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By R. J. Leary

Iron and steel scrap has accounted for 45 to 50 percent of the metallics used by the steel industry. In an electric furnace which utilizes a 100-percent cold charge consisting of about 99 percent scrap and 1 percent pig iron, sensible heat from molten pig iron is not present as it is when hot metal is charged to open hearths and converters. A study of means for more efficient utilization of iron and steel scrap in steelmaking indicated that the time and fuel requirements to melt scrap were important cost factors, particularly in arc-furnace steelmaking. A process to preheat scrap economically prior to charging into the arc furnace has been developed, utilizing efficiently the heat from combustion of fossil fuels as a substitute for electric-arc heating in the initial stage of arc-furnace steelmaking. Scrap is loaded into a portable vertical cylindrical furnace body that is open at the top and has a perforated dropout door at the bottom. In the heating operation, the furnace body containing scrap is placed upon a hollow base connected to a flue, and then the burner and combustion-chamber unit is lowered on top of the furnace body. The stream of hot-combustion products flows down through the bed of scrap imparting heat to it, and the cooled gases exhaust through the flue. After the heating operation the furnace body containing hot scrap is transported to the arc furnace for charging. Thus, the furnace body serves as a charging bucket for top-charged arc furnaces, enabling this preheating process to be integrated into existing material-handling patterns in many arc-furnace plants.

Jan 1, 1961

By V. T. Dow

In April 1957 the Bureau of Mines instituted a reconnaissance of titanium-and zirconium-bearing heavy sandstone deposits in the Four-State area of Utah, Wyoming, New Mexico, and Colorado. This report summarizes the study. Eighty-two deposits or groups of deposits, containing an estimated 27,920,000 tons of titaniferous sandstone, were examined in the Four-State area; 16 in southern Utah, 19 in Wyoming, 33 in New Mexico, and 14 in southwestern Colorado. The 16 deposits examined in Utah contain an estimated 1,043,000 tons with an average grade of 17.98 percent TiO2, 5.67 percent ZrO2, 20.98 percent Fe, and 0.09 percent equivalent Th02. The 19 deposits investigated in Wyoming are estimated to contain 21,873,000 tons of titaniferous sandstone having a weighted grade of 5.22 percent 702, 0.55 percent ZrO2, 24.8 percent Fe, and 0.01 percent equivalent Th02.

Jan 1, 1961

By J. W. Rutter, K. T. Aust

Observations are presented of the formation of annealing twins during the growth of a recrystallized grain into a striated, melt-grown crystal of high-purity lead. The formation of an annealing twin resulted in replacement of the original migrating boundary by a large-angle grain boundary of the caincidence-site type or by a near-twin boundary. The results support the Fullman-Fisher theory of annealing twins and demonstrate the usefulness of the coincidence-site model. FULLMAN and Fisher1 have advanced the following theory to account for the formation of annealing twins during grain growth. Whenever a grain A grows into a matrix of grains S1 and S2, a twin A' of grain A may form, as shown in Fig. 1, if the following energetic condition is satisfied: where "E" and "a" refer to the specific interfacial free energy and the area, respectively, of the boundaries indicated by the subscripts. In effect, the twinned grain will persist when the energy of the boundary between the twin(A') and the matrix grain (S, or S,) is less than that of the boundary between the original growing grain (A) and the matrix grain by an amount which exceeds the energy of the coherent twin boundary between A and A'. Experimental observations on the changes in grain boundary free energy accompanying the formation of twins1 are in agreement with the theory outlined in Eq.[l]. Direct observations of the formation of annealing twins at moving grain corners1"3 and the depend-

Jan 1, 1961

An investigation into the causes of variable sulphur content in blast furnace metal produced at No. 4 blast furnace at the Port Kembla works of Australian Iron and Steel Pty. Ltd. was carried out. Theprogramme included an extended and detailed experimental study of a great number of the operating variables of the furnace, on a cast-bycast or four-hourly basis, over fourteen days.Possible causes of the variation were found in irregular operation due to sinter variability, and it was also clearly shown that slag conditions were most important in controlling sulphur contents of pigiron. Some decrease in sulphur variability was achieved, arising partly from this investigation, and it is hoped to try magnesia additions to modify slag conditions for better desulphurizing.INTRODUCTIONSulphur in pig iron is a problem common to many blast furnace operators throughout the world, but the direct causes and means of overcoming them are functions of the available raw materials, and are hence more particular to each plant and its operating practice. Sulphur in hot metal influences the steel-making operations, the rolling operations and the quality of the finished steel. The main problem associated with high sulphur in steel is "hot shortness", which leads to cracking of ingots and billets in rolling, to poor surface finish and to poor welding properties in the finished steel. On the other hand, sulphur is sometimes a desired additive to steel in order to promote free machining properties.Normal means of controlling sulphur A small degree of control of sulphur in steel is available to open hearth operators by alteration of slag volumes and basicity, but any large degree' of sulphur elimination is...

