7
V O L U M E 2 1 , N O . 1, J A N U A R Y 1 9 4 9
Strong, F. C., ANAL.CHEV.,19, 968 (1947). Tech. Assoc. Pulp and Paper Industry, Paper Trade J., 125,
D. W., “Chemical Equilibrium and Qualitative Analysis,” Ann Arbor, Mich., Edwards Brothers, 1946. PlochBre, G., and G., “PlochBre Color System,” Los Angeles, G. and G. PlochBre, 1948. Richardson, E. E., J . Optical SOC.Am., 38,657 (1948). Rider, B. F., with Mellon, M. G., IND.ENG.CHEM.,ANAL. ED., 18, 96 (1946). Sandell, E . B., “Colorimetric Determination of Traces of Metals,” New York, Interscience Publishers, 1944. Savost’yanova, M. V., Bull. acad. sci. U.R.S.S., Sdr. phys., 11,
(44) Pearce, (45) (46) (47) (48)
(49)
442 (1947).
Troland, L. T., etal., J . Optical SOC.Am., 6 , 527 (1922). Tunnirliff, D. D., ANIL.CHEM.,20, 828 (1948). Turner, A F., and Ullrich, 0. A, J . Optical SOC.Am., 38, 662 (1948).
Weissler, A., IND. EVG.CHEM.,ANAL.ED., 17, 695 (1945). Welcher, F. J., “Organic Analytical Reagents,” New York, D. Van Nostrand Co., 1947. Will Corp., “Kromotrol Photometer.” Yoe, J. H., and Jonea, A. L., IND.ENQ.CHEM.,ANAL.ED., 16,
424 (1947). (50) Scott, R. E., and Johnson, C. R., IND. ENG.CHEM.,ANAL.ED., 17, 504 (1945). (51) Stillman, J. W., Proc. Am. SOC.Testing Materials, 44, 740 (1944). i62) Snell. F. D.. and Snell. C. T., “Colorimetric Methods of Analysis,” New York, D. Van Nostrand Co., 1948
111 (1944).
Zscheile, F. P., J . Phys. Colloid Chem., 51, 903 (1947). RECEIVED October 7, 1948.
INFRARED SPECTROSCOPY R . BOWLING BARNES American Optical Company, Southbridge, Mass. AND
ROBERT C . GORE American Cyanamid Company, Stamford, Conn.
A
T T H E time of the installation of the first industrial infra-
red spectrometers during 1936-37, little was it realized t o what uses the field of infrared spectroscopy would be put or to what extent it Tl-ould become accepted as an industrial tool. Under the pressure of the war years, however, industry found so many applications for infrared, particularly in connection with the petroleum and synthetic rubber programs, that its merits were demonstrated repeatedly and its place as a n important tool for research, analysis, and control was assured. In direct response t o the demands of industry spectrometers were made available commercially and in large numbers. These instruments have resolving powers comparable to most of the academic research spectrometers and have the additional features of convenience, stability, and uniformity. The commercial availability of these spectrometers has made possible the adoption of infrared by many industrial laboratories which deal with a nide variety of organic chemicals other than hydrocarbons and also bv university laboratories interested only in organic research rather than in infrared spectrometrv itself. Infrared has nou become a research tool widely accepted by chemibts and no longer remains only a branch of the broad field of spectroscopy practiced by a small group of physicists. The technique, and uses of infrared are now taught in a great many universities and colleges rather than in a limited few as was the case prior to its recent popular acceptance. As is to be expected, several publications of a general nature have appeared since 1936 which serve t o document this expansion. A small book covering general applications, published in 1943 by Barnes, Gore, Liddel, and Williams ( d o ) , included a bibliography of 2701 previously published papers. Herzberg’s classical volume on “Infrared and Raman Spectra of Polyatomie Molecules,” including over 900 references ( I @ ) , appeared in 1945. llathieu in France has written a comparable volume (190). A conference on spectroscopy a t the Museum of Science and Industry held in Chicago during 19-14 (238) included many papers of interest. I n 1945 the Faraday Society held a Symposium on the Application of Infrared Spectra to Chemical Problems (279) 1%ith 19 timely papers. The American Petroleum Institute in collaboration with the Xational Bureau of Standards has collected from various research workers and made available through its Research Project 44 over 700 spectra of hydrocarbons and related substances. This project is continuing. The Ohio State University has sponsored interesting and valuable symposia on infrared spectrometry and directlv related sub-
