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By Claude H. P. Lupis, John F. Elliott

QUITE generally an increase in the temperature tends to bring a system closer to ideality. It is reasonable as a first approximation to consider that the excess free energy will vary linearly with the temperature, or: where t may be defined as the "characteristic temperature" of the solution, or the temperature at which the system would become ideal if the results at T were linearly extrapolated. It must be emphasized that consideration of this hypothetical property is an appeal to intuition rather than an established physical concept. The order of magnitude of 7 for dilute solutions will depend on the nature of the solvent; a value of 3000° + 1000°K may be suggested for ordinary metallic solutions. In terms of free energy, entropy, and enthalpy first-order interaction coefficients, differentiation of the above equations with respect to composition leads to The concept of t offers a simple and plausible interpretation of Chipman and corrigan's3 recent empirical correlation between and a for a number of groups of ternary systems 1-24. The authors found that in each group the ratio was approximately constant. The corresponding calculated from their data by Eq. [4] are listed in Table I. The expected order of magnitude is obtained for 7. As noted by Darken,4 if a regular solution is not assumed, thus if utj) # 0, Chipman and Crrigan's results imply that, as T is increased, ultimately changes in sign, Fig. 1. Clearly Eq. [4] is valid only in a limited range of temperatures since at the temperature 7 at which the system becomes ideal not only should become null but also and . Thus, both and are functions of

Jan 1, 1967

Feb. 5. Society for Applied Spectroscopy, 6 pm, supper, Tosca's; 8 pm, meeting, Socony-Vacuum Training Center, 63 Park Row, New York. Feb. 6, AIME, Chicago Section, Chicago Bar Assn., 29 S. La Salle St., Chicago. Feb. 18-21, AIME, annual meeting, Hotel Statler, New York. Feb. 19, Michigan College of Mining and Technology, alumni reunion, Skytop Room, Hotel Statler, New York. Feb. 21, AIME, Utah Section, Newhouse Hotel, Salt Lake City. Feb. 28, Bituminous Coal Research, Inc., annual meeting, Edgewater Beach Hotel, Chicago. Mar. 3-7, ASTM, spring meeting and committee week, Hotel Statler, Cleveland. Mar. 5, AIME, Chicago Section, Ladies' Night, Chicago.

Jan 1, 1952

PRESIDENT BENJAMIN B. THAYER,1 NEW YORK, N. Y. PAST PRESIDENTS JAMES F. KEMP,1 NEW YORK, N. Y. CHARLES F. RAND,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS,1 NEW YORK, N. Y. TREASURER GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y.