Jan 1, 1961

By Alla D. Mah

No experimental heat-of-formation value has been reported in the literature for cerium sesquioxide. The heat of formation of bismuth sesquioxide has not been determined in recent years, and the older value was subject to large uncertainty. Accordingly, the heats of combustion of cerium sesquioxide and bismuth metal were measured by the Federal Bureau of Mines. The heats of formation were: ?H°298.15 = -427.01 ± 0.70 kcal. /mole for cerium sesquioxide and ?H°298.15 = -137.16 ± 0.30 kcal./mole for bismuth sesquioxide. The free energy of formation was estimated for cerium sesquioxide and accurately calculated for bismuth sesquioxide. The data were compared with values in the literature.

Jan 1, 1961

By L. Adler

Longwall caving, one of the most economical and attractive mining methods, is yet one of the most difficult and hazardous.1 This dualism is inherent in a method which manipulates the mine supports themselves to aid in excavation. The difficulty is further compounded by the lack of an analytical method to predict and control results. This paper is intended to meet this need by providing a first approximation to the mechanics involved. The analysis will be limited to materials which are linear-elastic, homogeneous and isotropic. The rock structure is assumed to consist of beds of uniform thickness with no interbed bonding.2 Consequently, the mine roof can be likened to a beam, in which the action characteristic of longwall caving is the controlled deflection of the barrier supports. This deflection causes load to be intentionally transferred from these barrier props to the working face.3 Two of the requirements of this method, shared in common with other mining methods, are the provision of (1) adequate and (2) safe working space. The third requirement is the one characteristic of longwall caving and is somewhat in conflict with the second; (3) the development of near-failure static loads at the face. Requirement (1) is handled by spacing the barrier props sufficiently far from the working face for efficient operation. Requirement (2) limits the static stresses in the structure to predetermined allowable values. This means that it is not desirable to induce a maximum load on the working face as requirement (3) may imply. Such a condition could produce collapse in the whole structure. It is the purpose of the undercut to limit the depth, and thereby control the failure of the face. Therefore, requirement (3) really means the development of an optimum, not maximum, load which, in conjunction with undercutting, produces failure at the working face, with minimum powder consumption. Stress analysis requires an exact delineation of the structure and loads. The structure will be defined as the immediate roof and its supports. Since the roof is severed at the caving line, the supports reduce to the barrier props and the working face, as shown in Fig. 1. The mechanics of failure within the working face itself are complex and beyond the scope of this study, since the face represents a typical mine invert structure.4 However, this lack can be made good by the judicious collection of field data. The primary load on the structure is its own weight or body load which can be considered uniformly distributed over its upper surface. Additional loading occurs due to interference of overbeds with the structure. Wherever this occurs, the effect can be approximated by a load uniformly distributed on the upper surface of the structure.5 When this interference is intermittent, as with a much thicker overbed, the elastic curve for the overbed is superimposed on that for the structure and the extent of interference noted, as Fig. 2 shows. However, for simplicity, this study will ignore such intermittent loads without impairing the generality of approach. Consequently, the free-body diagram is that of a uniformly loaded cantilever beam with an inter-mediate support, as shown in Fig. 3. For convenience of analysis, the diagram will be divided just to the

Jan 1, 1961

By G. W. Govier

The origin and limitations of the conventional and empirical equation for the interpretation of the results of back pressure tests on gas wells are discussed. Difficulties in data interpretation arise from many causes, including Jack of flow stabilization, uncertainties in connection with the friction calculation, and the effect of turbulence near the sand face in the reservoir. A procedure is developed to ac-count for the turbulence effect. This is based upon the theoretical equation for laminar steady state flow and current knowledge of turbulent steady state flow. The procedure involves the expression of the equation for combined laminar-turbulent steady state flow in terms of a turbulence contribution factor. This factor. is shown to be dependent mainly upon the flow rate per unit of pay thickness and the reservoir permeability. The method of interpretation permits the use of judgment based upon the theory and present day under-standing of laminar-turbulent flow and is considered an improved method

