V O L U M E 21, NO. 1, J A N U A R Y 1 9 4 9 (140) Khite, J. W., Jr., and Dryden, E. C., ANAL. CHEM.,20, 853 (1948). (141) Wieland, T., Ber., 77, 539 (1944). (142) Wilkes, J. B., IND. ENG.CHEM., ANAL.ED.,18, 702 (1946). (143) Williams, R. J., and Kirby, H., Science, 107,481 (1948). (144) Williams. T. I., “Introduction t o Chromatography,” London, Blackie and Son, 1946. (145) Winsten, W.A,, Science, 107, 605 (1948). (146) Winsten, W. A , , and Spark, A. H., Ibid., 106, 192 (1947).
81 (147) (148) (149) (150) (151) (152)
Zechmeister, L., Am. Scientist, 36,505 (1948). Zechmeister, L., Ann. S.Y.Acad. Sci., 49, 145 (1948). Ibid.,49, 220 (1948). Zechmeister, L., Chem. Revs.,34, 267 (1944). Zechmeister, L., Chem. Zentr., 1944, I, 1028. . Zettlemoyer, A. C., and Walker, W. C., Ind. E ~ J Chem., 39, 69 (1947).
RECEIVED November 8 , 1948.
DISTILLATION ARTHUR ROSE The Pennsylvania S t a t e College, S t a t e College, P a .
T
H I S paper is written from the point of vievi of developments during the years 1946 to 1948. A few earlier papers are commented on or listed as references, but in general it is assumed that the earlier items of interest will be obtained by consulting the references in the more recent papers, or found in bibliographies or indexes. Analytical distillation may be defined in various ways, but in this paper it is assumed to include simple laboratory distillation procedures and all the forms of distillation that involve rectification or fractionation regardless of whether quantitative analysis, qualitative separation, or mere detection is the objective. Production operations are naturally excluded, but preparative distillation, even on a pilot plant scale, is often of analytical interest. Significant trends and developments in analytical distillation during the past several years have included the following: Extensive utilization of fractionation in the analysis of complex mixtures of hydrocarbons, fluorocarbons, and many other types of compounds. Efficient fractionation has become a powerful and frequently used tool, so that success in achieving difficult separations or analyses is often a mere incident in solving broader problems. Recognition of the limitatioris of distillation as a method of separation and analysis, and consequent combination of the process with various physical and chemical methods of analysis. Realistic evaluatioq of analytical fractionation apparatus, with emphasis on time required, ease of operation, and actual separation a t finite reflux in addition t o the older use of theoretical plate standards a t total reflux. Improvement of older apparatus, particularly as to details and accessories, as n-ell as t’he introduction of several entirely new types of contacting devices. Development of special distillation apparatus such as rotary columns for vacuum distillation, small molecular stills, and apparatus for semimicro and microdistillation. Further study and improvement of low temperature distillation, particularly by use of automatic controls to gain reproducible operation, and also by the use of simple isothermal distillation a$ low pressures to take advantage of the improved relative volatility, small sample size, and speed of analysis. Limited progress in practical application of theoretical concepts, but considerable interest and activity along these lines. Continued improvement and extension of A.S.T. RI. distillation tests and similar methods involving simple standardized distillation as part of an analysis. The relatively slow progress in catching up on the part of European scientists, except for general use of Podbielniak columns. Publication of basic data and general bibliographies. UTILIZATION OF FRACTIONATION
A classical example of successful analytical fractionation is the work of the National Bureau of Standards and its cooperating groups, dealing with the composition of petroleum (45, 53-56, 119, 120, 13X, 152). This work is particularly notable for the balance between the use of distillation and other separation processes such as selective adsorption. Similar use of fractionation has been reported by the Bureau of Mines and others (83, 126, 147). Various complete fractionating columns have been developed or improved for general laboratory use (40, 52, 61, 66,
65, 85, 90, 98,113, 1S1, 136, 141, 143). Extensive application of precise fractionation has also occurred in the development of fluorine chemistry (11, 50, 104). Almost all the papers in the 1947 A.C.S. Symposium on Fluorine Chemistry ( 4 9 ) describe or mention the use of distillation as a method of analysis or as a separation or purification step related to analysis. Other similar applications are widespread (107). The most recent involve the isolation of the oxygenated organics obtained from the FischerTropsch or related processes. The prevalence of azeotropes in these mixtures complicates the use of distillation. There are no published papers as yet. SPECIAL METHODS
