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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 Xuling Chen, Zhiyun Ji, Min Gan, Wenqi Li, Xiaohui Fan, Zhiyuan Yu

"Specularite and vanadium-titanomagnetite are difficult to granulate, and with the increase of their proportions, the permeability of sintering bed is deteriorated together with the combustion velocity of fuel for the shortage of air through the sintering bed, which can lower sintering speed and specific production capacity significantly. The biomass fuel has a higher combustion velocity than coke breeze, therefore the productivity of specularite and vanadium-titanomagnetite ore can be improved remarkably by replacing coke breeze partly with biomass fuel .The results showed that, when the proportion of biomass fuel replacing coke is 40%,the sintering speed and specific production capacity of 35% specularite were improved from 19.06mm/min, 1.33 t/(m2·h)to 21.45mm/min, 1.47 t/(m2·h),and that of 55% vanadium-titanomagnetite were improved from 17.23mm/min, 1.11 t/(m2·h)to 22.80mm/min, 1.44 t/(m2·h). As a conclusion, biomass fuel is effective to strengthen sintering of refractory iron ore.IntroductionThe iron and steel industry of our country has achieved significant development in the recent years. In 2010, the output of steel has reached to 0.627 billion tons. The increasing scale of iron and steel has led to rigorous domestic iron ore environment, and the reserves of hematite and magnetite that have superior sintering characteristics are on the decline with continually exploiting and utilizing [1]. Therefore, the RIO (refractory iron ores) SP (specularite) and VT (vanadium-titanomagnetite) have to be applied vastly. However, the quality of sinters can be deteriorated when utilizing RIO in high proportion due to their poor granulation and metallogenic performances [2, 3]. Generally, the ratio of SP is 3~5%,which should not exceed 10% in our country currently [4]. Though high rate of VT is adopted in PZH steel for a long time, the productivity is obviously low compared with normal sintering [5]."

Jan 1, 2012

By Stuart M. Buck, J. H. Bramwell, Edward H. Williams

The Southwest Virginia Improvement Company began operations in the Bluestone Flat-Top coal-field, situated in Tazewell County, Virginia, in the fall of 1881. In May, 1883, the company had built 200 coke-ovens, and by March, 188-1, had 9000 feet of entries, exclusive of air-ways, in the Nelson or Rig coal-bed of this district (which here averages eleven feet in thickness), and had extracted 200,000 tons of coal, representing an area of about twenty acres. About this opening has grown the recently incorporated city of Pocahontas, and the completion of the New River branch of the Norfolk and Western Railroad to this point enabled the company to make large contracts for supplying coal and coke, so that it was deemed necessary, on account of the limited area developed, to work the mine day and night to fill orders. At 1.30 Thursday morning, March 13th, the inhabitants of Pocahontas were awakened by a violent shock, and within a few minutes all knew that the East mine had been the scene of an explosion of so general a nature that, of the 114 men at work, not one had escaped. The daily papers gave more or less distorted accounts of the number of victims, the scenes in and about, the mine, and the probable cause of the disaster. At the request of the company, the President of the American Institute of Mining Engineers appointed the undersigned a committee of three to investigate the matter, and the committee thus constituted presents the following report, accompanied by a copy of the testimony taken daring the investigation, for preservation in the archives of the Institute. Pocahontas was reached on Thursday, April 24th, and left on Friday, May 2d. During this interval the committee made repeated visits to the mine, especially to the points, of most importance, examining it carefully in every part; and summoned a number of witnesses, twenty-six of whom appeared and testified. The mine had been left in the same state as when the bodies were

Jan 1, 1885

By E. Bakhtavar

All parameters influencing the decision for selection of a suitable extraction method were first selected as the base of this study. Then these parameters were categorized in two main groups. The first group of the parameters includes ?geomechanical and inherent characteristics of the dimension stones? such as hardness, RQD, compressive strength, joints plane orientation and spacing, and water content. The second group was named ?technical and economical parameters associated with the investor?s objectives? like for example extraction capacity (production rate), blocks recovery, mechanization, capital investment and operational costs. Finally, the influences of all mentioned parameters on the selection of the most applicable extraction methods have been assessed and discussed.