Jan 1, 1961

By John Chipman

THE equilibrium between titanium in liquid iron and titanium oxides has been studied by Hadley and Derge.' They have shown that a minimum occurs in the oxygen content of the metal between 0.1 and 1.0 pct Ti, but its exact level was not fixed. The oxide phase in this minimum range was principally TiO, containing some iron oxide. On the other hand, for concentrations above 5 pct Ti the oxide phase was TiO and the oxygen content of the metal increased rapidly with increasing titanium content. From their observations and the free energy of Ti0 and TiOz reported by Kelley and ah,' it is possible to derive approximate values for the activity coefficients of titanium and oxygen in liquid iron-titanium alloys and the conditions for equilibrium in steel deoxidation. Neglecting possible departures from the stoichio-metric composition, the condition of equilibrium with Ti0 may be expressed as follows: TiO= Ti_ + C) log K = log NTl + log [% O] + log yTi + log fQ Here as a matter of convenience the titanium concentration is expressed in mol fraction while that of oxygen is in weight percent. The activity coefficients are yTi and fo. The value of log fo approaches zero as the concentration of titanium approaches zero, while that of log yTi approaches a limiting value of In Fig. 1 the sum of log NTi + log [% 0] is plotted for mol fractions of titanium between 0.05 and 0.50. The smooth extrapolation gives a value of —4.15 which corresponds to log K — log y:i . We therefore have the equation: According to the data of Kelley and Mah,' the free energy of formation of Ti0 at 1900°K is -82,400 cal. The free energy of solution of half a mol of oxygen in iron, taking 1 pct 0 as the standard state, is -29,300 cal. From these we write: From these equations the activity coefficient of titanium at infinite dilution in iron is found to have a value of 0.011 or log y°. = -1.96. This is only an approximate value but is certainly better than the estimated 0.05 in Basic Open Hearth Steelmaking To obtain approximate values for the activity coefficient at intermediate concentrations, it is as- sumed that log yTi(l is constant and equal to -1.96. This corresponds to a value of E;: = 3 In yTi/aNTi = 9.0 which is not unreasonable We now have the value for the activity of titanium and the percentage of oxygen in equilibrium with TiO. It is therefore a simple matter to calculate the activity coefficient of oxygen which is shown in Fig. 2. The effect of titanium is rather large, being comparable to that of vanadium, but not so large as has been reported for aluminum. The slope of the line at low concentrations corresponds to E: = aln yo/ aNTi=-0.37. At concentrations below 1 pct Ti the deoxidation constant and oxygen content for equilibrium with TiO, can be calculated from the foregoing data and the free energy of formation of TiO,, which according to Kelley and Mah is -144,600 cal at 1900°K. The free energy of solution of oxygen has been given; that of Ti to form a dilute solution with 1 pct Ti as the standard state is RT ln (0.5585 y:i/47.9) = -34,800 cal. From these data we find (for concentrations in wt pct): TiO, = Ti + 2 -0; hFTgO0= + 51,200 cal log if =-5.89 The interaction coefficients, concentrations being expressed as wt pct, are e;: = alogfTi/a[% Ti] = +0.048 and e:' = a logfo,/a[ojTi] = -0.187. The calculation gives the following results which, in view of the impurity of the oxide phase, must be regarded as approximate:

Jan 1, 1961

By J. E. Miller

This paper reports experimental determinations by the Bureau of Mines of compressibility factors to 4,000 pounds per square inch absolute (p.s.i.a.) for helium at temperatures from -10° to 130° F. and for 16 helium-nitrogen mixtures at 70° F. This information is needed for computing accurate discharge volumes and is necessary for determining an average-density value for use in orifice-meter formulas. In thermodynamic calculations, several functions of the compressibility factor with pressure and temperature are required. The data in the original publications (6, 8)5 of this study have been reexamined and have been given a more comprehensive treatment. The recalculated compressibility factors are higher by approximately 0.2 percent because in the earlier work a linear relationship between the compressibility factor of helium and pressure was assumed.

