phys. Acta, 326, 245 (1973). (255) Sakamoto, A,, Yoshino, K., Kubo, U.. Inuishi, Y., Jpn. J. Appl. Phys., 13, 1691 (1974). (256)Spiker, R. C., Jr.. Levin. I. W.. Biochim. Biophys. Acta, 388,361 (1975). (257)Vergoten, G.. Fleury, G., Mol. Cryst. LiquidCryst., 30, 213 (1975). (258)Dvorjetski, D.. Volterra, V., Wiener-Avnear, E., Phys. Rev. A, 12,681 (1975). (259)Takase. A,, Sakagami, S..Nakamizo, M., Chem. Lett., 1975,797. (260)Simova, P., Savatinova, I. T., Dokl. Bolg. Akad. Nauk. 27, 173 (1974);Chem. Abstr., 81,
31364y (1974). Surface Adsorption
(261)Hendra, P. J., McOuillan, A. J., Turner, i.
D.M., DECHEMA-MOnogr., 78,271 (1975). (262)Cooney, R . P., Curthoys. G., Nguyen The Tam, Adv. Catal., 24, 293 (1975). (263) Schrader. G. L., Jr., Hill, C. G.. Jr., Rev. Sci. Instrum., 46, 1335 (1975). (264)Black, G., Wise, H., Schechter, S., Sharpless, R. L.. J. Chem. Phys., 60, 3526 (1974). (265)Nagasao, T., Yamada. H., Chem. Lett., 1974, 1045. (266)Hendra, P. J., Turner, I. D. M., Loader, E. J., Stacey, M.,J. Phys. Chem., 78,300 (1974). (267)Nguyen The Tam, Curthoys, G. C., Cooney, R. p., Appl. Spectrosc., 27,484 (1973). (268)Nguyen The Tam, Cooney. R. P., Curthoys, G., J. Colloid lnterface Sci., 51, 340 (1975). (269)Fleischrnann, M., Hendra, P. J., McQuil-
Ian, A. J., Chem. Phys. Lett., 26, 163 (1974). (270)Winde, H., Z.Chem., 14,323 (1974). (271)Nagasao, T., Yamada, H., J. Raman Spectrosc., 3, 153 (1975). Matrix Isolation
(272)Ozin, G. A.. “Vibrational Spectroscopy of Trapped Species 1973”, Hallam. H. E., Ed.. Wiley, London, p 373. (273)Andrews, L., Spiker, R . C., Jr.. J. Chem. Phys., 59, 1863 (1973). (274)Howard, W. F., Jr.. Andrews, L., inorg. Chem., 14, 1726 (1975). (275)Howard, W. F., Jr., Andrews, L., inorg. Chem., 14,767 (1975). (276)Giguere, P. A,. Srinivasan, T. K. K., Chem. Phys. Lett., 33,479 (1975).
UItravi oIet Spectrometry Richard Hummel’ and Donald Kaufman Analytical Laboratories, The Do w Chemical Company, Midland, Mich. 48640
This review covers publications available to the authors from December 1973 to November 1975 and follows the format of the previous review (103).References included in the review were abstracted directly from the journals. Publications falling within the scope of the review appeared a t about the same rate as the preceding four years but there were variations in the number of references falling within the various sections of the review. To prepare a concise review, it was again necessary to be selective in the publications which were included.
BOOKS The third edition of “Spectrometric Identification of Organic Compounds” (218) and the book “Absorption Spectroscopy of Organic Molecules” ( 171) contain chapters on ultraviolet spectroscopy and both also contain chapters on interrelating data from several spectrometric methods. The book “Introduction to Spectroscopic Methods for the Identification of Organic Molecules” contains a chapter “An Introduction to Ultraviolet Spectroscopy with Problems” which covers the subject in a different manner than most introductory chapters (132). Review articles, which were listed in a Books and Reviews section previously, are placed under the appropriate subject headings in this review.
