Search Documents

By AIME AIME

WITHOUT frills, but with an admirable program of technical papers and discussion, many opportunities for social contact, and all New York for a playground, the 142d Meeting of the Institute will make the Engineering Societies Building a lively place from Feb. 20 to 23. Prices are down, even in New York. Come and forget the depression listening to the stories of old friends. Hear at first hand what is going on in your professional world. The fare is varied, of wide appeal. The program on the opposite page has been arranged carefully to minimize conflicts between the subjects in which you are interested. If it is not possible to come for all four days, check over the sessions that are most important to you. No changes in the scheduling are likely.

Jan 1, 1933

By C. E. Cottrell, G. W. Preckshot, N. D. Delisle, D. L. Katz

Most crude oils contain asphaltic substances that may be naturally or artificially precipitated. In the Greeley field, California, this asphaltic bitumen is precipitated during the flow of the oil from the reservoir to the stock tank The mechanism of such precipitation is not well understood. This paper presents the progress that has been made by using the electron microscope as a new tool and by observing the effects of the streaming potential on the formation of bitumen particles. Crude oils at atmospheric pressure viewed in the electron microscope in very thin films under a vacuum showed no asphaltic particles. A technique of preparing slides of thin films by dilution of the oil with benzene and washing in petroleum ether was used at first, and these observations showed that the solvents caused the formation of the particles, varying from 0.01 to 0.2 micron in diameter. The electrical effects of fluids flowing through porous solid were studied, with emphasis on the formation of colloidal particles by the streaming potential. The streaming potential of crude oil flowing through sand was measured and was shown to be responsible for the formation of bitumen particles. These results bring out a new phenomenon, which may occur when crude oil flows through the porous oil reservoir. mechanisms. Asphalt has been the subject of widespread investigation but, owing to the complexity of the substances being considered, progress has been slow. Investigators working primarily with the asphaltic substances have treated the subject from the colloidal standpoint and have developed theories that picture the asphaltic particles as surrounded by adsorbed materia1s.14,15,17,24 The deasphaltization of lubricating oil by the use of solvents treats the subject primarily from the standpoint of liquid-liquid equilibria.'' A complete understanding of asphaltic substances would make possible the following of the material from its initial state in the crude oil through precipitation processes to the final plastic stage, the most common form of which is used in asphaltic pavements. Since these asphaltic particles are very small, it appears 'hat the electron microscope4 might be a useful tool in studying the precipitation processes. Specimens are examined by the electron microscope in a vacuum and as very thin films, requiring special techniques in preparation of samples. A brief description of the electron microscope and its operation will bring out the difficulties and advantages of its use for this problem. The first work was done with crude oils that had been diluted with solvents for the preparation of the film to be examined. Later a technique was developed by which the undiluted oil film could be made thin enough for direct examination. These two techniques show vastly different results Asphaltic particles have been precipitated from crude oils by a variety of

Jan 1, 1943

By G. W. Preckshot, C. E. Cottrell, D. L. Katz, N. D. Delisle

Most crude oils contain asphaltic substances that may be naturally or artificially precipitated. In the Greeley field, California, this asphaltic bitumen is precipitated during the flow of the oil from the reservoir to the stock tank The mechanism of such precipitation is not well understood. This paper presents the progress that has been made by using the electron microscope as a new tool and by observing the effects of the streaming potential on the formation of bitumen particles. Crude oils at atmospheric pressure viewed in the electron microscope in very thin films under a vacuum showed no asphaltic particles. A technique of preparing slides of thin films by dilution of the oil with benzene and washing in petroleum ether was used at first, and these observations showed that the solvents caused the formation of the particles, varying from 0.01 to 0.2 micron in diameter. The electrical effects of fluids flowing through porous solid were studied, with emphasis on the formation of colloidal particles by the streaming potential. The streaming potential of crude oil flowing through sand was measured and was shown to be responsible for the formation of bitumen particles. These results bring out a new phenomenon, which may occur when crude oil flows through the porous oil reservoir. mechanisms. Asphalt has been the subject of widespread investigation but, owing to the complexity of the substances being considered, progress has been slow. Investigators working primarily with the asphaltic substances have treated the subject from the colloidal standpoint and have developed theories that picture the asphaltic particles as surrounded by adsorbed materia1s.14,15,17,24 The deasphaltization of lubricating oil by the use of solvents treats the subject primarily from the standpoint of liquid-liquid equilibria.'' A complete understanding of asphaltic substances would make possible the following of the material from its initial state in the crude oil through precipitation processes to the final plastic stage, the most common form of which is used in asphaltic pavements. Since these asphaltic particles are very small, it appears 'hat the electron microscope4 might be a useful tool in studying the precipitation processes. Specimens are examined by the electron microscope in a vacuum and as very thin films, requiring special techniques in preparation of samples. A brief description of the electron microscope and its operation will bring out the difficulties and advantages of its use for this problem. The first work was done with crude oils that had been diluted with solvents for the preparation of the film to be examined. Later a technique was developed by which the undiluted oil film could be made thin enough for direct examination. These two techniques show vastly different results Asphaltic particles have been precipitated from crude oils by a variety of

