(276) Ibid., 8,17 (1960). (277) Ibid., p. 96. (278) Ibid., p. 129. (279) Ibid., p. 316. (280) Ibid., 9,21(1960). (281) Ibid., p. 353. (282) Ibid., 10,17 (1961). (283) Ibid., p. 76. (284) Ibid., p. 371. (285) Sverdlov., L. M., Optika Spektroskopiia 4,697 (1958). (286) Sverdlov, L. M., Prokofeva, N. I., Optics and Spectroscopy 9,97 (1960). (287) Szigeti, B., Proc. Roy. SOC.(London) 2588,377 (1960). (288) Tadokoro,. H.,, J . Chem. Phus. 32, . 1558 (1960). (289) Ibid., 35,1050 (1961). (290) Tadokoro, J., Nishiyama, Y., ru’ozakura, S., Murahashi, S., Bull. Chem. SOC.Javan34.381(1961). (291) Takaha&, S., ’J. Opt. SOC.Am. 51, 441 (1961). (292) Tasumi, M., Shimanouchi, T., Spectrochim. Acta 17,731 (1961). (293) Taylor, J. H., Amberg, C. H., Cam. J . Chem. 39,535 (1961).
(294) Terenin, A., Roev, L., Spectrochim. Acta 15.946 (1959). ~. (295) Terhune, R. W., Peters, C. W., J . Opt. SOC.Am. 51,530 (1961). (296) Thompson, H. W.,. Spectrochim. . Acta 16,239 (1960). (297) Thompson, H. W. , Popplewell, R. J. L., 2. Elektrochem. 64, 746 I - - -
mfin). \ - - - - I -
(298) Thompson, W. E., Pimentel, G. C., Ibid., 84,748 (1960). (299) Thorson, W. R., Nakagawa, I., J . Chem. Phys. 33,994 (1960);, (300) “Titulos Spectroscopic, T. H. Zink, ed., Bibliotheca Central de Spectroscopia, Ellicott City, Md., 19131. (301) Tobin, M. C., J . Phys. Chem. 64, 216 (1960). (302) Tolk, A., Spectrochim. Acta 17, 511 (1961). (303) Vincent-Geisse, J., Ladd, J. A, Ibid., 17,627 (1961). (304) Weinstein, J., McIninch, E., J . Am. Chem. SOC.82,6064 (1960). (305) Weir. C. E., Liooincott. E. R., ‘ Van Valkenbure.’ A..*Buntine. E. N.. J . Research Naz: Sir. Stand&ds 63-4; 55 (1959).
(306) West, R., Baney, R. H., J . Phys. Chem. 64,822 (1960). (307) West, R., Glaze, W., J . Am. Chem. SOC. 83,3580 (1961). (308) Whiffen, D. H., Ann. Rev. Phys. Chem. 11,335(1960). (309) Wilmshurst, J. K., Can. J . Chem. 38,467 (1960). (310) Wilmshurst, J. K., Senderoff, S., J . Chem. Phys. 35,1078 (1961). (311) Wojtkowiak, B., Romanet, R., Compt. rend. 251,62,364 (1960). (312) Wood, R. W., “Physical Optics,” 3rd, p. 419, Macmillan, New York, 1934. (313) Wright, R. H., Daykin, P. K., Nature 189,212 (1961). (314) Yates, D. Y. C., Advances in Catalysis 12,265 (1960). (315) Yates, D. J. C., Lucchesi, P. J., J . Chem. Phys. 35,243 (1961). (316) Yates, J. T., Garland, C. W., J . Phys. Chem. 65,617 (1961). (317) Young, T. R., Rothrock, B., Conference on Gage Block Research Projects, Washington, D. C., March 1961; J . Opt. SOC. Am. 51, 1038 (1961) (summary).
Review of Fundamental Develonments in Analvsis
Light Absorption Spectrometry M. G. Mellon Purdue University, l a fayet te, Ind.
D.
F. Bolfz
Wayne State University, Detroit, Mich.
F
this ninth review of absorption spectrometry in t h e visible region of the spectrum, t h e literature was sampled for the period September 1959 through October 1961, as covered in OR
Chemical Abstracts. Since it was neither desirable nor possible to include all of these references, again the aim was to make a selection representative of what has been done. No doubt justice to all authors has not been achieved. Abstracts, unfortunately, are not equally revealing on what the actual contribution is or on its importance. It was impossible for t h e reviewers to read 1500 papers, in many different languages. Following the practice of earlier reviews, t h e material has been classified as chemistry, physics, and applications. One review covers recent developments in colorimetry (492). CHEMISTRY
By chemistry is meant any separations and/or transformations necessary to render the desired constituent, or something chemically equivalent to it, measurable. This chemistry, of course, is organic or inorganic. If it is
232 R
ANALYTICAL CHEMISTRY
interpretative-that is, directed to “why” things are as they are-it is physical. On this basis many abstracts were considered as not sufficiently relevant to include. For example, a paper was omitted if it reported for a given complex only the ratio of the two reactants and/or the values of the stability constants. Inorganic Constituents. Many papers present more or less minor modifications of well known methods, such as t h e dithizone procedure for zinc. Occasionally, of course, some such modifications render t h e method preferable to another method. Also m a n y papers represent obvious applications t o situations n o t previously reported. Extensive deletions were made for both types of papers. For example, more than 150 were rejected which involved t h e application of heteropoly chemistry. With t h e ever-increasing Fealth of methods there is more and more need for critical evaluations of those we already have. Good examples deal with methods for Zn (384), Au (48), G a (461),and the platinum metals (43). Yuasa (533) has proposed a n em-
pirical relation correlating the effect of p H and concentration of molybdate in the determination of As, Ge, and P by the heteropoly blue method. Related t o this is a study of the behavior of heteropoly acids in acidic media (87). Two papers deal with the products of ammonia and Xessler’s reagent (98, 93). Unless the reaction is adequately controlled, errors may result. Other examples of studies on the nature of reactions include Fe(II1) with kojic acid (306), Fe(II1) and thiocyanate (366), and starch and iodide (346). Two papers on the Fe(I1)-1,lOphenanthroline complex illustrate items of interest in many similar cases. One (196) reports the extent of interference of 10 mg. per 100 ml. each of 68 elements in the determination of 100 pg. of Fe. The other (3’7) reports the stability constants of Fe(II), Co(II), Ni (11), Cu(II), and Zn(I1) complexes with several 1,lO-phenanthrolines. Papers dealing with methods of studying complexes are illustrated b y the following examples: a n apparatus for mixing reactants and passing t h e solution by the spectrophotometer (18); relation between t h e stability constants and absorption spectra of metal che-