COLLECTIONS OF SPECTRA AND INDICES Volumes IX and X of the series, “Organic Electronic Spectral Data”, covering the years 1967 and 1968, have been published (177, 178). Volume XIX of “Absorption Spectra in the Ultraviolet and Visible Region” is the most recent volume of this series to come to the authors’ attention (124). The second edition of the “Atlas of Spectral Data and Physical Constants for Organic Compounds” is enlarged and continues to contain ultraviolet spectral data on many of the compounds which absorb in this region (80). Volume 2 of the “Atlas of Protein Spectra in the Visible and Ultraviolet Regions” has been published (116).No. X of a series of articles giving absorptivity values for proteins at selected visible and ultraviolet wavelengths has appeared (115).The Sadtler Standard Spectra collection now contains 38000 ultraviolet spectra of over 22000 compounds (199).The American Petroleum Institute Research Project 44 has added additional ultraviolet spectra to their collection bringing the total to 1178 compounds (255).The “Handbook of Spectroscopy” contains an ultraviolet spec268R
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tral data index (189). A computer-based storage and retrieval system for electronic absorption spectra has been described (206).
APPARATUS During the past two years, there have been several publications on applications of computers in spectrophotometry. These describe a Cary model 14 spectrophotometer interfaced to a computer (129),a double beam spectrophotometer designed for use with a computer (184), a computercontrolled system for reaction rate measurements (165), and computer control of rapid scanning spectrometers (148, 167, 242). Also, a digital correlator for spectrophotometric measurements was described (247). Other publications described a rapid scanning vacuum ultraviolet spectrometer (2401, a wavelength modulation spectrometer for simultaneous detection of absorption and derivative spectra ( 1 1 ) , an apparatus for measuring the transmission of thin layer chromatograms in two dimensions (77),the adaptation of a high-accuracy spectrophotometer to the ultraviolet region (145),and the application of a vidicon spectrometer to problems in clinical chemistry (169). High pressure (243) and high vacuum, high pressure, high temperature (72) spectrophotometer cells and a temperature controlled holder for square cells (245) have been described. Publications which discussed precision or errors include the results of a theoretical and experimental investigation of the factors affecting precision (196),an analysis of the effects of photometric errors in equilibrium and kinetic analyses (168), a discussion of procedures for estimating and correcting for errors due to stray light in single beam spectrophotometers ( 4 1 ) ,a description of sources of errors in spectrophotometric measurements in biochemical analysis ( 6 4 ) ,and an interlaboratory survey of the linearity and accuracy of spectrophotometers (230). Methods for measuring spectral bandwidth have been described ( I 72).
SPECTRAL STUDIES Studies of the spectra of a series of related compounds included studies on hydroxyazo dyes (219),para-substituted benzamidines (191),mono-, di-, and tri-substituted benzenes (130),para-substituted benzohydroxamic acids (216), diazines adsorbed on silica and alumina (179),styryl and benzyl derivatives of dibenzofuran (54),dicyanoesters (13), DDT-type compounds ( I ) , nitroacenaphthenes and nitro-
Rlchard A. Hummel is an associate analytical scientist in the Analytical Laborate ries at The Dow Chemical Co.. Midland, Mich. He received the B.S. degree from Iowa State College in 1949 and the M.S. from the University of Minnesota in 1951, at which time he joined The Dow Chemical Co. His fields of interest include all types of organic analysis including spectrophotometry, liquid chromatography, solution equilibria, purity of organic c o r n pounds, and thin-layer chromatography. He is a member of the ACS.
dimethylnaphthalenes (239), nucleic acid bases (102), linear sexiphenyls (105),pyrophthalones ( 5 ) ,Ypdiphenylpolyenes of all-trans configuration ( I 76), salicylaldehydes (210), N-p-tolylsulfonylsulfilimines and N-p-ethylbenzenesulfonylsulfilimines (211 ), and organic compounds with the S-Cl group (249).The chapter on “Identification and Determination of Quinones” in the book, “The Chemistry of the Quinonoid Compounds”, contains a section on the ultraviolet spectra of quinones (22). Substituent and solvent effects on the electronic spectra of p -nitrobenzyl derivatives (107) and phosphapyrimidine derivatives (193) were studied. Inorganic compounds studied include nitrosyl chloride (12),ferric chloride and mixed ferric chloridealuminum chloride vapor (215), trihalide ions ( 7 1 ) , and molybdenum(I1) and molybdenum(II1) species (30). The effect of pressure on the spectra of aromatic molecules was studied (89). The correlation between bandwidth and frequency of maximum absorption in para-substituted nitrobenzenes was examined (149).The correlation between the ultraviolet absorption spectra and the photoelectron spectra of thiocarbonyl heterocycles (83),azastilbenes (58) and spiro[4.4]nonatetraene, -triene and -diene ( 17 ) were studied. The photoacoustic spectra of compounds on thin layer plates was compared with their ultraviolet absorption spectra (195).
