Reaction rates mineral-water reactions

Mineral-water reactions that are controlled by transport in the dissolved phase are characterized by a rate equation that describes the flux of reactants through a laminar layer of thickness 8 adjacent to the mineral. Transport in this very thin layer is by molecular diffusion therefore Eq. (9.20) becomes... 

The saturation index module would be the location for additional enhancements to the system to make it applicable to waters from formations of more complex mineralogy, to include uncertainty in the thermochemical data used, and perhaps to consider mineral reaction rates and water residence times. The direction of such enhancements are sketched below. 

The rate of flow between fluids in fractures and in the rock matrix is a crucial factor for transport and reaction in fractures. For consistency with the formulation for flow between fractures and matrix used in the Yucca Mountain Project, the reactive surface area for minerals in unsaturated fractures has been related to the fracture-matrix interaction area based on a modified form of the Active Fracture Model (Liu et al., 1998 Sonnenthal el al., 2003). In this way, the wetted surface area for mineral-water reactions is consistent with that for flow and diffusion. 

Acidic Hydrolysis. Hydrolysis of esters by use of water and a mineral acid leads to an equiUbrium mixture of ester, alcohol, and free carboxyHc acid. Complete reaction can only be achieved by removal of alcohol or acid from the equiUbrium. Because esters have poor solubiUty in water, the reaction rate in dilute acids is fairly low. Therefore, emulsifiers such as sulfonated oleic acid or sulfonated aromatic compounds (TwitcheU reagent) are added to facihtate the reaction. 

Less detailed information is available concerning the rates of reactions of most hydroxy salts of inorganic acids indeed, the qualitative changes occurring during stepwise or overall removal of water have not been established for many systems. The behaviour characteristics of a number of hydroxy halides are mentioned below, as are the dehydroxylations of representative minerals. Some aspects of the relationships between the reactions of minerals and structurally similar metal hydroxides are critically discussed by Brett et al. [92]. 

At 0.9 °C the rate of bromination of biphenyl relative to benzene was approximately 1,270, compared to 26.9 in the presence of mineral acid, and this latter value is fairly close to that obtained with 50 % aqueous dioxan. The possibility that the positive brominating species might be protonated bromine acetate, AcOHBr+, was considered a likely one since the reaction rate is faster in aqueous acetic acid than in water, but this latter effect might be an environmental one since bromination by acidified hypobromous acid is slower in 50 % aqueous dioxan than in... 

In the absence of added mineral acid, the effective chlorinating species was concluded to be chlorine acetate. Like the catalysed chlorination, the rate of chlorination (of toluene) falls rapidly on changing the solvent from anhydrous to 98 % aqueous acetic acid, passes through a shallow minimum and thence to a maximum in 50 % aqueous acid this was thus attributed to a combination of the decrease in concentration of chlorine acetate as water is added and a solvent effect. By correcting for the change in concentration of chlorine acetate in the different media it was shown that the reaction rate increases as the water content of the media increases. 

Soil water flow is decidedly episodic. During dry times the water solutions in the soil are probably fairly concentrated and not very reactive. Time-averaged reaction rates should be roughly proportional to the fraction of time reacting minerals are in contact with thermodynamically imdersaturated (and reactive) water. In a study of the relationship between denudation rate and runoff for rivers draining igneous and metamorphic rock in Kenya, Dunne (1978) obtains the relationship of (denudation rate in tons/km per year) = 0.28 (runoff in mm/ year)°. ... 

Once the initial equilibrium state of the system is known, the model can trace a reaction path. The reaction path is the course followed by the equilibrium system as it responds to changes in composition and temperature (Fig. 2.1). The measure of reaction progress is the variable , which varies from zero to one from the beginning to end of the path. The simplest way to specify mass transfer in a reaction model (Chapter 13) is to set the mass of a reactant to be added or removed over the course of the path. In other words, the reaction rate is expressed in reactant mass per unit . To model the dissolution of feldspar into a stream water, for example, the modeler would specify a mass of feldspar sufficient to saturate the water. At the point of saturation, the water is in equilibrium with the feldspar and no further reaction will occur. The results of the calculation are the fluid chemistry and masses of precipitated minerals at each point from zero to one, as indexed by . 