Jan 4, 1914

By J. H. Brophy, S. J. Michalik

A constitution diagram for the system Mo-Ir has been determined. The maximum solubility of iridium in molybdenum is 16 at. pct at 2110ºC and decreases to less than 5 at. pct at 1500°C. The solubility of molybdenum in iridium is 22 at. pct. Three intermediate phases appear in the system: 8 MoJr, having the p-tungsten structure; a phase, a cornplex tetragonal structure; and the hcp ? phase. Metallography, melting point determinations, X-ray diffraction and fluorescence, and electron micro-probe unalyses were employed in establishing the diagram. PREVIOUS to the present investigation, the intermediate phases in the Mo-Ir system were identified, but no detailed account of the phase diagram has been reported in the literature. Raub1 investigated alloys of Mo-Ir over an extensive range of composition between the temperatures of 800º and 1600°C. The in-termetallic compound MosIr was found to exist with nearly pure molybdenum, as the solubility of iridium in molybdenum was not detectable parametrically in this temperature range. MO3Ir was found to be iso-morphic with a ß-tungsten type structure, having a parameter of 4.959Å. An intermediate hcp phase, designated as the ? phase, ranged in composition from 52 to 78.5 at. pct at 800ºC, and from 41 to 78.5 at. pct Ir at 1200°C. Parameters noted for the ? phase were as follows: at 42.7 at. pct Ir, a = 2.771i0, c = 4.4366, c/a = 1.601; at 78.5 at. pct Ir, a = 2.736A, c = 4.378A, c/a = 1.600. Molybdenum was found to be soluble in iridium up to 16.5 at. pct Mo (83.5 at. pct Irj, with the parameter of iridium increasing to 3.845A at the solubility limit. Knapton,2 who investigated alloys between 15 and 85 at. pct Ir, essentially agreed with Raub's data, but, in addition, found a a phase in as-melted alloys near 25 at. pcto Ir. The oaphase lattice parameters were a = 9.64Å, c = 4.96Å, c/a = 0.515. The a phase was replaced by the 8 -tungsten phase on annealing at 1600°C. Knapton concluded that the a was stable only at elevated temperatures, and placed the composition of the a phase at approximately 30 at. pct Ir. The intermetallic compound Mo3Ir, with a lattice parameter of 4.965A, was included among the 8-tungsten structures reported by ~eller.' Matthias and Corenzwit,4 and Bucke15 studied the superconducting nature of MosIr, and reported a superconducting transition temperature of 8.$K. The present investigation describes the phase relationships in the Mo-Ir alloy system determined by melting point measurements, X-ray diffraction and fluorescence, and metallography. EXPERIMENTAL PROCEDURES Alloys for the determination of the phase diagram were prepared from powders. Commercial 99.9 pct Mo from Fansteel Metallurgical Corp. and 99.9 pct Ir powder from J. Bishop and Co. Platinum Works were used. The powders were weighed to nominal compositions, mixed, and then pressed, without binder, into compacts weighing 4 to 6 g. These were presintered in uacuo between 1200' and 1400°C for 1 hr, to reduce the degree of spattering during subsequent arc-melting. The compacts were arc-melted in a nonconsumable tungsten electrode furnace six times on alternate sides on a water-cooled copper hearth in an atmosphere of zirconium-getter ed argon at 500 mm of mercury pressure. In almost all cases, this procedure yielded buttons of satisfactory homogeneity. The composition of all melted buttons were confirmed by X-ray fluorescent analysis using the experimentally determined ratio of the iridium La1 line intensity to that of the molybdenum Ka1 line as a function of composition. In this determination four alloys analyzed by wet chemical methods were used as standards. An uncertainty range of ±1 at. pct has been attributed to all indicated compositions. All heat treatments and solidus measurements were carried out in tantalum resistance heating elements in vacuum conditions of 10-4 to 10-5 mm of mercury. A detailed account of this procedure has been reported by Schwarzkopf and Brophy.8 In the heat treatment and solidus measurements of iridium-rich alloys (50 at. pct Ir or greater), a tungsten lining was inserted into the tantalum resistance heating element because of a eutectic reaction which occurs between iridium and tantalum at 1948ºc.7 Heat treatments and solidus measurements carried out at compositions less than 40 at. pct Ir both with and without tungsten linings within the resistance

Jan 1, 1963

By A. F. Lucas

The discovery of oil in 1901 on the Spindletop dome, Texas, inaugurated a new industry on the Gulf Coast, an industry which has gran with the discovery of successive fields, until today it engages the services of thousands of workers and employs enormous capital. New fields are being discovered from time to time and doubtless some still remain to be found, though of late years discoveries have become more infrequent. Nowadays several hundred dry holes are drilled each year in a fruitless and blind effort to discover new fields, for as yet geologic science has developed no effectual method of locating the coastal oil deposits in advance of drilling. Moreover despite the occasional discovery of new fields, the total production of the Gulf Coast is today no greater than it was in 1906, for the added production of the new fields has been offset by the rapid decline and more or less complete exhaustion of some of the older ones. Careful geologic work within the fields has in some cases increased the production temporarily, but has developed no really new supplies. The Gulf Coast oil industry seems to have passed its period of greatest expansion and to be declining at a fairly steady rate, and this condition is naturally viewed with alarm by the more farsighted operators. In my opinion, the time has come for the adoption of radical and aggressive methods of prospecting; and a fraction of the money wasted yearly in drilling shallow wells in hopeless locations might well be devoted to this purpose. Many facts lead me to believe that all the salt-dome oil has had a common origin; that it has migrated up from considerable depth along lines of structural weakness; and that a deep well, properly located, stands an excellent chance of discovering the parent reservoir and thus of developing new and probably great supplies. This paper is presented as a discussion—necessarily hypothetical and based largely on personal opinion—of the possibility of encountering deep-seated oil deposits beneath the salt domes. Salt-dome Structure All of the oil produced in the coastal region of Texas and Louisiana is probably associated with salt domes, though in Goose Creek, Edgerly, and one or two other fields no salt has yet been actually penetrated. As

