Review of Fundamental Developments in Analysis
Inorganic Microchemistry Phirip W. West Louisiana State University, Bafon Rouge, La.
W
ITHOUT QUESTION the most important contribution to the genera1 field of inorganic microchemistry during the past two years was the appearance of the fifth edition of Feigl’s “Spot Tests in Inorganic Analysis” ( 5 3 , This reviewer must confess that he had come to take for granted this claspic treat,ise, but the preparation of this review, coupled with a variety of events and activities, has brought about the realization that few if any of the rapidly changing areas in chemistry are kept on as current B baeis as is the field of spot test analysis, with the regular appearance of Feigl’s revisions of his books. During the past two years, over 3000 art,icles n-ere classified in abstract form and set aside for possible consideratioii in the preparation of this review. Comparison of these collected references with the latest edition of “Spot Testdl discloses that the book revision has been done so carefully that no significant lvork has been omitted. While it is true that spot tests will present only one part of the general field of inorganic microchemistry, it seems safe to say that t h h ia the most important area in this general field. The present review covers the period from the 1938 review (227) through October 1959 of Analytical Abstracts and the Yovember 1959 edibion of ANALYTICAL CHEMISTRY.The scope of the revien. is liniited in general to the conventional microanalytical techniques in titrimetry, gravimetry, and spot teste;. Significant developments of new apparatus and equipment having special uses in microchemistry have been reviewed, and relatively great emphasis has been placed on methods of separation. ils has been point,ed out in previous reviews, inorganic microchemistry draws upon many disciplines a i d many of the most significant advances actually occur in such fields as niii,!tvnics, chromatography, ion exchange, arid spectroscopy. Colorimetric and spectrophotometric methods of analysis are usually applied at the niicroanalytical level. All of these very important fields justify separate reviews, and it would be a senseless duplication of effort and space for them to be included here. .4 balanced perspective of developments in inorganic microchemistry, however, cannot be obtained without reference to
the accompanying reviews of these associated techniques. The number of publications dealing with any given procedure, reagent, or discipline must not be interpreted aa the criterion of importance. Classifying areas of activity, however, does yield interesting and sometimes useful information. The present review has disciosed. for example, that there is increasing activity in the development of methods of separation. Although conventional methods of separation appear in most analytical methods, it is of significance that unique separation steps are either the subject of, or n t least part of, 537, of the articles reviewed. More and more emphasis is being given to microanalysis and trace anaiysis; consequently, it is logical that separation or gathering operations are receiving more attention. Almost 70Oj, of the articles considered for review included the use of organic reagents. Organic reagents are the heart of colorimetric, spectrophotometric, and spot test methods. I n addition, precipitants used in gravimetry are usually organic compounds, and some of the most important titrants are organic complexing agents. It has long been the hope of many analytical chemists that specific organic reagents would appear for each of the metal ions and there is even hope that specific reagents will be available for the various anions. With the passage of t k e , this ideal situation has appeared less and less likely and instead has come the realization that selective or even general reagents can be most useful. Much emphasis has been placed on the conditioning of nonselective reagents so that highly selective and specific reactions can be obtained. It is interesting and encouraging to note. however, that one of the most unlikeiy ions has now been conquered by the introduction of glyoxal bis(o-hydroxyanil) which provides a specific teat for calcium (76). Many contributions of considerable importance lie buried in manuscripts where only careful study will bring them to their proper perspective. illthough inorganic microchemistry might seem to be a restricted field, it still is too broad and too complex for a truly comprehensive review. The follow-ing discussion. therefore, represents a critical sum-
mary of the more obvious developments of the past two years. REVIEWS
The mathematics of colorimetric analysis with the ring oven have been discussed by Knodel and Keisz (102). Semiquantitative analysis can be done using the ring-oven technique (227). Only a visual estimation is required, and a weighed mean taken of a series of rings can be interpreted with remarkable accuracy. This reviewer has applied this method to the determination of a, few micrograms c ~ fmaterial separated b y conventional ring-oven techniques. The results were impressive that special emphasis is given tr: this contribution. Reviews of inorganic microchemical analysis have been presented by West (227) and Korennlan if 07:;. Alimarh has reviewed ultraniicroanalysis (3)and the role of amperometric titrations in ultramicroanal3.sis has a1.c~ been disc m e d (160). Hendlin has discussed the advantages and limitations of microbiological assay methods 1~86):snd the role of nucleation in analytical chemistry is of considerable interest (101). Other reviews of general interest are those of recent advances in the preparation and uses of ion exchange resins (81)and the use of the electron microscope in microchemical analysis ($47). Shlenskaya (192) has reviewed the advances made in the use of organic reagents for inorgsnic analysis in t h e U.S.S.R.. and Yoe (241) has discussed the use of orgmiC reagents in colorimetric analysis. ‘:‘he applications of (ethylenedinitrilo) tetraacetic acid (EDTA) as a masking agent have been reviewed by Flaschka (6‘3); Barnard and Ruechl have reviewed the uses of sodium tetraphenylboron (16). Iwantscheff h m discussed the various uses of dithimne (96), and Williams has reviewed the analytical chemistry of cobalt (235) with considerable emphasis given to microchemical methods. Methods for the determination of traces of iodine have been reviewed by Komarek (106). The significance of the new edition of “Spot Tests” has already been discussed. The reference volume on solvent extraction by Morrison and Freiser VOL, 32, NO. 5, APRIL 1960
71 R
(147) will be a most useful edition to the library of the microchemist and may be expected to take ita place alongside the standard references such as Sandell’s “Colorimetric Determination of Traces of Metals.” Extraction separations are extremely important to the microanalytical laboratory and the literature includes an increasing number of references to this technique. A review of extraction methods in analysis has been presented by Korenman and Sheyanova (109). Fisher has presented an intemting discussion of the chronopotentiometrio method of analysis (69), and Hull (88) has discussed the effect of temperature on the performance of microchemical balances and has proposed a rhythmic procedure for use in making weighings a t room temperature.
APPARATUS A N D INSTRUMENTS
Balances are always of interest to microchemists and the quartz beam microbalance described by Czanderna and Honig is of interest because of its sensitivity, which permits the detection of changes in mass of the order of 5 x 10- gram with an accuracy of h l O - 7 gram (47) The Cahn electrobahnce is familiar to most microchemists. The use of this balance has been discussed and a number of suggestions have been made for utilizing some of its unique characteristics (32). A recording colorimeter for use in microchemical work has been described by Solomon and Caton (197). A microliter absorption cell for use with the Beckman D U spectrophotometer has been developed (?4) and a high-sensitivity scanning b e spectrophotometer has been designed by Kelley and his associates (la)). A device for filling microbureta has been designed by Mayer and Koch (139) and a distillation apparatus which incorporates an efficient absorbing vessel has been developed especially for the microdetermination of fluorine (12). Recommendations have been made for the specifications applying to micropipets in the microliter range (4). Bhuchar (29) has designed a glass support ring for use in spot tests, a spot marker, a nozzle for steaming spots, and a paper support for use in fuming operations. hlcCarthy and Stevens have suggested the use of a sample tank that permits the introduction of a flowing sample through reagent paper in conducting multiple codned-spot analyses of gecchemical samples. By use of the apparatus described and the spot-test technique, semiquantitative estimations of a number of metals can be made conveniently at the submicrogram level (127). hlicrochemical investigations are now including studies made in molten salts. Microscopical observations have been
72 R
ANALYTICAL CHEMISTRY
made in the past and now spectrophotometric studies are being made through the use of a special high-temperature cell described by Young and White (943). SEPARATIONS