jects during June of 1946, 1947, and 1948. At the last of these symposia, which have rapidly become the outstanding yearly event in the field of infrared, some 330 persons were in attendance. At these meetings discussion is lively and ideas are interchanged freely between individual and groups. Publication of the papers presented is left t o the individual authors, and no attempt is made t o collect them in one volume. The Optical Society of America has also conducted important symposia in the field, and the abstracts of the papers have appeared in its journal (208,209). Preparation for the writing of this present review revealed some 1000 papers published since 1943 review article (20). I X attempt can be made here to refer to each of these papers. 0 the contrary, only those are cited which serve t o show the majo trends in the various phases of this rapidly evpanding field. INSTRUMENT4TIOX
-4comprehensive review on instrumentation and experimental techniques was published recently by Williams (291). This paper covers the history, techniques, and applications as well as the advances in instrumentation in the very near infrared from 13,300 t o 4000 cm.-l, the near infrared from 4000 t o 400 ern.-’, the far infrared from 400 to 30 cm.-l, the microwave region, infrared filters, and gas analyzers as well as many miscellaneous apphcations of infrared radiation. With its 210 references, this review is required reading for anyone interested in this phase of infrared. Since 1943, if one excepts the general commercial availability of suitable spectrometers, the major trends in instrumentation have been the following: The substitution of breaker type direct current amplifiers (180, 236) in place of galvanometers or photorelay.amplification. This introduction of a satisfactory and comniercially available amplification system capable of handling the small energies obtainable from spectrometm receivers has enabled the almost universal use of fountain pen type recorders. Interrupted beam alternating current amplification systems introduced to eliminate the bothersome zero drift encountered in direct current systems (179,236). A persistent demand for infrared spectrophotometers or direct reading percentage transmittance s ectrometers has been met by the Baird Associates (12,205) and $he Perkin-Elmer Corporation in this country and by Adam Hilger (121) in England. Several other spectrophotometers have been described (17, 173, 188, 231, 299, 300). This trend is undoubtedly in the right direction; however, there still remain many instrumental problems which must be overcome before these spectrophotometers are accepted universally.
ANALYTICAL CHEMISTRY
8 Major improvements have been made in the field of radiation detectors, such as vacuum thermocouples of higher sensitivity and better construction (118, 143, 179, 243). Photoconductors sensitive to short wave-length infrared, such as thalofide cells and lead sulfide cells, were developed for military purposes and have only recently been applied to spectrometers (38, 247, 256). Such detectors should become increasingly useful. DISPERSING SYSTEMS
