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ELECTROREFINING Canadian 1,023,691 -Removal of bismuth from slime filtrate in the Betts process refining of lead. The filtrate is subjected to electrolysis in a cell having an anode of crude lead and a cathode of refined lead under operating conditions to preferentially deposit bismuth on the cathode. The substantially bismuth-free filtrate is recycled for use in the process as the electrolyte for producing high-purity lead. S. Hirakawa and R. Oniwa, assigned to Mitsui Mining & Smelting Co., Ltd. Jan. 3, 1978. 8 pp. (204-73). Filed: 2-18-74 (192,810). Same: U.S. 4,026,776, dated May 31, 1977.

Jan 1, 1979

By Charles Y. Clayton

A study of the literature shows that the greater part of research work on annealing of cold-worked iron has been for the purpose of studying the effect on grain-size and properties other than hardness. No reference has been found of experimental work of the same nature as that explained in this short paper. The material used throughout was Vismera iron, an iron containing 0.03 carbon and made several years ago by the Inland Steel Co. One-half inch stock was cut into cylinders % in. long. The cylinders were then compressed for 60 sec. in a Reihle testing machine under loads as indicated below: CoMPressiON, Average Length, Series Pounds Inches 1 10,000 0.693 2 15,000 .599 3 20,000 .501 4 25,000 .426 5 30,000 .378 6 35,000 .351 7 40,000 .311 Fig. 1 shows these cylinders after compression. Each series consisted of 17 specimens lettered 0, B, C, D, E, F, G, H, I, J, K, L, M, N, P, Q and R. One specimen of each series was reserved for study of the properties in the cold-worked condition. The other specimens were annealed in a Hump furnace for 1/2 hr. at the following temperatures: TEmpeRa- TempeRa- Letters tuRe,° C. LettERs tuRe °C. B............................... 250 J.............................. 650 C............................... 300 K............................. 700 D............................... 350 L.............................. 750 E............................... 400 M............................. 800 F................................ 450 N............................. 851 G............................... 500 0. . :........................... 900 H............................... 550 P.............................. 950 I................................ 600 Q............................. L000

Jan 1, 1926

By Harold Price

PRIOR to Sept. 1, 1928, there had never been constructed what might be termed a long pipe line with electric-welded field joints. Nevertheless, by Sept. 1, 1929, within the period of a year, more than 2500 miles of electric-welded lines have been completed. These lines vary in diameter from 6 to 20 in., and in length from 50 to 700 miles. Before Sept. 1, 1928, no such line had been constructed .longer than 50 miles, and only one of nearly that length, a 40-mile 7-in. gas line in Louisiana. This was in reality the first pipe line to use electric-welded field joints. During the past year the following lines have been electric-welded by the Welding Engineering Co. alone: Texas Pipe Line Co.-157 miles of 8-in. line from Corsicana, Texas, to San Augustine, Texas. (This was the first electric-welded oil line.) Texas Pipe Line Co.-80 miles of 8-in. from Lafors, Texas, to Childress, Texas. Texas Pipe Line Co.-39 miles of 10-in. from Monahans, Texas, to Jal, New Mexico. Texas Pipe Line Co.-50 miles of 6-in, from San Antonio, Texas, to San Marcus, Texas. Texas-Empire Pipe Line Co.-424 miles of 12-in. from Cushing, Okla. to Chicago, Illinois. In addition to the field welding mentioned above,1 250 miles of 12-in. line was electric-welded into double joints at the pipe mill at Indiana Harbor, Ind.