Increasing interest in methods of s e p aration and techniques for concentrating trace amounts of material is evident and, undoubtedly, this trend will continue and, in fact, probably accelerate. The use of solvent extraction is attracting the most interest a t present. Not only is this technique of general use, but it also possesses unique advanin the separation and isolation of trace materials. Unlike precipitation, where fixed limitations are imposed by an inefficient separation, the extraction process can be used with ultimate efficiency even in those cases where a single pasa fails to effect complete separation. By the simple expedient of multiple extractions, complete separation can be a p proached. Gathering agents are now being studied with renewed interest. Although this is an old and wellestablished technique, collection or gathering of traces has shown greatly increased activity. Miscellaneous methods of separation are to be noted. Of particular importance is the continued interest in the Weisz ring-oven procedure. Volatilization finds some use in the separation of inorganic materials and, of course, chromatographic and ion exchange methods are very popular. The combination of solvent extraction and ring4ven techniques has proved to be an elegant, efficient means of separation. West and Mukherji (998) have used these combined methods in the separation and identification of 35 m e tallic ions. By a sequence of separations combined with selected spot tests, they have been able to analyze complex mixtures in a matter of a few minutes. The ring oven has been used by Ballczo and Weisz (13) in the concentration and detection of fluoride and Antikainen has used the Weisz ring-oven method for the separation and determination of. micro amounts of uranium in the presence of thorium, bismuth, and lead (6). Lawson and Kahn (120)have used adsorption on powdered borosilicate glass together with solvent extraction procedures for the separation of indium from cadmium. Pohl has separated trace amounts of boric acid from silicic acid by extracting boric acid with methanol-isopropyl ether, using a perforator as a means of enhancing extraction efficiency (166). The use of solvent extraction has many attractive possibilities when used as an aid in flame spectrophotometry. This work has been pioneered by Dean and his coworkers, who have shown that
a number of key separations can be obtained by extraction. When the extracted species is fed into t h e flame for evaluation, enhanced sensitivity is obtained in many cases. This approach has been used by Eshelman and Dean for the isolation and determination of aluminum (64); chromium has been determined in this manner by Bryaa and Dean (29), and hfenis and Rains (140) have used extraction and flame spectrophotometric measurements for the determination of lanthanum. Alimarin and Gibalo (2) have utilized complexation as a means for varying the selectivity of extraction processes. By proper selection of extraction systems combined with selected reagents for spectrophotometric estimation, hIaeck and his coworkers (25, 132-4) have shown that specific procedures for the determination of uranium are possible. The analysis of complex ferrous alloye can be simplified through the use of acetylacetone (129) extractions. The nonspecific aluminum-alizarin reaction can be greatly improved by prior removal of interfering metals such as vanadium] titanium, zirconium, and iron by extraction of these metals as their respective N-benzoylphenylhydroxylamine complexes (8’46). Sen (188) haa introduced p henyl-a-pyridyl ketoxime as a chelating agent that is useful in the extractive separation of cobalt, copper, iron, gold, and ruthenium. The extraction of zinc dithizonate into various organic solvents has been studied (185) and comparative studies have been made on the extraction of ferric chloride into various organic solvents (14). Likewise, the comparative effectiveness of various organic solvents in the separation of niobium thiocyanate has been studied by means of tracer techniques (810). The extraction of ferric chloride n-ith isobutyl methyl ketone and amyl acetate has been investigated (39) and a thorough study of acetylacetonate extractions has been made (114). Dioctyl phosphate has been used for extracting yttrium, lanthanum, and praseodymium (168). A thorough study of various methods of separating cadmium has been made (50) and the dithizone extraction is recommended. The removal of trace impurities from high purity selenium has been accomplished (104) by extracting the contaminating metale using a mixture of 8-quinolinol and dithizone. The extracted material subsequently is examined spectrographically, and detection limits as low as 0 . ~ 1 % have been achieved. The use of multiple fractional extraction processes has yet to be ~ i d e l y applied in separating inorganic materials, although Berg and Senn have used countercurrent extraction for the s e p aration of some of the platinum-group metals (20, 21). This approach has considerable merit and will undoubtedly
find increasing use in the future. A surprising lack of interest has been shown in the extractive separation of anions. Studies of anion extractions have been going on for the past year in the author’s laboratories but the first published account of such separations seems to be the work of Hesford and McKay, who have studied the use of tri-n-butyl phosphate for the extraction of nitrates (86). A summary of m m e of the more interesting individual separations that can be accomplished b y extractive procedures is presented in Table I. Most collecting of traces has been accomplished by the use of hydrated metal oxides as carriers or by the carrying action of precipitated metal sulfides. Organic coprecipitants are proving to be of value for collecting and a number of interesting publications have appeared dealing with this approach (37). Hankins has concentrated traces of copper, cobalt, zinc, molybdenum, and nickel prior to spectrographic analysis by the carrier action of aluminum precipitated by 8quinolino1, tannic acid, and thionalide (84). Korenman and his associates have studied ccprecipitation of various metals with the precipitation of anthranilates (1082 10). Organic coprecipitants have been used for the separation of cerium and europium from uranium (I%), bismuth from chromium and nickel (116), and protactinium from radium and other radioactive elements (199). These and other methods of separation are included in Table I. A novel method of gathering traces of metals in very small volumes of solution employs the use of ion exchange granules. I n effect, the ion exchange granule serves as a collector, and spot test identification of concentrated metal ions is applied directly to the concentrate on the granule surface. B y this technique the sensitivity of some tests may be increased by one or two orders of magnitude (67,69, 71,99,1@). The use of ion exchange methods is particularly impressive in many cases where conventional methods of separation fail or are inefficient. In some cases, the choice of method must depend on the amount of material being handled. For example, Pressly has shown that small amounts of americium and promethium can be handled b y ion exchange methods, but larger amounts of these metals are best separated b y precipitation procedures (171). The value of various types of chromatography is well established, and this general technique is particularly attractive in separating trace amounts of metals (63, 184, 196). Volatilization methods of separation are often overlooked in the case of inorganic materials. Often such metals have distinct advantages, and it seems
safe to predict that more use of this approach will be seen, especially when used as a p r e l h h a r y step in trace snaly&. Westland and Beamish have studied volatilization methods in the separation of noble metals (831, B8), and Geilmann (78) and Benedetti-Pichler and Schneider (19) have made general
Table 1.
Subject Ac Al As Sb Ba Be Bi Cd Ca Ce co
cu Cr Eu Ge Pb
Hg Si0
NO,Pr’b
2
Method Copptn. Copptn. Masking Xtn. Xtn. Copptn. Xtn. Xtn. Copptn, Copptn. Copptn. Masking Copp tn . Copptn. Copptn. Copptn. Xtn. Copptn. Masking Copptn. Xtn. Copptn. Copptn. copptn. Copptn. Masking hiasking Xtn. Xtn. Copptn. Pptn. Xtn. Copptn.
studies of these methods. The separation of substances such as sulfur is usually done by volatilization (118) and isothermal distillation should find more use in the future than it has up to this time. Precipitation methods are so standard that little need be mid about them
Separation, Isolation, and Masking
Remarks With BaSO! With Al oxmate and thionalide and tannic acid Sulfosalic date CHC1, ( d C I soh.) Isopropyl ether With PbSO, Ethyl acetate (thiocyanate soln.) Acetylacetonate With HgS With methyl violet With HgS EDTA With -I,i’di(4-hydroxy-3-sulfophenylazo)diphenyl methyl violet With ZnS With AI oxinate thionalide and tannic acid With &O3. zH20 Pyridine thiocyanate Kith A1 oxinate thionalide and tannic acid Thiourea With AllOt. zHtO Trioctyfphosphhe oxide (acidic soh.) With 4,4’di( 4-hydroxy-3-sulfophenylazo)diphenyl . . methyl violet With FerOa.zHlO With BaCr04 With HgS With K I Thiosemicarbazide Acetylacetone CHCI, Tri-n-butyl phosphate (lanthanide, actinide, or 2 nitrate) Ppt. with tannin with SnCll for collection With T a diethyl (or pyrrolidine) dithiocarbamate Hexone (H2S04-HFsoh.) With LaF,
+
+ +
+
+-
Pod-’ Pa
Copptn. Copptn. Copptn. Xtn. Xtn. Pt metals Pptn. Xtn. Xtn. Copptn. Pu Xtn. Ra Copptn. Rare earths Copptn. Re Copptn. Sn Copptn. Se Copptn. Masking Ag Masking Ta Xtn. Tc Copptn. Te Copptn. T1 Copptn. Copptn. Xtn. Ti Xtn. Th Copptn. Copptn. u Xtn. Xtn. Masking V Xtn. Xtn. W Copptn. Masking Zn Copptn.