Jan 1, 1961

By C. S. Finney, John Mitchell

The decline of the beehive coking industry was inevitable, but it had filled the needs and economy of its day. A beehive plant required neither large capital investment to construct nor an elaborate and expensive organization to run. The ovens were built near mines from which large quantities of easily-won coking coal of excellent quality could be taken, and handling and preparation costs were thus at a minimum. The beehive process undoubtedly produced fine metallurgical coke, and low yields were considered to be the price that had to be paid for a superior product. Few could have foreseen that the time would come when lack of satisfactory coking coal would force most of the beehive plants in the Connellsville district, for example, to stay idle; and if there were those like Belden who cried out against the enormous waste which was leading to exhaustion of the country's best coking coals, there were many more to whom conservation was almost the negation of what has since become popularly known as the spirit of free enterprise. As for the recovery of such by-products as tar, light oil, and ammonia compounds, throughout much of the beehive era there was little economic incentive to move away from a tried and trusted carbonization method simply to produce materials for which no great market existed anyway. With the twentieth century came changes that were to bring an end to the predominance of beehive coking. Large new steel-producing corporations were formed whose operations were integrated to include not only the making and marketing of iron or steel but also the mining of coal and ore from their own properties, the quarrying of their own limestone and dolomite, and the production of coke at or near their blast furnaces. As the steel industry expanded so did the geographic center of production move westward. By 1893 it had moved from east-central to western Pennsylvania, and by 1923 was located to the north and center of Ohio. This western movement led, of course, to the utilization of the poorer quality coking coals of Illinois, Indiana and Ohio. These coals could not be carbonized to produce an acceptable metallurgical coke in the beehive oven, but could be so treated in the by-product oven. By World War I the technological and economic limitations of the beehive oven as a coke producer were being widely recognized. After the war the number of beehive ovens in existence dropped steadily to a low of 10,816 in 1938, in which year the industry produced only some 800,000 tons of coke out of a total US production of 32.5 million tons. The demands of the second World War led to the rehabilitation of many ovens which had not been used for years, and in 1941, for the first time since 1929, beehive ovens produced more than 10 pet of the country's total coke output. Production fell off again after 1945, but the war in Korea made it necessary once more to utilize all available carbonizing capacity so that by 1951 there were 20,458 ovens with an annual coke capacity of 13.9 million tons in existence. Since that time the iron and steel industry has expanded and modernized its by-product coking facilities, and by the end of 1958 only 64 pet of the 8682 beehive ovens still left were capable of being operated. Because beehive ovens are cheap and easy to build and can be closed down and started up with no great damage to brickwork or refractory, it is likely that they will always have a place, albeit a minor one, in the coking industry. The future role of the beehive oven would seem to be precisely that predicted forty years ago by R. S. McBride of the US Geological Survey. Writing with considerable prescience, McBride declared: "A by-product coke-oven plant requires an elaborate organization and a large investment per unit of coke produced per day. Operators of such plants cannot afford to close them down and start them up with every minor change in market conditions. It is not altogether a question whether beehive coke or by-product coke can be produced at a lower price at any particular time. Often by-product coke will be produced and sold at less than cost simply in order to maintain an organization and give some measure of financial return upon the large investment, which would otherwise

Jan 1, 1961

By Stephan I. Zajac, Roger A. Blais, John B. Stubbins

THE iron deposits of central Labrador occur within a relatively small area, herein called the Knob Lake Iron Range, in which a northwest-trending series of low hills and ridges defines the height-of-land at the boundary between provinces of Quebec and Newfound-land. Approximately two-thirds of the deposits are in Quebec and the remainder in Labrador, with several deposits straddling the inter-provincial boundary. These deposits are being exploited in open-pit mines by the Iron Ore Company of Canada centered at Schefferville, Quebec. Since 1954 this company has produced more than 56 million tons of iron ore to become Canada's leading iron ore producer. With indicated reserves of more than 375 million tons of direct-shipping ore and large tonnages of iron formation amenable to beneficiation, this mining district is assured of a long life. This paper describes the Knob Lake iron ores and their geological settings and stresses the features that lead to a better understanding of their origin. The

Jan 1, 1961

By J. A. Boyle

In the Frick District of U, So Steel Corporation, we have had more than 37 years of experience in the use of multiple-fan ventilation systems, in our coal mines. In our Colonial field, with a long belt installation, we have mined 85 million tons of coal with the use of the multiple fan system of ventilation. In our Palmer field, with the use of the same arrangement, we have mined 90 million tons of coal--a total of 175 million tons without one accident attributable to improper mine ventilation. The same system, fundamentally, has been installed in our expanding Robena operations and at its present stage of development we are using eight fans to ventilate this area. To date we have mined 55 million tons of coal with very encouraging results and again without any accidents attributable to ventilation.

