B. L. HARRIS, THE JOHNS HQPKINS UNIVERSITY, BALTIMORE 18, MD.
Recently interest has turned to the study of adsorption of mixed gases and the resolution of such mixtures. This interest was extended into analogous liquid phase systems; and commercial applications of both fields have been made. There has been a decrease in interest in chromatographic studies as compared to the recent past.
desorption is accomplished by vapor stripping, the adsorbent should be preheated; and steam has distinct advantages as a desorbentin this case. Hermanson (141) has proposed the use of inorganic gels to remove organic adsorbates of low molecular volume, from heavier organic molecules. The gels SO proposed are of carefully controlled pore size. The separation of isomers of xylene has been proposed by Plachenov and Kuzin, on activated charcoal (247). The use of adsorption on siIica geI and differential stripping with mineral acids has been shown by Beyer et al. t o be of value in concentrating hafnium from mixtures with zirconium (as oxides) ( S I ) . Elton discussed the use of the material balance to give the composition of the surface layer of a binary adsorption from the characteristics of the materials involved (104).
ERHAPS the most noteworthy thing which occurred in this field in the recent past was the gradual shift of interest t o the use of adsorptive means for resolving mixtures of gases or of liquids in quantity. I n the place of scattered references to resolution of gaseous mixtures there were, this past year, some fourteen references dealing with this subject. Several of these dealt with the hypersorption process first elucidated by Berg and his eoworkers (24-26, 277). MasIan and coworkers ($09) have proposed that equilibrium binary adsorption can be predicted from the single gas data when N12Vl2
=
K,V,
+
N2V-2
SURFACE AREA AND POROSITY STUDIES
where V is the volume of compressed gas a t ambient temperature and pressure equivalent to the vapor pressure a t that temperature, and N is the number of moles of adsorbed gas. Chernyshev et al. (63) proposed the use of a coefficient of separation capacity for separation of binary mixtures. This coefficient, K -equal to y,xz/xlyz-is a relative volatility term, where y is the mole fraction of one component in the gas phase and x is the mole fraction in the adsorbed phase. As would be expected, K varies with composition of the binary mixture. Cremer and coworkers (74, 7 5 ) report quantitative separation of acetylene and ethylene or acetylene and propylene (in 8 carrier gas such as hydrogen) by suitable choice of column length, velocity, and temperature. Detection of a gaseous component without complete separation is possible by observing the breakthrough time characteristic of a substance. This is possible only if this break time is independent of concentration. Theoretical studies of mixed adsorption have been developed (224, 259). Data are given by various authors for binary adsorption and separation of benzene from methanol (257); xenon from helium (193); hydrogen, oxygen, and nitrogen with carbon dioxide (148); as well as hydrocarbon gases (63, 74, 76, 146). I n one process for separation of cyclohexane from hexane, the heated desorbed silica gel is cooled by contact with liquid hexane, which vaporizes, fluidizing the gel and transporting it t o the top of the adsorption space where it is separated (388). Following close upon the release a year ago of the details of the Arosorb process of liquid phase separation of adsorbable mixtures, additional data have now been published. Patents on this process have been issued to Olsen (235, $336). He states t h a t the proper desorbing liquid to use is one having a n adsorption index (analogous t o aromatic index, but for the given agent) similar to the component of the mixture more strongly adsorbed. Data are given for numerous materials. Spengler and Krenkler (276) have shown that for selective adsorption of hydrocarbons, particularly separations of saturated from unsaturated by compounds, silica gel is superior t o other adsorbents, with activated charcoal second. The latter was superior for separation of substances based on length of side chains and on saturated groups, or on molecular weight. Seybert (274) has discussed the preparation of optimum silica gels for these various operations. Claussen and Shiftler (66), discussing a continuous adsorption process, claim that a desorbent should have a specific gravity at least equal t o the material to be extracted, and should be miscible with it. If
Numerous authors have discussed the Brunauer-Emmett-TO]ler (B.E.T.) theory of multilayer adsorption and some have compared it with the Hiittig equation on the grounds of violation of the principles of microscopic reversibility and incorrect equilibrium condition in the statistical derivation of the theory. Elimination of these difficulties leads to the B.E.T. theory. Barrer ( 1 1 ) stated that the Huttig isotherm complements the B.E.T., where vertical interactions of niolecules on a surface are introduced and lateral ones omitted. Theimer has presented a thermodynamic derivation and interpretation of the Iluttig isotherm wherein the isotherm corresponds t o the equation of state for a two-dimensional real gas, the molecules of which are associated partly in pairs and partly in larger groups (286). Troesch (295) presented a generalization of the two equations, linearizing the fit of experimental data to the neighboihood of p / p o approaching unity. Levin (197), Band and Emery (Q), and Aston and Mastrangelo ( 4 ) have discussed modifications of the B.E.T. equation. Liang has indicated areas of agreement between the B.E.T. and the Harkins-Jura equations. Barrer et al. have derived a number of B.E.T.