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By Horatio Sam-Aggrey, Margot Hurlbert

Small Modular Reactors (SMRs) have been touted as having the potential to spearhead a nuclear renaissance. Proponents of this view cite the relative advantages of SMRs over larger nuclear plants as reason for their optimism. Some of these merits include potential economies of mass production deriving from modular factory production, enhanced safety features, the ability to locate reactors in remote areas, and reduced requirements for technical workforces to install and maintain SMRs. Despite the optimism surrounding SMRs, nuclear power is still a contentious issue for many Canadians. The growth of nuclear power remains adversely affected by concerns over issues such as: the health and safety consequences of nuclear power generation, environmental impacts, proliferation of nuclear materials, terrorism, and radioactive waste disposal (Organisation for Economic Co-operation and Development (OECD) and Nuclear Energy Agency (NEA), 2010). Personal values, past nuclear accidents, and lack of trust in the industry are other factors influencing attitudes toward nuclear energy (IAEA, 2005). In Canada, three main areas where SMRs could be used have been identified. These include: a. Traditional, on-grid power generation, especially in provinces looking for zero-emissions replacements for CO2-emitting coal plants. B. Remote off grid communities that currently rely on diesel or fuel oil power generation. There are 279 off-grid communities in Canada, many of them being Aboriginal communities (NRCan, ND). Notably, all communities in each of Canada’s three territories qualify as remote. C. Resource extraction sites, such as mining and oil and gas extraction sites. Many of Canada’s principal producing mines and active mineral exploration projects are located within close proximity of Aboriginal communities. Any proposed implementation of small nuclear plants would, require the support of the local population, which is largely Indigenous in the northern regions. The possible deployment of SMRs raises important issue relating to consultation and accommodation of Aboriginal concerns regarding potential SMR deployment. This is especially pertinent given Canada’s pending implementation of the provisions of UNDRIP. One of the provisions of UNDRIP that has attracted a lot of attention is the one on Free Prior and Informed Consent (FPIC). Drawing on previously published information, this paper discusses some of the challenges posed by FPIC for the deployment of SMRs. The next section outlines the provisions of FPIC and its implementation in the Canadian context. Section 3, details some of the challenges posed by FPIC to the deployment of SMRs, while Section 4 provides some concluding comments.