With Zr bandelate Diisopropyl ketone (acidic sohs.) Tributyl phosphate (myobenzene soh.) As sulfides with thiourea . Trihutyl phosphate ( H a soln.) CHCIJ (quinoline-2selenol ppts.) With LaF3 2-Thenoyltrifluoroacetone in acetone With BaS04 With ThlC90,L With tctraphekylarsonium perchlorate K i t h CaSO, --. With As Complexed with Sa2S.,0a Thiourea Isobutyl ketone (HCl s o h ) With CuS With As With CdS With MnOt.zH20 Diisopropyl ether (HBr soh.) Trioctylphosphine oxide (thiocyanate soh.) With Hg(IO3)* With Bi,(P20a),in 2M HClO, Tri-n-octyl (or decyl) phosphme oxides Tri(iso-octyl) amine (HC1 soh.) HsOt Acetylacetone CHCl, Ether (HC1 soln.) With Fe203.zH20 Citrate With A1 oxinate thionalide and tannic acid ~
+
+
VOL 32, NO. 5, APRIL 1960
73 R
except when new precipitants are developed. A study has been made of the separation of strontium from calcium using calcium rhodizonate (222). Methods of precipitating hydrated oxides a t constant p H have been discussed by Tan& (806). This method has particular advantage in the concentrating and separating of minute amounts of metals such as iron and manganese. .4n interesting paper dealing with the separation of uranium has been published by Upor and his associates (214). Uranium precipitants are dissolved using an excess of carbonate. The tendency of uranium to adsorb on any aluminum hydroxide that may be formed is prevented by adding thorium hydroxide. Combinations of techniques are often used and, in particular, masking action finds \vide application in enhancing other separation methods (76). Although masking is not strictly a method of separation it serves the same funct,ion, and where it can be applied, has distinct advantages over most actual separation proceduws. I n the previous reviews considerable attention was given to masking agents, and tables were presented listing some of the more common complesing addenda. -4 number of masking agents are listed in Table I of the present review. The versatility of masking agents such as sulfosalicylic acid has been suminarized in a series of articles (94,203-205).j’i.The use of cyanide as a masking agenb has been common for decades: but occasionally unique applications are encountered. The recent paper by Platte and 3 h c y (165) is a good example of flexibility obtained by clever use of demasking action. These authors describe a method for the determination of zinc using Zincon i!: a solution containing cyanide to mask interfering effects. Because cyanide inhibits the reaction of zinc ion xith the reagent, t!ie zinc cyanide complex was demasked successfully b:. the addition of chloral hydrate. The use aE the mcrcix:- mthode for the electdytic spparation of metals is finding Increaseci use !lis~. S2hemes of separatif,n ar2 also of Gmsiderahle 1 particuiar attention is called to tile s:hemat,i:. use of paper chromatograph!- (94). ‘The nonsulfide separation schemes proposed by Thonipson Lnd ‘&Xson (208) as .sell as the one developed b:*. West and Tick (2SOj have at,tractit-e possibilities in microanalysis. REAGENTS
Hundreds of neiv reagents have appeared, and new uses for old reagents have been uncovered. The real value of a new reagent is diffimlt to ascertain,
74 R
-
ANALYTICAL CHEMISTRY
and generally, accurate appraisal: can only be made after some years of testing in actual practice. The actual need determines to a large extent the value of new reagents. So many fine reagents exist for use in detecting and determining iron and copper that any additions here must have unusual characteristics if they are to have much significance. On the other hand, almost any reagent that possesses sensitivity and even general selectivity for calcium or chromium(II1) can be considered significant. Finally, reagents that have flexibility often have unique uses and may prove to be of more value than selective or even specific reagents. The test of time is not necessary to establish the value of glyoxal bis(ohydroxyanil), which has recentlT- been introduced b y Goldstein and StarkMayer as a reagent for calcium ( 7 5 ) . This compound reacts with calcium, barium, and strontium, but the latter two do not interfere in tests for calcium if sodium carbonate is added. The authors claim a sensitivity of 0.05 y for calcium and noted t’hat of 33 ions studied only cobalt and nickel gave similar precipitates. Although the reagent is not specific for calcium, the reaction can be so conditioned that a specific test is evolved because only the calcium complex is extracted into chloroform from sodium carbonate solution. Although these claims seemed too good to be trile, they have been fully substantiated hy subsequent studies in this reviewer’s laboratories. A second interesting rmgent for calcium has just been introduced. It is 3,6-dihydroxy-2,4-bis [Y, LY’- di(carboxymethy1) - aminoniethy!] fluornn, which permits the fluorometric estimation of calcium aftcr hen\-:.- xctals have been masked by cyanide and triethsnolamine (219). It is interesting that well-estab1ishi.d reagents often find new uses. For example, chromotropic acid, n-hich has been used for years in the determinatior, of tit:rnium and formaldehyde, has now been shown by Kest and Snrnia to be of m l u e in the detection and determination of nitrates (2299). The systeniatic investigation of organic reagents provides very valuable fundamental knowledge and often results in the introduction of valunbie derivatives The best example of the value of systematic studies is found in the work of Smith and hk associates, who havtr done such classic investigations of the substituted phenanthrolines and dip>-ridines (181 196). A very interesting study has been made of rubeanic acid and its derivatives (2%), and a number of new phenylfluorine derivatives have been synthesized and studied (177). The reaction of various organic groups with aluminum has been studied in an effort to establish combinations that, hold promise in the detection and determination ~
of this metal (11.5). It is interesting to note that it is often possible to nchirve considerable improvements in a reagent by relatively slight changes. For example, Robinson and West fr?’3) have suggested the use of o-dianisidine molybdate as a new reagent for the detection of phosphate. The o-dianisidine serres the d u d purpose of weighing the precipitat,ed molybdophosphate and of serving es a chromophoric agent. Chloranilic acid is a very recent addition to t’he analyst’s reagent shelf. and although it suffers from a number of deficimcies, it still is proving valiiable in the colorimetric and spectrophotometric determination of small amounts of chloride, fluoride, and sulfate ( 2 2 ) . Ken- reagents that, map prove of interest include the following: phenylhydrazinodithioformic acid (150), which ma!- he used for the gravimet.ric determination of lead or the colorinietric estimation of silver and copper; 2,4.&tripyriilyl-~triazine (43): which is a new specific colorimetric reagent for iron ; 1-(2-pyridy1azo)-Bnaphthol ( 3 5 ) . used for the colorimetric estimation and extraction of traces of uranium; 7-amino-1-methylphenosaz-.%one ( l i j ) ,proposed for the detection of tin, chromium, titanium, as well as for chloride and bromide; N-oriminoacetylanthranilic acid ( J I ) , of value in the detection and colorimetric determinat>ionof cobalt; &nitro2-naphthol-8-sulfonic acid ( 5 ) , which gives an intense blue fluorescence with divalent tin; FI-amino-1-naphthalenesulfonic acid (62 which gives cryst,alline precipitates wit,h sodium and may be used for detecting sodium in the pre:ence of pot,assium, lead, magnesium, lithium, and ammonium ions: 442p!ridvlazo)resorciriol ( / 6 3 ) ,which gives colors with many heavy metal ions; a,8,-~,6tetraphenplporphine( l 5 ) >of particular interest because of its color reaction with zinc; 5-aminothiazoline2-thiccarhxyarnide (209), which forms a colored precipitate that may be of value ir. the detection and determination of pa,lladium; flavianic acid ( 1 which is claimed to k a specific p r e cipitant for zirconium: l,!j-diphenplcarbohydrazide (812j,a new sensitive spectrophotometric reagent’ for copper.
QUANTITATIVE MEMODS
-4 number of the more interesting c m ventional quantitative procedures have been listed in Table 11. I n most cases, colorimetric and spectrophotometric methods have been omitted because of the separate review dealing with this general subject. A number of papers overlap two or three disciplines and some of these h a w been included as a matter of interest. For example, spectrophotometric determinations of ions separated by means of paper chroma-
Table 11.
Subject Be Cd Ca Ce
Methods of Determination
Method Grav. Grav. Photo. Photo. Tit. Tit. Photo. Photo. Tit. Photo. Tit. Photo. Photo. Photo. Photo. Grav. Photo. Photo. Photo.
Reagent and Remarks References CO(NH,),+3 2-o-Hydroxyphenylbenaoxazole Picrolonic acid and methvlene blue Ultraviolet spectrophotometric ci Potentiometric Amperometric Ultraviolet spectrophotometric (iron-chloro complex) C SDemasking F Amperometric Au Spectrophotometric (Rhodamine B) Thionalide (indirect) Hg In Flame Fe Ultraviolet spectrophotometric (chloro complex) Flame hk Ultraviolet spectrophotometric (oxbate) hro Pptd. aa [Cr(NH3)sC1]MoS4 Thiocyanate (thiourea aa reducing agent) Nb Spectrophotometric (thiocyanate) KO3 Ultraviolet spectrophotometrio in HClO, Pd Grav. 5-Aminothiazoline-2thiocarboxamide P Photo. Ultraviolet spectrophotometric (molybdophosphate) K Tit. Tetraphenylboron (indirect) Rare earths Tit. EDTA 6 Photo. Demasking Te Photo. Thiocyanate Tb Photo. Ultraviolet spectrophotometric c Grav. Electrodeposition Zn Grav. Mercaptobenzothiazole
t o g n p h y have been used with direct measurement of colors developed on the paper (48,117). I n such cases, reflectance measurements are usually made, but it is possible a t times to measure trammittance. A new titrimetric procedure has been proposed in which the titration is carried out on paper steeped in an indicator (170). The titrations of various metal ions in nonaqueous media, using chelating agents such as 8 - q u h o h o l (67), show promise. Likewise, the infrared spectra of metal oxinates have been run (161) and some of the chelates cm be identified and possibly determined by this technique. 'EDTA titration without metal indicators has interesting possibilities in microchemical titrations (187), and
those who use chelometric titrations with indicators should consult the theoretical discussion of this subject by Flaschka (61). Sadek and Reilley (176) have proposed the use of chelometric titrations with potentiometric end-point detection. Hahn has discussed the determination of end points by potentiometric means in microanalysis (79). A number of special techniques warrant mention. Lithium, which is difficult to determine ordinarily, has been estimated a t the microgram level by mass spectrometry (194). Coulometric methods (12'3) and anodic stripping voltammetry (@) are very attractive microchemical procedures and it is possible that photometric methods (68) will find use. Moisture is still one
of the difficult determinations for the microanalyst, and therefore the reaction of magnesium nitride with water to form ammonia and subsequent nesslerization is of value (193). One of the most promising areas for development is that for hgh-temperature flame photometry (11). Both emission and absorption spectra may be used for rapid, sensitive, and highly selective d e terminations of many elements. Automatic methods in inorganic microchemistry will probably become common, although at present such methods are used only in special casea. The study of air pollution involves a highly specialized type of trace analysis, and here continuous analxzers are becoming common. A potentiometric recorder for hydrogen sulfide and hydrogen cyanide has been described by Strange (801) and a continuous sampling and measuring instrument has been developed for estimating nitrogen dioxide (96). Very small amounts of chloride can be determined in static and flowing systems by means of a new potentiometric analyzer (186), utilizing a silversilver chloride pellet electrode. The instrument can be used directly over the range of 0.1 to 100 p.p.m. of chloride. Very often extremely valuable information can be obtained from semiquantitative methods that are simply and rapidly performed. Detector tub( I W ) can be very effective in establishing concentration levels of trace pollutmts in air or gas streams. AIso, the ring-oven method has exceptional flexibility and is a truly elegant means of estimating minute amounts of material. By using a statistical approach in the evaluation of ring intensities, very rapid and remarkably accurate estimates of concentration can be made. The mathematics of this method and the procedures used have been summarized by Knijdel and Weisz (102).