Jan 1, 1929

By H. E. Lee, P. C. Feddersen, D. R. Gittinger, G. W. Dunn, J. B. Schuettenhelm

The new Bunker Hill slag-treatment plant, designed ior, a capacity of 300 to 400 tons of hot slag per day, was "blown in" April 5, 1943. In the ensuing I5-months period, 157,530 tons of slag was processed, with an average recovery of over go per cent of the zinc and practically all of the lead contained. In addition to this high metal recovery, utilization of the waste heat in the gas and fume venting, the process has enabled the generation of 231,376 tons of steam at 250-lb, gauge. Over the first six months opcration the volume of slag treated averaged somewhat under 300 tons per day. Reclaimed dump slag made up only about 1 5 per cent of the plant feed. In October 1943, preparations for the smelting of additional tonnages of dump slag were completed and the plant capacity was increased to an average of about 420 tons of slag per day. During the nine-months interval since that date, monthly averages of 450 toils per operating day have been maintained several times. The new plant (Fig. I) is constructed in close proximity to blast-furnace operations. The fuming furnace and other necessary equipment are housed in an eastward extension of the existing blast-furnace building. Beyond this housed extension the dust-laden gas is conveyed about the perimeter of a large rectangle formed by the flues, cooling towers and baghouses. The course of a 10-ft. balloon flue, which transports the fuming furnace gas, describes the west and south perimeters. This flue connects with a set of cooling towers located at the southeast comer. The flue and cooling-tower system serving the deleading kiln constitute the north side and the two baghouses, serving the kiln and furnace operations, -border the east side. From these baghouses the several discharge gas flows are come biped and conveyed in to the rectangle, being vented to atmosphere by means of a fan through a centrally located zoo-ft. brick stack. In general, the plant design and operation follow quite closely that dictated by experience gained in years of slag-fuming practice by the Anaconda Copper Mining Go., at East Helena, Mont., and the Consolidated Mining and Smelting Co. of Canada, Ltd., at Trail, B.C., and more recently by the International Smelting and Refining Co. at Toocle, Utah. : Fuming operations at the East Helena and the Tooele plants are more or less identical. Trail practice differs chiefly in the methods employed for the storage of the hot feed slag and in the methods utilized for the handling and cooling of the fuming furnace gas. The new Bunker Hill fuming plant closely follows Trail procedure in the treatment of the furnace discharge gas while East Hclcna methods have been adopted for the storage of feed slag.

Jan 1, 1944

By C. R. Wohrman

A melt of pure electrolytic iron with about 0.4 per cent. sulfur and 7 per cent. manganese was prepared in connection with a study of inclusions in iron. The alloy darkened rapidly when etched with a 10 per cent, alcoholic solution of nitric acid, and microscopic examination revealed the presence of a semimartensitic, semi-Widmanstättian structure (Figs. 1 and 2) closely resembling the structures found by Benedicks in his artificially prepared "meteoric iron."' The structures found by Benedicks were readily explained by the presence in his alloy of the two well-known iron-nickel solid solutions, taenite and kamacite, and of their eutectoid (?) aggregate, plessite. By analogy, one would infer the existence of similar phases in the iron-manganese alloy just described, such an inference being strengthened by the similarity displayed in many ways by nickel and manganese in their effects on iron. Iron-manganese Alloys are Regarded as Homogeneous Heterogeneity of iron-manganese alloys has not been recognized heretofore, judging from the data of standard metallographic books and those of original papers. In fact, iron and manganese are quite generally regarded as completely miscible in the solid state. Dr. Rosenhain,2 for example, writes: Alloys of group (a), of which those of gold-silver, iron-manganese, and copper-nickel are examples, when allowed to crystallize sufficiently slowly to attain their condition of final equilibrium, present a microstructure exactly similar to that of a pure metal—the homogeneous character of the molten solution is in that case so completely maintained that the microscope cannot detect the presence of any second constituent. Guillet and Portevin3 refer to the iron-manganese system as an example of the "case of metals completely miscible in the solid state."

