ANALYTICAL CHEMISTRY Strickland, J. D. H., and Spicei, G., A n a l . C h i m . Acta, 3, 517-46 (1949). Stromberg, A. G., Dityatkovskay, R. V., and Milovanova, N. V., Zavodskaya Lab., 14, 919-25 (1948). Sturnper, R., and Mettelock, P., Bull. SOC. chim., 1947, 674-6M. Suchenko, K. A , , and Yakovleva, S . P., Zawodslzaya Lab., 14, 625-7 (1948). Taganov, K. I., Ibid., 15, 105 (1949). Tanenaev, 1J. A . , and Murasheva, V. I.. J . A n a l . Chem. Russ.. 3, 3-6 (1948).
(88) Thrun, W. E.,
. ~ N A L .CHEhl., 20, 1117-18 (1948). (89) Waterkamp, Maria, Arch. Eisenhuttenw., 20, 5-8 (1949). (90) Weaver, J. R., and Brattain, R. R., AXAL.CHEW,21, 1038-41 (1949). (91) Wiberly, S. E., and Bassett, L. G., Ibid., 21, 609-12 (1949). (92) Wilson, H. N., Analyst, 74, 243-8 (1949). (93) Wood, A . A. R., Metallurgia, 39, 266-8 (1949). (94) Wranglen, Gustav, J . Metals, 1, 919-20 (1949). (95) Yakovlev, P. Ya., and Pen’Kova, E. F , Zavodskaya Lab., 15, 34-6 (1949).
RECEIVED December 2 2 , 1010
NONFERROUS METALLURGY H . \-.CHURCHILL, .IZuminum Company of America, .Yew Kensington, P a .
T
H E review in February 1949 (16) outlined the present status of analytical chemistry in the field of nonferrous metallurgy and particularly emphasized the trend toward the development and use of instrumental techniques. This review, while mainly concerned with developments and work during the past year, of necessity also touches upon data which actually appeared during the previous period but were not available when the first review u-as prepared. The trend toward instrumentation and special techniques in analysis continued in the field of nonferrous metallurgy. Typical procedures involving specialized instrumentation are covered in the following references. Apparatus of an automatic nature for the electrochemical analysis of nonferrous metals was described by Kovalenko (56), and Duval covered the subject of automatic gravimetry (24). Adsorption and absorption techniques, hitherto of little import in the nonferrous field, were discussed in seven papers (46, 52, 65,59-61,109). Although such procedures involving chromatography and similar methods are not in general use, their utility in specific applications should not be overlooked. Hillier (44) points out the possibilities involved in the use of the electron microscope as a tool for microanalysis. Such procedures have certain possible applications in the nonferrous field. I n the somewhat related field of x-rays, papers by A41exanderand Klug ( 2 ) , Geisler and Hill (SO), and Duwez and Ode11 (25) indicate that the nonferrous analytical chemist has a new technique available which may solve certain specific problems. POLAROGRAPHIC AND AMPEROMETRIC PROCEDURES
T h e growing importance of polarographic and amperometric procedures in the nonferrous field is attested by the fact that during the year upwards of 75 papers on such procedures specifically pertinent to nonferrous analytical chemistry have appeared. Only a few references are here cited as typical of the growing interest in this field of analysis. Kolthoff has discussed amperometric titrations (55). Heyrovskj. has given an optimistic but interesting discussion of modern trends of polarographic analysis ( 4 9 ) . Stross has published a most interesting and valuable survey article on the polarographic analysis of light metals and alloys (105). Moritz’s paper on the theory and development of polarographic equipment and methods in industrial laboratories (75) is a stimulating bit of work and well worth the attention of those interested in the possibilities in this field. Kolthoff’s article on voltammetry and amperometric titrations (64) in Frontiers in Chemistry should be a “must” on the reading list of all nonferrous analytical chemists, as should be Lingane’s polarographic theory, instrumentation, and methodology (64). References to the many articles on specific applications of polarographic or amperometric procedures to particular problems have been omitted, for such references are readily available in Chemical Abstracts and elsewhere. Two papers by Lingane on electroanalytical methods are well
