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By John Riegle

To date. utility company underground storage of gas has generally been restricted to depleted dry gas fields. The Playa del Rey project is probably the first to successfully store gas in a partially depleted oil reservoir with the recovery of large volumes of pas at high rates as the main objective. Oil recovery has been a secondary consideration. Problems encountered unusual to those of storage in a dry gas zone were: (1) the removal and retardation of formation of emulsion. (2) the upstructure movement of fluid during withdrawal periods which formed fluid blocks, and (3) reservoir shrinkage resulting from encroachment of edgewater. The solution of these problems as outlined in the paper has resulted in increasing the withdrawal rate from the original design capacity of 4,000 Mcf per hour to the current 10.000 Mcf per hour. Additional increase is anticipated as the operations continue. Migration. reservoir performance. operational procedure and a historical record are included to make this a resume of the project from its war-time inception in 1942 to the first of 1952. INTRODUCTION The Playa del Rey underground gas storage project is probably the first project in which gas has been stored in a partially depleted oil reservoir, with the recovery of large volumes of gas at high rates as the main objective and the recovery of oil a secondary consideration. Problems unusual to those of storage in dry gas zones have made this a pioneer endeavor. The total storage capacity of approximately 1,500,000 Mcf of this reservoir is small in comparison with other underground gas storage projects. However. by study and experiment the deliverability into transmission lines. operating at pressures in excess of 150 lbs., has been nearly tripled in the past three years. to the current 10.000 Mcf per hour late, without the use of compression. It is anticipated this rate will gradually increase as additional fluid is removed from the formation. LOCATION AND HISTORY Playa del Key is located on Santa Monica Bay about two miles south of the beach commuity of Venice and 15 miles southwest of the renter of the City city Los Angeles. Fig. 1. The discovery well was completed at 6,194 ft in 1929. An upper zone at 3,905 ft was found on June 18. 1930. Townlot development was very rapid and by the end of 1930 there were 141 producing wells in the field. The Union Oil Co. completed a lower zone well south of the Townlot Field in May, 1931, which was believed to be an extension, until additional drilling of about 50 wells during 1934 and 1935 indicated this area to be a separate accumulation as shown on Fig. 2. The lower oil horizon, which is now the storage zone, had no original gas cap and is believed to be a continental detrital deposit of conglomerate that accumulated in valleys and depressions of a weathered schist high. which later subsided and was overlain by an impervious nodular shale. This type of formation has rapid variation of porosity. permeability and thickness due to lack of sorting action common to marine deposition. and the uneven surface of the original schist high. Production was limited on the upstructure sides by the pinching out of the conglomerate, and downstructure by edgewater. Unrestricted production, together with high permeabilities, led to large wastage of gas from this new area as facilities were not available for transport of gas to market. The decline was very rapid and by 1942 the portion of the new area south of Ballona Creek was nearly depleted. ACQUISITION OF PROPERTY The rapid increase in industrialization of Southern California during World war 11 forced upon the local gas com-

Jan 1, 1953

By FLOYD T. TAYLOR

IN 1833, less than one hundred years ago, Michael Faraday discovered and stated the laws of electrolysis. His discovery formed the foundation of a new use of metals which has now reached a variety of application not ordinarily appreciated. Furthermore, things can be done with electro-deposited coatings which have thus far defied other methods. Some of the uses of electro-deposited coatings are interesting. The tonnage of metals already finding an outlet through such a channel is considerable. In general electro-deposits have two characteristics: ornament plus utility; utility plus ornament. Both these factors are usually found associated in electro- deposits. Ornament plus utility was probably the first use. For example, the silver-plating of tableware, having its real birth in Birmingham, England, about 1844. However, this same ornament plus utility retarded the development of electro-plating, because in the beginning, electro-plated articles were branded with the odium of imitation and shunned accordingly. The gold brick of the swindler may be an exception to this statement.

