ANALYTICAL CHEMISTRY Kolin, A., Federation Proc. 14, 238 (1955). Kolin, A., J . Chem. P h y s . 22, 1628 (1954). Ibid., 23, 407 (1955). Kolin, A,, Proc. Ahtl. Acad. Sei. U . S . 41, 101 (1955). Kolthoff, I. Vi., ANAL.CHEW26, 1685 (1954). Kunkel, H. G., “Methods of Biochemical Analysis,” Vol. I, pp. 141-70, D. Glick, ed., Interscience, K’ew York, 1954. Lakshmanan, T. K., Lieberman, S., Arch. Biochem. Biophgs. 53, 258 (1954). Laskowski, D. E., Putscher, R. E., ANAL.CHEM.24, 965 (1952). Lazarow, A., Cooperstein, S. J., Science 120, 674 (1954). Lederer, E., Lederer, XI., “Chromatography,” Elsevier, Houston, 1953. Lederer, AI., “Paper Electrophoresis,” Elsevier, Houston, 1955. Lerman, L. S., Biochim. et Biophys. Acta 18, 132 (1955). Lindberg, O., Ernster, L., Science Tools 2, 7 (1955). Linskens, H. F., ed., “Papierchromatographie in der Botanik,” Springer, Berlin, 1955. Loring, H. S., “Xucleic Acids (Chemistry and Biology),” Chap. 5, Vol. I, E. Charaaff and J. X. Davidson, eds.. Academic Press, Ken, York, 7955. lIcBay, A. J., hlgeri, E. J., Am. J . Clzn. Pathol. 24, 1139 (1954). McDonald, H. J., “Ionography. Electrophoresis in Stabilized Media,” Year Book Publishers, Chicago, 1955. AIcReady, R. hI., McComb, E. -4.,AN.~L.CHEM.26, 1645 (1954). Marschner, R. F., Chem. Eng. S e m 33, 494 (1955). Martell, A. E . , Chaberek, S., ANAL.CHEY.26, 1692 (1954). Martin, A. E., Smart, J., S a t u r e 175, 422 (1955). Martin, A. J. P., Brit. N e d . Bull. 10, 161-250 (1954). Mitchell, J., others, eds., “Organic Analysis,” T’ol. 111, Interscience, Sew York, 1955. Mellors, R. C., ”Analytical Cytology,“ NcGraw-Hill, New York, 1955. Mellors, R. C., Arias-Stella, J., Siege], A I . , Pressman, D., Federation Proc. 14, 254 (1955). Moore, S., Stein, W. H., J . B i d . Chem., 211, 893 (1954). Mould, D. L., Synge, R. L. XI., Biochem. J . 58, 585 (1954). Muendel, C. H., Selke, TV. A , , I n d . E n g . Chem. 47, 374 (1955). Oster, G., Pollister, A. W., eds., “Optical Techniques,” Vol. I of “Physical Techniques in Biological Research,” Academic Press, New York, 1955. Packer, L. F. J., Analyst 80, 638 (1955). Peterson, E. A., Wyckoff, h l . AI., Sober, H. -I., p. 42’2. Abstracts, 128th Meeting, ACS, Xlinneapolis, September 1955. Pies, K. A., Eagle, H., Science 122, 968 (1955). Porter, R. R.. Biochem. J . 59, 405 (1955). Price, T. D., Federation Proc. 14, 264 (1955). Price, T. D., Hudson, P. B., A N ~ LCHEY. . 26, 1127 (1954). Rasmussen, P. S.,Biochim. et Biophys. Acta 16, 157 (1955). Rehell, B., Scand. J . Clin. Lab. Inaest. 6, 335 (1954). Reilley, C. N., Schweiser, B., A s . 4 ~ CHEW . 26, 1124 (1954).
