Distillation Analysis ARTHUR and ELIZABETH ROSE The Pennsylvania State University, and Applied Science f aboratories, h e . , State College, Pa.
T
HIS review differs from its predecessors (QW) in t h a t no at-
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tempt has been made t o list all the specific examples of the use of distillation for analytical purposes. Attention is confined to significant applications and to improvements in apparatus, procedure, or technique t h a t are felt to be of general importance. -1study of an indexed compendium of abstracts of the literature on distillation covering a i-year period ( 9 4 ) develops the conviction t h a t the great majority of all papers on distillation are of prebent or potential intereqt to analysts. T h e only general wceptions are the papers dealing with the details of construction 01 operation of large s t d e equipment, and to a lesser extent the more specialized advanced theoretical treatments. All other papers are a t least potentially useful as the basis for improving a n existing analysis or devising a new one. The major part of this review deals with the development of new apparatus and techniques for analytical distillation involving rectification with a column. In addition t o citing the more important of these, it seems desirable to comment briefly on what i.j lacking, or what might have been published but did not appear. I n other words, an attempt has been made to note what analysts might like to see published, as far as distillation is concerned. These idem are preeented with full knowledge t h a t they are from a single point of v i m . Possiblv this will stimulate discussion and progress. There seem to be t v o prime needs. One is for simpler, less expensive but still effective, automatic or nearly automatic apparatus for general use. Possibly an entirely new approach to the problem is required. T h e second need is for a good practical laboraton- manual giving definite and specific instructions for construction and operation for the ineqerienced, for those who cannot afford to buy complete setups, and for those whose interest is of a short-term nature. The attainment of the first of these needs may be wishful thinking, but the second certainly is not. There is a wealth of scattered published information on practical techniques, and there are escnellent discussions on the basis for these. T h e lack is in integration and reduction t o practical terms. Xone of the published literature gives such information. ,4s far m the actual published literature is concerned, for the period Snvember 1, 1951, to November 1, 1953, the high spots seem to be:
1. Distillation research and development activity has passed the high quality peak evident in 1951. 2. -4pparatus developments of greatest interest are in rotary and spinning band columns for vacuuni distillation, and in continuous laboratory columns. 3. There is concern about flooding and flow properties in packed columns, and in column behavior under vacuum. 4. There is continued interest in low temperature distillation. 5. The Natural Gasoline .4ssociation of rlmerica is active in a systematic, constructive way through a school, seminars, cooperative a n a l g i e programs, and the publication of standardized procedures. 6 . -4good deal is being published on the distillation of fatty acids :rnd related compounds. 7 . .i Purprising propoi tion of significant references itre from foreign jnurnals T h e importance of safety precautions and considerations, even in low temperature distillation, is brought out by explosions during distillation of chlorine diovide ( 7 ) )dinitrochlorobenzene ( S d ) , and performic acid (115). GENERAL APPARATUS, PRINCIPLES, AND REVIEWS
