Calcium carbonate kinetics

Qualitative examples abound. Perfect crystals of sodium carbonate, sulfate, or phosphate may be kept for years without efflorescing, although if scratched, they begin to do so immediately. Too strongly heated or burned lime or plaster of Paris takes up the first traces of water only with difficulty. Reactions of this type tend to be autocat-alytic. The initial rate is slow, due to the absence of the necessary linear interface, but the rate accelerates as more and more product is formed. See Refs. 147-153 for other examples. Ruckenstein [154] has discussed a kinetic model based on nucleation theory. There is certainly evidence that patches of product may be present, as in the oxidation of Mo(lOO) surfaces [155], and that surface defects are important [156]. There may be catalysis thus reaction VII-27 is catalyzed by water vapor [157]. A topotactic reaction is one where the product or products retain the external crystalline shape of the reactant crystal [158]. More often, however, there is a complicated morphology with pitting, cracking, and pore formation, as with calcium carbonate [159]. 

The kinetics of the formation of the magnesium hydroxide and calcium carbonate are functions of the concentration of the bicarbonate ions, the temperature, and the rate of release of CO2 from the solution. At temperatures up to 82°C, CaCO predominates, but as the temperature exceeds 93°C, Mg(OH)2 becomes the principal scale. Thus, ia seawater, there is a coasiderable teadeacy for surfaces to scale with an iacrease ia temperature. 

The reactor has been successfully used in the case of forced precipitation of copper and calcium oxalates (Jongen etal., 1996 Vacassy etal., 1998 Donnet etal., 1999), calcium carbonate (Vacassy etal., 1998) and mixed yttrium-barium oxalates (Jongen etal., 1999). This process is also well adapted for studying the effects of the mixing conditions on the chemical selectivity in precipitation (Donnet etal., 2000). When using forced precipitation, the mixing step is of key importance (Schenk etal., 2001), since it affects the initial supersaturation level and hence the nucleation kinetics. A typical micromixer is shown in Figure 8.35. 

Hostomsky, J. and Jones, A.G., 1991. Calcium carbonate crystallization kinetics, agglomeration and fomi during continuous precipitation from solution. Journal of Physics D Applied Physics, 24, 165-170. 

Swinney, L.D., Stevens, J.D. and Peters, R.W., 1982. Calcium Carbonate Crystallization Kinetics. Industrial and Engineering Chemistry Fundamentals, 21, 31. 

Examples of reversible breakdown of structure have been reported for procaine penicillin dispersions (7), for model systems of calcium carbonate in polybutene ( ), and for numerous other systems. During shear the particles are forced into contact with each other with sufficient kinetic energy to overcome any natural barrier against their displacement of a lyosphere around each individual particle. A dispersion which is inherently stable can thus be forced by shear into a condition of instability. 

Juwekar and Sharma [1] described the kinetics of the above reactions. The formation of calcium carbonate is non elementary reaction which involves the number of elementary steps as shown in Scheme 7.2, steps (iv) and (v) assumed to be instantaneous. Absorption of C02 gas and dissolution of Ca(OH)2 affects the nucleation step, both are considered as rate controlling steps. 

Berner, R.A. Morse, J.M. 1974. Dissolution kinetics of calcium carbonate in seawater. IV. Theory of calcite dissolution, American Journal of Science, 274,108-134. 

Liu Z, Dreybrodt W. Dissolution kinetics of calcium carbonate minerals in H20-C02 solutions in turbulent flow—the role of the diffusion boundary layer and the slow reaction H20 + CO2 <-> H+ + HC03. Geochim Cosmochim Acta 1997 61(14) 2879-2889. 

Turner JV (1982) Kinetic fractionation of carbon-13 during calcium carbonate precipitation. Geochim... 

Although surfece waters are supersaturated with respect to calcium carbonate, abiogenic precipitation is imcommon, probably because of unfevorable kinetics. (The relatively rare formation of abiogenic calcite is discussed further in Chapter 18.) Marine organisms are able to overcome this kinetic barrier because they have enzymes that catalyze the precipitation reaction. Because fl declines with depth, organisms that deposit calcareous shells in deep waters, such as benthic foraminiferans, must expend more energy to create their hard parts as compared to surfece dwellers. 