QUALITATIVE TKHNIQUES
Table Ill.
Subject Ba(Sr) Cs CN Hydrazine Halides I Pb
Mg N03-
h'oble metals
os
PO, -a Se S03-' SO,+
Sn
Qualitative Procedures
Method
Reagents and Remarks
spot test Spot test Spot teat spot test spot test Microscopic spot test s p o t teet spot test spot test spot test Microscopic Microscopic Microscopic spot test spot test spot test Microscopic spot test spot test
Sodium rhodizonate Specific; glyoxal bis(ctbydroxyanil) Competitive reaction Benzidine ZNitroindane-1,3-dione Electron microscopy Chloramine T tetrabase Luminescence with ZnS Iodine-NaOH Chromotropic acid Diphenylamine 4-Piperidinc-1-phenylbut-kne Isoquinoline and thiocyanate 1,2,3,4Tetrahydro-6-methylquinoline o-Dianisidine molybdate 4Methylthio-l,2-phenylenediamine Induced reaction Electron microscopy
+
N-Benzoylp henylhydroxylamine
The schematic separation and concentration of metallic ions by means of solvent extraction and the ring-oven method have proved t o possess considerable merit (328). The concentration and isolation of ions by means of ion exchange granules continue to be of i n t e m t . The ion exchange surface serves as the site for subsequent color development, and the tests obtained in this manner have considerable enhancement of sensitivity over the normal spot test procedure (70, 89, 149). The specific test for calcium discussed elsewhere in this review is of special significance (75). Another difficult ion to detect is perchlorate, which has been studied by Feigl and Goldstein (66'). They show that this ion can be detected VOL. 32, NO. 5, APRIL 1960
e
75 R
b y fusion with cadmium chloride and then detecting the chlorine evolved in the presence of perchlorate using thioMichler's ketone. Feigl, Goldstein, and Rose11 have described a test for chloride (67) bmed on the evolution of chromyl chlorate, with subsequent color development using 4,4'-bisdimethylaminothiobenzophenone. Thorium and uranium can be detected with arsenazo in the presence of E D T A (64, and the rare earth ions can be detected as oxalates and cupferrates (216). The microscopical identification b y precipitated metal chloride-quinoline precipitates has been studied by Mutchler and Bradley (161). Table I11 includes a number of tests that are of value in identification work. Burger (SO) has proposed the use of
2,Cdinitro-l-t,hiocyanatobenzene for the detection and estimation of silver. LITERATURE CITED
(1) Aleksandrova, E. I., Trudy Karan. Khim. Teknol. Inst. im. S. M . Kirova 21, 127-32 (1956); Referat. Zhur. Khim. 1957, 41,395. Coprecipitation with manganese dioxide of chromium,
aluminum, and iron when present together in solution. (2) Alimarin I. P., Gibalo, I. hf., Vestnik Moskov. r?niv. 5, 55-9 (1956); Referat. Zhur. Khim. 1957, 8369. Use of complex formation for separation and determination of elements b s an extraction method. (3) Alimarin, I. P., Petrikova, hl. N., Zavodskaya Lab. 24, 29-32 (1958). Ultramicroanal sis. (4) iimerican Ciemical Society, Commttee on hficrochemical Apparatus, Division of Analytical Chemistry, ANAL. CHEM.30, 1702-3 (1958). Report on recommended specifications for microchemical apparatus. Volumetric glassware. Microliter pipets. (5) Anderson, J. R. A., Gamett, J. L., Lock, L. C., Anal. Chim. Acta 19, 2569 (1958). Use of naphthalene derivatives in inorganic analysis. New reagent for fluorometric detection of tin. (6) Antikainen, P. J., S w e n Kemistilehti 31B, 277-80 (1958). Separation and determination of micro amounts of uranium in presence of thorium, bismuth, and lead using Weisz ring oven. ( 7 ) Babenko, A. S., Zhur. Anal. Khim. 12, 220-3 (1957). Sensitivity of detection of magnesium b iodine. (8) Babenko, A . S., Domgrovskii, A. V., Ukrain. Khim. Zhur. 24, 99-102 (1958); Referat. Zhut. Khim.. 1958, 64,217: XIicrocrystalloscopic reaction for nitrate ion with 4piperidino-l-phenylbutr2ene. (9) Babko, A. IC., Marchenko, P. V., Zavodskaya Lab. 23, 1278-83 (1957). Use of coprecipitation for obtaining analytical concentrates of cadmium, lead, bismuth, and zinc in analysis of alloys (molybdenum and tungsten with nickel). (10) Bailey, D., Dowson, W. M., Harrison, R., West, T. s., Mikrochim. Acfa 1957, 137. Qualitative inorganic analysis. Test for detection of tin(1V). (11) Baker, hf. R., Fuwa. K., Thiers, R. E., Vallee, B. L., J . Opt. SOC.Am. 48, 576 (1958). Spectral excitation in high-temperature flames as function of sample flow. (12) Ballczo, H., Doppler, G., Lanik, A., Mikrochim. Acta 1957, 809-22. Rapid
76R
b
ANALYTICAL CHEMISTRY
microdetermination of fluorine by distillation and absorption. (13) Ballczo, H., Reisz, H., Ibid., 1957, 751-4. Detection of fluoride ion. (14) Bankmann, E., Specker, H., Z. anal. Chem. 162, 18-28 (1958). Comparative studies on extraction of ferric ch!oride by organic solvents. (15) Banks, C. V., Bisque, R. E., ANAL. CHEM. 29, 522-6 (1957). Spectrophotometric determination of zinc and other metals with a,B,r,&tetraDhenvl.. . . . . por hine. (16) arnard, A. J., Jr., Buechl, H., Chemist Analyst 47, 46-7 (1958). Sodium tetraphenylboron, 1957: a bibli. . ography. (17) Bad, Z., Plasil, Z., Stangl, R., Rudy (Praaue) 5. 124 (1957). Determination of arsenic by an extraction method. (18) Bastian, R., Weberling, R., Palilla, F., ANAL. CHEM. 29, 1795 (1957). Ultraviolet spectrophotometric determination of nitrate. Application to analysis of alkaline earth carbonates. (19) Benedetti-Pichler, A. A,. Schneider, H. E., Mikrochim. Acta 1957, 567-71. Heating in a stream of oxidizing or reducing gas for qualitative analysis of inorganic substances. (20) Berg, E. R., Senn, W. L., Jr., Anal. Chim. Acta 19, 12-17 (1958). Countercurrent extraction separation of some platinum-group metals. (21) Ibid., pp. 109-13. Separation of rhodium and iridium by multiple fractional extraction. (22) Bertolacini, R. J., Barney, J. E., 11, ANAL. CHEM.30, 202 (1958). Ultra\iolet spectrophotometric determination of sulfate, chloride, and fluoride with chloranilic acid. (23) Bhuchsr, V. M,,Mikrochin. A l a 1958,577-9. Glass apparatus for annular spot testing. (24) Blasius, E., Gottling, W., 2. a?!. Chem. 162. 433-9 (1958). Separation procedure 'for cations based on paper chromtoeranhv. - (26)Booman, Cf. L., Maeck, W. J., Elliott, hl. C., Rein, J. E., U. S. Atomic Energy Comm. Rept.,lDO-14437( 1958). Extr&ion-spectrophotometric method specific for microgram amounts of uranium. (26) Bouissieres, G., Vernois, J., Compl. rend. 244, 2508-10 (1957). Solvent extraction of quadrivalent protactinium. (27) Boyle, W. G., Jr., Robinson, R. J., ANAL. CHEM.30, 958 (1958). Spectrophotometric studies of chelates of 8quinolinol in some water-miscible organic solvents. Photometric titrations with Squinolinol. (28) Bricker, C. E., Schonberg, S. S., Ibid., 30, 928 (1958). Photonometric determination of vanadium and chromium. (29) Bryan, H. A., Dean, J. A,, Ibid., 29, 1289-92 (1957). Extraction and flamespectrophotometric determination of chromium. (30) Burger, K., Mikrochim. Acta 1957, 310-12. New microchemical identification of silver with 2,4dinitro-lthiocyanatobenzene. (31) Buscar6ns, F., hlunn8, L. hf., Anal. Chim. Acta 19, 432-4 (1958). Qualitative detection and colorimetric determination of cobalt by A'-oximinoacetylanthranilic acid. (32) Cahn, L., Cadman, IFr. J., ANAL. CHEM.30, 1580 (1958). Kew microtechniques. (33) Cannon, J. H., J. Assoc. Ofic. Agr. Chemists 41, 428-31 (1958). Rapid automatic determination of microgram quantities of chloride ion. (34) Cernf, P., Chem. listy 51, 735-8
8
r
(1957). Analytical uses of reaction of
bivalent iron with violuric acid.