Jan 1, 1920

By A. J. Hatch

Recent disclosures concerning strengthening of anisotropic sheet materials under biaxial stresses are reviewed. This biaxial strengthening has been termed "texture hardening" by Backofen and is related to the normal anisotropy parameter, R. Measurements of R made on three annealed titanium alloys indicate a Ti-4Al alloy will have the greatest potential for texture hardening, followed in order by Ti-5Al-2.5Sn and Ti-6Al-4V. Relative to sheet texture, a review of the deformation mechanisms in titanium alloys would indicate that a preferred orientation for "texture hardening" is where the (0001) pole is normal to the sheet plane. This was confirmed by determination oj (0001) pole figures for the above three alloys. High R values are related to pole figures with (0001) normal to the sheet plane, whereas low R values are related to pole figures with (0001) split in the transverse direction from the sheet normal. PUBLISHED work by Backofen et al. 1 and Hosford and Backofen2 based on hill's' mathematical theory of yielding in anisotropic metals has indicated that significant strength advantages under biaxial stresses are possible in hcp alloys, provided an ideal (0001) [1010] sheet texture exists. This tendency to strengthen under biaxial stresses has been termed "texture hardening".1 It can be quantita- tively characterized by a strain-ratio parameter, R, where R may be determined from the ratio of natural width strain to natural thickness strain as measured on a uniaxial test specimen cut parallel to the rolling direction. If R is greater than 1.0, then strengthening under biaxial tension would be predicted. Considering the a titanium alloys which have an hcp crystal structure, Williams and Eppelsheimer4 have reported that commercial-purity grades deviate from the ideal (0001) sheet texture mainly in an approximate 30-deg rotation of the basal plane, toward the transverse sheet direction. However, McHargue et a1.5 have shown that the angle of rotation of the basal plane is sensitive to alloy content. In particular, a titanium alloy with 3.8 pct Al was reported to have the ideal (0001) [1010] texture after cold rolling. Additionally, Backofen et a1.1 using plane-strain compression tests have reported R values greater than 5.0 for the commercial 0 alloy Ti-5A1-2.Sn (110-AT). In view of these findings, a program was initiated to further determine the potential of commercial Ti-5A1-2.5Sn and an experimental Ti-4A1 alloy with respect to "texture hardening". Also, because of its wide commercial use, Ti-6A1-4V was included in the investigation. BIAXIAL-STRESS THEORY FOR ANISOTROPIC MATERIALS Backofen ef al.,1 based on the mathematical theory of Hi11,3 has introduced the concept of "texture hardening". In this work, it was shown that possi-

Jan 1, 1965

By Michael Chender

The current outlook for financing new copper production is not very encouraging. At a time when companies are slogging through a protracted period of low prices as well as having to accept lower profits due to more stringent tax and royalty schedules, banks are beginning to require companies to take a greater equity interest in new projects. Mineral resource financing, including copper, seems to have lost much of its appeal to the lending institutions, and loans of any kind to many of the developing countries -from which over half of new copper capacity could be expected to come-are being examined much more critically than they were in the late 1960's and early 1970's.

Jan 12, 1976

SUCCESSFUL development of a new process for heat hardening of pellets made from taconite concentrates was announced by Arthur G. McKee & CO., steel plant engineering and construction firm of Cleveland, and Allis-Chalmers Mfg. Co. An order for the design, engineering, and materials for a plant incorporating the process, has been received by the McKee Co. from the Reserve Mining Co. for its new E. W. Davis Works at Silver Bay, Minn. It is estimated that this plant will cost around $19 million and when in full operation, will turn out 12,000 tons of pellets per day.