lates (268); determination of t h e composition of weak complexes (23); relations between metal-complex stability and t h e structure of t h e complexant (443); t h e limitations of t h e method of continuous variations for reactions in which species other t h a n t h e complex are produced (229); a new spectrophotometric method for determining the formulas and stability constants of complexes (101) ; extension of Job’s method of continuous variations to two-phase systems (213); a graphical evaluation of spectrophotometric d a t a for t h e determination of association constants from deviations from Beer’s la\T (263); and t h e determination of molar absorptivities of metal dithizonates (S14). Metals. Of t h e hundreds of publications dealing with metals some a r e of r a t h e r general interest. I n addition t o discussing t h e theory of complexing groups i n organic reagents, Yampol’skiI (,527) dealt specifically with t h e use of azo dyes, triphenylmethanes, and hydroxyanthraquinones for t h e determination of I n and Ga. Phillips et nl. (586) studied five chelating agents. each containing two 8-quinolinol functions, to determine whether both chelating functions operate. Ankudimora (16) decided t h a t molybdenum reacts with certain l12-dihydroxybenzenes, and t h a t substitution of mercapto for hydroxy groups improves t h e reagents. T h e following examples illustrate t h e application of several reagents for one or more ions: five derivatives of glycine thymol blue for Cu(I1) (248); 50 rhodanines for Ag, Hg(I), Hg(II), Cu(I), and Cu(I1) (497); four reagents for Os (33); four hydroxyanthraquinones for Ge (259); 34 azo dyes for Yt (261); three 9-alkyl- and nine 9 aryl - 2,6,7 - trihydroxyfluorones for Sb(II1) (297); and t h e 3- and 5sulfonic acids of 1,lO-phenanthroline (49), and 11 pyridyl-substituted triazines (119) for iron(I1). A number of papers deal with t h e use of one or more chelants for several ions. T h e following may be cited: three phenylfluorone derivatives for Ge, Ti, and Zr (431); N,N’-dibenzyland N,N’-diphenylrubeanic acids for Co, Cu, Ni, and Pd (526); 8-quinolinol and 8-hydroxyquinaldine for some 20 ions (552); 2”,6”-dichloro-4’-hydroxy - 3,3’ dimethylfuchsone 5,5’dicarboxylic acid for Be, Cu, and F e (236); dithio-oxamide for Co, Cu, and Ni (220); 4-(2-pyridylazo)resorcinol for Co, Pb, and U (595); rubeanic acid for Ag, Co, Ni, Pd, and Ru (526); seven 7-substituted 8-quinolinols for Cu, hlg, Ni, Pb, and V (501); sodium pyrrolidinedithiocarbamate for Bi, Cu, Sb, and Zn (264); di-l-naphthylthiocarbazone for Ag, Cu, and H g (485); nicotine and isonicotinohydroxamic
Table I.
Constituent
Material
AU
Be Bi
Biomaterials Alloys
Magnesium Serum Sodium
Ce
co (and Xi) Cr
cs cu
Uranium
Nonferrous
Method or Reagent Reference Dithiol (130) Acid Chrome Pure Blue (162) B-Hydroxy-l,4-naphthoquinone (6) Pyrocatechol Violet (18) Sendachrome AL (21) p-Dimethylaminobenzylidine rhodanine (104) Methyl violet (126) Rhodamine B t 366 ) o-Tolidine (163) Chromotrope 2C (317) 2-Phenoxyquini~arin-3~4-disulfonic acid I 367) Thorin ($4) 4-Hydroxy-3-nitrophenylphosphonicacid (387) Tetraphenylphos honium bromide (331) Glyoxal bis( (242) 1-[2-(2-Hydroxy-5-methylphenyl( azoxy)phenyl- ( 231 ) azo)]-2-naphthol A‘-Hydroxynaphthalene-1,s-dicarboxylicacid ( 169) imide Arsenazo (357) Erio SE (71) Na naphthohydroxamate (36) Acid Chrome Dark Blue ( 294 ) Cadion IREA (302) Ce(S04)a-2 (166) Fe( 11)-phenanthroline (109) 2-Thenoyltrifluoracetone 243 1 5-Vanillylidene-2-thiohy dantoin (390) 2-Carhoxyisonitrosoacetanilide (76) 1,2,3-Cyclohexanetrione trioxime (162) Diethylenetriamine i209 1 Isonitrosothiocamphor (129) Oxamidoxime (376) Carmoisin (267) Cd iodide-starch (176) 4,4-Diaminodiphenylamine (180) 2-Thenoyltrifluoroacetone (320) 8-hydroxy quinaldine (360) HBiId-dithizone (181) 2,2’-Bicinchoninic acid (158) 1,3-Dimethyl-4-imino-5-hydroxyiminoalloxan ( 74) NaXa ( 233 ) ”(4 hP207 (239) CuCll (292) Fast Grey R. A. Er(II1)
3-Acetyl-4-hydroxy coumarin N-Acet yl-N-phen ylhydroxylamine 2,6-Bis(4-ethyl-2-pyridyl)-4-phenylpyridine N,N-Bis( carboxymethy1)anthranilic acid 2-Chloro-l0-( -dimethylaminopropyl)phenothiazine Di-Na bathophenanthrolinedisulfonate EGTA Ferrocene
-
-
for Metals
2-h yzroxy anil)
Ca
Cd
Photometric Methods
(174) ( 466 ) (121) ( 829)
(60)
”a
Biomaterials Bronze Ga
AI Ge
-
MO
Be0
o-Hydroxybenzenesulfinic acid 3-Hydroxy-1-phenyl-3-methltriazene 3-Hydroxy-3-phenyl-l-(p-su~ophenyl)triazene Phenyl-2-pyridyl ketoxime 2-Pvridvl ketoxime 2,4,%-Th yridyl s triazene Dimethyfp-phe&lenediamine Diantipyr ylmethane N,N-Bis( 2-hydroxy-5-sulfophen~ - - ‘l)-S-CJ.anoformazan Triphenyltetrazolium chloride Basic Light Green I,1’-Dianthrimide o-Dihy droxychromenols cJuercetin, Hz02 1-( 2-Pyridylazo)-2-naphthol nL Teothoron 5#-Nitrobarbituricacid Phenazo (364) Xylidyl blue (11) Magon (19) Acid Chrome Blue 2K ( 264 1 Diphenylcarbazone (468) EDTA (280) 3-Hydroxy-1-p-sulfonatophenyl-3-phenyltri(470) azene 9-Methyl-2,3,7-trihydroxy-6-fluorone (316) (Continued)
VOL. 34, NO. 5, APRIL 1962
233 R
Table 1.
