Copper ion activation of synthetic sphalerites with various iron contents     

J. Solecki  A. Komosa  J. Szczypa 《International Journal of Mineral Processing》1979,6(3):221-228

The adsorption of copper ions on synthetic sphalerites of various iron contents was measured using a radiotracer technique. The correlation of Cu²⁺ ions adsorption with the pH of solution, the iron content of the solid and the degree of surface oxidation of synthetic sphalerite were determined. The experiments proved that oxidation of the surface of the sphalerite samples caused a decrease in Cu²⁺ ions sorption with the exception of samples of iron containing sphalerite. Acidity of the solution affected the adsorption of Cu²⁺ ions by deoxidized sphalerite surfaces, whereas the adsorption on oxidized surfaces did not depend on the pH.  相似文献   

Stability of ethylxanthate ion in neutral and weakly acidic media. Part 1: Influence of pH     

M. Maillot  J.-L. Cecile  R. Bloise 《International Journal of Mineral Processing》1984,13(3):193-210

Xanthates are used in the flotation of sulfide ores although their aqueous solutions are not stable under certain conditions. Their stability in acidic and weakly acidic aqueous solutions was therefore investigated, as these media are required for some processes.The peak absorbances of ethylxanthate ion and carbon disulfide were first determined in aqueous solution. The decomposition of ethylxanthate ion was analyzed by measuring variations in absorbance (at 301 nm) and pH with respect to time. A pH regulation system was then used while measuring variations in absorbance and productions of protons caused by xanthate decomposition.The results concerning xanthate half-lives show good agreement with the literature, but the kinetic results deviate substantially. The following relation was obtained for half-life: We established that ethylxanthate decomposition at pH 4 is a first order reaction with respect to ethylxanthate concentration, and postulating this order to the other pH values, the following kinetic relation was found: where v is the rate of decomposition (mol l^?1 min^?1), and [EtX^?]_∞ is the ethylxanthate concentration when the decomposition equilibria are reached (mol l^?1). The better concentration was found to obey the law:   相似文献   

Kinetic study of abstraction of ethyl xanthate ions by oxidized chalcocite surface     

Zbigniew Adamczyk  Wanda Barzyk  Jan Czarnecki  Andrzej Pomianowski 《International Journal of Mineral Processing》1980,7(1):57-77

The results of potassium ethyl xanthate (EtXK) consumption measurements by synthetic chalcocite (Cu₂S grain-sized classes of 60–75 μm and 120–200 μm, respectively) are presented. These measurements were done in a modified circulation apparatus in an argon or oxygen atmosphere at pH=9.5. The experimental results were compared with theoretical results predicted by a mathematical model based on the assumption that the EtX^? ions were immobilized as a result of a chemical reaction (or reactions), e.g., of an ion-exchange type, taking place within the oxidation product layer (OPL), formed on the Cu₂S surface.The experimental and theoretical results are in good agreement especially for small values of Q₀ (Q₀ is the initial mass of the EtX^? in solution per mass unit of Cu₂S). In this case both the theoretical and experimental results show that the EtX^? concentration in solution decays exponentially with time.  相似文献   

Decomposition of alkyl dixanthogens in aqueous solutions     

M.H. Jones  J.T. Woodcock 《International Journal of Mineral Processing》1983,10(1):1-24

Alkyl dixanthogens, (ROCSS)₂, decompose in aqueous solution in the presence of nucleophiles in many ways.It is proposed here that in alkaline solution the principal methods of decomposition of ethyl dixanthogen are by simultaneous attack of OH^? ions on the sulphur-sulphur bond to give products which include xanthate ion (ROCSS^?) and peroxide (H₂O₂) and on the carbon-sulphur bond to give products which include monothiocarbonate ion (ROSCO^?), sulphide ion (S^2?), and sulphur (S⁰). Above pH 12 reaction is complete in a few minutes, and more monothiocarbonate than xanthate is formed. At pH 9 the reaction takes over 20 h and more xanthate than monothiocarbonate is formed.The primary products react further to give various ions which depend in part on the pH of the system. In alkaline solution some of the xanthate and peroxide react to give perxanthate (ROCSSO^?). In acid solution both xanthate and monothiocarbonate decompose rapidly; CS₂ is formed from xanthate and OCS from monothiocarbonate.In the presence of other nucleophiles at pH 9.2, dissolved dixanthogen decomposes much more quickly than with OH^? alone, and other reactions occur. With thiosulphate a higher proportion of xanthate is formed together with some xanthyl thiosulphate and monothiocarbonate but no perxanthate. With sulphite (in the absence of oxygen) or cyanide the products include xanthate and monothiocarbonate but no perxanthate. With sulphite in the presence of oxygen, perxanthate is also formed.Suspensions of dixanthogens react slowly but in a similar fashion to dissolved dixanthogens.Longer-chain dixanthogens are much less soluble than ethyl dixanthogen but, in general, react in a similar way. Higher temperatures increase the rate of decomposition by OH^?.This work has various implications in operating plants.  相似文献   