Jan 1, 2012

Edward Halse, Puerto Berrio, Colombia, So. Amer. (communication to the Secretary*): The Taviche mining-district is generally known as " Taviches," being named from the two villages called respectively San Pedro Taviche and San Jero-nimo Taviche. It is so called by Jose G. Aguilera, in his paper on the Geographical and Geological Distribution of the Mineral Deposits of Mexico;' and in published reports by the late N. W. Rudston Read ;2 and by Juan de Dios Villarello3 The region is a large one, measuring about 24 miles long and 7 miles wide. Dr. Chance, in his interesting paper, tells us very little about the nature of the ores, and, with regard to the geology of the district, contents himself with observing that " the country, as a rule, consists of eruptive rocks; and no evidences of sedimentary strata appear near the mines." The latter part of the above statement is hardly correct. The formation is mainly

Jan 1, 1906

By R. L. Virta

Six companies mined fire clay in Missouri and Ohio during 2004. Production, based on a preliminary survey of the fire clay industry, was estimated to be 398 kt(438,700 st), valued at $9.81 million. This was slightly less than the production and value figures from 2003. Missouri was the leading producer state. It accounted for more than 70 percent of the U.S. production. Consumption Domestic producers sold or used fire clay primarily for refractory applications. This application accounted for 79 percent of the market. Refractory products made using fire clay include firebrick and block, grogs, high-alumina brick and specialties, refractory mortars and mixes, and saggers.

Jan 1, 2005

By N. Arbiter

The theoretical analysis of tumbling mill energetics and performance has largely neglected mill dimensionality, and, in particular, the importance of the length/diameter ratio. This is in spite of the fact that practice varies substantially in this area: geographically, for semi-autogenous and autogenous mills, as between North America and South Africa/Scandinavia; historically, for overflow ball mills, for which the L/D ratio has increased significantly from the earliest small mills to/the largest mills currently. The present study is concerned primarily with the influence of the L/D ratio on the design and operation of overflow ball mills; on the occurrence of the overload phenomenon; and on the limits, if any, it may impose on mill capacities because of critical pulp axial velocity limits. It will be shown that the shape face or is of major importance in this area; and that its adjustment to the extent that this is practical should remove the diameter limitations previously postulated for this mill type.

Jan 1, 1990

By Pierre Gauthier

Is the hydrogen economy of the future just another fish story? Absolutely not! There have been many changes affecting the energy equation over the last 10 years and conditions have changed. In this presentation, we will examine the reasons why, in the very near future, hydrogen production and distribution will be increasingly visible on many industries? radar screens.

May 1, 2007

By D. J. Donaven, Manuel Gomez, W. S. Landers

Bulk density tests were made on a Western U.S. coke oven plant blend to obtain bulk density control data that would be directly transferable to plant practice . Maximum bulk density values were obtained at zero surface moisture . Increase in surface moisture to about 6 percent decreased the bulk density to a minimum value . Increase in the fine grinding of the blend , at constant surface moisture , decreased the bulk density . The effect of oil on bulk density was observed with five oils at concentrations ranging from 1/8 to 1-1 / 2 gallons per ton . Maximum bulk densities were obtained within the 1 / 2- to 1 - gallon - per - ton range . Essentially the same bulk densities were obtained with petrolatum- and nonpetrolatum- containing oils . Storage effects were observed on samples tested at selected intervals from 0 to 56 days . No significant change in bulk density took place if no surface moisture was lost during storage .

Jan 1, 1964

NEW, MEMBERS The following list comprises the names of those persons who became members during the period July 10, 1916; to July 31, 1916: BOYD, ROBERT RUSSELL Supt:,-Arizona -Commercial Min Co., Globe, .Ariz. BRADLEY, HENRY FRANKLIN, Chem, American Smelt & Ref. Co. Murray,:Utah: BROWN, THOMAS ELLIS, JR..:'. L .:.::..55 Hill, St;; Morristown, N. J. CARY, WEBSTER P., Expert Operator,-General Engineering. Co:, Salt Lake City, Utah. CLARK, ALONZO WEBSTER 3223_ Scottwood Ave., Toledo, Ohio. CORP, CLIFFORD Old Dominion Copper Min. & Smelt. 60., Globe, Ariz. CROMBIE, W. RANSOM, Min. Engr Detroit Copper Min. Co., Morenci, Ariz. DELANEY, EUGENE A., Chief Engr., Berwind-White. Coal Mining -Co., Windber, Pa ELBELT, WILLIAM HENRY, Dept. Foreman., Chino Copper Co., Hurley, N. Mex. FOSTER, L. JULIO, Mgr., Minas i Fundicion ; ?La Junta," San Bernardo, Chile, South America. GASKILL, JAMES PHILLIPS, Genl. Mgr.,.Ajo Cons. Copper Co., Ajo, Ariz., via Gila, Ariz. .

