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By Wilbur C. Helt, Joseph J. Yancik

Throughout the history of mankind, the principal use of coal has been to produce heat through combustion. The heat is used in many ways: to warm air space for our comfort; to provide heat or energy to power industrial processes, such as cement and steel production ; and to produce electricity. Because it is our nation's most abundant fossil energy fuel, coal in the late 20th century is on the threshold of becoming a significant source for synthetic liquids and gas energy fuels for this country. This is made possible by conversion processes which can change solid coal into various synthetic gases and liquids. These coal-derived fuels are nearly identical to the processed fuels and chemicals provided by natural gas and crude oils, which presently provide almost all the petrochemical feedstocks and energy fuels needed for the residential, light commercial, and transportation markets. A revolution is beginning to take place, not only in the United States, but in many other countries with a return to a coal-based energy economy. Also, new combustion and conversion technologies which are compatible with national health and environmental goals are rapidly emerging. These technologies will allow coal's use to be expanded not only in its traditional markets, but also to supply markets held by natural gas and crude oil. With the worldwide decline in natural gas and crude oil reserves, coal is being looked upon to meet the energy demand. Because of these new coal conversion technologies, coal will no longer be only a combustion fuel, but a valuable raw material for production of a variety of clean fuels and chemicals. MARKETS FOR COAL: PAST AND FUTURE A simplified diagram of the marketing network for coal is shown in Fig. 1. As shown in this figure, coal is transported to its traditional

Jan 1, 1981

By Francis Foley

Small cracks in a plane normal to the axis of steels are found to be prevalent around the water hole of drill steels that have been in service for an unknown period of time. Cracks are not found on the exterior surface of the steels nor to any noteworthy extent even in the water holes of new drill steels. Undulations and serrations are found in the surface of the water hole in new steels; it is in the bottom of such defects that cracks appear to develop in used steels. The occurrence of the more serious of these cracks at the point in the steel to which it has been heated for forging or hardening is thought to account to a great extent for failures in that region. DURING the past, year, we have investigated the cause of 88 per cent, of the failures by breakage near the bit end of some 1-in. hollow, hexagon, drill steel used in a metal mine. This breakage in the region of the bit end of the steel was peculiarly interesting because we have been led to believe that breakage is most prevalent at the shank end of drill steels near the place where the steel is gripped in the chuck of the machine. Records from the mine showed, also, that the breakage was much more frequent in the short lengths of large gage than in the longer steels; this is shown graphically in Fig. 1. Because the shorter lengths of steels are usually those that have been made from broken pieces of long steels or from steels that have worn down in service, rarely being made from new stock, those who are wont to suspect steel of tiring and crystallizing in its old age through fatigue are quite apt to see in this instance an argument in favor of their idea. As usual, a careful examination of these steels reveals defects of a character hardly to be overlooked in favor of such a cause. The steel in question was rolled with a sand core and was of the usual drill steel composition: Carbon 0.85 per cent., manganese 0.60 per cent., silicon 0.25 per cent., phosphorus 0.02 per cent., and sulfur 0.02 per cent., with the exception that in some specimens there was vanadium, not exceeding 0.20 per cent.

Jan 3, 1924

By S. FROES ABRUE

No new oil fields were discovered in Brazil during 1945. Production for the year reached a total of 79.329 bbl., all coming from the four fields in the Baia basin; the Lobato-Joanes field produced 6728 bbl.; Aratu, 6717 bbl.; Candeias, 36,663 bbl. and Itaparica, 29,211 bbl. The total cumulative production from the Baia basin from 1939 to 1945 inclusive amounts to 210,000 bbl., all of which is utilized locally.

