(405) Koningstein, J. A,, ibid., 174, 477 (1968); Appl. Spectrosc., 22,438 (1968); Chem. Phys. Letters, 3, 303 (1969). (406) Koningstein, J. A., Toa-Ning, N., Canad. J . Chem., 47, 1395 (1969). (407) Koningstein, J. A., Mace, G., Chem. Phys. Letters, 3, 443 (1969). (408) Kiel, A., Damen, T., Porto, S. P. S., Singh, S., Varsanyi, F., Phys. Rev., 178, 1518 (1969). Stimulated, Hyper and Inverse Roman Effects
(409) Freedhoff, H. S., 47, 2554 (1967).
J. Chem. Phys.,
(410) Philpott, ibid., 49, 3558 (1968). (411) Wang, C. S., Phys. Rev., 182, 482 (1969). (412) Zubov, V. V., Kuzmina, N. P., Opt. Spektrosk., 24,634 (1968). (413) Grun, J. B., McQuillan, A. K., Stoicheff, B. P., Phys. Rev., 180, 6 1 (1969). (414) Johnson, Jr., W. D., Kaminow,
I. P., Bergman, Jr., J. G., Appl. Phys. Letters, 13, 190 (1968). (415) Bortkevich, A. V., Bobovich, Ya. S., Zh. Prikl. Spektrosk., 6 , 728 (1967).
(416) Rivoire, G., Beaudoin, J. L., J . Phvs. (Paris),29, 759 (1969). (417)”Maier, hi.,Kaiser, W., Giordmaine, J. A,, Phys. Rev., 177, 580 (1969). (418) Kurtz, S. K., Giordmaine, J. A,, Phys. Rev. Letters, 22, 192 (1969). (419) Clements, W. R. L., Stoicheff, B. P., Appl. Phys. Letters, 12, 246 (1968). (420) Decius, J., report to 1st International
Conference on Raman Spectroscopy, Ottawa, August, 1969. (421) Maker, P., ibid. (422) Stoicheff, B. P., ibid.
UIt raviolet Spectrometry Warren Crummett and Richard Hummel, Analytical laboratories, The Dow Chemical Co., Midland, Mich. 48640
T
HIS REVIEW summarizes the material which has come to the authors’ attention since the previous review (77) and covers the period from December 1967 to December 1969. Papers are selected for their application t o the practice of analytical chemistry. The criteria for this selection are cited under the appropriate headings.
regions, Kovner and Potapov (228) the electronic spectra of aromatic six-membered azacyclic compounds, Nurmukhametov (293) the electronic spectra of N-heteroaromatic compounds and their derivatives, and Eisdorfer, Warren, and Zarembo (107) amines of pharmaceutical interest. COLLECTIONS OF SPECTRA AND INDICES
BOOKS AND REVIEWS
I n their book entitled “Organic Structure Determination,” Pasto and Johnson (304) present a short introduction to ultraviolet spectrometry which is adequate for course work on the subject, Stearns (358) deals with the interpretation and use of spectral data in his book, “The Practice of Absorption Spectrophotometry.” The use and care of spectrophotometers and cells are considered in detail b y Edisbury (103) in “Practical Hints on Absorption Spectrometry.” A chapter b y Duncan, Matsen, and Scott (99) in “Technique of Organic Chemistry,” Vol. IX, surveys the field of molecular spectra, the theory of electronic spectra, and the interpretation of electronic absorption spectra. I n a chapter in “Visible and Ultraviolet Spectroscopy,” Hare (267) discusses the theory and applications of this approach to the structure of chelates emphasizing crystal field theory and its extensionligand field theory. Flammang (127) reviewed the applications of ultraviolet and visible spectrophotometry, Clementi (68) the electronic structure in aromatic compounds, RIerer and RIulliken (269) the ultraviolet spectra of ethylene and its alkyl derivatives, Milazzo and Cecchetti (274) optics and instruments used in vacuum ultraviolet spectroscopy, -4gashkin and Lyuts (2) the spectra of organic molecules in the far and vacuum ultraviolet
The Sadtler collection of ultraviolet spectra now numbers 28,000 spectra (335), u p 6000 since the last review. A 300 spectra collection of commonly used agricultural chemicals is also available. The publication of Volume V of “Organic Electronic Spectral Data” (309) brings this collection to more than
100,000. Four more volumes of “Absorption Spectra in the Ultraviolet and Visible Region” (236-239) have appeared. This makes a total of 2065 spectral curves and data published by Lang in eleven volumes. An index ($40)for the first 10 volumes has also been published. APPARATUS
The number of commercially available ultraviolet-visible spectrophotometers has increased dramatically. An excellent list has been compiled b y Industrial Research (188), Specifications are listed, but some of the most important ones such as photometric accuracy and photometric reproducibility are ignored. Considerable interest exists in the use of ultraviolet absorbance detectors for monitoring the effluent from liquid chromatography columns. Kirkland (217) described a detector consisting of a photometric analyzer fitted with a 1-cm flow through cell with a 7 . 5 ~ 1volume with a sensitivity of 0.01 absorbance
unit full scale a t 254 mp and a noise less than *0.0002 absorbance unit. Uziel and coworkers (380) devised a cation exchange chromatography-ultraviolet spectrophotometric monitoring device which separates nucleosides and related bases and assays the separated materials. Several special types of spectrophotometers were developed. Pimentel (311) reviewed rapid scan spectroscopy and lists instrument performance data. Wolken and coworkers (405) describe a recording microspectrophotometer which can obtain the absorption spectra of particles as small as 0.5-micron diameter, whereas a similar one described by Wetzel and coworkers (400) can measure the absorbance of particles with 1micron diameters. Klein and Ilratz (222) discuss derivative spectroscopy with recording spectrophotometers. Nihei and coworkers (286) describe a ratio-recording vacuum ultraviolet spectrometer in which rotating cells are used instead of beam splitting. Whittick and coworkers (402) summarize work on ultraviolet spectroscopy emphasizing instruments and techniques developed for the space program with special emphasis on life-detection techniques. Reule (326) used a supplementary light method to test the nonlinearity of the photometric scale of spectrophotometers. Considerable work was reported on the temperature control of cells and cell compartments. Feil and coworkers (121) describe a jacketed cell holder. Aurich (17) describes a low temperature cell for Cary Model 14 and 15 spectrophotometers, while Coe and Slaney (69) present a similar one for the Unicam SP500. Root (329) describes a high temperature cell for the Cary Model 14R spectrophotometer, as do Boston and Smith (41).
ANALYTICAL CHEMISTRY, VOL. 42, NO. 5 , APRIL 1970
239R
SPECTRAL STUDIES OF CLASSES OF COMPOUNDS
A growing body of ultraviolet spectral data is found as a part of the physical data presented when new compounds are synthesized. Since the data are given for compounds representative of classes, they are often useful to analytical chemists. Tables consisting of more than 20 compounds and of interest include substituted azines (108), ureidohydrofurans and related pyrimidones (52), ring-opened analogs of cyclopropylpyridines (155) 4-hydroxy-6-phenylpyrazols [3,4d]pyrimidines (20) 6aryl-7-aminopteridines (397), 2,4,7-triamino 6-heteroarylpteridines (398), derivatives of naphth[2,3-d]imidazole4,g-dione (105), spirobipyranes (341), pyrazolo- [4,3-6] [l14]-thiazine condensed ring systems (162), pyrazolo(4,3-g-]-pteridines and derivatives (161), AT-substituted derivatives of 2-benzothiazolinethione (357), phosphinimines (382), substituted-s-trizaolo [4,3-a] pyrazines and -quinoxalines (315), alkyl6-(4carboxybutylthio) purines (227), benzimidazole derivatives (206), quinoxaline derivatives (296), 8-azapurines ( 6 ) , ketimines (9), pteridines, pyrimidines] and isoalloxazines ( % I ) , substituted pyridones, pyridines, and pyridinethiones (45), pyrrolizidine alkaloids (350), derivatives of phenothiazine (229), o-acylphenols (%I), p-acylphenols (260),stilben and styryl derivatives (347), derivatives of glyoxal bisarylhydrazones (109) nitrophenylhydra(921), 3,4-dihydrocoumarins zones (386), 4-hydroxycoumarins (267), aromatic aldehydes and acetophenones (82), and disubstituted 1,4-benzoquinone-4-oximes (289). A great many studies were made on series of chemical compounds with a view to discovering new properties or predicting the spectral behavior of similar compounds. Some of these studies are of special interest to analytical chemists. Among the series are derivatives of phenylurea and s-phenylurea (163), 2,Pdiaminopyrimidines (SSO), vic-oxime imines (362), derivatives of benzonitrile N-oxide (408) substituted porphines (976), derivatives of pyridine (230), a-methyl and a-phenyl substituted 2- and 4-styrylpyridines (136), cyclopropyl aromatic systems (165), free allyl radical and some of its simple derivatives (51), cyclopropyl olefins and simple olefins (171), p-disubstituted benzene compounds with two substituent groups of opposite electrical properties (302), derivatives of bicyclo [3.2.2] nona-3, 6-dien-2-one (192), metal hexacarbonyls (29), diaminetetracarbonyl complexes of Cr, Mo, and W (337), tetraphenyl- and triphenylmethylarsonium salts (249), esters and arylides of anisic acids (385), monohalogenated anthracenes (298), isomeric naphtho240R
benzothiophenes and benzofurans (63), p-substituted phenols with o-methoxyl groups (16), ethoxycarbonyl derivatives of phenols and hydroxypyridines (243) I triphenylboroxines and corresponding boronic acids (338), p-aminobenzoic acid drugs (2829, phenothiazine drugs (&?I), N-aryl lactams (256), alkylaminos-triazines (396), I-phenyl-A2-pyrazolines (379), acids and esters of Aa-cyclohexene and A4-octalineseries ( l a ) ,monosubstituted benzene derivatives (346), acetyl and aroyl benzo (b) thiophenes (120), substituted naphthalenes (248), acetyl and benzoyl carbonyl compounds (410), substituted bicyclo (3.1.0)hex-3en-sones (129), a,p-unsaturated ketones (170),a-silyl and a-germy1 ketones (S), acyl diphenylamines (190), a-mercapto and a-alkoxyacetic (275), lactams with ring sizes to 13 (60), coumarins and cinnamic acids (268), benzene-trans-diazosulfonates (383) substituted benzhydrols (324), methoxy-substituted benzenediazonium cations (lis), arenediazothiolates (384), perhaloaromatic organosilicons (166), and titanium phenoxy compounds (94). Difference spectra of many proteins containing tryptophan (10) were studied with emphasis on the extremum a t 300 mp, the behavior of which (11) gave information about the electrostatic environment of tryptophyl residues. The effect of various substitutions on the ultraviolet spectra of cyclopropylacrylic esters was examined (202) and shifts in absorption maxima were observed ranging from a bathochromic effect of 29 mp to a hypsochromic effect of 3 mp. Other studies include the effect of alkyl groups in various positions on the spectra of acetyl-2-biphenyls and alkoxy1 (a-fury1)-sacetophenones (928), the steric effects in tetrasubstituted hydrazones (1879, phenacyl bromides as chromophoric reagents for a-chymotrypsin (348), the cationic species in sodium molybdate (233), the effects of composition and temperature on the first ultraviolet band of the nitrate ion in molten mixtures of alkali metal nitrites (40), the difference in the spectra of cis and trans isomers of the ethers of 3-hydroxy-2-aryl propane nitriles (54), the effects of the ClHg- and CIHgCH2- groups on the spectra of aromatic nitro compounds (345), identification of chemical types in ethanol solutions of cadmium iodide (139), and the effect of crowding on the ultraviolet spectra of N-alkyl and poly-N-alkyl derivatives of 113-diamino-2,4,6-trinitrobenzene (276). Unusual findings include a study of the decrease in absorptivity with increasing concentrations of some derivatives of isoxazole (23), and a possible correlation between biological activity and the electronic spectra of 10H-dibenzo[1,4]thirq1hosphorins and related compounds (403).
