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By P. Chiotti, R. J. Hecht

Vapov pressure data of solid and liquid alloys along with phase diagram data WERE employed in calculating the thermodynamic properties for the Ca-Zn system. The relative excess partial molal free energy for zinc in the liquid alloys was fitted to the relation wnvre i is we tvmpvrutiirc in ucgrees neivtu ana in is the tr~ole fvaction. Relations for the standard free energy of fortnation for the eight cornpounds were developed. ThE phase diagram for the Ca-Zn system as determined by Messing et a1.' is reproduced in Fig. 1. Earlier work on the phase diagram has been summarized by Hansen and Anderko2 and the very limited thermodynamic information for this system has been reviewed by Hultgren et a1.3 The heat of fusion for the compound CaZn2 has recently been determined to be 9260 cal per mole.4 Solubility data for calcium in zinc for the temperature range of 650" to 725°C were fitted by the relation and reported by Johnson and Dilloon5 In the present investigation zinc vapor pressure data were obtained by both the dewpoint and Knudsen methods in order to calculate the thermodynamic properties for liquid and solid alloys. The dewpoint method as employed in this work requires that only one of the components be significantly volatile, in this case zinc, and that the vapor pressure of pure zinc be known. For calculation purposes the vapor pressure data for pure zinc3 were fitted to the relations; for temperatures below 692.7K, the melting point of zinc. The corresponding free-energy relations for vaporization and sublimation of pure zinc are respectively. Some of the calculations also required knowledge of the free energy of fusion of zinc and calcium and the free energy for the 721°K allotropic transformation of calcium. The free energy of fusion of zinc was taken to be the difference between Eqs. [4] and [5], or The free energy of fusion and transition for calcium were based on the enthalpy values of 2040 and 222 cal per g-atom, respectively, as reported by Chiotti et al. 4 and the heat capacity data given by Hultgren et a1.3 and are represented by the relations, In the latter expression the difference in heat capacity between the a and 0 forms of calcium was neglected. MATERIALS AND EXPERIMENTAL PROCEDURES The metals used in preparing the alloys were Bunker Hill slab zinc, 99.99 pct pure, and Ames Laboratory calcium. The average impurities in the calcium in parts per million by weight, ppm, were N-17, H—77, Ba—216, Mg-15, Si—7, C—157, and Fe—9. The zinc was cleaned in dilute nitric acid and the calcium was used as received. The calcium was stored and handled in an argon-filled glove box and when removed from the dry box it was kept in an argon-filled desiccator. Tantalum was found to be a suitable alloy container. The alloy components were contained in a 1-in.-diam cylindri-

Jan 1, 1968

By D. Montagna

This Bureau of Mines report describes a salt-free, fluxless method for reclaiming metallic aluminum from aluminum dross. The dross is smelted under argon, nitrogen, or carbon dioxide, instead of a salt flux, in an externally heated pot furnace. Aluminum recovery, using argon, is equal to recoveries reported from commercial smelters that process dross in rotary-type furnaces This salt-free method could offer a reduction in air pollution, lower energy requirements by elimination of salts, and the production of up to 60 percent less solid waste for disposal than the salt method.

Jan 1, 1978

By George C. Bateman

WE in Canada want to see industry get back to a normal economic basis as soon as possible but wartime controls cannot be dispensed with immediately the war is over. Perhaps never again will we be entirely free from some of the types of controls such as those set up during the war. Certainly the taking over and disposal of surplus materials contemplates the continuation of some form of control for many years to come. However, to the extent that it is possible, the Allied nations are exponents of free enterprise.

Jan 1, 1944

By Noel C. Joughin, Orrie Fenn, Brian E. Protheroe

Work has shown that the use of high-pressure water jets enhances the performance of mechanical cutting in very hard rock. To assess the potential of this approach for use in conjunction with free rolling cutters, a series of tests has been conducted using both disc and button type cutters, to determine the relative effects, on cutter performance, of variations in relevant jet and cutting parameters. In these tests it was found that water jet assistance can result in reductions in the forces on a free rolling cutter typically of the order of 40%.