Jan 1, 1943

By Louise B. Freeman

Kentucky for the first time in its oil history passed the 10 million barrel mark. Of the total 10,019,641 bbl., 8,262,516 bbl. were produced in Western Kentucky, and Union County surpassed all others, with 4,056,142 bbl., or 40 percent of all the production for the state. There were 930 wells known to have been drilled during the year; 510 in Western Kentucky and 221 in the gas-producing area of Eastern Kentucky.

Jan 1, 1946

By H. H. Evinger, M. Muskat

A method has been developed whereby one may calculate the productivity factors of producing formations from a knowledge of the reservoir conditions. Account is taken not only of the heterogeneous character of the gas-oil flow system but also of the detailed variations with pressure of the shrinkage and viscosity of the oil, the solubility of the gas in the oil, and even the variability of the gas viscosity and the deviation of the gas from ideal behavior. Curves are shown giving the results of numerical calculations on the production rate as a function of the pressure differential for a high-prcssure and a low-pressure system, three values of gas-oil ratio being treated in each case. Curves are also given showing the variation with distance from the well of the pressure, oil saturation, and permeability. The effect of connate water is briefly discussed in relation to the apparently large discrepancies between the calculated and observed productivity-factor values. Introduction The significance of the productivity factor as a measure of the capacity of an oil-bearing formation to produce is well recognized; for it is the composite and integrated resultant of the physical prop-crties of both the porous medium and the fluid stream passing through it with respect to the ease with which the particular petroleum fluids present in the formation can flow through it and into producing wells. The most direct method of determining the productivity factor of a well consists, as is well known, in the simultaneous measurement of reservoir-pressure differentials and rates of production and the expression of the data in terms of rate of flow per unit pressure drop.' Actual measurements carried out in this manner on producing wells have given factors that generally lie in the range of o to Ioo bbl. per day per pound pressure drop. This wide range arises not only from variations in permeability but also from the varying sand thickness of producing formations. One of the aims of developing a theory of the mechanics of oil production obviously is that of predicting what the productivity factor should be from a knowledge of the individual characteristics of the producing formation and the fluids produced. For homogeneous fluid systems passing through a porous medium into a producing well, it has been known for some time that the steady-state rate of liquid flow Q is given by the formula:* Q ? u log r?/r? where k is the sand permeability, h its thickness, µ the liquid viscosity, ?p the pressure drop between the well and the distant parts of the reservoir, in particular that at a radius re, and r? is the well radius. This gives the productivity factor: f= Q/kh?p ? 2p/µ log re/r? f=Q/ kh?p ? 2p/µ log re/r? which will have a numerical value for a

