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By P. T. Carter, A. B. Murad, H. B. Bell

The distribution of manganese and oxygen between molten iron and FeO-MnO-SiO2 slags not saturated with SiO2 has been determined and used to calculate activities of MnO and SiO2 in MnO-SiO2 slags. These were found to be intermediate between the corresponding activities in FeO-SiO2 and CaO-SiO2 slags. THE equilibrium constant for the reaction between molten iron containing manganese and slags containing FeO and MnO, namely: FeO(slag) + Mn = MnO (slag) + Fe(1iquid) is most conveniently represented by: (MnO) Kmn== (FeOHMn] [Fe] is omitted, since for dilute solutions of manganese in iron, afe is approximately constant. When activities are used for (MnO), (FeO) and [Mn], Kmn is a true equilibrium constant and will apply to all types of slags, but when weight percentages are used, the values obtained for Kmn for different slags vary considerably. The equilibrium between iron containing manganese and relatively pure FeO-MnO slags has been investigated by several workers;1-4 the most recent investigation reported is that of Chipman, Gero, and Winkler.4 Their results, corresponding to slags containing up to 4 pct SiO2, were represented by the equation: 6440 log KMn = +2.95 In this case both slag and metal may be assumed to be ideal solutions, therefore the values of Kmn so derived represent the true constant for the manganese reaction. As the molecular weights of MnO and FeO are almost equal, weight concentration of these oxides may also be used in the above expression. Acidic oxides such as SiO2 and P2O5 affect the activities of FeO and MnO differently, so that when total concentrations by weight of FeO and MnO are used in the above expression for Kmn the values obtained are no longer constant. These will be denoted by K'mn. Körber and Oelsen5 investigated the manganese reaction using silica-saturated iron-manganese-silicate slags and found: 7940 logK'mn =3.172 This corresponds to Kmn values much higher than those obtained for pure oxide slags. The results of Körber and Oelsen, and Chipman, Gero, and Winkler are summarized in Table I. In the present investigation it was decided to study the manganese reaction using iron-manganese-silicate slags not saturated with silica, and which fell mainly between the orthosilicate join 2FeO . SiO2 - 2MnO.SiO2 and the FeO-MnO side of the ternary system FeO-MnO-SiO2. It has been shown" that the phases present in solidified slags of this part of the diagram are (FeO, MnO) and (2Fe0.Si02, 2Mn0-SiO,) solid solutions. Such an investigation would be of interest in deoxidation and also gives information on activities in liquid slags. This equilibrium has not as yet been investigated successfully. Hilty and Crafts7 attempted to examine this reaction in a rotating crucible furnace, but were unable to obtain suitable slag samples. In the present investigation one series of experiments was carried out in a rotating crucible furnace, because the success of Taylor and Chipman8 with such a furnace in their study of oxygen distribution between molten iron and (CaO, MgO) — FeO-Si0, slags suggested that it would minimize contamination of the slag by the crucible material. A second series was carried out using a wire-wound resistance furnace. Rotating Crucible Furnace Experiments In all cases the metallic charge consisted of 800 to 1000 g Armco iron containing 0.02 pct C, 0.03 pct Mn, and traces of Si. Manganese and silicon additions consisted of electrolytic manganese (99.9 pct)

Jan 1, 1953

By C. Max Bauer

THE most important development in the petroleum industry in Montana, during 1924, was the bringing in of the Hepp well on May 12, by the Midwest Refining Co. This followed three years of active prospecting and drilling in the state by this company. The well is located 35 miles west of Billings, in Stillwater County, and makes a high-grade paraffin oil from the Dakota sand at a. depth of 3825 ft. After flowing for several months at the rate of 150 bbl. per day, the well has been shut in for lack of storage, awaiting further development in the field. TABLE 1. Production Cat Creek and Kevin-Sunburst Fields Month Kevin-Sunburst Pipe- Estimated Cat Creek Pipeline Estimated line Runs Fuel Oil Used Runs Fuel Used January 3,214 0 133,400 140 February 3,250 0 134,248 490 March 11,989 595 163,129 910 April 116,897 1,155 125,918 980 May 179,726 2,310 152,179 770 June 126,131 2,697 122,270 910 July 132,173 2,170 118,034 770 August 202,001 2,695 142,313 1,120 September 187,201 2,135 110,012 350 October 162,589 1,995 121,683 350 November 130,392 2,520 139,900 350 December 107,465 1,780 124,169 0 Total 1,363,028 20,052 1,581,255 .7,140 There are two producing oilfields in the state-the Cat Creek and the Kevin-Sunburst, which produced a total of 2,971,475 bbl. in 1924. The only other field of proved value is Soap Creek, which contains a heavy black oil and is shut in for lack of marketing facilities. Gas is produced for local use at Havre, Chinook, and Baker, and a carbon-black plant is located at Baker.