Jan 1, 1985

By G. A. Irons, D. Guo

"The average spout height and width produced by bottom gas injection in a water model of a steel ladle were measured with an image processing technique. It was revealed that the spout height could be described by a Gaussian curve. A combined SIMPLE -VOF model was developed to simulate the liquid surface and flow. The results showed that, though the model produced reasonable velocity distributions and free surface positions, the spout height due to the dynamic head of the rising liquid was substantially lower than observed, indicating that the bubble dynamics at the bath surface play an important role in spout height.IntroductionDue to the enormous importance of gas injection and stirring in metallurgical processes, there have been numerous publications on water and numerical modeling of such vessels. The free surface of the bath has received considerably less attention, despite its importance. At the free surface there are often important chemical phenomena occurring that require a good understanding of the fluid flow; these would include reoxidation of steel, metal splash and fume formation. Furthermore, to understand the details of slag-metal interactions such as slag entrainment, metal losses to slag and the transport phenomena associated with refining reactions, it is necessary to understand the plume and spout interactions first.There have been few experimental studies of the free surface of liquid in gas-injected ladles [1- 3], and even fewer on numerical modeling. Brimacombe and co-workers [1] studied the gas void fraction in the spout region, using a double-tip electrical resistance probe. This sensor cannot distinguish between gas in bubbles about to break and gas in the freeboard. Thus, it is a matter of judgement as to the position of the free surface. Schwerdtfeger and co-workers [2] used a single probe configuration with a wire and a counter electrode in the liquid, so that the height of the continuous liquid phase was unambiguously determined. Irons and co-workers [3] measured the spout height by ultrasonic and electrical capacitance techniques. These techniques were as reliable as the resistance techniques, but were restricted to low flow rates."

Jan 1, 2001

By J. L. Viljoen

t has long been the drive of the industry and all operations to create an environment that is free of injury and illness. We have come a long way; the leaders, executives, managers, supervisors and workers are to be commended for relentlessly driving to create, what I call a ?White Flag Day Every Day?. Yet I am also aware of the huge shift we still need to create in the industry, on the operations and in the workplaces to have them free of injury and illness. Keywords People, values, care, trust, belief.

Jan 1, 2011

By A. Goulsbra, S. Gregory, P. Gelfil, V. Martins, R. Dunne

As a general rule for gold treatment the presence of reasonable amounts of 'coarse' free gold will dictate the use of a gravity circuit. The actual particle size of gold that constitutes the por­tion of' coarse' free gold can vary widely. The larger its size the more troublesome it is, mainly because of the tendency for this gold to quickly settle out from slurries in regions of relatively low velocities. There are a multitude of places where 'coarse' gold can find a resting place, namely, in chutes, between and behind lines, in pump hoppers and in pumps themselves. Fortunately, the problems associated with recovering very 'coarse' free gold, say greater than Imm, is rare on most gold mines that have grinding and cyanide leaching circuits. For these operations it is common practice to have a gravity circuit situated within the milling circuit to recover 'coarse' free gold. Should the 'coarse' free gold constitute 15% to 20% of the total gold in a deposit then its recovery by gravity separation is seri­ously considered. As a gold mine 'matures' the availability of soft oxide ore decreases and the likelihood that harder ore having sulphide gold association increases. To maintain gold production rates in this situation either the gold grade of the treated ore must increase or more ore needs to be treated. In the latter case this is achieved by installing more grinding capacity, an expensive option, or coarsing the grind, with the downside of loss in gold recovery. In general the less expensive capital options is fol­lowed. There is, however, some upside to improve recovery when reasonable quantities of sulphide containing gold are pre­sented that can be recovered by flotation or gravity separation. Concentrates produced from these unit operations can be finely ground and reintroduced to the cyanide leach circuit to improve gold recovery. This scenario is a much less costly option than one where all the ore is ground finer. In this paper the experiences of recovering gravity gold from the Telfer Gold Mine, and gold associated pyrite from the New Celebration Mine will be discussed.