Jan 1, 1942

By M. Muskat, H. H. Evinger

A method has been developed whereby one may calculate the productivity factors of producing formations from a knowledge of the reservoir conditions. Account is taken not only of the heterogeneous character of the gas-oil flow system but also of the detailed variations with pressure of the shrinkage and viscosity of the oil, the solubility of the gas in the oil, and even the variability of the gas viscosity and the deviation of the gas from ideal behavior. Curves are shown giving the results of numerical calculations on the production rate as a function of the pressure differential for a high-prcssure and a low-pressure system, three values of gas-oil ratio being treated in each case. Curves are also given showing the variation with distance from the well of the pressure, oil saturation, and permeability. The effect of connate water is briefly discussed in relation to the apparently large discrepancies between the calculated and observed productivity-factor values. Introduction The significance of the productivity factor as a measure of the capacity of an oil-bearing formation to produce is well recognized; for it is the composite and integrated resultant of the physical prop-crties of both the porous medium and the fluid stream passing through it with respect to the ease with which the particular petroleum fluids present in the formation can flow through it and into producing wells. The most direct method of determining the productivity factor of a well consists, as is well known, in the simultaneous measurement of reservoir-pressure differentials and rates of production and the expression of the data in terms of rate of flow per unit pressure drop.' Actual measurements carried out in this manner on producing wells have given factors that generally lie in the range of o to Ioo bbl. per day per pound pressure drop. This wide range arises not only from variations in permeability but also from the varying sand thickness of producing formations. One of the aims of developing a theory of the mechanics of oil production obviously is that of predicting what the productivity factor should be from a knowledge of the individual characteristics of the producing formation and the fluids produced. For homogeneous fluid systems passing through a porous medium into a producing well, it has been known for some time that the steady-state rate of liquid flow Q is given by the formula:* Q ? u log r?/r? where k is the sand permeability, h its thickness, µ the liquid viscosity, ?p the pressure drop between the well and the distant parts of the reservoir, in particular that at a radius re, and r? is the well radius. This gives the productivity factor: f= Q/kh?p ? 2p/µ log re/r? f=Q/ kh?p ? 2p/µ log re/r? which will have a numerical value for a

Jan 1, 1942

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 W. A., Wasley

THE EL TIGRE MINE is a highgrade silver and gold producer located in the northern part of Sonora, Mexico. It has been worked continuously since 1903, producing 50,000.000 oz. of silver and returning handsome dividends. During 1930 and 1931 falling silver prices compelled the Tigre company to make representations before the Department of Labor in Mexico City showing the necessity for drastic reductions in wages and personnel. The delays in obtaining permission from the Federal Labor Board to make these readjustments caused the company to suffer considerable financial loss during those years. After the reduction in operations was finally effected, the Sonora state government headed by Señor Francisco Elias (former Governor, now Secretary of Agriculture) and Señor Rodolfo Elias Calles (present Governor and eldest son of Señor Plutarco Elias Calles, recently Secretary of War and former President of Mexico) have cooperated with the company to make continued operation possible by revising downward certain state taxes that would have been a factor in forcing the closing of this mine. Also, permission to change our workmen over to another system of mining was essential to continued operation.

Jan 1, 1933

By Rossiter TV. RAYMOND, Charles H. Snow, THEODORE DWIGHT

SECRETARY'S NOTE.-The complete list of all officers of the Institute will be found on p. iv. of this number of the Bulletin. The following explanation may recall to old members, and convey to new ones, the relations of the two governing bodies, as determined by the, Certificate of Incorporation of the Institute, and the Constitution and By-Laws adopted in accordance therewith. The body legally responsible for the business management is the Board of nine Directors (three elected annually to serve three years), which elects its own officers. This body, for reasons of practical convenience, is composed of well-known members, residing in New York City, and able to attend, without serious inconvenience or expense, the necessary meetings of the Board. The officers of this Board are legally the officers of the Institute. But, apart from business manage-ment, the Board exercises no control over the election of members, or the professional and technical work of the Institute, except that its vote is required to elect honorary members, upon the recommendation of the Council. The Council is a. body, constituted in all respects (except that it has no Treasurer) like the Council existing before the incorporation of the Institute, in January, 1905, and charged with all duties and powers, except those which the Board of Directors must legally perform. It elects members, appoints the times and places of professional meetings, and controls the publication and distribution of papers and volumes, etc. Its members (President, Vice-Presidents and Councilors) are elected by the members of the Institute, voting in person or by proxy, and after publication of the nominations received ; and it is intended to repre¬sent, as far as practicable, both the professional and the geographical distribution of the membership. Consequently, whatever professional honor attaches to official position belongs to membership in the Council, rather than in the legal Board of Directors. This remark implies no disparagement of the members of the latter body, every one of whom has served, or is now serving, as a member of the Council. But it is only fair to explain that their election and continued re-election as Directors is simply a matter of legal convenience.