-type equations which, when applied to experimental systems together with the B.E.T. and Huttig equations, all give values of vm with a spread of 1.4 or 1.5 to 1. Statistical theories of adsorption were discussed by Toshima and Tanaka (283, 292), and fits of types 111, IV, and V isotherms were presented. Theimer (287) has introduced the concept of “maximum surface concentration” x*, which bears the same r e lation t o z, the number of adsorption sites on the surfaces, as the reduced volume bears to the real volume of a nonideal gas. The function of this parameter is to transform a n isotherm which does not follow the B.E.T., Huttig, or Langmuir isotherms into one which does. B a l h (7) has derived the isotherms of Langmuir, Cassie, and B.E.T. statistically, by the use of the grand canonical ensemble. Other isotherms were also derived; these latter have not yet been subject t o experimental verifications. Cook, Pack, and Oblad proposed a new type of adsorption potential associated with surface strain due to heterogeneity or elimination of unbonded electron orbitals. This has been applied t o adsorption of oxygen and nitrogen and mixtures thereof on anatase, over the entire range of relative pressure, with excellent agreement (67). Cabrera (64) suggested that “surface melting” is of importance. Bering and SerpinskiI have applied 24
January 1953
1
pr
*
-
INDUSTRIAL A N D ENGINEERING CHEMISTRY
cussed a theory of chromatography on honhomogeneous surfaces. They have presented a determination of the distribution function of portions of a solid surface over heats of adsorption from desorption curves, and the dynamics of adsorption of mixtures on such surfaces. James and Martin have extended the theory of the partition column to compressible mobile phases and discussed the factors affecting the separation (163). Chromatography of trace components was evaluated by a kinetic-diffusional theory and appropriate mass-transfer coefficients calculated by Vermeulen and Hiester (899). Thomas (989)derived equations for isotopic exchange which he stated could be used t o predict behavior in one column from that on another. Boulanger and Biserte have presented a general review (in French) of chromatographic theory, with applications to specific systems (39). Reviews have also appeared in Polish (306) and Italian (.@SO). The greatest amount of recent interest wm manifested in paper chromatography, owing to its convenience and its ability to handle small samples. Rockland et a2. have given ratings for 13 types of filter paper with resolution values for 18 amino acids in phenol. In general, the sequence of resolution was the same for the various papers (267). ProchBzka (961)found that paper gave better resolution and more rapid movement of the front when treated with hydrochloric acid. Marchal and Mittwer (607) proposed a technique of developing chromatograms in circular arcs, by placing the mixture to be developed on a small tab attached to a larger paper and dipping the t a b into the developer. Experimental data have been presented (190)t o indicate that the distribution of liquid ascending or deacending in 8 paper is not always uniform. Fujita has developed an equation to account for the amount of liquid per unit area of paper in terms of capillary flow and surface flow capacities of the paper. A comprehensive treatise presenting methodical directions for paper chromatographic methods, and covering theoiy as well as procedures, has recently appeared (71, in German). Quantitative paper chromatography for students has been discussed by Patton (248). Several authors dealt with the resolution of amino acids on paper (60, 607, 918, 966). Solvents giving usual sequences, inverted sequences, or useful for separating single, pairs of, or groups of amino acids have been studied (967). Miettinen (618) has revealed a new technique which improved separation and identiiication of the neutral amino acids, most of which (even the leucines) could be completely separated from hydrolyzates in oned i m e n s i o n a l experiments. The glycine peptides were studied by Brockmann and Musso (46), organic acids by Opiefiska-Blauth and coworkers (937), dyes by Maauyama and Takahashi (911),and fluoresceins by Graichen (150). Inorganic paper chromatography studies have yielded quantitative microgram separations of various metals. These include boron from silicon and molybdenum; vanadium from iron and aluminum; nickel and copper from cobalt and iron; vanadium from lead, zinc, and cadmium; aluminum, titanium, and COURTESY 0 . Me KEMP HPO. EO. vanadium from iron, chromium, and Figure 1. Semiautomatic Adsorptive Dryer molybdenum (198); aluminum from