ANALYTICAL CHEMISTRY, VOL. 42, NO. 5, APRIL 1970
ADSORBED MOLECULES AND CRYSTALS
A new technique was described to measure the absorption spectra of molecules adsorbed on metals. It was used to measure the spectra of acetylacetone on iron and nickel (221), p-diketones on various metals (218), quinolinol on metal films (219), and pyridine and 2,2'-bipyridyl on evaporated metal films (220). The reflectance spectrum of charge transfer complexes (hexamethylbenzene-trinitrobenzene) adsorbed on sodium chloride and silicon dioxide (49) was recorded. The polarized absorption spectrum of a single crystal of aspirin was determined (381). The intensities of the eight ultraviolet absorption bands of nickel(I1) in cubic perovskite fluorides were found to be directly related tothe number of nearest neighbor nickel ions per nickel ion (122). VACUUM ULTRAVIOLET SPECTRAL DATA
Four new electronic states of oxygen have been identified ( 7 ) . Rydberg transitions of ethylene have been examined in detail (270). Also studied were the first eight normal paraffin hydrocarbons (250), 1,l-dichloroethylene (393), trichloroethylene (392), cis-l,2dichloroethylene (391), aliphatic ketones (191), and the NO molecule (205). SOLVENT, TEMPERATURE, AND pH EFFECTS
The effects of solvents on the intensities of the ultraviolet spectra of ketones and nitroparaffins (28), diazine (244), and a-enones (36) were studied. Spectral shifts of polar molecules in polarnonpolar solvent mixtures were shown to be excessive (272). The effect of solvents on the spectra of thioamides (154), and anhydro salts derived from azacarbazoles and their nitro derivatives (340) was observed. Other solvent studies include their effect on the intensity of a forbidden electronic transition (27) and on anion structure (916). The change in the spectra of dimethyl-3,6dichloro - 2 , s - dihydroxyterephthalate was found to be due to three species in a solvent-dependent equilibrium (80). A study was made of the purification of solvents for ultraviolet spectrophotometry (176) and precautions necessary for the use of tetrahydrofuran in the ultraviolet analysis of gel permeation chromatographic effluents (147). Changes in the spectra of polyoxylonitrile on treatment with acid and base were explained (42). The effect of p H on the spectra of the perchlorates of thieno [2,3-b]and thieno [3,2-6]thiapyrylium (go), and molybdenum (VI) (26) was examined and the effect of temperature on the ultraviolet spectra of aqueous solutions of nitrophenols and nitrophenoxides (411) was studied.
SOLUTION EQUILIBRIA
Ultraviolet spectrophotometry is still being used extensively for measuring fundamental properties of absorbing species in solution. These properties include ionization, association, dissociation, hydrolysis, and formation constants, tautomeric equilibria, and transformation. Studies were reported on the tautomerism of dimeric 3-methylisoazolo-5one (287), 6-methoxy echibolin and its N-methyl derivatives (133), 3-thianaphthenone (333),thiazolidinic heterocycles (148), and 5-phenyl-2-amino-4selenazolinones (149). -4kinetic method for determining acid dissociation constants in methanol was reported in which the rate of reaction of thiolenoxide ion with 2,4dinitrofluorobenezene is measured (49). The protonation of water, alcohols, and diethyl ether was measured in acetonitrile by observing the effect on the spectrum of dibromothymolbenzein (224). Also studied was the protonation of aromatic sulfoxides in aqueous sulfuric acid (262) and the bisazo derivatives of chromotropic acid (339). Other equilibrium studies of interest include that between bis(salicylaldoximate)nickel(III) and cycloimine bases (327), cysteine and glutathione in reducing selenocystine to selenocysteine (93), and the hydration and protonation of formaldehyde (349). Ionization constants were reported for monoxides and dioxides of p-methylaminoazobenzene ( I 10), >acetylpyridine (292), 2-substituted uracils (178), and the pyridinium ion a t ionic strength 10-4M over the range of 5’ to 50°C (156). Other studies of interest include the measurement of the ultraviolet absorbance of aqueous thallium chloride solutions in mixture with other electrolytes a t 244 mp in order to calculate association constants (254), the effect of substituents on the equilibrium between N-substituted quinolinium ions and their pseudo-bases (71),and the effect of substituents on the cis-trans equilibrium of stilbene (146). The vapor phase equilibrium 21& 1 4 was the subject of an unusual ultraviolet absorption investigation (363). REACTION MECHANISMS
Attempts were made to correlate reactivity to ultraviolet absorption spectra. Substituted styrene monomers polymerize more rapidly as their absorption maxima shift to longer wavelengths (61). Vinyl-heterocylic monomers were also studied (62). The reaction of many materials can be followed by their ultraviolet spectra. The reaction of polystyrene, poly(amethylstyrene), and potassium cumyl carbanions with poly(2-vinylpyridine)
(l28), arylsulfinates with N,N-dialkylquinone diimines (I.%), selenious acid with cysteine, 2-mercaptoethanol, glutathione, or coenzyme A (138), amino acids and related amines with pyridoxal in methanol (264), and divalent transition metal ions with pyridoxal (265) were studied. The unusual chemical properties of phenyldiazene, including reaction with itself, 1,4benzoquinone, hydroxide ion, and diazene (184) were followed by ultraviolet absorption measurements. Studies of the interaction of large molecules is becoming increasingly important in biochemistry. Ultraviolet spectrometry often makes significant contributions to this field. Examples are: the catalytic action of the N oxides of pyridoxal, pyridoxamine, and their 5’-phosphates on both nonenzymatic and enzymatic systems (134), the binding of benzamidine and protons to trypsin (102), and the interaction of aromatic hydrocarbons with deoxyribonucleoprotein (223). Ultraviolet spectra are often used to show decomposition, degradation, or hydrolysis. The decomposition of allyl isothiocyanate in aqueous solution was followed in the production of a garlic-like odor (210). Difference spectra revealed that both tyrosine and tryptophan groups are exposed when glycinin is treated with urea and with acid (56). Spectra of naphthoxazolium iodides were similar to the corresponding hydrolyzed products, indicating ring cleavage (144). Absorbance a t 310 to 350 mp increased continuously, showing the release of p-nitrophenyl phosphate from deoxythymidine 5’phosphate by hydrolysis by staphylococcal nuclease (78). The hydration of a-nitrocrotonic ester was shown t o produce nitroacetic acid and acetaldehyde at p H 4 (31). Ring closure of N-formylcysteine (387)and the formation of the thiazoline ring in pantetheine (200) were studied. Isomerization mechanisms studied include the base-catalyzed isomerization of substituted 1,8-diphenylocta-3,5-diynes (185) and the catalytic cis-trans isomerization of planar diacidodiamminopalladium (11)complexes (57). Reaction intermediates are often shown to be present when reactions occur in aqueous systems. Interesting examples are the hydrolysis of phthalic anhydride (I18) and 2-(substituted phenyl)-3-ethyloxazolidines (125). REACTION RATES
The rate of hydrolysis of an aliphatic ester can be determined spectrophotometrically a t 204 mp because its molar absorptivity is greater than that of its corresponding acid (332). The rate of hydrolysis of p-nitrophenyl esters of leucine, glycine, and p-phenylalanine
was measured by means of the isosbestic point between the free phenol and its anion a t 315 mp (169). Other hydrolysis rates of interest include allyl esters (271), benzamides and salicylamides (226), halonitropyridines (323), citric acid anhydride (325), aliphatic aldehydes (313), organic phosphates (252),pbenzoquinone monoimine (73), croton aldehyde (367), nitroammine cobalt (111) complexes (59), and ruthenium (111) ethylenediamine (44). The rates of various reactions were studied by ultraviolet spectrophotometry. Some of the best of these are: various piperidines with fluoronitrobenzenes (310), p-benzoquinone with ferrous chloride (87), propionic anhydride with 2-dimethylaminethanethiol (186), alkyl hydroperoxides and tetranitromethane ( 3 3 3 , hesamethylborazolchromtricarbonyl with phosphites (88), pyridoxal with glycine and glycinaniide (266),sodium hydroxide with iodopentamminecobalt(II1) (85),and sodium ethoxide with 4-nitroquinoline-1-oside (299). The use of the ultraviolet spectrophotometric approach extends to the rate of sulfonation of fluorobenzenes (226), the chlorination of butylamine with tertbutylhypochlorite (SO), the nitration of cinnoline and 2-methylcinnolinium perchlorate (278). The rate of decarbosylation of 4-aminobenzoic acids (253), the dehydration of streptovitacin A (291), the acid degradation of aldopentoses to furfural (141), the thermal decomposition of p-and m-substituted benzenediazonium salts (342), the oxidation of nitrosophenol to phenol with dilute nitric acid (295), and the reduction of duBr4- by sulfite and thiocyanate (212 ) . Ultraviolet spectrophotometry was used to follow the rate of solvolysis of &substituted uridines (142) and 2-carbamoylphenyl mesitoate (374), the isomerization of anthrone to anthranol (361), and the formation of sugar osimes (273). The regulation of the kinetic and equilibrium properties of acyl glyceraldehyde 3-phosphate dehydrogenase by coenzyme (255) was studied. Rates of dissolution of polymorphic forms of chloramphenicol palmitate and niefenamic acid (4)were determined. THEORY AND CALCULATIONS
There have been many articles on calculation of the electronic spectra of compounds, but most of these are an extension of the use of previously described parameters. Almost all of them compare calculated results with experimental data. Examples of the types of calculations reported are calculation of the spectra of over 20 single-ring heterocyclic compounds by the Pariser-ParrPople method, using one parameteriza-
ANALYTICAL CHEMISTRY, VOL. 42, NO. 5, APRIL 1970
241 R