Mar 1, 1906

By John B. Hastings

The occurrellce of such a large amount of gold in the Hart-eel granite, even though the surmised existence of similar areas is not new, brings freshly to mind the pegmatite type of mag-matic differentiation lately brought again to attention by occurrences at Silver Peak, Nev., described by Spurr; and in Alaska, described by both Spurr and Brooks. In both localities granitic rocks or dikes are thought to pass into metalliferous quartz-veins. An interesting association in this connection is the occurrence of diamonds in residual pegmatitic clay of Sail Juao de Chapado, Brazil, described by Derby :' (P. 142) "Bodies of pegmatite are quite common in the older rocks of Brazil, both in the diamond regions and elsewhere, occurring not only in the gneiss and granite, but in the schistose series as well. Those that have been examined are dike-like in their mode of occurrence and granitic in composition.'' (P. 143) '" The question of the eruptive or secretionary origin of pegmatites has long been a subject of discussion among geologists.... The recent studies .. seen] to have clearly established that most if not all of them are essentially eruptive masses, though possibly modified in some way by aqueous agencies. Even before becoming acquainted with the literature of the subject this view had seemed to me to be the only acceptable one as regards the typical pegmatites of Brazil." What is pegmatite ? J. F. Kemp says :2 "... veins or dikes—it is an open question which is the more correct term— are met formed of very coarsely crystalline aggregates of the same minerals that constitute granite. These are called pegmatite and in them is the home of graphic granite, the curious intergrowth of quartz and feldspar, such that a cross fracture of the blades of quartz suggests cuneiform characters.... In regard to the larger veins or dikes it seems improbable that true igneous fusion could have afforded such coarsely crystalline aggregates, and so we are forced to assume such abundance of steam and other vapors, i.e, mineralizers, as to almost, if not quite, imply solution."

Jan 1, 1909

By H. J. Wogner

STORAGE of natural gas in underground reservoirs is one of the most important developments in the natural gas industry in recent years. However, it is only when we consider this development together with proved fuel reserves, the know-how of the fuel technologist, and the possibility of making manufactured gas available over large areas, that we begin to appreciate fully the impact that underground storage of gas may have on the future growth and development of large areas in the United States. During the past winter, shortages of natural gas in the industrial East were given wide publicity and domestic consumers were requested to reduce their requirements to a minimum, so that war plants might have sufficient gas to continue operations. Curtailments would have been more drastic except for the fact that large volumes of natural gas had previously been stored in underground reservoirs. Storage of natural gas in depleted or partly depleted gas or oil sands is not new, having originally been tried, as far as I know, about 1915. About five or ten years later an attempt was made to store manufactured gas in a depleted gas sand. This proved unsuccessful at first because the gas was not properly cleaned and the impurities plugged the pores in the sand.

Jan 1, 1945

By AIME AIME

AT a joint meeting of the Tulsa Geological Society and the Mid-Continent Section of the A; I. M. E., held at Tulsa on March 21, the history of unit development in the Kettle- man Hills field was discussed. Robert C. Patterson? Super- visor for the U. S. Geological Survey at Taft, Calif., was the speaker. An abstract of some of his remarks follows: On July 1, 1923, curtailment agreement for two years was made between the operators of North Dome Kettleman and the U. S. Department of the Interior. In this it was agreed to consider a plan of unit development, or other cooperate method of developing the structure. As a result, Kettleman North Dome Association was incorporated in December, 1930, as a non-profit cooperative corporation under the laws of California. Approved in January, 1931, by California Oil and Gas Supervisor and by Secretary of Interior. On Feb. 10, 1931, it became an active organization through election of executive officers and eleven- directors. General manager chosen. Association started to function April 1, 1931. Assumed control of 10,800 acres of proved and semi-proved land, as shown in Table 1.

