neither vision nor color. Obviously, too, there can be no ultraviolet, infrared, or "black" light, or colorless color. This usage conforms to the practice of the Photometry and Colorimetry Section of the Sational Bureau of Standards.
Feigl's review ( 5 7 )includes a discussion of the chemistry of the use of organic color-forming reagents, Nature of Absorbing Systems. In many cases absorptiometric determinations rest upon having the measured constituent in some particular form. Generally this involves preparing and handling complexea of various kinds. Basic to successful operation of the method i s J a n understanding of the nature of such systems, accompanied, as far as possible, by a knowledge of any variable factors and of the means for achieving their rontrol. The perennial question of the composition of the iron-thiocyanate comples is discussed in three papers. Polchlopek and Smith (152) decided that the complex formed in aqueous solution depends upon the relative concentration of the reactants. The results of Baldwin and Svirbely (9) for various water-organic pairs are interpreted in terms of two complexes, Fe2(SCN)6and Fe(SCN)6---. Ovensten and Parker (147)determined the effects of additives, such as beryllium sulfate and ammonium peroxydisulfate, on the reaction. Studies of other iron systems include that with S-hydroxyquinoline ( 1 6 7 ) , with &hydroxyquinoline-5-sulfonic acid (151), and with 2,2'-bipyridine (111). The cobalbthiocyanate system was studied by Babko and Drako ( 8 )and by Barvinok (11). Malyuga (128) worked on the mechanism of the reaction of cobalt with nitroso R salt. Several investigations bearing on more or less well known complexes include copper dithio-oxamide (196), oxidized nickel dimethylglyoxime ( 7 , 80), and molybdovanadophosphoric acid (126). Investigations of dithizone include its nature as an acid (88), and the nature of various metallic complexes (aO4). There seem to be analytical possibilities for the determination of certain metals according to the reports of work with 3-
CHEMISTRY
To the reviewer chemistry remains our major problem in this field. This category includes all preparative transformations required to produce a measurable system. Today measurement is rarely a serious problem, a t least if one has a t hand our best instruments. This is far from being the situation, in many cases a t least, when it comes to having a method even approaching the chemical ideal for such a system (136). Archibald (3)has discussed critically the important factors contributing to unreliability of many clinical determinations. Rather generally today these procedures employ absorptiometric nieasurement. Lack of attention to the chemical steps involved is probably the most important source of error. 2
V O L U M E 23, NO. 1, J A N U A R Y 1 9 5 1 thiosemicarbazone of isatin and its derivatives (84), and with 2isatoxime (8s). Solutions of plutonium ions of possible analytical significance have been studied (17). Four studies of the general nature of certain color systems cover three zirconium lakes ( 6 0 ) , aluminon (185), alkannin and naphthazarin (201 ), and antipyrene complexes of seventeen metals (104). There are difficulties in employing absorption spectra for qualitative purposes in case of interaction of several chromophores in the same molecule (103). Methods are described by Kiisana (144) for the spectrophotometric determination of complexity constants and the activity coefficient of complexes. Study of Old Methods. Studies of old methods usually aim at a better understanding and control of any variable factors employed, or at an adaptation of the method to a new situation, especially with respect to interferences. Each year produces its crop of such work, the over-all merit of which is difficult to evaluate in many cases. Examples of investigations of methods for various metals follow: cerium (162) and uranium (155, 184) with hydrogen perouide; magnesium with Titan yellow ( 8 5 , 178); beryllium with 2quinizarinsulfonic acid ( 3 2 ) and with aluminon (109); cobalt with nitroso R salt ( 7 6 ) ; aluminum, copper, iron, manganese, molybdenum, nickel, and tin with 8-hydroxyquinoline ( 6 5 ) ; manganese as permanganate ( 4 5 ) ; rhenium (606) and molybdenum (156) with thiocyanate; copper with diethyldithiocarbamate ( 9 6 ) ; chromium, copper, iron, manganese, molybdenum, nickel, silicon, titanium, and vanadium with various reagents (38); cobalt, copper, and iron with a thiocyanate-acetone system by simultaneous spectrophotometric measurement (106); molybdenum by acetone reduction of the thiocyanate complex (54); the simultaneous spectrophotometric determination of chromium and manganese in steel (117, 127); and the study of ten compounds containing the cyclic K-C-C--S group as reagents for copper (82). The following papers illustrate studies of miscellaneous methods: fading procedures for fluoride with (a)titanium plus hydrogen peroxide, in the presence of various interfering ions ( I @ ) , ( b ) iron plus thiocyanate (87), and (c) iron plus sulfosalicyclic acid (114); the use of mixtures of potassium dichromate and cupric sulfate as permanent standards for matching molybdovanadophosphoric acid