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Raman Spectrometry Derek J. Gardiner Newcastle upon Tyne Polytechnic, Newcastle upon Tyne, England, NE1 8ST
This review covers the literature from late 1975 to late 1977. The material has been selected to illustrate the analytical aspects of the technique. T o this end, work demonstrating quantitative and qualitative analysis is reported along with areas of endeavor having potential application in the field of analytical chemistry. Advances in instrumentation and sampling techniques are included, as are developments in our understanding of the theory of the Raman effect. The format follows closely that adopted in the previous review ( 1 ) . A simple introduction to Raman spectrometry (2),a book (3),and volumes 2 and 3 of “Advances in Infrared and Raman Spectroscopy” ( 4 )have been published. Other more specific reviews which have appeared are referenced in the relevent sections which follow. A comparison between various vibronic theories of Raman intensities has been made (5) and a direct relationship between infrared and Raman intensities has been developed (6). A comprehensive review of characteristic vibrational frequencies of compounds containing main group elements has been compiled ( 7 ) and reference spectra of several pesticides have been reported (8, 9). Identification of characteristic bands is fundamental to qualitative analysis, and computer search methods (10,11) are now being used to speed up this procedure. Applications of Raman spectrometry in industry also have been reviewed (12).
SOLIDS Much of the reported work on solids is more relevant to solid state physics than to analytical chemistry. However, there have been some publications which are of interest here. Papers on the measurement (53) and theory (54) of Raman scattering cross-sections for crystals and a Raman intensities study of Na2S04 single crystal (55) have appeared. The potential for Raman spectrometry in cement chemistry has been discussed (56, 57) and the analysis of discrete fine particles as small as 0.7 gm has been described (58).The study of phase transitions in solids continues with work reported, for example, on several electrolytes (59,60)and on perchloric and deuteroperchloric acids (61). A new oxygen molecule ion has been detected as a center in CaF2 by resonance Raman spectrometry (62). A thorough investigation of the Raman spectra of the polysulfides of sodium (63),barium (64),and potassium (65) has been undertaken. Further examples of work on solids include investigations of boron-polyol complexes (66),isotope effects in crystalline alkali-metal chlorates and bromates (67),studies of complexes of XeF,, XeOF4, and Xe02F2.with SbFj (68),and a frequency assignment for some cyclic silicates (69). Raman spectrometry has been used as a nondestructive method for partial analysis of individual phases in fluid inclusions in minerals (70). The structural units in potassium oxide-lead(I1) oxide-silicon oxide glasses have received some attention (71) and Raman scattering from amorphous ice films has been recorded (72).
INSTRUMENTATION AND SAMPLING A new method for calibrating the spectral sensitivity of a spectrometer using a gaseous sample has been devised (13) and Raman scattering, in turn, has been used to calibrate other laser scattering devices (14). The slit width dependence of depolarization ratios also has been investigated (15). On-line computer facilities are now becoming widespread, making for more efficient data acquisition and reduction. Several systems have been reported (16,17) along with programs for sine drive to linear wavenumber drive conversion (It?), baseline modeling (19),and difference spectrometry (20). Other improvements in technique have included optical optimization of sample cells (21),stray light rejection (22), automated photon-counting (23),and fluorescence suppression ( 2 4 ) . New cell designs for molten salts (25) and corrosive melts (26) have been published as have systems for measurements a t low temperatures (27-29). Rotating cells for photosensitive samples continue to be used (30,31)and have been modified to allow measurement to be made a t low temperature (32). High pressure Raman spectrometry has been reviewed (33) and cells for liquids (34, 35) and solids (36) have been described. A useful method for selecting diamonds for anvil pressure cells has been devised (37). A variety of information is available through the analysis of Raman scattered light. Techniques have been described for measurement of circular and linear polarization (38)and direct scanning of isotropic components (39)and the reversal coefficient (40). Applications of difference spectrometry (41,42)and addition spectrometry (43) also have been reported. Raman spectra of thin films continue to attract some interest and new methods of making such measurements have been examined (44, 45). There are clear analytical applications to be found for the Raman microscope which has been developed (46, 47) to observe samples in Raman scattered light. Also, further attention has been given to remote Raman analysis of air pollutants (48, 49) Hollow optical fibers containing liquid samples amplify Raman scatter and have been employed to observe weak spectral features (50,51). Finally, in this section, use of a multichannel Raman spectrometer has been reported (52) which permits the simultaneous recording of all the elements of a spectrum excited by a single laser pulse of a few picoseconds duration. 0003-2700/78/0350-13IR$OlOO/O