the general form of the equation of the two-dimensional pressure as a function of the number of molecules adsorbed per unit area for various sets of conditions to give expressions for adsorption .on homogeneous surfaces (98). Heterogeneity of surfaces has been discussed by various authors. T h e dual surface theory was further explored a t Lehigh University (196). Liang has shown that, up to 30% of a B.E.T. monolayer, none of the proposed theories for a uniform surface is followed (199). Honig a n d Reyerson (161)found a distribution of surface energies for nitrogen very different from that for argon or oxygen. Halsey (134) explained deviations from the Langmuir equation in terms of nonuniformity of the surface and showed that refined treatment of a uniform surface leads to the conclusion that heterogeneity and interaction operate simultaneously. Orr a d Bankston have proposed an adsorption index type of rapid surface area determination for use on clays, involving the adsorption of fatty acids from methanol (638). Surface area, studies of various materials have been reported: on coal (816),.lignites (69), silica gel (16, 180,997), charcoal (68), metals (964),carbons ( 8 7 4 clays (108), as well as others noted above. A large number of studies dealt with porositx of sorbents. The consensus indicated that surface area could be determined from the usual isotherms but that additional study was necessary to deduce pore structure and pore-size distribution. Chr6tien and Papbe differentiated between microporosity and macroporosity of silica gels (66). Foster has further discussed his openpore theory and concluded that hysteresis should occur in large pores for most liquids (116). Pierce has discussed some of the limitations of the Kelvin equation for pore size calculations (6441, whereas Carman and Raal (68) show that multilayer sorption must be taken into account when using that equation. Barrer and Grove (18) discussed the effect of adsorption on flow of gases in pores, and Jones (166) has treated sorbed gas as a two-dimensional gas, deriving equations for flow thereof through various types of geometrical systems. The effect of porous adsorption of the freezing point depression of carbon tetrachloride was shown by Iwakami t o agree with theory (169). Joyner et al. have demonstrated confirmation of the Barrett, Joyner, a n d Halenda theory, using a comparison study of the pore size distribution by nitrogen isotherm and mercury porosimeter (168). Juhola and coworkers (169) have shown that the above theory gives good agreement between nitrogen and water studies on charcoal and that water is useful over a wider range of pore sizes than nitrogen. Many pore size distribution and pore structure studies have been conducted on charcoals (67, 68, 82, 86, 96, 11.4,168, 169, 181, 90.4), silica and other gels (16, 46, 67, 140, 699, 934), clays (66, 176), and other materials (131,170). CHROMATOGRAPHY
Fewer studies appeared during the past year in this area than have appeared for the last several years. Fewer still have been papers dealing with theoretical subjects. RoginskiI and Yanovskil (168)dia-
25
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
26
iron (136);and tellurium from zirconium (195). Separation of various anions was achieved by DeLoach and Drinkard (90). Ortho-, meta-, pyro-, and polyphosphates were separated by Ebel and Volmar using a two-dimensional system with acidic and basic solvents (99). Separation of various anions and cations by development with water was discussed by MiliEeviE (660). Studies have likewise been made on various other adsorbents. Robert (655) has presented a partial classification of various organic compounds on charcoal, silica gel, and alumina to use in predicting chromatographic separations. Faucher et al. (113) showed t h a t isotopic separations on clay operated under nonequilibrium conditions. I n addition to improvements in technique mentioned above, two studies on apparatus are of note. Mowery (333)described a laboratory apparatus operating at premures up t o 120 pounds per square inch and air-blowing t o improve flow rate and elution of finely powdered absorbents. Lynam and Weil (602) presented exact data on a radial chromatographic pilot plant, including layout, flowsheet, and scheme of operation. Lapidus and Amundson (194) presented mass transfer equations based on diffusionrate mechanisms, for initially empty radial adsorption disks. Other chromatographic separations published include the separation of anthracene, anthraquinone, and carbazole (121, 132, 212), sugars (WSb), fatty acids (163), mercapto compounds (154), flavones (123), and ortho-, pyro-, and triphosphate anions (810). LlOUlD PHASE ADSORPTION
I n contrast to the field of chromatography, liquid phase studies of other types were quite on the increase. Most of these studies were of the type that were primarily concerned with considering specific systems as discussed below. There were, on the other hand, a number of more general papers. Swietoslawski suggested a classification system for sorbents and ion exchangers, dividing them into ideal and nonideal types. The first type included those characterized by one function only, whereas the second contained acidic or basic groups (389). Temperature dependence of sorption was discussed by Bartell and associates ( 1 7 ) as being due t o the effect of solubility as well as the normal temperature effect. Hansen (135) has indicated that the adsorption of either gas or liquid is related t o Gibbsian surface excesses by multiplicative constants which are experimentally determinable. Mathematical treatment of equilibrium and nonequilibrium cases was presented by Edeskuty and Amundson (100). Calvet (55) measured the heat of adsorption by microcalorimeter and found that there was a discontinuity