solutions (17 2 ) ; the use of the tetraiodopalladinate ion for determining palladium (195)and the ruthenate ion for determining ruthenium (13’0); the spectrophotometric determination of six of the rare earth metals (139); and a modified method using titanium plus hydrogen peroxide for estimating nionofluophosphate ion through a determination of the hydrolyzed fluoride (76). Similar papers for the determination of organic systems follow: l,l0-phenanthroline with iron (108); formaldehyde with chromotropic acid ( 2 6 ) ; creatine and creatinine by an improved method using the Jaffe reaction ( 2 8 ) ; ethyl alcohol in blood by reaction with dichromate in an autoclave (100); ascorbic acid by reduction of molybdophosphoric acid to a heteropoly blue (129); uracil and derivatives by reaction of the -CONHCS group with isopropylamine and cobalt acetate reagent ( 7 9 ) ; sulfaquinoxaline by coupling with iV-( 1-naphthyl )et hylenediamine dihydrochloride ( 4 9 ) ; sulfanilamides by coupling with 1-(p-diethylaminoethylamine)naphthalene ( 1 7:7), trichloroethylene by absorption in anisole and application of the Fujiwara reaction ( 2 0 ) ; longchain alkylsulfates through reaction with rosaniline ( 9 7 ) ; and p-pyridylcarbinol through reartion with cyanogen bromide and p-aminoacetophenone (215). Ta o papers on testing spectrophotometric methods of analysis may be mentioned. Jones ( 9 1 ) reported a study of four dyes by eight collaborators, the spectrophotometers being four General Electric, three Beckman (DT), and one Coleman (10s). The lack of concordance of results needs clarification. As a continuation of prior work, Sclar (169) reported results on the dye, D and
3 C orange S o . 17. The use of the spectrophotometer as an aid to dyeing and as a means of evaluating dye characteristics has been considered (180, 182). Development of New Methods. The endless discovery of new organic compounds maintains the analyst’s hope that some will serve as reagents to provide methods better in some way than those now available. Although advances are made each year, the immediately noticeable changes are not striking. I n some cases, of course, time is required t o convince conservatives. Thus, 1,lO-phenanthroline established itself for iron only after some years and many thousands of determinations by enthusiasts. Only personal eyperience with surh a new method will enable one to evaluate the procedure in comparison with others. From the publications available the reviewer was not always certain that a given method is really new. I n one category may be listed new reagents for metals, the following being representative: alkannin or naphthazarin (605) and dithiocarbaniidohydrazine ( 6 9 ) for beryllium; solochrome cyanine R 200 (154)and diamino bright blue FFG (174)for aluminum; ethyl alcohol, as a color-producing solvent, for cobalt ( 5 ) ; 3-nitrososalicylic acid for cobalt and nickel together ( 1 4 ) ; fading of a standard iron-thiocyanate solution by oxalate for calcium (12s); chloroform extraction for gallium and thallium( 111) in the form of their oxinates (140); a lanthanum sol for lanthanum (141); 2-niercaptobenzoxazole for rhodium (16s); 4,4’-bis(dimethy1amino)thiobenzophenone for mercury(I1) ( 6 4 ) ; thiourea for molybdenum (217) and for osmium ( 6 ) ; benzohydroxamic acid for vanadium (181); l-(o-arsenophenylazo)-2-naphthol-3,6disulfonic acid for thorium (199); isonitrosodimethyldihydroresorcinol for cobalt (177); and the sodium salt of tetrabromophenolphthalein for copper (81). Nash determined fluorine (145) by measuring the bromine liberated from sodium bromide, while Richter (158) and Thrun (600) determined fluoride ion through its decolorizing action on aluminum eriochromcyanine lake; boron may be determined by means of 1,l’-anthrimide ( 5 3 ) and by carmine ( 7 6 ) ; chromate8 and dichromates may be determined with sodium pyrosulfite by measuring the reaction immediately and 24 hours later (119); nitrates (and nitrites) are determinable by means of resorcinol (165)or 3,4-xylenol (78); phosphate is determined by dissolution of ammonium molybdophosphate in ammonia and subsequent reaction with oxalate and hydrazine hydrochloride to give a reddish-orange color ( 5 8 ) . As examples of new methods for organic constituents the following were selected: for Chloromycetin, reduce the aryl nitro group, diazotize, and couple to give a red color ( 1 6 ) ; for serum lipase, couple the 2-naphthol, produced on hydrolysis, with diorthoanisidine (110); for tryptophan, condense with p-dimethylaminobenzaldehyde and develop the color with sodium nitrite (188); illdrin reacts with phenylazide to give dihydrotriazole, which is then coupled with diazotized 2,4dinitroaniline (SJ); indene reacts with benzaldehyde in presence of alkali (183); lactic acid reacts with concentrated sulfuric acid and veratrole in absolute ethyl alcohol to give a red color (132); reducing sugars react with triphenyltetrazolium chloride to yield formazan (131); resorcinol iodinates in the presence of catechol to give a precipitate which dissolves in acetone to give a colored system (212); ethanolic extracts of nordihydroguaiaretic acid react with ammonium molybdate to give an orange color ( 4 7 ) ; triethylene glycol in sulfuric acid reacts with 1-naphthol to give a yellow color (99). M7inslowand Liebhafsky (21s) studied spot tests spectrophotometrically. Stotz et a!. (192) reported the spectrophotometric characteristics of a half dozen stains of the thiazine group. Clark et al. ( 2 7 )used spectrophotometric curves to evaluate the changes and deterioration of engine lubricants. PHYSICS