Jan 1, 1996

By M. C. J. van der Merwe

"Carboxymethyl cellulose is an organic binder used in the iron ore pelletizing industry. The basic principles of how carboxymethyl cellulose (CMC) solutions behave during the pelletizing process and how these principles affect the drop and compression strengths of the pellets are poorly understood. The aim of the investigation was therefore to gain knowledge on the behaviour of CMC during the pelletizing of haematite concentrate.Haematite pellets with different additions of CMC (0.1–0.4 wt%), were subjected to drop tests, compression tests, and free moisture content analysis. The relationship between the drop strength, compression strength, free moisture content, elapsed time, and CMC concentration was analysed.The drop strength had a strong correlation with the free moisture content of the haematite pellets, with a correlation coefficient of 0.94. The compression strength of the CMC-bonded haematite pellets increased as the free moisture content decreased, reaching a maximum upon depletion of the free moisture content. Haematite pellets with CMC concentrations of 0.1 and 0.2 wt% developed most of their strength within the first day after pelletizing, whereas pellets with concentrations of 0.3 and 0.4 wt% developed most of their strength between one and two days after pelletizing. The time within which CMC-bonded haematite pellets develop most of their strength is therefore dependent on the CMC concentration. IntroductionFines are produced during the beneficiation of iron ore. These fines are separated from the lump ore and can be upgraded to produce a concentrate, which is used as a raw material for the production of pellets. Pellets in turn form a key burden material for direct reduction processes as well as the blast furnace (Zhu et al., 2015).Inorganic binders such as bentonite have been used predominantly in the iron ore pelletizing process to obtain pellets with suitable properties (Eisele and Kawatra, 2003). These binders, however, have the disadvantage of introducing impurities into the pellets. This has resulted in organic binders being pursued as suitable replacements for inorganic binders, of which carboxymethyl cellulose (CMC) shows good potential. Although CMC has been used as an organic binder in iron ore pelletizing, the fundamental principles of how it behaves during pelletizing and how these impact on pellet properties are poorly understood."

Jan 1, 2017

By P. G. Shewmon, W. M. Robertson

The derivative of the surface tension with orientation, ??/??, for copper has been measured over the entire unit triangle. This derivative or torque term was determined from the variation of the dihedral angles at the intersection of twin boundaries and free surfaces. High-temperature anneals in graphite with a hydrogen atmosphere gave torque terms of 0.097 at (111), 0.066 at (100), and 0.0257 at (110). A variation from -36oto +23oC in the dew Point of the H2 had no effect on these values, nor did a change from 99.98 to 99.999 pct Pure copper. The removal of graphite from the system decreased ??/?? slightly. Considering the surface near a low-index plane to be smooth except for occasional steps, the free-energy increment per cm of step is calculated, and it is shown that the observed variation of ??/?? is consistent with a random distribution of steps and an interaction energy between steps. Integration of ??/?? gave the relative values of y at (100), (110), and (111) as comPared to ymax: (Y111/Ymax) =0.974, (Y110/Ymax) =0.996, (y100/Ymax) = 0.983. The ratio of the surface tension of coherent twin boundaries to the surface tension of the free surface was found to be (yT/ys) = 0.027 * 0.011. In a crystalline solid the surface tension y (surface free energy per unit area) depends on the orientation of the surface relative to the crystallographic axes of the crystal. Measurements of this variation of y with surface orientation have been reported for metals only within the last few years. Consider the grain boundary groove shown in Fig. 1. Here the three surfaces are all normal to the plane of the paper, and each has a different surface tension, y1, y2, and y3. If the system is at equilibrium, the total surface free energy must remain unchanged for a slight vertical displacement of the intersection (points A, B, and C are kept fixed). As shown by Herring,' the following equation is obtained:

