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By J. J. Arps

n approach to the study of the electrical properlies of drilling muds, their cakes and their filtrates was made by treating the drilling fluid as a porous medium. Lluring this study it was found that the weight pararneter was omitted from previous investigations on electrical properties. Patnode in 1949 made a similar approach to ,his investigation. His work showed that there was a variation of resistivity relationships with per cent Puid present in a given suspension. This present study ex-tends Patnode's investigation to one in terms of the solids fraction of the drilling fluids. Previous investigations were made on low weight muds where the effect of the rolids fraction was obscured. The following equationr were fitted to data taken from 94 field muds and 47 laboratory muds (see Tables I and 2). The parameter, C, is a complex function of the solidr content, or mud weight, of a drilling fluid. It was also found that for all drilling muds examined. A nomograph is presented combining Eqs. I and 2. INTRODUCTION It is generally recognized that the materials present in drilling muds affect the relationship between mud filtrate and mud resistivities. However, most electric log interpretations proceed with the assumption that the mud resistivity and temperature are the only important parameters needed to obtain a filtrate resistivity or a mud cake resistivity. Lamont1 suggests that only average relationships exist between mud cake, mud filtrate and mud resistivities. He indicates that there is limited accuracy when these intercorrelated factors are used since no other measure-able variable is apparent. A previous paper by Patnode indicates that drilling fluids may be considered to be a system of fluids in solid particles which may be correlated electrically in a manner similar to rock solids. 1 he equation for the resistivity factor. F = (per cent fluid) is satisfied for a given clay type in water, but the value of m varies as different materials are used in the water. The resistivity factor is not constant for a given amount of clay. As is suspected it varies as the solids fraction conducts electrical current. Since both weighting material and clay solids are present in commonly used drilling fluids, it is expected that both materials contribute to the variation of the m factor in Eq. 3. An extension of Patnode's work is presented in this paper to show some of the interrelations which exist between the resistivities of mud cake, mud filtrate and mud. Use of these data enable a more accurate calculation of mud filtrate and mud cake resistivities if only the mud resistivity and weight are measured. EXPERIMENTAL The measurements of mud weight, fluid and solids resistivity, alkalinity, and chloride content of mud samples were made in this research. Mud samples representing drilling fluids from 94 Louisiana and Texas wells (Table 1) and 47 laboratory-constructed systems (Table 2) were used in the experimentation. The measurements of the mud properties were made both in the field and in the laboratory. The tests on the properties of weight, alkalinity and chloride ion were standard tests as described by API specifications. The resistivity measuring devices were constructed in the laboratory for this study. For details on the resistivity equipment see Fig. 1. The fluid cell

By F. L. Kadey

The petrographic microscope is a well known tool in nonmetallic materials research. Its utility in the study of perlite is, therefore, not surprising. Valuable information has been derived on samples smaller than those needed by most other methods of analysis. Relatively little has been written about the petrographic analysis of perlite for two chief reasons: perlite is a material of relatively new commercial interest; and the independent prospector or expander, responsible for most studies, attacks the problem from an immediately practical viewpoint. Hence, petrographic studies of perlite have been limited to academic aspects. Rapid development of commercial interest in perlite has changed the situation. Mining and expanding companies now have effective research tools; and such instruments as the petrographic microscope have added materially to practical knowledge about this mineral. Petrographic techniques employed in the search for suitable deposits screen worthless samples rapidly and inexpensively compared with large-scale expanding tests. Hence, only samples of potential quality are selected for further testing. Field appearance of perlite reveals little about its true identity and practically nothing about its commercial significance. Consequently, any method that can be used to separate the "wheat from the chaff" is valuable. In addition to the conventional thin-section and immersion methods used in evaluation of crude perlite, petrographic microscope techniques have contributed to the study of expanded perlite. When apparently similar materials behave as differently in use as perlites, the internal structure of the individual particles becomes a subject of great interest. The purpose of this paper is to discuss some of the petrographic techniques used to characterize this material. WHAT IS PERLITE AND WHERE IS IT FOUND? Perlite was at first described as a glassy rhyolite possessing a pearl-like luster and exhibiting numerous concentric cracks resembling an onion skin appearance.' Fig. 1 is an illustration of perlite in this classical sense. Recently, its definition has taken on a commercial connotation: an acid volcanic containing 2 to 5% of combined water that, when heated rapidly to the softening point of the glass, coincident with the volatilization of the combined water, expands or "pops". Fig. 2, although hardly fitting the classical description given by Johannsen, is an excellent perlite in the commercial sense. It may occur as a breccia in rhyolite, (Fig. 3) and sometimes it is associated with obsidian nodules, as illustrated in Fig. 4. The term perlite includes the expanded product also. In the United States, perlitic rocks are restricted to the western part of the country. 2 Elsewhere in the northern hemisphere, European occurrences follow a belt beginning in Iceland and extending in a southeasterly direction through Scotland, County Antrim in Northern Ireland, and through the Massif Central of France, Germany, and Hungary; thence, into Italy and Sardinia, and through some of the Aegean Islands. A general oriental belt extends from Japan through Australia and New Zealand. Rhyolitic areas elsewhere in the world undoubtedly contain perlite.

