Solubility product, determination

The ion product of water depends on the ionic strength of the system and on its temperature. At 25 °C and in low ionic strength solution, log = -13.99, whereas in 3 M NaC104 (the ionic medium used by Schindler et al., 1963 for solubility product determination), log = -14.22 + 0.1 the value chosen must correspond to the ionic strength of the system involved. 

The design of the experiment is not well suited for an equilibrium analysis, but definitely showed that Ag2Se03(cr) is dissolved by an excess of SeOj. No equilibrium constants were derived in the paper from these data. The review calculated ((A.22), 298.15 K) from the data at the lowest total selenite concentration and pH < 6. The protonation constants from the first series were used in the calculation. The result was log Ai, ((A.22), 298.15 K) = - (15.20 + 0.15). Hence there is a significant difference between the values of the solubility product determined by the two techniques, which cannot be accounted for and apparently not observed by the authors. 

Green, D. B. Rechtsteiner, G. Honodel, A. Determination of the Thermodynamic Solubility Product, Xsp, of Pbl2 Assuming Nonideal Behavior, /. Chem. Educ. 1996, 73, 789-792. 

The thermodynamic solubility product for Pbl2 is determined in this experiment by measuring its solubility at several ionic strengths. 

Before the equivalence point, the concentration of Cr04 is controlled by the solubility product of PbCr04. After the equivalence point, the concentration of Cr04 is determined by the amount of excess titrant added. Considering the reactions controlling the concentration of Cr04 , sketch the expected titration curve of pH versus volume of titrant. 

Potentiometric electrodes are divided into two classes metallic electrodes and membrane electrodes. The smaller of these classes are the metallic electrodes. Electrodes of the first kind respond to the concentration of their cation in solution thus the potential of an Ag wire is determined by the concentration of Ag+ in solution. When another species is present in solution and in equilibrium with the metal ion, then the electrode s potential will respond to the concentration of that ion. Eor example, an Ag wire in contact with a solution of Ck will respond to the concentration of Ck since the relative concentrations of Ag+ and Ck are fixed by the solubility product for AgCl. Such electrodes are called electrodes of the second kind. 

Solubilization. The solubiUty product of a slightly soluble salt determines the concentration of metal ion that can be present in solution with the anion of that salt. For the salt MX the solubiUty product is... 

Note that the brackets, [ ], refer to the concentration of the species. K,p is the solubility product constant hence [Cu " ] and [OH] are equal to the molar concentrations of copper and hydroxyl ions, respectively. The K p is commonly used in determining suitable precipitation reactions for removal of ionic species from solution. In the same example, the pH for removal of copper to any specified concentration can be determined by substituting the molar concentration into the following equation ... 

In many instances the degree of solubility of the acidic reaction products determines whether autocatalysis occurs. Thus, the reaction of 5-chloroacridine with piperidine is autocatalytic in ethanol but not in toluene where most of the piperidine hydrochloride formed precipitates. ... 

The general approach illustrated by Example 18.7 is widely used to determine equilibrium constants for solution reactions. The pH meter in particular can be used to determine acid or base equilibrium constants by measuring the pH of solutions containing known concentrations of weak acids or bases. Specific ion electrodes are readily adapted to the determination of solubility product constants. For example, a chloride ion electrode can be used to find [Cl-] in equilibrium with AgCl(s) and a known [Ag+]. From that information, Ksp of AgCl can be calculated. 

The solubility of copper(II) iodide, Cul2, is 0.004 g/liter. Determine the value of the solubility product. 

Other useful solid-state electrodes are based on silver compounds (particularly silver sulfide). Silver sulfide is an ionic conductor, in which silver ions are the mobile ions. Mixed pellets containing Ag2S-AgX (where X = Cl, Br, I, SCN) have been successfiilly used for the determination of one of these particular anions. The behavior of these electrodes is determined primarily by the solubility products involved. The relative solubility products of various ions with Ag+ thus dictate the selectivity (i.e., kt] = KSp(Agf)/KSP(Aw)). Consequently, the iodide electrode (membrane of Ag2S/AgI) displays high selectivity over Br- and Cl-. In contrast, die chloride electrode suffers from severe interference from Br- and I-. Similarly, mixtures of silver sulfide with CdS, CuS, or PbS provide membranes that are responsive to Cd2+, Cu2+, or Pb2+, respectively. A limitation of these mixed-salt electrodes is tiiat the solubility of die second salt must be much larger than that of silver sulfide. A silver sulfide membrane by itself responds to either S2- or Ag+ ions, down to die 10-8M level. 

STRATEGY First, we write the chemical equation for the equilibrium and the expression for the solubility product. To evaluate Ksp, we need to know the molarity of each type of ion formed by the salt. We determine the molarities from the molar solubility, the chemical equation for the equilibrium, and the stoichiometric relations between the species. We assume complete dissociation. 

The value of Kip is the same as that listed in Table 11.4. Many of the solubility products listed in tables were determined from emf measurements and calculations like this one. 