worth the attention of those interested in such procedures and their possibilities: controlled electroanalysis (6.5) and some new developments in electroanalytical chemistry (66). An ever-present problem in nonferrous analytical laboratories is that of distinguishing common metal alloys by means of spot tests or similar procedures. Bennett has presented an interesting paper on distinguishing the common metal alloys ( l o ) ,while Winslow and Liebhafsky have looked into the spectrophotometric aspects of spot testing (110). Other papers on the identification of alloys of various types are available. Goldberg covers zinc die casting alloys (Sb’), and Witcoff and Simpson touch on aluminum alloys (111))as do Niessner ( 7 7 ) and Kuznetsov (57, 58). The latter author also presents valuable hints for increasing the sharpness of color tests. SPECTROCHERIIC4L ANALYSIS
There has been a veritable flood of publications concerning nonferrous analysis by means of spectrographic procedures. Although “Practical Spectroscopy,” by Harrison, Lord, and Loofbourow (38),is the most recent comprehensive text on spectrochemical analysis, the texts cited in last year’s review are still pertinent; no startling new developments have occurred. Rowever, specific mention is made of the volume entitled “Modern Instrumental Analysis” ( 1 2 ) . This teat is a compilation of review articles by authorities in various fields of instrumentation. The chapters on spectrochemical analysis by J. R. Churchill are of special interest to nonferrous chemists and are illuminating, instructive, and comprehensive. Although a number of references are cited to published work on spectrochemical analysis pertinent to the field of nonferrous metallurgy, such papers are not discussed in this review, other than t o say that in the reviewer’s opinion they do not represent any particularly novel approaches to the problem of analysis, but rather refinements in existent procedures or the application of specific practices to specific materials and problems. The titles are many and varied and the interested reader can doubtless select those of particular interest to him (1, 3-9, 12-15, 17-23, 26-29, Sl-34, 36, 37, 59-42, 45, 47-51, 62, 65,67-74, 76-102, 104-108). The status of spectrochemical analysis in the nonferrous field has not changed materially during the year, though possibly in the references cited there are seeds of progress, the fruition of which will be greater and better use of such procedures. There has been steady progress in the field of direct-reading spectrographic instruments and procedures. In one industrial metallurgical concern, 28% of the reported determinations, about 1,120,000 out of 4,000,000, were made on direct-reading spectrographic instruments. Two types of instrumentation are commercially available at the present time-that of Baird Sssociates of Cambridge, Mass., and that of Applied Research Laboratories of Glendale, Calif. Other instrument houses are doing work in this field and additional sources of instrumentation may be shortly available.