Constituent
Kb S i
Material Steels Tantalum U alloys
Steel S p
OS
Pb
Pd
Pt
Pll
Rare earths Re Rh
Ru
Sb
sc Sn Sr Tc Th
Ti
U
Meteorites
Photometric Methods for Metals (Confinued)
Method or Reagent Reference Unithiol 3,3',4',5,7-Pentahydroxyflavanone N-Benzoyl-N-phenylhydroxylamine Thiocvanate 8-Qui~olinol 2,6-Diacetylpyridine dioxime Solochrome Red ERS Triphenylmethylarsoniumbis( dithio-oxalic) acid Murexide Thorin Anthranilic acid l-Naphthylamine-4,6,8-trisulfonicacid Tiron 4"-Nitrobenzene-1 ",4-diazoamino-l, 1'-azobenzene-2"-arsonic acid Salfarsaxen 1-.4cetyl-3-phenylselenourea N,N'-Bis( 3-dimethylaminopropy1)dithio-oxamide 5-(p-Dimethylaminobenzy1idene)rhodamine 2-Mercapto-4,5-dimethylthiazole 4-Methy1-lJ2-cyclohexanedione dioxime 1-Phenylthiosemicarbazide Quinoxaline-2,3-dithiol Thiomalic acid Anthranilic acid N,N'-Bis( 3-dimethylaminopropy1)dithio-oxamide o-Phenylenediamine Pu +3 Tetrapropylammonium nitrate Arsenazo Chlorides 6-Chloro-8-mercaptoquinoline SnClz; Na2SOa; HCl A',Ah"-Bis(3-dimethylaminopropy1)dithio-oxamide sym-Diphenylcarbazone SnClz Thiomalic acid Acetylacetone N,N'-Bis{3-dimethylaminopropyl)dithiooxamide l-Naphthylamine-3,5,7-trisulfonic acid Thiocyanate 1,4-Diphenylthiosemicarbazide Ag sulfamoylbenzoic acid H2TiFe; H202 Methvlfluorone Rhodkmine B Sulfonazo Bi-o-anisidine Pyrocatechol Violet 5-Nitrobarbituric acid Thioglycolic acid Toluene-3,4-dithiol Arsenazo 1-(o-Arseno henylazo)-2-naphthol-3,6-disulfonic acid' Chromotropic acid-azo dyes Eriochrome Black T Maleanilic acids Tri-n-octylphosphine oxide Diantipyrinylmethane Dihydroxylamine salt of dihydroxymaleic acid Disulfophenylfluorone 9-Methyl-2,3,7-trihydroxy-6-fluorone Salicylic acid; pyridine Arsenazo Arsenazo(11) Benzohydroxamic acid Dibenzoplmethane l-Phenyl-3-methyl-4-( carboxy-4-hydroxyphenylazo)-5-pyraeolone 4-(2-Pyridy1azo)resorcinol 8-Quinolinol-N-oxide Theonyltrifluoroacetone Methylene blue Molybdic acid Phenylanthranilic acid I-( 2-Pyridylazo)-2-naphthol Sulfonazo (Continued)
234R
ANALYTICAL CHEMISTRY
acids for Fe(II1) and V(V) (342); four o-dihydroxychromenols for Hf and Zr (265); hydroquinone for Nb, Ti, and W by means of a background correction technique (308); tin(I1) bromide for Au, Ir, Pd, Pt, and Rh (370); and thiourea or chloro complexes for the platinum elements (374). Hollingshead (205) reported a number of new derivatives of 8-quinolinol containing both solubilizing groups and groups which sterically might hinder chelation, and tested them for 12 metals. Jacobs and Yoe (221) used N,N'bis(3 dimethylaminopropy1)dithiooxamide for the simultaneous determination of Co, Cu, and Xi. More specific papers are summarized in Table I. Nonmetals. Three papers, more or less general, deal with t h e determination of boron. One concerns t h e variables involved in t h e quinalizarin method ( 2 @ ) . One is a n evaluation of the use of thionine and nine of its derivatives for the extraction and direct photometric determination of t h e element (373). And one reports t h a t Celliton Fast Blue Green B is the most sensitive of 13 derivatives of anthraquinone tested (260). A process patent covers the use of N,N,iV',iV'-tetraphenylbenzidine for t h e determination of C1, Br, and NO (392). A composite method for combined arsenate, phosphate, and silicate involves formation of t h e molybdo acids, selective extraction by organic solvents, and reduction to heteropoly blues (96). More specific papers are summarized in Table 11. Organic Constituents. A general s t u d y of 23 polynitro aromatic compounds (438) resulted in procedures for determining a number of them. Related to this is a study of various systems, including procedures for determining azo dyes, stilbene, and SchX base derivatives, and methods for carbazole in air (437). A method for analyzing acrylic monomers provides for determining hydroquinone, benzoquinone, and the monomethyl ether of hydroquinone (128). Another method provides for determining 1,3,5-trinitrobenzeneJ2,4,6trinitrophenol, or 2,4,7-trinitrofluorone in polynitro compounds of naphthalene and its derivatives (247). A mixture o f catechol, hydroquinone, and resorcinol in aqueous solution was analyzed by several reactions (177). Mixtures of D-, I.-, and Dbtryptophan, or ~ r D-,, and Dbkynurenine were determined by means of electrophoresis and spectrophotometry (175). Determination of benzidine, diphenyline, o-tolidine, and o-anisidine was based on tetrazotization of t h e amines and coupling with N-ethyl-1-naphthylamine (165). For use in identification and quantita-
-
tion Wilson (526) determined t h e absorption spectra of A5-3P-hydroxysteroids in ethanolic sulfuric acid reagents. Solvent effects were studied for t h e spectrophotometric determination of aromatic primary amine and carbonyl derivatives of weak organic acids (436). T h e influence, if any, of 12 amino acids on t h e anthrone reaction of uronic acids was studied (190), and several different methods used for t h e determination of bascorbic acid (414). For t h e determination of -OH, =CO, and aliphatic -NH2 groups t h e formation, respectively, of a n ester, hydrazone, or arylamine containing aromatic -X02 groups with a n organic base in dimethylformamide was recommended (380). Iron(I1I) hydroxamates have been used for t h e determination of esters of a number of saturated, unsaturated, straight, or branched-chain fatty acids (389). Also t h e formation of hydroxamic acids was the basis for the determination of various dicarboxylic acid derivatives (146). Methods for various specific organic systems are summarized in Table 111. PHYSICS