Flotation of germanium n and p with potassium ethyl xanthate     

M.M. Kielkowska  J. Lekki  J. Drzymala 《International Journal of Mineral Processing》1982,9(2):145-156

Steady-state potential of the germanium electrode, flotation tests and results of spectrophotometric ATR (Attenuated Total Reflection) measurements of germanium surface in the presence and absence of potassium ethyl xanthate are presented.On the basis of the steady-state potentials of the germanium electrode in ethyl xanthate solutions, the standard potential E⁰ of the reaction: Ge + 2EtX^? = Ge (EtX)₂ + 2e is estimated. The pH ranges of the dixanthogen (EtX)₂ and the germanium xanthate Ge(EtX)₂ species predominance in the bulk solution are calculated. It has been established that flotation of germanium is greater than the natural floatability (in the absence of collectors) in the pH ranges where (EtX)₂ or Ge (EtX)₂ are present in the bulk solution. Spectrophotometric results reveal the presence of (EtX)₂ and Ge (EtX)₂ on the surface in the same pH ranges as is calculated for the bulk reactions.No significant differences in the surface properties and the flotation behaviour between germanium n and p have been found.  相似文献   

Flotation of galena. Influence of grain size,of pulp deoxygenation,and of cleaning with ammonium acetate     

Claudio Gutiérrez  Faustino Martin-Poveda 《International Journal of Mineral Processing》1981,8(2):111-123

The flotation of < 10, 10–20, and 20–40 μm galena fractions was studied. For uncleaned galena a given collector coverage produced better floatability with increasing grain size. Nitrogen had a detrimental effect only for the < 10 μm fraction, producing at a given collector coverage a recovery smaller than that obtained with air.Galena cleaned with 400 g/l ammonium acetate had very poor floatability, although xanthate abstraction was fairly high; this confirms that strong xanthate adsorption is necessary for flotation. Formation of monothiocarbonate was small in all cases, which points to a very minor influence, if any, of this compound in the flotation process.In blank flotation tests, or for very low residual xanthate concentrations, a peak at 208 nm and a shoulder at 255 nm were observed. The former was assigned to the uncomplexed Pb²⁺ ion, and the latter was tentatively attributed to the PbOH⁺ ion.Lead in solution results from dissolution of the oxidation products of galena, as galena itself has an exceedingly low solubility. The curve for total lead in solution vs. initial xanthate concentration, had a minimum for an initial xanthate concentration of 10^?5M, the further increase in dissolved lead is attributed to formation of complexes such as PbX⁺ (X = xanthate). Dissolved lead concentrations were nearly as high for cleaned as for uncleaned galena, which indicates a high oxidation rate of the mineral.  相似文献   

Sedimentary iron monosulfides: Kinetics and mechanism of formation     

Albert J Pyzik  Sheldon E Sommer 《Geochimica et cosmochimica acta》1981,45(5):687-698