matic or mechanized apparatus (28, 82), and two other. are 7pecialiaed [porous bubble plates (101); metal column for corrosive mixtures (74)l. No completely new ideas are involved. There are several general discussions of principles (11, 39, 107, 108). For those interested in making calculations of theoretical plates and reflux ratio, there are new papers involving finite reflux (83) and pole height (IH), constant distillate composition (do), holdup (79, 93, 124, 125), and a n elementary exposition of methods of calculating plates from composition and vapor-liquid equilibrium data ( 9 6 ) . Recent vapor-liquid equilibrium data have been indesed (94), and the exhausthe Horsley tables of azeotropes have now been put out as one of the Advances in Chemistry Series (46). The appearance of details on schizoid surface phenomena (41 ) is worthy of mention in connection with vapor-liquid equilibrium under vacuum, -4new edition of the .4ST>f Standards has been published, as well as a 50-vear index to the technical papers and reports of t h a t society ( 1 , 2 ) . PACKED COLUMN OPERATING VARIABLES AYD TESTIIVG
Considerable interest is evident in flooding and related phenomena. Dell and Pratt (13) have extended the range of a n equation originally derived for liquid extraction columns, so t h a t it is applicable to gas-liquid systems. Pratt ( 8 4 ) has reviewed wetted wall columns and given data and equations on the wetting of packing and on film resistance. TTilliamson (117 )has described liquid distributorq and splash eliminators. He aLw gives an equation, basetl on IITU conqidcrationq, for calculating the optimum velocity i n n p:wketl toner with gas film controlling. Several theses have dealt with flooding and f l o ~distribution in packed toners (43, 62, 66, 9 9 ) . Once again a modification of the Sherivood correlatloii has been shon n to give satisfactory results ( 7 3 ) ,in an investigation of the effect of surface tension on flooding, when vetting agents and soaps were added to water passed countercurrent to air in a column packed with Rerl saddles. The same article review the literature on flooding. >lurch ( 6 8 ) has presented an equation for calculating H E T P in terms of mass velocity of vapor, ton er diameter and height, liquid density, viscosity and relative volatility, and packing shape-side constants. Ellis ( 2 0 )proposes a somea hat similar formula. Kolling (51) has tabulated extensive performance data for packings of various types. ,4 patent has been issued to D k o n ( 1 7 ) covering his method of flooding and operation with gauze packing. K o r k on testing and performance line dealt mostly with operation a t reduced preqsure. Zuiderweg (122) suggests the use of n-decane-trans-decalin and n-hexadecane-n-heptyl benzoate as test mixtures in this held. Feldman and Orchin (dS), after some extensive work on the separation of the 1- and 2niethylnapthalenes, now propose them for evaluation of vacuum columns. €Ialdcn\vangpr (83)also suggestq nii\tures of 1- and 2-methylnaplithaleneq for this purpose, and p - :rnd nt-xi lenes as a test mixture when man\- plates are involved Bli-q et al. ( 3 )use o-dichlorobenzene-o-diethylhenzene a t lon throughputs to demonstrate that the effect of temperature on the liquid film is the main cause of H T U variations when distillation pressure is changed from 18 t o 50 mm. in a 3-inch tower packed n i t h '/*-inch Raschig rings. Peters and Cannon (77, 7 8 ) have found that each of several packings behaves differently when studied a t various pressures between 10 and 740 mm. They give the equation
Only a few descriptions of complete apparatus have appeared. two relate to autoOne of these indicates European practice (98),
101
ANALYTICAL CHEMISTRY