Jan 9, 1916

By Ivan Imris

The common problem of new and conventional technology of copper production is the copper losses in the slags, which may be divided into mechanical and physico-chemical losses. In the first group can be included particles of mechanically entrained or floated unsedimented matte particles which coexist with slag. On the other hand, the physico-chemical losses are caused by solubility of copper in the slag in the form of sulphide and oxide. The copper losses in the slags from different processes has been predicted by calculation from thermodynamic data and compared with those determined by microscopic examination and quantitative electron microprobe analysis. Depending on the forms of copper losses in the slag the reduction of copper losses in the slag or the slag cleaning process could be suggested.

Jan 1, 2003

By George J. Tamara

The urban environment presents special challenges for the design and construction of earth retention systems. Complications arising from difficult subsurface conditions are compounded by the presence of urban infrastructure and existing and prior construction. The proximity of adjacent structures as well as intense prior use can cause special concerns including the potential for archeological artifacts or contaminated ground or ground water. Utilities and structures may be particularly vulnerable to the effects of ground movement, dewatering and vibrations. Difficulty of access, congestion and limited work areas may severely restrict means and methods of construction. Dewatering may be limited or prohibited because of concerns for disposal of clean or contaminated water, depletion of aquifers, drawing of contaminants to the site or dewatering induced settlements.

Jan 1, 2003

Alexander Forsyth, Southport, Me. (communication to the Secretary): In Mr. Irving's able and interesting paper he describes minutely the appearance of the wolframite and its association with the refractory siliceous gold-ore. He also describes this gold-ore, but fails to mention the important pockets of metallic gold found in the Lead City occurrence of it. I use the term " metallic " in preference to the more usual " free," for it has been found that this gold is not easily amalgamated. Metallic gold is comparatively rare in the refractory siliceous gold-ores of the Black Hills; hence its occurrence in considerable amounts in the Lead City wolframite district deserves notice. I possess a beautiful specimen from the Harrison mine. It is a lump of drusy, granular ore, about 6 in. in diameter. The gold .is " shot" through it in large and small pin-heads; and in two specially oxidized areas, each about 11/2 in. in diameter, it is peppered full. The famous " Grantz strike," made in the Lead City wolframite locality, produced many beautiful gold specimens. This district affords an excellent example of the repeated discovery of new mineral values upon old ground. By reason of its proximity to the Homestake vein, this wolframite deposit was inevitably traversed many times by experienced geologists, mineralogists and mining engineers, who evidently must have thrown aside, with no thought of wolframite, the lumps of " black iron " lying about. I have the admission of an able geologist that, six months before the wolframite was discovered, he visited some of the very mines where it occurred, and passed it by as magnetic iron-ore. At the time of the discovery, the mineral was scattered over the gold-mine dumps in no small quantities, having been culled as worthless out of the gold-ore. It remained for

Jan 1, 1902

By A. Dienenthal

"The casthouse floor has always been one of the most dangerous working places on a blast furnace or a ferro-alloy/nonferrous furnace. Apart from working in an atmosphere including toxic gases, fumes, and dust, the workers have to perform hard and heavy manual work close to runners and ladles filled with hot liquid metal and slag.Before the invention and installation of tapping equipment the tap-holes were opened and closed manually. Opening was done by means of steel bars and sledgehammers, whereas the tap-hole was closed by repeatedly ramming small amounts of clay or refractory material into the tap-hole, again with the help of long, heavy bars. In addition, on blast furnaces the blast had to be stopped, since it was impossible to close the tap-hole properly against the blast furnace pressure. This stoppage of the blast resulted in regular losses of production. Around 1900 a major change in technology occurred. Samuel W. Vaughen, superintendent of the blast furnace department of the Cambria Iron company at Johnstown, Pennsylvania (USA), invented the first clay gun in 1895 (Wiley, 1896) (Figure 1)."