Jan 1, 1946

By David B. Scott

The Mogollon mining district, New Mexico, has received little public attention, although for 15 years it has been the leading silver producer of the state; it is situated in a region remote from the principal lines of travel, and its activities have usually been limited to the operations of two or three companies. The value of the total production of the district in the 44 years of its history has been estimated at $15,000,000. For the years 1904 to 1917, inclusive, the output was: gold, $4,370,000; silver, 10,042,000 oz.; copper, 874,862 lb.; total value, approximately $10,500,000. In 1913 the district contributed 80 per cent. of the total silver production of New Mexico, but in 1917 only 41 per cent., due to serious interruption in the operations of the leading producer. Since 1914 the silver output has diminished one-half, and the present high value of silver is nearly offset by the increase in cost of production. The output of gold has rarely exceeded 35 per cent. of the total for New Mexico. The ratio of silver to gold, by weight, has averaged 46:1 based on the whole output of the district. Location and Topography The town of Mogollon is 75 mi. (121 km.) by a poorly located highway ,. from the nearest railroad terminals, at Silver City and Tyrone. All supplies are transported by motor trucks and teams. The area, sometimes called the Cooney Mining District, lies on the western flank of the Mogollon Mountains, which occupy the western part of Socorro County. The elevations drop steeply on the west to the valley of the San Francisco River, adjacent to the Arizona boundary. The topography is very rugged, the whole area being sharply dissected; deep canyons with steep gradients and rugged walls are characteristic of the whole western slope of the Mogollon Range. The main canyons i run east and west, and usually maintain a flow of water during the entire year. As would be expected in a region of such deep dissection, the mines are generally dry. The mountain ridges between the canyons have altitudes varying from 7000 to 10,000 ft. (2130 to 3050 m.) and drop sharply, on their western face, to the floor of the San Francisco Valley at an elevation of 5000 ft. (1525 m.). Erosion has been rapid, and the

Jan 1, 1920

The work of Americanism is getting under way slowly but surely. The purpose of the Auxiliary is to build for all time and it therefore wishes to lay its foundations securely, feeling that the true understanding and adoption of the ideals of Americanism are the safeguards of our country from the perils of anarchy, and the bond of union between labor, brains, and capital. We hope to have reports from several directors to print next month and here append the report of the Director for the New York Section, Mrs. W. Y. Westervelt.

Jan 5, 1919

ARTHUR F. BRAID,* New. York, N. Y. (written discussion ?). -I have read Mr. Cain's paper with a very great deal of interest. The subject is one that is worth a great deal of thought and research at this time. It is a well-known fact that the strong affinity of steel or, iron for oxygen is perhaps the main detriment to sound production, and, as the author states, it is-indeed remarkable that today there are no analytical methods in general use in steel works for determining the gaseous con-stituents of steel.

Jan 10, 1919

By A. J. Erickson, W. W. Atkinson

Concepts developed in a geologic data recording system at the Victoria, Nevada breccia pipe-skarn copper mine, are not fundamentally new, but represents expansion of earlier ideas. The basic philosophy is that a high quality geologic data base is necessary and should be complete, clear, standardized, neat, quantitative, and readily useable. It may be multi-colored or simply black and white. Graphic, descriptive and quantitative recording of data is essential. A format for core logging is presented and discussed, as well as a mu1tiple overlay system for recording data gathered in surface mapping.