Jan 1, 1929

By Theron Wasson

Michigan reports another record year. Its production of 18,605,000 bbl. exceeds any previous year's total and is 2,000,000 bbl. over 1937, the previous record year. Production in 1938 brings the accumulated total for the state to a little over 100,000,000 bbl. It has taken 14 years to reach this accumulative figure, which would meet the needs of our country for about one month. Twelve new oil and gas fields were opened in 1938 and 978 tests for oil and gas were completed, of which 566 were oil wells, 25 gas wells and 387 dry holes. The new oil discovered is probably about equal to the oil produced during the year. Activities in 1938 The Temple field, Clare County, was the discovery of the year. Since July, 46 wells have been completed, and although not yet outlined it appears that more than 2000 acres have been proved for production from the Monroe of Devonian age, at a depth of 3900 ft. This discovery is the result of a wildcat test along a trend northwestward from the older fields of the central basin. The Edenville pool, Midland County, ranks second among the new fields. Thirty-five producing wells have been drilled to the Dundee at 3800 feet. The surprise development was in southwestern Alichigan, Allegan and Van Buren Counties, where six new Traverse lime pools were opened with a daily production of about 8000 bbl. at the end of the year. This is the first consistent Traverse production in the state and is about 100 miles southwest of the producing areas of the central basin. These fields have had a rapid development because of the shallow depths, which range from 900 to 1500 ft. Bloomingdale, Van Buren County, had a town-lot boom, and 72 wells have been drilled there since August 1938. Small operators from many states have been attracted to this shallow territory, and the coming year will see much drilling in these and surrounding counties. The Buckeye field, Gladwin County, led the state in amount of oil produced. Its total of over 7,000,000 bbl. was far ahead of that of any other pool.

Jan 1, 1939

By Theron Wasson

Michigan reports another record year. Its production of 18,605,000 bbl. exceeds any previous year's total and is 2,000,000 bbl. over 1937, the previous record year. Production in 1938 brings the accumulated total for the state to a little over 100,000,000 bbl. It has taken 14 years to reach this accumulative figure, which would meet the needs of our country for about one month. Twelve new oil and gas fields were opened in 1938 and 978 tests for oil and gas were completed, of which 566 were oil wells, 25 gas wells and 387 dry holes. The new oil discovered is probably about equal to the oil produced during the year. Activities in 1938 The Temple field, Clare County, was the discovery of the year. Since July, 46 wells have been completed, and although not yet outlined it appears that more than 2000 acres have been proved for production from the Monroe of Devonian age, at a depth of 3900 ft. This discovery is the result of a wildcat test along a trend northwestward from the older fields of the central basin. The Edenville pool, Midland County, ranks second among the new fields. Thirty-five producing wells have been drilled to the Dundee at 3800 feet. The surprise development was in southwestern Alichigan, Allegan and Van Buren Counties, where six new Traverse lime pools were opened with a daily production of about 8000 bbl. at the end of the year. This is the first consistent Traverse production in the state and is about 100 miles southwest of the producing areas of the central basin. These fields have had a rapid development because of the shallow depths, which range from 900 to 1500 ft. Bloomingdale, Van Buren County, had a town-lot boom, and 72 wells have been drilled there since August 1938. Small operators from many states have been attracted to this shallow territory, and the coming year will see much drilling in these and surrounding counties. The Buckeye field, Gladwin County, led the state in amount of oil produced. Its total of over 7,000,000 bbl. was far ahead of that of any other pool.

