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By R. E. Delavault, H. V. Warren

In normal soils there are usually 10 to 50 parts of copper in every million parts of .soil. Only 0.2 to .5 pct of this copper can be found by any simple cold chemical attack. Now, with rubeanic mid reagent paper, a prospector or field geologist can detect as little us 4 ppm of readily available copper ill soil. This degree, of sensiticity is enough to determine the presence. of copper anamalous an as and, ecentually, to discouer copper mineralization. Circumstances determine whether it is better to make analyses in the field or in a permanent laboratory. The rubeanic acid test described in this article has been designed primarily for field use: it is simple and virtually foolproof, and it requires a minimum of field kit." It is sensitive, easily de- • Ed. Note: Persons Interested in purchasing kits suitable for rubeanic acid prospecting can obtain information by writing Eldrico Geophysical Sales Ltd., 633 Hornby Street. Vancouver 1, B.C. The University of British Columbia does not produce these kits for sale and has no financial interest in their production tecting 4 ppm of readily extractable copper in a soil. This is by no means a quantitative test, but it is accurate enough to provide a valuable indicator of copper anomalous areas for both prospectors and field geologists. The easiest method for detecting metal deposits that do not produce visible float or stains is to make a simple chemical test for the metal in overlying soil, or in the silt of a stream that may have picked up metal farther upstream. In Brief: Testing for copper may be done easily by shaking a soil sample with strong acetic solution in a small test tube and pouring the mud into a small filter, the tip of which rests upon a strip of reagent paper impregnated with rubeanic acid (di-thio-oxamide). When copper is present—and only when it is—a blue spot develops. The more copper, the darker the spot. If the copper content is merely the small amount present everywhere, there is a pale blue or hardly visible spot; if it is abnormally high, the spot will be dark. There are, of course, intermediate cases where the experienced geochemist cannot tell offhand whether a medium-strength spot represents rich agricultural soil, weak copper mineralization, or distant rich copper mineralization. Reagents and material are inexpensive; the test may be readily done on the spot with a simple kit easy to pack and handle. Anyone interested in general problems of soil sampling as applied to prospecting may refer to an article recently presented to the AIME. In exploration work it is the contrast between the metal content of anomalous and background areas that is important; absolute values become of greater interest when an anomalous area is being investigated in detail. With specific reference to copper, it has been the authors' experience that the amounts of metal extracted from anomalous and normal soils with buffer solutions of decreasing pH show better contrast if an acid reagent is used. This contrast tends to increase with increasing acidity until 3 to 4 pH is reached. Using a short cold attack on unheated soil, it has been found that further increases in acidity do not produce better results, and only increase the hazards involved in carrying strong acids. An acidity of about pH 4 is satisfactory for direct determination of copper by dithizone. But dithizone itself introduces some problems: it must be made up fresh at frequent intervals, and with some soils, notably those with much ferric iron, oxidation mag take place before all the copper has reacted with the dithizone. Rubeanic acid keeps its strength unimpaired for long periods, is unaffected by oxidation, and is practically specific for copper at pH 4. Consequently it seems an ideal reagent to use in prospecting for copper. History and Background: Rubeanic acid (systematic name: dithio-oxamide (SC-NH2) has long been known as a spot test reagent for some heavy metals with which it gives a number of compounds. Only copper and some metals of the platinum family are believed capable of providing any ru-beanate compounds under conditions of moderate

Jan 1, 1959

Discussions of the paper of Mr. Gayley read by title at the Lake Superior hieeting, but first presented at the New York meeting of the Iron and Steel Institute, October, 1904 (see p. 746). With the exception of Mr. Pourcel's discussion (p. 1038), these papers are here published under a mutual agreement between the Councils of the two Institutes, and will also be found, with others, in the Journal of the Iron and Steel In-slitute for the pear 1904, Mr. E. Windsor Richards, Past-President,' said that in 1799 Mr. Dawson, of Low Moor, read a paper before a scientific society in York pointing out the great diff'erence in the moisture of the air going into the blast-furnace in the hot months of the year and in the winter months. A cold blast-furnace was a very sensitive instrument, and showed this very clearly, for in June, July and August the furnace did not drive so well; it did not make the quality of iron and required more fuel; so that Mr. Gayley was on the right road to effect an enormous improvement in this direction. He considered that Mr. Gayley was on the way to great success, and hoped that the apparatus would not be a very expensive one. He supposed it mas too early for Mr. Gayley to let them know what the saviug was