Jan 1, 1984

By M. D. Hassialis

[Surface Areas of Concentrates and Collector Coatings (T.P. 2002, by A. M. GAUDIN and G. S. PRELLER, Min. Tech., May. Discussion by M. D. HASSIALIS and the authors) . I Activation of Minerals and Adsorption of Collectors (T.P. 2082 by J. ROGERS and K. 1'. SUTHERLAND, Min. Tech., Nov. Discussion by A. F. TAGGART and the authors). . . . 3 Correlation between Mineral Behavior in Cataphoresis and in Flotation (T.P. 2005 by A. If. GAUDIN and S. C. SUN, Min. Tech., May. Discussion by M. D. HASSIALIS). . . . . . 8] Surface Areas of Concentrates and Collector Coatings M. D. HASSIALIS.*-In the current flotation theories there exists a common gap spanned by a common assumption pertaining to the arrangement and orientation of the collector ions at the solid surface. Also common is the belief that contact angle and flotation performance are dependent upon the arrangement and orientation of collector ions. This stimulating and informative paper sheds some light upon this general problem. One of the indices of arrangement is the area available per collector ion; in this connection, Gaudin and Preller have applied the B.E.T. method for surface determinations. In a surprising number of cases, their results show a greater specific surface for tailing than for concentrate. This cannot be accounted for by the differences in specific gravity and is attributed to the presence of clay minerals of "primary" sluices in the tailing. This is not a satisfactory explanation, for experience shows that when free slimed clay minerals are present in a flotation cell they will be carried mechanically into the concentrate. A part of the answer to the decreased specific surface of the concentrate would appear to be its usual flocculated condition, yet this should not entirely account for the large spreads reported. The possibility occurs that the nitrogen adsorption isotherms for clean mineral and collector-coated mineral are different. If that were true, and if the coated mineral surface exhibited decreased adsorptive powers, the discrepancy might vanish. In discussing the disposition of collector ions at mineral surfaces, the authors adopt the more consistent viewpoint that there exists some agreement between the ions of the substrate and those of the superstrate. In the case of xanthate ions on galena, a possible arrangement is shown in Fig. 2. This arrangement shows every xanthate ion being shared by two lead ions, whereas the chemical composition calls for two xanthate ions for each lead ion (p. g). This whole discussion is misleading. In the first place, it is known that xanthate ions are not abstracted by unoxidized galena, hence Fig. 2 should show as the substrate not Pbs but PbS„ Om. It would be equally erroneous to use the lattice arrangement of PGSO4, since the surface properties of xanthate-conditioned anglesite differ from those of xanthated galena. It is highly probable that the state of the galena surface exploited in its flotation is ephemeral, since weathered galena is only poorly, if at all, collected by xanthate. Just how a substrate of oxidized galena is to be pictured depends upon one's conception of the transformation from galena to anglesite. This writer is inclined to the following sequence of events. Surface sulphide ions undergo progressive oxidation. As more oxygen is taken up by the sulphide ions they become displaced from their equilibrium positions in the galena lattice, thus accommodating for the larger volume of the S„ Om ions. Concomittant with this change the forces acting on the lead ions

Jan 1, 1946

By W. L. Zeigler

THE tailing from the gravity concentration plant of the Hecla Mining Co., Gem, Idaho, was former-ly loaded into railroad cars to be used for ballast, highway surfacing material, or concrete work, or dis-posed of by an aerial tramway, which dumped it into another gulch. The tailing averages about 1.2 per cent lead and 0.8 oz. silver to the ton. Further treatment for the recovery of the valuable metals had been investigat-ed several times with results that did not warrant the construction of a retreatment plant; but early in 1925 experimental work was again started with small tests, and later with a 10 tons per day flotation test plant. This showed that the tailing could be ground and treat-ed by flotation at a profit. It was decided to make the new flotation plant an addition to, rather than incor-porate it in the old concentrator, the original capacity of which had been increased many times, the present arrangement being by no means ideal. The old mill buildings were of timber and board contruction, creat-ing more or less fire hazard, so all new construction was made fireproof. Construction work on the new plant was started in the middle of July, 1925, and the plant was placed in operation early in December. The building is of concrete and steel with hollow tile walls, steel sash and corrugated asbestos roofing. The ball-mill floor has for its foundation a cellular reinforced concrete block about 14 ft. deep, extending to cemented river gravel, and the cells filled with tailing to give weight to the block. Overhead, built into the steel frame, is a 5-ton hand-operated traveling crane. With both ball-mills running fully loaded, there is not the slightest trace of vibra-tion in the foundation or building. The flotation floor is of reinforced concrete beam construction and spans Canyon Creek. Adjustable plunger feeders are arranged under the the tailing-bin, which feed by gravity to a 14-in. eleva-tor, discharging to a short 18-in. conveyor. From the conveyor the tailing is discharged into a dividing hop-per, from which point the plant is arranged in three separate units. Each unit consists of a ball-mill in closed circuit with a classifier, and an 8-cell flotation machine and has an approximate capacity of 300 tons per 24 hours.