at the completion of a monolayer. Heat of wetting studies showed t h a t absorbability of solutes from solution increased with increasing heat of wetting of the solute (656, 680) and with decreasing heat of wetting of the solvent (62) as would be expected. The melting point of ethylenediamine on silica gel indicated a lowering of the melting point of the adsorbate by 6.8’. Separable films were coated on metal plates to produce adsorption surfaces for liquid phase studies. These films developed adsorption spectra using methylene blue solutions, which could be used to deduce conclusions conccrning dynamic adsorption, diffusion, or fluid flow (185). Radioactive tracer techniques have been used in various of the studies, and were discussed by Aniansson (S),Bernard et ol. (SO), and Loos (301). Banks (10) has patented a device for adding solid adsorbents to a flowing stream of liquid hydrocarbons in such manner as to reduce interference by moisture. Adsorption of ions from solution by solids is at times interrelated with ion exchange, elsewhere discussed. However, adsorption can and does occur alone in Borne cases and simultaneously with ion exchange in others. Venture110 and Burdese (898)found t h a t alumina adsorbed cupric ions in part reversibly and that the irreversible amount increased with time of con@
Vol. 45, No. 1
tact. The role of anions in cation exchange media was discussed by Kantor and coworkers (174). Molecular adsorption on ion exchange resins was discussed by Davies and Thomas (84). The sorption of electrolytes was variously studied on gels (226), on freshly prepared colloidal surfaces (188), and on freshly precipitated, difficultly soluble salts (60). Various other ionic adsorptions were discussed in other papers (87, 134, 126, 190, 281). The role of ionic adsorption in catalytic decomposition of hydrogen peroxide was studied by Kolarov (184). Iodine adsorption from various organic solvents was studied by Iwakami (160) who attributed the brown color in polar solvents to combinations n ith the solvent, and the violet color in nonpolar solvents to tho presence of the free element. Adsorption fiom liquids onto small areas of plane surfaces were studied in a number of cases. These included tetrafluoroethylene polymers (117), platinum (6, 41, 80, 117, 171, 215), various other metals (41,80),and paraffin (202 ). Kahan (171) suggested t h a t the metal-cleaning activity of sodium metasilicate is due t o tbe effect of the colloid on hydrophobic film formation. The use of radioactive metal foils as a tool in the study of thiclmess of the adsorbed layer was proposed by BOM den and Moore, who state that it is sufficiently sensitive to detect chemical reaction of a monolayer over 1 sq. mm. of the surface ( 4 1 ) . Adsorption of organic molecules fiom solution by solid adsorbents was responsible for a great deal of interest. Several studies dealt with dyes on various adsorbents. Modification of charcoal by treatment n ith diphenylamine increased adsorption of methylene blue aa compared to oleic acid-coated charcoal (149). The adsorptive power of charcoal for methylene blue, iodine, and acetic acid was found to inci ease by treatment of the char n ith oxidizing agents (233). Orientation of methylene blue and other materials on various surfaces n-a. studied by polarized light and found to depend on the crystal face of the substrate (59, 515). The adsorption of various dyes on oxide SUIfaces and on starch was shown t o depend on the acidity of the dye and of the solvent (97, 685). Rules for the application of activated carbon as a decolorizing agent nere set forth (311). Bhatnagar (32, 53) found t h a t organic adsorbents prepared from natural tannins adsorbed organic acids with reversal of Taube’s order, owing to orientation a t the resin-water interface according to the theory of Langmuir and Harkins. Condensed phenolic resins followed the rule for acid-condensed resins adsorbing acids and reversed it for alkali-condensed resins adsorbing amines. Adsorption by charcoal of benzyl alcohol (61), and mixed adsorption of oleyl alcohol and aniline (187); of silica gel for phenol (186); of clay for hydiocarbons (94); by colloidal systems of silicates for dyes (118); by charcoal of essential oils (306, 303); and by asbestos of sugar (150) were presented by various authors. The adsorption of organic molecules on coal showed that the area per molecule decreases with decrease of rank and with oxygen increase (288). Kipling has prepared a review of the adsorption of nonelectrolytes from solution (178). Other studies of interest coneerned sodium hydroxide and hydrochloric acid (107, 129, 147, 175), aqueous xanthate ( I S S ) , water (119), and high polymers (78,164). In the studies concerning monolayel s on liquid substrates, only two authors dealt with adsorption of gases thereon. Hayes and Dean (88, 158) investigated the adsorption of isomeric hexanes on condensed stearic monola>cis and on clean water suifaces. Type T’ monolayers were observed on the former; type I11 on the latter. Hayes and Dean described a balance for such studies and presented a t,heorctical discussion of such studies. When binary mixtures of organic acids of the same number of carbons (within two carbon atoms) were compared to the data for the components by Isemura and Haniaguchi (158),the same pressure-area curves were observed, but the area per molecule
s
January 1953
i.
