Solids chemical equilibrium

Precipitation involves the alteration of the ionic equilibrium to produce insoluble precipitates. To remove the sediment, chemical precipitation is allied with solids separation processes such as filtration. Undesirable metal ions and anions are commonly removed from waste streams by converting them to an insoluble form. The process is sometimes preceded by chemical reduction of the metal ions to a form that can be precipitated more easily. Chemical equilibrium can be affected by a variety of means to change the solubility of certain compounds. For e.xample, precipitation can be induced by alkaline agents, sulfides, sulfates, and carbonates. Precipitation with chemicals is a common waste stream treatment process and is effective and reliable. The treatment of sludges is covered next. 

Chemical equilibria often involve pure liquids and solids in addition to gases and solutes. The concentration of a pure liquid or solid does not vary significantly. Figure 16-4 shows that although the amount of a solid or liquid can vary, the number of moles per unit volume remains fixed. In other words, the concentrations of pure liquids or solids are always equal to their standard concentrations. Thus, division by standard concentration results in a value of 1 for any pure liquid or solid. This allows us to omit pure liquids and solids from equilibrium constant expressions. For a general reaction (2A + iBt= C D-l-. S where S is a pure solid or liquid ... 

If chemical equilibrium between the melt and the solid is assumed throughout the melting column, the definition of the partition coefficient (D) ... 

If the electrolyte components can react chemically, it often occurs that, in the absence of current flow, they are in chemical equilibrium, while their formation or consumption during the electrode process results in a chemical reaction leading to renewal of equilibrium. Electroactive substances mostly enter the charge transfer reaction when they approach the electrode to a distance roughly equal to that of the outer Helmholtz plane (Section 5.3.1). It is, however, sometimes necessary that they first be adsorbed. Similarly, adsorption of the products of the electrode reaction affects the electrode reaction and often retards it. Sometimes, the electroinactive components of the solution are also adsorbed, leading to a change in the structure of the electrical double layer which makes the approach of the electroactive substances to the electrode easier or more difficult. Electroactive substances can also be formed through surface reactions of the adsorbed substances. Crystallization processes can also play a role in processes connected with the formation of the solid phase, e.g. in the cathodic deposition of metals. 

In its simplest form a partitioning model evaluates the distribution of a chemical between environmental compartments based on the thermodynamics of the system. The chemical will interact with its environment and tend to reach an equilibrium state among compartments. Hamaker(l) first used such an approach in attempting to calculate the percent of a chemical in the soil air in an air, water, solids soil system. The relationships between compartments were chemical equilibrium constants between the water and soil (soil partition coefficient) and between the water and air (Henry s Law constant). This model, as is true with all models of this type, assumes that all compartments are well mixed, at equilibrium, and are homogeneous. At this level the rates of movement between compartments and degradation rates within compartments are not considered. 

When a solid acts as a catalyst for a reaction, reactant molecules are converted into product molecules at the fluid-solid interface. To use the catalyst efficiently, we must ensure that fresh reactant molecules are supplied and product molecules removed continuously. Otherwise, chemical equilibrium would be established in the fluid adjacent to the surface, and the desired reaction would proceed no further. Ordinarily, supply and removal of the species in question depend on two physical rate processes in series. These processes involve mass transfer between the bulk fluid and the external surface of the catalyst and transport from the external surface to the internal surfaces of the solid. The concept of effectiveness factors developed in Section 12.3 permits one to average the reaction rate over the pore structure to obtain an expression for the rate in terms of the reactant concentrations and temperatures prevailing at the exterior surface of the catalyst. In some instances, the external surface concentrations do not differ appreciably from those prevailing in the bulk fluid. In other cases, a significant concentration difference arises as a consequence of physical limitations on the rate at which reactant molecules can be transported from the bulk fluid to the exterior surface of the catalyst particle. Here, we discuss... 

The effect of a Plasma is to shift the Chemical Equilibrium of a Reaction toward the Solid, lowering the Deposition Temperature... 

Exp-6 potential models can be validated through several independent means. Fried and Howard33 have considered the shock Hugoniots of liquids and solids in the decomposition regime where thermochemical equilibrium is established. As an example of a typical thermochemical implementation, consider the Cheetah thermochemical code.32 Cheetah is used to predict detonation performance for solid and liquid explosives. Cheetah solves thermodynamic equations between product species to find chemical equilibrium for a given pressure and temperature. From these properties and elementary detonation theory, the detonation velocity and other performance indicators are computed. 

Advances continue in the treatment of detonation mixtures that include explicit polar and ionic contributions. The new formalism places on a solid footing the modeling of polar species, opens the possibility of realistic multiple fluid phase chemical equilibrium calculations (polar—nonpolar phase segregation), extends the validity domain of the EXP6 library,40 and opens the possibility of applications in a wider regime of pressures and temperatures. 