Jan 1, 1905

By E. Mcl. Tittmann

Deep-seated human instincts urge us to positively mark the passage of time. We celebrate the passage of each year. Years give way to decades, and decades to half centuries and centuries. At all these mileposts we are inclined to pause, take a look around and catch our breaths before embarking on the next leg. We are at such a point now and this meeting I am sure will give direction to the road ahead into the decade of the seventies. In looking around at this point, 1979, it is obvious to all of us that the environment in which we must mine, mill, smelt and refine lead and zinc has radically changed. These changes have, of course, occurred over a long period of time. They have, however, all been in the same general direction. They have all had the same motivation. The period of greatest contrast is probably the fifteen years just before World War II and the fifteen years following the end of that war. I thought that I might review briefly with you what seems to me to be four of the more important changes that have developed since World War II that profoundly affect our activities in the lead and zinc industry. I mentioned before that all these changes have been in the same direction; that is, they have all tended to restrict our freedom of action in pursuing our objective of producing lead and zinc on a competitive basis at a profit. Consequently, in discussing them you may think that I am merely viewing with alarm. This is not the intent. This is merely supposed to be an objective analysis. I think it appropriate before discussing these trends in detail to examine the position of lead and zinc today.

Jan 1, 1970

By Freeman Bishop

The first session of the 91st term of Congress became so completely snarled up in economics and politics that no one knows how things will go in 1970 including the White House. Everything from mineral depletion allowances to tax deferments kept the Republican President and the Democratic Congress from settling their differences. But as these reconcilements approach definition, a new battleground develops around the President's authority to make trade and tariff adjustments.

Jan 1, 1970

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 James Aston

INDICATIVE of the practical importance of the achievement of James Aston , recipient of the Robert W. Hunt Medal for 1930, is the following prosaic item from the financial columns of a recent issue of a New York newspaper. "According to private advices from Pittsburgh, production costs of the A. M. Byers Co. for 1929 were reduced about $5 a ton by the use of the Aston process for making wrought iron pipe. A greater saving is anticipated for 1930, when more of the company?s requirements will be produced by the new method."

Jan 1, 1930

[PRESIDENT ASD DIRECTOR LOUIS S. CATES 3 .New York, N. Y. PAST PRESIDENT AND DIRECTOR CHESTER A. FULTON1 .Baltimore, Md. HARVET S. MUDD 2I Los Angeles, Calif.]