Jan 1, 1932

By George A. Roche

Investment in growth stocks is the most assured way of achieving superior, long term investment accomplishment. There are many criteria used to select growth companies but the most important is a combination of superior management operating in an industry with above average growth potential. This growth stock approach is the cornerstone of investment strategy for two of the three mutual funds sponsored by the Price organization and for its private clients. However, during the past five years inflation has accelerated due to a variety of factors including the inability of government to meet seemingly unlimited needs with limited revenue sources.

Jan 4, 1972

Both drilling and production of oil decreased in Rumania during 1935. The drilling totaled 1,042,041 ft. and production 61,973,938 bhl., being a decrease of 8.5 and 1.6 per cent, respectively. Wells completed during the year totaled 198, of which 168 were oil wells, compared with 238 and 215, respectively, of 1934. No important discovery was made during the year. The only new field found was Valea Calugareasca, where the Credit Minier completed a small well on the westward plunge of the anticline. Drilling higher on the structure will probably prove the field to be of greater importance than the results of the discovery well indicate. The only other developments of importance were the extension of the Bucsani field, the opening up of a new area on the northeast of the salt at Moreni by Credit Minier and a minor extension of the West Gura Ocnitei field. At Calinesti, on the cast extension of the Moreni field, exploration work continued and a gas well was completed, but oil in commercial quantities is yet to be found.

Jan 1, 1936

Both drilling and production of oil decreased in Rumania during 1935. The drilling totaled 1,042,041 ft. and production 61,973,938 bhl., being a decrease of 8.5 and 1.6 per cent, respectively. Wells completed during the year totaled 198, of which 168 were oil wells, compared with 238 and 215, respectively, of 1934. No important discovery was made during the year. The only new field found was Valea Calugareasca, where the Credit Minier completed a small well on the westward plunge of the anticline. Drilling higher on the structure will probably prove the field to be of greater importance than the results of the discovery well indicate. The only other developments of importance were the extension of the Bucsani field, the opening up of a new area on the northeast of the salt at Moreni by Credit Minier and a minor extension of the West Gura Ocnitei field. At Calinesti, on the cast extension of the Moreni field, exploration work continued and a gas well was completed, but oil in commercial quantities is yet to be found.

Jan 1, 1936

By M. H. Gidel, D. C. Bard

These notes are based on the megascopic study of a suite of 2,400 specimens of minerals and ores from the Butte mines, combined with field observations at intervals over a period of several years. The estimate of average vein composition is based on field acquaintance with the veins. It is probably correct in its broader proportions, and should be of use for comparison. Chemical and Mineral Composition of Unoxidized Vein Matter. Per Cent. Oxygen,......48.00—Quartz, rhodonite, rhodochrosite, sericite, kaolinite, barite, calcite, and hübnerite. Silicon,...... 36.O0—Quartz, rhodonite, sericite, kaolinite, and willemite (very rare). Sulphur,.....5.0—Sulphides of iron, zinc, copper, lead, and sulphates of barium and rarely calcium. Iron,.......5.00—Ferric sulphides (pyrite, bornite, chalcopyrite), also in sphalerite, tetrahedrite, and rarely hematite and siderite. Manganese,.... 2.00—Rhodonite, rhodochrosite, and hübnerite. Zinc,.......1.00—Sphalerite, very rare wurtzite and willemite, and tetrahedrite and tennantite. Carbon,......0.50—Rhodochrosite and calcite. Capper,......0.75—Cuprous ( + ) and cupric (—) sulphides. Aluminum,.... 0.50—Sericite and kaolinite. Hydrogen,.... 0.50—Water, sericite, and kaolinite. Potassium,.....0.20—hicite. Lead,....... 0.20—Galena. Arsenic,......0.10—Tennantite and enargite. Barium,......0.10—Barite. Calcium,.....0.10—Fluorite, calcite, and rare gypsum. Antimony,.... 0.02—Tetrahedrite, famatinite, and silver sulphantimonites. Fluorine,.....0.05—Fluorite. Silver,.....1 —Argentite, and sulphantimonites. Tungsten,.... —Hübnerite. Phosphorus, • —Wavellite. Bismuth,' .... 0.05—Sulphide (?) Tellurium,... 1 —Telluride (?) Selenium,.... —Selenide (?) Cadmium,.... —Sulphide (?) Gold,..... —Native and telluride (?)