Jan 3, 1925

By P. J. Burkhardt, L. V. Gregor

The oxidation kinetics of single-crystal silicon has been investigated using extremely dry oxygen as the oxidant. Two techniques were used. The first involved a flow system with which incremental thickness measurements were made. This sytem provided an oxygen ambient at atmospheric pressure which had a moisture content of less than 0.1 ppm of water. The second technique involved measuring the change in volume of oxygen with time in a closed system. A temperature range of 900O to 1200 "C and a pressure range of 20 to 760 Tory were covered. Both techniques showed that a simple parabolic rate law holds only at the higher temperatures. At lower temperatures, the data up to 5000Å can be fitted well to a linear-parabolic equation. The two constants in this rate equation are examined in terms of a physical model. The parabolic portion of the low-temperature oxidatLon fits along the high-temperature curve of an Arrhenius plot. The parabolic rate constant for the flow-system technique can be expressed by k = 2 x 10-9 exp (L 31 kcalRT) sq cm per sec. The manostatic technique gave k = 1 x 10-exp (- 23 kcalRT) sq cm per sec. By extending the thickness range to over 104. a rate law of X = At seems to fit all of the data better than the linear-Pavabolic law. Here the exponent n increases from 0.518 at 1150 V to 0.637 at 900°C. PASSIVATION of silicon planar devices through thermal oxidation is of such great importance that considerable effort has been devoted to the study of the process.17 Much of this work involves hydrothermal oxidation, in which H2O is the oxidant: whereby H2 is produced. It has been proposed that the reaction proceeds by the formation of Si-OH groups and hydroxyl diffusion through the film to react with the silicon surface. Thus, the silicon oxide layer probably contains residual hydrogen in some form after oxidation in H2O and it has already been established that hydrogen has a marked effect on the electronic properties of oxide-passivated silicon surfaces. Silicon is oxidized by oxygen at elevated temperatures; but the rate of oxide formation is considerably lower than that for 0." By using dry O2 as the sole oxidant, the presence of residual hydrogen is presumably avoided. At present, the mechanism of thermal oxidation by dry O2 is a matter for conjecture, and the presence of small amounts of H2O was reported to have a marked effect on the rate of oxide formation10 (perhaps on the electronic properties of the surface, as well). Hence, this study of the kinetics of silicon oxide growth in 0, was undertaken: 1) to determine the oxidation rate at atmospheric pressure in a system designed to exclude rigorously all traces of H2O in the ambient 0,; 2) to obtain oxidation-rate data in situ in dry O2 by means of a continuous monitoring of the amount of 0, consumed during oxide growth. These objectives are complementary—the first assesses what effects (if any) are obtained by excluding H2O from the reaction, and the second expands this information while at the same time avoiding the uncertainty inherent in relying upon incremental measurements of oxide growth to furnish kinetic data. EXPERIMENTAL PROCEDURE The conventional silica open tube in a resistance-heated oxidation furnace is subject to sources of trace H2O, even after the input O2 is thoroughly dried and the outlet gas stream is passed through a trap to prevent