As yet f e laboratories ~ engaged in analytical research (206) have employed spectrometers equipped with diffraction gratings. Whereas the earlier spectrometers were equipped almost exclusively with sodium chloride prisms, it is now possible to obtain prisms of the folloviing materials: sodium chloride, lithium fluoride, synthetic fluorite (CaF1), potassium bromide, and a mixed crystal of thallium bromide-thallium iodide called KRS-5 (23, 24, 70, 123, 146, 216-817, 872, 280, 297). Each of these materials has a definite function and with KRS-5 the useful range of prism spectrometers has been extended to about 250 em.-' ( 4 0 ~ ) . OSCILLOGRAPHIC RECORDING
Folhving the original publication of Baker and Robb (17) in 1943, both Sutherland (77-79) and Thompson (160, 269) in England have described spectrometers employing cathode ray oscillographic recording. This technique should ultimately be of considerable use in following the course of certain chemical reactions in short spectral intervals. CELLS, WINDOWS, AND OTHER ACCESSORIES
The necessity for using soluble halide cell windows has for a long time limited the application of infrared spectroscopy to samples essentially of a nonaqueous nature. Several halide cells have been described recently (44, 57, 120, 207)) but the simple cell developed by Colthup (62) appears to offer one of the most feasible solutions to the cell problem. Silver chloride windows offer good transparency ( 7 , 105, 14?, 165) and low solubility. They are, however, not the ideal window material because of their reactivity, ductility, and the difficulty encountered in repolishing them. Eastman Kodak has produced a glass (EK Yo. 25) which shows excellent transmission from 300 millimicrons to about 4.5 microns, This glass, however, cannot be worked in the same manner as ordinary glass. One of the prime disadvantages of the S u j o l mull techniquenamely, the obscuring of the C-H absorption bands-may now be eliminated throug'i the use of perfluorokerosene (Du Pont). The reduction of the effect of scattered radiation in,spectrometers is now regularly accomplished by the use of filters, powder filters ( 1 3 3 , or echelette gratings (390). Using cells of silver chloride plates, Barnes, Gore, and Peterson (1%'') have explored the field of aqueous phase infrared. As solvents DtO, DCl, and KaOD along with their hydrogen analogs were successfully used. POLARIZED RADIATION
Pfund (214) has recently improved his original selenium reflection method for polarizing infrared. Elliott, Ambroae, and Temple (92-94) have described a transmission polarizer using their selenium filters, and Halford (202) and Wright (296) have discussed silver chloride transmission polarizers. These are important developments and there is now no reason n hy the uw of polarized infrared should not be accepted Tvidely for the studv of the orientation of infrared active groups in crystals and other solid phase samples. GAS ihALYZERS
An important development, from the industrial point of view, is the introduction of infrared gas analyzers which employ no dispersing systems (96, 186, 298). These instruments are in general very sensitive and are capable of detecting selectively as little as a few parts per million of many gases or vapors which
exhibit strong infrared absorption. The simplicity and ruggedness of these devices make them very useful for obtaining coiltinuous analyses of gas streams and also for control purposes I n general, they may be classed either as the positive (46, 186) or the negative filter type (298). Luft in Germany (186) constructed a positive filter type which is now being manufactured in England. Practical instruments of the negative type are sold by Baird Associates. The use of such gas analyzers should increase. EMISSION SPECTRA