tion for different typesof molecules calculation of the spectra of 42 heterocyclic compounds (116), 11 sulfur-heterocyclic compounds (114), 12 aromatic amine oxides (407‘1, and the 12 chlorobenzenes (58) by a Pariser-Parr-Pople type calculation, interpretation of the spectrum of six mercaptobenzenes using the Pariser-Parr-Pople method (115), calculation of the spectra of saturated and unsaturated aldehydes and ketones using a method which made allowances for the inductive effect of alkyl groups ( 8 ) ,use of a modification of the AdamsMiller S C F method which included a variable bond order procedure for situations in which molecular geometry is unknown with application of the method to 20 hydrocarbons (396),investigation of the electronic transitions of conjugal ed carbonyl compounds by the molecules-in-molecules method (1O4), calculation of the electronic spectra of indolizine and 12 of its aza derivatives b y the SCFNO-CI method (135), calculation of the spectra of 14 P-aminovinyl carbonyl compounds using Huckel’s approximation (131), and calculation of the spectra of nitrate, nitrite, and cyanide ions by a modified CNDO method (172). A modification of the Pariser-Parr-Pople method has been described (92). A review of the r-electron approximations compares the different approximations and the choices of parameters (203). Other articles relating to ultraviolet spectrophotometric calculations include a description of 22 modular computer programs for performing basic numerical computations of absorption spectrometry ( d o l ) ,a simplified application of the Kubelka-Munk theory to absorption spectrophotometry to facilitate interpretationof theoutput of logconverterswhen considerable scattering is present (I32), use of ultraviolet spectrophotometric data to calculate the molecular masses of inner-complex compounds (263), and description of a system for determining the position of tautomeric equilibrium solely from ultraviolet or infrared data (111). ELUCIDATION OF STRUCTURE
Ultraviolet spectral data are occasionally used to aid in structure determinations. The location of tyrosyl and tryptophyl groups in proteins (174) and in pepsin, rabbit muscle aldolase, and serum (175) has been studied using such data. By spectrophotometric titration at 295 mp five of 25 tyrosyl residues per mole of the protein enterotoxin C were deduced to be “free,” while the other 16 are embedded in the interior (39). Spectrophotometric titration at 295 mp was also used to identify “exposed” and “buried” tyrosine residues in subtilisins (259). Also, changes in the ultraviolet absorption produced by alteration of 242 R
protein conformation were studied (96). The difference spectra of 1-tryptophan and 1-glutamic acid copolymers at p H 4.68 us. p H 7.60 show specific bands a t 292 and 234 mp due to formation of the a-helix in the polypeptide (297). A bathochromic shift in the thyroxine spectrum of human serum albumin was used as proof that the principal binding site is in the region of the amino terminus (377). Thirty-four di-, tri-, and tetranucleotideswere examinedat p H 1,7, and 12 and the spectrophotometric constants calculated by computer (372). The angle of twist of substituents from planarity has been estimated from spectral data for the nitro groups on 2,4,6-trinitroaniline (208) and for a phenyl or naphthyl group in hydrocarbons (371). Spectral shifts in the presence of certain additives were used to locate the hydroxyl groups on xanthones (247). The ultraviolet absorptions of cyclic multisulfur compounds a t the higher wavelengths have been interpreted as due to d-orbital interactions between nonbonded sulfur atoms (404). Spectral data were used to help establish the structure of macromolecular polyradicals of the diphenyl nitrogen oxide type (97‘)and the structure of the tautomeric imido and amido forms of chloroacetyla-chloropropionyl-2-aminothiaand zoles (74). Phenyldiazene structure was proved b y its spectra and the spectra of phenylhydrazine obtained on reduction (183). The structure of the products obtained on ether cleavage of dimethoxydihydro-4 (1H)-isoquinolones was ascertained using their spectra (159). The origin of the spectrum of styrene and its dimers in 98yo sulfuric acid was elucidated (34). COMPLEXES
The number of articles reporting on the investigation of complexes by ultraviolet spectrophotometry is increasing, but the complexes investigated are becoming more exotic and of less potential use in analysis. Studies on metal complexes of possible interest include fluoro complexes of vanadium(V) (193) and molybdenum (VI) (209), tellurium( IV) with hydrochloric acid ( 3 4 4 , iron(II1) with sodium triphosphate ( I S ) , iron(II1) chloro complexes in dimethylformamidestyrene (83), complex formation by iron(II1) chloride and ammonia in an alcohol-dioxane mixture (317 ) , peroxide complexes of niobium(V) and tantalum (V) in sulfuric acid (65), complexes of uranium(1V) and plutonium(1V) with chloride and oxygen containing ligands (316),nickel P-ketoenolates (117),complexes of copper(I1) with carboxylic acids (SZO), complexes of copper(I1) and the uranyl ion with thioglycolic acid and pyruvic acid (S19), N-salicylideneglycinato complexes with manganese(II), nickel(II), copper(II), and zinc ( U S ) ,
ANALYTICAL CHEMISTRY, VOL. 42, NO. 5, APRIL 1970
ethyl xanthate complexes with cadmium, zinc, nickel(II), and cobalt(I1) (284), a complex of maltol with the uranyl ion (66), the silver(1) perchlorate-pyridinecomplex (25),mercury(I1)cyanide-iodide complexes (70), mixed chlorothiocyanato complexes of palladium(I1) (37), the copper(II)-5-chloro8-hydroxyquinoline-7-sulfonate complex (21), selenocyanato complexes of thorium in acetone and dimethylformamide (151), chromate in sulfuric acid (257), platinum(1V)-dinitroethylenediamine complexes (64), gallium(II1) ethylenediaminetetraacetic acid (63), diethylenetriaminepentaacetic acid with gadolinium(II1) and lutetium(II1) ( 2 3 4 , and triethylenetetraminehexaacetic acid with cerium(II1) and (IV) (164). A generalization of the method of proportional absorbances and application to the determination of the complex composition A,B, was described (48). I n many of the above studies nltraviolet spectrophotometric data were used to calculate stability constants as well as composition. Other types of studies on complexes include investigation polymerization of titanium (IV) in chloride solutions (283), determination of the relative stability of eight metal ions bound with conalbumin (364), investigation of a ribonuclease .&-inhibitor complex (189), a study of the antihistamine properties of thyrocalcitonin through complexes (359), comparison of charge-transfer complexes in solution and in the gas phase (232),a study of the hypsochromic shift of the spectra of phenylglyoxylic acid in polar solvents (I79),interaction of some polar solvents with chloranil in carbon tetrachloride (353),and the determination of the energies of formation of complexes of benzoic acid with ethers by measuring changes in absorbance with temperature (101). Other investigations include pyridine addition compounds (173), complexes of sulfur dioxide with polar compounds ( I O O ) , amides with nitrobenzenes and benzaldehyde (38), halogenated aromatic amines with dinitrobenzenes (378),nitric acid with acetic (146), and iodine in hydrocarbon solvents (604). i l n empirical method for obtaining dissociation energies of iodine complexes was described (231). A description of the ultraviolet spectrophotometric method was included in an article on methods of studying hydrogen bonding in nonaqueous systems (177). INORGANIC ANALYSIS
The main application of ultraviolet spectrophotometry to inorganic analysis continues to be the determination of metals as complexes. Cadmium, cobalt, bismuth, and molybdenum complexes with pyrrolidinedithiocarbamate have been measured in the 260- to 390mp range after extraction (207). Cobalt has also been extracted as the 2,2-
dipyridylketoxime complex and measured a t 388 mp (180). Titanium in iron and steel was determined by measuring its reaction product with diantipyrylmethane a t 390 mp (72) and titanium in steels, thoria, and silicate rocks was determined by extracting the gallic acid complex with a toluene solution of isooctylamine and measuring a t 390 mp (15). Chromium was determined by measuring the peroxychromic acid-2,2’ -bipyridyl complex in ethyl acetate a t 308 mp (303). Selenium(1V) has been determined a t 370 mp as a complex with 2-mercaptobenzothiazole in strong hydrochloric acid (33) and a t 345 mp as a complex with cyclohexanone (76). Palladium in titanium-base alloys was determined by extraction of a complex with dimethylglyoxime and measurement a t 380 mp (86) and palladium in solutions was determined by precipitation with 2,1, 3-benzoselenadiazole and measurement of the decrease in absorbance a t 330 mp (50). Europium oxide can be determined in the presence of other rare earths by measuring its complex with dimethylformamide in hydrochloric acid solution a t 272 mp (319). Rare earths have been determined by extraction of a double complex compound of calcium and rare earth with 8-hydroxyquinoline and measurement at 380 mp (215). The uranyl ion has been determined by extraction of a complex with l-pyrrolidinecarbodithioate and measurement a t 385 mp (375). Vanadium was determined by measuring the absorbance of molybdovanadophosphoric acid at 323 mp (195) and by measuring molybdate from molybdovanadophosphoric acid at 228 mp (194). The ultraviolet spectra of germanium dioxide in sulfuric acid solutions has been reported (412). Cobalt has also been determined by its catalytic effect on the rate of oxidation of tiron by hydrogen peroxide, measuring the oxidation product a t 336 mp (235). An automatic method for the determination of potassium was described which involved precipitation with sodium tetraphenylborate and measurement of the excess at 254 mp (352). Phosphorus was determined by extraction as molybdoranadophosphoric acid and measurement at 308 mp (196). Silica in natural silicates was determined by measurement of p-molybdosilicic acid a t 370 mp (241). Sulfate was determined by measuring the ferric sulfate complex in the 325- to 360-mp region (150). Hydrogen peroxide and peroxysulfuric acids in mixtures were determined using ceric sulfate and ferrous sulfate as reagents (258). Oxygen in gases was determined by conversion to ozone and measurement a t 253.7 mp (211). An ultraviolet monitoring systern for nitric oxide in exhaust gases was described (351).