Early enthusiasm for efficient fractionation led to the extreme of even attempting the separation of materials of almost identical volatility. This has been succeeded by a period of the development of a multitude of special tests which can identify components in the fractions resulting from the distillation. Such procedures are not new, but during the past fern years there have been much more attention and activity in the perfecting of the special physical and chemical methods than in the associated distillation itself. Typical publications are cited (30, 72, 78, 89, 119,120). EVALEATION OF APPARATUS
Early evaluation of fractionating colunins ww confined almost entirely to the determination of the number of theoretical plates a t total reflux. It has become increasingly evident that this is but one among many factors that determine the utility of a particular apparatus, and that it is easier to satisfy and measure plate requirements than some others. The American Petroleum Institute Symposium on High Temperature Analytical Distillation in Soveniber 1946 was a major contribution in the direction of overall evaluation. This series of papers dealt in detail with the results obtainable with heligrid, helices, perforated plate, and screen packings, and in columns ranging in size from those for samples of a few milliliters to gallon scale operation (17 , 21, 34, 4O,57, 66, 90, 114, 116, 162). Among the factors considered were the time required to reach equilibrium, throughput rates, holdup, pressure drop, and deterioration, as well as theoretical plates a t total reflux. Some attention has been given to determination of the ]atter at finite reflux (34, 67, 117) and to expression of results in terms of actual distillation curves instead of theoretical plates (21, 57, 90). Hilberath ( 7 1 ) has presented an interesting and thorough paper on column evaluation Willingham and eoworkers (153) have compared various columns and packings through use of the A factor. The evaluation of vacuum columns has progressed to the extent that several additional binary test mixtures have been developed ( 4 7 , 106, 151). IMPROVEMENT OF APPARATUS
A great variety of column heads and other devices has been presented for controlling and determining reflux ratio, for auto-
ANALYTICAL CHEMISTRY
82 matic fraction collection, and for automatic pressure control ( 7 , 8, IO,24, 25?39, 48, 63, 74, 79, 80, 87, 93, 121, 122, 146, 143, 149). Lloyd and Hornbacher (87, 1947) listed 44 references to such devices. A critical summary and evaluation of these is much needed. Those for intermittent operation seem most practical, even though reflux and distillate streams may not always be divided in the exact proportions indicated by a n automatic timer. There has been further discussion of the use of vacuum jackets compared with heated jackets to maintain adiabatic operation (b?, 66, 115) and of the desirability of maintaining a forced temperature gradient (108). X o clear-cut conclusions have been reached. Most laboratory colunins are heated by electric heaters, but with larger apparatus the time saving in bringing the charge to boiling with steam heaters is being recognized. Searly uniform boilup rate is achieved by automatic controllers actuated by pressure drop between the still pot and the atmosphere (21). Improvements in relays have made it possible to simplify control circuits and t,o use water manometers t o make and break the relay circuit. The use of a stream of nitrogen to prevent slow condensation of vapors from the still pot in the manometer lines is still common practice but will probably be succeeded by the simpler device of using a heated air reservoir. Langdon ( 8 4 )has compared various still heating methods, and Schiff (124) has described a safety device for use with still heating jackets. A great variety of details regarding auxiliaries for fractionating columns is given in the papers of the American Petroleum Institute Symposium on High Temperature Analytical Distillation already cited, as well as in other descriptions of complete apparatus cited in connection with utilization or evaluation. Mitchell and O'Gorman ( 9 6 ) have described a packing consisting of a wire helix of small diameter, wound in helical fashion around a central core to produce a device somewhat similar to the well known heligrid packing. Wire screen packing in the shape of Berl saddles has been developed and is known as McMahon packing (88). Dison (38)has patented another type of screen packing. Protruded packings represent an entirely new type with unusual wetting characteristics (29). These will be valuahle for the analytical columns of larger diameter.