Jan 1, 2020

By D. Turnbull, J. C. Fisher

ACCORDING to the "reaction-path" modell,2 of martensite nucleation, the shear angle of the embryonic martensite plate must be treated as a variable, and included in any calculation of nucleus critical size. Also, as can be deduced from this model, the interfacial free energy between austenite and martensite does not reach its final value until the shear is completed. It is zero for zero shear angle. However, in order to account for the kinetics of the martensite transformation, some sort of interfacial energy barrier appears to be necessary even with the reaction-path model, for otherwise the volume and the energy of formation of the critical size nucleus both collapse to zero.3 Cohen independently suggested that surface energy could be incorporated into the reaction-path model, with the overall free energy of a martensite embryo being a function of its volume and shear angle.' It is possible to estimate the energy associated with the formation of a critical-size martensite nucleus starting with the reaction-path model and including a surface free-energy barrier. As the dependence of interfacial free energy upon shear angle is unknown, a simple type of dependence will be assumed, with the belief that the true dependence would not lead to appreciably different results. Consider the work required to form a lenticular martensite plate with radius r, thickness t, and shear angle 8. There are three contributions; one being the interfacial free energy, one being the free energy change in the martensite plate, and one being the free energy increase in the surrounding austenite. The interfacial free energy u is assumed to depend upon the shear angle 0 according to the relationship s=s0(?/?0)n [1] where 8, is the equilibrium shear angle and n is an exponent that may lie in the range 0 n 2. The work required to form the interfaces of a martensite plate then is W. = 2pr² s0(?/?0)n [2] The free energy change per unit volume of martensite is composed of two parts, one the ordinary volume free energy ?f1. which is negative, and the other the elastic strain energy G?m²/2, where G is the shear modulus and 7, the shear strain relative to the martensite structure. This expression for the strain energy is valid only when the shear strain ym, is sufficiently small that the martensite is within its linear elastic range. There is no doubt that ym, lies beyond the linear elastic range for embryos that are considerably subcritical. However, for critical nuclei it will be shown that ym, is 1.5 pct or less, within the linear elastic range of martensite. For embryos of nearly critical size, then, the strain energy of the martensite is correctly given by G?m²/2. The shear strain in the martensite is ym, = 8, — 8, and the work required to form the strained martensite is Wm --= (pr²t/2) [?fv + G(?O - ?)²/2] [3] The free energy change in the austenite is entirely that due to elastic distortion. The elastic strain is not uniformly distributed in the austenite, being large near the martensite plate and small elsewhere. Approximately, however, the energy corresponds to a uniform shear strain ya= (?t/2)/r [4] throughout the volume 4pr³/3 surrounding the plate. The work required to strain the surrounding austenite then is Wa = (4pr³/3) (G?a²/2) = (G?²/6) prt² [51 For simplicity, the same shear modulus G is assumed for each structure. The total free energy for forming a plate then is W = W3 + Wm + Wa. = 2pr² s0 (?/p?0)n + (pr²t/2) [?fr+G(?0-?)²/2] + (G?²6) prt2 [6] This expression is correct for nuclei and for embryos of nearly critical size, where, as will be shown, the strain energy in the martensite is correctly given by the expression G (? — ?)². Having W as a function of r, t, and 8, as in Eq. 6, there is a saddle-point where W has a stationary value, W subsequently decreasing indefinitely as the nucleus volume increases along the reaction path. The stationary value of W is the energy of the critical nucleus. The critical nucleus has radius, thickness, and shear angle such that ?W/?r - awlat: = ?W/?p? = 0. Performing these differentiations and calculating the critical nucleus energy, W* = [8192p(G?/6)²;s/27 ?fv4] [7] where a= (?/?0)3n+1[l +G(8"-8)'/2af.]' [7a] and where 8 is to be determined from the equation (1 + 3n/4) + G8(6O - (9)/[Af. +G(6>o-6>)72] = 0 [8] For ?f, near —200 cal per mol or —10" ergs per cc, and 8, near 1/6, as for iron-base alloys, Eq. 8 gives ?0 - ? ~ - (4 + 3n) ?f1./4G0O [9] as the difference between the equilibrium shear angle and the actual shear angle for a critical nu-

Jan 1, 1954

By P. P. Gregory

NATURAL petroleum gas occurring in the oil-bearing reservoirs is found to exist either as free gas associated with the oil and/or in solution in the oil. In some virgin fields practically no free gas is encountered under the reservoir conditions of pressure and temperature, although in other fields a considerable section of the ``pay" horizon is occupied by free gas. In other words, a given oil field may or may not have a gas cap before the exploitation takes place. However, when the reservoir pressure is reduced to a point below the critical saturation pressure by withdrawals of fluids from the producing formation, the gas dissolved in the oil inevitably begins to come out of solution and becomes free gas. Under the con-trolled methods of production and drilling, a portion of this gas is pro-duced with the oil to the surface and a portion of it remains within the reservoir to accumulate at higher structural levels toward which it migrates by virtue of its low specific gravity. The rate of growth of a gas cap in a-given structure depends primarily upon the rate of decline in the reservoir pressure. If the rate of pressure decline is rapid, the gas cap likewise will grog rapidly. On the other hand, shrinkage in the gas-cap area was noted in some fields in which reservoir pressures were increasing.