(35) Cheng K. L., AXAL.CHEY.30, 1027 (1958). betermination of traces of uranium with l-(%-pyridylazo)-Z-naph-
thol.
(36) Chenley, R. B., Hunter, G. J.,
Webber, T. J., Atomic Energy Research Establ. Gt. Brit. C/M 327, (1958). Study of accuracy and precision of lanthanum fluoride coprecipitation method for determination of plutonium. (37) ChIko, V. T., Zhut. Neorg. Kham. 2, 685-95 (1957); Referat. Zhw. Kham. 1957, 69,089. Methods of copcentfating traces of metals by coprecipitation. (38) Cimerman, C., Frenkel, S., A d . Chzm. Acta 16, 305-11 (1957). hficrovolumetric determination of mercury with thionalide. (39) Claassen, A., Bastings, L., 2 . anal. Chem. 160, 403-9 (1958). Extraction of ferric chloride with isobutyl methyl ketone and amyl acetate. (40) Cline, R. W., Simmons, R . E., Rossmassler, W. R., AXAL. CHEM. 30, 1117 (1958). Determination of trivalent chromium in presence of (41) chromate. Coldwell, B. B., hlclean, S R., Can. 3. Ch&. 36, 652-5 (1958). New s ot test for nitrate ion. (42P Coll, H., Dissertation Ab&. 17, 1659 (1957). SDectroohotometric determination of cgloride'ion. (43) Collins, P. F., Diehl, H., ANAL. CHEM.31,1862 (1959). 2,4,6Tripyridyla-triazine as reagent for iron. Determination of iron in limestone, silicates, and refractories. (44) Comerman, C., Pavlovec, R., Mikrochim. Acta 1958, 259-65. Gravimetric microdetermination of cadmium with 2-o-hydroxyphenylbenzoxazole. (45) Crouch, E. A. C., Swainbank, I. G., Atomic Energy Research Establ. Gt. Brit. C/R 2843 (1959). Ultramicromethod for estimation of rare earths by complexometric titration. (46) Crouthamel, C. E., ANAL. CHEM. 29, 1756 (1957). Thiocyanate spectrophotometric determination of technetium. (47) Czanderna, A. W., Honig, J. .M., Ibid., 29, 120F10 (1957). Sensitive quartz beam mcrobalance. (48) Damon, J. hl. O., hlellon, M. G., Zbid., 30, 1849 (1958). Spectrophotometric determination on filter of germanium, phosphorus, and arsenic. (49) DeMars, R. D., Shain, I:, Ibid., 29, 1825 (1957). Anod/c stripping voltammetry using hangng mercury drop electrode. (50) DeVoe, J. R., hfeinke, W. ,W., Ibid., 31. 1428 (1959). Radiochemlcal separations of cadmium. (51) Dranitskaya, R. hl., Dremlyuk, R. L.. Ukrain. Khim. Zhur. 22, 821-3 (1956); Referat. Zhur. Khim. 1957, 41,436. %Amino-1-naphthalenesulfonic acid ae reagent for sodium. (52) Efremov, G. V., hlekseeva, I. P. Uchenye Zapiski Leningrad Gosudarst. Univ. im. A . A . Zhdanova 1957, 87-91; Referat. ,Zhur. Khim. 1958, 14,168. Coprecipitation of trivalent thallium nith quadrivalent manganese hydroxide. (53) Efremov, G. V., Andreeva, I. Yu., T'estnik Leningrad Univ. Ser. Fiz. i Khim. 1958, 117-21. &precipitation of thallium with cadmium sulfide. (54) Eshelman, H. C., Dean, J. A., hlenis, 0.) Rains, T. C.. ANAL. CHEM. 31, 183-7 (1959). Extraction and flame spectrophotometric determination of aluminum. (55) Feigl, F., "Spot Tests in Inorganic Analysis," 5th ed., Elsevier, Kew York, 19R8.
(56) Feigl, F., Goldstein, D., Mikrochem. J . 2, 105-8 (1958). Detection of perchlorate in spot-test analysis. (57) Feigl, F., Goldstein, D., Rosell, R. A., Z. anal. Chem. 158,421-7 (1957). Detection of traces of chloride in fine chemicals. (58) Feigl, F., Jungreis, E., Zbid., 161, 87-92 (1958). Ultramicro detection of iodine in inorganic and organic comDounds. (56) Fisher, D. J., U. S.Atomic Energy Comm. Rept. CF-55-10-38 (1956). Investigation of the chronopotentiometric method of analysis. (60) Flaschka, H., Angew. Chem. 69, 707-12 (1957). (Ethvlenedinitrilo) tetraacetic acid as masking agent in analytical chemistry. (61) Flaschka, H , Talanta 1,60-75 (1958). Theory of visual indication and selectivity of complexometric titrations. (62) Forsythe, J. H. W., Magee, R. J., Wilson, C. L., Zbid., 1, 249-51 (1958). .4nalytical chemistry of yridine thiocyanates. Separation o r cobalt and nickel by solvent extraction. (63) Frierson, \V. J., Rearick, D. A., Yoe, J. H., ANAL.CHEM.30, 468 (1958). Separation by paper chromatography and spectrophotometric determination of trace amounts of cobalt. nickel, copper, and zinc. (64)Fritz, J. S., Bradford, E. C., Zbid., 30, 1021 (1958). Detection of thorium and uranium. (65) Fritz,-J. S., Richard, hl. J., Lane, W. J., Zbid., 30, 1776 (1958). Spectrophotometric determination of rare earths. (66) Fudge, A . J., Woodhead, J . L., Chem. & Znd. (London) 33, 1122 (1957). Solvent extraction of protactinium m t h phosphate esters. (67) Fujimoto, M., Bull. Chem. SOC. Japan 30, 83-7 (1957). blicroanalvsis with aid of ion exchange resins. betection of small quantities of bismuth with thiourea. (68) Zbid., pp. 93-6. Detection of small amounts of nickel with dimethylglyoxime and bromine water. (69) Zbid., pp. 274-8. Detection of millimicrogram amounts of nickel with dithio-oxamide. (70) Zbid., pp. 278-83. Detection of millimicrogram amounts of cobalt with nitroso-R salt. (71) Zbid., pp. 283-7. Detection of mil!microgram amounts of iron with 2,2 dip idyl. (72) g i l m a n n , W.,Z. anal. Chem. 160, 410-26 (1958). Use of evawration analysis for detection of minute traces of material. Experimental technique. (73) Gilbert, P. T., Jr., Spectrochim. A d a 12, 397-400 (1958). Determination of indium by flame photometry. (71) Glick, D., Grunbaum, B. W., ANAL. CHEM. 29, 1243-4 (1957). Microliter absorption cell and its adaptation to Beckman Model DU spectrophotometer. (75) Goldstein, D., Stark-Mayer, C., Anal. Chzm. Acta 19, 437-9 (1958). Xew specific test for calcium. (76) Goldstein, G., Manning, D. L., hlenis, o., ANAL.CHEM.31, 192 (1959). Spectrophotometric determination of cobalt with 1-(2-pyridylazo)-2-naphthol. Separation from interfering ions. (77) Greenhaus, H. L., Feibush, A. hl., Gordon, L., Zbid., 29, 1531-4 (1957). 'I'ltraviolet spectrophotometric determination of cerium(II1). (78) Grimaldi, F. S.,Jenkinp, L. B., Fletcher, M.H., Ibzd., 29,484-51 (1957). Selective precipitation of thorium iodate from tartaric acid-hydrogen peroxide medium. Application to rapid spec-
trophotometric determination of thorium in silicate rocks and ores. (79) Hahn, F. L., Mikrochim. Acta 1958, 394-401. End-point determination by interpolation in potentiometric microanalysis. (80) Hahn-Reinheimer, P., Z . anal. Chem. 162. 161-7 11958). Determination of trades of noble metals in rocks. (81) Hale, D. K., Amlys! 83, 3-9 (1958). Recent advances in preparation and uses of ion exchange resins. A review. (82) Hamaguchi, H., Kawashima, T., Japan Analyst 7, 627-30 (1958). Comecipitation of cobalt(I1) with zinc sulfide. (83) Hanker, J. S.,Gelberg, A., Witten, B.. ANAL.CHEM.30.93 119581. Fluorometric and colorimetric esdmation of cyanide and sulfide by demasking reactions of palladium chelates. (84) Hankins, B. E., Dzsserlation Ab&. 