ORGANIC ANALYSIS
A few of the procedures reported for the determination of organic compounds did not require a separation step before the ultraviolet spectrophotometric measurement: determination of Imidan insecticide in animal dips and sprays (81), determination of diquat herbicide in formulations which was studied collaboratively (65), determination of styrene and ethyl benzene in air by absorption in isooctane for measurement (409), determination of a-methyl styrene and cumene simultaneously using a calibration diagram (%), determination of 0- and p-hydroxybenzoic acid and phenol in mixtures b y measurement a t three wavelengths (24), determination of 2,2-dicinchonic acid in a study of its compounds with metals (157), and determination of the amount of grafted l-phthalirnid0-1~3-butadiene on polypropylene fiber by measuring the spectra of a thin film (366). Extraction was used as a method of separation before ultraviolet spectrophotometric measurement in the determination of biphenyl in citrus fruits (399), determination of mustard oils in plant material (242), determination of caffeine in tea which was studied collaboratively (285), determination of caffeine in soluble coffee and drug combinations (124), determination of benzoic acid or sorbic acid in fruit beverages (137), and determination of ascorbic acid, chlorogenic acid, and catechins in apples (91). A method for determining ascorbic acid using a hydrochloric acid-potassium chloride buffer solution has also been reported (294). Phenolic stabilizers in polymeric materials have been identified and determined by ultraviolet spectrophotometry after extraction (334). The perfume content of soaps was calculated from the spectra of extracts (214). Dinobuton, an alkyl dinitrocarbonate, was extracted and then hydrolyzed for spectrophotometric measurement (76). Procedures using chromatographic methods of separation include the detection of 4-methylpyrene and pyrene in fractions of airborne polycylic hydrocarbons (370), determination of polynuclear hydrocarbons using an ultraviolet monitor after separation by liquid-liquid chromatography (198), determination of nicotinic acid in the presence of nicotinamide using a polyamide column (245), determination of melamine, ammeline, ammelide, and cyanuric acid after separation by ion exchange chromatography (18), and determination of coumarins and furocoumarins in essential oils using separation b y thin-layer chromatography and recovery from the plate (67). A collaborative study of the determination of sulfoxide in formulations using a silicic acid column was reported (168).
Triazine herbicides separated by thinlayer chromatography were measured by ultraviolet reflectance spectroscopy and established absorption methods (130). trans-Aconitic acid, a plant metabolite, was separated by paper chromatography and eluted for measurement (277). The same technique was used to determine individual polyphenols in tea (35). Several methods using a chemical reaction to form a compound suitable for ultraviolet spectrophotometric measurement were reported. Succinimide was assayed by measurement as N hydroxysuccinimide (290), mixtures of glucose, fructose, and sucrose were analyzed by measuring hydroxymethylfurfural produced under various conditions (143), vic-diols and specifically tartrate in the presence of citrate were oxidized by periodate and the iodate formed measured as triiodide by adding iodide (288), primary and secondary amines were acylated with trans-cinnamic anhydride, then extracted and measured (181), tyramine was made to react with 4’-nitroazobenzene-(4)-carboxylic acid chloride (365), keto acids were made to react with 3-methyl-2benzothiazolone (356), oximes were made to react with p-nitrobenzaldehyde (199), and isothiocyanates and oxazolidinethiones in digests of seed meals were measured after conversion of the isothiocyanates to thioureas (14 ) . BIOLOGICAL A N D PHARMACEUTICAL ANALYSIS
Many applications of ultraviolet spectrophotometry to biological analysis continue to be reported. Among these are a method for elution and ultraviolet spectrophotometric measurement of phenylthiohydantoin derivatives of amino acids (355), determination of protein concentration without interference from nucleic acid by using wavelengths between 224 and 240 mp (160), determination of peptides after reaction with glyoxal or methylglyoxal ($07), determination of peroxidized polyenoic fatty acids in rat lung lipids after exposure to trace levels of nitrogen dioxide by measurement a t 230 t o 235 mp (369), measurement of the rate of return of monoamine oxidase activity after inhibition by adding a benzylamine hydrochloride and measuring the appearance of the corresponding benzaldehyde ( I l a ) , assay of leucine aminotransferase by measuring the 2,4-dinitrophenylhydrazones of the keto acids produced by transamination (322),and the determination of ribose and deo oxy-^ribose by measuring the chromophore produced by heating with acid (140). The following determinations of compounds in biological media were reported: direct measurement of pmethoxycinnamate in serum at 308 mp
ANALYTICAL CHEMISTRY, VOL. 42, NO. 5, APRIL 1970
243 R
(406), dihydroxypropyltheophylline in plasma by extraction and measurement at 268 mp (98),pemoline and mandelic acid in biological fluids by oxidation to benzaldehyde for measurement (79), phenaglycodol, a tranquilizer, in body fluids and tissues by oxidation to a carbonyl derivative and formation of a semicarbazone (Sag), phenylbutazone by extraction and oxidation to azobenzene (390), diphenylhydantoin by extraction after alkaline permanganate digestion of the sample (388), anisotropine methylbromide in urine b y measurement after extraction (308), and 2-dimethylamino-3’,4’-dihydroxyacetophenone hydrochloride in biological fluids after separation b y ion exchange chromatography (46) Thin-layer chromatography was used as a separation method in the ultraviolet spectrophotometric determination of sultiam in serum and urine (300), determination of 5-(p-hydroxyphenyl)-5-phenylhydantoin in urine (301)) determination of amitriptyline and its metabolites in urine, blood, and tissue (280), and determination of metabolites of trifluoperazine in rat urine (182). Ultraviolet spectrophotometry was used to show the presence of monaquinones, Zpolyphenylphenols, and ubiquinones in bacteria after separations using column and thin-layer chromatography (401). I n a study of the detection and determination of phenothiazine drugs in urine it was found that most could be recovered by distillation and recognized by their ultraviolet spectra (373). Among the applications of ultraviolet spectrophotometry to pharmaceutical analysis are a direct determination of niacin in drug mixtures (106), determination of morphine in paregoric using extraction (360) and partition chromatographic (354) separation, determination of strychnine in commercial bait formulations b y extraction and calculation from the difference in absorbance a t 254 and 287 mp (394), determination of tetracycline hydrochloride in the presence of anhydrotetracycline and epianhydrotetracycline by an absorbance ratio technique (306), determination of salicylamide, acetaminophen, and caffeine in mixtures by direct measurement of absorbances a t different p H values (343),determination of droperidol, a tranquilizer, in the presence of fentanyl using extraction (197), determination of mephobarbital and diphenylhydantoin in tablets after chromatographic separation (96),determination of acetaminophen, phenylephrine hydrochloride, codeine phosphate, and pyrilamine maleate in tablets after partial separation by ion exchange chromatography (89), determination of allopurino after separation from alkaline decomposition products by ion exchange chromatography (158), determination of carbinoxamine maleate after separaI
244R
tion from other drugs using a carboxymethylcellulose column (279), determination of phenylephrine hydrochloride after separation from other drugs by partition chromatography (314), d e termination of chlorpheniramine in the presence of other drugs after separation b y partition chromatography (318), and analysis of anovulatory formulations for gestogens using separation b y extraction (213) and for progestins and estrogens using separation b y gel filtration (183). Single tablets of isoxsuprine hydrochloride were assayed using an automatic analyzer system (47). Thin-layer chromatographic separation was used in the assay of diamorphine injection solutions (84) and the separation of noscapine and papaverine from impurities and other alkaloids (119). Methotrexate samples were assayed using a paper chromatographic technique (22). Conjugated ketosteroids in pharmaceutical preparations were determined by measuring the decrease in absorbance on reduction of the C-3 carbonyl group with sodium borohydride (152). Ultraviolet spectrophotometry was used to study the solubilization of some steroids in solutions of a steroidal nonionic surfactant (368). A proposal was made to use the ratio of orthogonal function coefficients instead of extinction ratios as an index of drug purity ( 5 ) . The results of a collaborative study of an assay method for lysergic acid diethylamide (LSD) were reported (251). Four different procedures for the separation of salicylic acid from aspirin before measurement were compared (163). Aspirin in the presence of salicylic acid was measured after precipitation of the bulk of the salicylic acid b y addition of acid (305). Phenobarbital and diphenylhydantoin in combination were determined by spectrophotometric titration ( I ) . LITERATURE CITED
(1) Agarwal, S. P., Blake, M. I., ANAL. CHEM.,41, 1104 (1969). (2) Agashkin, 0. V., Lyuts, A. E., Russ. Chem. Rev. (Eng. transl.), 36, 427 (1967). (3) Agolini, F., Klemenko, S., Csizmadia, I. G., Yates, K., Spectrochim. Acta, 24A, 169 (1968). (4) Aguiar, A. J., Zelmer, J. E., J . Pharm. Sci.. 58. 983 (1969). (5) A&; I. U’., Glenn, A. L., J . Pharm. Pharmacol. Suppl. 19,76S (1967). (6) Albert, A., J . Chem. SOC.,1968 C , 2076. (7) Alberti, F., Ashby, R. A., Douglas, A. E.. Can. J . Phvs.. 46,337 (1968). (8) Allinger, N. L , Stuart, T. W.; Tai, J. C., J . Amer. Chem. SOC.,90, 2809 (1968). (9) Al-Sayyab, A. F., Lawson, A., Stevens, J. 0..J . Chem. SOC..1968 C . 411. (10) Ananthanarayanan, V. S . , Bigelow, C. C., Biochemistry, 8, 3717 (1969). (11) Zbid., p. 3723.