The subject of measurement in the visual region of the spectrum is characterized chiefly by refinement of technique and by in-
4
creased recognition of its analytical possibilities. Broad aspects of absorptiometric measurement are presented in several books (15, 157, 203, 210). Gibson (66) reviewed the subject of spectrophotometry for the spectral region 200 to 1000 mp. Part of the optical apparatus discussed by h m u s (4)concerns this subject. Miscellaneous Instruments. The following equipment may be noted: a multiple-standard comparator for microdeterminations employing the Gillespie drop-ratio method (168); a portable comparator for gas analysis (125); a fluorometer for small quantities of thiamine (189) ; and the new variable-sensitivity fluorometer of Friedemann and Liebeck (25). A compact grating monochromator has been announced by Bausch & Lomb (14). Using all reflecting optics, it covers the range 200 to 1400 mp in the first order. The Dognon instrument has been adapted to strongly absorbing solutions (10). The Welch densichron (211) and the Macbeth-Ansco color densitometer (122, 198) represent devices designed for general photometri’c work. Filter Photometers. The dominant activity in instruments concerm filter photometers, even though by this time the total number described must exceed two score. Both new instruments and modifications of old ones are to be noted. Mikhal’chuk (138) presented a Russian review of current photoelectric instruments. The Weichselbaum-Varney “universal spectrophotometer” (56) is primarily a new flame photometer. By the use of a tungsten source and a continuously variable interference filter, it is possible to obtain a spectrophotometric curve from 370 to 770 mp. The resolution, of course, is not comparable to that obtainable with spectrophotometers operating on very narrow spectral band widths. Tannheim’s 2-cell photoelectric instrument is described (197) as being new. The Bausch & Lomb single-beam instrument, ( I S ) uses B and L interference filters. The Coleman Nepho-colorimeter (Model 9 ) is designed for both absorptiometry and nephelometry (30). Particular items may be mentioned in several filter photometers. Rouy’s (161) has tables reading directly in terms of specific desired constituents for given instrumental values. This obviously assumes reproducible calibrating and operating techniques. Dechering’s (41 ) uses a thermoelement as receptor. Boyer’s (18) employs a turretlike multiwindowed water jacket to improve thermal stability of the filters. Lange’s (116) absorption cells range from 1 to 100 ml. and the instrument uses Schott and Genossen interference filters. Ellis and Brandt’s (51) provides an absorption cell 10 cm. long holding 0.4 ml. for microanalysis. Modifications of two well known instruments are of interest. The IB/7 Zeiss-Pulfrich photometer has been changed to accommodate two photovoltaic selenium receptors (44). Various instrumental details are included in the changes incorporated in the new Hilger Spekker absorptiometer (89). Improved performance of this modified instrument is reported by Wokes and Slaughter (214). Spectrophotometers. Davenport (34) described a nonr-cording photoelectric instrument designed for reflection measurements in the range 400 to 650 mp, with emphasis on accuracy, compactness, and simplicity of operation. Loofbourow (1 28) suggested a combination of microscope optics for obtaining absorption spectra of very small samples. Eberhardt’s technique (51) provides for an estimate of the wrors introduced into spectrophotometric measurements when using slits of finite width. A report has been made (67) on the performance of glass standards issued by the National Bureau of Standards for checking photometric scales of spectrophotometers. Brode ( 1 3 ) reviewed methods of presenting absorption spectra data and made some personal recommendations. iiccessory equipment recommended for the Beckman DU instrument (101, 124) includes various holders for samples and an absorption
ANALYTICAL CHEMISTRY cell to work with as little as 50 cu. mm. of solution. Kirk (102) recommended a technique for ultramicro work, and Shugar (179) gave details of construction for a microcell. Davis (39) proposed lycopene from tomato paste as a spectrophotometric standard. Hiskey (7’7) has elaborated on his suggested use of transmib tance ratios for precision absorptiometry. For this technique Bastian et al. ( 1 2 )use the term “differential analysis,” and for the systems tested they claim an accuracy comparable to most gravimetric and titrimetric methods. Multicomponent mixtures have been analyzed with a “differential absorption meter” (26) The absorption equation used takes into account a summation of concentrations of absorbing substances and an integral absorption coefficient. Stimulus