LIQUIDS AND SOLUTIONS Liquid and solution phases probably provide the most varied and interesting results for the analytical chemist. Several studies of the spectra arising from pure liquids have been reported. Anhydrous hydrogen fluoride has been reexamined (73)and a versatile method for isotopic analysis has been described and used to analyze for deuterium in H20-D20 mixtures (74). Work on the conformations of some conjugated hydrocarbons has been published (75). Pressure effects on the Raman spectra of liquids are now beginning to be reported. Ammonia (76),carbon dioxide (77),and water (78)have been examined and the results are interpreted in terms of intermolecular associations. The absolute Raman intensities of bands in the spectra of cyclohexane and chloroform have been determined (79). There seem to be fewer reports of work on molten systems. Notable among those which did appear are a study of aluminum oxide solutions in molten cryolite and melts containing aluminum fluoride (go), molten XeF2-MF, (M = Sb, Ta, or Nb) systems (811, and some tungstate- and molybdate-containing melts (82). Raman spectrometry continues to be applied to the study of solution systems and to the analysis of solvated species. Vibrational spectra of nonaqueous solutions have been reviewed (83). Liquid ammonia solutions of electrolytes have received considerable attention (84-88) and Raman spectrometry has been used convincingly in conjunction with NMR for studies of solvates in nonaqueous solvents (89). Ion-pairs in liquid sulfur dioxide ( g o ) ,and ion--solvent interactions in formic acid solutions have been detected (91). Many reports of work on species in aqueous solution have appeared including cadmium nitrate solutions (92),hydrolyzed aluminum(II1) salts (93), and polyborate and fluoropolyborate ions (94). Aqueous calcium nitrate solution has been examined at high pressure (95). The Raman spectrum of carbon dioxide in H20 and D 2 0 solutions has been studied (96) and the Aerosol OT-water system has been investigated (97). Ionic association in the Fuoss-Onsanger dilute solution range has been measured and compared with values obtained from conductance studies (98). The detection limits for NO1-, S042-, C03*-, C
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HC03-, HP04'-, H2P04-,AcO-, and AcOH have been determined (99),and a technique for the remote detection of aqueous acid solutions has been described (100). Raman spectrometry of liquid crystals has been reviewed (101) and a study of orientational order in uniaxial liquid crystalline phases has been reported (102).
GASES AND MATRIX ISOLATION Laser Raman spectrometry of gases has been reviewed (103). Along with the more conventional studies of simple gases, are reports of work on flames, gas temperature measurements, and jets. A review of Raman scattering studies of combustion has appeared (104). Rotational temperature measurements in multicomponent gases (105),hot, flowing gases (106),and in flames (107) have been described. Raman scattering has been used to determine local temperatures in an expanding jet beam of COz (108) and in the inviscid and viscous regions of flow from an open jet supersonic nozzel (109). A laser cavity, modified to encompass an exhaust jet, has allowed concentration measurements to be made on a subsonic jet (110). Several high resolution studies of gases have been made. Frequency calibration has been discussed (111) and stable isotope ratios in nitrogen and oxygen have been determined (112). The pure rotational spectra of fluorine (113) and chlorine (114) have been measured and a Fabry-Perot interferometer has been used to detect the rotational spectrum of nitrogen (115). I t is thought possible that this latter technique may find application in the remote detection of atmospheric pollutants. The relative intensity calibration of rotational spectra has been discussed (116) and the absolute Raman intensities of methane have been measured (117). Spectra of hydrazine and hydrazine-d4have been reported (118) and a study of chemical vapor deposition systems has revealed the presence of intermediates (119). Raman spectrometry of matrix isolated species is now a well established technique (120) which approximates a gas phase environment for species that are unstable as gases. The experimental method continues to be improved (121, 122). Several ionic species have been matrix isolated, including the iodine molecular ion (123),the trifluoride ion in M'Fy species (124),and the trichloride ion in M+Cly species (125). Binary and mixed mercury halides (126)and ferric chloride in frozen aqueous solutions (227) have been studied. Several other halides have been matrix isolated, including uranium hexafluoride (128),tri-p-chlorohexachlorotrirhenium (129),monomeric trichlorides of aluminum, gallium, and indium (130), and some interhalogen diatomics have been studied using resonance Raman spectrometry (131). Methylamine (132) is typical of organic compounds which have received attention. Spectra of hydrogen and deuterium peroxides (133) and various oxides of sulfur (134, 135) as matrix isolated species have been reported.