REVIEW OF FUNDAMENTAL DEVELOPMENTS IN ANALYSIS
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0
I Distillation Analysis I
’I’ T
ARTHUR ROSE
and
JERRY ACClARRl
Applied Science Laboratories, Inc., State College, Pa., and The Pennsylvania State University, University Park, Pa.
pace of advance in analytical distillation seems to have slowed, compared with earlier periods (80). The most exciting development, vapor-liquid chromatography, is not even recognized by some workers as distillation. Within the scope of conventional analytical distillation, the developments have been mainly in improving and extending previously described ideas and applications; the more important of these are indicated in the following sections. Particularly significant are the adBances in multistage countercurrent molecular and l o r pressure distillation apparatus, and in micro distillation methods. HE
(114) Reiner, AI., ed., “Standard Methods of Clinical Chemistry,” Academic Press, Sew York, 1953. (115) Rideout, L. A., Prichard, R. W., Science 121, 374 (1955). (116) Saroff, H. A., ’Tuture 175, 896 (1955). (117) Scheinberg, I. H., Harris, R. S., Spitzer. J. L., Proc. NatZ. Acad. Sci. C . S . 40, 777 (1954). (118) Schmits, H., Potter, V. R., Hurlbert. R. B., White, D. >I., Cancer Research 14, 58 (1954). (119) Schreiber, R., Cooke, IT. D., ANAL.CHEY.27, 1475 (1955). (120) Scott, J. F., in “Optical Techniques,” T’ol. I of ”Physical Techniques in Blological Research,” Oster, G., and Pollister, A. IT., eds., .Icademic Press, Sew York, 1955. (121) Scott, R. W., .&F.~L. CHEM.27, 367 (1955). Ibid., 27, 725 (1955). (122) Shapiro, L., Brannock, W.W., (123) Sharpe, L. H., Ibid., 26, 1528 (1954). (124) Shibata, K., Benson, A. A , , Calvin, N., Biochim. et B w p h y s . Acta 15, 461 (1954). (125) Smith, J. D., Chap. 8, T’ol. I, “Sucleic Acids (Chemistry and Biology),” E. Chargaff and J. K , Davidson, eds., Academic Press, Sew Tork, 1955. (126) Sober, H. d.,Peterson, E. .I.,J . Am. Chem. Soc. 76, 1711 (1954). (127) Sorof. S., Ott, 11. G., Young, E. 11..Federation Proc. 14, 284 (1955). (128) Steele, J. l l . , ed., “Methods in Medical Research,” Vol. 7, Year Book Publishers, Chicago, 1954. (129) Strain, H. H., AN.AL.CHEM.26, 1869 (1955). (130) Strain, H. H., Carnegie I n s t . W a s h . Year Book 48, 87 (1949). (131) Svensson, H., I V A 25, 252 (1954). (132) Svensson, H.. Brattsten, I., Arki?; K e m i 1, 401 (1949). (133) Svensson, H., Valmet, E., Science Tools 2, 11 (1955). (134) Tamiya, K., Toshino, Y., Soda, T., BUZZ.Chem. Soc. J a p a n 27, 393 (1954). (135) Theorell, H., Nygaard, 4.P.. Acta Chem. Scand. 8 , 877 (1954). Angew. Chem. 67, 245 (1955). (136) Tiselius, -I., (137) Tiselius, a,, Arkic R e m i 7, 443 (1954). (138) Tiselius, 8., Claesson, S.,Arkiz: Kemi M i n . Geol. 15, SO. 18 (1942). (139) Udenfriend, S.,Weissbach, H., Clark, C. T., J . BioZ. Chem. 215, 337 (1955). (140) Underwood, A. L., J . Chem. Educ. 31, 394 (1954). (141) Wade, H. E.. XIorgan, D. A I , , Biochem. J . 60, 264 (1955). (142) Werkheiser, W. C., Winder, R. J., J . Biol. Chem. 204, 971 (1953). (143) Werner, G., Rec. trar. chim. 74, 613 (1955). (144) Wingo, IT. J., ASAL. CHEM.26, 1527 (1954). (145) Wyatt, G. R., Chap. 7, Vol. I, “Nucleic Acids (Chemistry and Biology),” E. Chargaff and J. S . Davidson, eds., Academic Press, S e w York. 1955. (146) Young, A , , Sweet, T . R., Baker, B. B., ASAL. CHEX 27, 356 (1955). (147) Zahn, R. K., Stamm, IT.. Rauen, H. >I., A?IgeW. Chem. 63,280 (1951).