Jan 1, 2014

By Alexander Malahoff

A shipboard research system capable of operating in waters of up to 2,000 meters has been designed and implemented by the Hawai'i Undersea Research Laboratory (HURL) of the University of Hawai'i. It uses a remotely-operated ocean bottom survey camera system, an ROV, the Pisces V submersible, and a submersible emergency recovery system, all aboard the 222- foot R/V Ka'imikai-o-Kanaloa. All systems are operated from the stern of Ka'imikai with a mounted Caley telearm and articulated A-frame system. The system was designed for multipurpose use of the ship for launch and recovery of the Pisces V submersible on a lift recovery line (with or without diver assistance), or night-time operations with an electro-optical cable using either the HURL ocean floor sidescan or photo and video system operated at 10 meters above the ocean floor. The 1.14-inch diameter cable is also used to operate an ROV system. The garage/ROV system can also act as a submersible rescue system with a submersible lift capability. The ship is equipped with a SeaBeam and shallow penetration sediment profiling systems. This integrated system approach to deep ocean floor research will make it possible for HURL to carry out research pro- grams on seamount ocean resources and ocean chemistry and climate in Hawai'i and the equatorial Pacific.

Jan 1, 1995

By S Bankoff

INCE1 proposed that electrostatic attraction between oppositely charged particles was responsible for slime-coating. Del Giudice2 postulated the metathetic formation of a cementing compound. Wark3 suggested that prevention of slime-coating was related to peptization of the slime. [ ] In the experiments of Table I the technique employed was essentially that of del Giudice, with the difference that the particle was examined under a film of water rather than dry.4 In general, the polished particle was agitated for 2 min. in a pulp consisting of 12.5 grams of the slime (-200 mesh) and 50 c.c. of distilled water, washed in three baths of distilled water, and examined at 220 diameters with the Leitz Ultropak. Observations of Brownian movement were made at 850 diameters with dark-field illumination. Several of these experiments do not jibe with the metathesis theory. According to published solubilities,5,6 the lead salts of the anions in experiments c through g are more insoluble than lead carbonate, there- [ ] fore should prevent the formation of lead carbonate on the galena surface. In experiment i the calcium oxalate, which presumably was on the calcite surfaces, should have permitted the formation of a lead carbonate cement by virtue of its greater solubility. Experiments j through m show that the addition of lime accelerates the deposition of quartz onto a galena surface. The writer is unable to postulate a satisfactory cementing compound, according to the metathesis theory, to explain this effect. These experiments led to the conclusion that the metathetic formation of a cement-

Jan 1, 1941

By S.G. Bankoff

Ince1 proposed that electrostatic attraction between oppositely charged particles was responsible for slime-coating. Del Giudice2 postulated the metathetic formation of a cementing compound. Wark3 suggested that prevention of slime-coating was related to peptization of the slime. In the experiments of Table I the technique employed was essentially that of del Giudice, with the difference that the particle was examined under a film of water rather than dry.4 In general, the polished particle was agitated for 2 min. in a pulp consisting of 12.5 grams of the slime (—200 mesh) and 50 C.C. of distilled water, washed in three baths of distilled water, and examined at 220 diameters with the Leitz Ultropak. Observations of Brownian movement were made at 850 diameters with dark-field illumination. Several of these experiments do not jibe with the metathesis theory. According to published solubilities,5,6 the lead salts of the anions in experiments c through g are more insoluble than lead carbonate, there- fore should prevent the formation of lead carbonate on the galena surface. In experiment i the calcium oxalate, which precumably was on the calcite surfaces, should have permitted the formation of a lead carbonate cement by virtue of its greater solubility. Experiments j through m show that the addition of lime accelerates the deposition of quartz onto a galena surface. The writer is unable to postulate a satisfactory cementing compound, according to the metathesis theory, to explain this effect. These experiments led to the conclusion that the metathetic formation of a cement-