Jan 1, 1939

By J. A. Solomon, H. E. Shafer

As a result of the great demand for metallic aluminum and the scarcity of domestic bauxite, numerous processes have been proposed and developed to extract the oxide of this metal (Al2o3) from clays, shales, and other low-grade raw materials.1-4 An exploratory study was made to extract alumina with sulfuric acid from relatively impure coal-associated draw-slate and to establish an optimum calcination temperature for maximum recovery. Draw-slate is the term used to describe the hard, slaty material directly overlying many coal seams and may range from a few inches to a few feet in thickness. Alumina content of these draw-slates may range from as low as 15% to over 35%. Although the following results are limited in scope, some of the data should prove beneficial for further work. Coal-associated clay, shale, and gob heretofore have been considered nuisance products; any successful alumina extraction process would greatly enhance the worth of these almost limitless resources. This research demonstrated that an optimum calcination temperature for alumina extraction could be established for a coal-associated draw-slate and that this temperature was lower than those suggested in previous work with unspecified clay types. It should be noted that slightly higher acid concentrations and somewhat finer particle sizes were used in this series of tests as compared to previous work. EXPERIMENTAL WORK Essentially, alumina extraction proceeded in four steps: 1) grinding, 2) calcining, 3) acid leaching, and 4) precipitating of aluminum sulfate. An initial series of reference tests to determine the optimum temperature of solubility for alumina was run using relatively pure kaolin. Kaolin forming clays are hydrous aluminum silicates of the approximate composition 2H2O A12O3 2SiO and kaolinite is the mineral that predominates in most kaolins. 5 The kaolin was ground to -30 mesh and subsequently calcined at temperatures ranging from 100°C to 700°C. Each sample was calcined for 1 hr in a muffle furnace and in turn subjected to sulfuric-acid leaching (H2SO4, 9 molar) for a 2-hr period. The filtrates were analyzed for the amount of dissolved alumina recovered.637 Also, each sample of leached or barren residue was

Jan 1, 1968

By J. E. Tobey

THERE are a lot of good things about this great industry of ours. Let us stop commiserating and consider some of the things that are right in this business. Coal is number one in the basic material industries. Our civilization owes more to it than to any other basic commodity. We are literally immersed in the benefactions of coal. In cur man-made world it is indispensable and we are constantly surrounded by objects, materials, and services which owe their existence to coal. Practically all the important materials, such as iron, steel, brick, cement, lime, rubber, glass, cotton, and wood have felt its magic touch.

Jan 1, 1939

By T. C. Clarke

The history of iron construction in this country well illustrates the three phases of thought described by Auguste Comte, the French philosopher. The first is the era of faith, when belief in the safety of structures rests on the authority of the designer. The second is the era of criticism, when plans of structures are analyzed with much mathematical skill, but the data upon which the chain of reasoning depends is assumed upon insufficient experiment. The third, upon which we are now entering, is a scientific era, which demands experimental proof. It also demands that this proof shall be derived from experiments made on full-sized specimens, such as are in actual use, and not upon toy models. Until the construction of the United States testing-machine, now at Watertown Arsenal, it was impossible to make such experiments with accuracy. We now have a machine in which we can test full-sized specimens of every part of a bridge or other structure that we want to use, and under the same conditions in which it is actually used. The next thing is to get money to make these experiments available. No private individuals can afford to do it, and even if they could, they might wish to keep the results to themselves. So that the next point is that we want money, and that, I believe, everybodly thinks we should ask Congress for. We want also, as has been said, some one who shall make a business of testing, and who has plenty of time. Persons who are employed in private business are too much in a hurry; they want to do a thing and get done with it, and then do something else; but government officers are entirely free from this feeling; time to them is of no account, and in experimenting that is the very element that is of value; it does not do to be hurried; the great thing is to get it right and to test your results, and go over it, again and again. And the experimenter who operates the machine must be some person educated up to the use of it. We then want a general advisory board who will indicate a plan of experiments, collect the results; and publish them. Some experiments were made the other day at the Watertown Arsenal upon full-sized

Jan 1, 1882

By L. W. WALLACE

IN an engineering fashion we have made an assay of the engineering profession, using as a. sample the engineers listed in "Who's Who in America" (1928-1929). We are aware that some will say it is an unfair sample; that it came from the best mine. This is readily admitted, with this qualification: that all engineers and architects by virtue of their training and experience have been freed of most of the dross to which mankind is heir. They are -a selected group to begin with, having all the potentialities those in the sample possess. We are also aware that some will say a part of those included in the sample are not engineers. Our answer to that criticism is this: An engineer is no less an engineer because for the time being he is president of a bank, a university, an opera company, or a hotel company. Moreover, he is no less an engineer because he is a governor of a commonwealth, a United States senator, a member of the Cabinet, or the President of the United States.