102 for calculating maximum mass velocity in terms of a packing constant] K, the liquid density, molecular weight, pressure, temperature, and the gas constant. Hawkins and Brent ( 3 7 ) state that H E T P changes but little as pressure is reduced from atmospheric to 20 mm. They use benzene-chlorobenzene and n-heptanemethylcyclohexane test mixtures in spiral screen and glass Raschig ring columns 18 mm. in diameter. Sugimura and Reynolds (111) have made similar studies in several types of packed columns] but results are inconclusive as to the effect of pressure. Leva (58) has described the line of reasoning followed in development of a new ceramic tower packing in attempts to achieve high surface area and flooding velocity Rith minimum pressure drop. Other new packings have been described by Hayter (38), Shorland (102),and Teller (113). The latter ascribes an improved HTU to the relatively large holdup of the rozette-type packing] although superficial reasoning suggests the opposite effect. The counterbalancing effects of large holdup in prolonging the startup period, in reducing sharpness of separation a t high reflux ratios, and in increasing undistillable residues in batch distillation, must be considered in a n over-all evaluation of such a packing. Fuchs (27) points out the possible effects of the chemical nature and surface adsorption on H E T P values, and explains differences of various packings on this basis. Romanet’s work (91) on intermittent versus continuous take-off does not seem to settle this question, Many of the references on the effects of operating variables are to work on columns 2 inches or larger in diameter. COLUMN ACCESSORIES
There are many of these, and they are ingenious, but little fundamental and integrating work has been done on them. T h e writers never cease to wonder a t the continuing stream of articles on reflux divider devices. Miller (67) describes a device involving drainage from one or more fixed areas of a condenser. As usual, the functioning of this arrangement depends on clean condenser surfaces. Collins and Killcock (10) use a calibrated tube and orifice for a pilot scale column. Swarr (112) recommends simple tests and special study t o obtain accuracy with proportioning pumps that are often used for reflux division in pilot columns. A metering chamber drained through valves controlled by meniscus movement (12) might serve as the basis for reflux division as well as for operation of a fraction collector. Piros and Glover (80) describe a liquid seal trap and pressure equalizing line applicable to reflux dividers. The use of glass valves to control small liquid f l o m is likewise worthy of consideration and possible adaptation (30), as is a solenoid ball valve controlled by a photorelay (19). George ( 3 2 ) describes a compact refluxing head for a large fractionating column. There are many references on fraction collectors (8, 16, 46, 66, 63,87, 89, 104,114,118, 120). Some are designed for chromatography but should be considered for automatic distillation apparatus ( 4 2 , 69, 97’). Four new publications on manostats have appeared ( l 4 , 2 1 , 3 6 , 6 1 ) . Hancock (35)has described a controlled adiabatic jacket, and Pantages and Feldman ( 7 5 ) a removable packing support useful for glass columns. Glass tubes affixed with eyternal electrically conducting coating have been advertised but not evaluated in a scientific publication. Mason ( 6 4 ) has published a reminder that flooding at the base of a column may be avoided by use of a separate line for returning reflux to the still. Garrison and Rolfson (29) have patented some automatic controls. Many of these column accessories are related to automatic controls. LOW TEMPERATURE DISTILLATIOX, LIQUEFIED GASES, AND NATURAL GASOLINE ANALYSIS
The NGAA booklet ( 7 2 ) on specifications and test methods for liquefied petroleum gas was issued during 1951 but not reported in this revieiv for that year. This association has continued