Jan 1, 1963

By L. B. Underwood, C. J. Distefano

NORAD, when completed, will be housed in large chambers excavated out of the granite beneath the Cheyenne Mountain near Colorado Springs. A room and pillar layout for the chamber excavation was selected and executed. Many complex problems arose in designing a rock bolt system; this paper includes discussions on: rock strengthening following excavation, excavation and ground support problems, orienting rock bolts with respect to jointing systems, conducting pull tests, four-way chamber intersection problems, the need for grouting rock bolts, and loss of tension and permanency of anchorage in a rock bolt system. In the event of a sudden nuclear attack upon the United States, it is imperative that vital command and control centers have a high probability of survival. One such vital facility is the North American Air Defense Command Combat Operations Center at Colorado Springs, Colo. Known briefly as NORAD, this installation when completed will be housed in large chambers excavated out of granite beneath the eastern slope of Cheyenne Mountain (Fig. 1). The NORAD COC, a U.S. Air Force sponsored project, will serve as the primary collection and evaluation center for data concerning unknown aircraft, missiles, or space vehicles, which might bring destruction to North America. The data will be fed into high-speed computers and electronic equipment from outpost sources: radar, ballistic missile early warning stations and picket ships throughout the world. Electronically controlled display boards will make it possible to evaluate the tracking data instantaneously and to take appropriate defensive action.'

Jan 1, 1968

By D. J. Wynnemer, G. W. Preckshot

Precise electromotive force measurements have been made on the zinc-cadmium system over the temperature range 700° to 900°C. Activity coefficients, partial free energies, enthalpies, and entropies have been determined .for the entire composition range. The integral heat of mixing is positive and compares favorably with calorimetrically determined values. Vapor-liquid equilibrium compositions were determined .for a total pressure of 1 atm and these agree well with previous values determined in other ways. The use of electromotive force measurements to obtain thermodynamic data for liquid metal systems is a simple and well-known method. Several reviews of the various experimental methods and results have been published.2,3,11 However, most of the past work using this technique was carried out at temperatures slightly above the melting point of the alloy system where alloy composition changes due to vapor transport and increased metal solubility in the electrolyte are not important factors. One advantage of extending the electromotive force measurements up to and including the normal boiling point of the alloy is that it is then possible to evaluate the vapor-liquid equilibrium of the alloy at various pressure levels up to 1 atm. A detailed discussion of the thermodynamics of reversible electromotive force cells can be found in most advanced physical chemistry or chemical thermodynamic textbooks. The expression stating the inter-relation of the electromotive force and the thermodynamic functions is the Gibbs-Helmholtz equation.