Jan 8, 1927

By P. E. Baker

Approximate solutions are presented for the heat-flow equations in a loss-free linear system with a moving source and with heat transfer by convection and conduction, representing in situ combustion in an oil reservoir. The rate of heat generation and the velocity vf of the source (flame front) are assumed constant. A cold front or convection front caused by the cooling effect of in-jected air develops behind the flame front and moves with velocity vc, which is determined by the thermal properties of the air and rock. Because of thermal conduction the fronts are not sharp; i.e., they do not represent temperature discontinuities. The following solutions apply after a sufficiently long time. where Q is heat generated per unit volume of formation, k is thermal conductivity, CF is volumetric heat capacity, a is thermal diffusivity, and subscripts 1 and 2 refer to values behind and ahead of the flame front, respectively. The parameter CF2 is contained in v . Te is initial reservoir temper- . C2 e ature and air-injection temperature. Other mathematically possible solutions are presented. The different solutions result from the use of different values for various physical parameters. The solution just presented is thought to be most commonly applicable. INTRODUCTION In this paper, approximate analytical expressions are derived for the temperature profile developed in the underground combustion method of oil recovery. A qualitative description of the process may be found in a paper by Tadema.1 The flame front is regarded as a moving source with a constant rate of heat generation. Heat transfer is by conduction and convection. Previous publications, of which a few are cited here, 2-5 have also attacked this problem and have presented solutions pertaining to different methods of approximating or idealizing the process studied. The present paper also treats an idealized case: linear flow is assumed for heat and fluids, and vaporization and condensation effects are neglected. The results obtained are similar to those derived by Bailey and Larkin,3 but are obtained by an entirely different procedure. The method used here should give considerably greater insight into the physics of the in situ combustion process. Four types of cases are considered, distinguished by thermal and fluid-flow properties of the system. A constant rate of heat generation and constant rate of flame-front advance are assumed. Flame-front temperature is determined for each case using a heat balance which involves the entire temperature profile. The applicability of the different solutions to real systems is discussed after they are all presented. Again, this is done for the purpose of understanding better the physics of the process. Consideration of the nonapplicable solutions and of the reasons for their not applying is significant. In a paper by Cooperman,4 the only case solved is one considered here as not applicable. Fluid flow, as such (pressures, saturations, oil recovery, etc.), is not treated. This subject has been covered in a paper by Wilson, et al.6 Also, we are not concerned with requirements for continuance of the process; we only attempt to determine the temperature history for cases where the process has continued for some time. PHYSICAL SYSTEM AND APPROACH TO PROBLEM A linear flow (heat and fluid) system is assumed and the x-axis is taken parallel to the flow direction. The combustion zone (flame front) is vertical,

By D. E. Hyatt

Many flotation plants practicing pyrite depression, mills leaching gold and silver ores, blast furnace facilities, and many metal plating shops share at least one common waste-water constituent of particular environmental concern-cyanide. In free or complexed form, cyanide ion is an emotionally and technically problematical reagent whose removal from water deserves attention. The initial consideration of the fundamental nature of soluble cyanides is followed by a discussion of decomposition or removal options for simple cyanide species. Complexed cyanide reactivity is discussed as it relates to ongoing or proposed methods for the decomposition or removal of soluble cyanides. New approaches to cyanide removal are discussed.

Jan 1, 1977

In preparation for the 118th meeting, New York, Feb. 17 to 20, 1919, the following committees have been appointed: Committee on Arrangements ALLEN H. ROGERS, Chairman. W. S. Dickson, Secretary. J. E. JOHNSON, JR. F. T. RUBIDGE. H. C. PARMELEE. FOREST RUTHERFORD. P. G. SPILSBURY. Committee on Annual Dinner Committee on Luncheon F. T. RUBIDGE FOREST RUTHERFORD, Chairman. E. B. STURGIS. E. MALTBY SHIPP. Committee on Patriotic Meeting H. C. PARMELEE, Chairman

Jan 8, 1918

In preparation for the 119th meeting, New York, Feb. 17 to 20, 1919, the following committees have been appointed: Committee on Arrangements ALLEN H. ROGERS Chairman. NY. S. DICKSON, Secretary. J. E. JOHNSON, JR. F. T. RUBIDGE. P. G. SPILSBURY. H. C. PARMELEE. FOREST RUTHERFORD. Committee on Annual Dinner Committee on Luncheon F. T. RUBIDGE. FOREST RUTHERFORD, Chairman. E. B. STURGIS. E. MALTBY SHIPP Committee on Patriotic Meeting H. C. PARMELEE, Chairman.