DEVELOPMENT OF SPECIAL APPARATUS
The Bowman rotary vacuum still represents a completely new approach to the technique of fractionation (28,100). The use of a cooled rotating central core to the column and heated outer walls gives a new type of operation (thermal rectification) of particular importance in vacuum fractionation. The distillation group a t the National Bureau of Standards (153)has developed a more conventional rotary concentric tube column that operates by contact rectification, but has an unusually advantageous combination of height of equivalent theoretical plate (H.E.T.P.), holdup, pressure drop, and throughput characteristics. I t too seems particularly adapted to vacuum operation. Birch, Gripp, and Kathan ( 1 2 ) have described a spinning band column for high vacuum and/or microfractionation, as have several other European authors ( I S , 14, 7 6 ) . Donne11 and Kennedy (40) described small concentric tube columns with take-off rates of 0.2 to 2 ml. per hour and a 6-mm. H.E.T.P. Several other micro and semimicrocolumns have been described (32, 58, 59, 64, 01, 9 7 ) , as well as small molecular stills (62, 37, 70, 105). Although there has been a large amount published on the industrial use of azeotropes, surprisingly little has appeared recently on their use in analytical distillation (46, 154). Bowman and Sastry (10) have reported data extending Podbielniak's idea (112) that analytical percentages can be read directly from the temperatures along the length of a column that is operating at total reflux with the entire sample in the form of holduv.
LOW TEMPERATURE DISTILLATION
The Podbielniak low temperature apparatus (68, 108-111 ) has been steadily improved until it is a masterpiece of automatic and efficient separation of all except the closest boiling components such as the group of C, hydrocarbons boiling near 0" C. The use of various gaseous hydrocarbons in the manufacture of synthetic rubber and fuels has stimulated these developments. Procedures have been subject to ari increased degree of standardization (101). The careful studies and comparisons of Savelli and co-workers are still of interest (123). The preparation of synthetic samples for purposes of evaluation and standardization of apparatus has been emphasized ( 2 7 ) . Starr and eo-workers have shown that relatively high charging rates may be used without loss in accuracy (134). The same group has also studied distillation rates and rut points (133,135). Booth and McNabney have described an automatic column with anticipator control to decrease pressure surges (16). A few special accessories to low temperature apparatus have been described (6, 26, 41, 42, 67, 144). Shepherd (129) has reported the results of analysis of a standard sample of natural gas by laboratories cooperating with the Bmerican Society for Testing Materials. These demonstrated the need for standardization in procedures to obtain correct results. Shepherd and coworkers have also reported on sampling procedures (130) and on the Sational Bureau of Standards analytical procedures (128). Nelsen et ul. (102) have presented nomographs for conversion of distillation temperatures and pressures of low boiling hydrocarbons t o boiling points a t 1 atmosphere. Echols and Gelus ( 4 4 ) have given detailed descriptions of analyses of 2- to 50-ml. gas multicomponent samples by multiisothermal distillation. This involves simple vaporization and a series of observations on colligative properties such as vapor pressure, dew point, refractive index, and density. These data are used to calculate a curve of vapor pressure of the residual liquid versus per cent vaporization. The slope of this curve is related t o the composition of any three-component system, and by determination of the slope a t two points the composition of four-component systems may be fixed. By obtaining similar curves a t selected temperatures, up to 14 components have been delermined. Appleby, Avery, and Meerbott ( 4 )bave used multiieothermal distillation in studies of the thermal decomposition of nheptane. Boomer et ul. (15)have described an inverted apparatus for low temperature-low pressure fractionation. APPLICATION OF THEORETICAL COXCEPTS