By F. X. Tartaron

F. C. Bond (Consulting Engineer, Processing Machinery Dept., Allis-Chalmers Manufacturing Co., Milwaukee, Wis.) — Papers such as this one which deal in a lucid manner with the obscure fundamentals of comminution theory are always welcome. The author has attempted to bring together several diverse theories and handles them interestingly. However, some of the ideas expressed and conclusions drawn require critical reviewing, for which amenities alone will not suffice. The author points out that the theoretical energy required to break across crystal lattices is of the order of 1000 times the actual energy required to crush or grind, and that this energy in turn is perhaps 1000 times the measured surface energy of the new surface area produced. The energy required to grind commercially is controlled by flaws and dislocations, rather than by the inner strength of the lattice structure. The measured surface energy is only a slight residue left after the face atoms are adjusted to their new environment. The dislocations in the crystal lattice structure, with a spacing of about O.l,u, or

Jan 1, 1962

By Franklin Moeller

Considering the really short time that has elapsed since hydro-metallurgical processes of extracting copper from ores have been extensively developed, and the large scale on which this method is practised at Ajo, the successful operation of the plant must excite the admiration of every visitor. The application of the mechanical unloader to the purpose for which it is employed at Ajo is but an extension of the use for which it was originally designed, some 20 years ago, for unloading iron-ore vessels at the lower lake ports. At a time when the maximum output of a single machine, with men shoveling the ore into buckets, did not exceed 40 tons per hour, G. H. Hulett invented and constructed a mechanical unloader with a bucket of 10-ton capacity. This machine was of the steam hydrauIic type, and it is still in operation after nearly 20 years of service. Several more machines of the same type were built, but the difficulties of power transmission, and the rapid development of electrical machinery, soon led to the adoption of electrically operated machines, and practically all of the later installations have been thus equipped. This electrically operated unloader has proved so well fitted for the work that the design of the lake boats has been practically revolutionized, with special view to the ease and rapidity of unloading. It is now possible to unload a 12,000-ton vessel with four machines in a little over 2 hr. This has necessitated an increase in the capacity of the machine, and the largest yet built handles an average load of 17 tons, with a possible maximum of 20 to 21 tons. The Ajo excavator is somewhat simpler in design than the iron-ore unloader, in that it is not provided with a larry. In the unloader, the iron ore, picked up by the bucket, is delivered to a larry or transfer car which runs in the lower chord of the bridge; the larry then delivers the ore either into railroad cars, standing on several parallel tracks, or into the stock pile, thereby saving the time that would be required for the bucket to make the trip. At Ajo, the bucket delivers the tailing

Jan 1, 1920

By Benjamin Gi ldersleeve

Uniquely colored, thin-bedded quartzite is quarried between Crossville and Crab Orchard in Cumberland County, Tenn. It is produced in all sizes up to the limits of transportation from beds usually ranging in thickness from less than 1/2 in. to 6 in. The stone is very resistant to wear and weathering and is marketed throughout the country for many different purposes in exterior and interior construction. The annual production exceeds 36,000 tons, valued at nearly $1,000,000.

Jan 1, 1950

By T. G. Lovering

Nonparametric statistical tests have practical application to many geological problems because, unlike the standard statistical tests, they do not require assumptions regarding the form of the population frequency distribution. Many of them do not even require that the variable be susceptible to numerical measurement. These tests are useful either 1) for geological data representing population distributions of unknown form, or otherwise not meeting the requirements for standard parametric tests; or 2) for sample attributes that cannot be measured but only ranked in order of relative magnitude. The application of two such tests will be illustrated. The Kolmogorov-Smimov test will be used to test for significant differences in copper distribution in samples of two rock types; the Spearman rank-correlation method will be used to determine whether there is a significant association between intensity of rock alteration and copper content of the rock. Nonparametric tests are, in general, quicker and easier to perform than the corresponding parametric tests, and they may be applied to a greater variety of data. They are not as powerful as the standard tests if used on data to which the latter are applicable, and computer programs utilizing them are not generally available. The use of standard or parametric statistical procedures for the interpretation of measured geological data is familiar to most mining engineers and explora- tion geologists. The computation of product moment correlation coefficients on sample assays for more-than one component is already standard procedure in some company operations, as is the use of Student's F test and Snedecor's F test for the comparison of means and variances of sample groups. The application of these three tests is limited by the prerequisites that the samples must be random, independent representatives of normally distributed populations and that the variables involved must be measurable. If such tests are applied to data which fall short of fulfilling these prerequisites, then the probability level attributed to the computed statistic is invalid and the conclusions based thereon may be erroneous. A number of nonparametric, or distribution free, statistical tests have been developed for use with data which are not amenable to standard parametric procedures. These tests have been widely used in the behavioral sciences such as psychology and sociology for some time, but their application to geologic problems is relatively new. Nonparametric tests may be grouped into two main categories: those which test for significant differences in a single variable by comparing either sample values with a standard value or representative values between two or more groups of samples; and those which test for significant association between pairs of variables in a single group of samples. The versatile chi square test, the Kolmogorov-Smirnov one and two sample tests, the Wilcox matched pairs signed ranks test, the median test, the Mann-Whitney U test and the Cochran Q test are examples of nonparametric tests with demonstrated or potential geological applications that belong in the first category. The contingency coefficient, Spearman rank correlation coefficient, Kendall rank correlation coefficient and the