Under this heading are summarized all items which seem to be relevant t o t h e measurement of t h e chemical systems discussed under t h e heading of chemistry. Measurement is physics. Three papers are historical. One (321) considers the two absorption laws of Bouguer and Beer and notes t h e relation of Lambert and Bernard, respectively, to these l a m . T h e second is a historical review for t h e ultraviolet and visible regions (348). T h e third relates t h e development of methods of colorimetry in t h e first half of t h e 19th century-that is, before Beer's law was stated (496). Errors of measurement are discussed under the following subjects: scattered radiant energy (300) ; stray radiant energy (202); finite slit widths (187); inaccuracies in photometric and wavelength scales (491); and evaluation of major errors in microspectrophotometry (2411 * A least-squares treatment of spectrometric d a t a is recommended for polycomponent analyses (40). Matrix form of t h e application was used for a mixture of p-xylene and ethylbenzene (41) and for niivtures of ergosterol (477). Methods. T o avoid errors from impurities in reagents, t w o samples of different masses m a y be used rather than blanks (61). T h e effect of blank absorption on precision has been treated mathematically (253). Differential spectrophotometry has been reconsidered (156) and applied t o solutions containing one component
Table 1.
Constituent
W
Photorneiric Methods for Metals (Continued)
Material
Steels
Yt Zn
Water
Zr
AI-Mg alloys
Table 11.
Constituent
As B
Material Biomaterial Lewisite Petroleum stocks Be, Th, U, Zr Steel Alloys
Boranes C1 c1ClOr ClO, CN
-
Water NHiClOi Effluents
FFe(CT\'s)-'
Molasses
N2H4 NOz-
*
NOz-; NO:NO0 0 2
N'ater Water
0 0
P PHI S Se Si Te
Acetylene Steel UOI Sn Pu Semiconductors
Method or Reagent Il'-2-Thiophenecarbonyl-A'-phenylhydroxylamine Tungstic acid Vanillin dinitrofluorone Pyrocatechol Violet Stilbazo 2-(2-Hydroxy-5-methoxyphenylazo)-4methylthiazole 2- [2-(2-Hydroxy-5-methoxypheny1azo)phenylazo]-l-hydroxy-&aminonaphthalene-3,6-disulfonic acid Zincon m-Nitrophenylfluorone 7-(4-Sulfo-l-naphthylazo)-1,8-dihydroxy-2nitrosonaphthalene-3,6-disulfonicacid 4-Sulfo-2-phenylazochromotropic acid 2-( p-Sulfophenylazo)chromotropicacid 1-(2-Pyridylazo)-2-naphthol
Photometric Methods for Nonmetals
Method or Reagent Heteropoly Heteropol Ag diethyydithiocarbamate
Reference
Indirect heteropoly Diaminochrysazin Methylene blue Monomethylthionine Tetrabromochrysazin Triphenyltetrazolium chloride Tetrakis( p-dimethglaminopheny1)ethylene Dibromofluorescein Tyrosine H acid Benzidine Ag dithizone Pyridine-benzidine Eriochrome Cyanine R Th chloranilate FeCla Nay3 2,2-Dimethoxypropane U or V benzohydroxamate Plumbite; HCHO Ellagic acid Fe+3 Indirect; KO2C11 water; CeH,OH Nessler (new) Xi dimethylglyoxime Vanillin N-( 2-Aminophenyl) iperidine Na 1-(4-amino-2-suEophenylazo)-2-amino-8naphthol-6-sulfonate (4-+minophenyl)trimethylammonium ion N,N&methyl-I-naphthylamine Phenanthroxazine 3,3'-Dimethylnaphthidine Indigo carmine; glucose Diphenylaminesulfonate N-Phenyl-2-naphthylamine La chloranilate Eeteropoly Heteropoly N,N-Dimethy 1-p-phenylenediamine p-Rosaniline; HCHO Iodine SnClZ Heteropoly Heteropoly 1,l'-Dianthrimide Bismuthiol I1
VOL 34, NO. 5, APRIL 1962
235 R
Table 111. Constituent Acetic acid esters Acetyl groups Acetylacetone Acrolein Adrenaline Alcohol Alcohols Alcohols, secondary Alcohols, secondary and primary Aldehyde Aldehydes Alkylbenzenesulfonates Amines, aliphatic Amines, secondary Amines, secondary a-Aminonitriles Amprolium 3,6-Anhydrogalactose Aniline Anthracene Antipyrine Antioxidants, phenolic Axacyclonol Benzanthrone Benzene (and monochlorobenzene) Benzene Biphenyl Biuret Butylamine €-Caprolactam Carbazole Carboxyl Ceruloplasmin Chlorophylla Cholesterol Cholesterol Chromones Colchicine Collagenase Copper 8-quinolinate Crotonaldehyde Cyanamide Cycloserine Cysteine Deoxyribosyl compounds Diacetyl Dibutyltin dichloride 2,4-Dichloro henoxyacetate ($a) Dinitrochlorobenzene 3,5-Dinitro-o-toluamide
Photometric Methods for Organic Compounds Material Method or Reagent NH20H; FeC13 Fe hydroxamate Cu acetate IZir 4-Hexylresorcinol 2,4-Dinitrophenylhydrazine Air K2Cr207; Asnos;I V 8-quinolinolate 2,4-Dinitro henylhydrazine 3,5-Dinitro!1enzoylchloride Air Gases Water
Primary amines Feeds Polysaccharides Air Naphthalene Serum Rubber Urine Air Rubber cements Gases Paper wrappers Air Polymers
Starch Serum Plant extracts Serum Serum Urine
Urine
Air
Glucosamine Glucose Glutamic acid Glutathione Guanidine Hemoglobin Heroin Histidine
p-Phenylenediamine; HzO2 2-Hydrazinobenzothiazole Methylene blue Cu( 11); Azurol B CSz; Cu(I1) Salicylaldehyde; bromocresol green Benzidine; pyridine 2,7-Naphthalenediol Resorcinol p-Dimethylaminobenaaldehy de Naphthalenetetracyanoethylene N-( 1-naphthy1)ethylenediamine "02; p-nitroaniline ~a-2-naphthoquinone-4-sulfonate
Ni tartrate Ninhydrin Fe hydroxamate Xanthydrol; CHaCOOH Methylene blue Oxalic acid HzSO4; AczO; sulfosalicylic acid HClOi m-Dinitrobenzene FeC13 Ninhydrin 4Hexylresorcinol Pentacyanoammineferrate Heteropoly Azo dye KIO,; thiobarbituric acid Resorcinol Diphenylcarbazone 1,8-Dihydroxynaphthalene-3,6disulfonic acid Dinitromethylaniline Aliphatic diamines NaBH,
