Strong electrolytes phase equilibria

To test the validity of the extended Pitzer equation, correlations of vapor-liquid equilibrium data were carried out for three systems. Since the extended Pitzer equation reduces to the Pitzer equation for aqueous strong electrolyte systems, and is consistent with the Setschenow equation for molecular non-electrolytes in aqueous electrolyte systems, the main interest here is aqueous systems with weak electrolytes or partially dissociated electrolytes. The three systems considered are the hydrochloric acid aqueous solution at 298.15°K and concentrations up to 18 molal the NH3-CO2 aqueous solution at 293.15°K and the K2CO3-CO2 aqueous solution of the Hot Carbonate Process. In each case, the chemical equilibrium between all species has been taken into account directly as liquid phase constraints. Significant parameters in the model for each system were identified by a preliminary order of magnitude analysis and adjusted in the vapor-liquid equilibrium data correlation. Detailed discusions and values of physical constants, such as Henry s constants and chemical equilibrium constants, are given in Chen et al. (11). 

The form in which chemical analyses of sea water are given records the history of our thought concerning the nature of salt solutions. Early analytical data were reported in terms of individual salts NaCl, CaSO/i, and so forth. After development of the concept of complete dissociation of strong electrolytes, chemical analyses of sea water were given in terms of individual ions Na+, Ca++, Cl-, and so forth, or in terms of known undissociated and partly dissociated species, e.g., HC03 , In recent years there has been an attempt to determine the thermodynamically stable dissolved species in sea water and to evaluate the relative distribution of these species at specified conditions. Table 1 lists the principal dissolved species in sea water deduced from a model of sea water that assumes the dissolved constituents are in homogeneous equilibrium, and (or) in equilibrium, or nearly so, with solid phases. 

Let s consider the solubility equilibrium in a saturated solution of calcium fluoride in contact with an excess of solid calcium fluoride. Like most sparingly soluble ionic solutes, calcium fluoride is a strong electrolyte in water and exists in the aqueous phase as dissociated hydrated ions, Ca2+(aq) and F (aq). At equilibrium, the ion concentrations remain constant because the rate at which solid CaF2 dissolves to give Ca2+(aq) and F aq) exactly equals the rate at which the ions crystallize to form solid CaF2 ... 

Nitric acid is a strong electrolyte. Therefore, the solubilities of nitrogen oxides in water given in Ref. 191 and based on Henry s law are utilized and further corrected by using the method of van Krevelen and Hofhjzer (77) for electrolyte solutions. The chemical equilibrium is calculated in terms of liquid-phase activities. The local composition model of Engels (192), based on the UNIQUAC model, is used for the calculation of vapor pressures and activity coefficients of water and nitric acid. Multicomponent diffusion coefficients in the liquid phase are corrected for the nonideality, as suggested in Ref. 57. 

From Eqn. (14) it follows that with an exothermic reaction - and this is the case for most reactions in reactive absorption processes - decreases with increasing temperature. The electrolyte solution chemistry involves a variety of chemical reactions in the liquid phase, for example, complete dissociation of strong electrolytes, partial dissociation of weak electrolytes, reactions among ionic species, and complex ion formation. These reactions occur very rapidly, and hence, chemical equilibrium conditions are often assumed. Therefore, for electrolyte systems, chemical equilibrium calculations are of special importance. Concentration or activity-based reaction equilibrium constants as functions of temperature can be found in the literature [50]. 

The chemical potential of the solid crystal salt B is in phase equilibrium with the dissolved salt B in the liquid or aqueous phase. In aqueous systems we are primarily dealing with salts of strong electrolytes, which in water dissociate completely to the constituent cations and anions of the salt. The chemical potential of the dissolved salt is then given by... 

Using the equation, very strong concentration effects in small systems have been calculated. For instance, if the macroaqueous phase contains 1 M NaCl and 1 /rM NaTPB, the concentration of this electrolyte in the micro-organic phase at partition equilibrium is 1390/rM [14] This approach is valid if the phases in small systems are thick enough (> 1 /rm), in comparison to the Debye screening length, to fulfill the electroneutrality conditions. 

From the physical point of view there cannot exist, under equilibrium conditions, a measurable excess of charge in the bulk of an electrolyte solution. By electrostatic repulsion this charge would be dragged to the phase boundary where it would be the source of a strong electric field in the vicinity of the phase. This point will be discussed in Section 3.1.3. 

Displacement of equilibria in adsorbed layers. If an equilibrium exists in solution between two or more constituent substances, and one of these is adsorbed more strongly than another, that one will be more concentrated in the surface and the equilibrium in the surface layer will be shifted in the direction of that constituent. It often happens, owing to electrolytic dissociation or to hydrolysis, that a single pure substance when dissolved in water consists of such an equilibrium mixture, and if the bulk solution alone were under consideration, an aqueous solution of such a substance would naturally be treated, according to the phase rule, as a two-component system. But when surfaces enter into consideration, unless the ease of adsorption of both the constituents of the equilibrium mixture in solution is identical, the adsorption of each has to be considered separately and consequently the system must be regarded as consisting of three components at least, not two.5... 

Addition of salting-out type electrolytes to oil-water-surfactant (s) systems has also a strong influence on their phase equilibria and interfacial properties. This addition produces a dehydration of the surfactant and its progressive transfer to the oil phase (2). At low salinity, a water-continuous microemulsion is observed in equilibrium with an organic phase. At high salinity an oil-continuous microemulsion is in equilibrium with an aqueous phase. At intermediate salinity, a middle phase microemulsion with a bicontinuous structure coexists with pure aqueous and organic phases. These equilibria were referred by Vinsor as Types I,II and III (33). 

In general, the chemical potential of the solution in the micellar phase must equal that in the surrounding aqueous medium when thermodynamic equilibrium is established. Nonpolar solutes, such as the permanent gases, which do not interact strongly with either phase may be distributed rather evenly over the whole microheterogeneous system (39). On the other hand, typical electrolytes are practically restricted to the aqueous medium, while molecules of hydrophobic substances, e.g. hydrocarbons, are almost totally sequestered in the micelles. 

In the first mode, known portions of the polymer were equilibrated with solutions of CaCl2 and HCl, as well as with their mixtures of known concentrations. The final composition of the bulk solutions in equilibrium with the polymeric phase was determined by titrating the excess HCl acid with NaOH and hy complexometric titration of the Ca ions with ethylenediamine tetraacetate (EDTA). From these data the concentrations of the electrolytes within the porous space of the polymeric material were calculated and then the apparent phase distribution coefficients k of HCl and CaCl2, defined as the ratio between the equihbrium concentrations of the corresponding electrolytes within and outside the polymeric beads. These calculations are strongly facifitated by the outstanding property of the neutral hypercrossfinked polystyrene sorbents, namely that their swelling does not depend on the electrolyte concentration, so that the volume of the porous space remains constant in all experiments. Thus,... 

Fig. 1 A scheme of the energetics at an n-type semiconductor electrode in contact with a redox system in an electrolyte solution, (a) The situation under conditions of electronic equilibrium. The electrochemical potential of the electrons is the same in both phases, i.e. the electron Fermi-level in the semiconductor Ep.n has the same value as the Fermi-level of the electrons in the redox system fRed/Ox- (t>) Case in which the energy bands in the semiconductor are flat this situation, corresponding to maximum photovoltage, is reached under strong illumination at open circuit. Wsc is the width of the depletion layer and e(j>sc is the band-bending.

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