Jan 1, 1962

By C. R. Clark, G. Swift, D. S. Roberts

The purpose of this investigation was to measure PVT behavior of various types and combinations of heavy hydrocarbon components from the paraffinic, naphthenic and aromatic classes where the relative proportions Of the various components were selected to approximate those of natural gas or gas condensate systems. Synthetic mixtures were used so that the compositions Of the various components could be measured accurately. n-Heptane, methylcyclohexane and methylbenzene were used to represent the paraffinic, naphthenic and aromatic components of the heavy fraction. In the mixtures studied, the heavy fraction composition was held constant at O. O5-mole lraction, the balance being methane except for one mixture where 0.10-mo1e fraction of an intermediate component, propane, was added. The PVT data for the mixtures were determined in a variable-volume, constant-mass apparatus at psuedo-reducedtemperatures from 1.84 to 2.00, over a pseudo-reduced pressure range from 2.3 to 12.0. The experimental results showed that, regardless of the type of heavy material (paraffinic, naphthenic, aromatic, or combinations thereof) mixed with methane or methane and propane, the compressibility factors at equal values of pseudo-reduced temperature and pressure varied by less than 2.2 percent. INTRODUCTION PVT data is used for natural gas and gas condensate fluids in determining reserves of reservoirs and performance of wells, in metering produced fluids, and in recombining samples for laboratory studies. While there are vast amounts of PVT data reported for natural gas and gas condensate systems from which useful correlations have been developed, ' the compositional analyses for these systems and the resultant correlations typically were made with components analyzed through some arbitrary carbon number, usually C6, with the residue reported as a lumped "heavy" fraction. The heavy fraction was stoichiometrically recombined on the basis of an apparent molecular weight to give the final compositional analysis. It is virtually impossible to make a systematic analysis of the effect that variation of the relative amounts of paraffinic, naphthenic and aromatic constituents of the heavy fraction of natural systems might have on PVT behavior. Because there is considerable latitude in the relative amounts of these constituents, one speaks of crudes or condensate liquids as being "paraffin base", etc. It is of interest to determine if changes in the relative amounts of these three types of hydrocarbons in the heavy fraction cause significant changes in PVT behavior. If so, steps should be taken to describe better the nature of the heavy fraction in PVT correlations. If not, more confidence can be placed in the correlations presently employed. DESIGN OF THE EXPERIMENTAL INVESTIGATION We attempted to determine if changes in the base of the heavy fraction would cause significant changes in the PVT behavior of gas or gas condensate fluids. Synthetic mixtures were used to enable us to systematically vary the base of the heavy fraction and to analyze accurately the fluids. We found that the heavy fraction of naturally occurring condensate systems seldom exceeds 0.05-mole fraction. Thus, the mole fraction of the heavy fraction in the synthetic systems studied was set arbitrarily at 0.05, to maximize whatever deviations in PVT behavior that might occur. Further, we judged that since the C7 hydrocarbons normally are present in greater quantities than higher carbon number hydrocarbons in naturally occurring systems, the use of n-heptane, methyl cyclohexane, and methylbenzene to represent the paraffinic, naphthenic, and aromatic species in the heavy fraction would be most appropriate. Finally, to enable us to compare our

Jan 1, 1970

By K. A. Pauly

Compressed air has been and is still very extensively used in connection with mining-operations, but its application in the past has been almost entirely confined to supplying power to underground machinery. Its introduction was due to the difficulty of taking care of the steam which is exhausted underground, rather than to any advantage in efficiency to be gained by its use. The ease with which electric power may be carried to the remotest parts of the mine and the high efficiency of the electric motor have long been appreciated by mine-operators, and electric power is now extensively used underground in the more recent developments, while many of the compressed-air engines in the older workings are being rapidly replaced by electric motors. Recently, however, it has been suggested to use compressed air for driving the large shaft-hoists, the air for the engines being supplied by electrically-driven compressors, and an installation of this character is being erected at Butte, Mont. It is the object of this paper to compare the compressed-air system of hoisting with the various electrical systems, from the stand-points of first-cost and cost of operation. However, before entering into a discussion of the various systems, it will be well to consider briefly the conditions affecting the choice of a system of hoisting in which electricity is the ultimate source of power. The power required by a mine-hoist is extremely intermittent and fluctuates between very wide limits, the all-day average consumption of power not exceeding from 5 to 15 per cent. of the maximum demand during hoisting. The cost of supplying power for such a fluctuating load is necessarily higher than that for supplying an equal amount of