Jan 1, 1946

By E. Swartzman, G. C. Behnke

THE free-swelling index, a numerical value for the free-swelling properties of coal, is being used to an increasing extent in specifying coal for burning in various types of equipment. The empirical standard ASTM method for determining this index uses, as a source of heat, a gas burner which requires frequent calibration because gas pressures are not constant, relatively small changes in gas pressure resulting in rather wide variations in the temperature attained in a crucible and thus in the resultant size of the coke button. Furthermore, the quartz crucibles specified for the test are not standard equipment, and relatively small variations in dimension and wall thickness from those specified often result in rather wide variations in the resultant size of the button. A method of analysis to be satisfactory not only for a scientific laboratory but also for use in industrial control laboratories under varying conditions should employ equipment which is rugged, easily calibrated, and readily replaceable by standard materials. Gas is not universally available as is electricity, and it is generally easier to calibrate and control a simple electric furnace or heater than a gas burner, the voltage not usually fluctuating to the degree that gas pressure does. Quartz crucibles are fragile, and the size specified in the test is not normally used for any other purpose in the laboratory. Although more expensive, the 15-cc platinum crucible, available in all laboratories where volatile matter in coal is determined by the standard ASTM method, is sturdy and standard and easily replaced. Because of these considerations, a modification of the standard method has been developed which employs a standard laboratory 350-w cone heater and standard 15-cc platinum crucibles. The results of numerous tests conducted with such apparatus show conclusively that the free-swelling index values as judged by the buttons produced with this equipment are exactly the same as those obtained by the standard gas burner method. Thus it is suggested that this electric cone heater method employing standard 15-cc platinum crucibles be considered as an alternative to the ASTM method, Designation: D720-46. The free-swelling index of coal is determined by means of the ASTM method, D720-46. This method, which is an adaptation of the crucible swelling test for coal of the British Standards Institution, consists of heating 1 g of coal in a special covered quartz crucible in a regulated gas flame for a period of not less than 2.5 min in which time the temperature of the inner surface of the bottom of the crucible reaches a temperature of 82025°C. The residual coke button is then compared in size and shape with a series of standard profiles shown in Fig. 1 and designated by number from 1 to 9 in increasing order of size. As the method is empirical, it requires rigid standardization of the apparatus and repeated calibration of the gas burner. The dimensions of the low form quartz crucible recommended must be rigidly adhered to as small variations in diameter or wall thickness result in variations in the rate of heat transmission and thus in the resultant size and shape of the coke button. The gas burner must be calibrated almost every time a new set of determina-

Jan 1, 1952

By W. R. Seyfried

THE -problem of extracting alumina from clay and low-grade bauxites has been the subject of considerable interest for some time. The basic reason, of course, lies in the fact that known reserves of high-grade bauxite are not inexhaustible and that the present commercial process cannot successfully cope with low-grade bauxites or clay. Ultimately it may be necessary to use these poorer raw materials for all commercial operations, An unprecedented demand for aluminum during the war emergency and the constantly threatened shortage of imported bauxite caused the United States Government to take an active role in this problem. Through the National Academy of Sciences, the War Production Board and the Defense Plant Corporation, it investigated processes and finally selected four to be used in the construction and operation of four experimental plants. Each plant was to be designed in such a way as to facilitate its incorporation into a larger commercial plant should the need arise. The Chemical Construction Corporation process, or "Chemico" ammonium sulphate process as it is better known, was one of the four selected. The extensive literature and patents on record before the war generally follow one of two process-types depending upon the extracting reagent used. One group uses an acid reagent, the other an alkali. The Chemico process uses an acid reagent. For those interested in other processes described in literature, there is a short bibliography at the end of this paper, The basic steps of all acid extraction processes are: (I) to make the aluminum silicates acid soluble, (2) to separate the released alumina from impurities and insoluble gangue, and (3) to recover the reaent for re-use. THE PROCESS AS PLANNED In April 1941, a group of chemists and engineers of the Chemical Construction Corp, became interested in the problem of extracting alumina from clays and low-grade bauxites and, under the leadership of Mr. Blakeslee Barnes, Vice President and General Manager of the Company, first drafted a process in July of that year-five months prior to Pearl Harbor. The work continued in our research laboratories and with a small pilot plant, By June 1943, the work had progressed to a point where it was possible to apply for a patent on the process which was U.S. patent 2,405,426, granted August 6, 1946. Immediately prior to the development of the Salem plant, the process was envisaged to be as follows: I. The first step was to make the aluminum silicates acid soluble. It was planned: (a) Clay or low-grade bauxite would be roasted at 700 to 800°C (1292° to 1492°F). (b) The roasted ore would then be leached .with hot aqueous ammonium bisulphate to form a slurry. In this way the

Jan 1, 1948

[PRESIDEST ASD DIRECTOR ................................................... HARVEY S. MUDD 3. .Los Angeles, Calif.]

Jan 1, 1946

PRESIDENT. CHARLES F. RAND,1 NEW YORK, N. Y. PAST PRESIDENTS. CHARLES KIRCHHOFF,1 NEW YORK, N. Y. JAMES F. KEMP,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT. BENJAMIN B. THAY ER,1 NEW YORK, N. Y. TREASURER. GEORGE C. STONE,1 NEW YORK, N. Y.