There have also been some good papers on precision laboratory fractionation, Mair’s use of fluorochemicals as azeotrope formers with hydrocarbons is also worthy of special mention (60). VAPOR-LIQUID CHROMATOGRAPHY
Vapor-liquid chromatography involves establishment of composition differences between a liquid phase on the surface of a stationary solid adsorbent, and a moving vapor or carrier gae phase. The liquid phase of the mixture undergoing separation
72 1
V O L U M E 28, NO. 4, A P R I L 1 9 5 6 is partially converted to vapor of different composition from the liquid by the flow of carrier gas, as in steam distillation, desorption, and other examples of codistillation. A resemblance to extractive distillation arises from the presence of a purposely added nonvolatile liquid on the surface of the adsorbent, in which the components of the mixture being separated are dissolved. The presence of the purposely added nonvolatile liquid and the adsorbed character of the liquid phase, undoubtedly result in major changes in relative volatilities, and are probably the chief basis for the remarkably sharp separations that are achieved. The vapor-liquid nature of the separation system allow the principles of distillation or desorption to be applied. I n doing this, i t must be recognized that vapor-liquid chromatography lacks the countercurrent flow characteristic of conventional distillation and absorption or desorption. The very small samples necessarily used make the process an example of microanalysis, and limit its use to cases where samples of the separated materials are not desired after analysis. A limited number of papers have been published on this new technique, and on the related process of gas chromatography (4, 41, 49-46, 58, 65, 7 2 ) . LOW PRESSURE DISTILLATION
Alair, Pignocco, and Rossini ( 6 1 ) have described in detail a relatively simple 50-stage apparatus for distillation a t 0.01 to 0.1 mm. of mercury with countercurrent flow of the vapor and liquid streams. The important feature of this apparatus is that there is no pressure drop from one end of the apparatus to the other. The equipment consists essentially of a slanting tube with baffles located inside along the heated bottom side to prevent too rapid flow of liquid, and a cooled tube inside along the top, on which vapor condenses before it passes into collecting tubes that direct it to a point in the liquid stream, higher up in the tube. Vertical baffles in the vapor space prevent diffusional mixing in the lengthwise direction. Arrangements a t the ends provide for introduction of reflux. The liquid throughput is only 80 ml. per hour, so a t a reflux rate of 55 to 1, many hours of operation are needed to distill a charge of several liters. Typical results on the distillation of C17 to Czsparaffin mixtures are given. Aldershoff (1) has described a somewhat similar apparatus for use a t lower pressures, in the molecular distillation range. Illelpolder, Washall, and Alexander ( 6 3 ) described a different multistage, countercurrent distillation apparatus for the molecular distillation pressure range. This apparatus consists of 20 glass molecular stills of conventional design, interconnected in series in such a way as to provide the desired countercurrent operation. With 19 small and one large (1250-ml.) stage, the total capacity is 1500 ml. Tests with 2-ethylhexj-1 phthalate2-ethylhexyl sebacate showed 0.8 theoretical plate per stage. Automatic safety controls permit operation unattended for long periods. A single distillation is stated to require of the order of 24 hours. Earlier patents issued to B u r r o w (13) describe a somen-hat similar apparatus. Cantoni, Feldman, and Orchin ( 1 7 ) have described the use of repeated molecular distillation in a cyclic still, with the addition of a solvent or carrier, to separate the closely related polycyclic hydrocarbons, fluoranthene and chrysene. Two equilibrium-type high vacuum stills suitable for 5- to 50-gram samples are described by Zaugg and Shave1 (101). An external magnetic drive on a horizontal axis is used to rotate a barrel-like surface from which vaporization occurs, and heat is supplied from infrared lamps. A nerr self-contained vacuum distillation column mounted in a metal shield, and of standardized design for ASTM distillation of lubricating oils and reduced crudes, is available ( 6 ) . PRECISION DISTILLATIOIV WITH FRACTIONATING APPARATUS