The reaction between hydrous iron oxides and aqueous sulfide species was studied at estuarine conditions of pH, total sulfide, and ionic strength to determine the kinetics and formation mechanism of the initial iron sulfide. Total, dissolved and acid extractable sulfide, thiosulfate, sulfate, and elemental sulfur were determined by spectrophotometric methods. Polysulfides, S₄^2? and S₅^2?, were determined from ultraviolet absorbance measurements and equilibrium calculations, while product hydroxyl ion was determined from pH measurements and solution buffer capacity.Elemental sulfur, as free and polysulfide sulfur, was 86% of the sulfide oxidation products; the remainder was thiosulfate. Rate expressions for the reduction and precipitation reactions were determined from analysis of electron balance and acid extractable iron monosulfide vs time, respectively, by the initial rate method. The rate of iron reduction in moles/liter/minute was given by $\text{d(}\text{reduction}\text{Fe)}\text{dt}\text{= kS}{}_{\mathrm{t}}{}^{0.5}\text{(J}{}^{\mathrm{+}}\text{)}{}^{0.5}\text{A}{}_{\mathrm{FeOOH}}{}^1$ where S_t was the total dissolved sulfide concentration, (H⁺) the hydrogen ion activity, both in moles/ liter; and A_FeOOH the goethite specific surface area in square meters/liter. The rate constant, k, was 0.017 ± 0.002m^?2 min^?1. The rate of reduction was apparently determined by the rate of dissolution of the surface layer of ferrous hydroxide. The rate expression for the precipitation reaction was $\text{d(FeS)}\text{dt}\text{= kS}{}_{\mathrm{t}}{}^1\text{(H}{}^{\mathrm{+}}\text{)}{}^1\text{A}{}_{\mathrm{FeOOH}}{}^1$ where $\text{d(FeS)}\text{dt}$ was the rate of precipitation of acid extractable iron monosulfide in moles/liter/minute, and k = 82 ± 18 mol^?1l²m^?2 min^?1.A model is proposed with the following steps: protonation of goethite surface layer; exchange of bisulfide for hydroxide in the mobile layer; reduction of surface ferric ions of goethite by dissolved bisulfide species which produces ferrous hydroxide surface layer elemental sulfur and thiosulfate; dissolution of surface layer of ferrous hydroxide; and precipitation of dissolved ferrous specie and aqueous bisulfide ion.  相似文献   

The kinetics of the oxidation of ferrous iron in synthetic and natural waters     

W Davison  G Seed 《Geochimica et cosmochimica acta》1983,47(1):67-79

The rate of oxidation of ferrous iron in a seasonally anoxic lake was measured on 39 occasions with respect to both depth and time. Sample disturbance was minimal as only oxygen had to be introduced to initiate the reaction. The data were consistent with the simple rate law for homogeneous chemical kinetics previously established for synthetic solutions. The rate constant for the oxidation reaction in lake water was indistinguishable from that measured in synthetic samples. It did not appear to be influenced by changes in the microbial populations or by changes in any particulate or soluble components in the water, including iron and manganese. Analysis of the errors inherent in the kinetic measurements showed that the estimation of pH was the major source of inaccuracy and that values of the rate constant determined by different workers could easily differ by a factor of six.The present data, together with a comprehensive survey of the literature, are used to suggest a ‘universal’ rate constant of ca. 2 × 10¹³ M^?2 atm^?1 min^?1 (range 1.5–3 × 10¹³) in the rate law $\text{?d[Fe II]}\text{dt}\text{= k[Fe II]pO}{}_2\text{(OH?)}{}^2$ for natural freshwaters in the pH range 6.5–7.4. Discrepancies in the effects of ionic strength and interfering substances reported in the literature are highlighted. Generally substances have only been found to interfere at concentrations which far exceed those in most natural waters.  相似文献   

Formation and recognition of alkyl xanthyl thiosulphates in sulphide ore flotation liquors     

M.H. Jones  J.T. Woodcock 《International Journal of Mineral Processing》1981,8(2):125-145