17, 2148 (1957). Carrier prehitation of trace elements prior to spectrographic analysis. (85) Hendlin, D., ANAL. CHEM.31, 970 (1959). Introductory remarks (microbiological assay). (86) Hesford, E., hlcKay, H. A. C., Trans.Faraday SOC.54, 573-86 (1958). Extraction of nitrates bv tri-n-butvl phosphate. Extraction a"t trace concentrations. (87) Horton, C. A., White, J. C., ANAL. CHEM.30, 1779 (1958). Separation of uranium by solvent extraction with tri- n -0ctylphosphine oxide. Direct colorimetric determination with dibenzoylmethane. (88) Hull, D . E., Zbid., 29, 1 2 0 2 4 (1957). Effect of temperature on precision and performance of microchemical balance. (89) Ichikawa, T., Shimoda, H., Murase, T., Kakihana, H., A'ippon Kagaku Zasshi, 79, 989-96 (1958). hlicrodetection by use of ion exchange granules. Detection of zirconium with catechol violet. (90) Imai, T., Seto, K., Japan Analyst 7, 4-8 (1958). Collector in analytical chemistry. Colorimetric determination of traces of cobalt by use of aluminum hydroxide as collector. (91) Inoshi, H., Mikochim. Acta 1959, 9-17. Spectrophotometric determination of traces of gold with Rhodamine B. (92) Ishibashi, M.,Shigematsu, T., Yamamoto, Y., Tabushi, M., Kitagawa, T., Bull. Chem. SOC.Japan 30, 433-7 ( 1957). Ultraviolet spectrophotometric determination of iron(II1) as a chloro complex. (93) Ishibashi, hl., Tahushi, hl., Japan Analyst 6, 7-10 (1957). Quantitative analysis of phosphoric acid. Concentration of trace amounts of phosphate in dilute solution or in sea water by coprecipitation with magnesium hydroxide. (94) Ibhibashi, XI., Tanaka, T., Kawai, T., Ibzd., 5, 609-13 (1956). Analytical studies on masking reactions. Masking reartions of aluminum, ferric, and titanic ions by sulfosalicylic acid. (95) Inantscheff, G., Angew. Chem. 69, 472-7 (1957). Dithizone procedures in chemical analysis. Review of developments of last 15 years. (96) Jacobs, hl. B., Hochheiser, S., ANAL. CHEM. 30, 426 (1958). Continuous sampling and ultramicrodetermination of nitrogen dioxide in air. (97) Johannesson, J. K., Chem. & Znd. (London) 1957, 480-1. Amperometric titration of microgram and submicrogram quantities of fluoride. (98) Juliard, A. L., ANAL. CHEM. 30, 136 (1958). Automatic titration of
micro amounts of chloride by convection amperometry. (99) Katou, K., Kakihana, H., h'ippon Kagaku Zasshi 79, 762-7 .(1958). Detection of micro amount of indium with anion exchanger and Alizarin Red S. (100) Kelley, hl. T., Fisher, D . J., Jones. H. C . . ANAL. CHEW 31. 178 ( 1959). High-sensitivity, recoiding, scanning flame spectrophotometer. (101) Klein, D. H., Gordon, L., Talanta 1, 334-43 (1958). Nucleation in analvtical che&stry. (102) Knodel, W.,Weisz, H., Mikrochim. Acta 1957. 417-20. Mathematics of colorimetric analysis with ring oven. (103) Kobayashi, Y., Japan Anallist 7, 560-4 (1958). Rapid determination of chromate ion by detertor tube. (104) Koch, 0. G., Mikrochim. Acta 1958, 402-5. Trace analysis. Trace analysis of selenium of high purity. (105) Iiorbl, J., Pfibil, J., Chem. listy 51, 667-71 (1957). Complexometlic titrations. Specific screening and determination of mercury. (106) KomBrelc, K., Chemie (Prague) 10. 105-12 (1958). Determination of trices of iodine. (107) Korenman, I. lr., Zhzrr. A n d . Khim. 12, 668-7 (1957). Inorganic microchemical analysis. (108) Korenman, I. M., Baryshnikova, hl. N . , l b i d . , 12, 690-4 (1957). c o precipitation of zinc, cadmium, and mercury with anthranilic acid. (109) Korenman, I. M., Sheyanova, F. R., l b i d . , 12, 285-95 (1957). Extraction as method of physicochemical analysis. 10) Korenman, I. hl., Tumanov, -4. A . , Glazunova, Z. I., Krainova, Z. V., Baryshnikova, &I. N., Zhur. Neorg. Khim. 1, 863-73 (1956); Referat. Zhur. Khim. 1957, 15,638. Coprecipitation with certain complex comvounds obtained by action of organic precipitants. (111) Kosta, L., Energia nucleare (Jfilan) 4. 37-42 11957). Sodium dihydrogen hi,pophosphate as reagent for quantitative coprecipitation of thorium. (112) Kraus, K. A., Garen, A., U . S. Atomic Energy Comm. Rept. TID-5223, 304-6 (1952). Method of analysis of ore residues for protactinium. (113) Kraus, K. A., Van Winkle, Q., Ibtd., 296-303 (1952). Chemistry of protactinium. Solvent extraction of protactinium. (114) Krishen, A., Dissertation Abstr. 17, 970-1 (1957)., Systematic study of solvent extraction m t h acetylacetone. (118) Kuznetsov, V. I., Drapkina, D. A., Trudy Vsesoyuz. ,~auch.-Issledovatel. Znst. Khim. Reukticov 1956, 18-25; Referat. Zhur. Khim. 1956, 78,434. Organic reagents for color reactions w t h aluminum. (116) Kuznetsov, V. I., Papushina, L. I., Zhzcr. Anal. Khzm. 11, 68G-8 (1956). Organic coprecipitants (collectors). Coprecipitation of bismuth. Detei mination of small amounts of bismuth in chromium-nickel base alloys. (117) Lacourt, A., Heyndryckx, P., Chem. Age (London)78,251 (1987). Chromatographic determination of micro amounts of metals. (118) Larsen, R. P., Ross, L. E., Ingher, N. hl., ANAL. CHEM.31, 1596 (1959). Separation and determination of microgram amounts of sulfur. (119) Lassner, E., Scharf, R., Z. anal. C h m . 159, 212-4 (1958). Maslung of uranium(V1) in complexometric titrations (pH 10). (120) Lawson, L., Kahn, bl., J . Znorg. & h'uclear Chem. 5, 87-92 (1957). Ad~~
'
'
VOL. 32, NO. 5 , APRIL 1960
* 77 R
sorption and solvent-extraction procedures for separation of carrier-free indium from cadmium. (121) Lefferta, D. T., Microcha. J . 2, 2 5 7 4 1 (1958). Microdetermination of chloride by nonaqueous potentiometric titration. (122) Lerner, 31. W., Pinto, L. J., ANAL. CHEM.31. 5-94 (1959). Separation of rare earths from beryllium, magnesium, zirconium, titanium, uranium, and stainless steel. (2.3) Lingane, J. J., Ibid., 30, 1716 (1958 j. 96,493 coulombs. (124) Lueck, C. H., Boltz, D. F., Ibid., 30, 183 (19%). Indirect ultraviolet spectrophotometric determination of phosphbrus, (125) Luke, C. L., Ibjd., 31, 572 (1959). Photometric determnation of traces of selenium or tellurium in lead or copper. (126) Ib,d., p. 904. Photometric determination of tantalum with -phenvlfluo" rone. 27) McCarthy, J. H., Jr., Stevens, R. E., Ibad., 30, 535 (1958). Apparatus and technique for multiple tests by confined-spot method of colorimetric analysis. Application to field estimation of nickel and copper. 28) XIcDuffie, B., Bandi, R. R., Melnick, L. >I.. I h d . . 31. 1311 (19593. Simdtaneous spectrophotometric determination of niobium and tungsten. Application to complex alloy and stainless steels. 29) McKaveney, J. P., Dissertation Abstr. 17, 971 (1957). Use of acetvlacetone extractions in ferrous analy&. 30) McKaveney, J. P., Freiser, H., ANAL.C x m . 30, 526 (1958). Analytical solvent extraction of vanadium using acetylacetone. 31) Ibid.! p. 1965. Solvent extraction of chromum with acetylacetone. 32) Xfaeck, W. J., Booman, G. L., Elliott, M. C., Rein, J. E., Ibid., 30, 1902 (1958). Separation of uranium from diverse ions. Methyl isobutyl ketone liquid-liquid extraction system. 33) Ibzd., p 1130. Spectrophotometric extraction methods specific for uranium. 3-1) Jfaeck, K. J., Booman, G. L., Elliott, 11.C., Rein, J. E., U. 8. Atomic Energy Cornm. Rept., IDO-14415 (1957). Separation of uranium from diverse ions-study of hexone (methyl isobutyl ketone) liquid-liquid extraction svstem. (133) bfakshovi6, Z. B., Bull. Inst. iVuclear Set. "Boris Kidrzch" (Belgrade) 7, 49-52 (1957). Separation of cerium and europium from uranium by~-organic coprwipiiants. (136) LIalissa, H., 24ibrochim. Acta 1958, 72630. Tests on microchemical determination of niobium and on niobiumtantalum separation by tetramethylenedithiocarbamate. (137) Manna, L., Struck, D. H., Adams, s. L., ~ A L CHEV. . 29, 1885 (1957). Flame spectrophotometric determination of microgram quantities of magnesium. (138) Matauura, If.,Kojima, hI., Iguchi, A, Japan Analyst 7, 792-4 (1958). Goprecipitation and ion exchange adsorption of technetium. (139) Mayer, S., Koch, 0. G., Mikpzhim. Acta 1958, 576-7. Filling devlce for simple microburets. (140) Menis, O., Rains, T. C.,Dean, J. A., ~ A LCHEM. . 31,187 (1959). Extraction and flame spectrophotometric determination of lanthanum. (141) Meshcheryakov, A. M., Iztwt. W e 1 Estestvera Nauk Akad. Xauk Tadzhik S.S.R. 1956, 3-16; Referat. Zhur. Khim. 1957, 57,811. Colorimetric determination of molybdenum.