BIOLOGICAL MOLECULES AND POLYMERS There has been a significant amount of effort over recent years directed towards the development of Raman spectrometry for the study of biological molecules. One of the distinct advantages which Raman spectrometry enjoys over infrared techniques is its ability to cope easily with aqueous solutions. A further advantage depends upon the resonance Raman effect and, for this reason, several of the chromophoric biological molecules are dealt with under that section. Several reviews in this area have appeared (136-138) including applications in virus research (139). Strategy and tactics in the Raman spectrometry of biomolecules has been discussed (140). Nucleic acids have received some attention and the A + B transition of DNA in fibers and gels has been characterized (141). The thermal unfolding of ribonuclease (142, 143), complexes of polylysine with deoxyribonucleic and polyriboadenylic acids (144), and structures of aqueous polyribocytidylic acid (145) have been studied. The effect of protein on water structure has been determined (146) and a vibrational analysis of polyglycine I has been made (147). Bovine serum albumin has been studied (148, 149). The possibility of studying sequential, in vivo, metabolic activity of cells and the effects of gases on them has been demonstrated with Escherichia coli cells exposed to carbon monoxide (150). Different forms of crystalline cholesterol and its derivatives have been examined (151)and Raman spectra of lipid systems
containing amphotericin B have been reported (152). Carotenoids (153)and deuterated fatty acids (154,155)have been used as Raman active probes to investigate membrane structures. Raman studies of polymers continue to yield useful results. Measurement of lamellar thickness in polymethylenic systems has been described (256) and helix formation in polydimethylsiloxane has been studied (157). Raman spectra from polythene (158,159),polystyrene and polymethylmethacrylate (160),and chloroprene polymers (161) have been reported. The rotatory lattice modes in n-alkanes and polyethylene have been assigned (162)and the intermolecular forces in crystalline PVC (163)and crystalline n-alkanes (164)have been discussed. An interesting application in this field has been the study of structural changes, due to annealing, in wool fibers (165).
SURFACE ADSORPTION The use of laser Raman spectrometry in surface chemical problems has been reviewed (166) and a variable temperature sample cell has been described (167). The relative intensities of spectra from several chlorinated hydrocarbons, tetramethylethylene, tert-butylcyanide, benzene, and cyclohexane adsorbed on a silica surface have been compared with the values for the liquids (168). The formation of complexes in solution and on solid surfaces is similar for donor molecules chemisorbed on acid surfaces (169). The resonance Raman spectrum of iodine adsorbed on silica has been recorded (170) and the surface area of a silica sample has been determined (171). Silica, porous glass, and y-alumina have been used as surfaces to study the spectra of adsorbed benzene, naphthalene, and diphenyl (172). Molybdenum hexacarbonyl adsorbed on porous silica and pyridine on supported nickel oxide also have been examined (173). The isomerization of olefins over alumina has been followed and spectra have been interpreted in terms of adsorption and isomerization mechanisms (174). Zeolites are of particular interest in this field of surface adsorption and pyridine (175),acetylene (176), dimethylacetylene ( 177), and pyrazine ( 178) have all been studied in this respect. Pesticides and related compounds have been examined on thin-layer chromatography adsorbents (179) and adsorbed molecules have been reported to produce novel spectra from tungsten and nickel surfaces (180). Organic molecules adsorbed a t model sediment surfaces have allowed an evaluation of Raman spectrometry as a technique for studying environmental problems at a i s o l i d and water-solid interfaces (181). There have been several attempts to use Raman spectrometry to investigate electrode surfaces (182). Copper electrode surfaces have been examined (183)and the spectrum of adsorbed iodine on a platinum electrode surface has indicated that end-on coordination of I2 is preferred (184). Anomolously intense spectra, possibly arising from a resonance effect, have been obtained from pyridine at a silver electrode surface (185). Corrosion of lead electrodes in aqueous chloride media has been studied (186). Resonance Raman spectrometry has been applied in the study of an adsorbed surface-active dye a t an oil-water interface (187) and methyl orange bound to proteins and cationic surfactants (188)have been studied under resonance conditions.