ANALYTICAL CHEMISTRY, VOL. 42, NO, 5, APRIL 1970
(12) Anttrkulova, L. Sh., Kugatova-Shemyakins, G. P., Nikolaev, G. M., Andreev, V. M., J . Org. Chem. (USSR) (Engl. transl.), 3, 1757 (1967). (13) Andrusenko, L. P., Sheka, I. A,, Russ. J . Znorg. Chem. (Eng. transl.), 13,1363 (1968). (14) Appelquist, L. A., Josefsson, E., J. Sci. Food Agr., 18,510 (1967). (15) Athavale, V. T., Krishnamurthy, K. R., Venkateswarlu, Ch., Talanta, 15, 315 (1968). (16) Aulin-Erdtman, G., Sanden, R., Acta Chem. Scand., 22, 1187 (1968). (17) Aurich, F., J . Sci. Instrum. [2],2,109 (1969). (18) Bacaloglu, R., Csunderlik, C., Ostrogovich, G., 2. Anal. Chem., 240, 244 (1968). (19) Bailey, M. L., Theor. Chim. Acta, 13, 56 (1969). (20) Baker, B. R., Kozma, J. A,, J. Med. Chem., 11, 656 (1968). (21) Balachandran, K., Banerji, S. K., 2. Phys. Chem. (Leipzig), 241, 267 (1969). \----,-
(22). Balazs, M. K., Anderson, C. A., Lim, P., J. Pharm. Sci.,. 57,. 2002 (1968). (23) Ballard, R. E., Park, C. H., Spectrochim. Acta, 24A, 1975 (1968). (24) Balme, N., Berny, M. F., Bull. SOC. Chim. Fr., 1968, 3447. (25) Bando, Y., Nagakura, S., Theor. Chim. Acta, 9, 210 (1968). (26) Bartech, A., Dembricka, D., J. Inorg. Nucl. Chem., 29,2907 (1967). (27) Bayliss, N. S., J . Mol. Spectrosc., 31, 406 (1969). (28) Bayliss, N. S., Wills-Johnson, G., Spectrochim. Acta, 24A, 551, 563 (1968). (29) Beach, N. A., Gray, H. B., J . Amer. Chem. SOC.,90,5713 (1968). (30) Bekiaroglou, P., Drusm, A., 2. Phys. Chem. (Frankfurt am Main), .. 64,. 288 (1969). (31) Belikov, V. M., Belokov, Yu. V., Bull. Acad. Sci., USSR, Diu. Chem. Sci. (Eng. transl.), 1967, 1017. (32) Bencze, K., 2. Anal. Chem., 246, 244 (1969). (33) Bera, B. C., Chakrabartty, M. M., Anal@, 93, 50 (1968). (34) Bertoli, V., Plesch, P. H., J . Chem. Soc., 1968 B, 1500. (35) Bhatia, I. S., Ullah, M. R., J . Sci. Food Agr., 19, 535 (1968). (36) Bienvenue, A., Dubois, J. E., Bull. SOC.Chim. Fr., 1969,391. (37) Biryukov, A. A., Shlenskaya, V. I., Russ. J . Inorg. Chem. (Engl. transl.), 12, 1362 (1967). (38) Bonner, 0. D., Woolsey, G. B., Tetrahedron,24,3625 (1968). (39) Borja, C. R., Biochemistry, 8 , 71 I\ -1-969 - - r - ). (40) Boston, C. R., James, D. W., Smith, G. P., J . Phys. Chem., 72, 293 (1968). (41) Boston, C. R., Smith, G. P., J . Sci. Instrum. [2], 2 , 543 (1969). (42) Brandrum J., Kirby, J. R., Peebles, L. H., Jr., Luacromolecdes,1 , 59 (1968): (43) Braun, W., Kortum, G., Z . Phys. Chem. (Frankfurt am Main), 61, 167 (1968). (44) Broomhead, J. A., Kane-Maguire, L., Znorg. Chem., 7,2519 (1968). (45) Brunskill, J. S. A., J. Chem. SOC., ~
_ _ c. sfin.
1068 _ -
I
(46) Bryan, G. T., Takahashi, H., J . Chromatog., 36,229 (1968). (47) Bryant, R., Mantle, D. E., Timma, D. L., Yoder, D. S., J. Pharm. Sci., 57, 658 (1968). (48) Budesinsky, B., J . Znorg. Nucl. Chem., 31, 1345 (1969). (49) Bunnett, J. F., Nudelman, N. S., J . Org.Chem., 34, 2043 (1969). (50) Bunting, T. G., Meloan, C. E., ANAL. CHEM.,40, 435 (1968).
(51) Callear, A. B., Lee, H. K., Trans. Faraday SOC.,64, 308 (1968). (52) Campaigne, E., Ellis, R. L., Bradford, &I., Ho, J., J . Med. Chem., 12, 339 (1969). (53) Campaigne, E., Osborne, S. W., J . Hcterocycl. Chem., 5, 655 (1968). (54) Cariou, AI., Bull. SOC.Chim. Fr., 1969.198. (55) Carlstrom, -4.A., J . Ass. Ofic. Anal. Chem., 51, 1304 (1968). (56) Catsimpoolas, N., Campbell, T. G., Meyer, E. W., Arch. Biochem. Biophys., 131, 577 (1969). (57) Cattalini. L.. Martelli. 11..J . Amer. Chem. SOC..91.312 (1969j. (58) Chalvet, O., Leibovici, C., Theor. Chim. Acta, 14,65 (1969). (59) Chan, S. C., Leung, P. Y., J . Chem. SOC.,1967 A, 2089 (60) Chen, C. Y. S., Swenson, C. A., J . Phys. Chem., 73, 1642 (1969). (61) Chernobai, A. V., Grachev, N. hl., Tirak’yants, Zh. S.,Delyatitskaya, R. Ya., Polymer Sci. USSR (Eng. transl.), 9, 1645 (1967). (62) Chernobai, A. V., Tirak’yants, Zh. S., Delyatitskaya, R . Ya., Ibid., 9, 742 (1967). (63) Chernova, T. A., Astakhov, K. V., Barkov, S. A., Russ. J . Phys. Chem. (Eng. transl.), 43, 337 (1969). (64) Chernyaev, I. I., Zheligouskaya, N . S . , Vasil’eva, N. P., Russ. J . Inorg. Chem. (Eng. transl.), 13, 547 (1968). (65) Chernyak, A. S., Khomutnikov, V. A,, Batsuev, A. A,, Maslennikova, R. D., Zbid., 14, 655 (1969). (66) Chiacchierini, E., Havel, J., Sommer, L., Collect. Czech. Chem. Commun., 33, 4215 (1968). (67) Cieri, U. R., J . Ass. O$c. Anal. Chem., 52, 719 (1969). (68) Clementi, E., Chem. Rev., 68, 341 (1968). (69) Coe. J . S..Slanev. It. E..’ J . Sci. ‘ Ikstru?;i. 121, i, 98 (1969). (70) Coleman, J. S.,Penneman, R . A., Jones, L. H., Kressin, I. K., Inorg. Chem., 7, 1174 (1968). (71) Cooksey, C. J., Johnson, M. D., J . Chem. Soe., 1968B, 1191. (72) Corbett, J. A., Analyst, 93, 383 (1968). (73) Corbett, J. F., J . Chem. SOC.,1969B, 213. (74) Costakis, E., Canonne, P., Tsatsas, G., Can. J . Chem., 47,4483 (1969). (75) Cresser, ?*I.S., West, T. S., Talanta, 16,416 (1969). (76) Crossley, H., Lynch, V. P., J . Sci. Food Agr., 19,57 (1968). (77) Crummett, W., Hummel, R., ANAL. CHEM.,40,330R (1968). (78) Cuatrecasas, P., Rilchek, M., Anfinsen, C. B., Biochemistry, 8, 2277 (1969). (79) Cummins, L. hI., Perry, J. E., J . Pharm. Sei., 58,762 (1969). (80) Curtin, D. Y., Byrn, S. R., J . Amer. Chem. Soe., 91,6102 (1969). (81) Czech, F. P., Mack, AI. D., Evans, G., J . Ass. Ofic. Anal. Chem., 52, 1017 (1969). (82) Dandegaonker, S. H., J . Indian 46, 148 (1969). Chem. SOC., (83) Dass, N. N., George, hI. H., J . Polymer Sci., B 5, 1119 (1967). (84) Davey, A. E., Murray, J. B., Rogers, A. R.. J . Pharm. Pharmacol.. Suml. 20,518 (1968). (85) Davies, hI. B., Lalor, G. C., J . Inorg. Nucl. Chem., 31, 2189 (1969). (86) Davis, W. F., Talanta, 16, 1330 (1969). (87) Davydov, R. >IFomin, ., G. V., Russ. J . Phys. Chem. (Engl. Transl.), 42. 481 11968). (88) ’Deckelman, E., Werner, H., Helv. Chim. Acta, 52, 892 (1969). ~
I
A
I
(89) DeFabrizo,. F.,. J . Pharm. Sci.,. 57,. 644 (1968). (90) Degani, I., Fochi, R., Spunta, G., Ann. Chim. (Rome),58, 263 (1968). (91) Delaporte, N., Macheix, J. J., Chim. Anal. (Pami-),50, 187 (1968). (92) Del Bene, J., Jaffe, H. H., J. Chem. Phys., 48, 1807, 4050 (1968). (93) Dickson, R. C., Tappel, A. L., Arch. Biochem. Bwphys., 130, 547 (1969). (94) Dijkgraaf, C., Rousseau, J. P. G., Spectrochim. Acta, 25A, 1831 (1969). (95) Diliberto, J. J., J . Pharm. Sci., 58, 747 (1969). (96) Donovan, J. W., J . Biol. Chem., 244, 1961 (1969). (97) Dqefahl,‘G., Horold, H. H., Hofman, K. D., J.Prakt. Chem., 37,137 (1968). (98) Driever, C. W., J . Pharm. Pharmacol., 21, 470 (1969). (99) Duncan, A. B. F., Matsen, F. A., Scott, D. R., “Chemical Applications of Spectroscopy,” W. West, ed., “Technique of Organic Chemistry,” Vol. IX, Interscience, New York, 1968. (100) Dunken, H., Winde, H., Z . Phys. Chem. (Frankfurt am Main), 58, 246 (1968). (101) Dunken, H., Winde, H., Z. Phys. Chem. (Leipzig), 237, 347 (1968) (102) East, E. J., Trowbridge, C. G., Arch. Biochem. Bwphys., 125, 334 (1968). (103) Edisbury, J. R., “Practical Hints on Absorption Spectrometry,” Plenum Press, New York, 1967. (104) Edwards, T. G., Grinter, R., Theor. Chim. Acta, 12,387 (1968). (105) Efros, L. S., Kul’bitskii, G. N., J . Gen. Chem. USSR (Eng. transl.), 38, 943 (1968). (106) Egli, K . L., Romano, A., J . Ass. Ofic. Anal. Chem., 51, 11 (1968). (107) Eisdorfer, I. B., Warren, R. J., Zarembo, J. E., J . Pharm. Scz., 57, 195 (1968’1. --, (108) Elguero, J., Jacquier, R., Martin, C., Bull. SOC.Chim. Fr., 1968, 713. (109) El Khadem, H., El-Sadik, M. M., hleshreki, M. H., J . Chem. SOC.,1968C, 2097. (110) Ellerhorst, R. H., Jaffe, H. H., J . Org. Chem., 33, 4115 (1968). (111) Erastov, 0. A., Remizov, A. B., Ignat’eva, S.N., Bull. Acad. Sci., USSR Diu. Chem.Sei. (Eng. transl.), 1968,1794. (112) Erwin, V. G., Simon, R. J., J . Pharm. Sci., 58, 1033 (1969). (113) Evleth, E. &I.,Cox, R. J., J . Phys. Chem., 71, 4082 (1967). (114) Fabian, J., Fabian, K., Hartmann, H., Theor. Chim. Acta, 12,319 (1968). (115) Fabian, J., Mehlhorn, A., Troger, G., Ibid., 9, 140 (1967). (116) Fabian, J., Mehlhorn, A., Zahradnik, R., Ibid., 12,247 (1968). (117) Fackler, J. P., Jr., h‘littleman, M. L., Weigold, H., Barrow, G. M., J . Phys. Chem., 72, 4631 (1968). (118) Fagley, T. F., Oglukian, R. L., Zbid., 73, 1438 (1969). (119) Fairbairn, J. W., El-Masry, S., J . Pharm. Pharmacol., Suppl. 19, 93s (1967). (120) Faller, P., Bull. SOC.Chim. Fr., 1969,941. (121) Feil, P. D., Kubler, D. G., Wells, D . J., ANAL.CHEM.,41, 1908 (1969). (122) Ferguson, J., Austr. J . Chem., 21, 323 (1968). \ -
’
R.’ L., Wernimont, G., J . Org. Chem.; 34,2083 (1969).