Jan 1, 1962

By H. W. Reinhardt, J. W. Dally

A dynamic photoelastic analysis of stress waves interacting with a free surface is described. The free surface is that of a bench with a fixed bottom so common in quarry applications. The stress waves are generated by line charges of lead azide (Pb N,). Four models of identical geometry are investigated with the direction of detonation of the line charge varied between the four models. Dynamic photoelastic patterns are recorded and analyzed to indicate which method of detonating the line charge produced the largest magnitude of tension at the free surface. The mechanics of rock breakage by means of explosives has received considerable treatment by many investigators including Duvall, Obert, Broberg, Rinehart, and Langefors1-11 over the past two decades. Indeed in more recent years several texts12-15 have been written on the topic, treating a wide variety of subjects which are logically related to the modern technique of rock blasting. In rock blasting the chemical energy of a concentrated explosive contained in a relatively small diameter borehole is utilized to fragment the rock. The explosive is transformed into a gas with enormous pressures which exceed 10-5 bars18 This high pressure shatters the rock in the area adjacent to the borehole and produces dilatational and distortional stress waves which propagate radially away from the borehole. The state of stress associated with these outgoing waves produces a system of cracks which extend for a few feet from the borehole. The breakage produced in this manner is limited as the dynamic stress in the pulse attenuates markedly with distance. In the absence of a free surface, the stress wave propagates away from the source without further fracture. With a free face of rock near the drill hole, another mode of breakage occurs which is due to scabbing failure of the layer of rock adjacent to the free face. These scabbing failures are produced by the reflection of the incident waves and the conversion of compressive stresses into tensile stresses sufficiently large to fracture the rock. The detailed nature of the interaction of the stress waves with the free surface is complex and difficult to treat analytically. However, dynamic photoelasticity offers an experimental approach which gives a fullfield visual display of propagating stress waves and the reflection process. Applications of static photoelasticity to solution of problems related to mining technology have become relatively common (see, for instance, Refs. 17 and 18) with a plastic model loaded to produce a state of stress representative of that occurring in the workings of a mine. The application of dynamic photoelasticity is ex tremely limited. Tandanand and Hartman19 have used a multiple spark camera to study fracture in glass and plastic plates impacted by a chisel-shaped tool. This paper describes a dynamic photoelastic analysis of stress waves interacting with a free surface. The free surface is that of a bench with a fixed bottom so common in quarry applications. The stress waves are generated by line charges of lead azide (Pb-N6). Four models of identical geometry are investigated with the direction of detonation of the line charge varied between the four models. Dynamic photoelastic patterns are recorded and analyzed to indicate which method of detonating the line charge produced the largest magnitude of tension at the free surface. Experimental Procedure The model illustrated in [Fig. 1] was fabricated from a sheet of Columbia Resin CR-39 to represent a bench with a fixed bottom. Properties of the CR-39 pertaining to these dynamic experiments are listed in [Table 1]. Scribe lines on 1-in. centers are used to identify locations along the bench face. The bench height was 8 in., the burden was 3 in., and the overall dimensions of the sheet, 16 and 18 in., were large enough to eliminate reflections from nonessential boundaries during the period of observation of the dynamic event. To simulate a charge in a borehole, a groove 0.062 in. wide and 0.080 in. deep groove was cut into the sheet from one side. The lower end of the groove was 1 in. or 1/3 the burden distance below the bottom of the bench. The upper end of the groove was 3 in. or one times the burden distance below the upper level of the bench. The groove was packed with 60 mg of Pb No per in. of length, and ignited with a bridge wire detonator. Four different ignition procedures were used to examine the effects of detonation direction on the stress wave interaction with the free face of the bench. In Test 1 the line charge was ignited at the top and the line charge detonated downward. In Test 2 the line charge was ignited at the bottom and the charge burned upward. In Test 3 the charge was ignited in the center with the top half burning upward and the bottom half burning downward. Finally in Test 4 the line charge was ignited at both ends simultaneously. Sixteen high-speed photographs of the photoelastic fringe patterns representing the stress wave propagation were recorded for each of the tests. A Cranz-Schardin multiple spark gap camera 20,21 was operated at framing rates which were systematically varied from 110,000 to 250,000 frames per sec during each test.

Jan 1, 1972

By Zhigang Zak Fang, Michael L. Free, Jaehun Cho, Syamantak Roy, Amarchand Sathyapalan

Leaching characteristics of impurity removal from the Upgraded Titania Slag (UGS) using hydrochloric and boric acids has been investigated. Specifically, this study has focused on removal of iron oxides from the UGS that has been reduced by hydrogen gas and magnesium at 750oC for 5 hours. Reduced UGS is mainly composed of titanium hydride and impurities like iron oxides, silicon oxide, aluminum oxide, and magnesium oxide. The concentration of hydrochloric and boric acids and the leaching temperature have been chosen as the prime variables to identify the optimum conditions and leaching characteristics for removal of iron oxides. It was observed that under the constraint that 1 wt % of titanium hydride loss is the maximum amount tolerable, 0.1M HCl with 1M boric acid and 90oC are the most effective parameters for iron removal from the reduced UGS. Also, the overall rate of reaction seems to follow interfacial reaction controlled kinetics. The calculated activation energy of the reaction is 73.90kJ/mol.

