Minerals equilibria

A calculation procedure could, in theory, predict at once the distribution of mass within a system and the equilibrium mineral assemblage. Brown and Skinner (1974) undertook such a calculation for petrologic systems. For an -component system, they calculated the shape of the free energy surface for each possible solid solution in a rock. They then raised an n -dimensional hyperplane upward, allowing it to rotate against the free energy surfaces. The hyperplane s resting position identified the stable minerals and their equilibrium compositions. Inevitably, the technique became known as the crane plane method. 

With the arrival of the Pitzer method for calculating activity coefficients at high ionic strengths (si m), research by Harvie and Weare (1980) led to computations of equilibrium mineral solubilities for brines. They could calculate... 

Empirical models predicting the rates of mineral-specific dissolution as a function of pH are summarized within the section on mineral composition in an attempt to provide a useful database for predicting dissolution rates for both laboratory and field systems. Equations describing near-equilibrium mineral dissolution and precipitation rates are summarized in the section on chemical affinity. 

Figure 3. pe-pH diagram for equilibrium mineral stabilities in the As-O-S-HiO system at 298.15 K and I atmosphere pressure. Total dissolved sulfur = /O" m. 

Note General reaction types or conditions that correspond to the differential rate equations are given parenthetically. Some reactions are irreversible (denoted by — ) and others reversible (denoted by double arrows). Note that the rate constant, k is always positive. In the integrated rate expressions the concentration of A = Ao, at r = 0, and A = AJ2 at half-time (ti/i). A denotes the equilibrium, mineral saturation or steady state concentration of species A. 

Because the vent fluid compositions are determined largely by fluid-rock interactions that take place in the source region, the equilibrium mineral assemblage that is precipitated during mixing will depend to a large extent on the chemistry of the source rocks. Fluids that are buffered to lower values produce a... 

In order to handle separate yet interacting processes in fractures and matrix, the dual permeability method has been adopted, such that each grid block is divided into matrix and fracture continua, characterized by their own pressure, temperature, liquid saturation, water and gas chemistry, and mineralogy. Simulations of THC processes include coupling between heat, water, and vapor flow aqueous and gaseous species transport kinetic and equilibrium mineral-water reactions and feedback of mineral... 

Simulations of THC processes were performed using the TOUGHREACT code (Xu and Pruess, 2001 Xu et al 2003). TOUGHREACT is based on TOUGH2 (Pruess, 1991) and in addition to the coupling between heat, water, and vapor flow for multiphase systems, it solves aqueous and gaseous species transport, kinetic and equilibrium mineral-water reactions, and feedback of mineral precipitation/dissolution on porosity, permeability, and capillary pressure. 

Gr. aktis, aktinos, beam or ray). Discovered by Andre Debierne in 1899 and independently by F. Giesel in 1902. Occurs naturally in association with uranium minerals. Actinium-227, a decay product of uranium-235, is a beta emitter with a 21.6-year half-life. Its principal decay products are thorium-227 (18.5-day half-life), radium-223 (11.4-day half-life), and a number of short-lived products including radon, bismuth, polonium, and lead isotopes. In equilibrium with its decay products, it is a powerful source of alpha rays. Actinium metal has been prepared by the reduction of actinium fluoride with lithium vapor at about 1100 to 1300-degrees G. The chemical behavior of actinium is similar to that of the rare earths, particularly lanthanum. Purified actinium comes into equilibrium with its decay products at the end of 185 days, and then decays according to its 21.6-year half-life. It is about 150 times as active as radium, making it of value in the production of neutrons. 

Cortisol-Cortisone Conversion. Under normal conditions, this equilibrium slightly favors the oxidized compound. Similarly, the conversion of corticosterone to 11-deoxycorticosterone is also mediated by the liP-hydroxysteroid dehydrogenase enzyme system and requites NAD(P) /NAD(P)H. This conversion is especially important both in the protection of the human fetus from excessive glucocorticoid exposure, and in the protection of distal nephron mineral ocorticoid receptors from glucocorticoid exposure (14). The impairment of this conversion is thought to result in hypertension associated with renal insufficiency (15). 