Jan 1, 1943

By S. G. Bankoff

Ince1 proposed that electrostatic attraction between oppositely charged particles was responsible for slime-coating. Del Giudice2 postulated the metathetic formation of a cementing compound. Wark3 suggested that prevention of slime-coating was related to peptization of the slime. In the experiments of Table I the technique employed was essentially that of del Giudice, with the difference that the particle was examined under a film of water rather than dry.4 In general, the polished particle was agitated for 2 min. in a pulp consisting of 12.5 grams of the slime (—200 mesh) and 50 C.C. of distilled water, washed in three baths of distilled water, and examined at 220 diameters with the Leitz Ultropak. Observations of Brownian movement were made at 850 diameters with dark-field illumination. Several of these experiments do not jibe with the metathesis theory. According to published solubilities,5,6 the lead salts of the anions in experiments c through g are more insoluble than lead carbonate, there- fore should prevent the formation of lead carbonate on the galena surface. In experiment i the calcium oxalate, which precumably was on the calcite surfaces, should have permitted the formation of a lead carbonate cement by virtue of its greater solubility. Experiments j through m show that the addition of lime accelerates the deposition of quartz onto a galena surface. The writer is unable to postulate a satisfactory cementing compound, according to the metathesis theory, to explain this effect. These experiments led to the conclusion that the metathetic formation of a cement-

Jan 1, 1943

By L. A. Neumeier

A refinement of the tungsten-cobalt phase diagram is presented for compositions to 85 at. pct cobalt and for temperatures to the solidus. Preparation of alloys by powder metallurgy methods is described, and the results of studies made by a combination of techniques involving microscopy, X-ray diffraction, thermal analysis, and dilatometry are discussed. The existence of u-W6Co7 is confirmed (rhombohedral D85 structure). The W6Co7 phase forms periectically at 1,685'115° C by reaction of liquid with primary W; the peritectic melt is at 71 at. pct cobalt. The homogeneity range of u-W6Co7 extends to both sides of the ideal stoichiometric ratio, through a compositional range of about 5 at. pct. The compositional limits for u-W6Co7 vary slightly below 1,471°±5° C, the temperature of the eutectic reaction forming u-W6Co7 plus a. The eutectic composition is at 79 at, pct cobalt. The existence of WCo3 is confirmed (hexagonal D019 structure). WCo3 forms peritectoidally at 1,093°±5° C by reaction between a and u-W6Co7 and exists over a narrow homogeneity range of 0.5 to 0.6 at. pct. The solid solubility of cobalt in tungsten is low (maximum 0,9 at, pct cobalt) and results in contraction of the tungsten lattice. Tungsten is extensively soluble in a-Co at higher temperatures; the a-Co lattice is expanded by the presence of tungsten in solid solution. There was no indication of the formation of a o-phase nor of any intermediate phases other than WeCo7 and WCo3. The WeCo7 and WCo3 phases are compared with similar phases in other systems.

Jan 1, 1967

By Seth C. Schaefer

[As part of the Bureau of Mines effort to provide thermodynamic data for advancement of mineral resources technology, the standard Gibbs energies of formation (?G°f) of MnS (manganese sulfide) and Fe0.9 S (pyrrhotite) were investigated with a high-temperature galvanic cell employing stabilized Zr02 (zirconia) as the electrolyte. Potential measurements were obtained for the cell Pt, MnS, MnO, S02 (g, 1 atm)//Zr02//02(g, 0.0114 atm), Pt with the overall cell reaction MnS (s) + 1.5 02 (g, 0.0114 atm) = MnO (s) + S02 (g) . (1) These results give the standard Gibbs energy of formation of MnS for the reaction Mn (s) + 0.552 (g) = MnS (s) (2) ?G°f = -66.487 + 15.19 x 10-3T±0.207 kcal/mole (896.4 - 1,208.1 K) (3) where temperature (T) is expressed in kelvins. Similar measurements were obtained for the cell Pt, FeO .9S, Fe304 , S02 (g, 1 atm) //Zr02//02 (g, 0.0114 atm) , Pt with the overall cell reaction 10/3 FeO .9 S (s) + 16/3 02 (g, 0.0114 atm) = Fe.,04 (s) +10/3 S02 (g). (4) These results yield the standard Gibbs energy of formation for the reaction 0.9 Fe (s) + 0.5 S2 (g) = Fe0.9 S (s) (5) ?G°f = -35.229 + 12.67 x 1073T+-0.104 kcal/mole (839.5 - 1,086.6 K). (6) A third-law analysis of MnS data yields a standard enthalpy of formation (AH°f) for the reaction Mn (s) + S (rh) = MnS (s) (7) ?H°f298 = -51.16±0.21 kcal/mole (8) A similar third-law analysis for Fe0.9S data yields a ?29°f298 for the reaction 0.9 Fe(s) + S(rh) = FeO .9S(s) (9) ?HO\°f298 = -24.01±_0.15 kcal/mole. (10) ]

Jan 1, 1980