V O L U M E 2 2 , NO. 2, F E B R U A R Y 1 9 5 0 Mention should be made of the trend toward the wider use of flame photometry in the nonferrous field. Acceptable instrumentation of two types is currently commercially available. T h e Perkin-Elmer Corporation markets an instrument of the filter type tvhich is of considerable interest. This instrumentation has been more generally acceptable since the incorporation of the necessary elements which made possible the use of internal standard methods. T h e other type is that popularly called the Beckman instrument, produced by National Technical Laboratories. This instrument is of the monochromator type and has been successfully applied in various phases of the nonferrous field, particularly where the rapid and accurate determination of the alkali metal elements and calcium is of essential import,ance. There is a graving use of colorimet,ric or photometric methods in the nonferrous field. This growing interest has been great,ly stimulated b y the progressive activit,y of Committee E-3 on Chemical Analysis of the American Society for Testing hIaterials. T h e expanding use of statistical methods for the evaluat,ion of the adequacy of particular methods as regards accuracy and precision is worthy of notice. Quality control statistical methods ordinarily used to control quality of products, both step and final, are being more and more widely used to evaluate the analytical work of routine analysts in many industrial analytical laboratories. I n general, chemical analysis in the nonferrous field is in a healthy, dynamic state of gron-th and development. The author of this review feels that this condition is reflected by the contributions t h a t have been made during the recent past to the literature pertinent to the nonferrous field, which includes not only items of general interest but also items concerned w.ith the determination of specific elements or groups. IN STRUM ENTA L METHODS
It, may seem that this review unduly stresses the importance of inst,rumental methods of analysis. The author feels that the emphasis given is but an accurate mirroring of what actually is occurring in the field, but he also has a n-ord of caution. Many of these instrumentalized techniques are essentially repetitive in nature. T h e validity and integrity of the results obtained depend fundamentally upon the standards b y the use of 11-hichthe instrument$ techniques are set up, calibrated, adjusted, and maintained. These standards must be calibrated and evaluated by the more laborious and time-consuming classic or traditional methods, which are satisfactory in general from the standpoints of accuracy and precision of results, but are woefully lacking in speed. Speed and ease of application are major advantages of most of the newer repetitive instrumentalized procedures and speed in obtaining reliable and trustworthy analytical dat,a is essential t’omodern nonferrous metallurgical practice. Curiously enough then, refinement and improvement of the traditional methods become more and more important as their actual use in routine metallurgical laboratories diminishes. More dependable and reliable assignment of values to standards for use in instrumental analysis makes the quality of results obtained by traditional methods of paramount importance. B remarkable and somewhat paradoxical trend in nonferrous metallurgical analytical chemistry is that fewer traditional analytical chemists are required but their importance is growing. T h e t,rend in modern nonferrous analytical laboratories is for more workers who can be trained to push buttons, throw switches, and read dials, and fewer but better real analytical chemists. LITERATURE CITED
(1) Addink, N. W. H., Rec. trae. chim., 67, 690 (1948). (2) Alexander, Leroy, and Klug. H. P . , ANAL. CHEY., 20, 886 (1948). (3) Argyle, a., and Price, W.J., J . Soc. Chem. I n d . , 67, 187 (1948). (4) Bachelder, M. C., ANAL.CHEM., 21, 1366 (1949). (5) Bannister, L. C., and Price, R. H., J . I n s t . Metals, 75, 1511 (1948).
239 (6) Barbosa, P. E . de F., and Barbosa, L. M.de z4., A n a i s acad. hrasil. cienc., 18, 165 (1946). (7) Barnes, E. C., Piros, W.E., Bryson, T. C., and Wiener, G. W., ANAL.CHEJI.,21, 1281 (1949). (8) Batta, G., Duykaerts, G., and Leclerc, E., Congr. groupe. aaance. mdthod. anal. spectrograph. produits. mdt., 9, 29 (1948). (9) Bayliss, N. S., and David, D . J., J . Sot. Chem. I n d . , 67, 357