INDUSTRIAL AND ENGINEERING CHEMISTRY
was found to be smaller for the mixtures. Vold (304) discussed the packing of fatty acids on water in terms of molecular area. Giles and Neustadter (127) conducted similar studies on aromatic azo compounds. Daviesand Kingstudied the distribution of ions under a charged monolayer and dkcussed an equation of state for charged films (86). Thme studies were discussed in relation to proteins. Other studies on protein films were made by Cumper and Alexander ( 7 7 )and by Deborin and Gorbacheva (89). Surface active agents were considered in several studies (156,269,270). The effect of oxygen on formation of layers of naphthacene was found to be such as to render the film unimolecular, whereas rigid exclusion of oxygen gave multilayers (126). Fatty acids were found to form stable monolayers a t the middle of the p H range where ionization was incomplete. Wolstenholme and Sohulman (312) studied the p H dependence of myristic acid films on salt solutions. The time dependence of soluble surface layers maintained at constant area was shown theoretically and experimentally to be explained by desorption (262). D a t a on time dependence of boundary tensions was presented by Ward and Tordai (307). Adsorption on nonaqueous substrate8 was represented by three studies. Various alcohols in p-dichlorobenzene were studied by Starobinets and Starobinets (278, 279) and aliphatic alcohols and acids in naphthalene by Pamfilov el al. (140). PREPARATION AND PROPERTIES OF V A R I O U S ADSORBENTS
-
Clays were prepared by Folliet and Sainderichin (115)by acid treatment with hydrochloric acid to remove calcium and iron, removal of sand and gravel by decanting the slurry, then activation with sulfuric acid, and drying with stirring for 24 to 72 hours. The resultant clay is of use for decolorizing vegetable oils. Escard (108) showed that montmorillonites can be activated t o 80 square meters per gram by careful transformation t o the hydrogen form, exact saturation with sodium or calcium and heating to 300” in vacuo. Various carbons were prepared by Smith (276) by heating oxygen-containing compounds in nitrogen. Areas ranged from 8 square meters per gram for melanoidin to 1650 for barium mellitate and 2125 for hexachlorobenzene. Treatment of nonactivated charcoals with oxidizing agents increased the adsorptive power for methylene blue, iodine, and acetic acid (233). Silica gels and other hydrogels have been prepared in bead type for many years. Recent patents were granted on production of such gels in organic solvents immiscible with water and washing out sodium ions (271) or distilling out water (246). A continuous process for microspheroidal silica alumina gel production using ammonia to precipitate the alumina was patented by Rex and Nelson (263). Preparation of aquasol from neutral aquagel was patented by Trail (293) and desorptive drying of silica gel was patented by Weeks (308).
UA
CHEMISORPTION
Schuit (272) reiterated that physical adsovtion gives information about surface area and pore structure, but that chemisorption studies are of value in catalyst surface structure work. He postulated that activated adsorption of hydrogen on nickel is due to surface oxygen atoms. Application of chemisorption studies to catalysis is discussed by Eucken (110) and Eyring and coworkers (112). The adsorption of nitrogen and hydrogen on iron catalysts was discussed by deBoer (36), de Bruijn (48),Sastri and Srikant (ass),and Trapnell(294). Eley (103)found that heats of chemisorption calculated according to Pauling’s equation for covalent bondi were in good agreement with experimental values for hydrogen on tungsten, copper, and nickel but that for oxygen on tungsten the film is not atomic. Ammonia was fpund to give heats of sorption on silica
27