Jan 1, 1967

By R. E. Cech, T. D. Tiemann

It has been shown that hydrogen may be made to serve as a rapid and eflicient reducing agent for Cu, Ni, Co, and Fe sulfides if a scavenging agent for hydrogen sulfide is intimately mixed with the sulfide particles being reduced. Accelerated reduction kinetics are demonstrated for nickel sulfide. Copper, nickel, and cobalt sulfides, when treated at certain temperatures in a combined reducing agent-scavenging agent system, are converted to voluminous masses of fibrous metal product. Studies have been carried out to determine the conditions which lead, on the one hand, to irregular poly crystalline fibers and, on the other, to long single crystal filaments a few microns in diameter. A mechanism is proposed to account for the formation of single crystal filuments. The sulfide minerals of Cu, Ni, Co, and Fe are an important source of these metals yet there has been comparatively little scientific effort devoted towards understanding reduction mechanisms of these minerals. This may be, in part, due to the fact that the most convenient reducing agents for carrying out such studies, viz., hydrogen and carbon, do not react appreciably with sulfides. We have found that the reaction of hydrogen with metal sulfides can be markedly accelerated by placing a scavenging agent for hydrogen sulfide in close proximity to the metal sulfide. A brief series of experiments demonstrating relative reduction rates is reported in this paper to illustrate the effect. With the reduction process thus accelerated we have observed an unusual type of reduction behavior on some of the sulfides investigated. Under certain conditions the metallic product of the reduction reaction takes the form of filaments growing outward from the sulfide particles. The present paper deals largely with efforts to classify the various types of growth forms observed. This study has shown that filamentary growths from sulfides take a much greater variety of forms than has heretofore been reported by Ercker,1 Hardy,2 and Nabarro and Jackson3 in their reviews of metallic growths from copper and silver sulfides. THERMODYNAMIC CONSIDERATIONS The thermodynamics for hydrogen reduction of metal sulfides is quite unfavorable. For the sulfides considered here equilibrium constants typically range from 10-3 to 10-5. These low equilibrium constants impose severe kinetic limitations on reduction since hydrogen sulfide must be transported out of the system at concentrations of only a few hundred ppm. Unless extremely high gas flow rates are employed the atmosphere surrounding any sulfide particle will always be essentially in equilibrium with the sulfide. If, however, one places an efficient scavenging agent for hydrogen sulfide in close proximity to the metal sulfide particles the concentration of H2S near the metal sulfide will be held to a very low value. This would permit the reduction reaction to proceed with little or no inhibition from a buildup of reaction product gas. It is well known that calcium oxide is capable of removing hydrogen sulfide from a hydrogen gas stream of low dew point.4 If a sufficient quantity of calcium oxide is mixed with the metal sulfide particles the reaction: CaO+H2S=CaS+ H2O [l] will substitute moisture in place of hydrogen sulfide in the gas stream and this will not affect, in a direct manner, the reaction: MeS +H2=Me + H2S [2] A convenient method of considering the thermodynamics of the combined reducing agent-scavenging agent system is to consider the atmosphere when the partial pressure of hydrogen sulfide is the same over both the metal sulfide and the scavenging agent, i.e., pH2S (1) =pH2S (2). As a consequence: pH2O (1) pH2(2) =K1K2 The chemical driving force for reduction will depend inversely upon the moisture content of the gas and will be 0 when, in the system, pH2O = pH2.K1K2. Table I lists values of the equilibrium constants for reduction and H2S scavenging reactions for a number of sulfides at several temperatures. Data are taken from Rosenqvist4,5 and Kelly.6 The equilibrium constant products calculated from this data show that the limiting level of gaseous reaction product has been increased by a factor of 10' to l04 as a result of substituting a reducing agent-scavenging agent system for a simple reducing agent system. One possible side effect which must be considered is the possibility that the moisture evolved in the scavenging reaction might cause the atmosphere in the system to be sufficiently oxidizing to favor the formation of oxide rather than metal. This possibility was examined by comparing the equilibrium constant products listed in Table I with equilibrium constants for hydrogen reduction of the respective metal oxides. It was found that for copper, nickel, and cobalt the combined reduction-scavenging reactions could not develop a sufficiently high oxidizing potential in the

Jan 1, 1970

By Fred Chappell

Pyrophyllite, a hydrous aluminum silicate, physically similar to talc, receives its name from the Greek word Pyr, for fire and phyllite, a rock or stone. Firestone refers to its first recorded use as firestones or hearthstones. Composition and Properties Pyrophyllite is an aluminum silicate A12O34SiO2H2O (alumina 28.3 pct, silica 66.7 [ ] pct, water 5.0 pct) (Table 1). Vanderbilt1 gives pH value of pyrophyllite as 5.6 to 8.4. Pyrophyllite is usually white or cream, though it may be found in shades of pale green, pale yellow, buff or light gray, and in darker shades and other colors principally due to oxidation of contained iron minerals. It is opaque to translucent in thin sections. Its hardness is 1 to 2 in the Mohs scale. Its specific gravity is 2.8 to 2.9. Its luster is pearly to dull; it is recognized chiefly by its micaceous structure and cleavage, and its soft greasy feel. Two other varieties occur, one in which there are radiated needles in the crystalline form, and there is also a massive homogeneous structure found. Fine grinding reduces pyrophyllite to fiat plates or scales but aggregates of minute foliated plates may be formed.1 Distribution of Deposits Pyrophyllite is found in metamorphic rocks throughout the world but it is only in comparatively recent years that it has assumed much commercial importance. The principal

Jan 1, 1960

By G. R. Purdy, J. G. Parr

The intermetallic compound Ti2Co was studied by X-ray diffraction and metallographic techniques. The phase occurs off stoickzometric composition, with its greatest variance at high temperature. The solubility limits of the phase have been cletermined, and an amendment to the titanium-cobalt phase diagram is suggested. THE first intermetnllic compound to appear at the titanium-rich side of the titanium-cobalt system was found by Laves and wallbauml to be Ti2Co. They described this compound as isomorphous with Ti2Ni and Ti2Fe, and demonstrated that it had a face-centered-cubic structure with 96 atoms per unit cell. This contention is supported by the work of Duwez and Taylor2 and Orrell and Fontana3 who also determined the lattice parameter to be about 11.30A. Rostoker4 believed that Ti2Co did not exist, and that the phase considered by the other workers to be Ti2Co was Ti,Co20. However, Orrell and Fontana determined oxygen and nitrogen contents and found that their alloys did not contain sufficient of these elements to produce significant quantities of a stoichiometric oxygen compound. The present investigation was initiated to determine the composition limits of the phase Ti,Co.