its cooperative analysis program ( 7 0 ) and is operating a school lor analysis ( 7 1 ) in natural gasoline plants. A book on light hydrocarbon analysis (6) was the outgrowth of similar work by the Butadiene Committee] Office of Rubber Reserve. Standard calculation procedures, sample calculations, and routine calculation sheets for low temperature distillation have been published (62, 86). Preston (85) has improved the method of correcting for vapor holdup. Legatski and co15orkers (66, 57) have developed the absorption indei procedure as a means of reducing the number of conventional analvses required for establishing the composition of natural gas. Metal valves and Teflon packing glands are recommended by Brown and Skahan ( 5 ) . A vacuum isothermal vaporization method of analysis for hydrocarbon gas mixtures containing oxygen and nitrogen has been patented by Clothier (9). Two papers discuss refrigerant supply (4, 110). Fookson et al. (24) have evaluated Stedman packing in the d i s tillation of hydrogen isotopes. Orrick and Gibson’s ( 7 4 ) complete metal apparatus for low temperature distillation of coriosive materials is worthy of study foi use in other connections. VACUUM DISTILLATION, ROTARY DEVICES
Aside from the performance and testing data mentioned in a previous paragraph] the most interesting papers relating to vacuum distillation involve rotary apparatus. Murray and Schoenfeld (69) and Horn and Hougen (44)have used amplified distillation in a small spinning band column to separate alcohols from carnauba wax and to recover g l ~ c ~ ofrom l s wool 11ax. Zuiderweg (123) makes a careful comparison of performance data and mass transfer in a spinning band column 6 mm. in diameter and a Vigreux column 11 mm in diameter. The data show more pronounced loss of efficiency R ith decreasing pressure for the spinning band column than for the i‘igreux. This seems contrary to the generally accepted idea that spinner columns are most effective under vacuum. Rotary c) linder columns or similar devices have been studied by Jost (47, 48)) Gel’perin ( S l ) , a n 1 Kaarsemaher (49). Perry’s patent (76) covers a rotatable brush fractionating column l ~ h o s ecooled center achieves thermal rectification, and eliminates droplet and rivulet formation on the outer wall. ,4pparently all rotary and spinning band columns to date have been designed empirically, with no effort to predict the dimensions, clearances, rates, etc., for optimum separation tluc to the several diffusional processes involved. Smith (106) has patented a column packed with a perforated spirally rolled sheet of stainless steel in which relatively thick liquids are distilled. The entire column is arranged so that i t mal be rotated in a plane forming a 14’ angle with the horizontal. Rotation of the pot also eliminates bumping. Radin (88) tlescribes a simply constructed still pot shaking device. Several other papers (66, 103) describe magnetic stirring devices for prevention of bumping. Michell eliminates stuffing box problems by locating the rotor within the evacuated glass syFtem J5hile the magnetic field is generated (Jutside. Foster and Green (26) use a similar arrangement for the magnetic drive of a spinning band column. Feldman and Pantages (62) suggests a small hot wire coil immersed near the bottom of a still pot to control bumping. .4 self-pumping still has been advertised but not devribed or evaluated in any published paper. LABORATORY CONTINUOUS DISTILLATION
Three additional laboratory continuous columns have been described. Kiguchi’s apparatus (60) also serves for batch distillation of 5- to 17-gallon charges. His column, 3 inches in dirtmeter, with 100 inches of protruded packing, has 60 plates a t low boilup rates, 40 plates near flooding, but only 23 to 31 plates in continuous distillation tests. D i m c k and Simone ( 1 6 ) have constructed a perforated plate column 28 mm. in inside diameter with 25 plates above and 15 below the feed. TT’ilcox, Coulter, and Lloyd (116) give complete and detailed descriptions of glass