Rate constants for the dissolution and precipitation of quartz, for example, have been measured in deionized water (Rimstidt and Barnes, 1980). Dove and Crerar (1990), however, found that reaction rates increased by as much as one and a half orders of magnitude when the reaction proceeded in dilute electrolyte solutions. As well, reaction rates determined in the laboratory from hydrothermal experiments on clean systems differ substantially from those that occur in nature, where clay minerals, oxides, and other materials may coat mineral surfaces and hinder reaction. 

In this equation, and are the values of reaction progress at the beginning and end of the step nj is the mass in kg of the fluid (equal to nw, the water mass, plus the mass of the solutes) nk is the mole number of each mineral nr is the reaction rate (moles) for each reactant Mwk is the mole weight (g mol-1) of each mineral, and Mwr is the mole weight for each reactant and T, jsp is the fraction of the fluid displaced over the reaction step in a flush model (Adlsp is zero if a flush model is not invoked). 

Different reaction mechanisms can predominate in fluids of differing composition, since species in solution can serve to promote or inhibit the reaction mechanism. For this reason, there may be a number of valid rate laws that describe the reaction of a single mineral (e.g., Brady and Walther, 1989). It is not uncommon to find that one rate law applies under acidic conditions, another at neutral pH, and a third under alkaline conditions. We may discover, furthermore, that a rate law measured for reaction with deionized water fails to describe how a mineral reacts with electrolyte solutions. 

Many minerals have been found to dissolve and precipitate in nature at dramatically different rates than they do in laboratory experiments. As first pointed out by Paces (1983) and confirmed by subsequent studies, for example, albite weathers in the field much more slowly than predicted on the basis of reaction rates measured in the laboratory. The discrepancy can be as large as four orders of magnitude (Brantley, 1992, and references therein). As we calculate in Chapter 26, furthermore, the measured reaction kinetics of quartz (SiC>2) suggest that water should quickly reach equilibrium with this mineral, even at low temperatures. Equilibrium between groundwater and quartz, however, is seldom observed, even in aquifers composed largely of quartz sand. 

But within the pH range of natural waters, the dissolution (and precipitation) of carbonate minerals is surface controlled i.e., the rate of dissolution is rate determined by a chemical reaction at the water-mineral interface. Fig. 8.1 gives the data on the dissolution rates of various carbonate minerals in aqueous solutions obtained in careful studies by Chou and Wollast (1989). 

Chemical relaxation methods can be used to determine mechanisms of reactions of ions at the mineral/water interface. In this paper, a review of chemical relaxation studies of adsorption/desorption kinetics of inorganic ions at the metal oxide/aqueous interface is presented. Plausible mechanisms based on the triple layer surface complexation model are discussed. Relaxation kinetic studies of the intercalation/ deintercalation of organic and inorganic ions in layered, cage-structured, and channel-structured minerals are also reviewed. In the intercalation studies, plausible mechanisms based on ion-exchange and adsorption/desorption reactions are presented steric and chemical properties of the solute and interlayered compounds are shown to influence the reaction rates. We also discuss the elementary reaction steps which are important in the stereoselective and reactive properties of interlayered compounds. 

Examination of Figure 1-12 provides some clue to qualitatively gauge the interface reaction rate for reactions in water. Figure 1-12 shows that, for mineral with low solubility and high bond strength (characterized by (z+z )max, where z+ and z are valences of ions to be dissociated), the overall dissolution rate is controlled by interface reaction otherwise, it is controlled by mass transport. Because diffusivities of common cations and anions in water do not differ much (by less than a factor of 10 Table l-3a), when the overall reaction rate is controlled by interface reaction, it means that interface reaction is slow when the overall reaction rate is controlled by mass transport, the interface reaction rate is rapid. Therefore, from Figure 1-12, we may conclude that the interface reaction rate increases with mineral solubility and decreases with bond strength (z+z )max to be dissociated. 

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