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Determination of the Solubility Product Constant of Calcium Hydroxide

J.R.A. Ibale Institute of Chemistry, College of Science University of the Philippines, Quezon City, Philippines Date Performed: January 30, 2013 Instructors Name: Maro R. Pea

ABSTRACT The objective of this experiment is to determine the solubility product constant, Ksp, of Ca(OH)2 through titration of a saturated solution of Ca(OH)2. This experiment also aims to investigate the factors that influence the changes in the Ksp of an partially soluble ionic compound. The precipitate of Ca(OH)2 was produced from 1.0 M Ca(NO3)2 and 1.0 M NaOH. This was then dissolved unitl saturation in different media including deionized water, Ca(NO3)2(aq), and media of varying concentrations of KCl which was all titrated with 0.1 M HCl. The data was then computed to yield concentrations for [OH-] and [Ca2+], where the latter is also the solubility of the compound. Further calculations gave values for the solutions ionic strengths and each sets solubility product constant. When the data of the KCl media were plotted, it showed that the solutions decreased in solubility through increasing ionic strength. Solubility also decreased when Ca(OH)2 was dissolved in Ca(NO3)2(aq). The experiment was a failure in the common-ion effect part (former), but was successful in the diverse-ion effect (latter). This experiment can be improved by accuracy in the saturated solution preparation as well as in titration techniques.

INTRODUCTION Sparingly soluble ionic solids undergo an equilibrium reaction when placed in water. The equilibrium reaction for this basically resembles the following reaction of the hypothetical solid, AxBy, AxBy(s) xAy+(aq) + yBx-(aq) (1)

Where a[Ay+] and a [Bx-] are the activities of the ions, which basically comes from (expressed here for the hypothetical species Ay+), aAy+ = (3)

From this reaction, the equilibrium constant Keq, for any type of reaction, can be directly referred to as the solubility product constant, Ksp, of the ionic solid. Basically, Ksp is the quantification of the relationship of the ionic solid and its constituent ions. It is calculated, similarly as the Keq was. Ksp = (2)

where, aAy+ is the activity of Ay+, is the activity coefficient, is the equilibrium concentration of , and A is the concentration for the reference state of . In this experiment, the equation of the Ksp was simplified into Ksp = [ ][ ] (4)

Since, for ideal cases (such as dilute solutions in this experiment), approaches 1 while A is merely 1 mol L-1.

So that, a x [Ay+] and a y [Bx-] Also, a = 1 for pure solids and liquids.

In this experiment, the solubility product constant, Ksp, of calcium hydroxide, Ca(OH)2, was obtained using titration. The equilibrium reaction of Ca(OH)2 can be expressed as, Ca(OH)2(s) Ca2+ + 2OH(5)

Temperature Diverse-ion effect Common-ion effect Simultaneous equilibria

From this expression, the Ksp of Ca(OH)2 can be represented by, Ksp = [Ca2+][OH-]2 (6)

Where, particularly, [Ca2+] and [OH-] are equilibrium concentrations of Ca2+ and OH-, respectively. In application of the equilibrium concepts, a reaction quotient, Qsp, can also be obtained from the equilibrium reaction of Ca(OH)2, expressed as, Qsp = [Ca2+]init[OH-]2init (7)

The common-ion effect is an application of the Le Chateliers principle. It states that when a common ion is added into the solution of dissociated solids, the tendency would be towards the precipitation of the dissolved solid. This arises from the solutions shifting equilibrium which actively balances the reaction system in order to attain and maintain an equilibrium state. In this case, it is the addition to the product side (dissolved ions/products) that needs to be depleted by formation of the original solid (towards reactants).[1] The diverse-ion on the other hand deals with the interionic interactions of the ions present in the solution.[1] As the ionic concentration or strength of the solution then rises, these interionic contacts becomes stronger until these interaction s are not negligible. Due to the increase attractions, the activities of the participating ions or their effective concentration become lesser causing a considerable increase in solubility. METHODOLOGY In a beaker, 10 mL 1.0 M Ca(OH)2 and 20 mL 1.0 M NaOH was mixed. The precipitate that formed was then allowed to settle. With a Pasteur pipette, the supernate was removed, leaving the precipitate behind which was later washed with 3 portions of 5-mL portions of water. The first two were decanted, while the third was poured through a filter together with the precipitate. The paper with the precipitate was then allowed to dry for about two days. It is notable that this experiment was done in groups in order to maximize time. The precipitate that was formed by each group was then mixed in different media, namely, deionized water, 1.0 M KCl, 0.5 M KCl, 0.1 M KCl, 0.05 M KCl, 0.01 M KCl, 0.005 M KCl, 0.001 M KCl, and 0.10 M Ca(NO3)2, wherein all of the KCl solutions used were