Jan 11, 1918

In preparation for the 118th meeting, New York, Feb. 17 to 20, 1919, the following committees have been appointed: Committee on Arrangements ALLEN H. ROGERS, Chairman. W. S. Dickson, Secretary. J. E. JOHNSON, JR. F. T. RUBIDGE. P. G. SPILSBURY. H. C. PARMELEE. FOREST RUTHERFORD. Committee on Annual Dinner Committee on Luncheon F. T. RUBIDGE. FOREST RUTHERFORD, Chairman. E. B. STURGIS. E. MALTBY SHIPP. Committee on Patriotic Meeting H. C. PARMELEE, Chairman

Jan 10, 1918

By Thomas Fraser, Robert MacLachlan

The dry cleaning of coal is a relatively new art and, as might have been expected, a number of unforeseen problems have been brought to light in the few years that dry methods of treatment have been in commercial use. The pneumatic concentrators that were first adapted to the cleaning of coal had already been developed to a fair degree of efficiency, although at low ratings, in the field of ore dressing. The concentrating machines, therefore, were in a relatively more perfected state than the general technology of dry cleaning and, for this reason, the major difficulties encountered in the early plants were in the accessory operations involved in the servicing of the cleaners rather than in the functioning of the cleaners themselves. The crudities of a new technology were further aggravated, in some cases, by meagerness of appropriations which precluded even the provision of adequate storage bins and such other facilities as had been long recognized as indispensable to the proper functioning of older types of cleaning plants. The practice of dry cleaning is now sufficiently established so that we may examine critically auxiliary equipment and operations. The cleaning processes have been so simplified, with respect to presizing of the raw coal required and the quantity of air circulated, that stinting of expenditures for auxiliary equipment is not necessary to keep the per ton cost of installation in line with complete and well designed plants of other types. Furthermore, sufficient operating experience has been accumulated to ascertain the conditions most conducive to effective operation of dry-cleaning machines; at least the essentials of a definite technology of dry cleaning has been established. Early Operating Problems The problems that have occupied the builders and operators of dry-cleaning plants from the beginning have been relatively few, but difficult of solution. The principal difficulties have been: 1. The proper sizing of the raw coal to suit the cleaning process. 2. The handling of raw coal when it is delivered wet from the mine. 3. Dust collecting. 4. The maintenance of uniformity in cleaning performance.

Jan 1, 1931

By R. E. Lamborn

A summary of oil and gas development in Ohio for 1935 must necessarily be brief. As attention of the state government to the oil and gas industry has never included the collection and compilation of statistics on production, either by producing sands, by counties, by fields, or for the state as a whole, such information as requested in Table 1 of this symposium is impossible to secure for this state. In the absence of production data chief attention must be directed to drilling activity for the year. Information such as can be compiled from various sources, including weekly drilling reports to operating companies and trade journals, is given in the following paragraphs with the realization that the data may not be complete in all its details. Drilling Activity by Fields Drilling activity during 1935 was similar to the preceding year in , that the major operating companies were generally content to drill lease-requirement and offset wells and in that comparatively little effort was made to discover new pools. A compilation of completions recorded in weekly reports to drilling companies and in trade journals show 1022 tests completed for the year in 53 counties of the state. Of this total number, 653 wells were commercial producers and 369 were classed as dry holes. Production was secured in 40 counties from formations ranging in depth to 5700 ft. and ranging in age from Middle Ordovician to upper Pennsyl-vanian. From the standpoint of new production for the year, the most important sands are the Clinton of Silurian age, the Berea of Mississippian age and the Shallow sands of Mississippian above the Berea and of Pennsylvanian age. Trenton Sand Field Production in the field of Trenton sand, which originally included parts of 15 counties in northwestern Ohio, is now on the decline. Seventy-three completions were reported in this field during 1935, of which 33.8 per cent were dry holes. Activity centered in Allen County with 12 completions, two of which were dry holes; in Hardin County with 11 producers; and in Wyandot County with 12 producers and 2 dry holes.