Jan 1, 1912

Jan 1, 1920

By A. J. Miller, G. R. Brophy

THE Grossmann principle1 for the calculation of hardenability of steel from composition is attractive because of its simplicity. It postulates that the hardenability of a steel for any particular grain size may be expressed in terms of an ideal critical diameter, which is the product of an ideal critical diameter for a "pure" iron-carbon base multiplied by a succession of factors for each element of composition contained, including the incidentals. It infers that the multiplying factor for a given quantity of an element is constant for all combinations of composition. Grossmann has stated that in the great majority of cases the experimental values of hardenability are found to be well within 10 per cent of the calculated values. The validity of the scheme has been confirmed in principle by Crafts and Lamont2,3 and by Kramer et al .4 Their results differ from the original in the magnitude of the effect of some elements but, since they accepted the product concept and followed its direction, it is to be expected that similar results would be obtained. Crafts and Lamont, in their second paper, recognized that the factor relations for manganese and nickel were not continuously linear, but beyond certain critical amounts increase sharply. Austin, Van Note and Prater5 demonstrated nonlinear relations between hardenability and alloy contents. Their curves for chromium, silicon, manganese and nickel were all convex upward to show decreasing incremental effects. They concluded that Grossmann's factors underevaluate the hardening effect of low percentage additions of these elements, and overevaluate the larger additions. [ ] More recently W. Steven6 has found that the factor method fails when applied to complex steels containing two or three principal alloying elements other than carbon. Multiplying factors derived from his results bear a complex relation to composition and are not constant for a given amount of an element as the base composition varies. C. A. Liedholm7 found that, using either the Grossmann or the Crafts-Lamont multiplying factor values, not only were

Jan 1, 1945

By G. T. Lineberry, L. Adler

Due to safety-imposed constraints on clearances for mobile bulk handling equipment, it is necessary to optimally select a unit based on speed and size. The unit cannot be both large and fast. Since output is proportional to both size (or capacity) and speed, the combination must be carefully examined to maximize output. A simple graphical procedure and a calculus-based solution are presented to accomplish this. While the procedure applies to all mobile bulk handlers, as an example of the solution technique, attention is focused on shuttle cars. Background Major variables To fully define a bulk handling problem, the conditions, equipment, and activities must be characterized. The conditions and activities, when lumped together, are termed "encumbered space," since they "act to impede motion, as with a burden" (Lineberry, 1979). The insertion of mobile bulk handling equipment into what is already a difficult set of conditions and activities compounds the state of encumbrance, as limited space is competed for by many normal and life support systems. Long (1972) recognized the effects of design criteria, including road width, on haulage vehicle speed and, therefore, on production. Velocity-clearance curves Velocity-clearance curves are either available or can be constructed in the field. A preliminary set of curves for average conditions and activities is shown in Fig. 1, where clearances are only for the side of the vehicle (Lineberry and Adler, 1984). These curves set the safe speed limits for a vehicle operating at given clearances, under given conditions and activities. When feasible, velocity-clearance curves should be constructed through field measurement and observation. Curve construction should also consider haulway roughness, distances, and operator skill, as well as loading and dumping characteristics. It should be noted that haulage capacity determination is a total systems problem, not one just dependent on velocity and clearances. Production requirements and company capabilities also influence capacity determination.

Jan 1, 1986

JOINT convention week has become a feature of the year with western mining men. The first was held at Denver in 1926, the second at Salt Lake City in 1927, and the third is about to take place at Los Angeles. Holding in the same city in one week the meetings of a number of related organizations has been .found to permit the development of a well-rounded program at the same time that it economizes time and money for the members, many of whom belong to several of the participating organizations. For the third time, the American Mining Congress, represented by its Western Division, of which Philip Wiseman is chairman, is taking the lead and assuming the main responsibility. The A.I.M.E. is furnishing the papers for two sessions and the California Development Association for one. The Southern California Section, Robert R. Boyd, chairman, is host for the Institute, but the Northern California, Nevada and Arizona sections have each contributed papers to the program, and will be represented at the meeting. It will be a real reunion of the mining men of the Southwest.

Sep 1, 1928

By H. J. Freyn

The American iron and settl manufacturer finds himself to-day barely at the threshold of enormous possibilities for practicing rational economy in the use of fuels.