Alkyl xanthyl thiosulphates (R.OCSS.S₂O₃^?) (RXT^?) are formed in solution by mild oxidation (e.g. by I₂) of solutions containing both xanthate and thiosulphate. They can also be formed by reaction of Cu²⁺ with xanthate and thiosulphate, reaction of dixanthogen with thiosulphate, and by reaction of xanthate with tetrathionate; these last three reactions can occur in flotation pulps in slightly acid or alkaline solutions (pH 5–10).Alkyl xanthyl thiosulphates are stable in acid and neutral solution; the solutions have a UV absorption maximum at 289 nm. In strongly alkaline solution (pH 12) RXT^? decomposes within a few minutes to yield a xanthate (mostly) plus a little perxanthate. At pH 10 this decomposition to xanthate takes about 48 h. At pH 7–9 RXT^? is relatively stable. RXT^? is not extracted from aqueous solution with common solvents (chloroform, iso-octane, cyclohexane, or ether). It forms a water-insoluble adduct with cetyltrimethyl-ammonium bromide (CTAB); this adduct can be extracted into chloroform, and the extract has a UV absorption maximum at 296 nm.RXT^? was found in solutions from the gangue-sulphide flotation section at Renison Ltd, the zinc flotation circuit and the copper flotation circuit at Mount Isa Mines Ltd, and the lead flotation section of The Zinc Corporation Ltd. The presence of RXT^? in operating flotation plants has various practical and theoretical implications.  相似文献   

A study of the surface electrical properties of titanium oxide     

A.M. Marabini  M. Barbaro 《International Journal of Mineral Processing》1980,7(2):159-166

The surface electrical properties of rutile have been studied by means of electrophoretic zeta potential measurements, potentiometric titration measurements and sedimentation rate measurements. The point of zero charge has been found to be $\text{pH}\text{= 3.8}$. Two other points where the charge is zero, have also been discovered, $\text{pH}\text{= 2.2}$ and $\text{pH}\text{= 0.7}$; these have been interpreted as iso-electric points due to specific adsorption on the mineral surface of ClO₄^? and Ti⁴⁺ ions present in the solution.  相似文献   

Kinetics and thermochemistry of amyl xanthate adsorption by pyrite and marcasite     

H.H. Haung  J.D. Miller 《International Journal of Mineral Processing》1978,5(3):241-266

The kinetics and thermochemistry of the xanthate adsorption reaction on pyrite and marcasite were evaluated with respect to the existing theory. The rate of xanthate adsorption was studied in a stirred reactor and the xanthate concentration was determined by UV spectrophotometry as a function of time. The heat of the adsorption reaction was measured with a microcalorimeter. The results from both experiments indicate that xanthate adsorption by pyrite or marcasite involves the formation of dixanthogen by an electrochemical reaction at the solid surface which supports the conclusions of other investigators: The rate of the adsorption reaction was found to be approximately one-half order with respect to the xanthate concentration and to have an activation energy of 7.5 kcal/mole. Additionally, the rate was found to have a slight dependence on pH under certain conditions. In view of these results, it appears that the adsorption reaction is controlled by electrochemical discharge at the pyrite surface. Analysis of the data in terms of an electrochemical kinetic model successfully explained the observed rate phenomena.The measured heat of the adsorption reaction at low pH was found to be between ?63 and ?56 kcal/mole of adsorbed dixanthogen and independent of surface coverage. These experimental heats of adsorption agree with the value of ?57 kcal/mole of dixanthogen calculated for the oxidation of xanthate by oxygen from thermodynamic data reported in the literature.  相似文献   

Adsorption of barium ions by β-manganese dioxide and its activation in oleate flotation     

M.A Arafa  A.A Yousef  M.A Malati 《International Journal of Mineral Processing》1974,1(3):267-275

The Ba²⁺ ion adsorption isotherms on β-MnO₂ were of the Langmuir type. The endothermic heat of adsorption (40 kJ mol^?1) is ascribed to entropy contributions associated with the $\text{Na}{}^{\mathrm{+}}\text{Ba}{}^{\mathrm{2+}}$ ion-exchange mechanism. The Ba²⁺ ion adsorption density was higher at pH 10 than that at pH 7, due to the more negative surface charge at the higher pH. Ba²⁺ ions were found to reverse the sign of the ζ potential of the MnO₂ particles.More oleate was adsorbed by β-MnO₂ in the presence of Ba²⁺ ions than in their absence. The oleate adsorption isotherms on Ba²⁺-activated MnO₂ were of the Freundlich type and indicated an exothermic process. Hallimond flotation recovery of Ba²⁺-activated MnO₂ was higher at pH 10 than at pH 7, although less oleate was adsorbed at the higher pH. At pH 7, Mn²⁺-activation led to higher recoveries than Ba²⁺-activation. It seems that the attraction between the surface and the activator plays an important rôle in determining the flotation recovery.  相似文献   