Jan 1, 1914

By Oscar A. Glaeser

INDUSTRIAL relations in the United States Smelting Refining and Mining Company's Western operations covers the field of personnel and labor relations, and the principal aims are to render service to the employes of the Company and to its operating departments. Accident prevention Safety is a primary function. A safety engineer is employed at each operation. The wholehearted support of Company officials, staff, and the working force has been most successful in preventing accidents. Constant vigilance has been combined with a policy of building safety into all operating activities whether these are in the construction of a new facility, the developmnt of a mining system, or the direction of the working force. That this policy has produced results is attested to by the fact that the accident frequency rate at the Company's major mining operations in Utah has been reduced approximately 75 per cent in the ten-year period ending Dec. 31. 1946.

Jan 1, 1948

By Clyde E. Williams, V. N. Krivobok, C. H. Herty

THE extreme effect of the depression on the steel industry is well illustrated by the fact that the amount of iron ore shipped from the Lake Superior district was the lowest in 47 years. Something over 3 1/2 million tons of ore was shipped in 1932, compared with over 65 million tons in 1929. It is not surprising then that practically no advancement in iron ore beneficiation has been made. Improved research and development work, however, was continued at the Michigan College of Mines in the survey of the lean iron ores of Michigan with reference to the possibility of their concentration; at the University of Minnesota in its large-scale jigging studies of Lake :Superior ores; and at Battelle Memorial Institute in the development of improved jigging of iron ores. The successful operation of the new Hadsel mill at a gold property in California gave such low grinding costs on a quartz ore as to give much encouragement in the iron ore industry for a cheapening of the cost of grinding lean ores for concentration.

Jan 1, 1933

By Erwin H. E. Gaertner

The brown-coal opencast mines in Germany's Rhineland have to cope with several problems. Predominant are densely populated areas with highly productive farmland, many railroads, highways, and rivers, as well as towns and farm settlements which have to be removed before or during the lifetime of a mine. Also the ground- water table has to be lowered to keep the deep opencast mines dry and stable. These problems urged a development towards deep opencast mines with powerful machines; the large material movement and the high coal production are the basis for the economic success in working the Rhenish brown-coal deposits. Up to now, bucket wheel excavators with a daily capacity of 100,000 m3 (130,000 cu yd) are in operation. Machines of twice this capacity are under construction. Corresponding to the excavators development, the stackers' capacity has to be increased too. The new stackers will reach a daily capacity of 240,000 m3 (310,000 cu yd). The haulage in the mine is performed by conveyor belt systems, which are arranged in such a manner that the belt lines meet at a belt switching point. Here the incoming lines may be connected to the outgoing ones so as to direct the material flow to the desired receiving stations. At the moment there are conveyor belts in operation with a width of 2.2 m (7.2 ft); the new belts will have a layout for 37,000 t/h (40,770 stph), the width of which amounts to 3.0 m (9.8 ft). All belts and driving stations on benches are shiftable.