Better knowledge of the theory of batch fractional distillation could be of major assistance in analytical fractionation. Thi. applies particularly t o the choice of the quantity of charge and of the reflux ratio, and to estimates of the sharpness of separation t o be expected. Various aspects of the theory have been presented (18,19, 33, 116) but useful generalities are lacking. Khen holdup is appreciable, the effect of change of composition mith time in batch distillation greatly complicates the relatively simple relations of steady state distillation. As a result, the use of a large charge may give a poorer separation than a small charge and separation may be as sharp a t finite refluv as a t total reflus. Westhaver (163) has made a further extension of basic theory in connection with the study of the rotary concentric tube column. Berg and James ( 9 ) and Coulson ( 3 5 ) have given information on the rate of approach t o equilibrium in larger fractionat ng columns. Additional equations for estimating relative volatility from boiling point have appeared (36, 94). SIMPLE DISTILLATION PROCEDURES
The applications of simple standardized distillation procedures and improvements are too numerous for specific mention. The 1947 A.S.T.M. Index (3) now contains 37 different procedures under the heading of distillation tests. These range from am-
V O L U M E 21, NO. 1, J A N U A R Y 1 9 4 9 nionia in phenol-formaldehyde molded materials to white linseed oil paints. few other typical publications on specific analyses are cited (2, 5 , 51, 43, 51, 60, 65,76, 86, 32, 127, 140, 148, 150). l l a n y others no doubt exist, but are difficult t o locate IT-ithout special knowledge or the most detailed reading of the original literature. The bibliography of Rose and co-workers (118) contains a substance index which gives references to materials separated or det,ei,iuined by distillation, as obtained from papers or abstracts for the years 1941-45. Codistillation was studied by LIEtayer in connection n-ith the analysis of nicotine ($5). EUROPEAS ADVAhCES
Journal articles of European origin vary a great deal in an areness of advances elsewhere. Some authors are up to date, but others lack an appreciation of the analytical possibilities of modern fractionating devices. A fevi only of the more comprehensive articlps are cited (1, 62, 81, 86, 103, 126, 137). BIBLIOGRAPHIES
The extensive vapor pressure tabulations of Stull (139) are of frequent application in approaching a new separation. Walas (146) has presented vapor pressure charts for organic materials. The compilations of properties presented by the National Bureau of Standards (99) and by Brown, Kate, and co-workers (23, 7 7 ) are similarly useful. Horsley ( 7 3 )has presented a condensed and systematic summary on azeotropes and nonaxeotropes. Bibliographies of various degrees of selectivity and completeness have been published by Vilbrandt (145),Stage and Schultze (132),and Rose (118). T h e latter covers the years 19-11-45 and includes abstracts of all papers on distillation as n-ell as a subject and a substance index. T h e Stage and Schultze bibliography covers 1920-44 (though t h e war years are not complete) and has references with titles arranged according t o subject matter. The Vilbrandt publication is highly selective Tvith an engineering bias and covers the publication period of the principal American and English engineering and industrial journals to about 1946. LITERATURE CITED
(1) Abeee. H.. Chimia (Switz.).2. 133-41 (1948). (2) Altigr?, V. J., et al., PTOC.’Am. Soc. Testing JIaterinls, 45,
340-1 (1949). Aromatic hydrocarbons. (3) Am. SOC.Testing Materials, Philadelphia, “Index to A.S.T.M. Standards,” 1947. (4) Appleby, W. G., Avery. W.H., and Meerbott, F.K., J . 4 m . Chem. SOC., 69,2279-85 (1947). (5) Aruina, A. S., and Chernikhov, Y . A., Zawdskaya Lab., 13, 33-7 (19471 (in Russian). Zinc in allovs. (6) Askevolh, R.’J., and Agruss, M. S.,IN;. ESG. CHEY.,A x i L ED., 17, 241 (1945). (7) Baker, A. T.,and Dixon. 0. G., J . SOC.Chem. Ind., 66, 189-91 (1947). (8) Bartleson, J. D., Conrad, A. L., and Fay, P. S., IND.Esc. CHEM.,ANAL.ED., 18, 724 (1946). (9) Berg, Clyde, and James, I. J., Jr., Trans. Am. Inst. Chem. Engrs., 44, 307-14 (1948). (10) Berg, Lloyd, IKD. ESG. CHEM.,ASAL.ED.,18, 54-5 (1946). (11) Bigelow, L. A., Tompson, R. Y., and Tarrant, Paul, Ind. Eng. Chem., 39, 363 (1947). (12) Birch, S . F., Gripp, V., and Nathan, W.S., J . SOC.Chem. Ind., 66, 33-40 (1947). (13) Bjorkman, Anders, and Olavi, Sven, Svensk Kem. Tids., 58, 145-50 (1946) (in English). (14) Boivin, M., Mem. seroices chim. &at (Paris),31, 29-34 (1944). (15) Boomer, E. H., Gillies, A., and Hugill, J. T., Can. J . Research, 26B, 202-14 (1948). (16) Booth, H. S.,and hlcNabney, R., IXD. EKG. CHEM.,ASAL. ED.,16, 131-3 (1944). (17) Borns, W.J., Coffey, B. L., and Garrard, L. G., Proc. -4m. Petroleum Inst., 26, 111, 32-40 (1946). (18) Bowman, J. R., and Briant. R. C., Ind. Eng. Chem., 39, 745-51 (1947).