Measuring Instruments. Apparatus designed to match, by means of a suitable combination of known stimuli. the stimulus of the system measured, may be designated as stimulimeters. Developments in instruments for sud.1 purposes include the following items: (1) a modified Stammer comparator (981. (2) an Arons chromoscope modified for the production of any hue, chroma, and value (160); (3) a new photoelectric colorimeter (56); (4) an automatic small difference colorimeter for use in the range of raw cotton colors (146); ( 5 ) the Hunter goniophotometer, using tristimulus filters, to measure color as a function of illumination and direction of view, and the Hunter color and color-difference meter ( 6 6 ) ; and (6) two automatic tristimulus integrators which yield I.C.I. trichromatic values directly from spectrophotometric curves (37,150). 4PPLICATIONS
The chief justification for the development of equipment and methods is the possibility of applring the procedures to the determination of desired constituents, or the measurement of certain properties of systems. Extension of the uses of absorptiometric methods continues unabatrd, as evidenced by several books and many papers. Chemical Analysis. Among the books the Snell treatise (186‘) is pre-eminent as a general compilation. Volume I1 of the new edition, dealing with inorganic substances, covers 950 pages. The works of Delory (42) and of Fister (59) are much less comprehensive and more specialized. Thus, the latter work contains sdected methods for the clinical lahoratory. Perhaps mention should be made of the wide scattering of papers on applied analysis in Chemical Abstracts. One may expect t? find them from Section 7, Analytical Chemistry, to the end with the exception of Section 10. Section 7 does include occasional cross reference to other sections, but by no means to all relevant papers. Examples of the application of absorptiometric methods to alloys are the green chromium-phosphate complex for chromium in 18-8 steels (dog), the green benzoin-a-oxime complex for copper in ferrous alloys (48), and the 1,lO-phenanthroline complex for iron in high temperature alloys (148) and aluminum alloys (164). Various colorimetric methods are used for chromium, cobalt, molybdenum, tungsten, and vanadium in high-speed steel (116), and for molybdenum, nickel, silicon, and titanium in stainless steels (176). Wrightson (816)determined iron, nickel, and vanadium colorimetrically in petroleum oils. Other methods for metals are the alizarin sulfonate complex for thorium in cerite earths and monazite (143), the uranyl ferrocyanide complex for uranium ( I ) , the nitroso R salt complex for cobalt in iron-nickel ores ( 1 7 1 ) , the thiazole yellow method for magnesium in plant tissue (191), and the dithizone complex for copper in sewage and industrial wastes (194). The following applications, based on heteropoly complexes, may be noted: silicon in cast iron and steel (198, 206) and in biochemical materials (68) by the heteropoly blue method; silicon in materials high in silica and containing fluorine (113), silicon in the presence of arsenates and phosphates (86), and fluosilicate in
V O L U M E 2 3 , NO. 1, J A N U A R Y 1 9 5 1 various fluorides (90) by the molybdosilicic acid method; and phosphorus in plant tissue (190) and calcium and magnesium, through their phosphates, in biological materials (137), by the heteropoly blue method. Procedures for gases in air include the lead acetate method for hydrogen sulfide (I&-), the formaldehyde-fuchsin (110) and t,he ethyl alcohol-hydrogen peroxide-lead nitrate (153) methods for sulfur dioxide, and the sulfanilic acid-1-naphthylamine inet#hod for nitrogen dioxide (153). Procedures for silicate materials include the aluniinon (plus thioglycolic acid) method for aluminum (159), the morin method for beryllium (166), and the 1,lO-phanthroline method for iron (173). T h e alkali liberated by glass is determined by t,he color of bromothymol blue (43). For various organic mat,erials the procedures include the Fehling solution method for sugars (112), the decolorization of the iron-ferron complex for oxalate (34),the use of Schiff’s reagent for determining formaldehyde and acetaldehyde (208), or for determining formaldehyde and 2-furylaldehyde (207) when present together; the use of 1,3-dichloro-2-propanol for vitamin .I in milk (187) and in whale oil (19), and an absorbancy-ratio method ( a t 480 and 555 nip) for carbon monoxide in blood (107). Clarke (29) improved the mercuric nitrate~iphenSlcarbazorlo method for chloride in water. Hale et nl. ( 7 1 )detjerminetlnitrogen in petroleum products. Color Specification. Thc specification of color, or the determination of color as color, i3 increasingly a problem in analytical and testing laboratoriea. .I survey of ideas concerning the basis for color &-as presented by Halbertmm ( 7 0 ) . 