gel of 13 to 15 kcal. per mole up to one third of a monolayer. The chemisorption was interpreted as resulting from complex formation between the ammonia and the hydroxyl groups remaining on the surface of the silica gel. Chemisorption of oxygen by manganese oxide catalysts was credited with being the dominant factor in carbon monoxide oxidation, by Saito (261). Chemisorption of water by carbon was discussed by Pierce et al. (245). Sorption studies of water by alum (34)and by cellulose (139) were also reported. Quite a few studies on particular chemisorption systems on metallic and other adsorbents were discussed in addition to the catalytic studies mentioned above. These included: oxygen on silver ( 5 1 ) ,platinum (172), copper ( 2 ) ,carbon (96), and tungsten (221); hydrogen on zinc-molybdenum oxides (264), platinum ( I l l ) , copper (173),iron (265),nickel (219, 273), palladium (284)’ and tungsten (221); ethylene and acetylene on nickel (219); carbon dioxide on nickel ( 7 6 ) ; and potassium on tungsten (182). GlembotskiI found in flotatidn experiments that the smaller the particles, the higher the chemisorptive activity (128). Lubrication studies of graphite (269) and friction studies of clean metals ( 4 9 ) showed that the presence of a chemisorbed gas film is a requirement. Even a t room temperature, sufficiently clean metal surfaces seize when allowed to touch. Joy and Dorling (167) have restudied the known fact that chemisorption of carbon monoxide does not affect the quantity of physically adsorbed nitrogen taken up. Ishiguro (159) found the heats of sorption of hydrogen and oxygen on molten metals (lead, tin, and bismuth) to be of the same order as those on solid metals. THERMOCHEMISTRY OF ADSORPTION
Two studies on heat of wetting showed that heat-of-wetting measurements are only general criteria of adsorptivity. Robert (256) found the heats of wetting for 15 organic compounds on silica or alumina gel to be in the same order as the relative absorbability, whereas Zwietering et al. showed that the heats of wetting gave results many times too high for the surface area of coal (315). Heat of wetting studies on alumina showed preferential sorption for water but none for hydrocarbons (280). Liquid phase adsorption studies (62) showed that the adsorption on charcoal decreased with heat of wetting of the solvent, as would be expected. Pierce found the heat of sorption of water vapor on charcoal to be zero for the first molecules and positive for later ones (246). Studies of heat of sorption of water by potato starch (267), montmorillonite (227),and polyvinyl chloride films (191) suggest that the state of the sorbed water changes according to the state of the surface; and there was some evidence of layer formation. A number of studies yielded data on adsorption heats for a variety of systems. These included polar gases on proteins (a,%’), radon (232), and benzene (86) on activated charcoal and silica gel, water vapor on oxide gels (222),oxygen on magnesium chromite (208), and ammonia, phosphine, and arsine on charcoal (18). Heats ,of adsorption and other thermodynamic functions of adsorbed molecules were discussed by Hill and Kemball (146) from the standpoint of surface tension measurements, and by Kemball and Schreiner (177) on the basis of the B.E.T. “singleisotherm’’ method. This latter can be used only if the entropy of adsorption is known, since values of the ratio of the kinetic con3tants in the B.E.T. c term may differ markedly from unity. Calorimeters of sufficiently high sensitivity for measurement of heats of adsorption were developed by Morrison and Los (230)and by Beeck, Cole, and Wheeler (21); the calorimeter mentioned in (21 ) was stated to be capable of measuring heats as a function of surface coverage of metal films.
28
INDUSTRIAL AND ENGINEERING CHEMISTRY
The heat capacities of helium and of argon adsorbed layers were m a s u r e d by Mastrangelo and Aston (210)and by Morrison, LOB,and Drain (229, 231). The former study was correlated with bulk liquid properties in therms of the observed shift in lambdapoint with coverage. The heat capacity for argon was found to approach that of bulk phase as the adsorption became multimolecular. These data were treated by Meyer and Long (217) thermodynamically for the first- and second-order transitions. Thermodynamic treatments for various cases were presented by Hill et al. (144, 145), Elton (105), Buff ( 4 9 ) , and Chessick and coworkers (64). INDIVIDUAL STUDIES OF EQUILIBRIUM DATA