Jan 1, 1961

By Roy J. Helfinstine

One of the most urgent needs in the field of coal combustion is the ability to predict the performance of a coal from knowledge gained from small-scale tests. Numerous types of analyses and tests are conducted on coal, including the proximate and ultimate analyses, heating value, varieties of sulphur, ash analysis, ash fusion temperatures, free swelling index, petrographic analysis, and Gieseler plasticity. The Illinois Geological Survey has made an intensive study of the value of these tests for judging the performance characteristics of the coal as actually utilized. To date, three reports 1 2 3 have been is- sued, and another is being prepared. The present paper briefly summarizes some of the results found in the studies.

Jan 1, 1949

By O. Skiredj, J. F. Elliott

It has been necessary to collate the available data on the solubility of graphite in Fe-Si-Mn alloys for a study of slag-metal equilibria in ferromanganese production. That study will be reported later; the collation is reported here. The carbon content of graphite-saturated liquid iron above 1153ºC by Chipman and co-workers1 is: %C= 1.34 + 2.54 x 10~3t(°C) [l] For graphite-saturated manganese above 1322ºC it is: %C = 2.68 + 3.52 x 1CT3 t(°C) [2]

Jan 1, 1963

1. What Effect Has Sulfur Or Vanadium (In The Oil) On The Steel With Your Burner? 2. Also, what is the decibel rating on the floor when your burner is on? AUTHORS' REPLY 1. There is no effect. 2. The decibel rating is 98-99 decibels.

Jan 1, 1972

By AIME AIME

THE list of deaths reported during the year 1904 comprises the following names (the figures in parentheses indicate the year in which the persons named were elected to membership). Honorary Members.-Sir Lowthian Bell, Dr. Thomas M. Drown. Members and Associates.-Jacob Neff Barr (1884), John Walter Best (1899), A. Poyntz Blandy (1903), A. Cass Canfield (1876), William E. Carroll (1901), William E. C. Coxe (1874), Russell W. Davenport (1877), Isidor Davidov (1893), Louis M. Davis (1884), Edward Doerr (1897), Edward M. Ferguson (1878), C. Le Neve Foster (1893), Geo. Clinton Gardner (1878), Wm. J. Harris (1871), Richard P. Heckscher (1893), H. D. Hoskold (1.894), Wm. S. Hungerford (1882), Edwd. K. Landis, (1882), August Lengemann (1902), Wm. M. Lippitt (1900), Henry McCalley (1888), Robert J. McCartney (1897), Arthur McClellan (1871), Arthur S. Mahony (1888), Philip W. Moen (1888), Henry G. Morse (1881), Charles Parkin (1875), Clarence V. Page (1900), Rubens P. Patterson (1886), Henry Paul (1889), W. H. Pettee (1871), James B. Randol (1879), Irving H. Sevier (1904), Win. J. Sims (1902), John H. Slavens (1901), Chas. B. Squier (1886), Chas. W. Stickney (1891), Homer H. Swaney (1903), Walter B. Wilson (1892), Whittaker Wright, The following paragraphs, constituting the concluding portion of the Annual Report of the Council for 1904, have been withheld from publication until now, in order to make them as accurate and complete as possible. Jacob Neff Barr, a mechanical engineer of note, died on May 5, 1904. Being especially interested in railroad work, he invented the Barr contracting-chill process of casting car-wheels,

Jul 1, 1905

By J. B. Hiskey, W. J. Schlitt, W. G. Pitt

Aqueous SO2 (sulfurous acid) is an interesting chemical compound. It functions as a reagent in various hydrometallurgical systems, but also represents an undesirable constituent in gyro- and hydrometallurgical effluent solutions. When present in such streams, SO2 can be oxidized to the more stable sulfate form to avoid exsolution of SO2 as a source of fugitive emissions and to simplify standard water treatment plant operation. This study provides information on the stoichiometry, kinetics, and mechanism of SO2 oxidation using oxygen and an iron salt catalyst with solutions containing 0.05-20 g/L (0.002-0.7 oz per gal) SO2. The effects of iron salt concentration, oxygen pressure, temperature, degree of agitation, and pH on SO2 oxidation are also described.