2,4Dinitrophenylamino groups Diolefins Diosgenin Ethanol 2-Ethyl-l,3-hexanediol Flavanoids 9a-Fluorohydrocortisone a-Fluoroprednisolone Formaldehyde Formaldehyde 2-Furaldehyde Furazolidone Gibberellic acid
Reference
Fermentation broths Triamcinolone Air Tissue
Serum Wheat Erythrocytes Plasma Blood
Nails
4-Nitrobenzenediazoniumfluoborate HClOi KzC~z0,; HZSO4; & ) a ; I 4Dimethylaminobenzaldehyde Isonicotinic acid hydrazide Fructose; cysteine
Fructose; cysteine Sulfamic acid 2-Naphtholsulfonic acid Aniline: CHaCOOH Phenylhydrazine 2,4-Dinitrophenylhydrazine; KOH Xanthydrol Coupled enzyme Ninhydrin Bis(p-nitrophenyl) disulfide Sakaguchi reagent NaN02; KCN; NaHC03 "03; HaPo, KIa Dimedon or phenylmethylpyrazolone Diazobenzenesulfonic acid ( Continued)
236 R
ANALYTICAL CHEMISTRY
(417 ) . Designated as indirect spectrophotometry, four variations have been discussed (409). A number of papers deal with some specific aspect of the general problem of measurement. The following are examples: curvature inversion technique in absorbance compensation spectrophotometry (201); the use of capacity flow technique in determining spectra of transient species (368); a review of absorption spectrometry of dispersed substances (421); a procedure for t h e rapid determination of spectra of instable systems (184); a new system for documenting absorption data based on codeless scanning (984); use of thin sections in the examination of paintings (137); sensitivity limits of analytical reagents (354); a technique for t h e determination of very small amounts of dissolved substances (189); methods for determining absorbances of dithizone and lead dithizonate (516); measurements involving inter- and/or intravariance among standards (12); resolution of mixtures by kinetic colorimetry (429); and the use of reflection techniques with powdered salts (171) and for the kinetic study of reactions with substances in powder form (31). Instruments. T h e past t w o years have produced few really new instruments. R a t h e r t h e period has been marked b y refinements, improvements, various accessories, a n d design of more or less automatic assemblies for specific determinations. Filters. Filters for photometers still have some interest, as indicated b y t h e following papers: transmittance spectra for 55 glass a n d 35 gelatin filters, a n d for 98 two-filter combinations (457); spectra for several poly(methy1 methacrylates) (416); combinations of glass and solution filters (450); the properties of interference filters (257) and the production of such filters passing 80% of the light by using alternate layers of dielectrics (269); and a holmium glass (Corning CS 3-138) for checking wavelengths (506). Cells. T h e following modifications a n d adaptations are of interest for specific situations: quartz cells for continuous analysis of column effluents (14); a cell for 3 ~ 1 (499); . a simple glass variable-thickness cell (64); a 100-mm. cell for 0.7 ml. of sample (164); an anaerobic cell (307); a cell for temperatures u p to 780' (531); a cell for the temperature range of -170' to $200' (200); a low temperature cell (194); modified cells for dithiaone determinations (191); precision temperature control of cells (310); multiple-traverse cell design (134); a cell for 0' to 250' and 0 to 1000 p.s.i. (510); rotor aperture for use with rotating ultracentrifuge cells (413); and use of transparent plates
Table 111. Photometric Methods for Organic Compounds (Continued) Constituent Material Method or Reagent Reference HomocysteinethiolacNinhydrin (330) tone 17-Hydroxycorticoids Plasma Phenylhydrazine (203) Hydroxyl groups 3,5-Dinitrobenzoyl chloride (412) 17a-Hydroxy-1 l-deoxyHzSO, (345) corticosteione 5-( Hydroxymethy1)Sirup Benzidine; CH3COOH furfural Hydroxyproline Biomaterials p-Dimethylaminobenzaldehyde (401) Hydroxysteroids 3,5-Dinitrobenzoic acid (100) 3 0-Hydroxysterols Anthrone ( 504 1 p-Dimethylaminobenzaldehyde (S26) Indican Indoles Na glyoxalate; FeCla (411) Isopropyl alcohol Salicylaldehyde (160) Ketohexoses Cysteine; H2SOc (122) Lauryl sulfate XaOC1; o-tolidine (168) Levulinic acid 2,4-Dinitrophenylhydrazine (226) Lysine “02; 4-nitroaniline (430) Mercaptans Air N,N-Dimethyl-p-phenylenedi(5’47) amine 3-Methoxy-4-hydroxy- Urine “02; 4-nitroaniline mandelic acid N-Methylamino acids Ninhydrin Monamine oxidase Several reagents 1-Xaphthyl-AT-methyl- Crops 4-Nitrobenzenediazonium fluocarbamate borate Nitrobenzene Air Zn; NaOC1; phenol Nitroparahs PDiazobenzenesulfonic acid Nitrophenols, haloWater Na2BI0, buffer genated Organolead compounds Dithizone Oxytetracycline Par athion
Urine Stomach
Peroxides, organic Phenol Air
Phenylalanine 4-Phenylenediamine derivatives Phygon Protein
Blood Rubber Water
Psicofuranine Pyridine and derivatives Pyridoxine Resochin Urine Rutin Tablets Sesamex Shikimic acid Silicones Foods Sorbic acid Sterculic acid Succinic dehydrogenase Taurine (2-Thenoy1)trifluoroacetone Thioctic acid Thiola Tocopherols
Vrine
Tolylene diisocyanate Tributylphosphine Triose phosphate Tryptophan Turpentine Xanthurenic acid Xylitol
Air Air
Air Urine
FolinJs uric acid reagent HNOz; 1-(2-aminoethylamino) naphthalene CHIOH; N,N-dimethylphenylenediamine sulfate Benzoyl leuco methylene blue “02; 4nitroaniline ”02; 4-nitrobenzene-fluoborate 4-Aminodimethylaniline sulfate; Ca(OCl)n 4-Dimethylaminobenzaldehyde L-Amino acid oxidase Cupric acetate
KOH Cu tartrate; Na diethyldithiocarbamate NaBH,; diphenylamine ClCN; barbituric acid