Interstellar organic matter in meteorites     

Jongmann Yang  Samuel Epstein 《Geochimica et cosmochimica acta》1983,47(12):2199-2216

Hydrogen which is highly enriched in deuterium is present in organic matter in a variety of meteorites including non-carbonaceous chondrites. The concentrations of this hydrogen are quite large. For example Renazzo contains 140 μmoles/g of the 10,000‰ δD hydrogen. The $\text{D}\text{H}$ ratios of hydrogen in the organic matter vary from 8 × 10^?5 to 170 × 10^?5 (δD ranges from ? 500‰ to 10,000‰) as compared to 16 × 10^?5 for terrestrial hydrogen and 2 × 10^?5 for cosmic hydrogen. The majority of the unequilibrated primitive meteorites contain hydrogen whose $\text{D}\text{H}$ ratios are greater than 30 × 10^?5. If the $\text{D}\text{H}$ ratios in these compounds were due to enrichment relative to cosmic hydrogen by isotope exchange reactions, it would require that these reactions take place below 150 K. In addition the organic compounds having $\text{D}\text{H}$ ratios above 50 × 10^?5 would require temperatures of formation of < 120 K. These types of deuterium enrichments must take place by ion-molecule reactions in interstellar clouds where both ionization and low temperatures exist. Astronomically observed $\text{D}\text{H}$ ratios in organic compounds in interstellar clouds are typically 180 × 10^?5 and range between about 40 × 10^?5 and 5000 × 10^?5. The $\text{D}\text{H}$ values we have determined are the lower limits for the organic compounds derived from interstellar molecules because all processes subsequent to their formation, including terrestrial contamination, decrease their $\text{D}\text{H}$ ratios.In contrast, the $\text{D}\text{H}$ ratios of hydrogen associated with hydrated silicates are relatively uniform for the meteorites we have analyzed with an average value of 14 × 10^?5; very similar to the terrestrial value. These phyllosilicates values suggest equilibration of H₂O with H₂ in the solar nebula at temperatures of about 200 K and higher.The ${}^{13}\text{C}{}^{12}\text{C}$ ratios of organic matter, irrespective its $\text{D}\text{H}$ ratio, lie well within those observed for the earth. If organic matter originated in the interstellar medium, our data would indicate that the ${}^{13}\text{C}{}^{12}\text{C}$ ratio of interstellar carbon five billion years ago was similar to the present terrestrial value.Our findings suggest that other interstellar material, representing various inputs from various stars, in addition to the organic matter is preserved and is present in the meteorites which contain the high $\text{D}\text{H}$ ratios. We feel that some elements existing in trace quantities which possess isotopic anomalies in the meteorites may very well be such materials.  相似文献   

Rates of reaction of pyrite and marcasite with ferric iron at pH 2     

C.L Wiersma  J.D Rimstidt 《Geochimica et cosmochimica acta》1984,48(1):85-92

The relative reactivities of pulverized samples (100–200 mesh) of 3 marcasite and 7 pyrite specimens from various sources were determined at 25°C and pH 2.0 in ferric chloride solutions with initial ferric iron concentrations of 10^?3 molal. The rate of the reaction: was determined by calculating the rate of reduction of aqueous ferric ion from measured oxidation-reduction potentials. The reaction follows the rate law: where m_Fe³⁺ is the molal concentration of uncomplexed ferric iron, k is the rate constant and $\text{A}\text{M}$ is the surface area of reacting solid to mass of solution ratio. The measured rate constants, k, range from 1.0 × 10^?4 to 2.7 × 10^?4 sec^?1 ± 5%, with lower-temperature/early diagenetic pyrite having the smallest rate constants, marcasite intermediate, and pyrite of higher-temperature hydrothermal and metamorphic origin having the greatest rate constants. Geologically, these small relative differences between the rate constants are not significant, so the fundamental reactivities of marcasite and pyrite are not appreciably different.The activation energy of the reaction for a hydrothermal pyrite in the temperature interval of 25 to 50°C is 92 kJ mol^?1. This relatively high activation energy indicates that a surface reaction controls the rate over this temperature range. The BET-measured specific surface area for lower-temperature/early diagenetic pyrite is an order of magnitude greater than that for pyrite of higher-temperature origin. Consequently, since the lower-temperature types have a much greater $\text{A}\text{M}$ ratio, they appear to be more reactive per unit mass than the higher temperature types.  相似文献   