There have been two comprehensive papers on the practical details of precision laboratory fractionation. Winters and Dinerstein ( 9 7 ) have described a group of eight columns used for gen-
era1 purposes in a petroleum research laboratory. These are used for 15- to 50-ml. samples and include spinning band, Hypercal, and concentric tube types, each giving a height equivalent to a theoretical plate of about 1 cm. One of the columns in this same laboratory has 300 theoretical plates (19). A precisely controlled power supply is stated to be essential to ensure smooth operation, and mixing of fractions must be avoided, as one drop can result in 10% contamination of a fraction. The spinning band apparatus is recommended for vacuum distillation. Adiabaticity is achieved by vacuum jackets and radiation shields, without use of external heaters. The latter are recommended, however, by Cooke and Jameson (N),who also describe a group of laboratory fractionating columns for routine analytical distillations. They emphasize the importance of avoiding condensation in the column or reflux divider, and recommend Cannon protruded packing. Several good general discussions of laboratory fractional distillation have appeared in the foreign literature (18, 24, 28, 49, 69). The classic work of the Rossini group has appeared in book form ( 8 4 ) , and a 20-page pamphlet describes the Todd apparatus and gives numerous practical working instructions (90). Several references to continuous laboratory distillation were found ( ~ 9 7 ~ 574, 4 , 92). AUTOMMTIC DISTILLATION AND COLUMN COIVTROL ACCESSORIES
There has been little nen- information reported, as has been indicated by Patterson (71) in reviewing automatic analytical operations. Because so many laboratory fractionating columns have for some time been arranged to operate with a minimum of operator attention, i t is not surprising to reach a point of diminishing returns. Some foreign articles have appeared (12, 51). The idea patented by Bresee ( 9 ) is probably applicable to laboratory columns. A packed column is provided with a restricted section in which flooding takes place before it occurs generally. Flooding in the restricted section is used a8 the basis for automatic or manual action to prevent general flooding. A patent was issued on the Podbielniak ( 7 5 ) device for a movable thermocouple whose motion spans the zone of condensation a t the head of the column. Wilson ( 2 1 ) has described a still head t h a t permits continuous analysis by a measurement of the capacitance of a condenser formed by two concentric metal cylinders surrounding a tube through which condensate flows. A w a y and others ( 2 ) describe a fraction cutter actuated by changes in refractive index or similar properties of the product. Other new fraction-collecting or -cutting devices are characterized by utilization of dielectric constant (50), drop counting (87), constant volume (99, 52), continuous chain belt drive (95), siphons ( 7 ) , Teflon plugs (SP), and other devices (58, 42, 59, 64, 79, 93, 95). Other accessories of interest are a vertical umbrella-type agitator to promote smooth boiling in vacuum distillation (831, an automatic safety trap for laboratory steam distillations (CO), an entrainment catcher ( S I ) , and a multipurpose apparatus suitable for direct heating, or heating by hot water: steam, or air (47). MECHQSICS OF FR.4CTIONATION
A number of Russian and other eastern European papers have discussed factors affecting theoretical plates (11, 14-16, 65-67, 86) and the effect of pressure (89). Kuhn, Baertschi, and Thurkauf ( 5 3 ) have discussed the relation between various operating variables, Manning and Cannon (62) have presented interesting information on channeling, and Rose and Biles ( 8 1 ) have described a new method of measuring relative volatilities in an operating column. Fastovskil, Gel’perin, Yoshida, and their coworkers have measured the effectiveness of certain packing materials-namely, gauze plates, porcelain rings, and coke (53, 36, 100).