83 (19) Bowman, J. R., and Cichelli, M. T., “Minimuni Kumber of Plates and Minimum Reflux in Batch Distillation,” Division of Industrial and Engineering Chemistry, 112th Meeting of AM. CHEM.SOC., 1947. (20) Bowman, J. R., and Sastry, S. L., “Analysis by Continuous Rectification,” Division of Analvtical and LMicro Chemistry, 112th Meeting of AM.CHEM.So;., 1947. (21) Biandt, P. L., Perkins, R. B., Jr., and Halverson, L. K., PTOC. Am. Petroleum Inst., 26, 111,57 (1946) ; Oil Gas. J . . 45, 86-90. 102 (1946). (22) Breger, I. A , , . ~ ~ Y . L LCHEM., . 20, 980-1 (1948). (23) Brown, G. G., Katz, D. L., Oberfell, G. G., and Alden, R. P., “Katural Gasoline and the Volatile Hydrocarbons,” Tulsa, Okla., Natural Gasoline Assoc. of America, 1948. (24) Blown, T. F., and Coles, K. F.. ANAL.CHEM.,19, 935-6 (1947). (25) Biirk, R. E., and Walsh, T. J., U. S.Patent 2,410,045 (Oct. 29, 1946). (26) Burrell, G . H., and Guild, L. V., Ibid., 2,399,095 (April 23, 1946). (27) Rusey, R. H., Barthauer, G. L., and Metler, -4.V.,IND. ENG. CHEM.,ANAL.ED., 18,407-11 (1946). (28) Byron, E. S.,Bowman, J. R., and Coull, James, “New Thermal Rectifying Column,” High Vacuum Symposium, Cambridge, Mass., 1947. (29) Cannon. M.R.. Drivate communication. i30) Cerveny, W.J.,’Hinckley, J. A., Jr., and Corson, B. B., ANAL. CHEM.,19, 82-6 (1947). (31) Chand, Ram, J . Indian Chem. SOC.,24, 167-8 (1947). Ammonia. (32) Cheronis, K. D., and Levin, N.. J . Chem. Education, 22, 85-9 (1945). (33) Colburn, A. P., and Steams, R. F., Trans. Am. Inst. Chem. Engrs.. 37, 291-309 (1941). ENG.CHEM.,ANAL.ED.. 18, (34) Collins, F. C., and Lants, V., IND. 673-7 (1946); Proc. Am. PetroleumZnst., 26, 111,72- (1946). (35) Coulson, E. A., J . SOC.Chem. Ind., 64, 101-4 (1945). (36) Davis, D. S.,Chem. Ind., 61, 872 (1947). (37) Distillation Products, Inc., Chem. Eng. .Vews, 25, 3713 (1947). (38) Dixon, 0. G., and Imperial Chemical Industries, Ltd., Brit. Patent 578,309 (June 24, 1946). (39) Donahoe, H. B., Russell, R. R., and VanderWerf, C. A,, IND. EKG.CHEM.,ASAL.ED.,18, 156 (1946). (40) Donnell. C . K., and Kennedy, R. RII., PTOC.Am. Petroleum Inst., 26, 111,23-31 (1946). (41) Douslin, D. R., U.S. Patent 2,379,953 (July 10, 1945). (42) Ibid., 2,888,312 (Kov. 6 , 1945). (43) Duffau, F., Bull. soc. chim. biol., 28, 873-7 (1946). Furfural. (44) Echols, L. S.,Jr., and Gelus. Edward. ANAL.CHEX, 19, 668-75 (1947). (45) Epstein, 2f. B., Mair, B. J., Willingham, C. B., and Rossini. F. D., Separation of the 177Oto 200’ C. Fraction of Petroleum and the Isolation of Normal Undecane,” Division of Petroleum Chemistry, 114th Meeting of AM. CHEM.SOC.. September 1948. (46) E w 4 , R. H., and Welch, L. M., Ind. Eng. Chem., 37, 1224-31 (1945). (47) Feldman, J., Myles, M.,and Orchin, M., “Binary Test Mixtures for the Evaluation of Vacuum Rectification Columns,” Division of Petroleum Chemistrv. 113th Meetine of AM. CHEM.SOC.,1948. (48) Fisher, H. E., ANAL.CHEM.,20, 982 (1948). (49) Fluorine Chemistry Symposium, Ind. Eng. Chem., 39, 230-434 (1947). (50) Fowler, R. D., et al., Ibid., 39, 294 (1947). (51) Franc, 8.. Chimie et industrie, 57, 453 (1947). Boric acid. (52) Galstaun, L. S.,Bisso, L. A., Harrison, R. D., and Keever. E. R., “Automatic Laboratory Batch Distillation Column with Automatic Reflux Ratio Advance,” A.C.S. California Section, Pacific Chemical Exposition, San Francisco, 1947. (53) Glasgow, A. R., Krouskop, N. C., Sedlak, V. A., Willingham, C. B., and Rossini, F. D., “Analysis of Recycle Styrene.” Division of Analytical and iMicro Chemistry, 114th Meeting of -hf. CHEM.SOC., 1948. (54) Glasgow, A. R., Streiff,A. J., Willingham, C. B., and Rossini, F. D., Proc. Am. Petroleum Inst., 26, 111, 127-69 (1946); J . Research S a t l . B U T .Standards, 38, 537-81 (1947). (55) Glasgow, A. R., Willingham, C. B., and Rossini, F. D., “Analysis of a Gasoline Produced by Catalytic Cracking,” Division of Petroleum Chemistry, 114th Meeting of AM. CHEM. sac., September 1948. (56) Glasgow, A. It., Willingham, C. B., and Rossini, F. D., J . Research, S a t l . BUT.Standards, 38, 621-6 (1947). (57) Goldsbarry, A. If-., and Askerold, R . J., PTOC. Am. Petroleum Inst., 26, 111, 18-22 (1946). .