The circumvention of the natural biopurification of calcium along nutrient pathways by atmospheric inputs of industrial lead     

Robert W. Elias  Yoshimitsu Hirao  Clair C. Patterson 《Geochimica et cosmochimica acta》1982,46(12):2561-2580

Biopurification factors for Ca with respect to Sr, Ba, and natural, uncontaminated Pb were measured for different nutrient-consumer pairs in a remote subalpine ecosystem. The factor for Sr is expressed as: (nutrient $\text{Sr}\text{Ca}$) ÷ (consumer $\text{Sr}\text{Ca}$). Similar expressions were used for $\text{Ba}\text{Ca}$ and $\text{Pb}\text{Ca}$. It was found that Ca was biopurified of Sr 3-fold, of Ba 16-fold, and of Pb 100-fold in going from rock to sedge leaves. In going from sedge leaf to vole, Ca was biopurified of Sr 4-fold, of Ba 8-fold, and of Pb 16-fold. In going from meadow vole to pine marten, Ca was biopurified of Sr 6-fold, of Ba 7-fold, and of Pb 1.1-fold. Similar ranges of values for these factors were obtained for detrital and amphibian food chains. Fluxes of industrial lead entering the ecosystem as precipitation and dry deposition were measured and it was found that 40% of the lead in soil humus and soil moisture, 82% of the lead in sedge leaves, 92% of the lead in vole, and 97% of the lead in marten was industrial. The natural skeletal $\text{Pb}\text{Ca}$ ratio in carnivores (4 × 10^?8) was determined by means of corrections for inputs of industrial lead, food chain relationships, and measured biopurification factors for the ecosystem studied. This represents a 1700-fold reduction of the average $\text{Pb}\text{Ca}$ ratio in igneous rocks at the earth's surface (6.4 × 10^?5) by the compounding of successive Pb biopurification factors in transferring Ca from rock to carnivore. The natural ratio is similar to the value of 6 × 10^?8 observed for $\text{Pb}\text{Ca}$ in the bones of Peruvians who lived 2000 years ago but is 1/900th of the value of about 3.5 × 10^?5 for the skeletal $\text{Pb}\text{Ca}$ ratio found in present day Americans.This study shows experimentally how the $\text{Ba}\text{Ca}$ ratio in average surface igneous rock (3 × 10^?3) has been reduced 800-fold through compounding of successive biopurification steps to provide the skeletal $\text{Ba}\text{Ca}$ ratio of about 4 × 10^?6 observed in humans. It also provides biopurification factors for Sr and Ba among a number of nutrient-consumer pairs which anthropologists can use to delineate degrees of herbivory in diets of hominids within the last 10,000 years.  相似文献   

Gibbsite solubility and thermodynamic properties of hydroxy-aluminum ions in aqueous solution at 25°C     

Howard M. May  Philip A. Helmke  Marion L. Jackson 《Geochimica et cosmochimica acta》1979,43(6):861-868

