Of weak electrolytes

As the titration begins, mostly HAc is present, plus some H and Ac in amounts that can be calculated (see the Example on page 45). Addition of a solution of NaOH allows hydroxide ions to neutralize any H present. Note that reaction (2) as written is strongly favored its apparent equilibrium constant is greater than lO As H is neutralized, more HAc dissociates to H and Ac. As further NaOH is added, the pH gradually increases as Ac accumulates at the expense of diminishing HAc and the neutralization of H. At the point where half of the HAc has been neutralized, that is, where 0.5 equivalent of OH has been added, the concentrations of HAc and Ac are equal and pH = pV, for HAc. Thus, we have an experimental method for determining the pV, values of weak electrolytes. These p V, values lie at the midpoint of their respective titration curves. After all of the acid has been neutralized (that is, when one equivalent of base has been added), the pH rises exponentially. 

The shapes of the titration curves of weak electrolytes are identical, as Figure 2.13 reveals. Note, however, that the midpoints of the different curves vary in a way that characterizes the particular electrolytes. The pV, for acetic acid is 4.76, the pV, for imidazole is 6.99, and that for ammonium is 9.25. These pV, values are directly related to the dissociation constants of these substances, or, viewed the other way, to the relative affinities of the conjugate bases for protons. NH3 has a high affinity for protons compared to Ac NH4 is a poor acid compared to HAc. 

A biologically important point is revealed by the basic shape of the titration curves of weak electrolytes in the region of the pK, pH remains relatively unaffected as increments of OH (or H ) are added. The weak acid and its conjugate base are acting as a buffer. 

B. Ionisation constants of weak electrolytes and their temperature variation ... 

Complete and Incomplete Ionic Dissociation. In the foregoing chapter mention has been made of electrolytes that are completely dissociated in solution, and of weak electrolytes where free ions are accompanied by a certain proportion of neutral molecules. In the nineteenth century it was thought that aqueous solutions of even the strongest electrolytes contained a small proportion of neutral molecules. Opinion as to the relation between strong and weak electrolytes has passed through certain vicissitudes and we shall describe later how this problem has been resolved. 

The great importance of the solubility product concept lies in its bearing upon precipitation from solution, which is, of course, one of the important operations of quantitative analysis. The solubility product is the ultimate value which is attained by the ionic concentration product when equilibrium has been established between the solid phase of a difficultly soluble salt and the solution. If the experimental conditions are such that the ionic concentration product is different from the solubility product, then the system will attempt to adjust itself in such a manner that the ionic and solubility products are equal in value. Thus if, for a given electrolyte, the product of the concentrations of the ions in solution is arbitrarily made to exceed the solubility product, as for example by the addition of a salt with a common ion, the adjustment of the system to equilibrium results in precipitation of the solid salt, provided supersaturation conditions are excluded. If the ionic concentration product is less than the solubility product or can arbitrarily be made so, as (for example) by complex salt formation or by the formation of weak electrolytes, then a further quantity of solute can pass into solution until the solubility product is attained, or, if this is not possible, until all the solute has dissolved. 

According to modem views, the basic points of the theory of electrolytic dissociation are correct and were of exceptional importance for the development of solution theory. However, there are a number of defects. The quantitative relations of the theory are applicable only to dilute solutions of weak electrolytes (up to 10 to 10 M). Deviations are observed at higher concentrations the values of a calculated with Eqs. (7.5) and (7.6) do not coincide the dissociation constant calculated with Eq. (7.9) varies with concentration and so on. For strong electrolytes the quantitative relations of the theory are altogether inapplicable, even in extremely dilute solutions. 

Hence, the theory of electrolyte solutions subsequently developed in two directions (1) studies of weak electrolyte solutions in which a dissociation equilibrium exists and where because of the low degree of dissociation the concentration of ions and the electrostatic interaction between the ions are minor and (2) studies of strong electrolyte solutions, in which electrostatic interaction between the ions is observed. 