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ANALYTICAL CHEMISTRY
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(58) Gould, C. W., Jr., Holeman, G., and Niemann, C., ANAL. CHEM.,20, 361 (1948). (59) Grant, W. M., IND. ENG.CHEM.,ANAL.ED., 18, 729 (1946). (60) Griffith, R. B., and Jeffrey, R. N., ANAL.CHEM.,20, 307-11 (1948). Nicotine. (61) Griswold, John, Morris, J. W., and Van Berg, C. F., Ind. Eng. Chem., 36, 1119-23 (1944). (62) Groll, H., Reichsamt Wirtschaftsausbau, Priif.-Nr. 43 (PB 52,003) 59-88 (1940). (63) Grossberg, A. L., and Roebuck, J. M.,Chem. Eng., 54, No. 1, 132-3 (1947). (64) Haendler, H. M . , ANAL.CHEM.,20, 596 (1948). (65) Kahn, F. L.,Ibid., 19,811-12 (1947). Ammonia. (66) Hall, H. J., and Jonach, F. L., Proc. Am. Petroleum Inst., 26, 111, 48-56 (1946). (67) Hamblen, G. T., and Thorstenberg, J. C., IND. ENG.CHEM., ANAL.ED., 18, 153 (1946). (68) “Handbook of Butane-Propane Gases,” 31d ed., Los dngeles, Jenkins Publications. 1947. (69) Hepp, H J., and Smith, D. E., ISD. ENG. CHEY.,ANAL. ED., 17, 579-82 (1945). (70) Hickinan, K. C. D., “Small Laboratory Centrifugal Still,” High Vacuum Symposium, Cambridge, Mass., 1947 (71) Hilberath, F., Oel u. Kohle, 39, 875-80 (1943). (72) Hwmer. J. H. D.. Anahst. 72. 513-20 (1947). (73) Horsley, L. H., ANAL.HEM., 19, 508-600 (i947). (74) Howard, F. L., Ibid., 19, 144 (1947). (75) Huckabay, W.B., Welch, E. T., and Metler, -4.V., Ibid., 19, 154-6 (1947). Fluorine. (76) Jost, W.,Reichsamt Wirtschaftsausbau, Prilf.-Nr. 43 (PB 52,003), 89-91 (1940). (77) Kate, D. L., and Rzasa, M. J., “Bibliography for the Physical Behavior of Hydrocarbons under Pressure and Related Phenomena.” Ann Arbor, Mich., Edwards Bros., 1946. (78) Kent, J. R., and Beach, J. Y., AXAL.CHEY.,19, 290-3 (19471. (79) Kieselbach, Richard, Ibid., 19, 815 (1947). (80) Kipnis, Frank, and Ornfelt, John, Ibid.. 19, 934 (1947). (81) Kirschbaum, Emil, Angeu,. Chem., B19, No. 1, 13-14, 33-5 (1947). (82) Koch, H., Reichsamt Wirtschaftsausbau, Priif.-Kr. 43 (PB . 52,003), 93-102 (1940). (83) Kurtz, S. S., Jr., Mills, I. W., Martin, C. C., Harvey, W.T., and Lipkin, M. R., ANAL.CHEM.,19, 175-82 (1947). (84) Langdon, W. M., Ibid., 20, 338 (1948). and Tobin, D. J., IKD.ENG.CHEM.,ANAL. (85) Langdon, W. ED.,17,801-5 (1945). (86) Lindsay, W.N., Ibid., 18, 69 (1946). Water. (87) Llovd. L. E.. and Hornbacher. H. G.. A4NAL. CHEM..19. 