Solubility curves were determined for a synthetic gibbsite and a natural gibbsite (Minas Gerais, Brazil) from pH 4 to 9, in 0.2% gibbsite suspensions in 0.01 M NaNO₃ that were buffered by low concentrations of non-complexing buffer agents. Equilibrium solubility was approached from oversaturation (in suspensions spiked with Al(NO₃)₃ solution), and also from undersaturation in some synthetic gibbsite suspensions. Mononuclear Al ion concentrations and pH values were periodically determined. Within 1 month or less, data from over-and undersaturated suspensions of synthetic gibbsite converged to describe an equilibrium solubility curve. A downward shift of the solubility curve, beginning at pH 6.7, indicates that a phase more stable than gibbsite controls Al solubility in alkaline systems. Extrapolation of the initial portion of the high-pH side of the synthetic gibbsite solubility curve provides the first unified equilibrium experimental model of Al ion speciation in waters from pH 4 to 9.The significant mononuclear ion species at equilibrium with gibbsite are Al³⁺, AlOH²⁺, Al(OH)⁺₂ and Al(OH)^?₄, and their ion activity products are $\text{1K}{}_{50}\text{= 1.29 × 10}{}^8$, $\text{1K}{}_{\mathrm{s1}}\text{= 1.33 × 10}{}^3$, $\text{1K}{}_{\mathrm{s2}}\text{= 9.49 × 10}{}^{\mathrm{?3}}$ and $\text{1K}{}_{\mathrm{s4}}\text{= 8.94 × 10}{}^{\mathrm{?15}}$. The calculated standard Gibbs free energies of formation (ΔG°_f) for the synthetic gibbsite and the A1OH²⁺, Al(OH)⁺₂ and Al(OH)^?₄ ions are ?276.0, ?166.9, ?216.5 and ?313.5 kcal mol^?1, respectively. These ΔG°_f values are based on the recently revised ΔG°_f value for Al³⁺ (?117.0 ± 0.3 kcal mol_?1) and carry the same uncertainty. The ΔG°_f of the natural gibbsite is ?275.1 ± 0.4 kcal mol^?, which suggests that a range of ΔG°_f values can exist even for relatively simple natural minerals.  相似文献   

Armalcolite stability as a function of pressure and oxygen fugacity     

John J Friel  R.Ian Harker  Gene C Ulmer 《Geochimica et cosmochimica acta》1977,41(3):403-410

The stability of synthetic armalcolite of composition (Fe_0.5Mg_0.5Ti₂O₅ was studied as a function of total pressure up to 15 kbar and 1200°C and also as a function of oxygen fugacity (?O₂) at 1200°C and 1 atm total pressure. The high pressure experiments were carried out in a piston-cylinder apparatus using silver-palladium containers. At 1200°C, armalcolite is stable as a single phase at 10 kbar. With increasing pressure, it breaks down ($\text{dT}\text{dP}\text{= 20°C/}\text{kbar}$), to rutile, a more magnesian armalcolite, and ilmenite solid solution. At 14 kbar, this three-phase assemblage gives way ($\text{dT}\text{dP}\text{= 30°C/}\text{kbar}$) to a two-phase assemblage of rutile plus ilmenite solid solution.A zirconian-armalcolite was synthesized and analyzed; 4 wt % ZrO₂ appears to saturate armalcolite at 1200°C and 1 atm. The breakdown of Zr-armalcolite occurs at pressures of 1–2 kbar less than those required for the breakdown of Zr-free armalcolite. The zirconium partitions approximately equally between rutile and ilmenite phases.The stability of armalcolite as a function of ?O₂ was determined thermogravimetrically at 1200°C and 1 atm by weighing sintered pellets in a controlled atmosphere furnace. Armalcolite, (Fe_0.5Mg_0.5)-Ti₂O₅, is stable over a range ?O₂ from about 10^?9.5to 10^?10.5 atm. Below this range to at least 10^?12.8 atm, ilmenite plus a reduced armalcolite are formed. These products were observed optically and by Mössbauer spectroscopy, and no metallic iron was detected; therefore, some of the titanium must have been reduced to Ti³⁺. This reduction may provide yet another mechanism to explain the common association of ilmenite rims around lunar armalcolites.  相似文献   

Chemical and thermodynamic constraints on the hydrothermal transport and deposition of tin: I. Calculation of the solubility of cassiterite at high pressures and temperatures   总被引：1，自引：0，他引：1  

Kenneth J. Jackson  Harold C. Helgeson 《Geochimica et cosmochimica acta》1985,49(1):1-22