Jan 10, 1954

PRESIDENT WILLIAM L. SAUNDERS,1 NEW YORK, N. Y. PAST PRESIDENTS CHARLES F. RAID;1 NEW YORK N. Y. BENJAMIN B. THAYER,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT PHILIP N. MOORE,1 ST. Louis, Mo. TREASURER GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON, NEW YORK, N. Y.

Jan 3, 1915

By R. Stefanko, Y. J. Wang, H. R. Hardy, R. Y. Kim

Since 1964, the Dept. of Mining at The Pennsylvania State University has been carrying out extensive studies associated with the phenomena of microseismic activity and inelastic behavior in geologic materials. Briefly, the program to date has involved the following stages 1) Study of the microseismic noise and energy rates for selected geologic materials under incremental, uniaxial tension.1,2 2) Investigation of the frequency spectra of microseismic activity of selected geologic materials under incremental, uniaxial tension.3,4 3) Investigation of the time-dependent inelastic deformation of geologic materials and the analysis of such deformation in terms of mechanical models.5, 6 4) Simultaneous study of microseismic activity and time-dependent inelastic deformation in geologic materials under incremental, uniaxial compression.7,8 Details of the research involved in stage 4 of the program constitute the subject of this chapter. It should be noted that the majority of the experimental data quoted in this chapter forms part of a thesis to be presented by one of the authors (Kim) in partial fulfillment of the requirements for the Ph.D. degree in mining engineering at The Pennsylvania State University. During the last two or three years, a number of important papers have been published which deal primarily with the fundamental structure and mechanical behavior of geologic materials. Recent papers 9,10 have provided research workers in the rock mechanics field with a meaningful overall picture of rock as a structural material. The concept that many

Jan 1, 1970

Page Fundamental Principles Involved in Segregation in Alloy Castings. By R. M. Brick. (With discussion)............................* Review of Factors Underlying Segregation in Steel Ingots. By B. M. LarseX.. (With discussion)............................. 4x4 Introduction to the Session on Segregation in Steel. By Earle C. Smith......436 Relation of Open-hearth Practice to Segregation in Rimmed Steel. By J. W. HaLley and G. L. Plimpton, Jr. (With discussion)................438 Segregation in a Large Alloy-steel Ingot. By S. W. Poole and J. .4. Rosa. (With discussion) .............................459

Jan 1, 1945

By Mason K. Banks

A process has been developed which produces spodumene concentrates assaying 6.0 pct Li2O and 0.45 pct Fe2O3, with 70 to 75 pct recovery of spodumene. Two flotation separations are required: the simultaneous removal of mica, feldspar, and quartz as a froth product using a cationic collector, and the subsequent removal of iron-bearing minerals as a froth product while spodumene is depressed as a tailing. SINCE the close of World War II there have been numerous developments resulting in the increased use of lithium by industry. Notable among these has been the development of an industrial lubricant, based on lithium stearate, which is fluid at low temperatures, stable at high temperature, and insoluble in water. A new bleaching agent, lithium hypo-chlorite, has also been developed recently.' Other well-known uses are listed below: 1—Lithium oxide in ceramics reduces firing time, lowers melting temperatures, lowers thermal expansion, raises refractive index, and improves chemical resistivity. 2—Lithium carbonate and lithium strontium nitrate are used in pyrotechnics for their brilliant red color.' 3—Lithium chlorides and fluorides are used as fluxes for welding aluminum and magnesium.' 4—The affinity of lithium for nitrogen is the basis for a process used in purifying helium." 5— Lithium chlorides and bromides are used in air conditioning for their powers to absorb organic amines, ammonia, and smoke.6-—Lithium hydride has been used as a source of hydrogen to inflate life rafts and balloons used by the Air Forces and Navy.' 7— Lithium metal and lithium hydride are useful in the atomic energy program in connection with the production of the isotopes of hydrogen." During the 1942-45 period of World War 11, Solvay Process Co. operated a flotation plant with a daily capacity of 300 tons of ore for the production of spodumene concentrate near Kings Mountain, North Carolina. The operation was shut down upon reduction of wartime demand for lithium chemicals, and until recently there has been no production from the Carolinas. In April 1950 an investigation of the problem of spodumene flotation from North Carolina ores was begun at North Carolina State College Minerals Research Laboratory at Asheville, N. C. This laboratory, operating under the combined auspices of North Carolina State College, North Carolina Department of Conservation and Development, and the Tennessee Valley Authority, undertook the spodumene project at the request of Foote Mineral Co. of Philadelphia. The work, involving a period of 15 months of intensive batch and pilot plant investigation, was completed in June 1951 and resulted in development of a process for concentration of spodumene by flotation which has been hereto unrecorded in the literature. A similar approach has been used before on iron, ilmenite, and other minerals, but the literature shows no record of its having been applied to spodumene. Parts of the process are now being used on a commercial scale at the Foote Mineral Co. plant near Kings Mountain, N. C., which has been in production since July 1951. It is the purpose of this paper to describe some of the results of the investigation. The Orebodies Spodumene-bearing pegmatites occur in a narrow belt 24.5 miles long and 1.8 miles wide extending southwestward from Lincolnton to Grover, N. C. According to statements judged to be conservative, the tin-spodumene belt of the Carolinas contains an estimated 4,300,000 tons of pegmatite ore averaging 15 pct spodumene. This amounts to "a reserve of at least 650,000 tons of spodumene (more than 20,000 tons of metallic lithium) to a depth of 100 ft."' This figure includes only bodies having an average thickness of 35 ft and length of 550 ft. There are hundreds of pegmatites in the belt, many of which are less than 10 ft wide. The largest pegmatite in the area has a maximum thickness of 395 ft and maximum length of 3250 ft.' These larger pegmatites are composed principally