Jan 4, 1913

PRESIDENT. CHARLES F. RAND,1 NEW YORK, N. Y. PAST PRESIDENTS. CHARLES KIRCHHOFF,1 NEW YORK, N. Y. JAMES F. KEMP,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT. BENJAMIN B. THAYER,1 NEW YORK, N. Y. TREASURER. GEORGE C. STONE,' NEW YORK, N. Y. SECRETARY EMERITUS. ROSSITER W. RAYMOND NEW YORK, N. Y. SECRETARY. BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 9, 1913

PRESIDENT BENJAMIN B. THAYER,1 NEW YORK, N. Y. PAST PRESIDENTS JAMES F. KEMP,1 NEW YORK, N. Y. CHARLES F. RAND,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS,1 NEW YORK, N. Y. TREASURER GEORGE C. STONE1 NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y

Jan 3, 1914

[PRESIDENT SAMUEL A. TAYLOR, . . . . District 3 . . . . PITTSBURGH, PA. PAST PRESIDENTS WILLIAM KELLY, District 5 . IRON MOUNTAIN, MICH. J. V. W. REYNDERS District 3., NEW YORK, N. Y. FIRST VICE-PRESIDENT E. DEGOLYER, NEW YORK, N. Y. TREASURER CHARLES F. RAND, NEW YORK, N. Y. SECRETARY H. FOSTER BAIN, NEW YORK, N. Y. ASSISTANT SECRETARY THOMAS T, READ, NEW YORK, N. Y.]

Jan 1, 1928

PRESIDENT. CHARLES F. RAND,1 NEW YORK, N. Y. PAST PRESIDENTS. CHARLES KIRCHHOFF,1 NEW YORK, N. Y. JAMES F. KEMP,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT. BENJAMIN B. THAYER,1 NEW YORK, N. Y. TREASURER. GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS. ROSSITER W. RAYMOND, ..... NEW YORK, N. Y. SECRETARY. BRADLEY STOUGHTON, NEW YORK, N. Y.

Jan 7, 1913

[PRESIDENT E. DEGOLYER, District 0 NEW YORK, N. Y. PAST PRESIDENTS J. V. W. REYNDERS, District 0 . NEW YORK, N. Y. SAMUEL A. TAYLOR, District 3 PITTSBURGH, PA. FIRST VICE-PRESIDENT GEORGE OTIS SMITH, District 4 .WASHINGTON, D. C.]

Jan 1, 1928

PRESIDENT WILLIAM L. SAUNDERS,1 NEW YORK, N. Y. PAST PRESIDENTS CHARLES F. RAID;1 NEW YORK N. Y. BENJAMIN B. THAYER,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT PHILIP N. MOORE,1 ST. Louis, Mo. TREASURER GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON, NEW YORK, N. Y.