Jan 1, 1963

When the writer first began his search for the early history of coal he was amazed at the paucity of information in literature about it, and while after six years many of the reasons for such a scarcity are understood, there are still many cases, even within the last two centuries, when one who can appreciate the tremendous part coal has played in the development of modern times, finds it hard to realize how little attention was paid to this material in those early clays. Occasionally a traveller or observer is found who foresaw how valuable coal was to be when industries were developed, but these were few and to most of those recording its occurrence it was just another mineral. George Washington was farsighted in his view of the development of this country and the need for means of transportation across the mountain barrier, but it was at least sixteen years after he must first have known of coal before he made any reference to it in his journals. He did, however, knowingly or not, select some valuable coal properties in the lands lie obtained in the West. This was then almost entirely an agricultural country, and what industries there were found a great abundance of wood fuel within easy access, there were no steam plants, and all iron was made with charcoal; in fact, the "captive mines" of the iron industry then were large timber "plantations," and when these were exhausted the furnace usually was abandoned and another one built elsewhere, as transportation of charcoal was quite expensive. Along the seaboard the cities and industries began to import coal from England and Nova Scotia early in the eighteenth century, but until the war of the Revolution began the total quantity of coal used yearly in this continent did not exceed nine thousand tons. In 1800 only two places, Pittsburgh and Richmond, Virginia, were using coal to any extent for domestic purposes and it was much later. than this that the amount of coal used in Philadelphia, New fork, and Boston exceeded that of wood. Practically all of the early travellers and writers mentioning coal are noted in the following pages. Several Englishmen who were evidently familiar with its use and value at home, mention its presence as being of great future promise to the young nation, but to nearly all it was more or less of a curiosity and the smoke caused by its use an abomination, and it

Jan 1, 1942

Shoemaker: We've all heard a lot about epoxy liner backings. This brings up the question-do zinc furnaces still have a place in a new plant? Meaders: I would, you must understand, be prejudiced in this question because we introduced epoxy backing into the industry. Naturally, we wouldn't have done so if we didn't think it should be done. With that background maybe I could give a little more information on this particular subject than some of the others, because we now have been in this business for some three or four years.

Jan 11, 1967

By B. W. Gandrud

WET-PROCESS coal-washing tables as we know them today have been in use in this country for approximately 25 years. The literature records only a few table installations worthy of note prior to adoption of the present-day differential-motion table. According to Phillips,' six Campbell bumping tables were being operated by the St. Bernard Coal Co., Earlington, Ky., in 1893. As late as 1923, according to Richardson, 72 such tables were in operation in the Rosedale washery of the Cambria Steel Co., at Johnstown, Pa. Bumping tables probably were not used to any considerable extent except in the plant at Earlington, and at two or three plants in Pennsylvania, but they may be considered as forerunners of the present-day coal-washing table. The transition from bumping tables to the type of tables now in use signalized a revolutionary change iii table design. The advantages of the new design over the old were so outstanding as to make its adoption inevitable. BUMPING TABLES Bumping tables, as the name implies, utilized a bumping action for conveying the refuse and discharging it over the refuse end. The tables were hung from rods attached to overhead supporting beams. A shaft and cam arrangement at one end of the table served as ,the actuating mechanism and imparted to the table an endwise, back-and-forth, swinging motion. A bumping block was fixed in the proper position at the shaft end, so that the table would strike against it at the end of each backward swing. The hanger rods or stirrups were so adjusted as to give the table a slight uphill slope toward the refuse end; that is, the end next to the driving mechanism. The feed box was near the upper end of the table and designed to spread the mixture of coal and water over the width of the table. Wash water was added a short distance below the feed box. With the table in motion and coal mixed with water being fed to it through the feed box, a certain amount of stratification took place, depositing heavy refuse at the bottom of the bed in contact with the surface of the table. Constant bumping and a certain amount of