The large number of references published during the past year precludea complete discussion of the individual studies of equilibrium data. For the convenience of persons interested in such studies, a cross-index reference list follows. Adsorbents of Major Interest. CHARCOAL. (5, 14, 18, 24, 25, 61-6S, 66, 81, 82, 86, 95, 104, 107, 132, 137, 142, 148, 149, 15S1 157, 160, 161, 168, 169, 181, 183, 184, 204, 209, 215, 263, 236, 245, 24Y, 252, xT6,302, 303, 311). CARBON (other than charcoal). (Sa, 56-58, 66, 68, 96, 109, 114, 168, 179, 181, 236, 245, 248, 269, 275, 288, 301, 315). SILICA GEL. (15,16,19,35,46, 47, 57,65, 66, 75, 119, 123, 132, 141, 148, 161, 162, 180, 186, 196, 209, 228, 234, 235, 240, $41, 247, 255, 256, W1, 272, 274, 276, 293, 297, 308). GELS OTHERTHANSILICA. (35, 140, 141, 180, 189, 196, 241, 246, 247, 25.3, 256, 271, 272, 297). CLAYS. (8, 14, 52, 53, 94, 108, lis, 115, 142, 175, 176, 200, 223, 227, 2S8). OXIDES OTHER T u GELS. (56, 57, 66, 68, 73, 121-124, 126, 161, 164, 184, 210, 212, 222, 229, 291, 261, 264, 276, 280, 285, 298). hfETALS. ( 2 , 6, 21, 36, 41-44,51,58, 64, 76, 80, 101, 109, 111, 117, 146,155,169, 164,16Y, 171-173, 182,184,196,215,219, 221, 254, 266, 266, 272, BYS, 284, 294, SOO). Adsorbates of Interest. NITROGEN.(9, 16, 38, 48,76, 104, 1S4, 146,165, ,209, 2S1, 239, 252). RAREGASES. (4, 9, 64, 68, 132, 161, 193, 196, 199,209, 210, 216, 21Y, 219,229, Z S 1 , 2 @ , 314). WATERVAPOR. (8, 14, 20, S4, 42, 55, 65, 66, 101, 119, 129, 131, 1S9, 169,170,176,181,191,2~3-206,222, 217,241, 246, 267, 269, 280, 292, SW,S05). HYDROCARBONS AND NONPOLAR ORGAXICCOMPOUXDS.(2, 8-10, 16, 24, S6,51, 64,66, 76,88, 96, 103, 109, 111, 122, 148, 150, 151, 159, 167, 172, 173, 196, 209, 219, 221, 239, 240, 250, 254, 255,261, M4-266,272, 273,280, 284,306,313). POLARORQANIC COMPOUNDS. (6, 6 , 8, 15, 22, 27, 29, 32, 41, 46, 47, 67, 68, 61, 62,65, 66, 70,80, 84, 91,QdJ120-123, 129, 137, 142, 1.49, 154, 156, 157, 180, 181, 186, 215, 225, 232, 235, 242, 262, 256, 256, 2Y8, ,979, 288, 296, 305). General Subdivisions of the Field. HEATSOF ADSORPTION AND THERMODYNAMIC CONSTANTS.(17, 18, 21, 22, 49, 55-58, 62, 64, 84, 99, 103,105, 1S1, 132, 135, 143-146, 159, 177, 191,208, 210, d i Y , 222, 224, 227, 229-281, 245, 264, 256, 267, 280, 289, 286, 291, 296, 312, 815). SURFACE AREA. (4, 13, 15, 29, 53, 56-58, 68, 82, 86, 93, 106, 108, 184, 151, 164, 168, 169, 180, 196, 204, 222, 234, 238, 254, 264, ,972, W4, xT5, 29Y, 315). PORE STUDIES. (12, IS,16,46,52, 53,56-68,66,82,86,95,106, i l 4 , 116, 131, 13.4, 140, 162, 166, 168-170, 176, 180, 181, 186, 187,196,198, 204, 221, 234,2&, 254,,972, 975,299, 315). BJBLIOGRAPHY
(1) Aerov, M. E., and Umnik, N. N., Zhur. Priklad. Khim., 23, 1009-17, 1071-8 (1950). (2) Allen, J. A., and Mitchell, J. W., Discussions Faraday SOC., 1950, No. 8, 309-14. (3) Aniansson, G., J . Phys. & Colloid Chem., 55, 1286-99 (1951).
Vol. 45, No. 1
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January 1953
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(291) Toshima, SbichirB, Busseiron Kenkyt?, No. 41, 89-95 (1951). (292)Tourneux, C., and Devin, C., Compt. rend., 232, 2430-2 (1951). (293) Trail, H. S., U.S. Patent 2,572,578(Oct. 23, 1951). (294) Trapnell, B. M. W., Trans. Faraday SOC.,48, 160-5 (1952). (295) Troesch, A., J . chim. phys., 48, 454-64 (1951). (296) Utsugi, Hiroshi, J. Chem. SOC.J a p a n , Pure Chem. Sect., 72, 812-15 (1951). (297) Van Nordstrand, R. A., Kreger, W. E., and Ries, H. E., Jr., J. P h y ~& . Colloid Chem., 55, 621-38 (1951). (298) Venturello, Giovanni, and Burdese, Aurelio, Ann. chim., 41, 155-62 (1951). (299) Vermeulen, Theodore, and Hiester, N. K., IND. ENG.CHEM., 44, 636-51 (1952). (300) Vernon, W.H.J., Nature, 167, 1037-8 (1951). (301) Vogt, Walther, Chem.-Ing.-Tech., 23, 580-1 (1951). (302) Voitko, L. M., and Kharin, A. N., Zhur. Prinklad. Khim., 22, 1237-48 (i949). (303) Ibid., 24, 509-19, 557-67 (1951). (304) Vold, M. J., J . Colloid Sci., 7, 1968 (1952). (305) Volman, D. H.,and Doyle, G. J., J . Phys. Chem., 56, 182-5 (1952). (306) Waksmundzki, Andrzej, WiudomoSci Chem., 3, 169-83 (1949). (307) Ward, A. F. H., and Tordai, L., Rec. trav. chim., 71, 396-408 (1952). (308) Weeks, R. L.,U. S. Patent 2,589,981(March 18, 1952). and Williams, T. I., Angew. Chem., 63,457-60 (1951). (309) Weil, H., (310)Westman, A. E.R., and Scott, A. E., Nature, 168,740 (1951). (311)Wittenberger, Walter, Chem.-Ztg., 76, 88-9 (1952). (312) ’&olstenholme, G. A., and Schulman, J. H., J . Oil & Colour Chemists’ Assoc., 34,571-80 (1951). (313) Yamane, Takeo, J . Sci. Research Inst., 45, 87-94 (1951). (314) Young, D. M., Trans. Faraday SOC.,47, 1228-33 (1951). (315)Zwietering, P., Oele, A. P., and Van Krevelen, D. W.. Fuel, 30, 203-4 (1951).