Jan 1, 1984

By GEORGE L. CHRISTIAN

T HE Tonopah Extension assay office is a two- story, concrete structure on a solid foundation of andesite, situated about 100 yd. from the company's mill, so that it will not be affected by the stamps or the tube-mills; also it will not be affected by under- ground blasting. On the second floor are the mine superintendent's office and drafting and blueprint rooms. On the ground floor are the assayer's office,' mixing room, furnace room, crusher room, chemical laboratory, parting room, store room, and change and shower room for the mine superintendent, assayers, and engineers. The crusher room is outside of the main building, and has four concrete walls, thus eliminating the jar of the crusher; it is so situated that the least possible amount of dust spreads through the main building. An 8 by 10-in. jaw crusher, which crushes to ¼ in., was made by a local foundry. Attached to the top is a small galvanized-iron hopper covered with a ¼ in. screen, on to which the sample is dumped. The fines-pass through the screen into the hopper, while the oversize is dumped into the crusher. The crushed sample and fines from the screen drop down to a set .of splits suspended from an iron rod below the crusher jaws. The small sample is caught below in a small pulp pan. The rejects drop from the splits through a 2-in. pipe on to a bucket conveyor, which dumps into a galvanized-iron hopper in an upper corner of the room. The rejects drop through a 2-in. pipe to a reject bin outside the build- ing. This bin is constructed high enough for a truck to be loaded from it by means of a chute door on the side.

Jan 1, 1921

By B. W. Levinger

THE system Ti-CI- has been studied by several investigators." ' Though titanium and chromium are completely miscible at high temperatures, an intermediate phase of the approximate atomic proportions TiCr, has been identified at various compositions between 60 and 68 wt pct Cr. The structure of this phase was established as the cubic C15 (MgCu2) type with 24 atoms per unit cell and a lattice parameter 6.929 kX.2 During a study of the ternary system, Ti-Mo-Cr,5 the existence of a high temperature modification of the TiCr, phase was discovered. In a series of alloys annealed at 1300°C and containing from 60 to 70 wt pct Cr and 5 pct Mo, a new phase was present which did not correspond to either ß solid solution or TiCr,. By trial, the new phase was identified to be of the hexagonal C14 (MgZn2) structure with 12 atoms per unit cell. Further work showed that the hexagonal structure was. in fact, also present in binary Ti-Cr alloys quenched from high temperatures. To make the identification more certain, the intensities of the various reflections were calculated assuming a composition TiCr2 and C14 structure. Table I lists reflection planes, interplanar distances, calculated intensities, and a comparison of these values with the lines of a binary Ti-Cr alloy (66 pct Cr) annealed for 20 min at 1385°C and water quenched. Since high angle lines were more diffuse, the correspondence between visually observed and calculated intensities was not as good at these angles. Lattice parameters were computed to be a = 4.922 kX, c = 7.945, c/a :- 1.614. The corresponding interatomic distances are: titanium to titanium distance, 3.00:, kx, chromium to chromium distance, 2.43, kX, titanium to chromium distance, 2.88,, kX. These compare to 3.00, 2.45, and 2.87 kX in the cubic phase, respectively.' The atomic positions in the C14 structure are as follows: Titanium 1/3, 2/3, Z; 1/3, 2/3, 1/2: 2/3, 1/3, i; 2/3, 1/3, (1/2-z); Chromium 0, 0, 0: 0, 0, 1/2; 2x, 2, 1/4; 232, x, %; X, 22, 1/4; X, 2x, 3/4; x. x, 1/4; x, x, 3/4; The values of x and z were calculated for the alloy mentioned and found as follows: z — 0.061, x = 0.165. The values assumed in the intensity calculations were those for an ideal close-packed lattice or z = 1/16, x = 1/6. Work in the Ti-Mo-Cr system indicates that y2 the hexagonal modification of TiCr2, is the stable phase above 1300°C, while y1 with the cubic structure is stable below 1000°C. X-ray examination of a number of alloys annealed at intermediate temperatures showed that the hexagonal and cubic phases can coexist. Alloys quenched from 1000°C and annealed at 1100" and 1200°C showed small amounts of y2 at the higher temperature. A considerable amount of y, seemed present, however, in cast alloys annealed at 1100°C. It further appears that there is a small but definite solubility range for both phases in the ternary system. Acknowledgment The results of this paper represent work carried out in conjunction with a project sponsored by Watertown Arsenal, Contract No. DA-11-022-ORD-272. References 'M. K. McQuillan: Journal Inst. Metals (1951) 79, p. 379. 2 P. Duwez and J. L. Taylor: Trans. ASM (1952) 44, p. 495. W. J. Van Thyne,. H.. D. Kessler, and M. Hansen: Trans. ASM (1952) 44, p. 974. 1 F. B. Cuff, N. J. Grant, and C. F. Floe: Trans. AIME (1952) 194, p. 848; Journal of Metals (August 1952). Unpublished Research, Armour Research Foundation. "H. J. Wallbaum: Ztsch. Krist. 103, p. 391.