Jan 1, 1938

By A. Mainza, I. Govender, Elbasher M. E. Ahmed

A mechanistic description of axial segregation in rotating drum flows remains an open question. Consequently, optimal mixing of grinding balls and rocks for efficient breakage, maximum production of fines, and slurry transport is seldom achieved. Experimental and numerical studies of granular mixtures in rotating drums identify alternating axial bands that eventually coarsen in the long-term limit. Most models of axial segregation are limited to binary mixtures and cannot always predict the logarithmic coarsening effects observed experimentally. A key missing factor is a robust description of the axial free surface profile that is valid across a wide range of flow regimes. We present a practical model of the axial free surface profile by linking it to readily-derived geometric features of the cross-sectional S-shaped free surface profile. A parametric study shows good agreement with experimental measurements reported in the literature and heuristically valid trends.

May 1, 2021

By Stephen Young

The continuous monitoring of free cyanide levels is an important part of gold recovery operations. Accurate and up to the moment knowledge of the free cyanide concentration can result in substantial cost savings by allowing reduced concentra­tions with lower fluctuations, while maintaining or increasing gold recovery. Reduced free cyanide levels also result in lower detoxification costs at the mill discharge which translates into further savings while meeting environmental requirements. As can be seen from the upper curve in Figure 1 (which is based on in-service measurements), without accurate monitoring and control, cyanide concentration fluctuates during the produc­tion cycle, and is maintained at a high level to err on the side of caution. The lower curve illustrates the improved control permitted by the installation of a CY ANCOR, giving a more consistent concentration over the process cycle, and safely allowing use of a lower concentration.

Jan 1, 1995

By Ethan Steward, Robert Eades, Kyle Perry

Shock tubes, either gas or explosively driven, are often used for physical modeling of free field explosions or arena testing. The use of shock tubes often requires less setup time of subjects and smaller driving forces to create pressure versus time waveforms similar to that of arena testing. However, the effects of the shock tube cross sectional geometry on waveform properties is uncertain while free field explosion wave propagation and estimation is well studied.

Jan 1, 2018

T. A. Rickard, Denver, Colorado: The observations made by the author concerning the treatment of gold-bearing ores, deal with the subject only briefly and in a general way; but, coming from an authority, they invite comment. In stating the fact that a " finely-divided condition " is a necessary characteristic of ores containing free gold, the author must be refer ring to those mining districts only with which he himself is ac quainted. The statement would not be true of certain gold-mining regions in America and Australia. The ores of some Californian mines and the mill-stuff treated at certain of the mills of Clunes and Ballarat in Australia, and of Otago in New Zealand, contain the gold in a free but in a coarse state. Moreover, "reduction to fine sand and flour" is not required by certain ores, even though the gold be in a finely-divided condition. In such cases the gold becomes de tached from the quartz before the gangue has been pulverized into particles as small as those in which the gold occurs. The dry-crushing of free-milling gold-ores is onknown in the new mining regions of the world. It is not clear whether the author has in mind any European district in which such a process is in actual use. If he has, a description of the method and the results obtained would be very valuable. Dry-crushing is, other things being equal, twice as slow and twice as expensive as wet-crushing. In the case of free-milling gold-quartz it serves no purpose, since such ore does not carry sulphides which contain any large percentage of value, and which, by being slimed, may carry away part of that value. The dry-crushing of a free-milling gold-quartz would be considered an absurdity by an American metallurgist. If the ore contain "free gold only," why submit it to a further treatment, such as concentration, after its passage over the amalga mating-plate ? What does the author propose to concentrate ? Again, why anticipate the treatment of tailings by the McArthur Forrest, or some other process ? The satisfaction felt by a mill-man in saving gold by a subsequent treatment of the tailings from his mill appears to me to be like that of the man who shoots at a rabbit,