The compound Cr(OH), is very insoluble in water therefore, electrochemical methods must be used to determine its fCsp. Given that the reduction of Cr(OH)3(s) to Cr(s) and hydroxide ions has a standard potential of —1.34 V, calculate the solubility product for Cr(OH)3. 

Gypsum is a relatively soft rock made of calcium sulfate. Rainwater percolates through g q)sum, dissolves some of the rock, and eventually becomes saturated with Ca ions and SOq ions. A geochemist takes a sample of groundwater from a cave and finds that it contains 8.4 X 10 M SO4 and 5.8 X 10 M Ca. (The ratio is not 1 1 because other sulfate rock contributes some of the SOq ions to the solution.) Use these data to determine the solubility product of calcium sulfate. 

Example deals with the second type of calculation, determining a concentration at equilibrium when the value of the solubility product is known. 

In the presence of a metal ion (M " ), a metal chalcogenide phase M2Sen will be precipitated upon exceeding the solubility product of [M and [Se ] (or [HSe ]). The concentration of free metal ions must be controlled by an excess of complexing agent, determining the applicable solubility of the metal and the overall competitive chemical reaction, in order to prevent the formation of sulfite, sulfate, and... 

Metal hydroxides (e.g., Fe, Mn, Al) can also be a problem (Rauten-bach and Albrecht, Membrane Processes, Wiley, New York, 1989). A chemical analysis of the feed solution composition along with consideration of solubility products allows one to determine the significance of precipitation. Solubility products can be affected by temperature, pH, and ionic strength. Seasonal temperature variations must be considered. Concentrations of silica need to be < 120 mg/L in the feed. 

Having introduced matters pertaining to the electrochemical series earlier, it is only relevant that an appraisal is given on some of its applications. The coverage hereunder describes different examples which include aspects of spontaneity of a galvanic cell reaction, feasibility of different species for reaction, criterion of choice of electrodes to form galvanic cells, sacrificial protection, cementation, concentration and tempera lure effects on emf of electrochemical cells, clues on chemical reaction, caution notes on the use of electrochemical series, and finally determination of equilibrium constants and solubility products. 

Figure 6.8 shows the Bjerrum plots for an weak acid (benzoic acid, pKa 3.98, log So — 1.55, log mol/L [474]), a weak base (benzydamine, pKa 9.26, log So —3.83, log mol/L [472]), and an ampholyte (acyclovir, pKa 2.34 and 9.23, log So — 2.16, log mol/L I/40N ). These plots reveal the pKa and pA pp values as the pcH values at half-integral % positions. By simple inspection of the dashed curves in Fig. 6.8, the pKa values of the benzoic acid, benzydamine, and acyclovir are 4.0, 9.3, and (2.3, 9.2), respectively. The pA pp values depend on the concentrations used, as is evident in Fig. 6.8. It would not have been possible to deduce the constants by simple inspection of the titration curves (pH vs. volume of titrant, as in Fig. 6.7). The difference between pKa and pA pp can be used to determine log So, the intrinsic solubility, or log Ksp, the solubility product of the salt, as will be shown below.

The solubility product is measured by determining the ion concentrations by a suitable analytical method and the results are extrapolated to zero ionic strength, where P — P. 

Equations (2.4.27) and (2.4.28) are employed for conductometric determination of dissociation constants and solubility products. 

Potentiometry is used in the determination of various physicochemical quantities and for quantitative analysis based on measurements of the EMF of galvanic cells. By means of the potentiometric method it is possible to determine activity coefficients, pH values, dissociation constants and solubility products, the standard affinities of chemical reactions, in simple cases transport numbers, etc. In analytical chemistry, potentiometry is used for titrations or for direct determination of ion activities. 

The crude product contains isomers other than that required and also nitrated phenolic compounds resulting from side reactions. The usual method of purification is to treat the crude product with sodium sulphite, which converts asymmetric trinitro compounds to sulphonic acid derivatives, and to wash out the resulting soluble products with alkaline water. The purity of the product is determined by the melting point, the minimum value for Grade I TNT commonly being 80-2°C. Unless adequate purity is achieved, slow exudation of impurities can occur during storage and the TNT then becomes insensitive. 

It follows from Equation 8.13 that aA/B can be expressed as the product of the diffusivity selectivity, DA/DB, and the solubility selectivity, SA/SB. Diffusion (or mobility) selectivity is governed primarily by the size difference between gas molecules and always favors smaller gas molecules. Solubility selectivity is controlled by the relative condensability of the gases in the polymer and their relative affinity for the polymer. Solubility selectivity typically favors larger, more condensable molecules. From Equation 8.13, it is seen that the product of gas mobility and solubility selectivity determines the overall membrane selectivity. It is clear that for a membrane to be C02 selective, it must have high diffusivity selectivity based on the affinity for C02 but it should be flexible enough to permeate larger molecules such... 

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