FAR ULTRAVIOLET STUDIES Compounds recently studied include chloroalkanes (186), aliphatic ketones (253),o-benzoquinone and p-quinones (121),stearic acid multilayers (157)and polycrystalline and amorphous films of naphthacene, pentacene and perylene (114). The spectra of organic molecules in the 200- to 120-nm region has been reviewed (201). SOLVENT AND pH EFFECTS There has been increasing interest in the effect of solvents on electronic spectra. Compounds whose spectra were studied in different solvents include nitrobenzenes (811, deuterated pyrene (158),aromatic amines (142),and diazines and related dye molecules (143).The effect of salts of alkali and alkaline earth metals on the spectra of solutions of substituted nitrobenzenes and substituted phthalimides was studied (133).Changes in the spectra of ligands such as acetone, cyclopentanone, and benzamide were used to study the solvation of alkali and alkaline earth cations (185).The blue shift of the n ?r* transition of carbonyl compounds on going to more polar solvents was discussed ( 8 5 ) .The effect of pH on the spectral properties of a phospholipase was studied (241). The book “Solutions and Solubilities” contains a chapter “Influence of Solvents on Spectroscopy” which discusses effects on ultraviolet, visible, and infrared spectra (112). The effect of solvents on electronic spectra has been reviewed (161).
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SOLUTION EQUILIBRIA Ultraviolet spectrophotometry was used to study the dissociation and, in many cases, to determine the dissociation constants, of amino-1,5- and 1,6-naphthridines (31),N,Ndialkylanilines ( 6 7 ) ,ethylbenzoylacetates (220),substituted acetanilides (75), benzimidazoles ( 9 6 ) ,and substituted oxocarbon acids (174). The effect of temperature on the ionization constants of salicylic acid was reported ( 6 1 ) .
Donald C. Kaufman is an analytical specialist in the Analytical Laboratories at The Dow Chemical Co., Midland, Mich.. where he has been since 1952. He received the B.S. degree from Juniata Coilege in 1950 and the M.S. degree from The Pennsylvania State University in 1956. His fields of interest include absorption spectrophotometry, liquid chromatography, polarography, functional group analysis, and physical property determination. He is a member of the ACS.
Thermodynamic parameters for the primary and secondary dissociations of croconic acid (207) and for the protonation of substituted pyridines and azine-N-oxides (47) were calculated from dissociation constant-temperature data. The influence of pressure on the ionization of substituted anilinium ions was investigated (90).The tautomeric equilibria of substituted 3-hydroxypyridines (144),polyhalogenopyridinethiols (106), 4,6-disubstituted pyrimidines (24), and 4-thiouracil derivatives (183) were studied. Equilibrium constants for the reaction of benzaldehyde with bisulfite and sulfite were determined (119). The equilibrium between bisulfite and pyrosulfite in aqueous solutions was studied (29).
REACTION RATES Applications of ultraviolet spectrophotometry to kinetic studies continue to be reported in significant numbers. The types of reactions followed include the hydration of pteridine (181) and 1-alkynylamines (232), the hydrolysis of tolunitrile (35) and phenyl substituted 2-methoxy-1,3dioxolanes (43), the addition of alcohols to substituted benzylideneanilines (164),the solvolysis of 5-iodocytosine ( 7 4 ) , the hydrazinolysis of methyl-p-nitrophenyl sulfate ( 3 4 ) ,the dehalogenation of halogenated uracils (194),the acylation of ascorbic acid in water (175),the reaction of cyclic anhydrides with anhydrous acetic acid (%), the ozonolysis of acetylenes (147),the aromatization of 4-carboxybenzene oxide (187),the reaction of iodate with iodide (205), the oxidation of sulfite by hydrogen peroxide (97), the complexation of copper(I1) with a variety of ligands (1901, the ligand substitution reactions of nickel and cobalt ions ( 4 2 ) , the formation of zinc salicylaldehyde Schiff Bases (141), and the reduction of americum(V1) by neptunium(V) (248). The rate of electron transfer from sodium anthracenide to cis-stilbene, leading to the isomerization of the latter, was measured (128).