(1948). (10) Bennett, F. C., Jr., MetalProgress, 50, 669, 661 (1946). (11) Bolts, D . F., “Modern Instrumental Analysis,” Vol. I, Ann Arbor, Mich., Edwards Brothers, 1949. (12) Borsora, -4.V.,and Sorokina, N. N., Zavodskaya L a b . , 14, 1098 (1948). (13) Bresky, Ladislav, Hutnicke L i s t y , 3, 212 (1948). (14) Burkhardt, Ch., Congr. groupe. avance. d t h o d . anal. spectrograph. produits mBt., 9, 59 (1948). (15) Carlsson, C. G., Jernkontorets Ann., 132, 467 (1948). (16) Churchill, H . V., ASAL. CHEY., 21, 246 (1949). (17) Clayton, H . R., J . SOC.Chem. I n d . , 67,270 (1948). (18) Coheur, P., Congr. groupe. avance. d t h o d . anal. spectrograph. produits d t . , 10, 37 (1948). (19) Coheur, P., Rea. universellemines, 3, 646 (1947). (20) Croissant, Paul, Fonderie, 24, 996 (1947). (21) Danko, A. IT., and iViener, G. IT.,-4x.4~.Cmhr., 20, 1175 (1948). (22) Drutskaya, L. V., Zavodskaya Lab., 14, 248 (1948). (23) Ibid.. p. 571. (24) Duval, Clement, A n a l . C h i m . A c t a , 2 , 432 (1948). (25) Duwez. Pol, and Odell, Francis, J . Am. Ceram. Soc., 32, 180 (1949). (26) Duyckaerts, G., A n a l . C h i m . Acta, 2, 649 (1948). (27) Fassel, V. 4..and TT7ilhelrn, H. A., J . Optical SOC.Am... 38., 518 (1948). (28) I b i d . , 39, 187 (1949). (29) Feldman, Cyrus, -%s.iL. CHEM.,21, 1211 (1949). (30) Geisler, A . H., and Hill, J. K., Acta Crystallographica, 1, 238 (1948). (31) Gentry, C. H. R., Newson, D., and Rushman, D . F., J . Soc. Chem. I n d . , 66, 323 (1947). ( 3 2 ) Giesecke, Paul, T r a n s . Am. Inst. Mining M e t . Engrs., 169, 706 (1946). (33) Girschig, R., Congr. groupe. auance. mdthod. a n a l . spectrograph. produits At.,10, 159 (1948). (34) Givord, J. P.. Ihid., 9, 109 (1948). ( 3 5 ) Goldberg. C., MetaZProgress, 54, 64 (1948). (36) Gruszecki, P. J., I r o n A g e , 159, 44 (1947). (37) Hannick. A . , Congr. groupe. anance. mdthod. anal. spectrograph. prodzcifs m i t . , 9, 49 (1948). (38) Harrison, G. R., Lord, R. C., and Loofbourow, J. R., “Practical Spectroscopy,” New York, Prentice-Hall, 1948. (39) Hartmann. Werner, and Prescott, B. E., J . Optical SOC.Am., 38, 539 (1948). 140) Herman, H., Spectrochim. A c t a , 3, 389 (1948). 141) Heros, Marguerite, C h i m . Anal.. 30, 208 (1948); 31, 11 (1949). (42) Ihid., p. 131. (43) Heyrovskg, J., A n a l . C h i m . Acta, 2, 533 (1948). (44) Hillier, James, Frontiers in Chemistry, 7, 103 (1949). CHEhr., 20, 1077 (45) Hirt, R. c., and Nachtrieb, K. H., .Is.AL. (1948). (46) Irving, Harry, Risdon, E. J., and Andrew, Geoffrey, J . Chem. Soc., 1949, 537. (47) Jean, &I.,Congr. grozlpe. avance. d t h o d . anal. spectrograph. produits d t . , 9, 89 (1948). (48) Kaiser, Henrich, Spectrochim. d c t a , 3, 278 (1948). (49) I b i d . , p. 297. (50) Kaiser, Henrich, 2. angew. P h y s i k , 1, 35 (1948). (51) Kaufman, David, and Derderian, S. K., ANAL.CHEM.,21, 613 (1949). (52) Kayas, George, Compt. rend., 228, 1002 (1949). (53) Kolthoff, I. AT., A n a l . Chim. A c t a , 2, 606 (1948). (54) Kolthoff, I. M., Frontiers in Chemistry, 7, 1 (1949). (55) Kostrikin, Yu. hf., Zavodskaya Lab., 14, 173 (1948). (56) Kovalenko, P. N., I b i d . , 14, 938 (1948). (57) Kuznetsov, V. I.,Doklady B k a d . S a u k S . S . S . R . , 50, 227 (1946). (58) Ibid., p. 233. (59) Lacourt, A., Sommereyns, G.. Degeyndt, E., Barugh, J., and Gillard, J., Metallurgia, 40, 181 (1949). (GO) Lederer, Michael, Anal. C h i m . Acta, 2, 261 (1948). (61) Lederer, Michael, Sature, 162, 776 (1948). (62) Leutwein, F., Arch. .Vetallkunde, 2, 75 (1948). (63) Levine, H., 4 i i . 4 ~CHELr., . 21, 424 (1949). (64) Lingane, J. J.,Ibid., 21, 45 (1949). (65) Lingane, J. J., A n a l . C h i m . Acta., 2, 584 (1948). (66) Lingane, J. J., Record Chem. Prouress, 10, 1 (1949). (67) Lopez de Azcona, J. M., and Camuiias-Puig, A., Congr. proupe. aaance. mdthod. anal. specfrograph. produits d t . , 10,55 (1948).