(127) Flammang, M., Bull. SOC. Chem. Fr., 1968, 5039. (128) Fontanille, M., Sigwalt, T., Ibid., 1967. 4087. 29) Fraisse-Jullien, It., Frejaville, C., Ibid., 1969, 2095. 30) Frei, R. W., Nomura, N. S., Mikrochim. Acta, 1968, 565. 31) Freimanis, Ya. M., Shkyudite, ill. R., J . Org. Chem. ( U S S R )(Eng. transl.), 3. 1028 11967). (132) Friauf, I$ S., . Appl. Optics, 7, 2417 (1968): (133) Fritz, H., Losacker, P., Justus Liebigs Ann. Chem., 709, 135 (1967). (134) Fukui, S., Ohishi, Tu’., Nakai, Y., Shimizu, S., Arch. Biochem. Biophys., 130. 584 (1969). (135) ’Galasso, V’., DeAlti, G., Bigotto, A., Theor. Chim. Acta, 9, 222 (1968). (136) Galiazzo, G., Bortolus, P., Cauzzo, G., Mazzucato, U., J . Heterocycl. Chem., 6,465 (1969). (137) Gantenbein, W. M., Karasz, A. B., J . Ass. Ofic. Anal. Chem., 52, 738 (1969). (138) Ganther, H. E., Biochemistry, 7, 2898 (1968). (139) Garcin, J., Bull. SOC. Chim,. Fr., 1968,2284. (140) Garrett, E . R., Blanch, J., Seydel, J. K., J . Pharm. Sci., 56, 1560 (1967). (141) Garrett, E. R., Dvorchik, B. H., Ibid., 58, 813 (1969). (142) Garrett, E. R., Yakatan, G. J., Ibid., 57, 1478 (1968). (143) Garrett, E. R., Young, J. F., Ibid., 58, 1224 (1969). (144) Gasco, A., Barni, E., DiModica, G., Ann. Chim. (Rome), 58, 1183 (1968). (145) Gegiou, D., Muszkat, K. A., Fischer, E., J . Amer. Chem. Soc., 90, 3907 (1968). (146) Genich, A. P., Eremenko, L. T., Nikitina, L. A., Bull. Acad. Sci., USSR, Diu. Chem. Sci. (Eng. transl.), 1967,733. (147) Giammarse, A. T., Alliet,, D. F., Pacco, J. M., J . Polymer Sci., B, 6, 499 (1968). (148) Girard, h$I. L., Dreux, C., Bull. SOC.Chim. Fr., 1968,3491. (149) Giudicelli, J. F., Menin, J., Najer, H., Ibid., 1968, 1099. (150) Goguel, R., ANAL.CHSM., 41, 1034 (1969). (151) Golub, A. bl., Kalibabchuk, V. A., Russ. J . Inorg. Chem. (Engl. transl.), 12. 1249 119671. (152j Gorog S.,‘J. Pharm. Sci., 57, 1737 ( 1968). (153) Grammaticakis, P., Bull. SOC.Chim. Fr., 1968, 1057. (154) Gramstad, T., Sandstrom, J., Spectrochim. Acta. 25A. 31 119691. (155) Gray, A.‘P., Kraus, H.,‘Heitmeier, D. E., Shiley, R. H., J . Org. Chem., 33,3007 (1968). ( l i56) Green, R. W., Austr. J . Chem., 22, 721 (1969). (157) Gregorowicz, Z., Piwowarska, B., Buhl. F.. Kania., K.., Z . Anal. Chem.. 237. 347 i1968’1. (158) ’Gressel, P’. D., Gallelli, J. F., J . Pharm. Sci., 57, 335 (1968). (159) Grethe, G., Toome, V., Lee, H. L., Uskokovic, M., Brossi, A., J . Ora. Chem., 33, 504 (1968) (160) Groves, W. E., Davis, F. C.. Sells. B.’H.,Anal. Biochem., 22,1195 (19G8). ’ (161) Guarneri, hf., Ferroni, R., Fiorini, F., Ann. Chim. (Rome),58, 684 (1968). (162) Guarneri, &I., Giori, P., Tomatis, R.. Ibid.. 58. 697 11968). (163j Guttmah, D.‘E.,-Qalomon, G. w., J . Pharm. Sci., 58, 120 (1969). (164) Hafez, M. B., Guillaumont, R., Bull. SOC.Chim. Fr., 1969, 1047. (165) Hahn, R., Howard, P., Kong, 8.-hI., Lorenzo, G., Miller, N., J . Smer. Chem. Sbc., si, 3559 (ism). ’
ANALYTICAL CHEMISTRY, VOL. 42, NO. 5, APRIL 1970
245 R
(166) Haiduc, I., Haiduc, I., Gilman, H., J . Organometal. Chem., 11,459 (1968). (167) Hare, C. R., “Visible and Ultraviolet Spectroscopy,” K. Nakamoto and P. J. McCarthy, eds., “Spectroscopy and Structure of Metal Chelate Compounds,” Wiley, New York, 1968. (168) Haus, J. B., Manolev, L., J . Ass. O$lc. Anal. Chem., 51,562 (1968). (169) Hay, R. W., Main, L., Austr. J . Chem., 21, 155 (1968). (170) Hayes, W. P., Timmons, C. J., Spectrochim. Acta, 24A, 323 (1968). (171) Heathcock, C. H., Poulter, S. R., J . Amer. Chem. Soc., 90,3766 (1968). (172) Hendrickson, D. N., Kuznesof, P. M., Theor. Chim. Acta, 15, 57 (1969). (173) Hensen. K.. Sarholz., W.., Zbid.. 12. ‘ 206 (1968).’ ’ (174) Herskovits, T. T., Sorensen, S. M., Biochemistry, 7,2523 (1968). (175) Zbid., p. 2533. (176) Hesse, G., Engelbrecht, B. P., Eneelhardt. H.. Nitsch. S.. 2. Anal. Chim., 241,’91 (1968). (177) Higuchi, T., Richards, J. H., Davis, S. S., Kamada, A., Hou, J. P., Nakano, &I.,Nakano, N. I., Pitman, I. H., J . Pharm. Sci., 58,661 (1969). (178) Hirata, M., Chem. Pharm. Bull., 16,430 (1968). (179) Hirota, M., Shinozaki, F., Bull. Chem. Soc. Jap., 42,2614 (1969). (180) Holland, W. J., Bozic, J., Talanta, 15, 843 (1968). (181) Hong, W., Conners, K. A., ANAL. CHEM.,40, 1273 (1968). (182) Huang, C. L., Bhansali, K. G., J . Phamn. Sci., 57, 1511 (1968). (183) Huang, P. C., Kosower, E. hf., J . Amer. Chem. Soc., 90,2362 (1968). (184) Zbid., p. 2367. (185) Hubert, A. J., Anciaux, A. J., Bull. SOC.Chim. Belges, 77, 513 (1968). (186) Hussain, A,, Schurman, P., J . Pharm. Sci., 58,684 (1969). (187) Iffland, D. C., McAneny, M. P., Weber, D. J., J . Chem. SOC.,1969 C, 1703. (188) Industrial Research, 52-5 (Nov. 20, 1968). (189) Irie, M. J . Biochem. (Tokyo), 64, 347 (lSS8j. (190) Itier, J., Casadevall, A., Bull. SOC. Chim. Fr., 1969,3523. (191) Ito, H., Nogata, Y., Matsuzaki, S., Kuboyama, A,, Bull. Chem. SOC.Jap., 42,2453 (1969). (192) Ito, S., Takeshita, H., Shoji, Y., Toyooka, Y., Nozoe, T., Tetrahedron Lett., 1969, 443. (193) Ivakin, A. A., Russ. J . Znorg. Chem. (Engl. transl.), 12,939 (1967). (194) Jakubiec, R., Boltz, D. F., ANAL. CHEM.,40,446 (1968). (195) Jakubiec, P., Boltz, D. F., Anal. Chim. Acta, 43, 137 (1968). (196) Jakubiec, P., Boltz, D. F., Mikrochim. Acta, 1969, 181. (197) Janicki, C. A., Brenner, R. J., Schwartz. B. E.. J . Pharm. Sei.. 57. 451 (1968). (198) Jentoft, R. E., GOUW,T. H., ANAL. CHEM..40, 1787 (1968). . . (199) Johnson, D. P., Zbid., 40, 646 (1968). (200) Jones, D. H., Nelson, W. L., Biochemistry, 8, 2622 (1969). (201) Jones, R. N., Appl. Optics, 8, 597 (1969). (202) Jorgenson, M. J., Leung, T., J. Amer. Chem. SOC.,90,3769 (1968). (203) Jug, K., Theor. Chim. Acta, 14, 91 (1969). (204) Julien, L. M., Person, W. B., J . Phys. Chem., 72, 3059 (1968). (205) Jungen, C., Miescher, E., Can. J . Phys., 47, 1769 (1969). I
I
,
I
246R
,
,
(206) Jurasek, A,, Kada, R., Sticzay, T., Collect. Czech. Chem. Commun.., 34,. 257 (1969). (207) Kalt, M. B., Boltz, D. F., ANAL. CHEM.,40, 1086 (1968): (208) Kamlet, M. J., Minesinger, R. R., Hoffsommer, J. C., Dacons, J. C., Adolph, H. G., J. Chem. Soc., 1968B, 1167