Jan 1, 2016

By W. Rosotoker

Using an expression for the free energy of a homogeneous phase as a function of composition, a relationship is derived which interrelates the phase boundaries extending from the allotropic transformation of the solvent metal. Comparisons between observed and calculated phase boundaries in the systems Fe-Ni, Fe-Mn, Fe-W, Ti-Mo, and Ti-Cb are presented. IT is the purpose of this paper to illustrate how the general free energy equations for two phases in equilibrium may be used to derive an expression which interrelates the phase boundaries extending from the allotropic transformation of the solvent metal. The free energy per gram atom of a disordered solid solution may, for many purposes, be represented by the equation:' F = ½NZ [C-V,, + (1-C) VbB + 2C (l-C)V] + K(T) +RT[C-lnC+ (l-C)ln(l-C) ] [1] where N is Avogadro's number; Z, the coordination number; C, the concentration of the solute element in atomic percent; the subscripts refer to concentrations at phase mixture boundaries; VAA, VBB, and V,, are the bond energies between like and unlike adjacent atoms, respectively, at the interatomic spacing characteristic of the phase. The bond energies are usually assumed to be independent of small changes in the lattice parameter occasioned by solute additions and variations in temperature; V = VAB ---------------—— ; K(T) is the sum of the heat con- tent and heat entropy; R, the molar gas constant; and T, the temperature in degrees Kelvin. The free energy of a homogeneous phase is there- fore the sum of an internal energy, a specific heat, and a configurational entropy term, respectively. The compositions of two phases in equilibrium at a given temperature are governed by the minimum total free energy principle. Graphically, this is represented by the points of tangency of the tangent common to the free energy vs. concentration curves of the two phases. Analytically, this may be expressed as: ( df) = (df) [2] dc dc Expanding both sides using eq 1, the following equation is obtained after convenient readjustment of the terms: RT In[(ca)(1-c)]-½N (Vaa-Vbb)(Za-Zb) +NV [Za(l-2Ca)-Z,(l-2C,)] [3] The following assumptions have been made at this point: 1—The specific heats of the two phases are independent of composition variations within the range under consideration. Accordingly, the K(T) terms disappear on differentiation. 2— (Vaa)o = (VAA); (VBB). = (VBB); Va = V, Theyjustification for these assumptions can lie only in the successful application of the resultant equation. It may be noted that Zener2 has used assumption 1 in the calculation of the boundaries limiting the (a+j3) phase mixture in the Cu-Zn system.

Jan 1, 1952

By E. G. King

The Bureau of Mines made experimental determinations of the heats of formation of forsterite and chrysotile at 298.15° K. The heat capacities of two polymorphs of serpentine, chrysotile and antigorite, were measured over the temperature range from 50° to 298° K and the entropies at 298.15° K were evaluated. The heat content of antigorite above 298.15° K was measured to 850° K. These thermochemical data were combined with other pertinent data to give heat and free energy of formation values at high temperatures. Free energy values are given for the reaction, forsterite + water = brucite + serpentine at different temperatures and pressures.

Jan 1, 1967

By Emil H. Geus

A process has been developed to recover aluminum from dross which does not require the use of salt flux as commonly employed, This results in a salt-free residue which has potential industrial uses or alternatively can be safely land-filled. The dross is first heated by an air-fuel or oxy-fuel burner in a sealable rotary furnace. At a suitable temperature the burner is turned off and the temperature of the dross thereafter controlled by means of an atmosphere of oxidative and inert gases. When the free metal has agglomerated it is first discharged from the furnace, followed by the residues.