ANALYTICAL CHEMISTRY
122 MICRO DISTILLATIOIV, ROTARY APPARhTUS, AND ISOTI1ERMAL DISTILLATIOV
Javes, Liddell, and Thomas ( 4 8 ) have described micro tiistillation methods for the analysis of petroleum, using about l-nil. samples and obtaining results in agreement with standard methods, but with three times t,he experimental error. Fatty oil and surface coating laboratories have also described usefL!l microapparatus. Polymerized methyl eleostearate ( 7 0 ) was subjected to distillation analysis by dispersing the sample on a small mass of glass wool suspended from a quartz helix and using a thermostatically cont’rolled aluminum block to control the distillation. The distillate could be collected in sealed ampoules. Various mixt,ures of monomers, dimers, and polymers were analyzed by Rushmau and Simpson (85)by placing 100-mg. samples in a small dish on a hot plate located in a zone having a pressure of 10-4 mm. of mercury or less. For radioactive materials, Block (6) has modified an old apparatus for microfractionation of very small quantities. Bolvden and Cooke ( 8 )have separated 0- and p-xylene a t loiv pressure and low throughput rates, using a novel rotary apparatcs in which unperforated disks are attached to a rotating shaf‘t. .4n all-glass rotary film evaporator is described by Volk ( 9 4 ) . Childs (22) uses isothermal distillation for determining molecular weights and Wust (98) has described simple apparatus for isothermal distillat,ion a t elevakd temperatures, to serve for microdetermination of nitrogen by diffusion of ammonia. ST4NDARDIZED AND LOW TEMPER4TURE DISrlLL4TIQVS
The ASTM Book of Standards (3)contains the latest versions of many tests and standard procedures that involve distillation, and a complete index of all its parts is available. Crozier (261 has reviewed the techniques of fractionation in the analysis ot petroleum products, from the French point of view. A number of papers have appeared on ASTM, Engler, and related standard distillation tests, apparatus, and procedure (10, 23, 27, 30, 34, 66-68, 88, 91, 96). These discuss correlation and prediction, improvement in technique, and apparatus. Preston (76, 7 7 ) has described improvements in low temperature distillation analysis. There have been further reports on the XG.4A analysis program, indicating that errors are due more to human factors than to procedure or apparatus (20, 13). Modified apparatus has been described by Deymer, Wustrow, Zdichynw, and Klimicek (29, 99, 102). GENER4L LITER4TURE AND BOOKS
-4large number of papers have described the use of f i actionation or distillation in connection with determination of specific substances. Prominent among these are methods for deterniination of fluorides, nitrogen or ammonia, crude oils and other petroleum products, oil shale and shale oil, wood, coal and coal byproducts, alcoholic mixtures, fatty acids and derivatives, and metals and their compounds. This general literature has again been indexed and abstracted through 1954, with indexing by substance as well as by method (82). The latest version of “Physico-Chemical Methods” by Reilly and Rae ( 7 8 )includes material on both experimental procedure and underlying theory. LITERATURE CITED
(1) Aldershoff, W. G., Booy, H., Lanpedijk, S.L.. Philippi. G . T.. Waterman, H. I., J . I n s f . Petroleum 39, 688-94 (1953). ( 2 ) Alway, C. D., others (to Upjohii Co.), U. S. Patent 2,692,820 (Oct. 26, 1954). (3) Am. Soc. Testing Materials, Philadelphia, “1955 Book of ASTM Standards,” 1955. (4) ANAL.CHEM.27, 638 (September 1955). (5) Ibid., pp. 58.i-59A (November 1955). (6) Block, Wolfram, 2. anal. Chem. 145, 424-6 (1955). ( 7 ) Boi.6, Josy, Anal. Chim. Acta 11, 431-7 (1954). (8) Bowden, C . V., Cooke, E. V. (to Imperial Chemical Industries), U. S. Patent 2,698,287 (Dec. 28. 1954).