(26ij’Karyakin, Yu. V., Kryachko, E . N., Russ. J . Znorg. Chem. (Engl. transl.), 12, 1355 (1967). (210) Kawakishi, S., Namiki, M., Agr. Biol. Chem. (Tokyo),33, 452 (1968). (211) Kaye, S., Koency, J. E., ANAL. CHEM.,41, 1491 (1969). (212) Kazakov, V. P., Konovalova, M. V., Russ. J . Znorg. Chem. (Engl. transl.), 13, 231 (1968). (213) Keay, G. R., Analyst, 93,28 (1968). (214) Kecskeme’thy, L., Szamoskozi, Z., Weber, C., Boeoki, G., Seifen-dleFette-Wachse, 93,807 (1967). (215) Keil, R., 2. Anal. Chem., 245, 362 (1969). (2i6) Kerber, R. C., Porter, A., J . Amer. Chem. SOC.,91,366 (1969). (217) Kirkland, J. J., ANAL. CHEM.,40, 391 (1968). (218) Kishi, K., Ikeda, S., J . Phys. Chem., 73. 15 (1969). (219j Zbid., p. 729. (220) Zbid., p. 2559. (221) Kishi, K., Ikeda, S.,Hirota, K., Zbid., 71,4384 (1967). (222) Klein, M. P., Dratz, E. A,, Rev. Sci. Znstrum., 39,397 (1968). (223) Kodama, M., Tagashira, Y., Naeata. C.. J. Biochem. (Tokvo). . - .. 64,. 81 71968). ’ (224) Kolthoff, I. M., Chantooni, M . K., J . Amer. Chem. SOC.,90,3320 (1968). (225) Kort, C. W. F., Cerfontain, H., Rec. Trav. Chim. Pays-Bas, 88, 1298 (1969). (226) Koshy, K. T., J . Pharm. Sci., 58, 560 (1969). (227) Kotva, R., Cerny, A., Semonsky, M.. Vachek. J.. Jelinek. V.. Collect. Czech. Chem.‘Commun., 34; 2114 (1969). (228) Kovner, M. A., Potapov, S. K., Russ. Chem. Rev. (Engl. transl.), 36, 620 I l Q f i 7,.) \--.-. (229) Kracmar, J., Blazek, J., Pharmazie, 23, 651 (1968). (230) Kracmar, J., Kracmarova, J., Zyka, J., Zbid., 23,567 (1968). (231) Krishna, V. G., Bhowmik, B. B., J . Amer. Chem. SOC.,90,1700 (1968). (232) Kroll, M., Zbid., 90, 1097 (1968). (233) Krumenacker, L., Bye, J., Bull. SOC.Chim. Fr., 1968,3099,3103. (234) Krumina, V. T., Astakhov, K. V., Barkov. S. A,. Russ. J . Phvs. Chem. (Engl. bans1.),’43, 665 (1969).(235) Kucharkowski, R., Doge, H. G., 2. Anal. Chem., 238,241 (1968). (236) Lang, L., “Absorption Spectra in the Ultraviolet and Visible Region,” Vol. VIII, Akademiai Kiado, Budapest, Hungary, 1967. (237) Zbid., Vol. IX. (238) Zbid., Vol. X, 1968. (239) Zbid., Vol. XI. (240) Zbid., Cumulative Index (VI-X). (241) Langer, K., 2. Anal. Chem., 245, 139 (1969). (242) Langer, P., Gschwendtova, K., J . Sci. Food Agr., 20, 535 (1969). (243) Larrouquere, J., Bull. SOC.Chim. Fr., 1968,329. (244) Launay, G., Wojtkowiak, B., Zbid., 1969, 3036. (245) Lehmann, G., Hahn, H., Schirra, M., 2. Anal. Chem., 243,554 (1968). (246) Leussing, D. L., Bai, K. S., ANAL. CHEM:, 40, 575 (1968). (247) Lins-Mesquita, A. A., de Barros Corr&a, D., Gottlieb, 0. R., Taveira MagalhLes, M., Anal. Chim. Acta, 42, 311 (1968).
ANALYTICAL CHEMISTRY, VOL. 42, NO. 5, APRIL 1970
(248) Lisitsyn, V. N., Didenko, L. A,, Dashevskii, V. G., J . Oro. Chem. U S S R (Eng. transl.), 4, 1049 (1968). (249) Loach, K. W., Anal. Chim. Acta, 45. 93 (1969). (250j Lombos,’ B. A., Sauvageau, P., Sandorfy, C., J . Mol. Spectrosc., 24, 253 (1967). (251) Look, J., J . Ass. Ojic. Anal. Chem., 51, 1318 (1968). (252) Lorentz. K.. 2. Anal. Chem.. 237. (253) ‘Los, J. hf.)Rekker, R. F., Tonsbeek, C. H. T., Rec. Trav. Chim. Pays-Bas, 86, 622 (1967). (254) Macaskill, J. B., Panckhurst, ?VI. H., Aust. J . Chem., 22, 317 (1969). (255) Malhotra. 0. P., Bernhard. S. A,. ‘ J.Biol. Chem.; 243, 1243 (1968). ’ (256) hfanhas, M. S.,Jeng, S., Bose, A. K., Tetrahedron,24, 1237 (1968). (257) RIarcantonatos, M.,Bernardo, R4. I., Monnier, D., Helv. Chim. Acta, 52, 291 (1969). (258) Mariano. AI. H.. AXAL.CHEM.. , 40., 1662 11968).’ ~
hedron Lett., 1969, 2833.’ (263) Matsekevich, T. N., Trailina, E. P., Savich, I. A,, Russ. J . Phys. Chem. (Eng. transl.), 43, 730 (1969). (264) Matsushima, Y., Chem. Pharm. Bull., 16, 2046 (1968). (265) Zbid., p. 2143. (266) Zbid., p. 2131. (267) Mehta, AI. J., Hegde, R. S.,Bhatt, R. A,, Patel, D. J., Bafna, S. L., J . Appl. Chem. (London),19,29 (1969). (268) Mendez, J., Lojo, RI. I., Microchem. J., 14,567 (1969). (269) Merer, A. J., RIulliken, R. S., Chem. Rev.,69, 639 (1969). (270) Nerer. A. J.. Schoonveld. Can. J .
245. (288) Nisli, G., Townshend, A., Talanta, 15, 1377, 1480 (1968).
(289) Norris, R. K., Sternhill, S., Austr. J . Chem., 22,935 (1969). (290) Notari, R. E., J . Pharm. Sci., 58, 1064 (1969). (291) Notari, R. E., Caiola, S. M., Zbid., 58, 1203 (1969):. (292) Novakovskii, Sf. S., Provotar, V. S., J . Gen. Chem. U S S R (Engl. transl.), 38, 1637 (1968). (293) Nurmukhametov. R. N.. Russ. ‘ Chem. Rev. (Engl. ’transl.), 36, 693 I1 OR7 ).
(294j-Ogata, Y., Kosugi, Y., Bull. Chem. SOC.Jap., 42,2282 (1969). (295) Ogata, Y., Tezuka, H., J . Org. Chem., 33, 3179 (1968). (296) Oguchi, S., Bull. Chem. SOC.Jap., 41, 980 (1968). (297) Ohnishi, A., Hayashi, K., Noguchi, J., Ibid., 42, 1113 (1969). (298) Ohno, I., Iguchi, K., Zbid., 41, 2264 (1968). (299) Okamoto, T., Xochizuki, >I.,Chem. Pharm. Bull., 17, 987 (1969). (300) Olesen, 0. V., Acta Pharrnacol. Toxicol., 26, 22 (1968). (301) Zbid., p. 222. (302) Ozaki, S., Chem. Pharm. Bull., 16, 1235 (1968). (303) Parker, G. A,, Boltz, D. F., ANAL. CHCM.,40, 420 (1968). (304) Pasto, D . J., Johnson, C. R., “Organic Structure Determination,” pp. 83-108, Prentice-Hall, New York, 1 q69
(305) Paulssen, R. B., Pitman, I. H., Higuchi, T., J . Org. Chem., 34, 2097 ( 1969). (306) Pernarowski, M., Searl, R. O., Naylor, J., J . Pharm. Sci., 58, 470 (1!)69). (307) Petershofer, G., Prey, V., Mikrochim. Acta, 1969, 981. (308) Pfeffer, kf., Schor, J., M., Gluck, X., Semmel, A I . G., Griboff, S., J . Pharm. Sci., 57, 36 (1968). (309) Phillips, J. P., Lyle, R. E., Jones, P. R., “Organic Electronic Spectral Data,” Vol. V, 1960-1961, Int,erscience, New York, 1969. (310) Piet,ra, F., Del Cima, F., J . Org. Chem:, 33, 1411 (1968). (311) Pimentel, G. C., Appl. Optics, 7, 2155 (1968). (312) Pobiner, H., ANAL. CHEM., 40, 564 (1968). (313) Pocker, Y., Dickerson, G., J . Phys. Chem., 73, 4005 (1969). (314) Ponder, C., J . Pharm. Sci., 57, 467 (1968). (315) Potts, K. T., Schneller, S. W., J . Heterocyc. Chem., 5, 485 (1968). (316) Pot,uraj-Gut#niak, S., Taube, M,, J . Inorg. Yucl. Chem., 30, 1005 (1968). (317) Prisyagina, I. G., Astakhov, K . V., Barkov, S. A., Tikhonova, E. V., Russ. J . Phys. Chem. (Engl. transl.), 43, 150 (1!369). (318) Rader, B. R., J . Pharm. Sci., 58, 1535 (1969). (319) Itamamoorthy, S., Raghavan, A., Vijayaraghavan, V. R., Santappa, M., J . Znorg. i\’ucl. Chem., 31, 1851 (1969). (320) Itamamoort,hy, S., Santappa, M., Ibid., 30, 1855, 2293 (1968). (321) Rappoport,, Z., Sheradsky, T., J . Chem. SOC.,1968B, 277. (322) Raunio, R.,Acta Chem. Scand., 23, 1168 (1969). (323) Reinheimer, J. D., McFarland, J. T., Amos, R. A., Wood, J. >I., Zahniser, RI., Bowman, W., J. Org. Chem., 34, 2068 (1969). (324) Rekker, R. F., Nauta, W. Th., Rec. Trav. Chim. Pays-Bas, 87, 1099 ilO6F;’i.