Jan 1, 1954

By CYRIL W., William Campbell, Henry M. Howe

THIS paper gives the results of an investigation of the behavior of the argentiferous cobalt-nickel arsenides of Temiskaming, Ontario, in roasting, made in the metallurgical laboratories of the School of Mines, of Columbia University in the City of New York. The ore was kindly given by the owners of the La Rose and Trethewey properties at Cobalt, Ontario, and Mr. E. J. Hall, Tutor in Assaying in Columbia University, has helped us much. I. OBJECT OF THE INVESTIGATION. The object of the investigation was to learn:- 1. The temperature at which the arsenic is most rapidly expelled; 2. The thoroughness with which it is expelled by prolonged roasting at this temperature; 3. The effect of adding charcoal (a) near the end of the roast and (b) at the beginning of the roast. II. NATURE OF THE ORE. The important ores mined in the Temiskaming deposits are native silver-with small amounts of dyscrasite (Ag6 Sb), argentite (Ag2S), pyrargyrite (Ag3SbS3)-smaltite (CoAs2), chloanthite (NiAs2) and niccolite (NiAs). Mispickel (FeAsS) and cobaltite (CoAsS) also occur in smaller quantities. The average composition of the ore shipped from this district for the first six months of 1905 -was: silver, from 4.1 to 4.8 per cent.; cobalt, from 6.9 to 8.2 per cent ; nickel, from 3 to 4.7 per cent ; and arsenic, from 30.9 to 34.6 per cent. The ore which we treated consists chiefly of smaltite ; In our laboratory-work

Jan 1, 1907

BECAUSE of the impetus given to placer mining since the price of gold was advanced to $35, several types of small dredges have made their appearance, especially in the Lincoln and Oroville areas of California. Some of these are known as "doodle bugs," and have been given considerable publicity, though many believe their performance has been overrated and that complete costs of construction and operation, if known would not put them in so favorable a light. Fig. 1 is a doodle bug owned by E. M. Clark and operated near Lincoln, Calif. It is understood that it was abandoned because of inability to handle deep ground. A similar machine that has been operated-profitably by Comstock Placers is shown in Fig. 2.

Jan 1, 1938

By E. Stamboliadis

Dithiophosphates are reaction products of phosphorous pentasulfide with various organic compounds such as phenols, alcohols, mercaptans, dioalcohols, amines, and nitrides. The products with alcohols are commercially known as "aerofloats" and these are investigated in this presentation. It appears that the formation of insoluble metal dithio phosphates is responsible for their collecting properties with minerals." In this aspect they are very similar to xanthates.3 The solubility of metal dithiophosphates depends on the number of carbon atoms in the organic chain of the corresponding alcohol. An empirical mathematical model is presented here. It allows one to predict the number of carbon atoms necessary to ensure that a certain metal dithiophosphate will form at a selected pH value of the water solution. The Nature of Dithiophosphates Dithiophosphoric acid is the product of the reaction of phosphorus pentasulfide with an alcohol, as shown in the following equation: [P2S3 + 4 ROH - 2 (RO)2 PS2H + H2S (1)] where R stands for a hydrocarbon chain. The acid so produced can be neutralized by a base to produce the corresponding salt as shown in the following: [(RO), PS2H + NH- (RO)2 PS, NH,. (2)] In this aspect dithiophosphates are similar to xanthates, the only difference being the substitution of the tetravalent carbon atom in the xanthate polar group by a pentavalent phosphorus atom in the dithiophosphate group. This difference implies at least two characteristics: (1) that there are two hydrocarbon chains associated with the polar group so that an increase in the number of carbons of the single chain is expected to have a pronounced effect on the flotation properties, and (2) that the bond between the sulfur and the central atom is stronger than in the xanthate group. This probably leads to a decrease in both the polarizability of the electronic cloud of the sulfur and the interaction with cations.3 However, what is lost in the dithiophosphates by having a weak polar group can be gained by an increase in the number of carbons as will be seen later. Taking into account the size of the atoms involved in a dithiophosphate molecule, as listed in Table 1, It is possible to draw an approximate diagram of its structure as shown in [Fig. 1]. It is assumed here that the length of the single hydrocarbon chain is equal to that of the corresponding alcohol. Preparation and Purification Acid dithiophosphates can be prepared, as previously mentioned, in accordance with Eq. 1. The rate of this reaction is too slow at room temperature and can be improved by increasing the temperature to about 60° or 80°C7 or by evacuating the system. In our investigation evacuation was performed by a water aspiration pump. The dithiophosphoric acid so produced is liquid and dissolves in the alcohol. At the end of the reaction the product is filtered from the remaining P2S3; and dissolved in petroleum ether. By blowing anhydrous ammonia gas into the ether phase the ammonium salt forms as a white precipitate and can be sepa-