Jan 1, 1894

By B. C. Parks

This paper is a report on the relationships between petrographic composition, chemical composition, physical properties, and thermal behavior of banded bituminous coal. It describes the relationships between petrographic composition, behavior in various laboratory tests, and carbonizing properties of different petrographic types of coal that occur in relatively thick benches in a single bed of high-volatile A bituminous coal - the Hernshaw bed of Boone County, W. Va. Thin-section microscopic analysis and free-swelling index determinations of the thin-section samples were made of a standard column sample. A standard face sample, a representative channel sample, and representative samples of two prominent petrographic benches of bright and dull coal were subjected to chemical analyses and free-swelling-index, plasticity, dilation, agglutinating, low-temperature carbonization, and BM-AGA retort tests. A float-and-sink separation was also made of part of the standard face sample. The fractions from this gravity separation were subjected to petrographic and chemical analysis and free-swelling-index, plasticity, and dilatation tests.

Jan 1, 1959

By J. S. Dunning

The objective of this research by the U.S. Bureau of Mines was to determine the effects of AI additions on the sulfidation resistance of Fe-Cr-Ni alloys. A series of Fe-Cr-Ni alloys with and without -additions of 4 pet AI were tested in a wet S vapor atmosphere at 677 C. A study of the morphology and composition of corrosion scales indicated a different corrosion mechanism for AI-free alloys compared with AI-containing alloys. Aluminum-containing alloys formed a compact, tightly adherent layer at the metal-scale interface that reduced corrosion rates by a factor of 3 to 10 compared with that of AI-free alloys. The thin, adherent AI-containing scale limited inward diffusion of 0 and S to the base metal and outward diffusion of Ni from the base metal. Aluminum-containing alloys formed a three-layer scale in oxidizing-S environments, while AI-free alloys formed a less protective two-layer scale.

Jan 1, 1989

By Floyd R. Anderson

Noise control of existing pneumatic drills is difficult and runs into cost, performance and weight penalties. A need exists for a start-from-scratch approach for quiet pneumatic rock drills. The designs based on Leavell Principles which has been successfully used in demonstrating a quiet and vibration free paving breaker, is the concept chosen here. This report shows the feasibility of a quiet stoper for drilling roof bolt holes in coal mines. The work is directly applicable to pneumatic percussive rock drills. The report shows an oscillator based on patented Leavell concepts which results in a vibration free tool and noiseless exhaust. Dynamics of the oscilator is analyzed. Independant rotation of drill rod is provided by an air motor (screw expander) and flushing of cuttings is accomplished by an air ejector in a compact lower housing. The feasibility of no exhaust noise, low drill machine noise, and vibration free casing is discussed.

Jan 1, 1977

Section 89 Virginia State Geological Survey, Box 329, University, Va. Arthur Bevan, State Geologist A list of publications will be sent free upon request. Publica¬tions are distributed free to residents of Virginia, and others are asked to pay the cost of postage. Selected Bulletins available are: Bulletin 3-A, Geology of the titanium and apatite deposits, with chapters on the Lower Cretaceous and The economic geology (1913), 4, Physiography and geology of the Coastal Plain Prov-

Jan 1, 1933

By S H. Li, H Z. Gu, A Huang

High aluminium steel is a promising advanced steel known for its exception properties and holds significant economic and strategic importance. However, the CaO-Al2O3-SiO2 based slag with high alumina content reacts vigorously with alumina refractories during the smelting process at high temperature, seriously affecting the safe and efficient production of furnaces and resulting in the formation of Al2O3-MgO non-metallic inclusions within the molten steel. This is a bottleneck problem for high-quality steel refining, and the key reaction path during the corrosion remains unclear. The dissolution reaction mechanism of alumina refractories in high alumina CaO-Al2O3-SiO2 slags under a weak static magnetic field was investigated in this work, using high temperature laser confocal microscopy and in situ radiation spectroscopy techniques. The results indicate that the interaction between the high alumina slags and the alumina refractories is governed by free radical reactions. The dissolution of alumina forms AlO and AlO2 radicals. The reaction rate increases with the C/S ratio of the slag due to its low polymerisation. The reaction between non-bridging oxygen and AlO2 free radicals accelerates the generation of AlO and O2ꞏ- radicals. The reaction layer composed of calcium aluminate is formed through the recombination of AlO, Caꞏ+ and O2ꞏ- radicals. The weak static magnetic field induces the Zeeman splitting of free radical pairs and intersystem crossing occurs, promoting the formation of triplet free radical pairs through the hyper-fine coupling effect. The reaction can be significantly inhibited as the triplet free radical pair does not meet Pauli’s incompatibility principle. This discovery perfects the structure theory of molten slags with radicals and provides supplement to the design of the highly slag-resistant refractories, and provides the theoretical basis for the development of external field protection technologies for high-quality steel refining.