Jan 1, 1936

By R. E. Lamborn

A summary of oil and gas development in Ohio for 1935 must necessarily be brief. As attention of the state government to the oil and gas industry has never included the collection and compilation of statistics on production, either by producing sands, by counties, by fields, or for the state as a whole, such information as requested in Table 1 of this symposium is impossible to secure for this state. In the absence of production data chief attention must be directed to drilling activity for the year. Information such as can be compiled from various sources, including weekly drilling reports to operating companies and trade journals, is given in the following paragraphs with the realization that the data may not be complete in all its details. Drilling Activity by Fields Drilling activity during 1935 was similar to the preceding year in , that the major operating companies were generally content to drill lease-requirement and offset wells and in that comparatively little effort was made to discover new pools. A compilation of completions recorded in weekly reports to drilling companies and in trade journals show 1022 tests completed for the year in 53 counties of the state. Of this total number, 653 wells were commercial producers and 369 were classed as dry holes. Production was secured in 40 counties from formations ranging in depth to 5700 ft. and ranging in age from Middle Ordovician to upper Pennsyl-vanian. From the standpoint of new production for the year, the most important sands are the Clinton of Silurian age, the Berea of Mississippian age and the Shallow sands of Mississippian above the Berea and of Pennsylvanian age. Trenton Sand Field Production in the field of Trenton sand, which originally included parts of 15 counties in northwestern Ohio, is now on the decline. Seventy-three completions were reported in this field during 1935, of which 33.8 per cent were dry holes. Activity centered in Allen County with 12 completions, two of which were dry holes; in Hardin County with 11 producers; and in Wyandot County with 12 producers and 2 dry holes.

Jan 1, 1936

By C. R. Breck

THERE has been a running discussion over the-past several years with respect to the life and adequacy of our natural gas reserves.. Some of the experts agree on one phase of the subject at least--that eventually it will be necessary to augment deliveries of natural gas in the northern markets by the development of a more or less comparable synthetic gas made from coal. The purpose of this paper is to point out: 1. It may be later than a good many people think-the demand for additional domestic and commercial pipeline gas in at least one section of the North will probably be felt rather keenly before an adequate synthetic pipeline-gas project, developed on economic lines, could be completed, even if ' initiated in the near future. 2. The evidence is considerable that such a project would be technically sound and economically self-supporting, although the margin of profit at first might be so small and the magnitude of an economic enterprise so great that financing would be impossible without Government aid in some form or other. The part of the country referred to is the heavily populated section in the northeast of the United States. To simplify an examination of the situation, let us take the potential marketing areas within range to the north and east of the three pipelines: 1. Tennessee Gas Transmission Co. as it enters Erie County, New York state. 2. Texas Eastern Transmission Corporation just before the tap that supplies the general Philadelphia area. 3. Transcontinental G& Pipe Line Corporation as it enters the state of New Jersey The sources of gas for these three pipelines are in Texas and Louisiana. The ultimate maximum combined capacity of the three lines at the points stated is approximately 1,200,000,000 cu ft per 24 hr at the maximum load factor probable of attainment in normal operation. The areas supplied by the three lines north and east of the points stated, or assumed as eventual markets, are: 1. Central New York state, from Buffalo to Albany (both inclusive).