Jan 1, 1943

Andy H. Vassiliou – Introduction Ladies and gentlemen,.good evening and welcome to the Paul F. Kerr Memorial Symposium dinner. I believe we are all here to honor the memory of a great teacher and advisor, and a true friend -- Professor Kerr, or Dr. Kerr, or to most of us who were his students, "Pappy" Kerr. Most of us who attended the Paul F. Kerr Memorial Symposium earlier today at the New York Hilton had the opportunity to read, or listen to, or discuss scientific papers presented in honor of Dr. Kerr. In addition, all of the speakers had the opportunity to reminisce about their association with Dr. Kerr, who was credited as having contributed substantially to their graduate education and the development of their careers. Dr. Kerr's two daughters -- Ruth and Nancy -- who attended the Symposium at the Hilton are also here with us tonight. I think we should keep tonight's festivities on an informal basis since we are all old friends or former students of Dr. Kerr. Some of us may want to say a few words about our experiences at the time we were students at Columbia, and hopefully include some anecdotes relating to Professor Kerr. I would like to invite everyone to do so, but first we have arranged for two of us to be the lead speakers, whom I will introduce in a few moments.

Jan 1, 1985

Sykes, W. P.-Effect of Temperature, Deformation, Grain Size, and Rate of Loading on Mechanical Properties of Metals. Discussed by Zay Jeffries, W. H. Bassett, F. E. Carter 3 Evans, Geo. Watkin.-Alaskan Coal Fields. Discussed by P. N. Moore, H. H. Stoek, G. S. Rice, H. Emerson 4 Eavenson, Howard N.-Run-off and Mine Drainage. Discussed by J. R. Campbell, Andrew B. Crichton, J. B. Warriner, R. V. Norris, H. G. Moulton, H. B. Wright 7 Andrews, Allen, and Garcia, John A.-Skip Hoisting for Coal Mines. Discussed by R. V. Norris, Geo. S. Rice, H. N. Eavenson, E. A. Holbrook, Robert Obert, Andrews Allen, T. M. Chance 12 Rice, Geo. S.-Coal-pillar Drawing Methods in Europe. Discussed by Carl Scholz, D. Harrington; H. 1. Smith 16 Knapp, Arthur.-Modified Oil .well Depletion Curves. Discussed by Roswell H. Johnson 21 Alvey, Glenn H., and Alden W. Foster.-Barrel-day Values. Discussed by Roswell H. Johnson 22 Matteson, W. G.-Secondary Intrusive Origin of Gulf Coastal Plain Salt Domes. Discussed by Eugene Coste, E. W. Shaw, Joseph E. Pogue, F. G. Clapp, E. DeGoIyer, W. G. Matteson, H. W. Hixon, R. Van A. Mills 23 Reger, David B,-Carbon Ratio of Coals in West Virginia Oil Fields. Discussed by J. T. Singewald, Jr 33