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V O L U M E 2 6 , NO. 1, J A N U A R Y 1 9 5 4 equipment for continuous distillation. This includes methods for introducing feed, controlling feed rate, reboiler details, and a variety of reflux dividers. Start-up and shutdown procedures and methods of rate determination are given. Lloyd previously (60) had summarized the advantages and disadvantages of laboratory batch and continuous distillation, and a theoretical comparison has also been made (95). Krell (53) has published a review of continuous distillation in the laboratory. MICRODISTILLATION
There are too many applications of simple and conventional niicrodistillation to permit mention of them. Piros and Glover (81) have patented a micro fractionating column of the rotary t j pe. Dubowski and Shupe (18) have described a standardized apparatus for semimicro simple or steam distillation. JVolff (119) conducts tests for micro quantities of acetyl and formaldelij de by distillation from an asbestos absorbent. Sims (106) describes a micromolecular still in which one drop of sample is diepersed on a small glass wool pad suspended from the end of a quartz spiral in the axis of a small tubular furnace, A cathetorneter is used to note movement of the spiral as the distillation progresses. Sherwin (100) emplo? a somewhat similar trchniqur for separation of radioactive elements from carriers. .MI SCE LLANKOU S
Amplified distillation haB been used by -Murray and Schoenfelti (69)to secure sharp separation of high boiling materials in vacuum distillation. Nothing has appeared regarding the theor!. of amplified distillation. An anal>.tical separation of metals by fractional distillation of their halides has re(-ently been reported by Fowler (26). Similarly, germanium in coal ash (109) may be determined by steam tiivtillntion of the volatile chloride, anti subsequent conversion t,o the oxide. Rollet (90) secured what is probably thermal rectification by using a n empty column so placed t h a t the lower side of the tube could be heated from below, while the upper side was cooled from above. A total reflux separation equivalent to illiout 90 plates per meter length vias obtained with benzene-ethylene dichloride test mixture at total reflux in a tube 100 cm. long by T.6 mni. in diameter. Kunxler ( 5 4 ) proposes constant boiling sulfuric acid as a material of precisely known composition for use :is a primary ptmtlard in acidimetry. LITERATURE CITED
(I) (2) (3)
(4)
(5)
(6)
(7) (9)
(9) (10)
(11) (12) (13)
(14)
.Lnierican Society for Testing Jlaterials, Philadelphia, “FiftyYear Index to ASThl Technical Papers and Reports,” 1952. American Society for Testing Materials, Philadelphia, “1952 Hook of ASTM Standards,” 1952. 13liss, Harding, Eshaya, -1.31., and Frisch, p\i. W., C ‘ h r v ~Eng. . Progr., 48, 627-32 (1952). Hox, G. F. H., and R a k e r , 31. S., J . Sei. Instr., 27, 314-15 (1950). Brown, R. A., and Skahan, D. J., “Application of Metal Valves and Teflon Packing Glands in Low Temperature Distillation Apparatus,” .Im. Petroleum Inst. Sleeting, riew York, M a y 1953. Burke. 0. W., Jr., Stilrr, C. E., Jr., and Tuemmler, F. D., “Light Hydrocarbon Analvsis,” New York, Reinhold Publishing Corp., 1951. Cameron, A. E., and Faloon. .i.V., Chem. Eng. S e w s , 29, 3196 (1951). Carlander, A. T., and Gardell, h e n , Arkit Kemz, 4, 461-7 (1952). (’lothier, A. T., U. S. Patent 2,600,158 (June 10, 1952). Collins, G. A , , and Willcock, H. G., Chemistry & Industry, 1951, 754. Coulter, K. E., Petroleum Refiner, 31, KO. 8, 95-104; No. 10, 145-50; NO.11, 156-8; NO.12, 137-8 (1952). (‘look, E. hl., and Datta, S. P., Chemistry & Industry, 1951, 718-19. Dell, F. R., and Pratt, H. R. C., J . A p p l . Chem. (London), 2, 429-35 (1952). Digney, F. J., and Yeraaunis, Stephen, ANAL.CHEM.,25, 921-3 (1953).