THEORY AND CALCULATIONS Several publications compared calculated and experimental electronic spectra of a series of compounds. The types of compounds studied included nitroaromatics ( 7 8 ) , paracyclophenes with side chains of 5 to 10 methylene groups ( 4 ) , terphenyls and quaterphenyls ( 7 3 ) , nitrogen heterocyclic compounds (235), substituted 1,2-dithiolium cations (84),diazines, symmetrical triazine and symmetrical tetrazine (188),unsaturated boron derivatives ( 3 ) ,carbonyl compounds (51),and aliphatic and aromatic unsaturated hydrocarbons (94). Theoretical and experimental values for the blue shift of the n T* transition of acetone were compared ( 5 5 ) .The cause of the red shift in conjugated carbonyl compounds was investigated using SCF-MO calculations (109).Molecular orbital calculations were also used to aid in assignment of the electronic transitions of thiocarbonyl chloride, thioacetamide and thiourea (15), and saturated organic sulfides (21).Publications discussing the calculation of stability constants of complexes included a theoretical comparison of chromatography and spectrometry as methods for determining weak complexation constants (65), a procedure for determining the stability constant of a complex from the experimental data of a single Job curve (221),and discussion of the calculation of equilibrium constants of 1:l complexes (44). Techniques for
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applying the mole ratio method to the identification of weak complexes (45) and a computer program for the calculation of stability constants (126) were described. Published methods for the spectrophotometric determination of equilibrium constants have been reviewed (140). Other articles relating to spectrophotometric calculations include a method for resolving overlapping absorption bands ( 1 4 ) , a method for choosing optimal analytical positions in the analysis of multicomponent systems (225),and the application of orthogonal functions to multicomponent systems (237). ELUCIDATION OF S T R U C T U R E Ultraviolet spectrometry has been used to study the conformation of substituted benzophenones (82) and, together with infrared spectrometry, has been used to study the conformation of diazoketones (16).Also studied was conjugation in skipped l,.l-diynes (146) and steric inhibition of interaction between rings by the substituent in a series of substituted p-phenylacetophenones (229). The ultraviolet spectra of 1,2- and 1,3-dianilides of squaric acid were used to complement other data in structure interpretation (160). COMPLEXES Ultraviolet spectral studies of complexes of a wide variety of metals have been reported. These include complexes of gallium, indium, and tin with halides ( 5 3 ) ,gold, platinum, and palladium with halides ( 1 8 ) ,aluminum and tellurium chlorides in potassium chloride a t 300 O C (233),tin and tellurium tetrachloride with substituted anilines (33), ruthenium and osmium with halogenoammines (231),molybdenum(V) with thiomalic acid (123), the molybdenum(V) dimer with EDTA (203),copper, nickel, cobalt, and zinc with 2-hydroxy-5-nitropropiophenone( 173), niobium with catechol derivatives (159), mercury-ethylenediaminediacetic acid with various anions (I6 2 ) , palladium, copper, mercury, and silver with thioglycolic acid derivatives (180),copper, cadmium, zinc, nickel, and aluminum with pyridoxamine analogues (138),nickel, bismuth, copper, palladium, mercury, cobalt, silver, and thallium with picoline-2-aldehyde thiocarbazone (127),and vanadyl ion with iodochlorhydroxyquin and diiodohydroxyquin drugs (2). The reduction of pentammine cobalt(II1) with chromium(I1) ( 9 ) and the reduction of the tetrachloroaurate(II1) ion by triphenyl derivatives of Group V elements (197) were studied. Other complexes studied include ether with boron trifluoride and phosphorus pentafluoride (182),iodine with substituted diphenylsulfides (202), iodine with aliphatic hydrocarbons in the vapor phase (25), menadione with cetylethylmorpholinium ethosulfate (I20), phenol with electron donors (521, and indol with electron donors (212). Chlorine association with bis(p-fluoropheny1)sulfides was studied by ultraviolet spectrophotometry and I9F NMR (244). The formation of charge transfer complexes was studied as a possible measure of the fully exposed amino acid residues on the surface of proteins (95). The difficulties of studying carbon tetrabromide-aromatic interactions by ultraviolet