(160) (363)
2,6-Dichlorobenzoquinone chlorimide Aconitic acid; acetic anhydride Anthrone 4-Phenylphenol Thiobarbituric acid Heteropoly K2Cr207; thiobarbituric acid CSn-sulfur reagent Phenazine methosulfate; 2,6dichloroindophenol Ninhydrin c u +2 Methylene blue 6-Chloromercuri-2-nitrophenol X-E thylmaleimide 4,7-Diphenyl-l, 10-phenanthroline Cellosolve; NaSO2 Heteropoly Cysteine-H2SOc Peracetic acid 4-Dimethylaminobenzaldehyde FeNHc(SOd2 CuS04; alkali
(66) ( 494 )
in test tubes having different optical properties (178). Photometers. A book of general interest is “Optics of t h e Electromagnetic Spectrum” (16). Falta’s survey (140) covers t h e development, construction, qualities, and application of various types of photometers. Petrash (584) derived t h e optimum conditions for recording spectra based on the conditions for minimum total mean square error. Filter Photometers. As spectrophotometers have become cheaper a n d more readily available, filter ins t r u m e n t s h a v e h a d less attention. T h e following examples h a v e some interest: one constructed especially for t h e determination of fluorine (391) ; one using photoconductive detectors of cadmium sulfide (C.20); a new FEK56 instrument having nine filters (305) ; and a unit having two filters for simultaneous measurement in t h e region of 660 and 800 mp (465). Spectrophotometers. T w o general papers discuss t h e critical selection of methods for absorption measurements (262), and t h e optimum absorbance for Shot noise-limited instruments (524). T h e new Cary Model 15 instrument covers t h e spectral range 175 to 700 mp (20). There are two new PerkinElmer double-beam instruments. Model 202 (578) covers t h e range 190 t o 750 mp, and Model 350 (S79) extends from 175 to 2700 mp. A photoelectric instrument incorporating a Fabry-Perot interferometer (236) provides high luminosity. An automatic “phase” instrument covers the region 210 to 2500 mp (118). An atomic beam spectrophotometer covers the visible region of the spectrum (616). Two components for spectrophotometers include a high-precision photoelectric photometer (280) and a grating for the range 100 t o 650 mp (465). Three accessories include a semiautomatic plotting attachment for t h e Beckman DU instrument (59)’a changed circuitry for t h e Beckman DK-2 instrument to enhance absorbance maxima (97)’ a log scale recorder (117),a sample holder for liquids having high absorbances (9), and a timing mechanism for t h e Beckman DK-1 instrument to obtain scans periodically (270). Several instruments are designated as microspectrophotometers or microcolorimeters. One has automatic recording for t h e region 420 to 640 mp (266); one provides for a n area as small as 0.5 micron in diameter in a microscope (156); one uses cadmium selenide detectors for in situ determination of pigments in living systems (481) ; one is for samples of 10 to 20 ~ 1 (48); . and a n attachment for the Cary Model 14 instrument provides for fields 0.1 t o VOL. 34, NO. 5 , APRIL 1962
237 R
1 mm. in diameter (6‘7). A new reflection oximeter is for in vitro measurements (394). Automatic Photometric Analyzers. T h e general trend toward automation of analytical processes a n d operations is illustrated well in this area. Deflandre (113) reviewed automatic recording photometers for process control, and equipment for automatic analysis by light absorption is part of the review by Hummel and Ebert (21I ) . Instruments as such include a n absorptivity recorder (496), a recording photometer (503),a recording microspectrophotometer for use with single cells (86), a n instrument particularly suitable for kinetic studies in which several components change their spectra simultaneously (698), and a spectral analyzer capable of measuring 120 spect r a per minute (299). Other measuring systems were designed for, or applied to, the determination of specific substances. Gases include boron hydrides in air (15S), nitric oxide in coke oven gas (54, S8‘7), carbon disulfide in air (464), fluoride in air ( I - S ) , oxygen in gas mixtures (388, 422), hydrocyanic or hydrochloric acid vapor ( I & ) , and oxygen in boiler feed water (72). Borok (57) discussed t h e performance of automatic photometric analyzers. Also a recording apparatus has been described for t h e continuous control of the composition of gases (SO). Other publications dealing with continuous analysis are a colorimeter for liquids or gases (S83), a dual-filter photometer for dichromate and uranium in plant streams (120), a colorimeter for in-line analysis of uranium and plutonium solutions (IOS), and recent developments in automatic colorimetric instruments (452). Other substances subjected to continuous measurement are uranium in radioactive process streams ( 4 4 4 , amino acids (489), adrenocortical hormones in mixtures ( I S ) , penicillin and streptomycin in fermentation media ( I @ ) , glucose in blood in vivo (520), alkylaryl sulfonates in water (426), and penicillin (36%). APPLICATIONS
I n Tables I, 11, and 111 many applications have been noted by including the kind of material in which the designated constituent was determined by t h e given method. Also various constituents are mentioned in the previous section in connection with automatic analyzers. Color. The specification of color is a n application of absorptimetry restricted to the visible region of t h e spectrum. B y definition there is no