RESONANCE RAMAN EFFECT The resonance Raman effect is now finding wide application in such disparate fields as biochemistry, matrix isolation, and the study of short lived species. Although most of the work of general interest to the analyst is cited here, some mention is made of the technique under other sections in this review. A short, but useful, review has been published (189)and some theoretical aspects have been developed. Approximate selection rules have been determined (190). Stokes-anti-Stokes intensity ratios (192),preresonance intensities (193, 194) and depolarization ratios (195, 196) have received attention. Raman tensor patterns have been calculated by a group theoretical method for the hexabromoiridate(V) ion (197). The use of fluorescence quenchers also has been discussed (198). Biochemical applications continue to command significant attention (199). Representative of this work are studies of hemoproteins (200-202) and vitamin BI2 derivatives (203). The ionization state of a sulfonamide bound to carbonic anhydrase has been determined (204) and nucleic acid
ANALYTICAL CHEMISTRY, VOL. 50, Derek J. Gardiner is a lecturer in the Department of Chemistry at Newcastle upon Tyne Polytechnic, England. He was born in Ipswich, Suffolk, and received his B.Sc. degree from London University in 1968. Then, as a research student at King's College, Cambridge, he worked with James J. Turner on vibrational spectroscopic studies of the oxygen fluorides, receiving his Ph.D. degree in 1971. He then moved to York University where, as a teaching fellow, he worked with Ronald E. Hester on Raman studies of molten salt hydrates and nonaqueous solubns. After two years, he took up his present lectureship at Newcastle upon Tyne where he teaches physical-inorganic chemistry. His research interests include Raman studies of electrolytes in nonaqueoussolutions and liquids at high pressure. He is a Fellow of The Chemical Society.
components have been studied using ultraviolet resonance Raman spectrometry (205). Of particular analytical interest is the determination of catecholamines a t M concentrations (206)and the determination of carotenoids a t concentrations of lo-@M in marine phytoplankton (207). Studies of manganese(III)-etioporph~TinI (208)and biphenylglutarate diacetylene polymer (209) have been reported. It has been demonstrated that food dyes, a t concentrations as low as 5 ppm, can be identified in solutions, solids, and emulsions (210). Resonance Raman spectra of chlorine molecular ion (211), aqueous peroxotitanium(1V) cation (212),anthracene (213), and other fluorescent aromatic hydrocarbons (214)have been reported. The dynamics of the Schiff base of bacteriorhodopsin have been studied by kinetic resonance Raman spectrometry using variable-speed continuous flow methods (215). A possible method for measuring short lifetimes through line broadening effects has been explored (216) and intensity transients in the millisecond range have been measured (217). The resonance Raman spectrum of the short-lived p-terphenyl free radical anion has been observed a t initial concentrations of 4 X 10" M using a single pulse from a dye laser. An optical multichannel system and TV camera were used to record the spectrum (218). The possibility of using resonance Raman spectrometry to detect air pollutants has been further examined (219, 220).
HYPER, STIMULATED, AND COHERENT ANTI-STOKES RAMAN SPECTROMETRY Nonlinear Raman effects have been reviewed (221)and a new experimental method for observing the hyper-Raman effect has been described (222). The applications of stimulated Raman scattering have been discussed (223). Reports of stimulated Raman scattering amplification by a dye (224)and of tunable, picosecond transient, stimulated Raman scattering in ethanol (225)have appeared. A fiber array technique (226) and the observation of scattering from silica-fiber waveguides (227) have further contributed to the field of stimulated Raman spectrometry. The technique and applications of coherent anti-Stokes Raman spectrometry (CARS) have been discussed (228). Methods of background suppression (229)and micro sampling and the use of flow cells (230) in CARS have been described. The possibility of CARS in the UV has been explored (231) and an improved experimental design allowing the observation of new higher orders has been reported (232). CARS has been applied to concentration and temperature measurements in gases (233),a study of methane gas (234),metal surfaces (235), the determination of fluorine atom concentrations in chemical lasers (236),and the measurement of vibrational temperatures in electric discharges (237). The use of resonance enhanced CARS also has been evaluated (238, 239).