Production of cyanohydrins is accompHshed through the base-cataly2ed combination of hydrogen cyanide and the carbonyl compound in a solvent, usually the cyanohydrin itself (17). The reaction is carried out at high dilution of the feeds, at 10—15°C, and pH 6.5—7.5. The product is continuously removed from the reaction 2one, cooled to push the equilibrium toward cyanohydrin formation, and then stabili2ed with mineral acid. Purification is usually effected by distillation. 

In this solvent the reaction is catalyzed by small amounts of trimethyl-amine and especially pyridine (cf. 9). The same effect occurs in the reaction of iV -methylaniline with 2-iV -methylanilino-4,6-dichloro-s-triazine. In benzene solution, the amine hydrochloride is so insoluble that the reaction could be followed by recovery. of the salt. However, this precluded study mider Bitter and Zollinger s conditions of catalysis by strong mineral acids in the sense of Banks (acid-base pre-equilibrium in solution). Instead, a new catalytic effect was revealed when the influence of organic acids was tested. This was assumed to depend on the bifunctional character of these catalysts, which act as both a proton donor and an acceptor in the transition state. In striking agreement with this conclusion, a-pyridone is very reactive and o-nitrophenol is not. Furthermore, since neither y-pyridone nor -nitrophenol are active, the structure of the catalyst must meet the conformational requirements for a cyclic transition state. Probably a concerted process involving structure 10 in the rate-determining step... 

As the amines become more weakly basic, the normal method of diazotization becomes progressively more difficult. The equilibrium between amine and ammonium salt increasingly favors the former which, usually because of its poor solubility in water, is prevented from taking part in the reaction. Research into the mechanism of diazotization has demonstrated that the important step is the addition of the nitrosating agent to the base of the amine. Thus, the acidity for each diazotization should be so chosen that the equilibrium concentration of base corresponds to that of its saturated solution. This rule leads to the use of higer concentrations of aqueous mineral acid for weakly basic amines. 

Derbyshire and Waters192 measured the rates of bromination of sodium toluene-m-sulphonate (in water) and of benzoic acid (in aqueous acetic acid) by hypobromous acid with sulphuric or perchloric acids as catalysts, all at 21.5 °C. No bromination occurred in the absence of mineral acid and the reaction was strictly first-order in aromatic and in hypobromous acid. The function of the catalyst was considered to be the formation of a positive brominating species, according to the equilibrium... 

Up to this point, we have focused on aqueous equilibria involving proton transfer. Now we apply the same principles to the equilibrium that exists between a solid salt and its dissolved ions in a saturated solution. We can use the equilibrium constant for the dissolution of a substance to predict the solubility of a salt and to control precipitate formation. These methods are used in the laboratory to separate and analyze mixtures of salts. They also have important practical applications in municipal wastewater treatment, the extraction of minerals from seawater, the formation and loss of bones and teeth, and the global carbon cycle. 

Once a layer-silicate clay forms, it does not necessarily remain in the soil forever. As conditions change it too may weather and a new mineral may form that is more in equilibrium with the new conditions. For example, it is common in young soils for the concentrations of cations such as K, Ca, or Mg in the soil solution to be high, but as primary minerals are weathered and disappear, cation concentrations will decrease. With a decrease in solution cations, a layer-silicate such as vermiculite will no longer be stable and can weather. In its place. 

Over the eons, the flow and evaporation of water inside a cavern creates a stunning array of rock sculptures. Stalagmites grow upward from the floor, sometimes joining stalactites to form massive columns. Limestone dams create beautiful pools of water. Limestone draperies fall like curtains from water flowing around overhanging rock. Delicate mineral flowers sprout from the walls. All these features result from the aqueous solubility equilibrium of calcium carbonate. 

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