Chemical composition equilibrium

The distribution of metals between dissolved and particulate phases in aquatic systems is governed by a competition between precipitation and adsorption (and transport as particles) versus dissolution and formation of soluble complexes (and transport in the solution phase). A great deal is known about the thermodynamics of these reactions, and in many cases it is possible to explain or predict semi-quantita-tively the equilibrium speciation of a metal in an environmental system. Predictions of complete speciation of the metal are often limited by inadequate information on chemical composition, equilibrium constants, and reaction rates. 

Most processes are catalyzed where catalysts for the reaction are known. The choice of catalyst is crucially important. Catalysts increase the rate of reaction but are unchanged in quantity and chemical composition at the end of the reaction. If the catalyst is used to accelerate a reversible reaction, it does not by itself alter the position of the equilibrium. When systems of multiple reactions are involved, the catalyst may have different effects on the rates of the different reactions. This allows catalysts to be developed which increase the rate of the desired reactions relative to the undesired reactions. Hence the choice of catalyst can have a major influence on selectivity. 

When the kinetics are unknown, still-useful information can be obtained by finding equilibrium compositions at fixed temperature or adiabatically, or at some specified approach to the adiabatic temperature, say within 25°C (45°F) of it. Such calculations require only an input of the components of the feed and produc ts and their thermodynamic properties, not their stoichiometric relations, and are based on Gibbs energy minimization. Computer programs appear, for instance, in Smith and Missen Chemical Reaction Equilibrium Analysis Theory and Algorithms, Wiley, 1982), but the problem often is laborious enough to warrant use of one of the several available commercial services and their data banks. Several simpler cases with specified stoichiometries are solved by Walas Phase Equilibiia in Chemical Engineering, Butterworths, 1985). 

By the term state we refer to such data as the chemical composition of the parts of the system (including allotropy and isomerism), their state of electrification, magnetisation, stress or strain, their state of division, temperature, and the like, and the second condition generalises the statement of equilibrium. 

The failure to identify the necessary authigenic silicate phases in sufficient quantities in marine sediments has led oceanographers to consider different approaches. The current models for seawater composition emphasize the dominant role played by the balance between the various inputs and outputs from the ocean. Mass balance calculations have become more important than solubility relationships in explaining oceanic chemistry. The difference between the equilibrium and mass balance points of view is not just a matter of mathematical and chemical formalism. In the equilibrium case, one would expect a very constant composition of the ocean and its sediments over geological time. In the other case, historical variations in the rates of input and removal should be reflected by changes in ocean composition and may be preserved in the sedimentary record. Models that emphasize the role of kinetic and material balance considerations are called kinetic models of seawater. This reasoning was pulled together by Broecker (1971) in a paper called "A kinetic model for the chemical composition of sea water."... 

Garrels, R. M. and Mackenzie, F. T. (1967). Origin of the chemical compositions of some springs and lakes. In "Equilibrium Concepts in Natural Water Systems" (W. Stumm, ed.). Advances in Chemistry Series 67, pp. 222-274. American Chemical Society, Washington. 

Assuming chemical equilibrium between Kuroko-forming minerals and Kuroko ore fluids, the chemical composition of Kuroko ore fluids can be estimated, using thermochemical data. Calculations for the purposes of estimating the chemistry of Kuroko... 

Several workers have intended to estimate the chemical compositions of Kuroko ore fluids based on the chemical equilibrium model (Sato, 1973 Kajiwara, 1973 Ichikuni, 1975 Shikazono, 1976 Ohmoto et al., 1983) and computer simulation of the changes in mineralogy and chemical composition of hydrothermal solution during seawater-rock interaction. Although the calculated results (Tables 1.5 and 1.6) are different, they all show that the Kuroko ore fluids have the chemical features (1 )-(4) mentioned above. 

There are different approaches to the study of hydrothermal alteration. For instance, Shikazono (1978a) showed the relationship between chemical composition of hydrothermal solution in equilibrium with the alteration minerals and Cl concentration in hydrothermal solution. 

Figure 1.86 illustrates the variations in the chemical composition of chloride-rich hydrothermal solution in equilibrium with common alteration minerals with temperature. Figure 1.86 demonstrates that (1) the chemical compositions of hydrothermal solution... 

Figure 1.86. Variation in chemical compositions (in molal unit) of hydrothermal solution with temperature. Thermochemical data used for the calculations are from Helgeson (1969). Calculation method is given in Shikazono (1978a). Chloride concentration in hydrothermal solution is assumed to be 1 mol/kg H2O. A-B Na concentration in solution in equilibrium with low albite and adularia, C-D K concentration in solution in equilibrium with low albite and adularia, E-F HaSiOa concentration in equilibrium with quartz, G-H Ca + concentration in equilibrium with albite and anorthite (Shikazono, 1978a, 1988b).

The dependence of concentration of K+, Na+, Ca + and H4Si04 in equilibrium with common alteration minerals (K-feldspar, Na-feldspar, quartz) on temperature is shown in Fig. 1.140 (Shikazono, 1988b). This figure demonstrates that (1) chemical compositions of hydrothermal solution depend on alteration minerals, temperature and chloride concentration, and K" " and HaSiOa concentrations increase and Ca + concentration decrease with increasing of temperature. In this case, it is considered that potassic alteration adjacent to the gold-quartz veins occurs when hydrothermal solution initially in... 