spectrophotometry were discussed (110). An equimolar dilution method was used to determine the stability constants of stable complexes (32). Interpretation and comparison of association constants of weak complexes determined by absorption spectrometry, NMR spectrometry, and gas-liquid chromatography was discussed (137). INORGANIC ANALYSIS Many metal ions are determined by measuring the ultraviolet absorption of their complexes. Bismuth(II1) and lead(I1) were determined using diethylenetriaminepentaacetic acid (63). Chromium(II1) was complexed with EDTA and determined by difference spectrophotometry a t 208 nm ( 5 6 ) ,while cobalt was complexed with sulfosalicylic acid and measured a t 325 nm (104). The reaction of gold(II1) with dithizone was studied by ultraviolet-visible spectrophotometry (49). Molybdenum in rocks and minerals was determined as a chelate with salicylhydroxamic acid (166).Palladium was complexed with diacetylmonoxime and extracted into chloroform (170) while rhodium was 270R
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complexed with EDTA or CDTA for spectrophotometric measurement (108). Tantalum was determined as the ferron complex (213) and vanadium was complexed as VO(I1) with hexacyanoferrate (20). The effect of pH and interferences on the determination of the platinum metals was studied (234). The ultraviolet absorption of the chloro complexes of osmium, ruthenium, and rhodium (100) and tellurium (122) was used for their determination. Vanadium was also determined by oxidative coupling with a-naphthol and p-phenylenediamine (87). Photometric titration with 5-sulfosalicylic acid was used to measure beryllium (57).A differential kinetics method was used to determine a number of cations including mixtures of zinc and magnesium (117). A variety of procedures were used to determine anions. Iodine was determined indirectly by measurement of the rate of reduction of cerium(1V) by iodide (125) and was determined directly as a thiocyanate complex (46). An addition method was used for the direct determination of nitrite in the presence of a large excess of nitrate (66). Nitrate and styphnate were determined in waste water (163). Sulfate was determined indirectly using 2-aminoperimidine hydrochloride (37) and hexathionate in mixtures with thiosulfate and sulfite was determined by conversion to thiosulfate and measurement of excess iodine for the reaction with thiosulfate (118). Mercury in the environment again received considerable attention. Mercury in rocks and minerals was liberated by heating and was measured in the vapor phase after an intermediate collection step (48, 246). Mercury in air was collected on silver (204),while mercury in stack gases having a high sulfur dioxide content was collected by amalgamation with gold ( I O ) . Sulfur dioxide in stack gases was measured by a novel analyzer which processed the signals from two hollow-cathode lamps of different wavelength to yield an output signal nearly linear with concentration (27).Particulate matter could be compensated for when present. Low levels of sulfur dioxide were also determined using a rapid scanning derivative spectrophotometer (224). ORGANIC ANALYSIS A review article on the use of spectroscopic methods for the identification of organic materials included a section on the use of ultraviolet spectrophotometry ( 7 ) .Environmental samples have been analyzed by a combination of ultraviolet spectrometry and mass spectrometry (76).The solubilization of acetophenone and benzophenone in aqueous micellar solutions was studied by ultraviolet and NMR techniques (68). 8-Hydroxyquinoline derivatives were determined by reflectance spectrophotometry after separation by thin layer chromatography ( 6 ) .A procedure was described for the photometric titration of weak bases in aqueous solution (40). Crown ethers were used as catalysts to form phenacyl esters of fatty acids to enhance sensitivity following separation by liquid chromatography (62). First derivative spectra were used for the simultaneous determination of phenol and phenyl mercuric nitrate (236).An automatic spectrophotometer was used to measure organic water pollution (155). Pentachlorophenol in water was determined by a ratio method using hollow-cathode lamps as the energy source (70). The interference of carbonyl compounds in the trinitrobenzenesulfonic acid method for amino groups was studied (36).Ultraviolet measurements were used to determine microscopic polarities