Jan 1, 1961

By A. W. Ruff

In the last ten years large gains have been made in the field of blasting. These gains have been both in the theoretical and in the practical application of explosives. One of the most publicized changes in the practical application of commercial explosives is the now-prevalent use of ammonium nitrate and fuel oil. The new water-compatible mixture of ammonium nitrate and TNT should also have a large field of application. Most of the theoretical gains have been concerned with the actual rock breakage obtained with explosives. In the last ten years, large gains have been made in the field of blasting. These gains have been both in the theoretical and in the practical application of explosives. One of the most publicized changes in the practical application of commercial explosives is the now prevalent use of ammonium nitrate and fuel oil. The new water-compatible mixture of ammonium nitrate and TNT should also have a large field of application. Most of the theoretical gains have been concerned with the actual rock breakage obtained with explosives. EXPANDING-GAS-BUBBLE THEORY There has been an outstanding change in the conception of how an explosive produces rock failure. The early theory which explained rock breakage was correct for some of the first force-producing agents such as quicklime. When a drillhole was filled with quicklime and water added, the material expanded and steam was generated. The expanding material and the steam exerted a slowly increasing pressure on the sides of the drillhole. The force broke the rock by splitting. Because a great quantity of gas was produced by the deflagration of gunpowder, the same process of the gas pressure splitting the rock was assumed to take place. Even after 80 years of use, the rock-breaking action of all high explosives was thought to be caused entirely by the expanding gas bubble which tore and split the rock. Fig. 1 shows a vertical section through an exploding spherical charge of high explosive. It illustrates the early theory which attributed the entire breakage to the expanding gas bubble. The basic idea of this theory is that the breakage started at the explosive charge and progressed toward the free face. REFLECTED-WAVE THEORY me expanding-gas- bubble theory has gradually been replaced by the reflected-wave theory. The reflected-wave theory explains rock failure by explosives in the following manner: The enormously high gas pressure in the drillhole produces fracturing of the rock on the sides of the drillhole. The fracturing around a 1 1/2-in. diam drillhole is usually confined to an area with about a 6-in. diam. In the fractured area, the pressure of the gas is reduced until the force on the walls is no longer capable of fracturing the rock. Although the gas pressure does not continue to fracture the rock, the pressure imposes a high impact stress on the wall rock. In addition, a pressure or seismic pulse is produced in the rock. The pulse is probably entirely a compression pulse when originally produced in the rock. But, with distance, part of the energy of the compression pulse is transformed into a tension pulse which follows the compression pulse. The explosive charges and burdens used in conventional mine blasting are such that the tension pulse of the original wave is probably too small to be considered in a practical evaluation of the theory. The compression pulse is transmitted through the rock with no associated fracturing.

Jan 1, 1961

By Robert K. Koch

The reactions of alumina and alumina monohydrate with wet hydrogen fluoride gas were studied by the Federal Bureau of Mines to determine the feasibility of producing commercial-grade aluminum fluoride from offgases generated by pyrohydrolysis of siliceous fluorspars. The test results showed than an aluminum fluoride reactor operating at maximum efficiency could retain 96 percent of the fluorine contained in off-gases generated by pyrohydrolysis of siliceous fluorspar. The requirements are a reactor temperature of 200° C. and a reactor entrance gas containing 5 mole-percent hydrogen fluoride. Partial pressure equilibrium constants were determined for the reaction of alumina monohydrate and wet hydrogen fluoride gas from 200° to 350° C. and for the reaction of alumina and wet hydrogen fluoride gas from 350° to 700° C. Both reactions are reversible, and they proceed in directions that are dependent upon the temperature and the relative HF:H2O concentration. Logarithms of the equilibrium constants were used to plot the reaction isobars; these can be used to calculate the theoretical maximum efficiency of a reactor processing wet hydrogen fluoride gas between 200° and 700° C. The theoretical maximum efficiency decreases with increasing temperature.