Jan 1, 1953

By Fred H. Klaer

Water supplies dependent upon induced infiltration can be developed by vertical wells, by infiltration galleries, or by horizontal water collectors. Each method is described and the advantages of water obtained by induced infiltration with respect to cost, chemical quality, and temperature are shown by specific water supplies. THE subject of ground water in industry is assuming increasing importance as new processes and new industries are developed. Industrial specifications of chemical quality and temperature for process water and for cooling purposes are becoming more rigid, and water must now have many properties to meet these requirements. As ground water is usually more constant in quality and temperature, many industries are turning to ground-water supplies to satisfy their growing need. As many published articles have stated during the past several years, the ever increasing demands have caused shortages of water supply in many localities throughout the United States. Although such shortages are generally of a local nature, they have given rise to many attendant problems, such as increased pumping costs, salt water encroachment, and rising ground-water temperatures. One partial solution to the problems of overdevelopment of the ground-water reservoirs in many areas can be accomplished by developing ground-water supplies that are dependent upon induced infiltration and by planning the use of underground reservoirs. These reservoirs can be filled during periods of excess precipitation and stream flow and can be emptied during periods of drought, in a manner similar to the use of surface reservoirs. In this way water that otherwise would be wasted into the oceans is salvaged during periods of excess. The development of water supplies dependent on induced infiltration is a relatively new concept and should be defined. When a well is pumped, the water level around the well is lowered in the shape of an inverted cone or cone of depression. As pumping is continued, the cone of depression will continue to expand, horizontally and vertically, until the quantity of water crossing the perimeter of the cone plus the recharge within the area of the cone is equal to the quantity of water being pumped.

Jan 1, 1954

By R. D. Pehlke, J. V. Gluck, R. L. Louvet

A study has been made of the effect of small additions of bismuth on the activity of zinc in dilute solution in molten tin. Free-energy interactions have previously been determined between zinc and various third elements where the solvents were molten bismuth or molten lead.'-4 In both of these solvents, the activity of zinc exhibits a strong positive deviation from ideal behavior (at 550°C y° for zinc in lead is 11.4 and for zinc in bismuth is 3.0). The present work, using tin as the solvent, is an extension to a case where the positive deviation is considerably diminished (y°Zn at 550°C is 1.63). Several previous investigators have studied the Zn-Sn binary system; however, little data is available in the range below 0.1 mole fraction zinc.5= Previous high-temperature galvanic cell studies in the Sn-Zn-Bi ternary system included the determination by Gluck and Pehlke of interactions in the bismuth-rich corner1 and separate investigations of the central region by Oleari and Fioriani6 and by Ptak and Moser.7 Yokokowa et al.8 conducted Knudsen effusion studies in the central region; however, their experiments at 625°K were conducted somewhat below the present experimental temperature range. Their results indicated an increase in zinc activity with the addition of bismuth. The present series of experiments was conducted in galvanic cells represented as follows: Zn Zn++ in LiCI-KC1 eutectic Zn + Bi in Sn (pure reference (fused salt electrolyte) (molten alloy) standard) The experimental apparatus. a multi-electrode system employing alumina crucibles and contained in a Vycor tube under a helium atmosphere, has been described previously, as have been the experimental procedures, precautions, and the methods of data reduction.1-4,- The experimental measurements were made over the range from 450° to 650°C. Between thirty and forty measurements were made in each run. The linearity of the electromotive force vs temperature relations was verified by linear regression techniques. The correlation coefficients exceeded 0.99. The experimental results summarized in Table I include the interpolated electromotive force at 550°C and the temperature dependence of electromotive force. Only results from stable and consistent cells containing more than 0.025 mole fraction zinc are reported. Attempts to run cells at 0.01 or 0.02 mole fraction zinc were not satisfactory. This is attributed to the closeness of the free energies of formation of the chlorides of tin and zinc. Calculations employing Wagner and Werner's criteria for displacement reactions10 indicated that reduction of the zinc content to 0.01 mole fraction places the cell near the borderline concentration for a 1 pct error in measured potential. The compositions shown in Table I are the actual weighed-in amounts. Previous experience has indicated that compositional changes during the running of a stable cell are negligible.' Over the range of compositions studied for the binary alloys, the activity coefficient of zinc was essentially constant indicating that Henry's law is followed to 0.05 mole fraction zinc. The temperature, OK, de-

Jan 1, 1969