Jan 1, 1977

By H. D. Wilde

GREAT emphasis is being placed today on petroleum as a source of chemicals. Such prominence is well merited, for rapid strides have been made in developing processes for the conversion of petroleum into synthetic chemical products, which are now being made on a huge scale. These marvelous accomplishments have resulted in some highly optimistic predictions as to what can be expected in the future. Many of these forecasts are well justified, but some writers, especially those contributing to the Sunday supplements and the popular-cience type of publications, have let their imagination run wild and present a rather distorted picture of the possibilities in this field in the postwar period. Commercial manufacture of synthetic organic chemicals had its beginning in England with the establishment of a plant by Sir William Perkin in 1857 for the manufacture of "Aniline Purple" or "Mauve." The preceding year he had discovered in the laboratory how this dyestuff could be made from aniline, one of the many derivatives of coal tar, and he soon made commercial application of his discovery. Influenced largely by his success, organic chemists began research on production of a vast array of synthetic dyestuffs, medicinals, flavors, scents, and explosives. Rapid progress was made and by the turn of the century hundreds of these products were being manufactured. Most of these synthetic chemicals were derived from materials obtained as by-products in the conversion of coal into coke. These by-products are generally referred to as "aromatics" and are obtained by processing coal tar recovered in the coking process, so they are popularly known as "coal-tar chemicals." During the early years of this century, coal-tar chemistry was the wonder of the age, and rightfully so, since the products so made seemed limitless.

Jan 1, 1944

By O. G. Paasche, Yuan-Shou Shen

THERE is a disagreement among the various authors about the exact manner of transformation of ZrCr2. Rostokerl and others2 stated that ZrCr2 had a C-14 (MgZn2) type of structure below 1000°C and a C-15 (MgCu2) type of structure at temperatures above 1000°C. Alisova3 and others4 reached the opposite conclusion and stated that the transformation temperature is close to the melting point of ZrCr2. A literature survey shows that various investigators3'= who homogenized the specimens at a temperature higher than 1000°C have concluded that ZrCr2 had the C-15 structure at room temperature. Meanwhile, Jordan et al.4 reached similar conclusions without annealing the specimen. Other investigators1,2,6,7 who X-rayed the specimens in the as-cast condition without annealing reached different conclusions. The investigation reported herein was conducted with the aim of exploring the exact manner of transformation of ZrCr2 by various heat treatment tests. The alloys for this examination were prepared from iodide-reduced zirconium crystal bars, 99.9 pct purity, and electrolytic chromium, 99.9 pct purity. They were melted in a nonconsumable electrode arc furnace with water-cooled copper crucible in a helium atmosphere. The melting loss of each alloy was less than 1.5 pct by weight. Chemical analysis of a randomly selected specimen indicated that there was a very close agreement between calculated and analyzed compositions. Before being heat-treated each specimen was encapsulated in a vycor or quartz tube inside which an argon atmosphere was maintained at a pressure of lower than 1 atm. In determining the crystal structure of each specimen with a Debye-Scherrer camera, the standard procedure8 for X-ray quality analysis (Hanawalt method) was followed. The different series of heat treatment tests in this investigation are tabulated in Tables I and 11. The tests in Series I, specimens from 1-1 to 1-9, which were similar to Rostoker's experiment1 indicated that the transformation temperature seemed to fall between 870° and 900°C and that the crystal structure of ZrCr2 at lower temperature seemed to be of the C-14 type. However, once the compound is transformed to C-15 type, it is impossible to reverse the transformation back to the C-14 type by first heating the specimen above 900°C and then annealing it slowly below 900°C as shown in Experiments II-1 to II-3. Thus, it appears that the specimen of ZrCr2 will transform from C-14 to C-15 structure when heated above 900°C but will not transform from C-15 to C-14 when annealed slowly passing 900° C even after the extremely slow cooling process such as indicated in the experiment of Specimen II-3. As a valid transformation temperature is a temperature at which the transformation is reversible, therefore the temperature 900°C (or other temperature close to 900°C) is not the transformation temperature for ZrCr2 and the C-14 structure is not the stable structure of ZrCr2 at lower temperatures. The C-14 structure is retained at room temperature because the transformation to C-15 structure is very sluggish and the fast cooling after melting does not allow enough time for the transformation to take place. Additional energy is required to alter the metastable condition of the C-14 structure. The sluggishness of this transformation was again demonstrated through another series of experiments. Four specimens with C-14 structure were taken. Then they were annealed at 900°C but each specimen was soaked for a different period of time, Table 11. X-ray diffraction patterns of this group indicated that the C-14 structure gradually disappeared as the soaking period was lengthened. The figures listed under the column "C-14 Structure, pct" were estimated from the intensity of the d = 2.330 line of the diffraction pattern corresponding to the structure. Notice that the intensity of this line became weaker for longer soaking periods. To determine the transformation temperature of ZrCr2, specimens with C-14 structure (as-cast condition) were annealed at 1300°, 1400°, 1500°, 1550°, and 1600°C, respectively. A final specimen was first heat-treated to 1500°C in order to transform it to C-15 structure, then heat-treated at 1600°C again. From the X-ray analyses of this series of tests, Specimen Nos. III-1 to III-6, it is evident that a transition from C-15 structure at lower temperatures to the C-14 structure occurs at some temperature between 1550° and 1600°C.