1,ovell f 120 I discussed idem culminating in the description of color by dominant wave lengt,li, colorimetric purity, and luminance. Judd (93, has prewntetl a general survey of the prohleni of color spccification and of means to do it. The iiew edition of Gardrier’s treatise ( 6 3 ) deals with color measurrnient for the paint industry. Recently ( 2 ) the American oil chemists recommended spectrophotometric specification of color of vegetable oils t o replace readings with Lovibond glasses. It should be noted that the absorbancy values, taken at four wave lengths, were made with a Coleman Model 6-B inst>rumcnt,which operates a t a wide band width. Furlong ( 6 1 ) reported an interest,ing intercomparison of the Gaertner and the General Electric spectrophotometers and the Donaldson trichromatic and the Nutting monochromatic colorimeters for the measurement of the color characteristics of various g l a s filters and for four different samples of fluorescent cloth. Hamly (?4) reviewed the background and use of Ridgway’s color standards, and also correlated a copy of these standards with Munsell standards ( 7 3 ) . Permanent glass color standards for maple sirup have been described by Brice et al. (21). Readings with a Klett-Summerson photometer, using filter No. 44,have been recommended as a color index for tomato paste (40). Meads and Gillett (134) reported St’ammer values for sugar liquors and sirups following specified preparative treatment. Judd ( 9 4 ) compared the results of direct colorimetry of titanium pigments with values obtained indirectly by spectrophotometry and the standard observer. .4 relocation and respacing of the Union color scale for lubricating oil and pet’rolatum has been proposed by Judd et al. (96). MacAdani (121 ) used punched-card accounting machines t o calculate colorimetric specifications by the weighted ordinate method. Calculation of tristimulus values of certain subtractive color mixt,ures in solution may be made by simple equations (36). Demonstration has been made of the utility of the automattic integrat,or for T.C.I. values for textile mill practice (36). LITERATURE CITED
Ahrland, S . , Suensk K e m . Tid., 61, 197 (1949). (2) Am. Oil Chemists SOC.,Chem. Eng. News, 28, 1743 (1950); .J. .4m. Oil Chemists’ Soc.. 27, 233 (1950). (1)
5 (3) Archibald, R.bl., ANAL.CHEhi., 22, 639 (1950). (4) Asmus, E., Chem. Ing. Tech., 21, 376 (1949). (5) Ayres, G. H., and Glanville, B. V., ANAL.CHEM.,21, 930 (1949). (6) Ayres, G. H., and Wells, W.Pi.,Ibid., 22, 317 (1950). (7) Babko, A. K., Zhur. Anal. K h i m . , 3, 284 (1948). (8) Babko, 9.K., and Drako, 0. F., Zhur. ObschchcE Khim., 19, 1809 (1949). (9) Baldwin, S., and Svirbely, W.J., J . Am. Chem. SOC.,71, 3326 (1949). (10) Barriol, J., and Chevalier, P., Bull. S O C . c h i n . biol., 31, 658 (1949). (11) Barvinok, M.S., Izzest. A k a d . Naitk S.S.S.R., Ser. Fiz.. 12, 636 (1948). (12) Bastian, R., et al., ANAL.CHEM.,22, 160 (1950). (13) Bausch & Lomb Optical Co., “Monochromatic Colorimeter Manual,” 1950. (14) Hausch & Lomb Optical Co., preliminary announcement, 1950. (15) Berl, W. G., “Physical Methods in Chemical Analysis,” Chap. V, by W. R. Brode on “Spectrophotometry and Colorimetry,” S e w York, Adademic Press, 1950. (16) Bessman,S. P.,andStevens,S.,J.Lab.Cldn. Med.,35,129 (1950). (17) Betts, R. H., and Harvey, B. G., Natl. Research Council Can., At. Energy Project, Diu.Research CRC-390 (1948). (18) Boyer. W. J., U. S. Patent 2,483,875 (1949). (19) Braekken. 0. R., ANAL.CHEM.,21, 1530 (1949). (20) Brain, F. H., Analyst. 74, 555 (1949). i21) Brice, B. A , , et ul.. r.6. Dept. Agr., Bur. Agr. I n d . Chem. AIC260 (1950). (22) Bricker, c. E., and Vail, It-..\.. ANAL.CHEM., 22, 720 (1950). (23) Brode, K. R., J . Optical SOC.A m . , 39, 1022 (1949). (24) Burrows, S.,Analyst, 75, 80 (1950). (25) Central Scientific Co., Circ. 1203 (1950). 126) Chulanovskii, V. XI.,et ul., Z h u r . Anal. Khim.,4, 345 (1949). (27) Clark, G. L., et d . , :\N.AI.. CHEM..21, 1485 (1949). (28) Clark, L. C . . and Thompson, H. I,.. Ihid., 21, 1218 (1949). (29) Clarke, F. E.. Ibid.,22, 553 (1950). (30) Coleman Instrument,s, Inc., Bull. B-215 (1950). (31) Coumou, D. J., Anal. Chim. -4cta, 2, 693 (1948). (32) Cucci, &I. W.,et al., ANAL.CHEM.,21, 1358 (1949). (33) Danish, h.h.,and Lidov, R. E., Ibid., 22, 702 (1950). (34) Davenport, T. B., J . SOC.Dyers Colourists, 66, 191 (1950). (35) Davidson. H. R., J . Optical SOC.Am., 40, 230 (1950). (36) Davidson, H. R., and Godlove, I. H., Am. Dyestug Reptr., 39, 78 (1950). (37) Davidson, H. It., and Imm, L. W..J . Optical SOC.Am., 39, 942 (1949). (38) Davis, H. C., and Bacon, A., J. SOC.Chem. Ind., 67, 316 (1948). (39) Davis, W.B., ANAL.CHEM.,21, 1226 (1949). (40) Davis, W. B., Ibid., 21, 1500 (1949). (41) Dechering, F. J. A., Chem. Weekblad, 45, 521 (1949). (42) Delory, G. E., “Photoelectric Methods in Clinical Biochemiatry,” London, Hilger and Watts, 1949. (43) Domange, L., Ann. pharm. jrang., 7, 259 (1949). (44)Domingo, W. R., e t a l . , Chem. Weekbkzd, 45, 425 (1949). (45) Dozinel, C. M., Ing. china., 30, No. 173, 53 (1948). (46) Dufrasne, G., Chim. anal., 32, 55 (1950). (47) Duisberg, P. C., et ol., ANAL.CHEM.,21, 1393 (1949). (48) Dunleavy, It. A., et al., Ibid., 22, 170 (1950). (49) Dux, J. P., and Rosenblum, C., Ibid., 21, 1524 (1949). (50) Duyckaerts, G., Anal. Chim. Acta, 2, 649 (1948). (51) Eberhardt, W. H., J . Optical Soc. Am., 40, 172 (1950). (52) Ellis, G. H., and Brandt, C. S., ANAL.CHEM.,21, 1546 (1949). (53) Ellis, G. H., Zook, E. G., and