78 R
ANALYTICAL CHMSTRY
(142) M6ve1, K.,Lacruche, B., hfikrochim. Actu 1958, 241-7. Volumetric
determination of potassium after precipitation as tetraphenylboron. (143) Miauike, A., Hirsno, S., Japan Analyst 7, 545-8 (1958). Colorimetric determination of trace amounts of cobalt in sirconium and titanium with mercury cathode electrolysis. (144) Moore, F. L., ANAL. CHEM.30, 908 (1958). Liquid-liquid extraction of manium and plutonium from hydrochloric acid solution with tri(ismty1)amine. Separation from thorium and fission products. 45) Ibid., pp. 1368-9. Radiochemical determination of neptunium-239 and plutonium-239 in homogeneous reactor fuel and blanket solutions. 46) Moore, F. L., Hudgens, J. E., Jr., Ibid., 29, 1i67 (1957). Separation and determination of plutonium by liquidliquid extraction. 17) Morrison, G. H., Freiser, H., "Solvent Extraction in Analytical Chemistry," Wiley, New York, 1957. 48) Murase, T., Nippon Kagaku Zasshi 79, 983-9 (1958). Microdetection .by use of ion exchange granules. Detecbon of bismuth with catechol violet. 49) Ibid., pp. 1389-93. Jlicrodetection with ion exchange r e i n beads. Detection of silver by catalytic reduction of tri- and quadrihlent manganese. 50) Musil, A, Haas, W., Nikrochim. Acta 1958, 756-6.5. PhenylhydrazinodithiOformic acid as an analytical reagent. (151) Mutchler, J. M., Bradley, H. B., ~ A L CHEM. . 30,13714 (1958). Chemical microscopy. Metal chloridquinoline compounds. (152) Xarjcatiu, T., Baiulescu, G., A d . rep. populure Romhe Studii cercetdri chim. 6, 31-5 (1958). Flavianic acid, a new selective reagent for zirconium. (153) Nedler, V. V., Zasodskaya Lob. 23, 1336-7 (1957). Spectrographic, determination of small amounts of mobiuni in ores and refining products. (154) Konowa, D. C., Mikrochim. Acta 1958, 111-16. Photometric microdetermination of calcium with picrolonic acid and methylene blue. (155) Onstott, E. I., Brown, C. J., Jr., .LYAL.CHEX., 30, 172 (1958). hbsorption spectra of terbium perchlorate and terbium chloride solutions. (156) Otterson, D. A., Graab, J. W,., Ibid., 30, 1282 (1958). Colorimetric determination of molybdenum in presence of tungsten. Modified mwcaptoacetate method. (157) Peattie, C. G . , Rogers, L. B., Spectrochim. Acta. 9, 307-22 (1957). Analytical studies of fluorescence of samarium in calcium sulfate. (1%) Peppard, D. F., Mason, G. IV.. Moline, S. W., J . Inorg. & Nucleur Chem. 5, 1 4 1 4 (1957). Use of dioctyl phosphoric acid extraction in isolation of carrier-free Yw, Lai40, Cei4', Prlrs, and Pr144. (159) Perey, &I., Hettler, A., Cornpf. rend. 243, 1520-2 (1956). Determination of actinium in minerals. (160) Petrikova, hI. N., Alimarin, I. P., Z h w . A d . Khim. 12, 462-5 (1957). Ultramicromethods of chemical analysis. Amperometric titration. (161) Phillip~,J. P., Deye, J. F., -4nal. Chim. Acta 17, 231-3 (1957). Infrared spectra of oxine chelates. (162) Pickett. E. E., Hankins, B. E., ANAL. CHEM.30, 47 (1958). Carrier precipitation of trace elements. b d i o isotope evaluation of aciency. (163) Pirtea, T. I., Mihail, G., Z. anal. Chem. 159, 205-8 (1958). New gravi-
metric micromethod for determination of beryllium. (164) Pirtea, T. I., Stroe, A., Rev. chim. (Bucharest) 8, 435-7 (1957). New microgravimetric method for determination of zinc. (165) Platte, J. A,, Jfarcy, V. M., ~ A L CHEM.31, 1226 (1959). Photometric &termination of zinc with zincon. .4pplication to water-containing heavy metals. (166) Pohl, F. A., Z. a n d . Chem. 157, 613 (1957). . Separation of trace amounts of boric acid from silicic acid by perforation. (167) PohI, F. A., Kokes, K., Mikrochim. Acta 1957,318-25. Microanalytical and polarographic determination of traces of thallium. (168) Pohl, H., Z . Erzbergbau u. Mefallhuttenw. 9, 530-1 (1956). Kew photometric determination of thallium in lead, zinc, and cadmium. (169) Pollard, F. H.,, Hamon, P., Geary, W. J.. Anal. Cham. Acta 20, 26-31 (1959): 4(2-Pyridylazo)resorcinol
as
possible analytical reagent for colorimetric determination of cobalt, lead, and uranium. (170) Polyakov, 11.P., Polyakova, V. P., Byull. Sauch,-Teckh. Inform. A r m . IVaiich. Inst., Zemled. 1957, 32-6; Referat. Zhur. Khim. 1958, 21,082. Sew principle in semiquantitative spot analySls.
(171) Pressly, R. S., U. S. Atomic Energy Comm. Rept., ORNL-2202 (1957).
Separation of americium and promethium. (172) Pshenitsyn, ?i. K., Prokof'eva, I. V., Zhiir. Newg. Khim. 3, 996-1001 (1958): Referat. Zhur. Kham. 1958, 73,729. Complex compounds of iridium and rhodium n-ith thiourea and their application to separation and determination of these met&. (173j Robinson, J. W., West, P. m-.,-%I& crochena. J . 1. 93-9 (1957). Selective test for detection of orthophosphate. (174) Rulfs, C. L., De, A. K., Elving, P. J., J . Electrochem. Soc. 104, 80-3 (1957). Electrodeposition of uranium a t mcrogram levei. (175) Rfiii&a, E., C h m . listy 52, 1716-19 i19583. 7-Amino-l-methylphenoxaz-3one as analytical reagent. (176) Sadek, F. S., Redey, C. K., Microchem. J. 1, 183-201 (1957). Ultramicro chelometric titrations with potentie metric end-point detection. (177) Sano, H., Bull. Chem.SOC.Japan 31, 974-80 (1958). Organic reagents for inorganic analysis. Syntheses of new phenylfluorone derivatives and their reactions with metal ions. (178) Sawicki, E., ANAL. CHEM. 29, 1376-7 (1957). Kew color test for selenium. (179) Schaeffer,r.H. F., Ibid., 31, 1111 (1959). Chemical microscopy of is* quinoline. Identification of noble met-
&.
(180) Ibid., p. 1112. bficrocrystalline test for osmium. (181) Schilt, 4. A., Smith, G. F., Anal. Chim. A& 16,401-5 (1957). New s u b
stituted 2,2'-dipyridines (2,2'-dipyridylo) and their chelation &s Fe+2 and Cu + complex cations. (182) Schwager, E. A., Fischer, A., Z. Physik 149, 347-52 (1957), Sensitive detection of lead and incorporation of lead in zinc sulfide. (183) Schweitzer, G. K., Homker, C. B., Anal. Chim. Actu 19, 22-1-8 (1958). Solvent extraction of zinc with dithizone. (1%) Scott, I. A. P., Msgee, R. J., Talunfa 1, 329-33 (1958). Separation
.