Jan 1, 1954

By John D. Clark

ONE'S lifetime does not usually offer the opportunity to observe and be a part of the commercial development of an entirely new material. Petalite has been known for over a century, but at first it was presumed rare. However, it was found to be so abundant that it has become a new and extremely useful industrial tool.

Jan 10, 1950

JAMES GAYLEY (President), R W RAYMOND (Secretary), FRANK LYMAN Treasurer) T A RICKARD NEW YORK, N Y CHARLES H SNOW NEW YORK, N Y R W RAYMOND NEW YORK, N Y (Terms expire February, 1906 ) JAMES GAYLEY NEW YORK, N Y FRANK KLEPETKO NEW YORK, N Y FRANK LYMAN NEW YORK, N Y (Terms expire February, 1907 ) JAMES DOUGLAS NEW YORK, N Y JAMES F KEMP NEW YORK, N Y ALBERT R LEDOUX NEW YORK, N Y (Terms expire February, 1908 ) Council PRESIDENT OF THE COUNCIL JAMES GAYLEY VICE-PRESIDENTS OF THE COUNCIL GEORGE W MAYNARD NEW YORK, N Y JULIAN KENNEDY PITTSBURG, PA CHARLES D WALCOTT WASHINGTON, D C (Terms expire February, 1906 ) WILLIAM P BLAKE TUCSON, ARIZ THOMAS F COLE ,DULUIH, MIFF IRVING A STEARNS WILKES-BARRE, PA (terms expire February, 1907 )

Jan 1, 1910

By Theron Wasson

The Central Michigan area held first place in the state during the year. Midland and Isabella, the leading counties in 1932, produced most of the oil in 1933. The Porter field southeast of Mt. Pleasant and along the same structural trend saw the greatest drilling activity. In Porter during the year 117 new wells were drilled. Under proration these wells produced 3,583,617 bbl., or nearly one-half the total for the state, which has been estimated at 7,947,695 bbl. The Porter field is already outlined on all sides except the northwest. It probably reached its peak in 1933. Unless a new field of some magnitude is developed in 1934, Michigan will see a continuous decline. The Greendale extension to the old Mt. Pleasant field furnished the new flush for 1932. In 1933