Jan 1, 1961

By D. Bienstock

In connection with air-pollution studies, the Bureau of Mines is cooperating with the U.S. Public Health Service in investigating the use of solids for removing sulfur dioxide in concentrations of less than 0.5 percent from combustion and waste gases. Removal of sulfur dioxide at flue-gas tempera¬tures would no longer result in the cooling of scrubbed gas, which is inherent to liquid scrubbing processes used exclusively in industry today. Results are reported of extensive investigation, using metallic oxides as absorbents, adsorbents, and oxidation catalysts at 130° and 330° C. (temperatures at which flue gas may be treated in powerplant practice). The most active absorbents tested were the oxides of manganese, cobalt, copper, and alkalized alumina; 23 to 33 grams of sulfur dioxidn were removed by 100 grams of absorbent at 130° C., while scrubbing more than 90 percent of the sulfur dioxide from a simulated flue gas, and 19 to 61 grams of sulfur dioxide were removed at 330° C. A more detailed study is reported on absorption and regeneration, using manganese oxides and alkalized alumina. Adsorption of sulfur dioxide on activated carbons and molecular sieves at elevated temperatures is considerably less efficient than removal by absorption--a maximum of 7 to 8 grams of sulfur dioxide could be removed with 100 grams of adsorbent at 130° C. A potash-promoted vanadium pentoxide is effective in converting sulfur dioxide to trioxide; complete conversion in a simulated flue gas containing 0.35 percent sulfur dioxide was obtained at 365° C. Pilot-plant and cost studies are being made by the Bureau to determine the economic feasibility of removing on an industrial scale the sulfur dioxide present in gases in low concentrations.

Jan 1, 1961

By W. R. Huff

This report describes the development and operation by the Bureau of Mines of a pilot plant designed for using high-volatile A bituminous coal-in-water suspensions as a source of preheated coal and superheated steam in the pressure gasification of coal with oxygen. Figure 1 on page 2 is a block diagram of the integrated gasification process, in which a total of 70 tons of coal was fed from slurry and gasified. The present work included (1) development of equipment and methods both for mixing pulverized coal and water to produce slurry and for pumping and metering the slurry at gasification pressure; (2) development of equipment for heating the flowing slurry and, because slurry that can be pumped produces more steam than is necessary as a gasification reactant, developing equipment for removing and metering the excess steam; and (3) demonstration of the process under actual gasifier operating conditions, at a coal rate of about 800 pounds per hour and gasification pressures in the range 100 to 300 pounds per square inch gage. By using the forced-convection principle, a flow of slurry made from a caking, high-volatile A bituminous coal can be continuously heated to 600° F. in a coil-type heater. The flow rate and concentration of the slurry and the temperature gradient along the length of the heating coil must be closely controlled. In a radiant-type heater, involuntary reductions in flow rate, even momentary, can lead to coking and plugging of the heater coil.

Jan 1, 1961

By Arden D. Fugate

The Federal Bureau of Mines conducted extensive studies on solid-state defluorination (laboratory scale) and tests on molten defluorination (intermediate scale) of siliceous fluorspars. The studies were made to develop a pyrohydrolytic process for liberating fluorine from offgrade fluorspars. Test results showed that more than 90 percent of the fluorine can be evolved by solid-state defluorination at 1,300° C., and more than 97 percent can be liberated by molten-state defluorination at 1,420° C. Solid-state defluorination conditions were established by conducting tests on mixtures of ceramic-grade fluorspars and high-purity silica flour. Pelletized mixtures were defluorinated under varying conditions of time, temperature, and relative concentrations of silica, calcium fluoride, and water. The effects of adding various amounts and combinations of aluminum oxide and iron oxide on defluorination were also studied. Investigations of solid-state defluorination indicates that the following two reactions are involved: 2CaF2 + 3SiO2 = 2CaSiO3 + SiF4, and CaF2 + Sio2 + H20 = CaSiO3 + 2HF, The second reaction is dominant, although significant defluorination can be achieved by the first reaction.