103 (15) Dimick, K. P., and Simone, -\I.J., Ind. Eng. Chem., 44,2487-90 (1952). (16) Dimler, R. J., et al., As.4~.CHEM.,25, 1428-30 (1953). (17) Dixon, 0. G., U. S. Patent 2,615,832 (Oct. 28, 1952). (18) Dubowski, K. hi., and Shupe, L. M., A m . J . Clin. Pathol., 22, 709-11 (1952). (19) Dutton, H. J., and Castle, F. J., ANAL. CHEM.,25, 1427-8 (1953). (20) Ellis, S. R. h i . , Chem. Eng. -Yews, 44, 4613 (1953). (21) Erner, W.E., and Campbell, K. K., ANAL.CHEX.,24, 1232-3 (1952). (22) Feldnian, Julian, and Pantages, Peter, Ibid., 24, 432 (1952). (23) Feldman, Julian, Svedi, .Inne, Connell, Samuel, and Orchin. Milton, I d . Eng. Chem., 45, 214-15 (1953). (24) Fookson, Abraham, Pomeranta, Philip, and Rothberg, Simon, J . Research i\Tatl.Bur. Standards, 47, 449-55 (1951). (25) Foster, 3.G., and Green, L. E., Jr., ANAL.CHEM.,24, 1869 (1952). (26) Fowler, R. M., “Separation and Determination of Kiobium. Tantalum, Titanium, Zirconium, Tungsten, Vanadium. lIolybdenum, and the Rare Earths,” Sixth Annual Summer Symposium, AM. CHEM.Sac., Division of Analytical Chemistry, Troy, N. Y., June 1953. (27) Fuchs, OttQ, Chem.-Ing.-Tech., 23, 537-40 (1951). (28) Calstaun, L. S., et al., “;iutomatic Distillation Column,” Divisions of Petroleum Chemistry and Analytical Chemistry, Symposium on -4utomatic Analytical Methods in the Petro. Roc., Chicago, leum Indnstry, 124th Aleeting, - 4 ~CHEM. September 1953. (29) . , Garrison, A. H., and Kolfson, F. B., U. S. Patent 2,577,615 (Dec. 4, 1951). (30) Geankoplis, C . J., and Hixson, -4.N., Ind. Eng. Chem., 44, 589-90 (1952). (31) Gel’perin, N. I., and Khatsenko, 11. S., Z h w . Priklad. Khim., 25, 610-15 (1952). (32) George, J. S., J . Sci. Instr., 30, 172 (1953). (33) Haldenwanger, H., Chem.-I?zg.-Tech., 23, 437-40 (1951). (34) Halpern, B. D., Chem. Eng. S e w s , 29, 2666 (1951). (35) Hancock, J. A., “Controlled Differential ildiabatic Jacket for Fractional Distillation Columns,” 28th Annual Meeting, Southwestern Div., ;im. :Issoc. Advancement of Science, Boulder, Colo., May 1952. (36) Haring, H. G., C h m . R’cekhlad, 47, 1013-14 (1951). (37) Hawkins, J. E.. and Brent, J. A4., Jr., Ind. Eng. C h e m . , 43, 261121 (1951). (38) Hayter, A. 6.,I d . Chemist. 28, 59-64 (1952). (39) Herington, E. F. G., Chemistry & Industry, 1953, 26-30. (40) Hibino, Shinichi, Proc. Fujiham Mem. Fac. Eng. Keio Unir., 3, 84-9 (1950). (41) Hickman. K. C. D., and Trevoy, D. J., Ind. Eng. Chem., 44, 1882-1911 (1952). (42) Hickson, J. L., and Whistler. R. L., 4 h - a ~CHEY., . 25, 1425-6 (1953). (43) Hoffing, E. H., Ph. D. thesis, University of Southern California, 1951. (44) Horn. D. H. S., and Hougen, F. W.,Chemistry & Industry, 1951, 670. (45) Horsley, I,. H., et al., A d m n c e s in Chem. Ser., No. 6 (1952). (46) James, A. T., Martin, A . J. P., and Randall, 8.S..Biochem. J., 49, 293-9 (1951). (47) Jost, W., Chem. Eng. .VPWS, 31, 2859-60 (1953). (48) Jost, W., Sieg, L., and Rrandt, H., Chem.-Ing.-Tech., 25, 291-2 (1953). (49) Kaarsemaker, S., and Coops. J., Rec. trat’. chim., 71, 125-36 (1952). (50) Kiguchi, S. T., “Combination Batch and Continuous Fractionation Column,” Division of Petroleum Chemistry, 123rd Meeting, AM. CHEM.Soc., Los Angeles, Calif., March 1953. (51) Kolling, Helmut, Chem.-Ing.-Tech., 24, 405-11 (1952). (52) Krause, W.F., Dystrup, A. C., and Buchanan, K. A , , Petroleum Refiner, 32, No. 8, 115-18 (1953). (53) Krell, E., Chem. Tech., 4, 443-50 (1952). (54) Kunaler, J. E., ANAL.CHEM.,25, 93-103 (1953). (55) Landucci, J. &I., Chim.anol., 35, 11-13 (1953). (56) Legatski, T. W., Tooke, J. W.. and Grundy. L. A , . Petroleum Refiner. 32. Xo. 7. 155-8 (19.53). \ , (57) Ibid.; KO. 8, pp. 105-8. (58) Leva, Ifax, ”Development of a New Ceramic Tower Packing,” Division of Industrial and Engineering Chemistry, 121st Meeting, - 4 ~CHEM. . SOC.,Buffalo, N. Y., March 1952. (59) Lien, 0. G., Jr., Peterson, E. A , , and Greenberg, D. M., ANAL. CHEY.,24, 920-1 (1952). (60) Lloyd, L. E., Petroleum Refiner. 29, N o . 2, 135-45 (1950). (61) Lowry, G. G., J . Chenr. Educ., 28, 535 (1951). (62) Lubin, Bernard, Microfilm Abstracts, 9, No. 3, 25-6 (1950); Univ. Microfilms, P u b . 1473.