ACKNOWLEDGMENT The author thanks Ian Winship and his staff at Newcastle upon Tyne Polytechnic library for help in collating the references for this review. LITERATURE CITED
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X-Ray Spectrometry G. L. Macdonald Central Materials Laboratory, Mullard Mitcham, Surrey, England
X-Ray Spectrometry is by now such a staid well-established and even elderly technique that it might be expected to offer few developmental surprises, and it is true that very few recent papers have produced significant advances in many of the traditional areas. Considerable developments have, however, taken place and this review will attempt to highlight them. The period covered is from the last review up to late 1977. Over 600 papers have been collected during the two years, but only a representative selection is included here, with reference to earlier work where it is felt to be appropriate. The technique breaks down naturally into excitation. dispersion, and data manipulation, and these three main areas have been separated. The final section draws together remarks on instrumentation, applications, and on some miscellaneous pointers t o the future.
EXCITATION X-Ray Tubes. The high power (usually about 3 kW) x-ray tube for wavelength dispersive spectrometers has not changed much in the past few years. Steady, unspectacular improvements in the generators providing the power, have been made such that a stability of 0.01% in both high voltage and current can be maintained over a temperature range of 15 “C and mains voltage variations of +IO% to -1570. For the energy dispersive spectrometer, Stewart e t al. ( 1 ) have followed up the pulsed, transmission target tube of Jaklevic et al. ( 2 )and show that for a given resolution pulsing allows a factor of two increase in the output rate for input count rates up to 40000 cps. Subsequent “resolution enhancement” is provided by convolving with the apparatus function to allow a resolution improvement of up to 20%. There is a danger, recognized by the authors, of over-correcting and producing wing lobes which could distort neighboring peaks. Used properly, however, this system is claimed to produce an increase in analysis rate of between 5 and 50 times OGG3-27G0/78/G35G-l35R$Ol O G / O
without loss of resolution or precision. The same authors are joined by Puumalainen (3) in agreeing about the advantages for certain applications of using selection filters in conjunction with x-ray tube excitation. The latter is particularly concerned to provide a more powerful source than a radioisotope, but without sacrificing the often monochromatic nature of the radiation. Also, filters between tube and sample can enhance relative excitation of wanted radiation and post-sample filters can absorb unwanted radiation. Electrons. The development of a scanning facility for most transmission electron microscopes has made it worthwhile to add a Si(Li) detector. Since most transmission microscopes can operate at higher voltages than normal scanning microscopes, it is worth studying the advantages and disadvantages of higher excitation potentials. Faulkner e t al. ( 4 see a clear resolution advantage, and have achieved 500resolution in 1500-A thick Ni/Fe films a t 200 kV. Russ (5) agrees that some improvement in resolution is likely for thin films but points out that the x-ray yield is reduced. For bulk specimens he suggests that peak t o background ratios drop for applied voltages of more than ten times the excitation energy of the x-ray lines of interest and that shielding of a n energy dispersive detector against stray high energy electrons is more difficult. The possibility of using K rather than L lines for the heavy elements is a seldom required advantage. Radioisotopes. The use of radioisotope excitation continues to grow slowly in the obvious areas such as on-stream analysis in mining. Kawatra ( 6 ) ,for example, demonstrates that entrapped air in a mineral slurry has little effect on the characteristic copper intensity but has a major effect on the density gauge used for monitoring. He points out that an x-ray scatter monitor is much more useful. Rhodes (7) reviews the use of portable units in mining in the U S A . and Cesareo et al. (8)list a wide range of Italian applications for portable units based on proportional counter detection.
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C 1978 American Chemical Society