Jan 3, 1915

By R. G. Hudson, L. Yang

In electrochemical separation of metals, it is necessary to control the potential applied between the electrodes so that only the desired electrode reactions can occur. A knowledge of the minimum potential needed for a given electrode reaction to take place continuously is therefore pertinent to the success of the process. In molten chloride systems at high temperatures, activation polarization is believed to be small,1,2 so the minimum potential needed for the electrolytic decomposition of a molten metal chloride MC1n (n = valence of the metal ion) is therefore essentially the equilibrium electrode potential E of the metal-chlorine galvanic cell in the solution. If the decomposition products are pure M and chlorine at a pressure of p atm, E*Eo-rt/nf in [i] Since EO (the standard electrode potential of MCln) is a constant at a given temperature and R (the gas constant), and F (the Faraday's constant) are all constants, the variation of E with the electrolytic bath conditions is largely determined by the effect of the latter on the activity of the metal chloride amcln (standard state = pure MC1,). Measurement of E and study of how amCin varies with temperature and concentration, the nature of the solvent, and that of the coexisting solutes are therefore pertinent in the selection of optimum operating conditions for the electrochemical separation of metals. Because of its low melting point, high decomposition potentials of its components, and the low solubility of heavier metals in it, the LiC1-KC1 eutectic melt is a useful solvent and has been used in the electrodeposition of Mo,3Ce,4 and u5 metals. Senderoff and Brenner3 measured the potentials of Zn/Zn++, Fe/Fe++, Cu/Cu+, Mo/Mo+++, and Ag/Ag+ against an Ag/AgCl (pure) reference electrode at 600°C and a concentration of 4.1 mole pct of each chloride and came to the conclusion that complex ion formation occurred in some of the melts. Laitinen and LiUe gave an electromotive force series at 450°C for a number of {Metal/Metal ions (unit activity)) electrodes in LiC1-KC1 eutectic melt, the {pt/pt++ (unit activity)) electrode being chosen as the reference. Walker and Danly7 studied the ther-modynamic properties of NiC12 in LiC1-KC1 eutectic melt over a wide range of temperatures and concentrations by measuring the electrode potential between a nickel electrode and a chlorine electrode in the melt. Since potential measurements made by using the chlorine reference electrode are of more direct significance both in the study of electrochemical separation and in the evaluation of the thermodynamic properties of the melt, it is therefore decided to measure the electrode potentials of cells of the type {M/MCin (mole fraction = N) in LiC1-KC1 eutectic melt/Cl2 over a range of N values and temperature for a number of metal chlorides. The results should indicate the order by which the various metals plate out on the cathode and how this order is affected by temperature and the concentration of the metal chloride in the solu-

Jan 1, 1960

By J. F. Butler, H. W. Paxton

The vapor pressures of manganese in equilibrium with several alloys in the iron-manganese-carbon system between 1200° and 1275°K have been measured using the Knudsen effusion technique in conjunction with a vacuum microbalance. The effect of orifice area of the effusion cell upon the measured pressure has been determined. The binary iron-manganese system shows small negative departures from ideality, and the system of mixed carbides, (Fe, Mn)7C3, in equilibrium with graphite behaves ideally. THIS work is a continuation of the investigations in which the Knudsen effusion method has been used to determine thermodynamic activities in systems and at temperatures of interest to metallurgists. In a previous publication,' the free energy of formation of Mn7C3 was determined and some preliminary work on the solution behavior of this carbide with the hypothetical "Fe7C3" was reported. The present work deals with this latter topic and also includes data on the binary ir-on-manganese system. EXPERIMENTAL METHOD The Knudsen effusion method was used to measure the vapor pressure of manganese in both the alloy and carbide sections of this investigation. This dynamic method of vapor pressure measurement presents a problem when studying solid alloy systems in which one of the components has a much larger vapor pressure than the others. Over-all depletion of the alloy in the most volatile component will occur during evaporation so that the pressure of that component will decrease. Even more serious than the over-all concentration change is the surface depletion of volatile component in the alloy brought about by the slow rate of diffusion of this component from the interior to the surface of the solid particle. Since knowledge of this surface composition is necessary in order to relate it to the activity determined through the measurements, changes in surface composition from the analyzed bulk composition are to be avoided in dynamic vapor pressure studies of solid alloys. The system under investigation in this study presents the problem of surface depletion of manganese since its pressure at 1230°K is 105greater than iron and 1020 greater than carbon. Since the existence of a volatile manganese carbide had been ruled out previously,' the high manganese pressure relative to iron and carbon insured that the only species leaving the effusion cell was manganese. Therefore, the effusing species required no analysis so that the manganese pressure was determined directly from the weight loss of the effusion cell. In order to detect small weight losses near the beginning of effusion, a vacuum microbalance was used to weigh the cell continually. These initial weight loss data allowed the rate of manganese effusion to be determined before the surface of the alloy became depleted in manganese. The apparatus used in this investigation is shown in Fig. 1. Temperature was measured using chro-

Jan 1, 1962