240
ANALYTICAL CHEMISTRY
(68) Lopez de Azcona, J. M., and Camurias-Puig, 8 . ,Rev. real acad. cienc. eract.fis. y nat. M a d r i d , 41 (1947). (69) hlaassen, Gerd., Z . Erzbergbau u . Metallhuttenw., 2, 103 (1949). (70) Marks, G. W., and Potter, E. V., U. S.Bur. Mines, Rept. Invest. 4377 (1948). (71) Ibid., 4461 (1949). (72) Milbourn, Maurice, Spectrochim. Acta, 3, 267 (1948). (73) IMilbourn, Maurice, and Hartley, H. E. R., Ibid., 3, 320 (1948). (74) Mladentseva, 0. I..Zavodskaya Lab., 14, 369 (1948). (75) .Merits, H., Metall, 1948, 189. (76) Mukherjee, B., Proc. S a t l . I n s t . Sci. I n d i a , 14, 169 (1948). (77) Niessner, Moritz, Berg- 7 ~ hiittenmiinn. . iMonath. montan. Hochschule Leoben, 93, 167 (1948). (78) Oldfield, J. H., Spectrochim. Acta, 3, 354 (1948). (79) Orsag, Joseph, Rev. AIurninitm, 144, 151 (1948). (80) Orsag, Joseph, Spectrochim. Acta. 3, 341 (1948). (81) Pastore, Salvatore, Ricerca sci., 13, 58 (1942). (82) Pheline, J. M.,and Castro, R . , Congr. groupe. a m n c e . d t h o d . anal. spectrograph. produits mbt., 10, 109 (1948). (83) Prokop’eva, -4. N., and Taganov, K. I., Zavodskaya Lab., 15, 299 (1949). (84) Ratsbaum, E. A., I b i d . , 15, 368 (1949). (85) Renouard, P., Congr. groupe. amnce. mithod. anal. spectrograph. produits d t . , 10, 65 (1948). (86) Sage, Max, Compt. rend., 228, 572 (1949). (87) Sanders, C., J . SOC.Chem. I n d . , 67, 185 (1948). (88) Scheibling, Gaston, Bull. sac. franc. mineral, 71, 259 (1948). (89) Schmidt, R., Congr. groupe. avance. mbthod. anal. sprctrograph. produits m&., 10, 137 (1948). (90) Schmidt, R., Manders, Henriette, and van Wijk, G. J . , Rec. trav. chim., 67, 745 (1948). (91) Schmidt, R., Manders, Heuiett,e. van WYk, G. J . , and Ver-
kerk, B., Congr. groupe. avance. method. anal. spectrograph. produits d t . , 10, 145 (1948). (92) Schnopper, Isidore, and Adler. Isidore, ANAL.CHEM.,21, 939 (1949). Schuhknecht, W., Optik. 2, 81 (1947). Seith, W., Metall, 1948, 117. Sempels, G., Spectrochim. A c t a , 3, 346 (1948). Short, H. G., and Dutton, W.L.. A s a ~CHEM., . 20, 1073 (1948). Sihvonen, Y . T., Fry, D. L., Nusbaum, R. E., and Baumgartner, R. R., J . Optical SOC.Am., 39, 257 (1949). (98) Sinclair, D. A4., Ibid., 38, 547 (1948). (99) Smith, A . L., and Fassel, V. A . , ASAL.CHEM.,21, 1095 (1949). (100) Smith, D. M., and Wiggins, G. M., Spectrochim. A d a , 3, 327 (1948). (101) Spicer, W. M.,and Ziegler, W. T., ~ N A L .CHEM.,21, 1422 (1949). (102) Staahl, G. E., and Halliwell, G. P., Trans. Am. Foundryman’s Assoc., 55, 191 (1947). (103) Stross, W., A n a l y s t , 74, 285 (1949). (104) Triche, H., Congr. groupe. avance. mbthod. anal. spectrograph. produits mbt., 10, 77 (1948). (105) Tuttle, H . A , , and Bryan, F. R., Iron A g e , 162, 57 (1948). 1106) Weaver, J. R., and Brattain, X. R., . ~ A L .CHEM.,21, 1038 (1949). (107) Werner, Otto, Metall, 114, 69 (1948). (108) White, M . M., I n d . Radiography Son-Destructive Testing, 5, 27 (1946). (109) Williams, T. I., A n a l . C h i m . Acta, 2, 635 (1948). (110) Winslow, E. H., and Liebhafsky, H.‘A., ANAL.CHEM.,21, 1338 (1949). ( I 11) Wtcoff, S., and Simpson, N. H., Modern Netals, 4, 24 (1949). (93) (94) (95) (96) (97)
RECEIVEU December 14, 1949.