Jan 1, 1995

By Byron K. nelson, David Mathieson

Until quite recently concentration of free gold in gravity circuits ahead of froth flotation and/or chemical treatment was considered an uneconomical pursuit in many gold pi.ants in Australia. Over the past 10 yenrs since initial introduction of the Knelson Gold Concentrator, over 600 hnvc been surpl led world wide and they have been developed to the stage that Lhey can now be utilised in almost all instances where free gold appears in significant quantltles ln grinding circuits. They out perform and displace more conventional gravity sepnration equipment such as spirals, tables, sluices, jigs, drum separators etc.

Jan 1, 1991

By Thomas E. Ricketts

Limited void volume blasting (LVVB) occurs when rock is blasted into a volume that is not sufficient to let the rock expand to its free-bulking value. The freebulking value is obtained when the rock particles have enough space to separate, tumble and rotate to produce the maximum amount of void possible between the fragments when they finally come to rest. Although bulking value depends on particle size distribution and shape, a typical free-bulking value for uniform, finely broken shale is about 1.67. LVVB occurs in almost every type of blasting used in both surface and underground mining operations. For example, in multiple-row bench blasting for surface mining, the final delays that are designed to fragment the rock furthest from the free-face are generally confined by previously blasted rock which results in a LVVB situation. In underground mining, the blasting is automatically confined and is commonly done intentionally to limited void volume to reduce mining cost and improve safety. LVVB primarily affects rubble bulking and thus the excavation of the broken rock which is related to the productivity and economics of a mining operation.

Jan 1, 1989

By E. A. Metz

It has been approximately four years since the International Agency for Research on Cancer (IARC) reclassified crystalline silica as a "group one" substance. Since then, crystalline silica has been considered a human carcinogen. Silicosis is a preventable disease, and several aggressive campaigns have been developed to increase awareness of silica-dust-related problems in the industrial environment. New analytical techniques are now being developed to determine quantitatively the amount of crystalline silica in materials. Yet, still much is to be learned about the surface properties of silica and the way in which the disease progresses into full-blown silicosis. This paper discusses the interaction of free radicals generated by the mineral particles and lung tissue. It is the cell injury and DNA damage that progresses to fibrogenesis. Freshly fractured surfaces of silica contain free radicals. These free radicals play an important role in the stimulation of the alveolar macrophage and the development of the inflammatory reactions leading to the fibrotic response caused by silica. Engineers, scientists and physicians need to discuss the mineralogy of silica and the technical issues concerning the development of silicosis.

Jan 1, 2000

By Walter J. Karplus

By means of a finite difference expansion a fluid flow field in cylindrical coordinates with axial symmetry, is simulated by a network of electrical resistors. A series of DC analog computing units, connected to the network bounrlary corresponding to the free surface effectively adjust the network parameterr to satisfy simultaneously Laplace's equation and the borrndary conditions. The system automatica1ly "re1axes" to the correct boundary shape in a fraction of a second. A detailed application of the method to the water coning problem in oil wells is presented. INTRODUCTION The water coning problem in petroleum production is a prime example of a class of problems known as free surface problems. A free surface arises in fluid flow regions when the shape of the boundary of a single phase flow region is affected in some manner by the pressure or potential gradients within the region. When there exists an interface of two fluids of different densities, the shape of this interface will be determined by the relative velocities of the two fluids and will therefore comprise a free surface. Other free surface problems of interest to petroleum engineers include the gas coning, water injection, and gravity drainage probIcms. In each case it is desired to predict the shape of the boundary of the oil zone as a function of the flow rate, the well penetration and the physical parameters and dimensions of the system. Such problems do not lend themselves to the classical analytical treatments of boundary value problems because in this case the boundary of the potential field and the potential distribution within the field are interdependent and must be calculated simultaneously. A further difficulty arises from geometric considerations. Since the fluid flow is of the radial type in most cases, such effective methods as conformal transformation and the hodograph are not applicable. It is the purpose of this paper to present a method whereby free surface problems of this type may be solved rapidly to the desired order of accuracy by means of a combination of a network of electrical resistors and conventional analog computer units. The water coning problem is treated in some detail. Then the procedure for extending the technique to other free surface problems is indicated. FORMULATION Most commercial oil reservoirs consist of an oil-saturated sand, bounded above by an impermeable strata and below by a water-saturated sand. Gravimetric separation results in a horizontal oil-water interface. When an oil well is drilled so that it partially penetrates the oil zone, and production is initiated at a constant rate, the oil-water interface will assume a new shape as a result of the pressure gradients in the oil zone. It should be emphasized that this is a steady phenomenon. After an initial transient period the water phase will be completely static and only the oil will be in motion. The new steady-state shape of the interface, as shown in Fig. 1, depends upon the depth of penetration, d, the thickness of the oil zone, I, the production rate, q, the hydraulic permeability zone of the sand, k, the viscosity of the oil, µ, and the densities of the oil and water, p.,. and pw.. The problem is to determine this relationship. Darcy's law + = - (P f g p z).....(1) it.

