Conditional solubility product

To avoid peeling of oleoresinous top coats from zinc-rich primers, a sufficient interval should be allowed between coats to permit the zinc-rich primer to weather first in sheltered conditions soluble products should be removed before recoating. 

If S0 = [M]m[L] is the stoichiometric solubility product for the species MmL at a given ionic strength, precipitation will not take place unless this ion product is exceeded. However if M or L undergoes side reactions, the analytical concentrations of the free ions left in solution will be reduced such that [M ] < [M] and [L ] < [L] and the effective or conditional solubility product, S o, is now given by... 

Figure 7.4 shows the conditional solubility product of magnesium silicafe as a function of pH (at an initial ion concentration of 1 mM). The region above the curve represents a system of higher concentration... 

The quantity Asp/aM i" may be regarded as a conditional solubility product, which is a function of the pH and of the reagent concentration. Equation (22-15) is also useful when one wishes to take into account the effect of hydrolysis or of masking agents that may be present. It is necessary only to make the appropriate calculation of the fraction from the hydrolysis constants [Equation (7-17)] or from the formation constants of the secondary complexes [Equation (11-16)]. 

The corresponding data in [82WAG/EVA] seem to originate from the conditional solubility product published in [56CHU]. 

The mean activity coefficients of the sulphates of Cd, Cu, Mg, Mn, Ni, and Zn are quite similar [50HAR/OWE]. The variation at a concentration of 0.5 m is less than 10%. Ojkova and Staneva [890JK/STA] made isopiestic measurement on aqueous solutions of the selenates of Co, Cu, Mg, Ni, and Zn. The mean activity coefficients obtained from these measurements also show a moderate variation between the salts. The value of for MgSe04, = 0.12, will be used to extrapolate the conditional solubility product to / = 0. The selected result is ... 

Tsp is called solubility product of the mineral and depends upon the ionic strength and on the temperature. If other reactions such as hydrolysis of cations M"" " and proton-addition of anions take place simultaneously, the solubility of minerals will be affected accordingly. A conditional solubility product can then be applied ... 

Assume Ksp is the conditional solubility product. FromEqs. (4.56) and (4.58), standard free energy for the above reaction can be calculated as ... 

The conditional solubility product where K sp is the conditional solubility product, similar to the conditional forma-value holds for only a specified pH. tion constant described in Chapter 9. 

EFFECT OF COMPLEXATION OF SOLUBILITY CONDITIONAL SOLUBILITY PRODUCT... 

Solving the quadratic equation gives [Ca " ] = 1.9 X lO"" M. This is the same as The answer is the same as when that calculated in Example 11.1, using the conditional solubility product approach, using (Example 11.1). after correcting for the consumed. In the present example, we corrected for the... 

As the name implies, a conditional solubility product is one whose value depends on solution conditions other than the presence of a common ion. Conditional solubility products are useful when determining the solubility of precipitates whose ions interact with solution constituents through reactions such as complexation or hydrolysis. This type of behavior is indeed the rule rather than the exception for the systems encountered in natural waters and treatment processes. Also, in many analytical measurements the total concentration of species is determined rather than the free ion concentration. 

Pj = conditional solubility product Ct,m = total concentration of the metal ion M in all of its complex forms and... 

The conditional solubility product of magnesium ammonium phosphate, struvite (MgNH4P04[s)) illustrates a situation where more than one of the dissolving species is affected by solution pH. These species are the ammonium ion NH4+) and the phosphate ion (P04 ). Because an increase in pH will decrease the ammonium ion concentration and increase the phosphate ion concentration, it follows that there should be a pH value where the solubility of MgNH4p04(s) is a minimum, that is, the pH where the product [Mg +][NH4 ][P04 ] is a minimum. Where is this point ... 

Fig. 6-19. Conditional solubility product, Ps = Ct.m3 Ct.nh, Ct.po, for magnesium ammonium phosphate at 25 C.

With the concentrations indicated in Table 6-6 we can compute the product Cr.Mg X Ct.nhj X Ct.po and if this significantly exceeds the conditional solubility product, Pj, then struvite should precipitate. 

Calculate the conditional solubility product for CaCOsts). Ps CT.caXCr.cOg), where Cy.ca andCr.coj represent the total concentrations of these species in a solution with (a = 10 , pH = 8.7, the temperature = 25 C. Include ionic strength effects. Assume that the only soluble calcium species is Ca +. 

It will be assumed that the conditional solubility product... 

Although the standard potentials are the fundamental values for all thermodynamic calculations, in practice, one has more frequently to deal with the so-called formal potentials. The formal potentials are conditional constants, very similar to the conditional stability constants of complexes and conditional solubility products of sparingly soluble salts (see [2c]). The term conditional indicates that these constants relate to specific conditions, which deviate from the usual standard conditions. Formal potentials deviate from standard potentials for two reasons, i.e., because of nonunity activity coefficients and because of chemical side reactions . The latter should better be termed side equilibria however, this term is not in common use. Let us consider the redox system iron(II/ni) in water ... 

The pH value influences the solubility of precipitates of hydroxides of metals, for which the coefficient a is >1. Using the concept of side reaction coefficients the conditional solubility products, fC o, can be calculated ... 

It is even possible to define a conditional solubility product by the expression... 

The notion of conditional solubility product is already an extension of the concept of conditional constants. Among other possible extensions, let s also mention the case for which in the studied complex, the metal and the hgand are combined in different ratios. For example, let s consider the case in which successive complexes ML and ML2 are forming. We ll consider that the complex under study is ML that is, it is considered the principal complex. After having adopted the same logic as that which prevailed in the adoption of conditional constants, we can write... 

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