In aqueous electrolyte solutions the molar conductivities of the electrolyte. A, and of individual ions, Xj, always increase with decreasing solute concentration [cf. Eq. (7.11) for solutions of weak electrolytes, and Eq. (7.14) for solutions of strong electrolytes]. In nonaqueous solutions even this rule fails, and in some cases maxima and minima appear in the plots of A vs. c (Eig. 8.1). This tendency becomes stronger in solvents with low permittivity. This anomalons behavior of the nonaqueous solutions can be explained in terms of the various equilibria for ionic association (ion pairs or triplets) and complex formation. It is for the same reason that concentration changes often cause a drastic change in transport numbers of individual ions, which in some cases even assume values less than zero or more than unity. 

Any one of these expressions for fCa represents what is known as Ostwald s dilution law, which has essentially been obtained by applying the law of mass action to solutions of weak electrolytes. It deals with the variation in the degree of dissociation with concentration or dilution of solutions of weak electrolytes. It is not applicable to solutions of strong electrolytes. The failure of strong electrolytes to obey Ostwald s dilution law is known as the anomaly of strong electrolytes. 

The single arrow directed to the right represents the condition of full ionization as mentioned. On the other hand, acetic acid and ammonia are examples of weak electrolytes, and are weakly ionized. In such cases, the molecules of the electrolyte are in equilibrium with its ions, and ionization of such electrolytes (e.g., ammonia) is represented as... 

It may be added that Kohlrausch s law does not lead to any method of deducing the contributions of the individual ions. The immediate practical application of Kohlrausch s law of independent contributions of the ions at infinite dilution is a method for deducing the limiting equivalent conductance, A0, of weak electrolytes. This will be illustrated by taking a specific example of a weak electrolyte. 

Jackson, M. J. Tai, C.-Y., Morphological correlates of weak electrolyte transport in the small intestine, in Dinno, M. A. (ed.), Structure and Function in Epithelia and Membrane Biophysics, Alan R. Liss, New York, 1981, pp. 83-96. 

Thus, in weak electrolytes, molecules can exist in a similar way as in non-electrolytes—a molecule is considered to be an electrically neutral species consisting of atoms bonded together so strongly that this species can be studied as an independent entity. In contrast to the molecules of non-electrolytes, the molecules of weak electrolytes contain at least one bond with a partly ionic character. Strong electrolytes do not form molecules in this sense. Here the bond between the cation and the anion is primarily ionic in character and the corresponding chemical formula represents only a formal molecule nonetheless, this formula correctly describes the composition of the ionic crystal of the given strong electrolyte. 

The first theory of solutions of weak electrolytes was formulated in 1887 by S. Arrhenius (see Section 1.1.4). If the molar conductivity is introduced into the equations following from Arrhenius concepts of weak electrolytes, Eq. (2.4.17) is obtained, known as the Ostwald dilution law this equation... 

At the end of the last century S. Arrhenius formulated the first quantitative theory describing the behaviour of weak electrolytes. The... 

The species appearing as strong electrolytes in aqueous solutions lose this property in low-permittivity solvents. The ion-pair formation converts them to a sort of weak electrolyte. In solvents of very low-permittivity (dioxan, benzene) even ion triplets and quadruplets are formed. 

Interionic forces are relatively less important for weak electrolytes because the concentrations of ions are relatively rather low as a result of incomplete dissociation. Thus, in agreement with the classical (Arrhenius) theory of weak electrolytes, the concentration dependence of the molar conductivity can be attributed approximately to the dependence of the degree of dissociation a on the concentration. If the degree of dissociation... 

The conductivity also increases in solutions of weak electrolytes. This second Wien effect (or field dissociation effect) is a result of the effect of the electric field on the dissociation equilibria in weak electrolytes. For example, from a kinetic point of view, the equilibrium between a weak acid HA, its anion A" and the oxonium ion H30+ has a dynamic character ... 