Estimation of equation of state parameters for Sn⁺⁺ and calculation of the thermodynamic properties of other aqueous species and dissociation constants for various stannous and stannic complexes as a function of temperature permit prediction of the high temperature solution chemistry of tin and calculation of the solubility of cassiterite in hydrothermal solutions. The results of these calculations indicate that in the absence of appreciable chloride and fluoride concentrations, Sn(OH)₂⁰ and Sn(OH)₄⁰ are the predominant tin species in H₂O up to 350°C at ~2 $\text{\$}\text{?}$pH $\text{\$}\text{?}$7.5. The calculations also indicate that chloride complexes of Sn⁺⁺ predominate by several orders of magnitude over their fluoride and hydroxide counterparts in 1–3 molal (m) NaCl solutions, except in the presence of geologically unrealistic concentrations of fluoride or a pH greater than ~3.5 at 250°C or ~5.0 at 350°C. At higher pH values, most of the tin in solution is present as hydroxide complexes, even at concentrations of NaCl as high as 3 m. Calculated values of the solubility of cassiterite at high temperatures compare favorably with experimental data reported in the literature. Depending on the fugacity of oxygen and solution composition, the solubility of cassiterite in hydrothermal solutions may exceed 100 ppm under geologically realistic conditions.  相似文献   

An evaluation of rate equations for calcite precipitation kinetics at pCO2 less than 0.01 atm and pH greater than 8     

William P. Inskeep  Paul R. Bloom 《Geochimica et cosmochimica acta》1985,49(10):2165-2180

We used a reproducible seeded growth technique with a pH-stat to study the kinetics of calcite precipitation at 25°C. We performed different experiments at initial Ca²⁺ and HCO₃^? concentrations ranging from 0.7–2 and 4–7 mmol L^?1, pH values ranging from 8.25 to 8.70, $\text{pCO}{}_2$ values ranging from 0.0006 to 0.01 atm, and ionic strengths ranging from 0.015 to 0.10 mol L^?1. With this experimental data set, we used initial rate measurements and integral methods to test several precipitation rate equations. Rate equations that possess a disequilibrium functional dependence, such as the BURTON et al. (1951) dislocation model, forms of the Davies and Jones (1955) model, and the model used by Reddy and Nancollas (1973), did not adequately describe the kinetics of calcite precipitation at pH greater than 8 and $\text{pCO}{}_2$ less than 0.01 atm. Rate equations that describe independent dissolution and precipitation mechanisms with elementary reactions, such as the equation presented by Plummeret al. (1978), and nancollas and Reddy (1971) were more successful. However, Plummer's model did not adequately describe the rate of all experiments due to the presence of an OH^? surface term in the precipitation rate equation. The elementary reaction of the Nancollas and Reddy model is written in terms of bulk Ca²⁺ and CO₃^? concentrations, and appears to be the most successful model which describes calcite precipitation at pH > 8 and $\text{pCO}{}_2\text{< 0.01}$ atm. The Nancollas and Reddy model, altered to account for varying ionic strengths, adequately described the rate of all experiments and yielded a precipitation rate constant of $\text{118.2 ± 13.9}$ dm⁶ mol^?1 m^?2 s^?1, with an apparent Arrhenius activation energy of 48.1 kJ mol^?1.  相似文献   

Experimental observations on carbon isotope exchange in carbonate-water systems     

A.A. Mozeto  P. Fritz  E.J. Reardon 《Geochimica et cosmochimica acta》1984,48(3):495-504

This study presents data from experiments investigating carbon isotope exchange between carbonate solution and solid calcite using carbon-13 as a tracer. All experiments were done with calcite saturated solutions and results show that a two-step adsorption-recrystallization reaction takes place. Isotope effects are caused by exchange by carbonate on the solid surface with carbon in the aqueous phase. Adsorption reactions are characterized by a maximum isotopic exchange capacity (IEC) on crystal surfaces of about 10¹¹ reaction sites per cm², following a second order rate law with respect to ¹³C concentration in solution ($\text{constant}\text{kex ? 10}{}^6\text{cm}{}^5\text{mole}{}^{\mathrm{?1}}\text{s}{}^{\mathrm{?1}}$ and $\text{half-life}\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{= 700}\text{s}$). The adsorption reaction was followed by a first order recrystallization which is characterized by a rate constant of the order of 10^?8 s^?1 and a $\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ of 10⁷ s. Negative isotopic gradient experiments and runs with calcite crystals in Mg²⁺ spiked solutions provided the preliminary basis for the characterization of the mechanisms of both proposed reactions.  相似文献