Jan 1, 1961

By M. A. Cook

Sutherland used an ion-pair adsorption model to derive the author's hy-drolytic pee-acid) adsorption equation for the contact bubble curves of Wark and Cox. To do so it was necessary to postulate that the sum of coverages of surface anion sites by the collector and depressant anions is practically unity. It is here shown that the free energy of Sutherland's postulated collector ion (x-)-depressant ion (OH-) exchange reaction (for no other than the OH- to compete with X-), namely EX + (OH-) Z SOH- + X-, is in some cases positive and X- should not even adsorb. Also, in many cases the (OH-) adsorption must be quite negligible even though the collector covers only about a sixth of the mineral surface at the threshold of air bubble contact. This, however, contradicts the postulate that permits one to derive the correct bubble contact eqwztion for the ion-pair model. Furthermore, the requirement for charge neutrality leads in the ion-pair model to the (impossible) constancy of the ratio @+)/(OH-) along a contact bubble curve in which pH may change by more than seven units. HYDROLYTIC ADSORPTION EQUATION Hydrolytic (free-acid or free-base) and ion-pair (H', X-, or R', OH-) adsorption models of the collector in metal sulfide and similar flotation systems are superficially alike and somewhat difficult to differentiate. This is because they yield, under seemingly valid assumptions, equivalent forms of the equations describing the distribution of the collector between the aqueous solution and the mineral surface. This has been discussed by the author and associates1-4 and more recently by Sutherland,' both for simple collector-mineral and for more complicated collector-depressant-mineral systems. In the hydrolytic adsorption model the equations describing the contact bubble curves of Wark and coxeJ7 are as follows :2 Here X is the collector anion, D- the depressant anion, 9, and On are the fractions of the free-acid sites S on the surface of the mineral covered by collector and depressant free acids, respectively, and @ is the fraction of uncovered sites. Kx is the free-acid collector dissociation equilibrium con- stant, K1 that for the free-acid collector adsorption, KD that for the free-acid depressant dissociation, and K2 the equilibrium constant for the free-acid depressant adsorption. Eqs. 1 to 5 yield upon simultaneous solution the result is the critical free-acid concentration for bubble contact in the absence of depressant-free acid. Eq. 8 expresses the conditions along a simple collector-mineral contact bubble curve for the case HD = 0, or V = 0. Last and Cook showed that Eq. 6 applies generally and with good accuracy in the collector-depressant-metal sulfide mineral systems. Inci-dentally, it has been shown by infrared absorption studies that in some cases the free-acid adsorption process splits out water.' In this case, Eq. 2 might be written SHOH + HX Z SHX + H20, with a similar equation replacing Eq. 4 for depressant-free acid-water exchange. This possibility does not change, however, the basic equations or considerations of the hydrolytic adsorption model. Indeed, this type of free acid-water exchange reaction was predicted for fluorite and iron ore flotation by oleic acid in the dry grinding and boiling processes.410

Jan 1, 1961

By F. E. Block

The metallic reduction of vanadium chlorides was investigated by the Federal Bureau of Mines as a possible new route for preparing vanadium metal in an effort to develop a production process that would be adaptable to large-scale plant production and would yield metal of uniformly high quality. Vanadium tetrachloride was usually prepared by chlorinating vanadium pentoxide in the presence of carbon. Although oxygen-?free tetrachloride was difficult to prepare this way, it could be prepared by the direct chlorination of vanadium carbide. Lower valent vanadium trichloride was prepared by the thermal decomposition of vanadium tetrachloride. Vanadium dichloride was also prepared by the thermal disproportionation of vanadium trichloride.

Jan 1, 1961

By M. F. Koehler

[THE LITERATURE contains relatively few thermodynamic values for interoxidic compounds, and these often are unreliable. This is especially true of data for ferrites and aluminates for which heat of formation determinations may involve extreme experimental difficulties. This report contains the results of new experimental work for obtaining the heats of formation of five ferrites (Ca2Fe2O5, CaFe2O4, MgFe2O4,, NaFeO2, and LiFeO2) and one aluminate (CaAl4O7), and a review and revision of previous similar work of this laboratory on five aluminates (Ca3A12O6,, 12/7 CaO-Al2O3, CaAl2O4, NaA1O2, and LiAlO2), The results for the 11 compounds are combined with entropy and high-temperature heat content data to derive tables of heats and free energies of formation (both from the oxides and from the elements) for the temperature range 298° 1,800° K, The relative stabilities of the compounds are discussed. The presented data all have application to ceramic reactions, and those for the calcium and sodium aluminates are applicable in considering soda-lime sintering processes for extracting alumina from silicate minerals such as day and labradorite.]

Jan 1, 1961