Jun 19, 2024

By J. C. Ingles

"A survey of possible methods for controlling cyanide concentration indicated that the simplest method would involve the use of a potentiometric technique. Such a method was suggested by a paper from the laboratory of Mines Safety Appliances, which described a method for determining hydrogen cyanide in air. In this application, the cyanide was absorbed in caustic and a silver electrode immersed in the caustic solution provided a measure of the cyanide concentration. However, our attempts to use the silver electrode in this simple manner to measure the cyanide concentration of solutions were not very successful. A study of the mechanism by which a silver electrode responds to cyanide concentration made it evident why this simple procedure is not satisfactory.Basically, the silver electrode provides an indication of the free silver ion concentration of a solution, and generally speaking, ignores the other ions' present. It can be used to measure an anion if this anion complexes silver. This technique has been used in complexing studies to determine the activities of such anions as acetate, citrate, oxalate and chloride. To do this, the electrode has to be placed in a solution which initially contains a known concentration of free silver ions. Addition of the complexing anion causes a drop in the free silver ion concentration and hence a change in the potential of the silver electrode. The change in potential can be expressed in terms of the concentration of the complexing anion, and used to indicate its concentration in the solution being analysed. The determination of chloride-ion by a silver-silver chloride electrode is an example of an application of this technique. The solubility of the silver chloride with which the electrode is coated provides the initial free silver-ion concentration. Depression of this free silver-ion concentration by the presence of the excess chloride ion of the sample solution results in a change in the potential of the electrode which is proportional to the chloride-ion concentration."

Jan 1, 1965

By A. C. Fieldner, F. H. Gibson, W. A. Selvig

A foRmer paper1 described in detail various methods of calculating coal analyses to obtain the composition and calorific value of the pure coal substance—that is, of the coal free from its mineral matter. The paper included a table showing calorific values of pure coal, as calculated from float-and-sink portions, by means of the Parr formula for "unit coal" and by the customary moisture-free and ash-free formula. A modification of the Parr formula was proposed, based on the assumption that one-half the sulfur present in Coal occurs as pyritic sulfur and one-half as organic sulfur. In the published discussion of the paper Cady gave a table of results on a large number of Illinois coals as obtained by the Parr formula and the proposed modification thereof. The results obtained by Cady indicate that the Parr formula applies better to Illinois coals than does the modified formula proposed by Fieldner and Selvig. The present paper gives results obtained by applying the modified Parr formula to the analyses of the float-and-sink portions of the coals shown in the former paper, and results obtained by applying the Parr formula, the modified Parr formula, and the simple moisture-free and ash-free formula to various coals of the United States ranging in sulfur content from less than 1 per cent to more than 4 per cent sulfur. A graphic method of estimating the calorific value of pure coal and determining the relation of the coal ash to the mineral matter of coal, as proposed by Stansfield and Sutherland,2 was applied to a number of coals, and the results are given herein. Testing Formulas with Float-and-sink Separations The former paper by Fieldner and Selvig gave heat values of pure coal of the float-and-sink portions of 21 coals, as calculated by the Parr formula