Jan 1, 1929

By Sherwin F. Kelly

MANY baffling problems of crustal geology-of warping and folding, elevation, subsidence, and great dislocations of the earth's surface-may now be on the verge of yielding to the science of geophysics. Electric, magnetic, gravitational, geothermal, and seismic methods are being turned to the gathering of geological evidence buried by deep layers of rock, or lying beneath the waters of the oceans. In this hope, B. L. Miller expresses the opinion that these geophysical studies will sup- ply useful data bearing-on some of the more theoretical problems of North American geology. Among these for example, is the explanation of how Appalachia disappeared. This ancient land mass is supposed to have foundered beneath the Atlantic Ocean after the close of the Paleozoic era and the question arises, was it warped or faulted downward? The geophysical data, though meagre, indicate that the surface of the dense, basal rocks, the probable remnant of ancient Appalachia now underlying the Continental Shelf, slopes downwards to a depth of some two miles below sea level at a distance of 140 mi. from shore: thus suggesting that the subsidence was the result of warping downward rather than abrupt faulting.

Jan 1, 1938

By Hollis Peacock

THE Bingham area in the West Mountain mining district on the eastern slope of the Oquirrh range, some 28 miles southwest of Salt Lake City, has been the most consistent producer for the United States Smelting Refining and Mining Company, production having been continuous, except for minor interruptions, since the organization of the United States Mining Co. in 1899. This production has come from fissures and mantos largely within limestone members aggregating something less than 10 per cent of a thick quartzite sequence of Pennsylvanian age which has been warped into an open syncline plunging northwesterly. Bedding on the easterly limb dips 10°-45° but steep-ens to 90° and even overturns on the westerly limb. Ore bodies cluster about the more northerly of two elongate interconnecting stocks of monzonite which have risen in an axial position within this syncline. Largely within the more northerly of these stocks is the low-grade copper ore body exploited in the Utah Copper open cut of the Kennecott Copper Corp. The values, in seams, minute fracture fillings, and disseminations of pyrite and silica, pervade not only the stock but adjacent sediments, and form a nebulous, sprawling mass which both mineralogically and geographically is the center of the district. The more southerly of the twin stocks appears to be comparatively inert and without obvious relation to mineralization. which

Jan 1, 1948

By Heinrich 0. Hofman

A T THE meeting of the Board of Directors on June 24, Prof. Heinrich O. Hofman was elected an honorary member of the American Institute of Mining and Metallurgical Engineers. Professor Hofman is best known to the world at large for his publications, and in this respect he is to this generation what Schnabel was to the previous one. The first edition of Professor Hofman's "Metallurgy of Lead and Desilverization of Base Bullion"; was published in 1893; the fifth edition in 1898. In 1913, he published his work on "General Metallurgy;" this was followed by "Metallurgy of Copper" in 1914, and a revised and enlarged edition of the "Metallurgy of Lead" in 1918. "Metallurgy of Zinc and Cadmium" is now in press. He also published, through the Massachusetts Institute of Technology, "An Outline of the Metallurgy of Iron and Steel" for students' use. Since the founding of "Mineral Industry" in 1892, he has been continuously the annual contributor on the metallurgy of lead, and all Institute members know that his contributions to the TRANSACTIONS have been liberal in the extreme. It is through this medium that the results of the extensive research work, which he has always carried on in connection with his work at the Massachusetts Institute of Technology, have been published. Of the greatest importance are his papers dealing with the formation temperatures of slags, but many other metallurgical subjects have been covered.