On the opposite end of the spectrum, thermodynamics cannot explain why some PIC can sink through undersaturated waters without dissolving to accumulate on the seafloor. This is a widespread phenomenon as evidenced by the spatial %CaCOj gradients seen in the surface sediments (Figure 15.5). If the saturation horizon dictated the survival of sinking and accumulating PIC, a sharp depth cutoff should exist below which calcium carbonate is absent from the surface sediment. The importance of this kinetic barrier to dissolution is also seen in the relatively high fraction of surfece-water PIC (20 to 25%) that accumulates in the sediments as compared to the low fraction of surfece-water POC (1%). 

Whereas McGee [188] did not verify any effect of particulate fillers (i.e., glass, calcium carbonate, and aluminum) on the reaction kinetics, Lem and Han [185], working with calcium carbonate and clay in an unsaturated polyester resin, concluded that the reaction rate increases by increasing the filler content. 

Carbonate minerals are among the most chemically reactive common minerals under Earth surface conditions. Many important features of carbonate mineral behavior in sediments and during diagenesis are a result of their unique kinetics of dissolution and precipitation. Although the reaction kinetics of several carbonate minerals have been investigated, the vast majority of studies have focused on calcite and aragonite. Before examining data and models for calcium carbonate dissolution and precipitation reactions in aqueous solutions, a brief summary of the major concepts involved will be presented. Here we will not deal with the details of proposed reaction mechanisms and the associated complex rate equations. These have been examined in extensive review articles (e.g., Plummer et al., 1979 Morse, 1983) and where appropriate will be developed in later chapters. 

The kinetics of calcium carbonate precipitation in simple solutions have received less attention than those of dissolution reactions. This perhaps reflects the fact that most sedimentary carbonates are initially formed biogenically and that the primary interest in carbonate precipitation reactions has been directed at reaction... 

A major portion of the studies on calcium carbonate reaction kinetics has been done in seawater because of the many significant geochemical problems related to this system. Morse and Berner (1979) summarized the work on carbonate dissolution kinetics in seawater and their application to the oceanic carbonate system. The only major seawater component in addition to Mg2+ that has been identified as a dissolution inhibitor is SO42- (Sjoberg, 1978 Mucci et al., 1989). Sjoberg s studies of other major and minor components (Sr2+, H3BO3, F-) showed no measurable influence on dissolution rates. Morse and Berner (1979) and Sjoberg (1978) found that for near-equilibrium dissolution in phosphate-free seawater, the dissolution rate could be described as ... 

Major complications arise because of bioturbation and the complex reaction kinetics of carbonates in deep sea sediments. These two factors will, to a large degree, determine the total amount of calcium carbonate available for neutralization of fossil fuel CO2 (e.g., see Broecker and Takahashi, 1977). 

Keir R.S. (1980) The dissolution kinetics of biogenic calcium carbonates in seawater. Geochim. Cosmochim. Acta 44, 241-252. 

Morse J.W. (1978) Dissolution kinetics of calcium carbonate in seawater. VI The near-equilibrium dissolution kinetics of calcium carbonate-rich deep sea sediments. Amer. J. Sci. 278, 344-355. 

Morse J.W. (1983) The kinetics of calcium carbonate dissolution and precipitation. In Reviews in Mineralogy Carbonates - Mineralogy and Chemistry (ed. R. J. Reeder), pp. 227-264. Mineralogical Society of America. Bookcrafters, Inc., Chelse, MI. 

Morse J.W. and Berner R.A. (1979) The chemistry of calcium carbonate in the deep oceans. In Chemical Modelling—Speciation, Sorption, Solubility, and Kinetics in Aqueous Systems (ed. E. Jenne), pp. 499-535. Amer. Chem. Soc., Washington, D.C. 

Reddy M.M. and Gaillard W.D. (1981) Kinetics of calcium carbonate (calacite)-seeded crystallization Influence of solid/solution ratio on the reaction rate constant. J. Colloid Interface Sci. 80, 171-178. 

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