Jan 5, 1921

By G. P. Boomslitter

In previous discussions on stresses in hoisting ropes, little has been said concerning the effect of the elasticity of the rope itself on the stresses due to acceleration. Laschinger1 has calculated acceleration stresses for several cases but he has ignored the elasticity of the rope as a factor, except as it compresses the drum and stretches itself as it winds thereon. He also deals with steam plants and he shows the effect of the "jerky" start of the engine. This effect would actually be reduced by the elasticity of the cable. With the advent of the motor-driven hoist, new conditions have arisen. The jerk mentioned by Laschinger has been eliminated and smoother starting made possible. But the elastic properties of the rope seem to introduce considerable periodic acceleration stresses in the rope. The following discussion of acceleration stresses is based on the assumption of a constant acceleration at the drum. To be exact, the mathematical work is based upon the assumption that the top is moving upward with a constant acceleration, and ignores the fact that the cable is shortening as it winds. However, the effect of the shortening would be inconsiderable during the first part of the acceleration period. Most hoisting engineers make the assumption of constant acceleration at the drum. Under the older method of calculating acceleration stresses, this would be true with a constant torque motor. But if stresses vary, as this paper attempts to show that they do, constant torque would not give constant acceleration, although the velocity-time curves obtained in the full size test herein described showed that they approach rather closely to this condition, at least as nearly as could be measured. Theoretical Discussion According to elementary physics, the force required to accelerate a Wf body of weight W at the rate of f ft. per sec.2 is wf . To raise the body Wf with acceleration of f ft. per see.2 the total force required is I + Wf, in if

Jan 1, 1927

By M. King Hubbert

In 1856 Henry Darcy described in an appendix to his book, Les Fontaines Publiques de la Ville de Dijon, a series of experiments on the downward flow of water through filter sands, whereby it was established that the rate of flow is given by the equation: q= - K(h2- h2)/I1 in which q is the volume of water crossing unit area in unit time, I is the thickness of the sand, h1 and h2 the heights above a reference level of the water in manometers terminated above and below the sand, respectively, and K a factor of proportionality. This relationship, appropriately, soon became known as Darcy's law. Subsequently many separate attempts have been made to give Darcy's empirical expression a more general physical fornzulation, with the result that .so many mutually inconsistent expressions of what is purported to he Darcy's law have appeared in published literature that sight has often been lost of Darcy's own work and of its significance. In the present paper, therefore, it shall be our purpose to reinform ourselves upon what Darcy himself did, and then to determine the meaning of his results when expressed explicitly in terms of the pertinent physical variables involved. This will be done first by the empirical method used by Darcy himself, and then by direct derivation from the Navier-Stokes equation of motion of viscous fluids. We find in this manner that: q = (N4(p/p)[g - (l/p) gradPI = WE, is a physical expression for Darcy's law, which is valid for liquids generally, and for gases at pressures higher than about 20 atmospheres. Here N is a shape factor and d a characteristic length of the pore structure of the solid, p and IL are the density and viscosity of the fluid, a = (Nd2)(pip) is the volume conductivity of the system, and E = [g - (l/p) grad p] is the impelling force per unit mass acting upon the fluid. It is found also that Darcy's law is valid only for flow velocities such that the inertial forces are negligible as compared with those arising from viscosity. In general, three-dimensional space there exist two superposed physical fields: a field of force of charucteristic vector E, and a field of flow of vector q. The force field is more general than the flow field since it has values in all space capable of being occupied by the fluid. So long as the fluid density is constant or is a function of the pressure only, curl E = 0, E = - grad F where F = gz + dp/p The field of flow, independently of the force field, must satisfy the conservation of mom, leading to the equation of continuity div pq = — f ap/at , where f is the porosity, und t is the time. For steady rnotion ap/at = 0. and div pq = 0 .

Jan 1, 1957

COMMITTEES Committee on Arrangements DAVID H. BROWNE, Chairman BRADLEY STOUGHTON, Vice-Chairman LAWRENCE ADDICKS BURR A. ROBINSON PERCY E. BARBOUR E. MALTBY SHIPP GEORGE D. BARRON JOSEPH STRUTHERS J. V. N.. DORR E. B. STURGIS J. R.. FINLAY T. T. READ Louis D. HUNTOON R. H. VAIL

Jan 4, 1916

By Chester O. Ensign

Many publications to date have advocated under- seas mining operations, optimistically overlooking the paucity of information on mineral distribution and the ocean environments in which minerals occur. Such articles (smattered with opinion, as is this article) are herein tempered by my more conservative views on the economics of mining under the seas. For purposes of this paper, underseas mining refers only to the deeper surficial deposits of the continental shelf and the deep sea floor, i.e., the deposits of phosphorite and manganese nodules.