Jan 1, 1932

By N. S. Dalal, X. Shi, V. Vallyathan

"Correlated spectroscopic and cytotoxicity measurements were made on newly crushed silica to find whether the fracture-induced, silicon related (Si-0· or Si· type) free radicals play a direct role in the mechanism of hemolysis by silica particles. The free radical content of the silica particles was controlled through the radical decay, thermal annealing, and boiling processes, and was followed with electron spin resonance spectroscopy. Portions of the same sample were evaluated for their hemolytic potential, employing sheep erthyrocyte and optical absorption techniques. The results indicate little, if any, correlation between the amount of the silicon-based radicals and the hemolytic potential of the fresh dusts, but these or related radical sites might be contributors to silica cytoxicity and fibrogenicity via peroxidative pathways .INTRODUCTIONIn an earlier convnunication (1.) from our laboratory it was reported that mechanical crushing of coal and quartz under normal air atmosphere generates free rad;cals on the particle surfaces, and that these radicals decay with time, hence pointing to a higher toxicity of fresh dusts in relationship to pneumoconiosis and silicosis. More recently Fubin; et al.(2) have also reported the detection by electron spin resonance (ESR) of the formation of SiO· and Si·-type of radicals from quartz particles crushed under atmospheric conditions. In agreement with earlier ESR studies on single crystals of quartz crushed under high vacuum (10-10 torr) (3) and subsequent exposure to air (3), and to other gases (4), these radicals were identified (2) as being formed by the hemolytic cleavage of the Si-0-Si bonds and the reactions of the Si· and SiO· ,radical with atmosphere. Fubin; et al. (2) also suggested that these radicals might be involved in the mechanism of the fibrotic action by silica, either by transforming the particle surface into a selective oxidating agent or as an initiator of a sequence of reactions leading to fibrosis. Earlier Gabor and Anea (5) had reported that lipid peroxidation caused by free radicals on the silica surface might be involved in the red blood cell membrane damage. Thus far, however, no parallel cytotoxicity, fibrogenicity, and free radical studies on a given Quartz dust sample have been reported, except for some earlier work from our laboratory (1,6,7). We now present more recent results obtained from parallel cytotoxicity, fibrogenicity, and free radical measurements on a freshly made quartz dust. The dust’s free radical content was measured using ESR spectroscopy while its cytotoxicity poteni1al was estimated via hemolysis. Hemolysis was employed as the tox1c1ty test because it 1s a widely used method for estimating the potential of a dust for disrupting the cell membrane (8). The f1brotic potential was followed.by measuring the dust-induced lipid perox1dat1on. us1ng linole1c ac1d as a model lipid. As discussed below, the results obtained suggest new clues.to the mechanism of the Quartz-related cytotoxicity and fibrogenicity."

Jan 1, 1988

By Robert M. Mann

The Ag/S specific ion electrode has been evaluated for analysis of both free and total cyanide. Metal cyanide solutions were prepared from reagent grade compounds and by stoichiometric fixture of the metal with a potassium cyanide solution. Solutions containing Cu+1, Ni+2, Fe+2, Fe+3 and Zn+2 complexes were analyzed prior to and following EDTA pre treatment. This effort provides an understanding of the effect of each metal cyanide complex on the SIE analysis of free and "total" cyanide.

Jan 1, 1981

Lead-zinc production in Canada accounted for 19% of the total value of metals and minerals produced in 1976, says Keith C. Hendrick, president of Noranda Sides Corp. Mine production of recoverable zinc w as 1. 158 million toils of 27.4% of free world production in 1976. Slab zinc pro¬duction was placed at 472,000 tons that year. Canadian mine production of recoverable lead was 247,000 tons or 10.6% of the free world production. Refined lead that year was at 177,000 tons.