Factors in controlling chemical compositions of gold in equilibrium with the ore fluids are temperature, pH, concentration of aqueous H2S and Cl in the ore fluids, concentration ratio of Au and Ag species in the ore fluids, activity coefficient of Au and Ag components in gold, and so on (Shikazono, 1981). In the Yamizo Mountains, as a result, Ag/Au ratios of gold are correlated with a kind of the host rocks and sulfur isotopic compositions of the deposits. This correlation could be used to interpret Ag/Au ratios of gold. 

Previous studies clearly indicated that the chemical compositions of geothermal waters are intimately related both to the hydrothermal alteration mineral assemblages of country rocks and to temperature. Shikazono (1976, 1978a) used a logarithmie cation-Cl concentration diagram to interpret the concentrations of alkali and alkaline earth elements and pH of geothermal waters based on thermochemical equilibrium between hydrothermal solution and alteration minerals. 

The chemical compositions of geothermal water plot in Figs. 23-2.9. All data plot near the equilibrium curves. This indicates that the geothermal waters considered... 

The chemistry of hydrothermal solutions from midoceanic ridges has been reasonably explained by the effect of buffering by alteration minerals (Seyfried, 1987 Bemdt et al., 1989). Therefore, it might be worth explaining the chemical composition of hydrothermal solutions from back-arc basins in terms of chemical equilibrium between hydrothermal solutions and alteration minerals. 

Chemical compositions of major elements (alkali, alkali earth elements. Si) in back-arc and midoceanic ridge hydrothermal solutions are not so different (Table 2.15). This is thought to be due to the effect of water-rock interaction. For example, Berndt et al. (1989) have shown that mQ i+ of midoceanic ridge hydrothermal fluids is controlled by anorthite-epidote equilibrium (Fig. 2.37). Figure 2.37 shows that /Mca2+/m + of back-arc hydrothermal fluids is also controlled by this equilibrium. 

The ends of a correctly constructed electrochemical circuit measuring electrical potential difference must always have metals or conductors with identical chemical composition. It is usually reached by simple connection of two metals by copper wires. The inclusion between two metal conductors of a third metal conductor according to Volta s law does not change the difference of potentials at the output of a circuit. The difference of potentials in an electrochemical circuit at equilibrium is caused by the change of Gibbs free energy during the appropriate electrochemical reaction ... 

The earliest or Level I fugacity models simulate the simple situation in which a chemical achieves equilibrium between a number of phases of different composition and volume. The prevailing fugacity is simply/ = M/Y.V, x Z where M is the total quantity of chemical (mol), V, is volume (m3), and Z, is the corresponding phase Z value (mol Pa-1 m-3). Although very elementary and naive, this simulation is useful as a first indication of where a chemical is likely to partition. It is widely used as a first step in chemical fate assessments. 

The dynamic viewpoint of chemical kinetics may be contrasted with the essentially static viewpoint of thermodynamics. A kinetic system is a system in unidirectional movement toward a condition of thermodynamic equilibrium. The chemical composition of the system changes continuously with time. A system that is in thermodynamic equilibrium, on the other hand, undergoes no net change with time. The thermo-dynamicist is interested only in the initial and final states of the system and is not concerned with the time required for the transition or the molecular processes involved therein the chemical kineticist is concerned primarily with these issues. 

The standard electrode potential [1] of an electrochemical reaction is commonly measured with respect to the standard hydrogen electrode (SHE) [2], and the corresponding values have been compiled in tables. The choice of this reference is completely arbitrary, and it is natural to look for an absolute standard such as the vacuum level, which is commonly used in other branches of physics and chemistry. To see how this can be done, let us first consider two metals, I and II, of different chemical composition and different work functions 4>i and 4>ii-When the two metals are brought into contact, their Fermi levels must become equal. Hence electrons flow from the metal with the lower work function to that with the higher one, so that a small dipole layer is established at the contact, which gives rise to a difference in the outer potentials of the two phases (see Fig. 2.2). No work is required to transfer an electron from metal I to metal II, since the two systems are in equilibrium. This enables us calculate the outer potential difference between the two metals in the following way. We first take an electron from the Fermi level Ep of metal I to a point in the vacuum just outside metal I. The work required for this is the work function i of metal I. 

The following hypotheses was tested in the first approximation if the vaporization of volatile oxides, sulfides, and metals of all the considered chemical elements at roasting and/or conversion temperature plays a significant role in the contamination of Karabash atmosphere, their calculated equilibrium pressure over the Cu-concentrate, slag, matte or copper melt (or their chemical composition) should strongly correlate with the detected abundance of these elements in snow samples. If such a significant correlation is detected, the corresponding process exerts primary... 

The papers of Wagner and Schottky contained the first statistical treatment of defect-containing crystals. The point defects were assumed to form an ideal solution in the sense that they are supposed not to interact with each other. The equilibrium number of intrinsic point defects was found by minimizing the Gibbs free energy with respect to the numbers of defects at constant pressure, temperature, and chemical composition. The equilibrium between the crystal of a binary compound and its components was recognized to be a statistical one instead of being uniquely fixed. 

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