Jan 1, 1915

OFFICERS AND DIRECTORS President and Director HOWARD C PYLE, '61, Los Angeles, Calif Past President and Director AUGUSTUS B KINZEL, '60, New York City President-elect and Director JOSEPH L GILLSON, '62, Wilmington, Del

Jan 1, 1959

By Alan Lawley

AS part of a programme of experimental work on single crystals of rhenium and ruthenium, it was found necessary to have the crystallographic angles for these elements. The angles given in Table I were determined to the nearest minute of arc, by Univac Computer. The angle $ between (HKIL) and (hkil) is given by the formula: The angles given for rhenium should be particularly useful in view of the increasing interest in this element. For completeness, angular values are also given for cadmium zinc and magnesium; these form a more complete set of values than those given by Salkovitz.' The assistance of Professor J. Hobstetter and Mr. J. Crozier in the programming of this data is acknowledged. The work is sponsored by the Office of Naval Research under contract No. NONR 551 (19).

Jan 1, 1961

By Charles H. Thurman

The data given herein were first included in a paper read before San Francisco Section, A.I.M.E., in October 1940, and are applicable to conditions existing until the gold-dredging industry was temporarily suspended by Order L-208 of the War Production Board in the fall of 1942. There is no doubt that gold dredging will be resumed at some future time, and on a scale equivalent to that of the recent past, but the cost data given herein will be affected to some extent by conditions existing at that time, and by labor rates and prices for materials then prevailing. Dragline vs. Bucket-line Dragline dredges should not be considered for mining large areas of low-grade placer gravel. In such deposits a dragline operator with a 5-cu. yd. dragline would be doing well to maintain an operating cost of 6¢ per cu. yd., while a bucket-line dredge with buckets no smaller than 7 cu. ft. each could be operated for less than 4¢ per cu. yd. By operating costs, I mean only field charges such as direct operating and overhead, which includes pay roll, power or fuel, repairs and maintenance, insurance, land clearing and general expenses, but not including such items as prospecting, depletion, depreciation of equipment, State Franchise Tax, or Federal Income Tax. It is not to be inferred that a dragline dredge cannot make a profit in small low-grade deposits, where the extent of a given property is too small to justify the use of the more costly bucket-line dredge. Consider small deposits of 106 gravel. It is obvious that a deposit of 5,000,000 cu. yd. of such gravel could not be mined profitably with a new 7-cu. ft, bucket-line dredge, costing upward of $250,000, and in operation costs at 4¢ per cu. yd., paying for land or royalties out of earnings; nor could a new combination 5-cu. yd. dragline and washing plant, worth upward of $125,000 and working at 6¢ Per cu. yd., make a profit. These comparisons are made because the hourly capacity of both types of dredges is nearly the same. The bucket-line dredge averages 93 per cent operating time in 24 hr., as against about 80 per cent or less for the dragline dredge. These Percentages of operating time are important factors in making a comparison of this kind- The bucket-line dredge has greater efficiency in cleaning soft bedrock, usually characteristic of dredging deposits, and a 7-cu. ft. bucket-line dredge can be efficient to a total digging depth of 80 ft- (65 ft. below water, 15 ft. above). A 5-cu. Yd. dragline dredge is limited to about 30 ft. of efficient digging depth, 5 ft. of which could be above water. In small areas of gravel not over 30 ft. deep, a 5-cu. yd. dragline dredge could make a profit where a bucket-line dredge could not do so. As an example: compare the dredging of 3,000,000 cu. yd. of 10 gravel 28 ft. deep with bucket line, costin 4¢ Per cu. yd., and with a 5-cu. yd. dragline dredge operating at 6¢ Per cu. yd. Because of small yardage, new equipment is not warranted, therefore we can assume that the dredges of both types are used equip-ment, fully depreciated. Dismantling, mov-

Jan 1, 1946

Jan 1, 1918

By Axel Sahlin

Since the days of the infancy of metallurgical industries, slags of various kinds have been accumulating. Until a comparatively recent date hardly any employment had been found for these waste products, which have had, consequently, little or no value. An exception to this rule is the basic Bessemer slag, the value of which has become universally recognized. It is to-day one of the standard fertilizers of the world, and a price of from $15 to $20 a ton is considered reasoiable for the ground slag, which, especially in Germany, finds a ready market as fast as it is prepared. The slags from puddling and re-heating furnaces have only found vol. xx.—25