I n this field an interesting paper by Kapff (154, 155) shoived that thin films of organic liquids when heated emitted characteristic spectra, whereas the emission from heated thick layers was largely of the gray body type. Simard et al. (246) showed the use of emission spectra in studying react,ions such as the thermal decomposition of ethylene oxide. QUALITATIVE ANALYSIS
Undoubtedly, the widespread acceptance of infrared a s a research tool is based primarily upon the speed, accuracy, and uniqueness with which chemical analyses can be performed through its use. Practically each issue of the journals presents the details of still another analytical problem which has been solved by infrared means. In this group are some which are solvable by no other means and many in which the application of infrared has made possible material savings in time or substantial increases in accuracy. Each of the individual spectra in literally hundreds of papers contributes to the general fund of data available for qualitative analyses. Unfortunately, space does not permit of a complete bibliography. General papers discussing the application of infrared spectroscopy to qualitative analyses have recently been published by Barnes et al. (19-21), Thompson (261-266, $TO), Sutherland (255, 858), Jones (158), Coggeshall et al. (55, 838), Brattain (4.9, Naylor (sal), Luft (185), and Lecomte (168, 169). These treat the methods of sample preparation, positions of known absorption bands, and interpretation of the spectra. The use of infrared in the identification of specific classes of compounds has been discussed in many papers. The moat coniplete collect,ion of spectra of any one class is the American Petroleum Institute Project 44 on hydrocarbons referred to above. Among the classes of compounds st,udied are: conjugated double bond systems such as di-, tri-, and tetraenes, azines, and furals (do), nucleic acids (39), methylcyclopropanes (27), penicillins (22, 112), deuterated benzenes (8-11), orthosubstituted cyclohexanones ( 6 l ) ,urinary ketosteroids (87, 108-11 I), disubstituted benzenes (82, ab), Pennsylvania lubricat,ing oils (139), synthetic rubber (26, 61, 97, 1&), the carbonyl stretching vibration in steroids (151, 153) and in ketones (c50),drying oils (164),amino acids and t,heir complexes (163, 174-177), polyalkylene sulfides ( l a g ) , alkylphenols (161), cyclopentanes and cyclohexanes (5?18), tocopherols and related molecules (237),fatty acids (226), octenes dienes, and mono-olefins (227-230), dicarboxylic acids (&id), indoles (249-861), useful infrared solvents (278), organosilicori polymers ( S o l ) , and cresols, xylenols, and cresylic acids (287). Other papers by Sutherland, Thompson, and Lecomte contain useful spectra on molecules. Those using infrared spectra for analytical purposes face a real problem in their efforts to keep up with the published results of others and to keep these results in ready reference form. .Is a step in this direction several important articles have appeared on the use of punched card systems (354, 277). At the last Ohio State Conference a committee was formed with E. Carrol Creitz of the Bureau of Standards as chairman. QUANTITATIVE ANALYSIS
The wartime use of infrared for rapid quantitative analysis by the petroleum and synthetic rubber industries is largely re-