PETROLEUM HARRY LEVIN, The Texas Compuny, Beacon, N. Y .
T
HE present review of progress in analysis in the field of petroleum takes into consideration the literature for approsimately one year from t h a t covered in the previous review ( 7 8 ) . As may have been espected, there has been an abundance of publications, doubtlessly still reflecting accumulated intellectual production of the war years. CRUDE OIL
Dickey and Sorg (28) described an elwtrometric titration procedure for determining inorganic chlorides directly in crude oil, avoiding the customary preliminary n-ater extraction, and thus permitting a determination to be completed in 20 minutrs. GAS
Parker and Goldblatt (101) identified isobutylene by absorption in phenols with catalyzed formation of 4-tert-butylphenol whose melting point he determined, and Kivensen et al. (68) described a n infrared chopped radiation analyzer for the determination of butadiene in r e q c l e streams of synthetic rubber plants. The instrument can be adapted for recording and control purposes. Jezl and Hablitzel ( 5 8 ) , working on butadiene, described a simple distillation apparatus for separating dimers from monomers; the column is adaptable presumably t o other separations in which small amounts of relativelr high boiling materials must be removed from volatile samples, Milsom et al. (94) combined infrared and mass spectrometry for analysis of gaseous mixtures, because infrared is more Ieliable for isomers ~1hereas mass spectrometry is more efficient when isomeric distribution is not required. I n the calculations the infrared calibration coefficients and mass spectrometer sensitivities are placed in the same reciprocal matrix. RIapstone and Beckmann (89) reviewed methods for determining total unsaturation and applied a reagent comprising mercuric
sulfate and sodium dichiomate in sulfuric acid t o refinery cracking gases. Webber (132) emploJed a carbon dioxide stripping and scrubbing procedure to determine butane in furfural when evaluating stripper efficiency. It was also applied to mineral seal oil recovered in oil absorption processes. Robey and ITiese (109) described a scheme of complete analysis for mixtures of C6 hydrocarbons involving high efficiency distillation and dilution of the fractions with a gas t o peimit the application of established methods of gas analysis. Included is a new colorimetric method for isoprene involving mercuric acetate reagent. Starr and Lane (117) studied the results of a great many tests from many laboratories employing instrumental, ordinary physical, and chemical procedures for the determination of gaseous hydrocarbons in the Rubber Reserve butadiene program and drew conclusions on the unique advantages of each of the procedures. Smittenberg (114) described a micromethod (0.5-ml. sample) for analyzing hydrocarbon gases based on low pressure evaporation and measurement of pressure increase in an evacuated receiver. Crouthamel and Diehl (21) analyzed binary mixtures such as air with methane, carbon dioxide, or hydrogen by measuring the velocity of sound in the mixture; the signal was amplified electronically and registered on a meter t h a t can be calibrated in terms of the composition of the gas mixture to give a continuous reading of composition of the gas flowing through a tube. The apparatus is distinguished in basic principles from t h a t of the General Electric Company. Len is (80) described an improved Blacet-Leighton apparatus for microanalysis of gas. Brooks et al. (11) described methods and apparatus for the analysis of fixed and hydrocsibon gas mixtures frequentlv encountered in the petroleum industry. The apparatus is comprised of unit sections permitting versatile applications and embodies mechanical mercury lifts. Specially prepared copper oxide is used in the determination of paraffins by combustion a t 700” C. without addition of air or oxygen. Orchin and Wender (100) de-