Jan 1, 1892

By J. K. Furst

THE reasons for manufacturing steel by the duplex process are, briefly: saving of time; increasing output for capital invested; and avoiding the difficulty sometimes experienced in obtaining scrap. On account of the latter reason, some plants duplex only at such times as the price and quantity of scrap in the open market warrant. At some plants the use of the duplex process enables, the blast-furnace practice to be simplified, because the furnaces run more smoothly and produce more iron when not held to a strict specification as to the silicon and phosphorus therein. The duplex process was practiced in Witkowitz as far back as 1878, but it was left to the steel makers of this country to develop it along practical, commercial lines. The American companies manufacturing steel by the duplex process at the present time are: Tennessee Coal, Iron & Railroad Co., Maryland Steel Co., Bethlehem Steel Co., Pennsylvania Steel Co.; Jones & Laughlin Steel Co., Colorado Fuel & Iron Co., Lacka-wanna Steel Co., Dominion Iron & Steel Co. of Canada. All of these companies, except the Dominion Iron & Steel Co., combine the acid Bessemer with the basic open-hearth process, while the latter combines the basic Bessemer with the basic open hearth. The Tennessee Coal, Iron & Railroad Co.'s Plant The installation of a converter of 15 tons capacity at the Ensley plant of the Tennessee Coal, Iron & Railroad Co. in 1904 marked the introduction into this country of the duplex system. The experience gained in the employment of the Bessemer converter had demonstrated that there was a shortening of .the time required in the open-hearth furnace and a reduction of the outlay for fuel and lime, thus affording substantial evidence of the economies resulting from this method.

Jan 10, 1914

By E. G. Woods, A. G. Comer

A mathematical model is presented and solved for determinution of the saturation distribution and pressure in a radial gas-storage reservoir. The model consists basically of two parts: (I) the growing gas-bubble core, and (2) the surrounding aquifer. Since the total pressure at the injection well is a function of the two-phase flow in the gas bubble and the unsteady single-phase flow in the aquifer, the resistance to flow in both zones was taken into consideration. The assumptions involved for both the radial equivalent of the Buckley-Leverett two-phase-flow equation and the injection-pressure equation are as follows: (I) the geometry is radial, (2) the gas bubble is free to expand or contract, (3) compression or expansion of the gas within the bubble may occur at the beginning of a time step, (4) the fluids are immiscible, (5) water is incompressible within the gas-storage region whereas it is compressible outside of this region, (6) a stable gas-water interface exists and (7) gas injection occurs at a constant rate or a series of constant rates. The mathematical model was solved numerically using an IBM 650 computer. A comparison is presented between the predicted results of the model, the results assuming steady-state flow and the actual initial injection-pressure history of an operating reservoir. Using the initial field pressure for a basis, the average deviation between the predicted pressure and the actual field pressure was less than 4.3 per cent. INTRODUCTION Underground storage of natural gas in abandoned oil fields, in abandoned coal mines, in caverns and in aquifers has had varying degrees of success. The lack of these first three facilities in the vicinity of most major gas marketing areas is leading more and more to storage in virgin aquifers. For the most part, this storage in aquifers has led to the study upon which this paper is based. Several excellent papers have been published discussing the problems involved in the underground storage of natural gas; however, to these writers' knowledge, none of them considered the two-phase flow of fluids in the gas bubble and the fact that the gas bubble will grow or shrink in size depending upon the injection and withdrawal history of the reservoir. Not only will both of these factors influence the required injection pressure, but also they will have a definite bearing upon the amount of water production occurring upon withdrawal from the storage area. To solve this problem on an IBM 650 computer, several simplifying assumptions were made. Only the drainage portion of the relative-permeability curve was considered, thereby neglecting any hysteresis effects introduced during an imbibition cycle. The quantity of gas withdrawn during the period of the field study was only a small percentage of the total gas in place; therefore, this assumption is justified. For the problem studied in this case, the combined effects of capillarity and gravity were assumed to be negligible. This assumption becomes less valid as the formation thickness or the average pore diameter increases markedly. The justification of these assumptions should be studied in each case. THEORY This mathematical model for the prediction of saturation distribution and pressure for a radial gas-storage aquifer is based upon the equations for radial two-phase fluid flow'.' and for radial, unsteady-state, single-phase fluid flow.' The two-phase flow is considered to take place in a "core" whose radius is equal to the maximum radius that the gas zone will attain, as indicated in Fig. 1. The injection-withdrawal history is approximated by a series of constant flow rates. Within the "core", gas is assumed to behave as a semi-compressible fluid; that is, the gas is assumed to have a constant density based on the average gas-zone pressure for the flow period. Between each constant-rate time increment, the gas density is allowed to change. This involves an iterative solution of the pressure equation. The liquid phase in this zone is considered to be incompressible, whereas it behaves as a compressible liquid outside of this region. The equations of incompressible flow in the "core" may be written for the gas phase