Baudisch, Oskar, Ibid., 21, 1345 (1949). (54) Ellis, R., Jr., and Olson, R. V., Ibid., 22, 328 (1950). (55) Eltenton, G. C., and Fallgalter, M. B., U. S. Patent 2,501,599 (1950). (56) Fearless Camera Co., Bull. 151-A (1950). (57) Feigl, F., ANAL.CHEM.,21, 1298 (1949). (58) Ferrari, C., Proc. Iatern. Congr. Pure and Applied Chem., 11, 125 (1947).,, (59) Fister, H. J., Manual of Standardized Procedures for Spectrophotometric Chemistry,” New York, Standard Scientific SUPply Co., 1950. (60) Flagg, J. F., et al., J . Am. Chem. SOC.,71, 3630 (1949). (61) Furlong, L. R.. Naval Research Lab. Rept. NRGH-3256 (1948). (62) Gardner (Henry A.) Laboratory, pamphlets, 1950. (63) Gardner, H. A., and Sward, G. G., “Physical and Chemical Examination of Paints, Varnishes, Lacquers, and Colors,” Bethesda, Md., Henry A. Gardner Laboratory, 1950. (64) Gehauf, G., and Goldenson, J., ANAL.CHEM.,22, 498 (1950). (65) Gentry, C. H. R., and Sherrington, L. G., Analyst, 75, 17 (1950). (66) Gibson, K. S., Natl. Bur. Standards, Circ. 484 (1949). (67) Gibson, K. S., and Belknap, M.A,, J. Optical Soc. Am., 40, 435 (1950).
6
ANALYTICAL CHEMISTRY
(68) Gohr, H., and Scholl, O., Beitr. Klin. Tuberk., 102, 29 (1949). (ti9) Gupta, J., and Chakrabartty, B., J . Sci. I n d . Research, 8B, S o . 8 , 133 (1949). (70) Halbertsma, K. T. A., “History of the Theory of Colour,” Amsterdam, Swets and Zeiltinger, 1949. (71) Hale, C. H., et al., ANAL.CHEY.,21, 1549 (1949). ( i 2 ) Hall, -4. J., and Young, R. S., Ibid., 22, 497 (1950). (73) Hamly, D. H., J . Optical Soc. Am., 39, 592 (1949). (74) Hamly, D. H., Science, 109, 605 (1949). (is) Hatcher, J. T., and Wilcox, L. V., ANAL. CHEM.,22, 567 (1950). (i6) Hill, H. J., and Reynolds, C. A., Ibid., 22, 448 (1950). (77) Hiskey, C. F., Ibid., 21, 1440 (1949). (78) Holler, -4.C., and Huch, R. V., Ibid., 21, 1385 (1949). (79) Holt, W.L., and Mattson, L. N., Ibid., 21, 1389 (1949). (80) Hooreman, M., A n a l . Chim. Acta, 3, 635 (1949). (81) Horvai, R., Ibid., 4, 91 (1950). (82) Hoste, J., Ibid., 4, 23 (1950). (83) Hovorka, V., and Divis, L., Collection Crechosluu. Chem. Communs., 14, 116 (1949). (84) Hovorka, V., and Holsbecher, Z., Ibid., 14, 248 (1949). (85) Hunter, J. G., Analyst, 75, 91 (1950). (86) HurB, J., and Ortis, T., Bull. SOC. chim. France, 1949, 834. (87) Ingols, R. S.,et al., ABAL. CHEY.,22, 799 (1950). (88) Irving, H., et al., J . Chem. Soc., 1949, 1847. (89) Isbell, R. A., Analyst, 74, 618 (1949). (90) Jewsbury, A., Ibid., 75, 256 (1950). (91) Jones, J. H., J . Assoc. O&. Agr. Chemists, 33, 401 (1950). (92) Jones, L. A , et al., J . Optical Soc. Am., 34, 183, 245 (1944). (93) Judd, D. B., Natl. Bur. Standards, Circ. 478 (1950). (94) Judd, D. B., Natl. Bur. Standards, Research Paper R P 2024 (1949). (95) Judd, D. B., et al., A S T M Bull., 1950, No. 167, 63. (96) Kartsten, P., et al., A n a l . Chim. Acta, 2, 705 (1948). (97) Karush, F., and Sonenberg, SI.,ANAL.CHEM.,22, 175 (1950). Kats, V. hl., Sakharnaya Prom., 23, No. 4, 25 (1949). Kaye, S., and Adams, A. C., ANAL.CHEM.,22, 661 (1950). Kingsley. G. R.. and Current, H., J . Lab. Clin. Med., 35, 294 (1950). Kinsey, V. E., ABAL.CHEM.,22, 362 (1950). Kirk, P. L., “Quantitative Cltramicroanalysis,” pp. 71, 268, New York, John Wiley & Sons, 1950. Kiss, A., et al., Acta Unic. Szegediensis, Acta Chem. et Phys., 2, 25 (1948). Kiss, A,, and BBcskai, G., Ibid., 2, 47 (1948). Kitagawa, T., Repts. T o k y o I n d . Researchlnst. Lab., 44, 1 (1949). Kitson, R. E., ANAL.CHEM.,22, 664 (1950). Klendshoj, N. C., et al., J . Biol. Chem., 183, 297 (1950). Kolthoff, I. M.,et al., J . Am. Chem. Soc., 72, 2173 (1950). Kosel, G. E., and Keuman, W. F., ANAL.CHEM.,22,936 (1950). Kozlyaeva, T. N., Zhur. A n a l . Khim., 4, 75 (1949). Kiumholz, P., J . Am. Chem. Soc., 71, 3654 (1949). Kulenok, M. I., Gigiena i Sanit., 1949, No. 1, 34. Lacroix, S., and Labalade, M..Anal. Chim. Acta, 3, 383 (1949). Ibid., 4, 68 (1950). Lange, B., Metall, 1949, 47. Lennard, G. J., Analyst, 74, 253 (1949). Lingane, J. J., and Collat, J. W., ANAL.CHEM.,22, 166 (1950). Loofbourow, J. R., J . Optzcal SOC.Am., 40, 317 (1950). L6pez-Rubi0, F. B., and Pacheco, J. R., I n f o r m q u h . anal. ( M a d r i d ) ,3, 113 (1949). Lovell, D. J., Am. J . Phys., 18, 104 (1950). MacAdam, D. L., J . Optical SOC.Am., 40, 138 (1950). Macbeth Corp., Bull. 144 (1950). MeGregor, A. J., Analyst, 75, 211 (1950). hlcGuine. T. H.. and lloss. W ,E.. J . Am. Oil Chemists’ SOC., 27, 159 (1950). Main-Smith, J. D., e / al.. U. S . Patent 2,489,654 (1949). Maksimova, N. V., and Koslovskii, &I.T., Zhur. Anal. K h i m . , 2, 353 (1947). Mal’tsev. V. F., and Davydor, A. L., Zacodskaya Lab., 13, 926 (1947). hlalyuga, D. P., Zhur. A n a l . K h i m . , 22, 323 (1947). hlanelli, G., Mikrochemze uer. Mikrochim. Acta, 35, 29 (1950). hlarshall, E. D., and Rickard, R. R., ANAL. CHEM.,22, 795 (1950). and Jensen. C . 0..Ibid.. 22. 182 (1950). (131) hlattson. . . ~ . ~A. ~ M.. , (132) Mauer, H., B i d h e m . Z., 319, 553 (1949). (133) hlayer, F. Y., &err. Chem-Ztg., 49, 156 (1948). (134) Meads, P. F., and Gillett. T. R., ASAL. CHEM.,21, 1494 (1949). (135) Mellon, M. G., Ibid., 21, 1 (1949); 22, 2 (1950). (136) Mellon, M. G., Proc. Am. SOC.Testing Materials, 44, 733 (1944). (137) Michaels, G. D., et al., J . Biol. Chem., 180, 175 (1949). (138) Mikhal’chuk, B. V., Zavodskaya Lab., 13, 949 (1949). (139) Moeller, T., and Brantley, J. C., ANAL.CHEM.,22, 433 (1950). (140) Moeller, T., and Cohen, A , , Ibid.. 22, 686 (1950). ~