120-3 (i947). McMahon, H. O., I d . Eng. Chem., 39, 712-14 (1947). Magat, Bull. assoc. franc. tech. petrole, No. 58, 3-31 (1946). Marschner, R. F., and Cropper, W.P., PTOC. Am. Petroleum Inst., 26, 111, 41-7 (1946). Martin Co., H. S., ANAL.CHEM.,19, 23A (August 1947). Meloche, C. C., and Frederick, W. G., IND.ENG.CHEM., ANAL.ED., 17, 796-8 (1945). Low-boiling gases. Melpolder, F. W., A N A L . CHEM.,19, 617 (1947). Melpolder, F. W., and Headington, C. E., Ind. Eng. Chem., 39, 763-6 (1947). MLIBtayer, G. L., Ann. chim., [12]2, 790-843 (1947). Mitchell, F. W., Jr., and O’Gorman, J. M., ANAL.CHEM.,20, 315 (1948). Morton, A. A., and Mahoney, J. F., IND.EXG.CHEM.,ANAL. ED., 13, 494-8 (1941). Naragon, E. A., and Lewis, C. J., Ibid., 18, 448-50 (1946) National Bureau of Standards, “Tables of Selected Values of Chemical Thermodynamic Properties,” Circ. C461 (1947). National Research Corp., Chem. Eng. News, 25, 3713 (1947). Natural Gasoline Association of America, “Recommended Procedure for Analysis of Saturated Hydrocarbon Gases by Low Temperature Fractional Distillation,” Tulsa, Okla., Publ. 1146, 1946. Nelsen, F. M., Brooks, F. R., and Zahn, Victor, ANAL.CHEY., 19, 814-5 (1947). Nikolaeva, V. G., Neftuanoe Khoz, 24, No. 12, 33-7 (1946). Park, J. D., et d.,Ind. Eng. Chem., 39, 357 (1947). Perry, E. S., ANAL.CHEM.,20, 392 (1948). Perry, E. S., and Fuguitt, R. E., Ind. Eng. Chem., 39, 782-7 (1947). Pickard, P. L., and Lochte, H . L . , . J . Am. Chem. Soc., 69, 14-16 (1947). Podbielniak, W. J., “Analytical Distillation and Its Application to the Petroleum Industry,”Chicago,Podbielniak, Inc. Podbielniak, W. J., IND. ENG.CHEM.,ANAL. ED., 13, 639-45 (1941). I
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(110) Podbieluiak, W. J., U.S.Patent 2,275,648 (.March 10, 1942). (111) Ibid., 2,342,366 (Feb. 22, 1944). (112) Ibid., 2,377,900 (June 12, 1945). (113) Proell, W.A , , Ibid., 2,416,404 (Feb. 25, 1947). (114) Reed, C. R., Proc. Am. PetroleumInst., 26, 111, 10-13 (1946). (115) Ibid., 26, 111, 14-17 (1946). (116) Rose, -4rthur, Johnson, R. C., and Williams, T. J., “Stepwise Plate to Plate Calculation of Batch Distillation Curves,” Division of Industrial and Engineering Chemistry, 113th Meeting of Aiv. CHEM.Soc., 1948. (117) Rose, Arthur, and Pfeiffer, Carl, “Effect of Reflux Ratio on the Separation Schieved in a Packed Fractionating Column in Continuous and in Batch Distillation,” Division of Industrial and Engineering Chemistry, 111th Meeting of AM. CHEM. Soc., 1947. (118) Rose, Arthur, and Rose, Elizabeth, “Distillation Literature, Index and Abstracts,” 1941-45, The Authors, State College, Pa., 1948. (119) Rossini, F. D., ANAL.CHEM.,20, 110-121 (1948). (120) Rossini, F. D., Chem. Eng. Nmw, 25, 230-3 (1947) ; Petroleum Engr., 18, No. 4, 57-64 (1947). (121) Runckel, W. J., and Oldroyd, D. M.,ISD. ENG. CHEM., AsAL.,ED., 18, 80-1 (1946). (122) Russell, R. R., and Yander Werf, C. A., A N ~ LCHEM., . 19, 698 (1947). (123) Savelli, J. J., Seyfried, W.D., and Filbert, B. SI.,TND. ENG CHEM.,ANAL.ED.,13, 868-79 (1941). (124) Schiff, H. I., ANAL.CHEX.,19, 503 (1947). (125) Schultae, G. R., Reichsamt Wirtschaftsausbau, Priif.