Jan 1, 1976

By C. Norman Cochran

The pllnse diagvam for the NaF-AlF3 system was used to calcutate an ionic model for the NaF-AlF3 system. Assuming an ideal solution,a series of simultaneous equations expressing equilibria be-tween solid and liquid phases at the euleclic, perilec-tic, and melting points were solved for the activities of the ionic species, the dissociation constants, and the entropies and heats of fusion. The calculations suggest the existence of A13F1415 ions in addition to the F-1+AlF6-3 , and AlF4-4 ions previously proposed by others. The calculaled valnes give better agreement with vapor pressures than the previous model without Al3Fl14-5. Additional possible vefinements of the model are proposed. CRYOSCOPIC1 investigations and density data2 for the NaF-A1F3 system have previously been used to study the dissociation mechanism of Na3A1F6 and to derive equilibrium constants for its dissociation to NaF and NaAlF,. Depending primarily on the heat of fusion assumed for cryolite, the dissociation constants ranged between 0.02 and 0.18 from cryoscopic studies, and from 0.09 at 1273°K to 0.16 at 1363°K from density data. In most cases the values were unable to reproduce satisfactorily the experimental liquidus lines very far on the A1F3 side of the Na3A1Fe composition. This suggested the existence of at least one other ionized compound in the melt besides NaA1F4 in the Na3A1F6-A1F3 side of the system. This is assumed to be liquid Na&13F14 (chiolite), which is already established as a stable solid in phase studies of this system. MODEL FOR THE MELT The melt is assumed to be an ideal solution with ion activities equal to anion fractions. The only cation in the model is sodium so that Temkin and simple anionic activities are identical. Although the compounds are completely ionized to Na' and the respective anion in the melt, molecular rather than ionic notation is used throughout this work. The Na3A1Fe is assumed to dissociate to NaA1F4 and NaF as in the former model, and Na&13F14 to dissociate to Na3A1Fe and NaA1F4. Other valid dissociation equilibria can be written involving these four compounds, but all of these can be obtained by combinations of the two described dissociation reactions and, thus, are automatically considered in these calculations. The model allows for no free AlF3 so that compositions for NAIF3 > 0.5 (mole fraction A1F3 on the NaF-A1F3 basis) cannot be treated. The question of the existence of free AlF3 in the melt will be discussed again later. The constants in the model were evaluated from points along the entire known liquidus line of the NaF-A1F3 system. Previous work employed only the liquidus line or densi- ties near the Na3A1F, composition. The liquidus line compositions used in the solution of the model are from unpublished work by Mr. P. A. Foster, Jr., for compositions between the Na3A1F6 melting point and the Na&13F14-A1F3 eutectic, and from the published works of Grjotheim,1 Phillips,3 and Foster4 for the remainder of the system. The relationships used in solving for the desired dissociation constants and heats and entropies of fusion are listed in Table I, and the points along the liquidus line at which each apply are indicated to the right of the relationships. The mole fractions of each of the separate species in the melt are symbolized by N. Relationships [I] and [2] are the respective dissocia-ation constants, Kl and K2, of Na3AIF6 and Na5A13F14 for this model. For simplicity, these constants will be assumed to be independent of temperature. Relationship [3] follows from the assumption of the ideal solution. The expression relating the values of N to the experimental values of NAIf3, is given in Relationship (41. Relationships [5], [6], and [7] each state the equilibrium between a compound in the melt and its pure solid phase for the portion of the liquidus lines where it precipitates. The heats of melting, AH,, and entropies of melting, AS,, used in [5], [6], and [7] are assumed to be independent of temperature. The compositions and temperatures of all five invariant points (two melting points, two eutectics, and one peritectic) along the liquidus lines from NAIF3 = 0 to NAIF3 = 0.5 were employed in the solution. The eutectic and peritectic compositions were particularly useful because each of these is involved in one more equation than other points along the liquidus lines and thus reduces the number of points required to solve for the constants. Also, their use assures that the inflection points in the derived liquidus line will correspond exactly with those on the experimental liquidus line. The total number of equations is 5k1 — 1, where n is the number of experimental composition points used. The number of unknowns is 4n + 5 (4n- 3 values of N, 3 values each of AH, and AS,, and 2 values of K). Thus, six points must be used in the solution to obtain an equal number of equations and unknowns. The one additional required experimental composition was taken on the liquidus line between the Na3A1Fe melting point and the Na3A1F6-Na5A13F14 peritectic. Previous work indicated this was a difficult portion of the curve to fit. The temperature used for the point was 1161°K, the same as for the NaF-Na3A1Fe eutectic. This choice of temperature gave two points with identical NNa3AIF6 values which simplifies the algebraic solution. The second point at this temperature is denoted 1161°'K. PROCEDURE FOR SOLUTION OF EQUATIONS Values were assumed for NNa,AIF and NNaF at the NaF-Na3A1F6 eutectic at 1161°k. By an iterative procedure, the corresponding values for NNa5A13F14 and NNaAlF4 at 1161°K were determined from 131 and 141. A value was assumed for NNaAlF4 at 1161°'K and

Jan 1, 1968