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ANALYTICAL CHEMISTRY
(63) Mader, Charles, and Mader, George, Jr., ANAL.CHEM.,25, 1423 (1953). (64) hlason, A. C. F., Ibid., 25, 533 (1953). (65) Metcalfe, T. B., “Study of Flooding in Packed Columns,” Ph. D. thesis, Georgia Institute of Technology, 1951. (66) Michell, D., J . Appl. Chem. (London),1, Suppl. 1, S8-9 (1951). (67) Miller, G. H., J. Chem. Educ., 29, 73-4 (1952). (68) Murch, D. P., Chem. Eng. News, 30, 520 (1952). (69) Murray, K. E., and Schoenfeld, R., J . Am. Oil Chemists’ Soc., 28, 461-6 (1951). (70) Natural Gasoline Association of ilmerica, Chem. Eng. News, 30, 432 (1952). (71) Ibid.,p. 2093. (72) Natural Gasoline Association of America, Tulsa, Okla., “Liquefied Petroleum Gas Specifications and Test hlethods,” 1951. (73) Newton, W. M.,Mason, J. W., Metcalfe, T. B., and Summers, C. O., Petroleum Refiner, 31, N o . 10, 141-3 (1952). (74) Orrick, N. C., and Gibson, J. D., ANAL.CHEM.,23, 1100-3 (1953). (75) Pantages, Peter, and Feldman, Julian, I d . Eng. Chem., 44, 2783 (1952): (76) Perry, E. S., L . 8. Patent 2,678,086 (Dec. 11, 1951). (77) Peters, &I. S., “Vacuum Distillation.” Ph.D. thesis, Pennsylvania State University, 1951. and Cannon, hl. R., Ind. Eng. Chem., 44, 1452-9 (78) Peters, M. S., (1952). (79) Pigford, R. L., Tepe, J. B., and Garrahan, C. J., Ibid., 43,2592602 (1951). (80) Piros, J. J., and Glover, J. A , U. S . Patent 2,573,807 (Nov. 6, 1951). (81) Ibid., 2,608,528 (-4ug. 26, 1952). (82) Podbielniak, mi. J., Deyle, C. hZ., Marco, Carl, and Turkal, Peter, “Recent Improvements in Mechanized Low-Temperature Analytical Distillation Apparatus,” Divisions of Petroleum Chemistry and Analytical Chemistry, Symposium on Automatic Analytical Methods in the Petroleum Industry, 124th Meeting, AM. CHEM.SOC., Chicago, Ill., September 1953. (83) Pohl, Herbert, Erdol u. Kohle, 5, 291-4 (1952). (84) Pratt, H. R. C., Trans. Inst. Chein. Engrs. (London), 29, 195210, discussion, 210-14 (1951). (85) Preston, S. T., Jr., Petroleum Refiner, 32, KO.4, 142-4 (1953). (86) Ibid., Yo. 8, pp. 109-14. (87) Putt, J. W., Smith. J. O., Jr., and AIcLean, J. O., U.S. Patent 2,622,062 (Dee. 16, 1952). (88) Radin, E.S., Ax.4~.CHEM.,24, 1686-7 (1952). (89) Renshaw, il., Chemistry & Industry, 1953, 294-5. (90) Rollet, A. P., Bull. soc. chim. France, 1952, 539-44. (91) Romanet. Ren6, Compt. rend., 235, 1390-2 (1952). (92)’ Rose. Arthur, h i . 4 1 , . CHEM.,24,60-4 (1952); 23, 38-41 (1951); 22, 59-61 (1950); 21, 81-4 (1949). (93) Rose, Arthur, Johnson, R. C., and Williams, T. J., Cheni. Eng. Progr., 48, 549-56 (1952). I
(94) Rose, Arthur, and Rose, E. G., “Distillation Literature Index and Abstracts, 194652,” State College, Pa., Applied Science Laboratories, 1953. (95) Rose, Arthur, Williams, T . J., and Kahn, H. A., Ind. Eng. Chem., 43, 2608-11 (1951). (96) Santos, M. S., Ion, 13, 11-13, 21 (1953). (97) Schram, Eric, and Bigwood. E. J., Ax.4~.CHEY., 25, 1424 (1953). (98) Schultze, G. R., and Stage, H., Dcchenm Monograph, 14, S o . 143/56, 17-40 (1950). (99) Schwartz, C. E., “Flow Distribution in Packed Columns,” Ph.D. thesis, Purdue L-niversity, 1951. (100) Sherwin, C. W., Rea. Sci. Instr.. 22, 339-41 (1951). (101) Shire, W. A., C. S.Patent 2,575,193 (Nov. 13, 1951). (102) Shorland, F. B., J. Appl. Chein., 2, 438-40 (1952). (103) Silverstein, R. M., and Englert. R. D., Chemist Amlust, 41. 