Bresee, D. P. (to Phillips Petroleum Co.), Ibid., 2,705,699 (-4pril 5, 1955). British Standards Institute, Brit. Standard 135, 458, 479, 571, 805 (1953) ; 1428 (1954). Buchel, T. I., Trudy Vsesoyuz. n’auch.-Issledoaatel. Inst. Khiin. Pererabotki G a z o ~(Khiiizgaz) 6, 177-95 (1951). Bukala, AI., llajewski. J., Senikowicz, A., Przemysl Chem. 9, 224-8 (1953). Burrows, Godfrey (to Metropolitan-Tickers Electrical Co.), U. S. Patents 2,614,973 (Oct. 21, 1952): 2,617,760 (Sov. 11, 1952). Bushmakin, I. N., Zhur. Obshchei K h i m . 21, 1197-206 (1951). Bushmakin, I. N., Lyzlova, R. V., J . A p p l . Chem. r.S.S.R. 25, 33141 (1952). Bushmakin, I. N., Lyslova, R. V., Avdeeva, 0. I., Ibid., 25, 315-30 (1952). Cantoni, hldo, Feldman, Julian, Orchin, Milton, A S A L . CHEM. 26, 1374-7 (1954). Capatani, C., Milani, E., Chimica e industria ( M i l a n ) 36, 671-84 (1954). Chem. Eng. News 31, 2941 (1953). Ihid., 32, 1474 (1954). Ihid., 33, 1186 (1955). Childs, C. E., AXAL.CHEN.26, 1963-4 (1954). Chu, J. A., Staffel, E. J., *4bstracts of Papers, 124th lleeting, ACS, Chicago, 1953, p. 4031. Clauson-Kaas, Niels, Liniborg, Frana, Acta Chem. Scand. 8, 1579-86 (1954). Cooke, G. AI., Jarneson, B. G., Abstracts of Papers, 127th Meeting. ACS, Cincinnati, 1955, p. 19P. Crozier, Rcr. iiisf. f/‘aii$.phfrole et Ann. combustibles liquides 9, 42-50 (1954). Czech, T., Preemysl Cheni. 31 (8), 406-7 (1952). Dement’eva, 11.I., Saumova, T. I., T r u d y Vsesoyuz. Nazich.Issledovatel. 1 m t . K h i m . Pererabotki Gazov (Khinigaz) 6, 275-82 (1951). Deymer. J., Rea. fac. sci. tmiz’. Istanbul 17A, 228-49 (1952). D I S 51751-2, Erdol u. Kohle 6, 633-6 (1953). Dohrowsky, Alfred, Austrian Patent 180,254 (piov. 25, 1954). Dumas, I. C., Perthel, Robert, Jr., Silverstein, R. RI., AKAL. CHEM.26, 1255-6 (1954). Fastovskii, V. G., Petrovskii, Yu. V., Khim. Prom. 1954, 357-
a,,
64.
Francis, J. O., Van Winkle, Matthew, Petroleum Engr. 24, No. 4, C26-30 (1953). Fraser, Dean, ASAL. CHEX. 26, 1858-9 (1954). Gel’perin, N. I., T’il’shau, K. Y.,Zhttr. Priklad. Khini. 28, 254-61 (1955). Gotthard, F., Rec. chim. (Bucharest) 5 , 65-9 (1954). Guilheau, W. F., Roberts, E. J., Chemist-Analyst 44, 53 (1955). Hahn, J. W., Xyman, AI., ASAL. CHEM.27, 330-1 (1955). Huhbard, E. AI., J . Chem. Educ. 32, 376 (1955). I n d . Eno. Chem. 47. 13.4-169 (October 1955). Jakob, fi. H., Chirnia (Switz.) 8, 195-6 (1954). James, A. T., Biochern. J . 52, 242-7 (1952). James, A. T., Martin, A . J. P., Analyst 77, 915-32 (1952). James, A. T., Martin, A. J. P., Biochem. J . 50, 679-90 (1952). (46) James, A. T., AlaItin, A . J. P., Smith, G. H., Ibid., 52, 238-42 (1952). (47) Janotik, Josef, Chem. Zzssti 9, 188-206 (1955). (48) Javes. A. R.. Liddell. Christian, Thomas, W. H., ANAL.CHEM. 27, 991-6. (1955). st. Akad. Y a u k S.S.S.R., Otdel. Kono, Tetsuro, J . Agr. Chein. Soc., J a p a n 27, 521-3 (1953). , Chenl. Listy 49, 1228-34 (1955). others, Ibid., 49, 1087-90 (1955). Kuhn, W., Baertschi, P., Thurkauf, AI., Chimia (Switz.) 8 , 109-22, 145-56 (1954). Latinen, G. A , , Am. Inat. Chem. Engrs. Meeting, Springfield, Alass., May 1954. Levin, A. I., Trudy Vsesoyuz. Sauch-Issledovatel. Inst. Khim. Pererabotki Gama (Khimgaz) 6, 139-56 (1951). Levin, A . I., ;Ivtonomova, N. Kh., Semenyuk, L. O., Ibid., 6, 157-77 (1951). Levin, 8.I., and Semenyuk, L. O., Ibid., 6, 124-39 (1951). Lichtenfels, D. H., Fleck, S. A,, Burow, F. H., A4NAL. CHEM. 27, 328 (1955). Lister, W. C., Chemistry & Industry 1955, 583-6. 3Iair. B. J., Abstracts of Papers, 128th Meeting, ACS, 1Iinneapolis, 1955, p. lOQ. Ifair, B. J., Pignocco, A. J., Rossini, F. D., ANAL. CHEX.27, 190-4 (1955). lIanning, R. E., Cannon, 11. R., Abstracts of Papers, 127th IIeeting, 4CS, Cincinnati, 1955, p. 11P.