Jan 9, 1966

By R. O. Williams

Analytical representation of the thermodynamics of solutions is highly desirable from the standpoint of accuracy, compactness, and numerical manipulations. In particular, computer calculations are greatly implemented. Mathematical considerations show that previous expressions have one or more serious defects. This investigation shows a Fourier series to be satisfactory but that it is also possible to derive a new series which fits certain additional conditions. Included examples show the value of analytical expressions in giving a simple characterization of each system using some two to five parameters, the elimination of the Gibbs-Duhem integration, and the es timation of the error for the experimental function as well as derived functions. It is further shown that the present characterization provides easy comparison between systems. IN the past, thermodynamic calculations have depended to a considerable extent on tabular and graphical methods. As the volume and precision of such data increase such methods become less satisfactory. Specifically, the selection of the optimum representation and the estimation of errors require statistical methods which in turn require analytical representation. The utilization of such data require further manipulations which are best done analytically for maximum precision. For example, phase equilibria are determined by common tangents to free-energy curves: a graphical determination is normally of low accuracy. As computers are increasingly used analytical representations become almost mandatory. Insufficient mathematical consideration has been given previously to the selection of empirical expressions. Those expressions having some theoretical justification are generally too inflexible and mathematically unattractive. We consider the problem in some detail and show that a Fourier series can be effectively used. Also a new series is defined which has certain advantages. ANALYSIS We wish to consider the analytical representation of the heat of mixing, AH, the excess free energy, ?Gxs, and the excess entropy, ?sXS, as a function of composition, X, for binary solutions relative to the pure components in the same state. When a distinction is not required, we use W to denote any one of the above functions. One may use a Taylor expansion around X = 0 to generate a power series. As the derivatives are un- known we represent the series as W = A + BX + CX2 + DX3 + EX4 + ... [l] where the constants A , B, C , ..- are to be selected to provide some optimum fit. For the extremes of composition W is necessarily zero so it follows that A = 0 [2a] B +C + D + E +••• = 0 [2b] Nonelectrolytes, which we are considering, appear to satisfy the condition that d3W/dx3 = 0 [3] in the terminal regions. This is the basis of the a, ß, and Q functions used by Hultgren et al.' and others. While this condition does not have a strong theoretical basis it does appear desirable that any analytical relation should satisfy this condition. Darken2 and Turk-dogan and Darken3 have shown that many systems exhibit this behavior over an extended range from each terminal region, departure being restricted to a limited intermediate region. Since we have no a priori knowledge as to where this transition occurs we can require that this condition be satisfied only as a limit at the extreme compositions as a general condition. We will show later how more restricted conditions can be included in specific solutions. Darken2 has called this behavior the quadratic formalism; we call our application the limiting quadratic formalism, LQF. This condition applied to the above power series requires that D = 0 [4a] 4-3-2E +5-4-3_F + 6 • 5 . 4G + ••• =0 [4b] The form of the power series normally used, due to Margules,4 is W=X(1-X)(A + BX + CX2 + DX3 + EX4 + •••) [5] where A, B, C, --. are a new set of constants. (Guggenheim5 has given a variation of this expression in a more desirable form. Since, however, it is contained in the above expression it does not require separate consideration.) This form is precisely what results by incorporating the conditions in Eq. [2] into the power series and regrouping the constants. The LQF requires that B =C [6a] and 4.3.2(D-C) +5-4-3(E-D) + ••• =0 [6b] Thus, the correct form of the Margules expression with two adjustable parameters is w =X(1-X)[A + B +X2-2/3x3)] 171 and the EX4 term must be included before three adjustable parameters are permitted.