in the cavities of dodecylammonium propionate aggregates containing different amounts of water (69). Mannose was determined in the presence of other sugars after dehydration with sulfuric acid (209). Long chain unsaturated and hydroxy fatty acids were determined in a similar manner (254). Mercaptobenzothiazole in flotation liquors was separated by solvent extraction and measured at 329 nm (113). Polystyrene in paper was dissolved by refluxing with chloroform and measured a t two wavelengths to correct for monomer absorption (223). BIOLOGICAL ANALYSIS Biologists frequently use ultraviolet spectrophotometry for the study of enzymes and enzyme activity. The second English edition of “Methods of Enzymatic Analysis” in-
cludes several ultraviolet procedures and also contains a section on absorption photometry (23). A review on the use of UV-visible spectrophotometry for the study of proteins also included enzyme systems (59).Recently-published enzyme assay methods include ones for zanthine oxidase activity based on the formation and measurement of uric acid (93), methyltransferase activity by measuring the decrease in absorption at 265 nm after adding an excess of adenosine deaminase (252), and catechol-D-methyltransferase activity using 3,4-dihydroxyacetophenoneas substrate (28). A procedure was described for the determination of serum urate by measuring the difference in absorption at 293 nm with and without ferricyanide oxidation (153).Two new assays of pineapple stem bromelains were reported (217). An enzymatic method of increased sensitivity was described for the assay of glycerol (150) and two enzymatic methods for the determination of glucose were compared (131).Michaelis constants for the @-lactamase reaction were determined (200). Glutaraldehyde was determined by reaction with hydroxylamine or hydrazine to give a product which absorbed strongly a t 240 nm (88). The determination of phloroglucinol was studied (238). Articles on protein determination included application of derivative spectrophotometry to the determination of amino acids and proteins (139), application of programmed monitoring of a liquid chromatographic column to the determination of protein and enzyme concentrations (154), direct measurement of proteins a t 205 nm (208), and determination of RNA and DNA using cetyltrimethylammonium bromide (152).
PHARMACEUTICAL ANALYSIS Ultraviolet procedures are used extensively in pharmaceutical analysis. The recent biennial review on pharmaceuticals and related drugs listed approximately 220 references to ultraviolet spectrophotometric procedures (101). The systematic identification of unknown drugs in powder form in forensic toxicology was recently described (135). Classification was based on spectra obtained using solvents of different polarity and pH. Ultraviolet difference spectrophotometry has been applied to the assay of drugs in dosage form without prior separation (60). A difference tech-
LITERATURE CITED (1) Abou-Donia, M. B., Appl. Spectrosc., 29, 261 (1975). (2) Abu-Eittah. R., Seif El-Nasar, M. M., Amer, M. M., J. Pharm. Sci., 63, 1666 (1974). (3) Allinger. N. L., Siefert, J. H., J. Am. Chem. Soc., 97, 752 (1975). (4) Allinger. N. L., Sprague, J. T., Liljefors, T., ibid., 96, 5100 (1974). (5) Amiel, J., Bull. SOC.Chim, Fr., 1974, 2154. (6) Amin, M., Jakobs, U., Fresenius' 2. Anal. Chem., 268, 119 (1974). (7) Ayling. G. M., Appl. Spectrosc. Rev., 8, 1 (1974). (8) Baczyk, S.. Swidzinska, K., Mikrochim. Acta, 1975, I, 259. (9) Balahura, R . J., Purcell, W. L., lnorg. Chem., 14, 1469 (1975). (10) Baldeck C. M., Kaib. G. W., Crist, H. L., Anal. Chem.. 46, 1500 (1974). (11) Baldini, G., Grilli. E., Guzzi. M., Appl. Opt., 14, 2687 (1975). (12) Ballash. N. M.. Armstrong, D. A,. Spectrochim. Acta, Pari A, 30, 941 (1974). (13) Banerjee, D. K., Kasturi. T. R., Srinivansan, A,, Sharma, V. K., Rao, C. N. R., J. lndian Chem. Soc., 51, 67 (1974). (14) Barker, B. E., Fox, M. F., Hayon, E., Ross, E. W., Anal. Chem., 46, 1785 (1974). (15) Barrett, J., Deghaidy. F. S., Spectrochim. Acta, PariA, 31, 707 (1975). (16) Bassani, R., DiFuria, F., Curci, R., Spectrosc. Lett., 7, 531 (1974). (17) Batich, C.. Heilbronner, E., Rommel, E.. Semmelhack, M. F., Foos. J. S., J. Am. Chem. Soc., 96, 7662 (1974). (16) Batiste, J. L. H.,Rumfeidt, R., Can. J. Chem., 52, 174 (1974). (19) Bauguess, C. T., Fincher, J. H.,Sadik, F., Hartman, C. W.. J. Pharm. Sci., 64, 1489 (1975). (20) Bembi, R., Malik, W. U., Fresenius' 2.