V O L U M E 28, N O . 4, A P R I L 1 9 5 6
723
llelpolder, F. IT., Washall, T. A .. Alexander, J. A . , -1s.t~. CHEM.27, 974-7 (1955). llilaeeo, G., Chimica e industria ( M i l a n ) 37, 115-16 (1955). IIuller, R. H., ANAL.CHEM.27, 33.1 (June 1955). IIyers, H. S.,Kiguchi, S.T., A S T M Bull. 195, 39-44 (1954). Sokay, Remei, Lamb, G. G.. Div. Petroleum Chem., ACS, Sew York, 1954, pp. 13-20. Oehler, H. A,, Van Winkle, Matthew, Petroleum Engr. 27, T o . 1, C10-12 (1955). Orchinnikov, B. X., Zhiryakova, S . I., N&yanoe Ichm. 32, SO. 12, 51-3 (1954). Pasrhke, R. F.. Kerns, J. R., Wheeler, D. H., J . A m . Oil Chemists’ Soc. 31, 5-7 (1954). Patterson. G. D., ANAL.CHEM.27, 574-89 (1955). Patton, H. W.,Lewis. J . S.,Kaye, W.I., I h i d . , 27, 170-4 (1955). Petroleum Refiner 33, S o . 4, 223 (1954). Pinkava. J., Chem. Listy 48, 455-7 (1954). Podbielniak, W.J., U. S. Patent 2,676,914 (.ipril 27, 1954). Preston, S. T., Jr., Podbielniak, W. J . , Petroleu~nRefi~ier33, SO. 4, 132-4 (1954). Preston, S. T., Jr., Smith, D. E., Ibid., 33, S o . 2. 137-9 (1954). Reilly, Joseph, Rae, 11‘. N.. “Physico-Chemical Xethods,” Vol. 11, 5th ed., Van Nostrand. New York, 1954. Riley. F. T., Chemistry d Industry 1955, 940. Rose, .h‘thur, A N A L . C H E l f . 26, 1 0 1 4 (1954); 24, 60-4 (1952); 23, 38-41 (1951); 22, 59-61 (1950); 21, 8 1 4 (1949). Rose, Arthur, Biles, W.R.. Chem. Eng. Progr. 51, 138-40 (1955). Rose. Arthur. Rose. E. G.. “Distillation Literature. Index and rlbstracts, ’1953-’54,” Applied Science Laboratories, State College, Pa., 1955. Rose, Arthur, Sanders, W , W...\x.%r..CHEU. 27, 331-2 (1955).