238 R
ANALYTICAL CHEMISTRY
such thing as ultraviolet or infrared light or color. Among the several publications in this area t h e following may be mentioned: t h e basis of colorimetry (285), a critical study of spectrophotometers and tristimulus colorimeters for the determination of color (WdS), and a direct-reading tomato colorimeter (212). I n a series of papers Reilley, Flaschka, and associates have discussed complementary tristimulus colorimetry and its applications for various purposes (1&6-149,408,410). CONCLUSIONS
Although it is difficult to see all of the developments in their true perspective, the following conclusions seem justified: (1) Some 1500 references collected for t h e period reviewed show undiminished interest in this area of analytical chemistry; (2) the large number of different periodicals cited show how widespread this interest is; ( 3 ) t h e 26 process patents cited reveal the slowly developing awareness of analysts to this kind of publication; (4) in instruments the principal developments have been general refinement and improvement of accessories; ( 5 ) and in chemistry most work has been on developing new reagents, applying old reagents to new situations, and improving old methods. Analysts concerned with literature sources may be interested in the following facts for the 535 references cited: One hundred and fifty different periodicals are included; 16 of these are cited five or more times; these 16 contain 57y0 of all references to periodicals; and patents constitute 5 7 , of the references. LITERATURE CITED
(1) Adams, D. F., ANAL. CHEX.32, 1312 (1960). (2) Adams, D. F., et al., J . Air Pollution Control Assoc. 9, 160 (1959). (3) Adams, D. F., Koppe, R. K., ANAL. CHEY.31, 1249 (1959). (4) Adaskin, E. M., Zamanskaya, R. I., Gidroliz. i Lesokhim. Prom. 13, S o . 1. 14 (1960). f5) ~, Ahenbere. L. N.. Zhur. Anal. Khim. 14,741 (19x9). ’ (6) Akerfeldt, S., Acta Chem. Scand. 13, 627 (1959). (7) Alimarin, I. P., Kuznetsov, D. I., Dokladu Akad. Nauk S.S.S.R. 131. 821 (1960).” (8) Al-Kassab, S., J . Fac. Med., Baghdad, Iraq 2 [K.S.] S o . 1, 35 (1960). Patent (9) Al’perovich, L. I., U.S.S.R. 127,857 (iipril 12, 1960). (10) Altshuller, A. P., Cohen, I. R., AKAL. CHEX 32, 1843 (1960). (11) Zbid., 33, 1180 (1961). (12) Anastassiadis, P. A., Can. J . Biochem. and Physiol. 38, 1223 (1960). (13) Anderson, F. O., Crisp, L. R., et al., ANAL.CHEM.33,1606 (1961). (14) Anderson, N . G., Zbzd., 33,970 (1961). (15) Andrew, C. L., “Optics of the Electromagnetic Spectrum,” PrenticeHall, Englewood Cliffs, N. J., 1960.
(16) Ankudimova, E. V., Zzvest. Vysshikh Ucheb. Zauedenii, Khim. i Khim. Tekhnol. 2,665 (1959). (17) Antipova-Karataeva, I. I., Kutsenko, Y. I., Zhur. Anal. Khim. 15, 581 (1960). (18) hltOn, -4.,A N A L . CHEM. 32, 725 i 1 m’i. \ - - - - I -
(19) .4pple, R. F., White, J. C., Talanta 8, 419 (1961). (20) Applied Physics Corp., Bull. 115-A (19611. ( 2 i ) Arikawa, Y., Kato, T., Tech. Repts. Tohoku Univ. 25, 55 (1960). (22) Artigas, J., et al., Anales real SOC. espa6. fis. y quim. (Madrid) 56B, 369 (1960). (23) Asmus, E., et al., Z . anal. Chem. 178, 104 (1960). (24) Athavale, V. T., et al., Anal. Chim. Acta 24,263 (1961). (25) Avres, G. H., Janota, H. F.. ANAL. C H E ~31, . 1985 (1959). ’ (26) Ayres, G. H., Johnson, F. L., Anal. Cham. Acta 23, 448 (1960). (27) Ayres, G. H., Sarong, B. D., Ibid., 24,241 (1961). (28) Babko, A. K., Get’man, T. E., Raboty Khim. Rastvorov i Kompleks. SoedzneniZ, Akad. Nauk Ukr. S.S.R. 1959, KO.2 , 186. (29) Babko, A. K., Volkova, 0. I., Dopovzdi Akad. h’auk Ukr. R.S.R. 1959, 1336. (30). Babushkin, A. A., et al., Fiz. Sbornak L’aov.Univ. 1957. No. 3. 360. (31) Baistrocchi, R., Ann. chinz. (Rome) 49, 1824 (1959). (32) Baiulescu, G., Ciurea, I. C., Anal. Chim. Acta 24, 152 (1961). 133) Baiulescu, G.. et al., Zbid.. 24. 463 (1961). (34) Banerjea, D. K., Tripathi, K. K., ANAL.CHEM. 32, 1196 (1960). (35) Banerjee, D. K., et al., Zbid., 33, 418 (1961). (36) Bankovskis, V., Lobauova, E., Latviias P S R Zincitnu Akad. Vhstis 1960. K O . 1, 97. (37) Banks, C. V., Bystroff, R. I., J . Am. Chem. SOC. 81,6153 (1959). (38) Banks, C. V., Smith, R. V., Anal. Chim. Acta 21,308 (1959). (39) Bark, L. S.. et al.. Chem. & Ind. ‘ (London) 1960,375. ’ (40) Barnett, H. A , Bartoli, A,, AKAL. CHEM.32, 1153 (1960). (41) Baumann, R. P., Appl. Spectroscopy 13, 156 (1959). (42) Beamish, F. E., AKAL.CHEM.33, 1059 (1961). (43) Beamish, F. E., hIcBryde, W.A. E., Anal. Chim. Acta 18, 551 (1958). (44) Belew, W.L., Wilson, G. R., Corbin, L. T., AKAL.CHEM.33, 886 (1961). (45) Bergstresser, K. S., Zbid., 31, 1812 (1959). (46) Bhat, A. N., Jain, B. D., J . Sci. and Ind. Research (India) 19B, KO. 1, 16 (1960). (47) Bhat, A. N., Jain, B. D., Talanta 5, 271 (1960). (48) Bicz, K.,et al., Bull. acad. polon. sci., ser. sci. biol. 7, 495 (1959). (49) Blair, D., Diehl, H., ANAL.CHEM.33, 867 (1961). (50) Blair, D., Diehl, H., Talanta 7, 163 (1961). (51) Blank, A. B., Zhur. Anal. Khim. 15, 359 (1960). (52) Blanquet, P., Chim. anal. 41, 247 ( 1959). (53) Bogdanova, E. V., Trudy Vsesoyuz n.auch.-Zssledovatel. Vitamin. Znst. 6, 249 (1959). (54) Bokhoven, C., Tommassen, P. H., Nature 190, 435 (1961). (55) Bolleter, W. T., Bushman, C. J., Tidwell, P. IF‘., ~ A L CHEY. . 33, 592 (1961). I
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I
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19. 542 (1958'1.