~
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(141) hloeller, T., and Quinty, G.H., J . Phys. & Colloid Chem., 54, 315 (1950). (142) hlonnier, D., et al., Helv. Chim. Acta, 33, 1 (1950). (143) Murthy, T. K. S.,and Raghavarao, B. S. V., Current Sci. ( I n d i a ) , 18, 248 (1949). (144) Sasiina, T., Acta Chem. Scand., 4 , 140 (1950). (145) Kash, L. K., ANAL.CHEM.,21, 980 (1949). (146) Kickerson, D.. et al., J . Optical SOC.Am., 40, 446 (1950). (147) Ovensten, T. C. J., and Parker, C. A., A n a l . Chim. Acta, 3, 277 ( 1949). (148) Pepi, 51. S.,h . 4 1 . . CHEM..22, 560 (1950). (149) Perry, 11. H.. and Serfass, E. J., Ibid., 22, 565 (1950). (150) Peterson, E. W., et al., J . Optical SOC.A m . , 39, 1055 (1949). (151) Phillips, J. P., J . Am. Chem. SOC.,72, 3159 (1950). (152) Polchlopek. S. E., and Smith, J. H., Ibid., 71, 3280 (1949). (153) Polezhaev, S . G . , and Girina, V. V.,Gigiena i Sanit.,1949, No. 11,26. (154) Pollak, F. F., and Pellowe, E. F., Metallurgia, 41, 281 (1950). (155) Kasin-Streden, R., -4nal. Chim. Acta, 4, 94 (1950). (156) Rasin-Streden, R., and Popoff-Asotoff, IT., Osterr. Chem.-Ztg., 51, 1 (1950). (157) Rassow, B., “Optische Messungen des Chemikers und des Rlediziners,” Band VI, Dresden, T. Steinkopff, 1949. (158) Richter, F., Chem. Tech., 1, 84 (1949). (159) Robertson, G., J . Sci. Food Agr., 1, 59 (1950). (160) Rosch, S., Farben, Lacke, dnstrichstofe, 4, 19 (1950). (161) Rouy, A. L. 11. A., U. S. Patent 2,477,208-9 (19491. (162) Kyabchikov. D. I., and Strelkova, Z. G.. Z h w . A n a l . Khini., 3, 226 (1948). (163) Ryan, D. E., ANAL.CHEM.,22, 599 (1950). (164) Ryan, J. A , . and Botham, G.H.. Ibid., 21, 1521 (1919). (165) SBnches, J. A,, Rev. asoc. bioqutm. argentina. 16, S o . 04, 3 (1949). (166) Sandell, E. B., A n a l . Chim. Acta. 3, 89 (1949). (167) Sandell. E. B., and Spindler, D. C.. J . A m . Chern. Soc., 71, 3806 (1949). (168) Schulze, H. O., Science, 111, 36 (1950). (169) Sclar. R. S . .J . Assoc. Offir. Aar. Chemists. 33, 118 (1950). (170) Selignian. A. M.,and Nachlas. 11. lf.,J . Clin. Inoest., 29, 31 (1950). (171) Shcherhov, D. P., Zaoodskuyrr Lab., 15, 1399 (1949). (172) Shcherbov, D. P., Zhur. A n a l . Khim., 4, 152 (1949). . 22, 326 (1950). (173) Shell, H. It., A N ~ LCHEM., (174) Shemyakin, F. M.,and Barskaya. 9. I., Zavodskrcyn Liih., 16, 278 (1950). (175) Shimosawa, G., and Yoshida, K., J . J a p a n Chem., 2, 29 (1948). (176) Shisterman, K. A , , and Yakouleva, 0. A , , Zacodskaya Lab.. 15, 782 (1949). (177) Shome, R. C., A n a l . Chim.Acta, 3, 679 (1949). (178) Shraihman, 9. S., Zavodskaya Lab.. 13, 930 (1947). (179) Shugar, D.. Bull. SOC. chim. biol., 31, 1659 (1949). (180) Simon, F. T., Textile Research J., 19, 567 (1949). (181) Singh, M.If., and Das Gupta, A. K., J . Sci. I n d . Reseorch, 8B, 186 (1949). (182) Skinkle, .J. H., et al., Am. Dystuf Reptr., 38, 812, 827 (1949’. (183) Skoog, D. A,, and DuBois, H. D., ANAL.CHEM.,21, 1528 (1949). (184) Smales. .L A., and Furby, E., Nature, 164, 579 (1949). (185) Smith, W.H., et al., ANAL.CHEM.,21, 133-1 (1949). (186) Snell. F. D., and Snell, C. T., “Colorimetric Methods of Analysis,” Vol. 11, New York, D. Van Nostrand Co., 1950. (187) Sohel, A. E., and Rosenherg, A. .1.,ANAL.CHEM.,21, 1540 (1949). (188) Spies, J. R., and Chambers, D. C., Ibid., 21, 1249 (1949). (189) Stephen, V. A . , J . Council Sci. I n d . Research, 21, 355 (1948). (190) Sterges, A. J., et al., J . Assoc. Ofic. B g r . Chemists, 33, 114 (1950). (191) Sterges, A. J., and NacIntire, W.H., . k x . i ~ .CHEM.,22, 351 (1950). (192) Stots. E., et al., Stain Technol., 25, 57 (1950). (193) Sweet, M . H., J . SOC.Motion Picture Engr., 54, 35 (1950). (194) Swoge. G. H., et al., Sewage Works J . , 21, 1016 (1949). (195) Tananaev, I. V., Zhu?. Anal. Iihim., 3, 276 (1948). (196) Tananaev, I. V., and Levitman, S. Y., Ibid., 4, 212 (1949). (197) Tannheim, H., Med. K l i n . , 45, 572 (1950). (198) Temirenko, T. P., Zavodskaya Lab., 15, 1367 (1949). (199) Thomason. P. F.. et al., ANAL.CHEY.,21, 1239 (1949). [ZOO) Thrun, W.E., Ibid., 22, 918 (1950). (201) Toribara, T. Y., and Underwood, A. L., Ibid., 21, 1352 (1949). (202) Tribalat, S., Anal. Chim. Acta, 3, 113 (1949). (203) Uher, F. M., “Biophysical Research Methods,” Chap. 13, Xew York, Interscience Publishers, 1950. (204) UBmura, T., and Miyakawa, S..Bull. Chem. SOC. J a p a n , 22, 115 (1949). CHEY.,21, 1348 (205) Underwood, A. L., and Seuman, TT’. F., -4x.i~. (1949).
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V O L U M E 2 3 , NO. 1, J A N U A R Y 1 9 5 1
T.I., and Orlo~a,T.Y . , Zaoodskayo Lab.. 15, 1365 (1949). (207) Veksler, R. I., Zhur. Anal. Khim., 4, 14 (1949). (208) Veksler. R. I., Ibid., 5 , 32 (1950). (209) Vredenburg, R. M., and Ssckter, E. A , , C ~ LChem. Process Ind., 34, 119 11950). (210) Weissberger, -4., “Physical Methods of Organic Chemistry,” T’ol. I, Chaps. XXI, S S I I , Ten. York. Interscience Puh(200) Usatenko,
lishers, 1950.