(32j)-lfurry, &I., Anal. Biochem., 23, 183 (1968). (356) Soda, K., Agr. Biol. Chem. (Tokyo), 31, 1054 (1967). (357) Sohar, P., Denny, G. H., Babson, R. D., J . Heterocyc. Chem., 6, 163 (1969). (358) Steams, E. I., “Practice of Absorption Spectrophotometry,” Wiley, New York, 1969. (359) Stekol’nikov, L. I., Katkovskii, S. B., Briskin, A. I., Tepelina, 0. M., Abdukarimov, A., Ryndina, E. A., Konopatskaya, V. M., Bayandurova, I. hf,, Biochemistry ( U S S R ) (Engl. transl. j, 34, 93 (1969). (360) Takazawa, ‘F., J . Ass. Oj’ic. Anal. Chem., 51, 1309 (1968). (361) Takemura. T.. Baba. H.. Tetra‘ hedron, 24,5311 (1968). (362) Talati, A. XI., Patel, T. I., J . Indian Chem. Soc., 45, 205 (1968). I
,
(363) Tamres, M., Duerksen, W. K., Goodenow, J. M., J . Phys. Chem., 72, 966 (1968). (364) Tan, A. T., Woodworth, R. C., Biochemistry, 8, 3711 (1969). (365) Tausend, H., Niclaus, W., Z . Anal. Chem., 245, 293 (1969). (366) Terada, A., J . Appl. Polymer Sci., 12, 35 (1968). (367) Terent’ev, V. A., Markevich, V. S., Shtivel’, N. E., J . Org. Chem. U S S R (Engl. transl.), 3, 434 (1967). (368) Thakkar, A. L., Kuehn, P. B., J . Pharm. Sci., 58,850 (1969). (369) Thomas, H. V., Mueller, P. K., Lyman, R. L., Science, 159, 532 (1967). (370) Thomas, R. S., Moore, G. E., Atmos. Environ., 2, 145 (1968). (371) Tinland, B., Theor. Chim. Acta, 11,385 (1968). (372) Toal, J. N., Rushizky, G. W., Pratt, A. W., Sober, H. A., Anal. Biochem., 23,60 (1968). (373) Tompsett, S. L., Acta Pharmacol. Tozicol.. 26. 303 11968). (374) Topping, R.‘RI., ‘Tutt, D. E., J . Chem. Soc., 1969B, 104. (375) Traub, A., Boltz, D. F., Mikrochim. Acta, 1969, 749. (376) Treibs, -4., Haberle, X., Justus Liebigs Ann. Chem., 718, 183 (1968). (377) Tritsch. G. L.. Arch. Biochem. Blophys., 127, 384 (1968). (378) Tronov, B. V., Polle, E. G., J. Gen. Chem. USSR (Eng. transl.), 38, 464 (1968). (379) Tsukerman, S. V., Buryakovskaya, E. G., Lavrushin, V. F., Opt. Spectrosc. U S S R (Engl. transl.), 26, 299 (1969). (380) Uziel, M., Kohl C. K., Cohn, W. E., Anal. Biochem., 25, 77 (1968). (381) Vala, &I., Jr., Tanaka, J., J . Mol. Spectrosc., 32, 169 (1969). (382) Van Allan, J. A., Reynolds, G. A., J . Hetarocyc. Chem., 5, 471 (1968). (383) Van Beek, L. K. H., Helfferich, J., Houtman, H. J., Jonker, H., Rec. Trav. Chim. Pays-Bas, 86, 975, 981 (1967). (384) Van Zwet, H., Kooyman, E. C., Zbzd., 86, 993 (1967). (385) Verzilina, M. K., Belotsvetov, A. V., J . Gen. Chem. U S S R (Engl. transl.), 39,626 (1969). (386) Vida, J. A., Gut, M.,J . Org. Chem., 33, 1202 (1969). (387) Walker, J., J . Chem. SOC.,1968C, 1522. (388) Wallace, J. E., ANAL. CHEM.,40, 978 (1968). (389) Wallace, J. E., J . Pharm. Sci., 57, 426 11968). (390) Wallace, J. E., ibid., 57, 2053 11968). (391) Walsh, A. D., Warsop, P. A., Trans. Faraday SOC., 64,1418 (1968). (392) Zbid., p. 1425. (393) Walsh, A. D., Warsop, P. A., Whiteside, J. A. B., Zbid., 64, 1432 (1968). (394) Wapensky, L. A., J . Ass. Oj’ic. Anal. Chem., 52, 1015 (1969). (395) Ward, T. M., Weber, J. B., Spectrochim. Acta, 25A, 1167 (1969). (396) Warren, K: D., ‘Yandle, J. R., Theor. Chim. Acta, 12, 279 (1968). (397) Weinstock, J., Dunoff, R. Y., Sutton, B., Trost, B., Kirkpatrick, J., Farina, F., Straub, A. S., J . Med. Chem., 11, 549 (1968). (398) Weinstock, J., Graboyes, H., Jaffee, G., Pachter, I. J., Snader, K., Karash, C. B., Dunoff, R. Y., Zbid., 11, 560 (1968). (399) Westoo, G., Analyst, 94, 406 (1969). (400) Wetzel, R., Zirwer, D., Schaelike, W., Gallowski, H., Schmidt, J., Knuepffer, H., Bonnke, H., J . Sci. Znstrum., [2]2, 841 (1969). ~
ANALYTICAL CHEMISTRY, VOL. 42, NO. 5, APRIL 1970
247 R
(401) Whistance, G. ,R., Dillon, J. F., Threlfall, D. R., Bzochem. J., 111, 461 (1969). (402) Whittick, J. S., Muraca, R. F.,
Cavanagh, L. A., “Analytical Chemistry Instrumentation,” National Aeronautics and Space Administration, Washington, D. c., NASA sp-5083,
1967. (403) WileY, R. A., J* H*,J *Med. Chem., 12, 146 (1969). (404) Williams, D. R., Coffen, D. L.,
Garrett, P. E., Schwartz, R. N., J . Chem. SOC.,1968B,1132. (405) Wolken, J. J., Forsberg, R., Gallik, G., Florida, R., Rev. Sei. Instrum.,
39, 1734 (1968). (406) W O O , W. s., J . Pharm. SCi.9 579 27 (1968). (407) Yamakawa, M., Kubota, T., Akazawa, H., Theor. Chim. Acta, 15, 244 (1969). (408) Yamakawa, M., Kubota, T., Akazawa, H., Tanaka, I., Bull. Chem. SOC. Jap., 41, 1046 (1968).
(409) Yamamoto, R. K., Cook, W. A,, Amer. Ind. Hyg. Assoc. J., 29, 238 (1968). (410) Yates, K., Klemenko, S. L., Csismadia, I. G., Spectrochim. Acta, 25A, 765 (1969). (411) Yudovich, E. E., .’ ’*, ~ ~ , ~ USSR ~ 1 $ transl.), ~ ~ * (412) Zangieva, Z. G., Gurevich, N. A,, Sokolova, El. I., Russ. J. Inorg. Chem. (Engl. trawl.), 13, 274 (1968).
X-Ray Absorption and Emission William J. Campbell, U.S. Department of the Interior, Bureau of Mines, College Park Metallurgy Research Center, College Park,
Md. 20740 and John V . Gilfrich, U.S. Naval Research laboratory, Washington, D. C. 20390
A s
REQUESTED by the editors of ANALYTICAL CHEMISTRY, this 1970 review is more condensed than the 1968 review (74). The sections on electron probe microanalysis were authored by J. V. Gilfrich, while the other sections were prepared by W. J. Campbell. Please forward your questions and comments to the appropriate reviewer.
X*RAY SPECTROGRAPHY
I n a discussion on current trends in X-ray analysis, Birks listed the following subjects: Calculation methods, energy dispersion, inhomogeneous samples, crystals and gratings, effect of valence on spectral line shape and position, and electron spectroscopy (41). I a m in general agreement with Birks and I have included all of the above in this review with emphasis on calculation methods, energy dispersion using radioactive isotopic sources, and low energy electron spectroscopy. A bibliography on X-ray analysis prepared from the files of J. L. DeVries has been updated (24). This extensive selected compilation of worldwide literature covers theory, instrumentation, and applications. Russian accomplishments in X-ray analysis were summarized from the period of approximately 1930 through 1966 (367). The “Resource Letters on X-Rays” provides a n excellent educator’s guide to principles and instrumentation (361). Recent textbooks and conference proceedings are listed in Table I. “Advances in X-Ray Analysis” (17, 370) provides excellent papers on new developments in X-ray emission and electron probe microanalysis. There are three new textbooks on X-ray emission (32, 58,42) and an outstanding conference proceedings on electron microprobe theory and practice (235). Progress in low energy X-ray spectroscopy is summarized by Fabian (156) and low energy
electron spectroscopy by Siegbahn and his associates a t the University of Uppsala (464). N. V. Philips in Eindhoven made available printed proceedings of X-ray symposia held in Brussels 1964; Sheffield, 1964; Lausanne, 1965; and Swansea, 1966. One area in X-ray spectrography where there is obvious duplication of effort is the preparation of 28 tables. Separate tables were published for LiF, topaz, and A D P (171-173). In our 1968 review, we strongly recommended the use of Bearden’s wavelength tables for any future 28 tables. The new tables (29) by the Bureau of Mines lists 28 values for nine analyzing crystals and includes over 2300 X-ray lines from Bearden’s tables. Since these data are available in computer format, it is a very simple and inexpensive task to prepare tables for additional crystals. The precision and accuracy of the wavelength scale is a continuing study. Burr (69) discussed secondary wavelength standards-CrKa, CuLa, O K a and ALKa-for use in the long wavelength region. The value of CrKaz (2.293606 A) is considered to be precise to one ppm. The X-ray waveleggth scale based on WKa, 0.2090100 A, is summarized and compared to previous scales based on the kx unit derived from calcite (487). Radiation safety recommendations for X-ray spectrographic and diffraction equipment were prepared by the joint effort of the Pennsylvania Department of Health and the National Center for Radiological Health. These recommendations are intended for use by operators, administrators, manufacturers, and State radiological health personnel (356). From the numerous accident reports that I have examined, it is apparent that operator carelessness together with inadequate interlocks is the prime source of trouble. Because of the highly localized nature of most
248R * ANALYTICAL CHEMISTRY, VOL. 42, NO. 5 , APRIL 1970
X-ray beams, film badges are of limited value in evaluating new experimental setups. I strongly recommend careful monitoring with detectors of adequate sensitivity for the radiation being used. INSTRUMENTATION
X-Ray Spectrographs. Instrument manufacturers continue t o provide the analyst with improved models having a n increasing level of automation (536). Most of these models provide increased precision of analysis, convenience, and ease of data processing; however, they do not necessarily represent improved analytical accuracy. I n general, accuracy is still limited by the degree of sample preparation and the validity of the matrix correction rather than by any instrumental factor. Two X-ray spectrographs are commercially available that employ direct electron excitation. These instruments offer a means for a very rapid determination of low atomic number elements (230, 283). Instrumentation for the analysis of solutions under vacuum conditions was described by Chan (90). A general purpose spectrograph that employs large spherically-curved crystals was constructed. The 10 by 10-cm single crystals are bent to a 63.5-cm radius of curvature and ground to the 31.75-cm radius of curvature of the focal circle. A motor-driven remotely-controlled interchange mechanism has positions for four crystals. Resolution and sensitivity are claimed to be greatly superior to conventional flat-crystal optics (148). A simple two-crystal spectrometer was constructed by modification of a flatcrystal X-ray spectrograph. The detector, originally attached to the 28 arm, was replaced by a second crystal. This detector was placed a t an appropriate position relative to the 28 arm. Wavelength dispersion in this mode of opera-