(84) Roqsini, F. D., AIair, B. J.. Strelff, Ai.J., “Hydrocarbons from
Petroleum,” Reinhold, Sew York, 1953. (85) Kushman, D. F., Simpson, E. 11. G . J . Oil and Colors Chemisfs’ ASSOC. 37. 319-22 (1954). ~, (8G) Serwinski, M., Seapiro, S., Zeszuty S a & . Politech. Lodz., S o . 6, Chem. No. 2, 15-26 (1955). (87) Sorcina, 11. D., Chim. A n a l . 37, 172-4 (1955). (88) Stanley, hI. E., Pingrey, G. D.. I n d . Eng. Chem. 46, 2182-5 (1954). (89) Srapiro, Salomon, Zeszyty N a u k . Politeck. Lodz., S o . 6 , Chem., No. 2, 33-7 (1955). (90) Todd, Floyd, “Modern Fract’ional Dihllation Equipment for Your Laboratory,” Todd Scientific Co., Springfield, Pa., 1953. (91) \-an Winkle, Matthew, Petroleum Refirier 33, S o . 11, 171-3 (1954). (92) Vignes, Roger, Compt. rend. 69th congr. i n d . gaz 1952, 903-8. (93) Voigt, K. D., Nase, Erhard, ’~ra‘atiLr~issenschalten 41, 117-18. (1954). (94) T’olk, RZ. E., . ~ N A L . CHEM. 27, 1207 (1955). (95) White, J. L. (to Cpjohn ‘20.1U. , S.Patent 2,701,789 (Feb. 8 , 1955). (96) Wiberley, J. S., Siegfriedt, R. K.. Petroleum Engr. 25, KO.8, C12-14 (1953). (97) Winters, J. C., Dinerstein, R. .A,, ANAL. CHERI.27. 546-50 (1955). (98) Wust, Heinz, Klin. Wochschr. 32, 660-1 (1954). (99) Wustrow, Werner, Erddl u. A-ohle 6 , 321-2 (1953). (100) Yoshida, Fumiktake, Koyaiiagi, Tetsushi, I n d . Eng. Chem. 47, 711-14 (1955). (101) Zaugg, H. E., Shavel, John, < ~ N A L .CHEM. 26, 1999-2001 (1954). (102) Zdichynec, T., Klimerek. 13.. C‘heilf. P r u m y s l 3 (28). 197 (1953). ~~~~
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Extraction LYMAN C. CRAIG The Rockefeller institute for
M e d i c a l Research, N e w York 27,
HE writing of this review has been undertaken with frank nikgivings about its ultimate worth, partly in view of recent excellent reviews (7S,105,106,147,148,150,152)and books (4, 74, 152, 166) on the general subject of extraction, and partly because the field has beconie so diffuse. That great strides in the use of extraction for separating and identifying compounds have been made during the past 10 years, no one will deny (74). But great strides aleo have been made with other separating techniques useful in analysis, such as chromatography, paper chromatography, ion exchange chromatography, gas chromatography, and zone electrophoresis. The advances made in all these fields taken together have greatly extended the range of the experimental chemist. Thus it is now possible with substances of molecular weight in the order of a few thousand to separate individual conipounds, prove purity, carry out degradations, isolate the degradation products, and determine structure according to the rules of classical orga,nic chemistry with as much or greater reliability than as previously possible with substances in the molecular weight range of a few hundred. Moreover, the published work in several fields, notably in the polypeptide antibiotics and the hormones of the pituitary, has demonstrated beyond doubt that it is now possible to isolate a n unknown natural product, prove purity, and determine its structure without depending on the crystallizability of the substance or its derivative,s. Only those who have spent months in previous
N. Y.
J ears patiently trying t o induce substances to crystallize, often with complete failure, will fully appreciate the advance that has been made. Extraction has played a very important role in this advance. It is certain that extraction as a precise separation method would be a much more highly developed and widely used technique than it now is, had not the majority of the research effort roncerned n ith analytical separations during this recent period been devoted to the various forms of chromatography. Only a relatively few laboratories have been concerned rvith the development of extraction designed for analytical purposes, b u t hundreds of laboratories throughout the world have devoted part of all of their time to research on some phase of chromatography. In spite of this imbalance, a surprising number of structural studies rightly regarded as epoch-making, such as those irith the pituitary hormones, have depended heavily or even been made possible by use of the most highly developed forms of analytical extraction.
FACTORS DETERMINING CHOICE O F SEPARATIOh- TOOL
The major factors which usually determine the choice of a separation tool which is t o be used in conjunction u i t h analytical method are:
1. The ease and speed of accomplishment 2. The amount of sample required