(211) Welch Scientific Co., pamphlet, 1950. (212) Wiliar, H. H., and Wooten, A. L., ANIL. CHEM.,22, 670 (1950). (213) Window, E. H., and Liebhafsky, H. A , , Ibid., 21, 1338 (1949). (214) Wokes, F., and Slaughter, G., Analyst, 74, 624 (1949). (215) Wollish, E. G., et nl.. ai^.^^. CHEM.,21, 1412 (1949). (216) Wrightson, F. M., Ibid.,21, 1543 (1949). (217) Zaichikova, L. B., Zooorlsbnyn Lub.. 15. 1025 11949). RECEIVED September 30, 1930.
Infrared Spectroscopy ROBERT C . GORE Stamford Research Laboratories, American Cyanamid Co., S t a m f o r d , Conn.
D
U R I F G 1950thegeneral trends in infrared spectroscopy have been similar to those reported in the review for 1949 (120). From the spectra given in the chemical journals it appears as if a growing number of chemists are utilizing the information obtainable from them. With this wide dispersion of published spectra the need for a compound index is becoming more acute. Papers on instrument design were about the same in number as heretofore, with perhaps a slight upsurge because of the renewed interest in the spectral interval between 0.8 and 2.5 microns. Several excellent empirical qualitative studies on specific classes of compounds appeared, along with a new edition of Colthup’s useful spectra-structure correlations chart (70). Over 12,000 copies of this chart have been distributed to interested perqons. Papers on quantitative analyses of specific compounds comprise about 5,8a/, of all papers included in this review. Fundamental vibrational analyses of simpler molecules continued to be a field of major activity. Two important symposia were held. The one a t Ohio State University included over fifty papers on several phases of infrared spectroscopy. The first general discussion since 1945 of the Faraday Society on Spectroscopy and BIolecular structure, held a t the University of Cambridge, included twenty-four infrared papers. Problems in the cataloging of spectra and the use of punch card systems have received considerable attention. The general topic was discussed by Hallett (131), with specific systems described by Clark ( 6 1 ) and Shreve (285). A committee appointed at the Ohio State Symposium, headed by E. C. Creita of the Sational Bureau of Standards, has studied such systems in detail. Brode (44)has discussed nomenclature and presentation of abaorption spectra data in general. Several reviews on infrared spectroscopy appeared during the year, most of them in publications outside of the United States (37,155, 255,301,303). Coggeshall included infrared methods in 3 general review on determination of organic structure (65). BOOKS
No books devoted exclusively to infrared spectroscopy were published in 1950, but infrared chapters were included in several of the compiled books and general works on spectroscopy. In this latter group are books by Candler on “Practical Spectroscopy” ( 6 2 ) )by Johnson on “Introduction to Molecular Spectra” (147), and by Pearse and Gaydon on “The Identification of 3Iolecular Spectra” (237). Herzberg has completely revised his classical work on “Molecular Spectra and hlolecular Structure, Volume I, Spectra of Diatomic Molecules” (137). Chapters on infrared spectroscopy in the compiled books were written by Coggeshall in Farkas’ “Physical Chemistry of Hydrocarbons,” Volume I (106); b y Jones and Dobriner in Harris and Thimann’s “Vitamins and Hormones,” Volume VI1 (132, 157); by Nielsen and Oetjen in Berl’s “Physical IIethods in Chemical Analysis,”
Volume I (25, 226); and by Brady in llellon’s “.%nalytical .It)sorption Spectroscopy” (212) INSTRUMENTATIOY
The year has seen another manufacturer of spectrometers, Grubb-Parsons in Fewcastlc-on-Tyne, announce the production of a percentage transmittance recording spectrophotometer This instrument can be made conveniently from the single-beam instrument by the substitution for the source section of a unit which includes the recorder. The Perkin-Elmer Model 21 doublebeam instrument has been described (190, 339) and its performance reported (336, 338). Several individual builders of spectrometers have described instruments with novel features. Bigay (30) reports the construction of a large aperture spectrometer useful in the ultraviolet and infrared. Bulloclr and Silverman ( 4 8 ) described a rapid scanning instrument with oscillographic presentation in the near infrared. Chapman and Torley (54)have constructed a mobile spectrometer which can be taken to the problem rather than having the problem come to it. Elliott et nl. described a lead selenide cell spectrometer (9‘7). Hales (129) tells of the installation of a double-beam instrument using a photocell amplifier. Hornig (142) has built a double-beam prism instrument with a servo slit control instead of cams. Savitzky and Halford (268) describe a double-beam instrument using phase discrimination rather than the usual attenuation of the reference beam. This latter principle is reviewed in an article by Schoen (269). Shurcliff (287)mentions a multislit double monochromator using no moving parts. An electronically determined double-beam instrument is described by Ganz and co-workers (353) Radiation sources are discussed by several authors ( $ 5 , 100, 649, 665). Prism materials are the subject of several papers. Davies (80) calls attention to the advantages of the synthetic silica over lithium fluoride in the near infrared up to 2800 cm - 1 Leconite (184, 185)has compared several prism materials, including some optical glasses. Plyler and co-workers (311, 312) have measured the refractive indexes of thallium bromide-iodide and silver chloride. Greig (123) describes a new mounting for an echelette grating. Radiation detectors and thermopiles are discussed by two authors (103, 139), while the absorptivity of certain metals is reported by another (335). >lathis et al. (204)report on the application of the lead sulfide cell to infrared spectrography. The infrared image converter and its use are the subject of four papers (11,13, 133,134). Infrared sensitive phosphors are discussed in three papers (12, 41, 79), while the theory of photoconductivity in infrared semiconducting films is reviewed by Ritter (666). Instrumental theory papers include the following: slit width effects (89), comatic aberration (93), slit dimensions and intensity (115),and the influence of resolution on band shape and intensity (243). Cells may be waterproofed by selenium films ( 6 ) , their thickness may be measured by a Rayleigh interferometer ( I $ 6 ) ,and they may be constructed to withstand 35 pounds per