Jan 1, 1921

By AIME AIME

THE iron and steel activities of this meeting opened on Monday morning with the steel melting session," with G. B. Waterhouse in the chair and A. L. Feild as vice-chairman. N. A. Zeigler's paper, on "Gases Extracted From Iron Carbon Alloys by Vacuum Melbing," created considerable interest and the discussion in general was most favorable. H. W. Gillett and Louis Jordan of the Bureau questioned the method of analysis for oxygen and C. H. Herty, Jr., and J. M. Gaines, Jr., I , expressed their surprise at the large amount of oxygen with the high ,carbon alloys. Whether the gases found existed as gas in blowholes or as oxide inclusions was also a moot point. A paper by C. D. King, on "Basic Open-Hearth Yields," was an extremely interesting and valuable contribution. It was discussed by C. E.Kinney and A. L. Feild and numerous questions were asked throughout the presentation. Mr. King then presented a critical analysis of the losses together with novel methods of calculating them. A paper by C. H. Herty, Jr., and J. M. Gaines, Jr., on "Unreduced Oxides in Pig Iron and Their Elimination in the Basic Open-Hearth Furnace," followed. The question of silicates and oxides in pig iron created much discussion, notably by Henry Hanson and W. J. MacKenzie, who gave figures on chipping cost as a function of blast-furnace practice.

Jan 1, 1929

By ANDREW McVILLIAM, WILLIAM H. HATFIELD

AT the 1902 May meeting of the Iron and Steel Institute, the, authors presented a paper on " The Elimination of Silicon in The Acid Open-Hearth," wherein they recorded a few typical examples of certain Siemens charges out of a very large number specially watched for the purposes of that research. The main deductions drawn from those experiments have been accepted in all the intelligent criticism during or after the discussion on the paper. One opinion, however, was rigidly held by all who mentioned the matter, with the single exception, perhaps, of Mr. Lange, and that was the necessity for the attainment and the maintenance of an abnormally high temperature in order that the percentage of silicon in the metallic bath might increase, or that an unusually large proportion of silicon might be retained in the metal. The original decision was ar-rived at on the results of scores of trials, and has since been the subject of frequent experiment. The authors still retain their opinion that although, naturally, a higher temperature will accelerate the (probable) action between the carbon of the steel and the excess silica of the slag, they then fairly proved, and have now abundantly confirmed the fact, that around the temperatures occurring in Siemens steel-making practice the chemical composition of the slag, particularly with regard to its acidity, is the factor which determines whether the percentage of silicon in the molten steel shall increase or decrease. In the discussion in 1902 Mr. Saniter called attention to Mr. H. H. Campbell's work, and in the reply the authors also mentioned that of Messrs. Winder and Brunton of 1892, the two

Mar 1, 1905

By H. N. Lawrie

Introduction. THIS study was undertaken on account of the lack of definite knowledge concerning the influence of bismuth on wire-bar copper, and the small elimination of bismuth from copper-matte during the smelting-operations. The early workers who studied the influence of bismuth on copper confined their investigations to malleability and ductility-two physical properties which are related to the others so intimately that their determination is of primary importance. Karsten ' and Levol,2 using bending- and mealleability-tests, seem to have been the first to take up the subject, and while their results are incomplete, they agree in the main with the later work of Hampe.3 The bending-tests used by the first investigators consisted in bending the specimen until it failed. The malleabilitytests were made by beating the material to a knife-edge with a hammer. Hampe not only determined the percentage of bismuth which would cause red-shortness and cold-shortness of the alloy, together with other influences of bismuth on the malleability and ductility of copper, but also took up the influence of the bismuth protoxide, BiO, on copper, and of bismuth sesquioxide, Bi2O3, on the copper protoxide, CuO. Hampe's conclusions of the influences of these two latter compounds of bismuth on copper are as follows "If the protoxide of bismuth be alloyed with metallic copper, it is not changed to metallic bismuth, but remains mechanically distributed throughout the copper.