nique was also used for the determination of ampicillin and cloxacillin in pharmaceutical injections (50). A procedure was reported for the determination of L-ascorbic acid and dehydro-L-ascorbic acid in vegetables (8). The spectra of theophylline in the presence of barbiturates (111) and the reaction of ozone with nicotinamide and its derivatives (156) were studied. Many determinations were based on a chemical reaction to form a suitable absorbing species. Diphenhydramine and related ethers were oxidized to products which exhibit strong absorption in the ultraviolet region (38).Amitriptyline was oxidized to anthraquinone prior to measurement (91) while hydrazine in plasma and urine was reacted with p-methoxybenzaldehyde to form the hydrazone derivative (251). An automated procedure for the assay of cefazolin employs a reaction with hydroxylamine and a double-probe sampling procedure (98). Complex formation was utilized for the determination of steroid sulfates (134), for the assay of alkaloids (226), and for the determination of ampicillin in powders and formulations (151). Extraction was utilized as a method of separation in the determination of chlorthalidone in biological fluids (228), 6-demethylgriseofulvin in urine (198), methadone in urine and tissues (92), and trichlocarban in blood (99). Thin layer chromatography was used as a method of separation in the determination of physostigmine (192), the determination of sodium penicillin G in disodium carbenicillin preparations (26), and in measuring the components of polyene macrolide antibiotic complexes (136). Partition chromatography was utilized for the separation of preservative chemicals used in cosmetic products prior to UV measurement (214) and for the determination of sodium levothyroxine or sodium liothyronine in tablets (79). A rapid column chromatographic procedure was described for the separation and determination of five antibiotics (227). Ion exchange was used in the determination of homatropine methylbromide in syrups (39).Kinetic measurements were utilized for the assay of nitric esters of antianginal drugs (250) and to study the alkaline hydrolysis of benzocaine and two homologues in the presence of a nonionic surfactant (222). Ultraviolet absorption at 245 nm was used to determine blood concentration profiles of acetaminophen (19).
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X-Ray Spectrometry L. S. Birks" and J. V. Gilfrich Naval Research Laboratory, Washington, D.C. 20375
With this review, we alter the approach from either the 1972 and 1974 reviews which concentrated exclusively on significant advances or the pre-1972 reviews which enumerated everything that had occurred in the field. This time we try to summarize the "state of the art" and point out where progress has been made or may be made eventually. In particular, the current status of instrumentation, applications, and data interpretation are described, and the various approaches are compared.
INSTRUMENTATION This section of the review is divided into two categories, namely, the commercial instrumentation for routine use and the specialized instrumentation under development. Routine Instrumentation. There are three classes of routine instruments for x-ray fluorescence analysis: a) The sequential wavelength-dispersion spectrometer in which the crystal and detector are scanned through the wavelength range and measure one element at a time; b) The multiple-crystal simultaneous wavelength dispersion instrument in which a fixed crystal and detector is set up for each of several elements (up to 24 elements in some commercial machines); c) The energy-dispersion instrument in
which a Si(Li) detector and multichannel analyzer record the photon-energy spectrum of all elements in the sample simultaneously. Sequential Spectrometer. This was and still is the "workhorse" instrument for most routine x-ray fluorescence analysis. The cost is about $40,000 for a complete instrument with usual accessories ($50,000 with a dedicated computer for data interpretation). It is the most versatile of the three x-ray instruments because crystal and detector turrets allow immediate selection of short wavelength or long wavelength range (high or low 2 ) .Thus it can readily measure any element above atomic number 5 (B). Recent improvements include new experimental values for crystal efficiency, Figure 1, and one new crystal material, InSb which is claimed to be 2 times better than EDDT for Cd La or C1 K a and 7 times better for Na or Si. The standard scintillation and gas proportional detectors have not changed much recently but there is great hope for improved resolution of the gas detector as discussed in more detail below in the section on special instrumentation. The current practice with sequential spectrometers is to use the new high wattage x-ray tubes, Cr target (up to 3000 W) to excite the long wavelengths and W target (up to 3500 ANALYTICAL CHEMISTRY, VOL. 48, NO.
5. APRIL 1976
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