-Nr. 43 (PB 52,003), 7-14 (1940). (126) Schwartz, F. G., Gooding, R. M., and Eccleston, B. H., Ind. Eng. Chem., 40, 2166-9 (1948). (127) Scribner, B. F., and Mullin, H. R., J . Research Satl. Bur. Standards, 37, 379-89 (1946). Uranium. (128) Shepherd, Martin, Ibid., 26, 227-44 (1941). (129) Ibid., 38, 19-51 (1947). (130) Ibid., 39, 435-51 (1947). (131) Smith, V. C., Glasebrook, A. L., Begeman, C. R., and Lovell, W.G., IND.ENG.CHEM.,ASAL. ED.,17, 47-52 (1945). (132) Stage, H., and Schultze, G. R., “Theory, Apparatus and Processes of Distillation and Rectification,” VDI Verlag, 1944; tr. and published by Hobart Publishing Co., Washington, D. C., 1947. (133) Starr, C. E., ANAL.CHEM.,20, 184 (194s). Preliminary report. (134) Starr, C. E., Anderson, J. S.,and Davidson, T‘. M., Ibid., 19, 409-12 (1947). (135) Starr, C. E., Anderson, J. S., and Davidson, V. M., “Studies of Laboratory Low Temperature Fractional Distillation. Optimum Distillation Rates and Fraction Cut Points,” B.C.S. Southwest Regional Meeting, Houston, Tex., 1947. (136) Steffens, Lester, and Heath, D. P., IKD.ESG.CHEM.,ANAL.ED. 16, 525-7 (1944). (137) Stern, G., Reichsamt Wirtschaftsansbau, Pruf.-AVr. 43 (PB 52,003), 15-56 (1940). (138) Streiff, A. J., et al., J . Research S a t l . Bur. Standards, 37, 331-78 (1946); 38, 53-94 (1947). (139) Stull, D. R., Ind. Eng. Chem., 39, 517-40 (1947). (140) Suomalainen, H., and Arhimo, E., Z. anal. Chem., 128, 299-303 (1948); Mitt. Lebensm. Hug., 37, 173-8 (1946). Fatty acids. (141) Taft, R. W.: Jr., and Vander Werf, C. A . , J . Chem. Education, 23, 82-4 (1946). (142) Thacker, G. O., and Walker, B. Y., J . SOC.Chem. Ind., 65, 259-61 (1946); 66, 32 (1947). (143) Todd, Floyd, IND.ENG.&EM., -ANAL. ED., 17, 175-81 (1945). (144) Tunnicliff, D. D., ANAL.CHEM., 20, 962-6 (1948). (145) S‘ilbrandt, F. C., et al., Bull. Virginia Polytech. Inst., Eng. Espf. Sta. Sei.. No. 62 (1946). Distillation bibliography. (146) Walas, S . M., Chem. Met. Eng., 53, KO.10, 124 (1946). (147) Ward, C. C., Gooding, R. M.,and Eccleston, B. H., Ind. Eng. Chem., 39, 105-9 (1947). (148) Weitkamp, A. W., J. Am. Oil Chemists Soc., 24, 236-8 (1947). Methyl esters of fatty acids. IND.ENG.CHEM.,ANAL. (149) Wilkinson, W.R., and Beatty, H. A4., ED.,18, 725-6 (1946). (150) Willard, H. H., Toribara, T . Y . , and Holland, L. N., ANAL. CHEM.,19, 343-4 (1947). Fluorine. (151) Williams, F. E., Ind. Eng. Chem., 39, 779-82 (1947). (152) Willingham, C. B., and Rossini, F. D., Proc. Am. Petroleum Inst., 26, 111, 63-71 (1946); J . Research, .%’atl. Bur. Standards, 37, 15-29 (1946). (153) Willingham, C. B., Yedlak, Y.A., Rossini, F. D., and Westhaver, J. W., Ind. Eng. Chem., 39,706-12 (1947). (154) Wing, H. J., ANAL.CHEM.,19, 216 (1947). RECEIYED November 19, 1948.