Jan 1, 1934

By Gail F. Moulton

In spite of an increase of 7 cents per barrel in the posted price of oil for the Panhandle field effective June 16, 1943, there was less drilling during 1943 than ir, any of the several previous years. The drilling statistics are compiled as Table 2 and show the material increase in the percentage of the total number of field wells completed as dry holes. This increase suggests that the productive area of the field is largely drilled up on the well-spacing pattern now followed and that new discoveries will be required to permit any important new activity in the area. The fact that only four wildcats were drilled in the area during the year indicates that some new prospecting technique or some ncw point of view is required to stimulate exploration. No new producing areas were discovered during 1943 and no additions to oil reserves were made through extensions or discovery 'of new pays. Accordingly, the proven reserves in the area declined by the amount of the production, or nearly 31 million barrels. These results of drilling are similar to those obtained during 1942, whcn no new oil areas were discovered as a result of wild-catting, a total of five wildcat wells in 1942 resulting in four failures and one gas-fieid discovery of undetermined merit. sion. The number of oil-producing wells reported by the Commission increased during the year by 163 to a total of 5576 as of December.

Jan 1, 1944

By Gail F. Moulton

In spite of an increase of 7 cents per barrel in the posted price of oil for the Panhandle field effective June 16, 1943, there was less drilling during 1943 than ir, any of the several previous years. The drilling statistics are compiled as Table 2 and show the material increase in the percentage of the total number of field wells completed as dry holes. This increase suggests that the productive area of the field is largely drilled up on the well-spacing pattern now followed and that new discoveries will be required to permit any important new activity in the area. The fact that only four wildcats were drilled in the area during the year indicates that some new prospecting technique or some ncw point of view is required to stimulate exploration. No new producing areas were discovered during 1943 and no additions to oil reserves were made through extensions or discovery 'of new pays. Accordingly, the proven reserves in the area declined by the amount of the production, or nearly 31 million barrels. These results of drilling are similar to those obtained during 1942, whcn no new oil areas were discovered as a result of wild-catting, a total of five wildcat wells in 1942 resulting in four failures and one gas-fieid discovery of undetermined merit. sion. The number of oil-producing wells reported by the Commission increased during the year by 163 to a total of 5576 as of December.

Jan 1, 1944

Section 67 Department of Conservation and Development, State of New Jersey, State House Annex, Trenton, N. J. H B Kummel, State Geologist For lists of publications, maps and geologic folios, address the above. Where price of postage is noted, in the following list of available publications on geology, the postage is only to New Jersey and

Jan 1, 1933

By H. A. Deans

A three-parameter mathematical model for one-dimensional flow in porous media is developed. The objective of the model is to predict accurately the longitudinal dispersion associated with the flow of either gases or liquids over a wide range of Reynolds number. A qualitative analysis of the model parameters is given. Published experimental pulse-response curves are compared with results predicted by the model. Several general types of problems are given for which the model can be used. INTRODUCTION The problem of multicomponent single-phase flow through porous media is encountered in the study of petroleum reservoirs, gas chromatographic and ion-exchange columns, industrial fixed-bed con-tacters and elsewhere. These particular examples span the wide range of flow conditions possible; Reynolds numbers of less than l0-4 are not unusual in oil-production problems, while values in excess of 103 are common in large fixed-bed operations. The study of flow-dependent transport phenomena is complicated both by the changes in the character of the flow over this range, and by the irregularity of the flow boundaries inherent to porous media. Dispersion is one of the important phenomena known to depend fundamentally on flow conditions as well as on fluid and medium properties. As used in this paper, the term "dispersion" refers to the observed mixing of fluid elements of different composition which occurs in flow systems. The actual mechanism may be one or more of a number listed below. Only dispersion in the direction of the mean flow (referred to as axial or longitudinal dispersion, or mixing) is considered here, although lateral dispersion arises as part of certain coupled mechanisms. MECHANISMS FOR LONGITUDINAL DISPERSION A number of distinct mechanisms are known3,5,7,8 to contribute to the phenomenon of longitudinal dispersion. The more important of these are as follows. 1. Molecular diffusion in the flow direction. 2. Turbulent (cell) mixing. 3. Lateral transport processes coupled with velocity and/or residence time distributions, including: (a) "Taylor" diffusion caused by the interaction of velocity profiles in individual voids with lateral molecular diffusion; (b) separation and remixing or interdiffusion of streams having different velocities around particles; and (c) the couplipg of gross velocity profiles, caused by viscous instability or inhomogeneous porosity, with lateral dispersion. 4. Finite mass-transfer rate between a porous matrix and the flowing phase, and finite diffusion rate inside elements of the porous matrix. It is a well documented fact that these mechanisms, whether acting individually or in combinations, produce essentially similar integral effects. The observed dispersion can be described approximately by solutions of the diffusion equation with a properly chosen dispersion coefficient. Necessary conditions for equivalence between dispersion and diffusion are discussed by Klinkenberg and Sjenitzer.7 Apparently these conditions are not satisfied exactly in many real systems. "Best fit" solutions of the diffusion equation often depart appreciably from measured breakthrough curves for the usual pulse- or step-forced experimental systems. In particular, pulse response curves usually show some degree of asymmetry and "tailing" which cannot be reproduced by the one-parameter diffusion model. The three-parameter model proposed herein attempts to produce these effects in a realistic manner. Asymmetry and tailing are predicted for certain sets of parameter values, while for other sets the new model agrees with the diffusion model. VELOCITY DEPENDENCE OF DISPERSION Molecular diffusion apparently controls at sufficiently low Reynolds number in both gas and liquid systems.*l3 At Re > 20, turbulent cell mixing is dominant for gases flowing at low pressure; the data of McHenry and Wilhelm8 show that the mixing cell is approximately 1 particle diameter long in random sphere packs. on the other hand, the data