Jan 1, 1970

By Milton E. Wadsworth, R. Ted Wimber

Cobalt sulfate solutions containing ammonium acetate and chloroplatinic acid were reduced by hydrogen in a pyrex-glass lined autoclave in the temperature range of 170o to 232°C and hydrogen partial pressure range of 115 to 830 psia. The reduction rate was directly proportional to the hydrogen partial pressure and surface area of the pyrex glass and was independent of the quantity of chloroplatinic acid added initially. Experiments involving the variation of the relative concentration of ammonium acetate indicated that the reducible cobalt complex was probably the diacetate complex of cobalt, Co(AC)4H20, or a new mononcetate complex Co Ac, which was in solubility equilibrium with a pink precipitate of CO(AC)-4HzO. THE reaction in which a metal is dissolved by an acid to produce gaseous hydrogen and a salt solution was discovered early in the history of chemistry. In 1859 Beketoff found experimentally that this reaction could be reversed; i.e., a salt solution could be reduced by gaseous hydrogen to produce a metal and an acid. A review of work done on this phenomenon since that time may be found elsewhere., The hydrogen reduction of a cobalt salt solution is facilitated by complexing the cobalt ion. An ammonia complex of cobalt has been reduced commercially in the recovery of cobalt metal. A new reducible complex of cobalt was discovered5 when it was found that a co-baltous sulfate solution containing ammonium acetate could be reduced by hydrogen at temperatures in the region of 200°C. When a cobalt sulfate-ammonium acetate solution was heated to a temperature below its normal boiling point, a violet color became apparent, indicating complex formation. The nature of this complex was investigated5 by the addition of NH4Ac to a CoSO4 solution maintained at 85o. During the first additions of NH, Ac, the pH of the solution remained fairly constant at about 5.85. However, as the ratio of NH,Ac to CoSO, approached two, the pH rose and then leveled off at about 6.05. The absorption spectra of a Co(Ac), solution and a CoSO,, NH Ac solution were obtained at 85°C and were compared and found to be the same. These findings suggested that the diacetate complex of cobalt, Co(Ac),.4H20, was formed at 85°C. When a cobalt sulfate-ammonium acetate solution was heated to a temperature above about 165o, a finely divided pink precipitate appeared. The X-ray diffraction pattern of this precipitate indicated that it was Co(Ac), - 4H,O. In addition, it was discovered that when chloroplatinic acid, H,PtCl;, was added initially to the cobalt sulfate-ammonium acetate solution, a faster reduction was obtained. The roles of the solution complex, pink precipitate and chloroplatinic acid in the reduction process were then investigated. APPARATUS The experimental work was carried out in a two-liter stainless-steel autoclave. Adetailed description of the autoclave and the auxiliary equipment used in maintaining constant temperature and pressure may be found elsewhere.= Because the stainless steel was corroded, and also because it acted as a hydrogena-tion catalyst, an all-glass liner was fabricated such that the solution came only into contact with flame-polished pyrex glass. EXPERIMENTAL PROCEDURE The solutions used in the experimental work were prepared by dissolving reagent grade chemicals in distilled water. Although variation of the brand of ammonium acetate appeared to have no effect on the experimental results, CoSO, 7H O from the J. T. Baker Chemical Co. of Phillipsburg, N. J.,was found to give faster reductions than that prepared by Allied Chemical and Dye Corp., N. Y. The former was used throughout the course of the experimental work and was weighed up at the outset of each experiment. The ammonium acetate was dissolved to form a 6M stock solution, which was stored under refrigeration. A 10 pct solution of chloroplatinic acid (J. T. Baker Chemical Co.) was diluted to a 1.15 x 1Q2 M stock solution, which was standardized by precipitation of K,PtCl, as outlined by Scott. The appropriate volume of the chloroplatinic acid, H,PtCl,, solution was pipetted into the clean, dry glass liner. The cobalt sulfate-ammonium acetate solution, which had previously been saturated with

Jan 1, 1962