V O L U M E 2 1 , NO. 1, J A N U A R Y 1 9 4 9 sponsible for its present popularity. As might be expected, many of the published papers on quantitative analysis are in these fields. Gtmeral articles in which methods and procedures for performing quantitative analyses are outlined have been published by Brittain (43),Beckman ( S l ) , Kent andBeach (158),Coggeshall and Saier (58, 238), Corin ( 7 1 ) , Fry, Nusbaum, and Randall [ I O & ) , Seyfricd and Hastings (8.44), Thompson (261), Sutherland (255,268), White et aE. (135),and Barnes et aZ. (20,22,25). Among the more specific papers may be cited: a procedure for determining trace impurities in iso-octane (4), low temperature analysis of octane mixtures ( 6 ) , crystalline penicillins (22, 1l a ) , synthetic and nat’ural rubber mixtures (85, 86), the andysis of gas streams for butadiene content (298), an analysis of the five isomers of 1,2,3,4,5,6-hexachlorocyclohexane (76), DDT (89), olefins in gasoline (150), specific hydrocarbon analyses (41,42, I d ? , 166, 170, 220-263, 235, 276, 286), ortho, meta, and para isomers, anti iso- and thiocyanates (156, 289). (;its ana1yzt~i.s have been applied quantitatively for the of toluene-benzene mixtures (106), an optical acoustical method (40, 282), and for butadiene and styrene in plant gas streams (298). Several important papers have appeared with aids and techniques related t o quantitative analysis but not reporting specific analyses. Among these are: an automatic simultaneous equation computer (1, 36, 63, 103, 133, 145, 198, 199, electrical and mechanical methods of plotting percentage transmission against wave length (36,107,232,292),a calibrated null circuit for Perkin-Elmer spectrometers for obtaining optical densities or percentage transmissions (49), an ihterference method for determining cell thicknesses (648), and an alternate method for cell thickness determinations (259). The influence on quantitative analyses of pressure broadening and of failure to obey Beer’s lalv has been discussed in detail by 172, 204, 241). several invcstigators (59,60,88,98,99, HYDROGEN BONDING
Always a popular subject, the use of infrared for studying inter- and intramolecular bonding in various molecules continues. In connection with these studies in crystals and other solid state samples polarized infrared has played an important role. Aniong the important articles on this subject are: a study of the stereochemistry of the hydroxyl group in vinyl alcohols ( 4 5 ) , hindered and unhindered phenols (56), a method for differentiation between inter- and intramolecular linkages in the near infrared (go), infrared dichroism in dibasic acids and nylon films (114, 116), three types of 0-H frequencies and the role of double bonds in chelation (101, l O d ) , association in alcohols (?4,75, 80, l 4 6 ) , the effect of bonding on the carbonyl frequencies ( 1 7 1 ) , crystals containing hydroxyl groups (181-184, 187), the broadness and other characteristics of association absorption bonds (213), a theoretical discussion of spectra and bonding (191, 219), evidence for the XH--N bond in ethgleneimine ( 2 6 7 ) , a review of bonding and vibration spectra (281),intensity measurements of the OH bond in the near infrared (283), arid a nitsthod for dctwtitig iritcraction in the near infrared (302). THEORETICAL ASD MOLECULAR
Structure Studies. .Is might be expected from the greater over-all activitJ- in the field of infrared, interest in the vibrational analysis of molecules is on the increase. Because oftheir siniplicit>-arid general utility the hydrocarbons hare received the bulk of the study, although several other molecular types have attracted attention. In connection with benzene and its derivatives the following studies have been reported: the potential function of benzene (13), combination bands and molecular symmetry (18), bond torsion in the vibrations of the molecule (32, 91, 128), the vibrations of benzene derivatives and the Class -Icarbon vibrations of toluene (33,52), the theor>-of t h r electronic structure of con-