15-17 (1952). (104) Simpson, D. A., and Sutherland, 31. D., ANAL. CHEM.,23, 13456 (1951). (105) Sims, R. P. A., “hlicromolecular Still,” Chemical Institute of Canada, Montreal, June 1952. (106) Smith, T. R., U. S. Patent 2,575,688 (Nov. 20, 1951). (107) Stage, H., Fette u. Seijen, 53, 677-82 (1951). (108) Ibid., 55, 217-24 (1953). (109) Steward, K., Gas World, 137, 794-5 (1953). (110) Stokes, C. S.,and Hanptschein, Murray, ANAL.CHEM.,24, 1526 (1952). (111) Sugimura, G. H., and Reynolds, T. W., “Evaluation of Packed Distillation Columnsat Atmospheric and Reduced Pressures,” Section 14, Physical and Inorganic Chemistry, XIIth Internatienal Congress of Pure and Applied Chemistry, S e w York, 1951. (112) Swarr, J. N., Trans. Am. Soc. Mech. E’ngrs., 74,891-903 (1952). (113) Teller, 9. J., “The Rosette, A New Packing for Diffusional Operations Based on High Interstitial Holdup,” Am. Inst. Chem. Engrs. Meeting, San Francisco, Calif., September 1953. (114) Varner, J. E., and Bulen. IV. .i., J. Chem. Educ., 29, 625-6 (1952). (115) Weingartshofer-Olmos, A . . and Giguere, P. A., Chem. Eug. News. 30. 3041 (1952). (116) Wilcox,’.4. ’C., Cdulter; K. E., and Lloyd, L. E., Petroleum Refiner, 31, KO.2, 134-6 (1952). (117) Williamson, G. J., Trans. I&. Chem. Engrs. (London), 29, 215-24, discussion, 224-5 (1951). (118) Wingo, W. J., and Browning. Iben, ANAL.Cmnr., 25, 1 4 2 6 7 (1953). (119) Wolff, C. J. de, Pharm. W e e l h l n d , 86, 273-5, 335 (1951). (120) Zahn, R. K., Chem.-Ing.-Tech.. 24, 620 (1952). (121) Zuiderweg, F. J., Chem. Eng. Sci. (London), 1, S o . 1, 8-17 (1951). (122) Ibid., NO.4, 164-74 (1952). (123) Ibid., pp. 174-93. (124) Zuiderweg, F. J., Chem.-Ing.-Tech., 25, 297-308 (1953). (125) Zuiderweg, F. J., Ingenieur, 64, CH 6 3 4 (1952).
Ion Exchange ROBERT KUNiN and FRANCIS X. MCGARVEY Rohm
A
& Haas Co., Philadelphia, Pa.
SURVEY of the literature on ion exchange during the past two years has shown a continued interest in the use of ion
exchange techniques in many analytical chemical problems. An indication of the role of ion exchange in analytical chemistry is evident upon examination of a recent text written by Samuelson (bS7), entitled “Ion Exchange in Analytical Chemistry.” This outstanding contribution reviews the theory and practice of ion exchange in its application to analytical chemistry and to many other allied fields. It is of particular interest in that Samuelson suggests procedures that have been investigated sufficiently so that they may be placed on a routine basis, thereby enabling the control analyst to conduct analyses with ion exchange with but a minor amount of exploratory research. Although the interest in the use of ion exchange in analytical chemistry is rapidly increasing, the actual number of quantitative methods that are of general use are few. T o date, the chief
analytical uses for this technique appear to be divided among separations in biochemical analysis; separations of metallic complexes from one another and from materials not capable of forming complexes; roncentration of dilute solutions; and t h e determination of total ionic concentration in various solutions, natural water supplies in particular. I n addition, several difficulties encountered with this technique have hindered the universal acceptance of ion exchange in analytical chemistry. Some of these difficulties are the impurities encountered in “run-of-the-mill” commercial resins; variations in results with various samples of the same commercial grade of ion exchange reqin; and unfamiliarity with the general principles of ion exchange. However, regardless of these difficulties, i t has been generally accepted by those experienced with the technique that a considerable number of useful analytical procedures employing ion