VI. TRANSMONOLAYER FLUX KINETICS OF WEAK ELECTROLYTE PERMEANTS... 

Many of the undesirable substances present in gaseous or liquid streams form volatile weak electrolytes in aqueous solution. These compounds include ammonia, hydrogen sulfide, carbon dioxide and sulfur dioxide. The design and analysis of separation processes involving aqueous solutions of these materials require accurate representation of the phase equilibria between the solution and the vapor phase. Relatively few studies of these types of systems have been published concerning solutions of weak electrolytes. This paper will review the methods that have been used for such solutions and, as an example, consider the alkanolamine solutions used for the removal of the acid gases (H2S and C02) from gas streams. 

Solutions of Weak Electrolytes Van Krevelen et al. (2) measured the vapor pressures of aqueous... 

About the same time Beutier and Renon (11) also proposed a similar model for the representation of the equilibria in aqueous solutions of weak electrolytes. The vapor was assumed to be an ideal gas and < >a was set equal to unity. Pitzer s method was used for the estimation of the activity coefficients, but, in contrast to Edwards et al. (j)), two ternary parameters in the activity coefficient expression were employed. These were obtained from data on the two-solute systems It was found that the equilibria in the systems NH3+ H2S+H20, NH3+C02+H20 and NH3+S02+H20 could be represented very well up to high concentrations of the ionic species. However, the model was unreliable at high concentrations of undissociated ammonia. Edwards et al. (1 2) have recently proposed a new expression for the representation of the activity coefficients in the NH3+H20 system, over the complete concentration range from pure water to pure NH3. it appears that this area will assume increasing importance and that one must be able to represent activity coefficients in the region of high concentrations of molecular species as well as in dilute solutions. Cruz and Renon (13) have proposed an expression which combines the equations for electrolytes with the non-random two-liquid (NRTL) model for non-electrolytes in order to represent the complete composition range. In a later publication, Cruz and Renon (J4J, this model was applied to the acetic acid-water system. 

Conclusions The correlation of vapor-liquid equilibria in aqueous solutions of weak electrolytes is important for the separation of undesirable components from gases and liquids. The major problem in such correlations is the estimation of the activity... 

In principle, this system of 20 equations can be solved provided the equilibrium constants, activities, Henry-constants and fugacities are available. While some results for most of these properties are available, there exists no approved method for calculating activities in concentrated aqueous solutions of weak electrolytes therefore, several approximations were developed. ... 

NH3-NHJ, NH3-HCO3 and NH3-HS- were fitted to 68 selected ternary data points (partial pressures of weak electrolytes) measured by Otsuka et al. for NH3-CO2-H2O at 40, 60, 80 and 100 °C ( ) and Ginzburg et al. for NH3-H2S-H2O at temperatures between about 40 and 90 °C ( 1 0). While with the original -numbers the mean deviations... 

The comparison between measured and calculated results for vapor-liquid equilibria in aqueous systems of weak electrolytes confirms the applicability of van Krevelen 1s method for moderate temperatures and concentrations. The comparison also indicates that the procedure of Edwards, Maurer, Newman and Prausnitz yields reliable results also at temperatures around 100 °C therefore, it may be expected that it is also useful at higher temperatures where experimental material, necessary for checking that procedure, is not available... 

Table 1. Thermodynamic Framework of Representation of Vapor-Liquid Equilibria of Weak Electrolytes...

DETERMINATION OF EQUILIBRIUM CONSTANTS FOR DISSOCIATION OF WEAK ELECTROLYTES... 

Conductance measurements also have been used for the estimation of dissociation constants of weak electrolytes. If we use acetic acid as an example, we find that the equivalent conductance A shows a strong dependence on concentration, as illustrated in Figure 20.2. The rapid decline in A with increasing concentration is largely from a decrease in the fraction of dissociated molecules. 

In the approximate treatment of the conductance of weak electrolytes, the decrease in A is treated as resulting only from changes in the degree of dissociation, a. On this basis, it can be shown that an apparent degree of dissociation a can be obtained from... 

Standard Gibbs Function for Formation of Ion of Weak Electrolyte... 

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