(267)Sato, Hideshi, J . Chem. SOC.J a p a n , Pure Chem. Sect., 72, 7903 (1951). (268) Saunders, L.,J . Pharm. Pharmacol., 3, 865-82 (1951). (269)Savage, R. H.,Ann. N . Y . Acud. Sci., 53, 862-9 (1951). (270) Schafer, Karl, Kolloid-Z., 124, 15-22 (1951). (271)Schexnailder, R.E.,Jr., U. 8. Patent 2,582,722(Jan. 12,1952). (272)Schuit, G.C.A.,Chem. Weekblad, 47, 453-65 (1951). (273)Schuit, G. C.A., and deBoer, H. N., Rec. trav. chim., 70, 106784 (1951). (274) Seybert, E. K., Petrolem Processing, 7, 1150-3 (1952). (275)Smith, T. D., J . Chem. SOC.,1952,923-7. (276) Spengler, G.,and Krenkler, K., Petroleum Refiner, 31, 111-14 (July 1952). (277) Standard Oil Development Co. Brit. Patent 661,741(Nov. 28, 1951). (278) Starobinets, G. L.,and Starobinets, K. S., Zhur. Fiz. Khim., 25, 753-8 (1951). (279)Ibid., pp. 759-67. (280) Stowe, V. M.,J . Phys. Chem., 56, 484-6,487-9 (1952). (281) Strazhesko, D. M., and Glazman, Yu, M., Dopovidi Akad. N a u k Ukr. R.S.R., 1950, 283-5. (282) Swietodawski, W., Przemyd Chem., 29, 6, 41-3 (1950). (283)Tanaka, Tomoyasu, Busseiron Kenky;, No. 14, 1-17; No.15, 29-37; NO.20,55-64 (1949); NO.40, 90-9 (1951). (284)Tarama, Kimio, Miyakawa, Toshio, and Morishima, Naomasa, Repts. Inst. Chem. Research, Kyoto Univ., 17, 108-11 (1949). (285)Tewari, S. N.,and Ghosh, Satyoshewar, Kolloid-Z., 124, 31-6 (1951). (286)Theimer, O.,Monutsh. 81, 1120-8 (1950). (287)Theimer, O.,Z. Elektrochem., 55,709-15 (1951). (288) Thomas, G. G.,Nature, 168, 474 (1951). (289) Thomas, H.C.,J . Chem. Phys., 19, 1213 (1951). (290) Todes, 0. M., and Bikson, Ya. M., Doklady Akad. N a u k S.S.S.R., 75,727-30 (1950).
CENTRIFUGATION J. 0.MALONEY UNIVERSITY OF KANSAS, LAWRENCE, KAN.
The principal contributions to the field of centrifugation this year have been made b y companies or individuals involved in the sugar industry. Storrow i s continuing his fundamental studies on hydroextraction. Smith has presented extensive information on the cost of centrifuges. The fife and safety factors of centrifugal baskets are receiving more consideration.
A
N INCREASING number of books describing the appli-
*
cation of the centrifuge to industrial chemical processing is appearing, The most extensive general treatment of the subject this year is found in 7Jllmann’s Encyklopadie der technischen Chemie” (48). It contains descriptions of a variety of centrifugal machines together with their fields of application. The theory receives only a cursory treatment compared with that found in Perry (83)but, on the other hand, the descriptions and illustrations are better. Several books on sugar technology include sections on the use of centrifugals. Tromp (58),in a n early book, previously overlooked by the reviewer, presents a treatment of the principles of centrifugation, the types and details of sugar centrifugal, and typical centrifugal data. Lyle (SY), in his recent book, gives a rather diffuse treatment of the subject. McGinnis (38) has presented a n excellent exposition of the qualitative factors which influence the performance of centrifugal machines in the beet sugar industry. He considers such significant items as rotational speed, acceleration time, time at which wash water is applied, increments of wash water, amount of wash water, wash water temperature, wash water distribution, amount of load, the correct cycle length, and centrifugal covers. Users of centrifugals in other industries might profit from the great backlog of knowledge the sugar refiners possess.
Kerr (35) describes briefly the use of centrifuges in the starch industry. A bibliography is included in his book which will be of interest t o those who follow the hi’storical development of the application of the centrifuge. Radley (4.4) also treats the application of centrifuges t o the manufacture of starch. His references extend back to 1883 but he has apparently overlooked the application of the Merco centrifuge t o this industry in t h e United States (7). A comprehensive treatment of t h e application of the Sharples and DeLaval units in the manufacture of varnish is found in Chatfield’s book (16). Martin (39) gives a brief description of the early patents in the centrifugal field which have been applied t o the soap and detergent industry. Southern (55)’ in “Marine Diesel Oil Engines,” describes DeLava1 and Sharples oil purifiers and enumerates their advantages as purifying devices for lubricating and fuel oils. Smith (54) continues to render a valuable service t o the users of centrifugal equipment. His most recent contribution gives purchase prices, installation costs, maintenance costs, operating labor, and performance and capacity figures for a large variety of centrifugal machines. This information is t h e most recently developed and probably the best for present day purposes. The number of review articles and nomograms for t h e calculation of centrifugal force has decreased. Some extensive descriptions of new installations in the sugar plants are available. Broadbent (IO)has furnished a thorough description of two recent installations in sugar factories. The descriptions of the drive,