Sep 1, 1909

By A. C. Fieldner

COKE and by-products have prime importance in the war program. The past year was marked by the construction of new and the rehabilitation of old by-product and beehive ovens and by the increase of production from existing plants to practically 100 per cent capacity. W. T. Brown's paper, "Plan to Improve Blast-Furnace Coke," presented at the Fuels Conference in St. Louis, Sept. 30, showed how the blending of low- and high-volatile coal improved the physical properties of coke and that improvement of the quality and uniformity of coke favored an increase of blast-furnace capacity- a vital need in the war program. Others in the industry have likewise increased production of coke or recovery of by- products by various innovations or changes in operation. Recognition of the value of pooling these developments for the benefit of the entire industry led to organization of a survey of coke- oven plants and blast furnaces by the Bureau of Mines in co-operation with the Solid Fuels Co-ordinator with a view to improving metallurgical coke production and recovery of by-products. This survey is being conducted with the help of an advisory committee consisting of representatives of the Bureau of Mines, the Solid Fuels Co-ordinator, the War Production Board, and the blast-furnace, coke-oven, and coal-mining industries.

Jan 1, 1943

By John T. Wizzard, R. P. Killmeyer, B. S. Gottfried

The Coal Preparation Branch of the Pittsburgh Energy Technology Center has developed a computer program to calculate the performance characteristics of coal washing devices. This program uses specific gravity analyses of the clean coal and refuse streams as input, and generates dependent and independent performance criteria for the washer. Partition curves are internally represented in a functional form by a Weibull function. Performance criteria generated by this computer program are compared to manually calculated performance criteria for air tables, Dynawhirlpools, Baum jigs, hydrocyclones, and dense medium cyclones. The comparisons show that the computer program gives results in close agreement with the hand- calculated values while greatly reducing the amount of time involved in performing the analyses.

Jan 1, 1983

By Simon D. Strauss

The world appetite for minerals in the, third quarter of this century grew at a higher rate than had been anticipated. To illustrate, consider the experience of four, commodities. Excluding the Communist bloc, sometimes referred to as the centrally planned economies, demand for aluminum increased at a compound rate of 8.6% between 1950 and 1975,; copper rose by 4.4%; iron ore by 5.5%; and tin, the laggard in the group, by 2%. Except for tin, the figures are substantially greater than growth rates anticipated in 1950 in the Paley Commission report and other studies. The growth rate was not evenly distributed in geographical areas. Professor Wilfred Malenbaum of the University of Pennsylvania did an interesting study breaking these figures down as among three principal sources of demand -- the United States, other industrialized nations (which he referred to as the "rich lands"), and the developing world (which he referred to as the "poor lands").

Jan 1, 1982

By Chas. H. Behre

MINING geology, both theoretical and practical, continued to make noteworthy progress during 1938. Mining companies generally, stimulated especially by the improvement in economic conditions during the latter part of the year, extended their workings and developed new ore bodies. Federal and state surveys expanded their search for favorable localities and actual ore bodies, with corresponding enlargement of regional knowledge. Theoretical investigations covered geochemistry of ore deposition, structural control of mineralization, and mineralogy of the ores (chiefly aided by the microscope). More geochemical work is greatly needed: ore searching is still too purely empirical, based on features that have been recognized else- where. Thus, clearer understanding of the conditions essential to transportation of metal salts is needed. Jean Verhogen has suggested that solubilities

Jan 1, 1939

By T. W. Atkins

ATHOUGH the magnesium industry in this country is about thirty years old, not until American industry began to amaze the rest of the world and confound our enemies with the extent and variety of our war production did the industry begin to come into its own. At the outset of the war, only three companies were producing and fabricating magnesium in this country. Today, about sixty companies are producing, casting, forging, extruding, rolling, and stamping this lightweight champion of metals. Experience in alloying, processing. and fabricating the metal gained during the war years is now being translated into hundreds of civilian peacetime applications. In no sense should magnesium be considered as a substitute for other metals. It has come into popular favor because If many unique properties in addition to is being the lightest known structural metal. These attributes are toughness, igidity, corrosion-resistance, and the ease with which it can be machined and worked. Magnesium is the third most abundant element in nature. Sea water, magnesite,