Jan 11, 1977

By R M. Yanamandra, S K. Tripathy, N Mangadoddy, P Sudikondala, P Ankireddy

Spiral concentrator is one of the most commonly used gravity concentration devices in mineral processing. The particles are classified based on their specific gravity and size. The present work analyses the experimental and numerical investigations of the water flow field, such as fluid depth and free surface primary velocity of two high gravity spiral concentrators at different flow rates. The measurement techniques use a flow depth gauge and flow visualisation technique adapting lycopodium powder as the tracer. Flow features in terms of liquid depth and primary velocity at the free surface of the flow are captured across the trough in two different high gravity spirals. A highspeed motion camera with an imaging frequency of 5400 frames per second and 768 × 768 pixel resolution is utilised to track the tracer particles in the liquid flow on the dark surface background. Further, the two-phase flow is studied numerically on high gravity spirals based on the volume of fluid (VOF) approach utilising the RNG k-ε model and Reynolds Stress Model (RSM) for predicting the fluid flow on trough surfaces such as water depth and free surface primary velocity. The CFD predictions of the flow field for the two spirals are attempted to validate against experimental data. The high gravity spiral concentrators show lower flow depths and free surface primary velocities but steep velocities on the outer trough zone compared to that of low gravity spiral concentrators (conventional coal spirals). Among the computationally tested high gravity spirals, higher pitch and higher secondary slope design shows greater flow characteristics.

Aug 24, 2022

By J. E. Hilliard, H. E. Cook

It is shown that for systems having a miscibility gap the spinodal composition (c,) in the vicinity of the critical temperature (Tc) is related to the equilibrium composition (c,) by where cc is the critical composition. This expression is exart for the limit T — Tc and is a good approximation down to (T/Tc) - 0.9. If the miscibility gap meets the composition of the pure components THE recent theoretical treatment by cahn1,2 on spinodal decomposition of solid solutions has revived interest in methods of estimating the chemical spinodal, * i.e., the locus on a binary phase By use of the appropriate expression, the spinodal can be drawn on the Phase diagram almost by inspection with an accuracy comparable to that of lengthy calculations in which a free-energy function is fitted to the phase diagram. Satisfactory agveemenf is also obtained with spinodals comPuted from experimental free-energy curves. where G is the Gibbs free energy of the homogeneous solution and c the atomic fraction of component 2, the derivative being evaluated at constant temperature (T) and pressure (P). (These subscripts will hereafter be omitted from the partial derivatives.) If experimental measurements of G as a function of c and T are available in a single-phase region above the spinodal, then these can be extrapolated to obtain a series of metastable free-energy isotherms in the two-phase region, and from these isotherms a series of spinodal compositions can be calculated. Because the value of is very sensitive to experimental errors, an elaborate analytic procedure is required for

Jan 1, 1965

By J. W. Evans

ONE possible method for the separation of hafnium from zirconium is by the vapor phase oxidation of the purified mixed chlorides. An important factor for success depends on the difference in free energies of the following reactions: ZrCl(g) + O2 = ZrO2(s) + 2C12 [1] HfCl4(g) + O2 = HfO2(s) + 2C12. [2] Prakash and Sundaram1 have calculated these values from certain data and carried out experimental work with partial success. However, their free energy values for reaction 2 diverge rather widely from other data which are presented here. The possibility of successful separation is briefly considered in the light of these alternative values. Table I shows the free energy values (?F°) for reactions 1 and 2 derived from the recent compilation of data on oxides and chlorides by Glassner.2 The corresponding values of Prakash and Sundaram for the same temperatures are also shown. The alternative values to those of Prakash and Sundaram for reaction 2 are substantially confirmed by the data of Kubaschewski and Evans" and Cough-lin' on heats of formation, entropies, and heats of vaporization. In spite of the considerable uncertainty in the hafnium data it is reasonable to suppose that the oxide-chloride free energy difference for two such chemically similar elements would not be very far apart. These figures indicate clearly that the oxidation of hafnium chloride is appreciable at all temperatures. Nevertheless, there is a significant difference between the values for reactions 1 and 2

Jan 1, 1959