Most industrial catalysts are heterogeneous catalysts consisting of solid active components dispersed on the internal surface of an inorganic porous support. The active phases may consist of metals or oxides, and the support (also denoted the carrier) is typically composed of small oxidic structures with a surface area ranging from a few to several hundred m2/g. Catalysts for fixed bed reactors are typically produced as shaped pellets of mm to cm size or as monoliths with mm large gas channels. A catalyst may be useful for its activity referring to the rate at which it causes the reaction to approach chemical equilibrium, and for its selectivity which is a measure of the extent to which it accelerates the reaction to form the desired product when multiple products are possible [1],... 

Whether a task can be performed concurrently with other tasks depends on two factors. One is whether the input information for the activity under consideration depends on the output from other activities. The other is the availability of manpower and equipment. Consider a team that has only one chemical engineer to design both the reactor and the crystallizer. Even though reaction kinetics, solid-liquid equilibrium data and crystallization kinetics can be measured in parallel, the total time for these activities is determined by what the single individual can achieve. 

Large concentrations of Fe + develop in the soil solution in the weeks following flooding, often several mM or tens of mM (Figure 4.5). Calculations with chemical equilibrium models show that the ion activity products of pure ferrous hydroxides, carbonates and other minerals are often exceeded 100-fold (Neue and Bloom, 1989). Evidently precipitation of these minerals is inhibited, probably as a result of adsorption of foreign solutes, such as dissolved organic matter and phosphate ions, onto nucleation sites (Section 3.7). However, once a sufficient supersaturation has been reached there is a rapid precipitation of amorphous solid phases, which may later re-order to more crystalline forms. Only a small part of the Fe(II) formed in reduction remains in solution the bulk is sorbed in exchangeable forms or, eventually, precipitated. 

Speciation is a dynamic process that depends not only on the ligand-metal concentration but on the properties of the aqueous solution in chemical equilibrium with the surrounding solid phase. As a consequence, the estimation of aqueous speciation of contaminant metals should take into account the ion association, pH, redox status, formation-dissolution of the solid phase, adsorption, and ion-exchange reactions. From the environmental point of view, a complexed metal in the subsurface behaves differently than the original compound, in terms of its solubility, retention, persistence, and transport. In general, a complexed metal is more soluble in a water solution, less retained on the solid phase, and more easily transported through the porous medium. 

The coexistence of various solids at equilibrium in a heterogeneous system may be opportunely described by chemical reactions involving the major components of the solid phases. If we observe, for instance, the coexistence of pyroxene, pla-gioclase, and quartz, we can write an equation involving sodic terms ... 

Phossy water, a waste product in the production of elemental phosphorus by the electric furnace process, contains from 1000 to 5000 mg/L suspended solids that include 400-2500 mg/L of elemental phosphorus, distributed as liquid colloidal particles. These particles are usually positively charged, although this varies depending on the operation of the electrostatic precipitators. Furthermore, the chemical equilibrium between the fluoride and flurosilicate ions introduces an important source of variation in suspended solids that is a pH function. Commonly... 

Figure 24.9a shows a plot of measured total carbon (CO plus CO2, mole percent) versus equivalence ratio. The solid line was calculated assuming chemical equilibrium at the measured temperatures. The data points represent the measured CO and CO2 mole fractions (dry basis) using the fast extractive-sampling system. Horizontal bars represent the uncertainty in (f> due to reading and calibration errors vertical bars represent the uncertainty in the CO and CO2 mole-fraction sum due to line strength and absorption measurement uncertainty. The data are consistent to within 4% of the equilibrium predictions at all values of (p, indicating reliable operation of the system. 

Figure 24.9 illustrates measured CO and CO2 mole fractions as a function of equivalence ratio. The solid lines represent chemical equilibrium calculations of CO and CO2 mole fractions at measured temperatures. The vertical bars represent the uncertainty in measured CO and CO2 mole fractions due to line... 

Since solid carbon vaporizes as a result of its vapor pressure, p p,c, the chemical equilibrium constant s defined as... 

The apparatus s step change from ambient to desired reaction conditions eliminates transport effects between catalyst surface and gas phase reactants. Using catalytic reactors that are already used in industry enables easy transfer from the shock tube to a ffow reactor for practical performance evaluation and scale up. Moreover, it has capability to conduct temperature- and pressure-jump relaxation experiments, making this technique useful in studying reactions that operate near equilibrium. Currently there is no known experimental, gas-solid chemical kinetic method that can achieve this. 

Biodiesel can be produced by a sustainable continuous process based on catalytic reactive distillation. The integrated design ensures the removal of water byproduct that shifts the chemical equilibrium to completion and preserves the catalyst activity. The novel alternative proposed here replaces the liquid catalysts with solid acids, thus dramatically improving the economics of current biodiesel synthesis and reducing the number of downstream steps. The key benefits of this approach are ... 

In this chapter, we focus on the batch melting model where melt maintains chemical equilibrium with solid, and stays with solid until the final extraction. 

Assuming chemical equilibrium between the residual solid and the residual melt, we have... 

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