and determination of niobium and tantalum by partition chromatography. 85) Segura, H. F., Garmendi, A. A , , Pella, E. L., Anales asoc. quim. arg. 45, 126-35 (1957). Determination of small amounts of germanium. 86) Seidel, H . L . , U. S. Atomic Energy Comm. Rept., KAPL-M-SMS-93 (1958). Chloride ion analyzer. 57) Sen, B., A n d . Chim. Acta 19, 551-4 (1958). EDTA titrations without metal indicators. ( 1 8 8 ) Sen, B., Chem. & I d . (London) 1958, 562, Phenyl-a-pyridvl ketoxime as chelating agent. (189) Senise, P., Mikrochim. Acta 1957, 640-3. Suot test for sulfites based on induced okidation of cobalt-azide solutions. (190) Shinagawa, M., Murata, T., Bull. Chem. SOC.Japan 31,162-5 (1958). Separation of alkaline-earth elements. Coprecipitation of barium in induced precipitate of lead aulfate. (191) &id., pp. 166-8. Coprecipitstion of radium in induced precipitate of lead sulfate. (192) Shlenskaya, V. I., Vestnik Moskov. U r i i v . 1957, 237-59. Advances in use of organic reagentv in inorganic analysis in U.S.$.R. during last 40 years. (193) Singliar, bl., ZubBk, J., Chem przimnsyl 6, 426-7 (1956). Determination of traces of moisture in gases. (194)Sladh-, R. E., U. S. Atomic Energy Comm. Rept., Y-1143 (1956). Assay of microgram samples of lithium with m spectrometer. (195) Smith. D. 31.. Haves. J. R.. ANAL. . CREM. 31, 898 (1959). ' Trace determination of copper and cobalt by chelate chromatography and dithizone phcc tometry. (1%) Smith, G. F., Banick, W. M., Jr., A d y s t 83, 661-6 (1958). 4,4'Subdtuted Z12'-dipyridyls in chelation reactions with ferrous iron. (197) Solomon, A. K., Caton, D. C., .4r.kr. CHEM.30, 291 (1958). Recording colorimeter for microchemical determinations. (198) Spacu, P., Gheorghiu, C., 2. anal. Chena. 159,209-12 (1958). Gravimetric micromethod for determination of molybdenum alone or in presence of other elements. (1%; S t a r k 1. E., Ratner, A . P., Pasvik, 11 .2., GheidIna, L. D., Zhur. Bnal. Khfm 12, 87-91 (1957). New method of determining protactinium. ( 2 0 0 ) Stewart, J. H., Jr., JIcIlhenny, R. C., V.S.iitornic Energy Comm. Rept., Y-1140 (1956). EDTA separation of calcium from uranium for flame-photonletric analysis. (201i Strange, J. I>., AKAL.CHEW 29, IS78 (193;). I'okntiometric recorder for hj-drogeu sulfide and hydrogen cyanide. (LW2; Tahushi, M., BuU. Insl. Chen:. Reeeurch h - y o b Gniv. 36, 156-62 (1956). Solvent extraction of beryllium as aceth-1ace t o n st e. ( 3 31' Tmaka, T.,,Japan.in~Zyst5,6'13-16 (1956). Masking of manganous, m a g nesium, and cupric ions by sulfosalicylic acid.. (204) ZEid., pp. 6 7 3 3 . 3Xasking of cadmium, zinc, and mckel ione by sulfosslicylic acid. ( 2 0 5 ) Ibid., pp. 677-9. 11mking of CGbaltous, chromic, and indium ions. (206) Tanaka, h l . , Mikmchim. Acta 1958, 204-11. Methods of precipitation of hydrated oxides a t cormant pH. Prin-
ciple and application to microanal) sis of chromium end molybdenum. (207) Theodore, 31. L., . h 7 . 4 ~ .CHEM.30, 465 (1958). Deternunation of tantalum in niobium. (208) Thompson, J. K., ITilson, C. L., Mikrochim. Acta 1957.33430. Chemical analysis on microgram scale. S e p aration and identification of cerium, thorium, lead, calcium, strontium, and barium. (209) T'ien, P., Wang, K., Acta Chim. Sinica 24, 42-6 (1958). 5-Aminothiazoline-2-thiocarboxyamide used as analytical reagent. Detection and determination of palladium. (210) Troitskii, K. V., Zhur. Anal. Khim. 12, 349-54 (1957). Study of process of extraction of thiocyanate complexes of uiobium by organic solvents by radioactive isotope Sb95. (211) Tufts, B. J., Lodge, J. P., Jr., + V A L . CHEM. 30,300,(1958). Chemical identification of halide and sulfate in submicron oarticla (212) Turkin&on,-R. IT.,Tracy, F II., Ibid., 30, 1699 (1958). Spectrophotcmetnc determination of ultramicro amounts of copper with l,&diphenylcarbohydrazide. (213) Umland, F., Hoffmann, F., Anal. Chim. Acta 17, 234-6 (1957). Separation of metal 8-quinolinol compounds between n-ater and organic solvents. Photometric determination of magnesium by extraction of its oxinate with chloroform in presence of amines. (214) Upor, E., Fekete, L., Nagy, G., Magyar Kern. Lapja 13, 305 (1958). Determination of uranium content of ores by separation with carbonate. (215) Vanag, G. Ya., hlatskanova, 31.rl., Zhur. Anal. Khim. 12, 149-3 (1957). . . Color reaction for hydrazine. (216) Van . b a n , R. E , Hollibaugh, F. D., and Kanzelmeyer, J. H., ~ A L . CHEM.31, 1783 (1959). Spectrophotometric determination of antimony with Rhodamine B. (217) Vanossi, R., A m l a asoc. quim. arg. 45, 215-26 (1957). . . Identification of beiyilium. (218) 1-olkova, A. I., Zakharova, K. N., C'krazn. Khim. Zhur. 23, 530-2 (1957); Rejererat. Zhur. Khim. 1958, 17,555. Determination of micro amounts of lead in m e t d i c indium. (219) Tt'allach, D. F. H., SurEenor, D. lI., Soderbera. J.. Delano. E.. - 4 ~ 4CEW. ~. 31, 456 (iU5d). Preparation and pro ertiw of ~ , 6 - d i h ~ ~ r o x ~ - Z , ~ b i s (c~~rbox~methj-l)aminomethyl] flu oran. Utilization for ultramicrodet,ermination of ca!cium. (220) Waiton, G. S.,Furby, E., ORen, I-., .Itomic Energy Research Latahl. C 2388 (1998). Courecioitation of smdl amounts of plutonium on lanthanum fluoride in presence of uranium. (221) R'aterbuq, G. R., Brickei, I;. E.) :hAL CHE>t. 30, 1007-5) (19%). &par:;rtion and spectrophotometric determnation of microgram amounts of nicbium. ( 2 3 2 ) R-eiss, H. V., S h i p m n , Jl-. 13.)Ibid., 29, 1764 (1957). Separation of strontium from calcium v+h potassium rhodizonate. .4pplication to radiochemie t'y. (223j Weisz, H., Xikrwchim. A c b 1959, 26-8. Color reaction for sulfate ion. (224) Ibid., pp. 2'-31. Detection of barium and strontium in a drop. ( 2 2 5 ) IDid., pp. 32-5. Detection of calcium ion. 1 ' R
( 2 2 6 ) JVendiandt, It-. I\-.,Hayes, D . \V., Science 126, 451-2 (1957). Detection of rare-earth ions as oxalates and cupfer-
rates.
(227) Re&, P. W., ANAL.CHEM.30,,71859 (1958). Inorganic microchemistrv. (228) ke&; P. Wy, Mukherji> -1. K., I W . , 31, 947 (1959). Separation and microidentification of metallic ions h v solvent extraction and ring- oven t w h -
niques.
(229) 11-est, P. W., Sarma, P. I,,, M i k r o chim. Acta 1957. 506-9. Suot t a t for
nitrates.
(230) \\-est, P. W.,Vick, 11. 11.. J . Chem. Educ. 34, 393300 (l,957). Quali-
tative analysis and analytical chemical separations without use of sulfides. (231) Westland, A. D., Beamish, F. E., ANAL.CHEY. 30, 414 (1958). Use of chlorine in attack of nohle metals. Quantitative recovery of micro amount,s of platinum, ruthenium, and osmium. (2321 Westland, A. D., Beamish, F. E., Mikrochim.A d a 1957,69539. Separation and determination of platinum metals on a micro scale. (233) White, J. C., U. S. A4toniicEnergy &mm. ReDt.. ORNL-2161 11956). Use of tridylphmphine oxides'= extractants in fluorometric determination of uranium. (234) Khite, J. C., ROES, W. J., Ihtd., ORNL-2326 (1957). Extraction of chromium with tri&t.ylphosphine oxide. (235) Williams, V.J., Talanta, 1, 88-104 (1958). Analytical chemiatr:; of ccbalt . (236) Xavier, J., Rby, P., J . Indian Chem. SK. 35,432-4 (1958). Rubeanic acid (dithiwxamide) and derivatives ne colorimetric reagents. Spectrophotometric determination of cobalt, nickel, palladium, silver, and ruthenium u-ith rubeanic acid. (2373 Ibid., pp. 725-32. S,X'-Dibenzyland Zi,.?"-diphenylrubennic acids. (238) Yamamota, S., N i p p o n K q a k u Zasshz 79, 1309-14 (1958). Chemical analysis and separation by extraction. Spectrophotometric determination of vanadium with phenylhydrazine. (239) Yankov, S. P., Zhur. Anal. K h ( n . 12, i59 (1957). Detection oi cyanide ioo. (240) T e n , J., Tno, T.,Acta Chim.Sinicu 24, 97-194 (1958). Separation of rhenium b,v roprecipitation and ib determiintion in molvbdenite. (211) I-=,J. H., Aii.4~.CHEU. 29, 17-16[ ~ 51 ~ - (1957). , ~ ' - ~ Colorimetric, analpis Kith organic reagents. (242) I-oung, J. P., JYhite. J. C., Ibid.,31, dr+3 lf)59). Extraction of titamurn rhioc>:nnate with td-n-oct,vlphosphine oxide. Direct colorimetric detcrminstion in organic phase. (243 I Ibid., p. 1892. High-teniperature cell assembly for epectrophotornetric studies of molten fluoride salts (241) Zelikman, -1.S.,Gorox-it.., S. S . , Zavodskaya Lab. 24, 940-1 ii958). Coprecipitation of tungsten for its determination in products containing moivhdenilm .. - - _- -.-. (215) 'Zemlyanova; L. I., Kushnir, Yu. M.,ISzd., 23, 10K-7 (1957 1. Use of electron microscoDe for microchemical ~
analysk.
(246) Zharovskil, F. G., S a & . Zapwki., Kits. Derzhac. Cniv. 16. 147-4(1957). Rejerat. Zhur. Khim. 1958, 28,41s'. Detection of aluminum with alizarin after removal of interfering elements b y ex-
traction.
VOL. 32, NO. 5 , APRIL 1960
79 R