By F. A. Olson, J. S. Cho, M. E. Wadworth

An infrared study of the states of hydration of MgSO4 revealed a hitherto unreported metustable dehydration state in the temperature range just below that of the stable anhydrous salt. Infrared, thermogvavimetric, and X-ray studies indicated that the state had bisulfate and hydroxide characteristics. A formula fitting all of the experimental evidence is hydrogen-bonded Mg(OH)HSO4, or possibly the chemically equivalent 1/2 Mg(HSO4)2. Mg(OH)2 Infrared spectra of the 7, 6, 1, and OH2O states of hydration are given as well as the spectra of the newly found state which is called the bisulfate state in this paper. Thermogvavimetric studies as a function of water-vapor pressure gave an enthalpy value of 16 cal per mole, and 25 eu for the conversion of the bisulfate state to that of the anhydrous salt. The free energies of the transition varied from 1.76 to 0.18 kcal per mole as the transition temperature varied from 279° to 336°C. The bisulfate state is believed to be of importance in catalytic dehydration phenomena using MgSO4 and may be of interest because of properties in sulfating reactions differing from those of the monohydrate. Also, an analogous state may exist as a hydration state of other sulfates. ANHYDROUS magnesium sulfate is a catalyst with a high degree of specificity for the dehydration of secondary alcohols.1'2 The only product obtained at the usual operating temperature range of 360" to 400°C other than the corresponding olefin is water. Thus, the bonding of water to the anhydrous salt as well as an understanding of the hydration states of MgSO4 became of interest in attempting to understand the catalytic mechanism better. In the process of this study using infrared, X-ray, and thermogravimetric analyses a dehydration state not previously reported was found. Proof of its existence, the nature of the state, and its role, if any, in the catalytic mechanism then became of interest. This paper is concerned principally with the first two aspects of this problem. Magnesium sulfate forms many hydrates, of which the monohydrate and heptahydrate (Epsom salts)3 are most important. Other hydrates4 are known with 1-1/4,5 l-1/2, 5 2, 4, 5, 6, and 12 H2O's. The hydrates with 1-1/4, 1-1/2, 2, 4, and 5 HzO's are unstable. The anhydrous salt is very stable thermally and has a strong affinity for water. It can be heated without additional decomposition to about 800°C.' At 900°C noticeable decomposition takes

Jan 1, 1964

By T. E. Brower

SHORTLY after our previous paper on this subject was printed,1 we located a source of uncertainty in the results arising from the unexpected fact that hydrogen slowly reduces silica at 1100° C. in presence of iron, even when the iron nowhere touches the silica, although in absence of iron it does not do so. This difficulty has been completely obviated by the use of a small high-frequency furnace, which enables us to heat the specimen for analysis without raising the temperature of the silica vessel to a point at which any appreciable reduction of the silica glass occurs. We now describe this modification of procedure, and present some typical results obtained with it. For any given specimen of steel, the results are entirely definite and. reproducible, but their precise significance is still open to some question, as indeed is true of all methods of oxygen determination so far developed. Further elucidation of this question is to be expected from the cooperative comparison of the several methods now under way under the auspices of the Bureau of Standards at the instance of the Iron and Steel Division of the A.I.M.E.

Jan 1, 1934