(67) 'DroGii, P.'K., J . O p t . SOC.A m , 51, 1000 (1961). (68) Hrown, K.D., Australian J . Erptl. Bioi. A f e d . Sci. 37, 523 (1959). (69) 1!ri.tlz. I-.G., ri al.. U.S.S.R. Patent 119,7(39 ( ? J a y 10, 1959). (50) Ibzd , 13@,7C3( l i i g . 5, 1960). ( i l ) I h s h , J. S.,.%SAL. C m x 33, 798 (1961). (72) Burhoff, 1,. S . , U. S.Patent 2,929,687 (March 22, 1960). (73) Buchoff, I,. S., Ingber, X . RI., Ibid. 2,967,092 (Jan. 3, 1961). (74) Burger, Ioui P.,Hurnblet, I;., Talnnia 3,
232 (1960). (499)Ullrich, K . J., Hampel, A , Arch. ges. Physiol. 268, 17'7 (1958). (500)Unihreit, G. R.,A N ~ LCHEM. . 33, 1572 (1961). (501)Umland. F..Meckenstock. K . U..
(504j v a h chem. Biophis. 86, 210 (1960). (505) Van A4man,R.E., Hollibaugh, F. D., Kangelmeyer, J. H., ASAL. CHEU.3 1, 1783 (1959). (506)Vandenbelt, J. M., J . Opt. Soc. Am. 5 1 , 8 0 2 (1961). (507)S'asil'eva. N. L..et al.. Zhur. Vsesoy u z . Khim. Obshchestva i m D.I. Mendeleeoa 5, 110 (1960). (508) Vernon, L. P., ANAL. CHEM.32, 1144 (1960). ~
(509)Vil'borg, S. S.,Drozdov, V. A., Izvest. Vusshikh Ucheb. ZavedSniZ, Khim. i Khim. Fekhnol. 3, S o . 1,75 (1960). (510) Waggener, W. C..Rev. Sci. Instr. 30. 788 11959). (5llj Wagne;, 'V. L.,Jr., Yoe, J. H., Talanta 2, 223 (1959). (512)Zbid., p. 239. (513)Kallace, G. IT-., Mellon, ill. G., h A L . CHEX. 32, 201 (1960). (5141 Wallace. G. W..RIellon. 11. G.. B&l. Chinz.'Acfa 23,'355 (1960). (515)Walworth, H. T., 1-irchow, IFr. E., Ani. Ind. Hyg. Assoc. J . 20, 205 (1959). (516)Weber, 0. A , , Touk, V. B., Analj~st85, 40 (1960). (517)IT-ebster, H. L., Halliday, J., Ibid., 84, 552 (195'3). (518) K&e, \-. K., et al., Clin. Chim. Ada 6, 79 (1961). (519) Keissbach, €1.. e l al., J . Biol. Chem. 235, 1160 (1960). (520)Weller, C., et ai.,Ann. S . Y . Acad. Sei. 87, 658 (1960). (521)IVestley, J., Lambeth, J., Biochim. et Biopkys. Acta 40, 364 (1960). (522)Wilson, H., Anal. Biochent. 1, 402 (1960). (523)Wolf, L., et al., Z . Chen?.1, 27 (1900). (524) Wybourne, B.G., J . Opt. Soc. Am. 50.84 f 1960). - ~ , (525)Savier, J., Ray, P., J . Indian Chem Soc. 35,432 (1958). (526)Zbid., p. 725. T r u d y Komissii (527)Yampol'skii, 11.Z., Anal. Khim.. A k a d . 'Vaitk S.S.S.R.. Inst. Geokhim. i .Anal. Khim. 11, 5 (1960). (528) Yanagihara, T.,et al., Bunseki Kagaku 8, 10 (1959). (529)Yaphe, IT;., i l s . 4 ~ .CHEM.32, 1327 (1960). (530)I7oshihiro, I-.,Sakamura, M., Seisan Kenkyu 10, 46 (1958). (531) Young, J. P., White, J. C., ANAL. CHEM.31, 1892 (1959). (532)Young, J . P.,White, J. C., Ball, R. G., Ibid. 32, 928 (1960). (533)Yuasa, T., A'ippon Kagaku Zasshi 80, 1201 (1959). (534)Zakhar'ina, S.B.,Zavodskaya Lab. 25,1192(1959). (535) Zil'berg, L. A., Gigiena Truda i Professional Zabolevaniya 4, No. 11, 57 (1960). ~