9 jugated systems ( 7 3 ) , the shift of an aromatic band near 815 om.-’ in substituted benzenes ( l a d ) , the normal coordinates of a monosubstituted benzene molecule (lis), the size and vibration frequency of the excited benzene molecule (125), the spectra of benzene in the solid liquid, and vapor states (189), some benzene molecules containing isotopic carbon atoms (82-85), the nonplanar vibrations and those of p-benzene-& and p-benzenedx (141, 196, 196), and a series of papers by Ingold and his coworkers (8-11,14l, 148, 1.49)on benzene and its deut’erated forms. I n the hydrocarbon field the following references are of interest (3, 5, 14, 26, 30, 33, 47, 54, 60, 72, 91, 95, 100, 159, 166, 167, 178, 192, 194, 200, 245, 252, 253, 257,260, 268, 284, 685). Other studies of interest include ozone (2, 117, 296), hexafluoroethane (212), methyl halides (15, 16), nitric acid (28), amuranium hexafluoride ( 3 7 ) , monium chloride and bromide (%I), Rochelle salts (48), ionic crystals such as orthorhombic carbonates (64-69), hydrogen sulfide (127, 293), halomethanes (34, 8 l ) , the use of polarized radiation in the structural analysis of longchained polymers (93, 116, 116), alcohols, ethers, and amines (119), ketene (132, 134, 197, 288), acrylonitrile (1.91, 271), carbon dioxide (138), fluoroform (34), urea (Is?),pyridine ( 1 6 0 , ammonia in the pure rotation and micro\vave regions (203), the potential barrier-hindering rotation of dimethyl sulfide (210), simple fluorocarbons (34, 211, Hb), 1,2-dichloroand dibromocthanes (126), dioxane and trioxane (Z64,265), the force constants of certain OH and S H linkages (234), and the active frequencies of quartz (639). General papers of unusual interest include those by Cleveland and Neister on the use of group theory (53, 193), Halverson’s review on the use of deuterium in spectroscopy (130), Halford’s studies on the condensed phases (by), and IT7ilson and Thorndike’s series on band intensities (273-67.5, 294). BIBLIOGRAPHY
(1) Adcock, W. A., Reu. Sci. Instruments, 19,181-7 (1948) J . Chem. Z’hus., 14..‘179-82 (2) Adel, Arthur, and Dennison, D. M., (1946). ( 3 ) hhonen, C. O., Ibid.,14,625-36 (1946). (4) Anderson, J. A,, Jr., AN+I,.CHEM.,20,801-4 (1948). (5) rlstor, J. G., and Saasz. G. F., J . Am. Chem. SOC.,69.:3108-14 (1947). (6) ..\very, W. H., and hlorriaon. J. R.,J . Appiied l’hys., 18, 960-7 (1947). (7) hxilrod, B. M.. and Lamb. J. J., Ibid.,19,213-16 (1948). (8) Bailey, C. R., Carson, S.C., Gordon, R. R., and Ingold, C. K., J . Chem. Soc., 1946,288-99. (9) Bailey, C. R., Carson. 6 . C., and Ingold, C . K., I h i d . , 1946, 252-5. (10) Bailey, C.R., Gordon, R. R., Hale, J. B., Herzfeld, N . , Ingold, C. K., and Poole, H. G., Ihid., 1946,299-316. (11) Bailey, C. R., Hale, J. B., Herzfeld, N., Ingold, C. K., Leckie, A. H., and Poole, H. G., Ibid.,1946,256-72. (12) Baird, W. S., O’Bryan, H. M , ,Ogden, George, and Lee, Dorothy, J. Optical SOC.Am., 37, 754-61 (1947). (13) Bak, B., Kgl. Danske Videnskah Selsknh, ,Ilaf.-fus. Jfedd., 22 No. 9 11945). (14) Ibid..22,No. 16 (1946). (15) Ibid.,24,3-7 (1947). (16) Ihid., 24, 3-14 ( l 9 4 h ) . (17) Baker, E. B., and Robb, C . D., Rec. Sci. Instruments, 14, 362-7 (1943). (18) Barchewita, P., C‘ompt. rend., 224,464-5 (1947). (19) Barnes, R. B.. “Major Instruments of Science and Their Ap plication to Chemistry,” pp. 123-47, Xew I’ork, Interscience Publishers, 1945. (20) Barnes, R. B., Gore, R. C., Liddel, Urner, and Williams, V. Z., “Infrared Spectrosopy, Industrial Applications and Bibliography,” New York, Reinhold Publishing Corp. 1944. (21) Barnes, R. B., Gore, R. C., Stafford, R. W., and Williams, V. Z., ANAL.CHEM.,20,402-10 (1948). (22) Barnes, R. B., Gore, R. C., Williams, E. F., Linsley, S. G., and Petersen, E. hl., IXD.ENG. CHEM.,AXAL. ED., 19, 620-7 (1947) (23) Barnes, R.B., McDonald, R. S., Williams, V. Z., and Kinnaird, It. F., J . Applied Phus., 16,77-86 (1945). (24) Ibid.,17,532 (1946). (25) Barnes, R. B., Williams, V. Z., Davis, A. R., and Giesecke, Paul, IND.ENG.CHEM.,ANAL.ED., 16,9-14 (1944).