By M. E. Wadsworth, J. S. Cho

The kinetics of silicate adsorption from aqueous colloidal (SO2 . nH2O) silicate sols on thoria (ThO 2) surfaces were determined at 100, 150 and 200°C in an autoclave system. The amount of chemisorbed silica on the thoria surface was determined by means of infrared spectroscopy. First order kinetics were observed in all cases with the anomalous result that the first order rate constant was found to vary with the initial amount of silica added to the system. These results have been correlated quantitatively by means of a strain model of adsorption involving two types of surface silicate bonding, both of which may be readily observed in the infrared spectrum. Initial adsorption occurs rapidly to produce one type of surface silicate followed by a slow transition to a second type of surface bonding, the latter transition representing the slow step in the adsorption process. Initial interest in silicate adsorption on thoria arose from the dispersive effect silica has on finely divided thoria in aqueous suspensions. Spaepen et al studied the equilibrium adsorption of silica on thoria and noted increased adsorption up to approximately 215°C with a notable decrease in adsorption at temperatures above 215°C. Similar results were observed by Cho and Wadsworth2 who identified two types of surface silica by infrared spectroscopy. At temperatures of 100°C and above, rapid initial adsorption occurred producing a surface species with maximum infrared absorbance at 9.4 After extended periods of time, the 9.4 species converted to a more strongly bonded surface silicate with maximum infrared absorbance at 10.3. The latter was very strongly bonded and difficult to remove by desorption in hot distilled water, while the 9.4 species could be removed more readily by similar treatment. The 9.4 and 10.3-p species were distinguishable from free unadsorbed silica which had maximum infrared absorbance at 9.1 The kinetics of the formation of the strongly chemisorbed silica (10.3) on thoria as determined by infrared examination are presented in this study. EXPERIMENTAL PROCEDURE As a source of silicate, Ludox SM (16.36% SiO2) or Ludox HS (30.25% SO2), DU Pont colloidal silica in aqueous suspensions, was added directly to a thoria slurry made up of one liter of distilled water and one gram of thoria. The thoria used was designated D-16-650 and was received from the Chemical Technology Div. of Union Carbide Nuclear Co. It was prepared by firing thorium oxalate at 650°C. The D-16 thoria had a surface area of 32.4 ± 0.6 sq m per g as determined by nitrogen adsorption.* This thoria 'Determined by Unlon Carbide Nuclear Co., ORNL. had a total adsorption capacity for silicate of approximately 19.4 mg of silica per gram of thoria.1 This amounts to approximately one SiO2 molecule for every surface thoria site. In all cases in this study.

Jan 1, 1963