Jan 1, 1946

By E. A. von Hahn, T. R. lngraham

Cementation rates ulere studied by rotating an elec-tropolished or etched copper strip in aqueous solutions, of either perchloric acid or alkaline cyanide, containing silver ions. The rates of cementation were more rapid in acidic media than in cyanide media. In both, the rates varied with the rate of rotation of the copper strip. The deposits formed in the acidic solutions were finely divided, loosely adhering powders. Those formed in the cyanide solutions were dense and adherent. The presence of the deposits influenced the cementation rates. In the acidic solutions the rate was enhanced, possibly because of the increased cathodic area. In the alkaline solutions the rates were decreased in the presence of the deposits. This has been attributed to restricting the diffusion of the copper ion from the rnetal outward into the bulk of the solution. In an earlier paper1 the authors described a kinetic study of the cementation of palladium on copper in perchloric acid solutions. That work indicated that there were two stages in the palladium cementation process. The first, more rapid stage was consistent with rate control by the diffusion of Pd11 ions to the copper surface and/or by chemical reaction at the surface. The second stage was consistent with rate control by the diffusion of copper ions from the copper surface, through the deposit, out into the main body of solution. The effect of the type of deposit on the rate of cementation is of particular interest because it may be one of the primary features involved when large quantities of metal are to be cemented from solution. No substantial investigations of the effect seem to have been made. Accordingly, an extension of the previous work was arranged to study the cementation of silver on copper. This system was selected because of the convenience of the analytical methods, the previously established technology with copper, and the fact that the system could be studied in both acidic and alkaline media. By selecting perchloric acid and alkaline cyanide solutions as the media, it was hoped that some assessment might be made of the effects, on cementation, of having the silver ion present in a virtually uncomplexed state and in a highly complexed state. EXPERIMENTAL The cementation rates were studied, as previously described,' by rotating a copper strip (1.0 by 23.2 cm) clamped to the peripheral surface of a lucite cylinder. The solutions were kept at constant temperatures (±0.05°C) under an atmosphere of purified nitrogen, and samples were taken periodically for analysis. The initial solution volume was 1000 ml and the sample volume 5 ml. The initial silver(1) ion concentrations were made low (0.5 to 1.0 x 10-4 moles per liter) to minimize the influence of the cemented deposit on rates. The solutions were prepared by dilution of suitable aliquots of silver perchlorate and silver cyanide stock solutions. Both stock solutions were prepared from purified silver powder (Johnson, Matthey, and Mallory Ltd.) with redistilled deoxygenated water, and they were kept under an atmosphere of purified nitrogen. To prepare the stock solutions, weighed amounts of silver powder were dissolved with nitric acid. For the AgC104 stock solution the silver nitrate solution was evaporated twice to near dryness with perchloric acid and then made up to volume: For the NaAg(cN)2 stock solution, the silver ions were precipitated with sodium hydroxide solution. The precipitate was filtered, washed thoroughly with redistilled water, dissolved with 1.1 times the required stoichiometric amount of sodium cyanide solution, and made up to volume. The small amounts of free perchloric acid and sodium cyanide present in the stock solutions were disregarded in the preparation of the solutions. The copper strips were cut accurately from 0.025-in. sheet (American Metal Climax OFHC brand) and annealed for 1.5 hr at 470°C in a stream of nitrogen. Analyses of the solution samples for silver and copper were done with a Techtron Model AA-3 atomic absorption spectrophotometer. Calibration standards of the same composition as the experimental solutions were prepared and analyzed simultaneously with the samples. No difficulty was experienced in the analyses, and the reproducibility was within 1 to 2 pct in both alkaline cyanide and perchloric acid solutions.

Jan 1, 1968