10
ANALYTICAL CHEMISTRY
(26) Barriol, J., and Chapelle. J., J . phys. radium., 8, 8-13 (1947). (88) Dobrowsky, A., Monatsh., 77, 185-96 (1947). (27) Bartleson, J. D., Burk, R. E., and Lankelma, H. P., J. Am. (89) Downing, J. R., Freed, W. V.. Walker, I. F., and Patterson, Chem. SOC.,68,2513-8 (1946). G. D., IND.ENGI.CHEM.,ANAL.ED., 18, 461-7 (1946). (28) Bauer, E., and Magat, M., Cahiers phys., 5, 37-44 (1941). (90) Dubois, J., Compt. rend., 219, 333-4 (1944). (29) Beck, Clifford,J. Chem. Phys., 12, 71-8 (1944). (91) Duchesne, J., Physica, 10, 817-22 (1943). (30) Beckett, C. W., Piteer, K. S.,and Spitzer, Ralph, J. Am. (92) Elliott, A., and Ambrose, E. J., Nature, 159, 641-2 (1947). C h a . SOC., 69,2488-95 (1947). (93) Elliott, A., Ambrose, E. J., and Temple, R. B., J . Chem. (31) Beckman, A. O., Petroleum Eng., 16 (4), 173-82 (1945). Phys., 16, 877-86 (1948). (32) Bell, R. P., Trans. Faraday SOC.,41, 293-5 (1945). (94) Elliott, A., Ambrose, E. J., and Temple, R., J . Optical SOC. (33) Bell, R. P., Thompson, H. W., and Vago, E. E., Proc. Roy.SOC. Am.. 38. 212-16 (1948). ( L o n c l ~ n )A192, , 498-507 (1948). (95) El’yashevich, M. A., and Stepanov, B. I., J . P h y s . Chem. (34) Bernstein, H. J., and Hereberg, G., J. Chem. Phys., 16, 30-9 (U.S.S.R.), 17, 145-58 (1943). (1948). (96) Fastie, W. G., and Pfund, A. H., J . Optical SOC.Am., 37,762-8 (35) Berry, C. E., and Pemberton, J. C., Instruments, 19, 396-8 (1947). (1946). (97) Field, J. E., Woodford, D. E., and Gehman, S.D., J . Applied (36) Bielak, W. M., J. Sci. Instruments, 25, 205 (1948). Phvs., 17, 386-92 (1946). (37) Bigeleisen, Jacob, Mayer, M. G., Stevenson, P. C., and Turke(98) Foley, H. M., P h y s . Rev., 69, 616-28 (1946). vick, John, J . Chem. Phys., 16, 442-5 (1948). (99) Ibid.. 69, 628-31 (1946). (38) Blackwell, D. E., Simpson, O., and Sutherland, G. B. B. M . , (100) French, F. A., and Rasmussen, R. S.,J . Chem. Phys., 14, Nature, 160, 793 (1947). 389-94 (19461. (39) Blout, E. R., and Fields, Melvin, Science, 107, 252 (1948). (101) Freymann; R..Cahiers phgs., 9, 1-15 (1942). (40) Blout, E. R., Fields, Melvin, and Karplus, Robert, J . A m . (102) Freymann, R., and Heilmann, R., Compt. rend., 219, 415-17 Chem. Soc., 70, 194-8 (1948). (1944). (41) Brady, L. J., IND. EKG.CHEM., A N - ~ ED., L . 16, 4 2 2 4 (1944). (103) Frost, A. A., and Tamres, Milton, J . Chem. Phus., 15, 383-90 (42) Brady, L. J., Oil Gas. J., 43, No. 14.87-90 (1944). (1947). (43) Brattsin, R. R., PetroIeum Refiner, 22 (4), 92-110 (1943). (104) Fry, D. L., Nusbaum, R. E., and Randall, H. M.,J . Applied (44) Brosdley, H. R., Rer. Sci. Instruments, 19, 475 (1948). P h y s . , 17, 150-61 (1946). (45) Buswell, A. M., Rodebush, W. H., and Whitney, R. McZ., (105) Fuoss, R. M., Rev.Sci. Instruments, 16, 154-5 (1945). J . Am. Chem. Soc., 69, 770-2 (1947). (106) Fuoss, R. M., and Mead, D. J.,Ibid., 16, 53-4 (1945). (46) Callisen, F. I., X a t u r e , 159, 167 (1947). (107) Ibid., 16, 223 (19451. 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(1948). R E C E I V E December D 3, 1948
RAMAN SPECTRA W. G. BRAUN AND M. R . FENSKE The Pennsylvania State College, State College, P a .