Jan 1, 1969

By Leo H. Duriez, James V. Neuman

THE Bayard property of the united States Smelting Refining and Mining Company is in south central Grant County in southwestern New Mexico about fifteen miles east of Silver City and one mile west of Santa Rita. The present holdings cover a belt roughly one mile wide by ten miles long, lying west of, and adjacent to, the holdings of the American Smelting and Refining Co., Kennecott Copper Corp., Empire Zinc Co., and Peru Mining Co. The area extends from the village of Bayard on the south to a point three miles northeast of Fierro. The property is a part of the well-known Central mining district which has been New Mexico's leading copper-zinc producer for many years. The property is segregated into three sections, the Bullfrog, Hanover Bessemer, and the Shingle Canyon sections. Of these, the Bullfrog section covers the area between the towns of Bayard and Hanover and includes the Bullfrog No. 1, Bullfrog No. 2, Slate, Hobo,

Jan 1, 1948

By Willard R. Jillson

Within the last ten years Kentucky has become celebrated for its low-sulfur bituminous coals. Prior to this time, many investigators had discnvered the abundance of this coal but the fact was unknown to the general public until the last extension of Kentucky's mountain railroads' was completed. The coals of. Kentucky are, broadly, separated into two geographic units—the eastern and the western coal fields. On a basis of their sulfur content these coal fields fall into three units, which are indicated on the accompanying map, by numbers, 1, 2, and 3. The area marked 1, the very southeastern part of the state, shows the lowest sulfur, all coals being averaged. In this field the maximum is 1.04 per cent. and the minimum as low as 0.68 per cent.—both averages and not individual analyses, which would of course show much greater variation. Included in this group are the following counties: Lawrence, 0.87 per cent.; Martin, 0.75 per cent.; Johnson, 0.73 per cent.; Magoffin, 0.87 per cent.; Floyd, 0.88 per cent.; Pike, 0.68 per cent.; Knott, 1.04 per cent.; Perry, 0.77 per cent.; Letcher, 0.80 per cent.; Leslie, 0.70 per cent.; Harlan, 0.79 per cent.; Knox, 0.86 per cent.; and Bell, 0.92 per cent. The total average sulfur content for these thirteen counties is 0.82 per cent. Bordering the restricted low-sulfur field of eastern Kentucky is the No. 2 belt (slightly darker), 'which is commonly known as the western border of the eastern coal field. Here the maximum sulfur is 2.91 per cent. and the minimum 1.05 per cent. Again these are averages and not individual analyses. The counties in this group are: Greenup, 2.60 per • cent.; Boyd, 1.67 per cent.; Carter, 1.07 per cent.; Morgan, 1.40 per cent.; Wolfe, 1.83 per cent.; Lee, 2.93 per cent.; Breathitt, 1.85 per cent.; Owsley, 1.09 per cent.; Jackson, 1.06 per cent.; Rockcastle, 2.30 per cent.; Clay, 1.09 per cent.; Laurel, 1.08 per cent.; Pulaski, 2.24 per cent.; Whitley, 1.05 per cent.; McCreary, 1.50 per cent.; and Wayne. The sulfur percentage average for this area including fifteen important counties is 1.65 per cent. In the western Kentucky field, the great increase in the percentage of sulfur is at once apparent. Ohio County with 3.78 per cent. is the highest and Hancock with 2.87 per cent. is the lowest. The percentages by counties is as follows: Hancock, 2.87 per cent.; Henderson, 3.22 per cent.; McLean, 3.27 per cent.; Muhlenberg, 3.31 per cent.; Hopkins,

Jan 1, 1920