Jan 1, 1957

By F. W. Jessen, R. W. Durie

The dissolution of salt in the development of salt cavities is controlled by free-convection boundary layer flow along the salt surfaces. It is the purpose of this paper to expand upon results published previously, and primarily to illustrate the influence of surface features on the boundary layer and hence the dissolution process in the development of underground salt cavities. General dissolution equations are presented that apply to a surface inclined to the vertical. A salt surface inclined so as to be overlain by water is dissolved by boundary layer flow, while an inverted surface is dissolved by a combination of boundary layer and cellular flow. Detailed investigation of the boundary layer was limited to laminar free-convection flow. Truly laminar free-convection boundary layer flow may be encountered only in laboratory solution cavities, but the boundary layer will control dissolution even where cavity dimensions are such that free-convection turbulence will occur. The factors found to significantly affect the laminar boundary layer will affect dissolution with a turbulent boundary layer. INTRODUCTION Underground salt cavities have been used extensively for the storage of LPG products, and the use of these cavities is expanding each year. The increasing requirements for such cavities suggest the need for a better understanding of the mechanisms involved, for the purpose of the control of cavity geometry and the most effective use of the injected water. A previous paper outlined a quantitative approach to the determination of salt dissolution rates in the laminar free-convection dissolution of salt. It is the purpose of this paper to expand upon the results previously published and to point out significant factors in the application of these results to the dissolution of field cavities. The dissolution of salt in laboratory scale cavities is controlled by the free-convection boundary layer, which is the region of flow along the salt surface caused by the difference in buoyancy forces resulting from the salt dissolution. The transfer of salt into solution at the salt face causes an increase in salinity, and hence a greater density, in the water at the salt surface. The region of higher density tends to fall through the lighter, less saline water and a flowing boundary layer is the result. The water remains stationary at the contact with the salt surface,l so the resulting velocity profile is such that the influence of gravity is opposed by a viscous shear force at the salt surface. For salt to be transferred into solution from a solid surface to a boundary layer of fluid, it must diffuse through a stationary film of water at the salt contact. According to Fick's first law, the rate of mass transfer by diffusion is the product of the diffusion coefficient and the concentration gradient, with diffusion transfer in the direction of decreasing salinity. Once the salt has passed into the boundary layer, it will be transferred by a combination of molecular diffusion and convection. The convection transfer will in turn affect the rate of dissolution by influencing the gradient of the salt concentration at the surface. In the previous investigation by the authors to determine the basic mechanism of the salt dissolution process, an equation was developed that agreed very well with the experimental rates of free-convection salt dissolution from a smooth vertical surface. The technique was taken from the work of Eckert2 in the analogous heat transfer system and will be referred to as the integral method. The rate of salt transfer from a vertical section of height H was found to be:

Jan 1, 1965

By E. G. King

Heat of formation values for mercuric sulfide appear in all the comprehensive listings of thermodynamic data, but experimentally determined entropy values have been lacking. Consequently, all free energy calculations involving mercuric sulfide have been based upon estimated entropy values. This paper reports Bureau of Mines measurements of the low-temperature heat capacity of red mercuric sulfide (cinnabar) and the entropy value at 298.15° K. derived therefrom. The entropy value was combined with heat data to obtain free energy values for the formation of red mercuric sulfide from liquid or gaseous mercury and from rhombic or gaseous diatomic sulfur.

Jan 1, 1962