I
S THE: 20 years since its discovery, the Raman effect has provided new approaches for studying molecular structure, the thermodynamic properties of materials, reaction kinetics, and the qualitative and quantitative analysis of natural and synthetic products. This paper is a brief review of the current literature relating to the application of this phenomenon to analytical chemistry. This review covers chiefly the period from 1943 to the present, although some earlier work is included. The theory and application of the Raman spectra have been rather well covered in several monographs on the subject. Particularly good are the books by Herzberg (29), Hibben (30), Kohlrausch (SS), and Sutherland (69). The paper by Glockler ( 2 1 ) brings t h e . work in Hibben’s monograph to July 19-12. Goubeau ( 2 3 )has written a review on the analytical applications of the phenomenon which covers the work t o 1939 very well. T h e paper by Stamm (67) gives a brief but good discussion of the theoi y. APPLICATIOYS
,
The variety of problems to which analytical Raman spectroscopy has been applied demonstrates the versatility and usefulness of the method, and, incidentally, often the ingenuity of the investigators. In cases where the constituents of the material being examined are known qualitatively and where the spectra of the individual compounds present are available for comparison, the analysis is usually straightforward. Hom-ever, when the spectra of the components are not available, or when the materials are of unknown molecular structure, the analysis becomes complicated. This is often the case in the study of natural products, and usually the best that can be done is to compare the spectrum of the unknown with those of structurally similar compounds. Most of the current applications are in the field of organic chemistry, particularly hydrocarbon mixtures. T h e earlier work on the analysis of petroleum products has been outlined by Hibben (SO), Glockler ( d l ) , and Kohlrausch (33), previously cited. Some review papers which have described the field of usefulness of the method in relation to other
physical methods of analysis are by Sielsen (@), Taylor (39), Schlesnian and Hochgesang (69), Adrianov ( I ) , Baroni (b), and Shorygin (6%‘). More specific data on the method as applied to petroleum mixtures are given by Bazhulin ( 3 ) \Tho presented the results of a semiquantitative analysis of a number of petroleum mixtures by the comparison with standard samples, and by Gerding and van der Vet ( 1 9 ) who applied the method t o t h e analysis of binary and ternary mixtures of pentenes. Shorygin (61) studied the composition of light motor fuels containing benzene, toluene, cyclopentane, cyclohexane, cycloheuene, pentenes, and octane isomers. Vol’kenshteln et al. (73, 7 4 ) analyzed Baku, Groany, and Syzran natural gasolines and seve‘ral cracked gasclines with the aid of Raman spectra. 3Iidzushima et al. (37, 38) determined the constituents of several Sanga-Sanga and north Sumatora gasolines. Deln-aulle, FranFois, and Weimann ( 1 2 ) and Okaaaki (45,44)analyzed several fuels prepared by the Fischer method using the Raman technique. Rank, Scott, and Fenske ( 6 3 )outlined a method using a n internal intensity standard and applied this to the analysis of hydrocarbon mixtures. Rosenbaum, Martin, and Lauer (58) report a procedure for analyzing four-component aromatic mixtures using known blends as standards. Fenske et al. (15), using a recording photoelectric spectrograph developed by Rank and Wiegand (54), gave the analyses of several four-, five- and six-component hydrocarbon mixtures and showed how the photoelectric method could be applied to analytical work. Glacet (90) studied the reduction products of crotonaldehyde with magnesium and acetic acid and, by means of Raman spectra, shonwl that the products contained a n ethylenic linkage b u t gave no indication of the presence of a carbonyl group. Pajeau (45) applied the Raman effect to the analysis of a mixture of dibromobutanes in his study of catalytic dehydrogenation in the presence of beryllium sulfate. Chiurdoglu (Y), in eyamining the ring enlargement of cis- and trans-l,2-dialkylcyclopentanes by aluminum chloride, used Raman spectra to analyze the reaction products, and showed that they are transformed into cyclohexanes and paraffins, Ducasse ( l a ) , in his work on the action