Where, conversely, [Ca2+]init and [OH-]2init are initial concentrations of Ca2+ and OH-, respectively. Through comparison, the reactions ability to produce precipitate (or proceed to the reverse direction, based on the reaction considered in this experiment) or the nature of the solution, i.e. saturated or not, can be predicted. In effect, if Qsp > Ksp then the addition of Ca2+ to OH-, or the other way, will produce the precipitate, Ca(OH)2. While, if Qsp = Ksp the solution is saturated, i.e. the solution has reached the maximum amount of solute it can dissolve. Lastly, if Qsp < Ksp the solution in unsaturated, i.e. more solutes are needed in order to push the reaction into equilibrium (or even completion). This concept of equilibrium has specific factors which affect it greatly. Generally, salts all have a Ksp. But salts of particularly high solubility, the activities of the ions must be considered instead of their concentrations. Of the many factors that could affect, Ksp, some of these are:

formulated through serial dilution starting from 1.0 M. Using 100 mL of each medium placed in a 250-mL beaker, Ca(OH)2 was added gradually, poking the precipitate every time which was done in lieu to stirring. After the solution was saturated, the suspension was left for about 15 minutes in order to reach its equilibrium. About 75 mL of the suspension was then filtered. From the supernate, an aliquot of 25 mL was obtained and was transferred into a 250-mL Erlenmeyer flask together with 3 drops of indicator, particularly 1 % phenolphthalein. This solution was then titrated with 0.1 M HCl, wherein the endpoint was the drop before the solution became colorless. The data that were gathered were used to calculate the Ksp afterwards. RESULTS AND DISCUSSION In this experiment, the solubility of the ionic salt Ca(OH)2 was tested and measured. The equilibrium reaction of Ca(OH)2 is expressed in (5). In the preparation of the solid ionic compound, the all Ca2+ ions were assumed to have completely reacted with the OHions which was physically exhibited in the addition of excess NaOH against Ca(NO3)2. Moreover, Ca(NO3)2 added dropwise in order to make sure that all of the Ca2+ ions added are able to react with the NaOH. Lastly, before it was dried, it was first washed with 95% ethanol. This was done for a few possible and practical reasons first is that it evaporates quickly, another is that if water was used some of the precipitate might dissolve back into the solution, and lastly was to remove the remaining excess OH- that may have remained with the precipitate after filtration. After drying, the precipitate was then added to a medium to make a saturated solution by mixing the prepared ionic solid in the medium and allowing it to settle (also allowing the solution to reach equilibrium). The solution indicated saturation when the

solution does not exhibit any significant dissolution of solutes through further addition of the solid. When the supernate of the suspension was obtained, filtration was necessary in order to exclude parts of the compound which were not dissolved, which is only proper since it is the amount of dissolved solids that should be quantified in order to obtain Ksp. Before the titration of an aliquot of the supernate with 0.1 M HCl, the solution was first added with an indicator. In this experiment, the colorless phenolphthalein, C20H14O4 or HIn, was used as an indicator. Note that the phenolphthalein ion, In-, is pink and phenolphthalein is a weak acid. Therefore, when it was added to the solution which in essence basic, the H+ from the indicator is removed forming more of the pink In- which is the reason why the initial color of the solution was pink. The titrations equivalence point was indicated by the drop immediately before the solution turns colorless. After every titration was done, the data was then calculated following that which is stated in the Appendix. The calculated values of the Ksp of Ca(OH)2 in the different media, [OH-]ANALYTE, [Ca2+]ANALYTE where this value is also the molar solubility value, and the ionic strength of each solution, then was tabulated in the data sheet. The calculated value for Ksp of Ca(OH)2 when it was dissolved in the deionized water was 1.05 x 10-6. When compared to the literature value of the Ksp of Ca(OH)2 [1], 5.5 x 10-6, the experimental value deviated by 80.93 %. Furthermore, by using Equation 12 as shown in the Appendix, the theoretical value for the solubility was also taken, which is about 0.011 M. When the data for the KCl media solutions are plotted, the following graph was obtained (Figure 1).

Molar Solubility (s), M

1.50E-02 1.00E-02 5.00E-03 0.00E+00 0 0.2 0.4 0.6


Ionic Strength of Solution (), M

CONCLUSIONS AND RECOMMENDATIONS The experiment conducted for the determination of the solubility product constant, Ksp, of Ca(OH)2 (with a balanced equation stated in (5)) through titration failed to comply with the theories in the relative magnitudes of the solubility constant as the ionic compound is dissolved to different types of media. From it, a Ksp for Ca(OH)2 in deionized water was obtained with a value of 1.05 x 10-6 which deviates from the literature value by 80.93%. In the use of the media with varying concentrations of KCl, the solubility of the ionic compound was observed to have been decreasing despite the increase of ionic strength of the solution. This part was considered a failure as it did not comply completely or closely with the theoretical results. In the use of a medium containing a common ion, Ca(NO3)2, as that of the dissolved Ca(OH)2, specifically Ca2+, the solution did show a decrease in solubility just as the theoretical result determined. This part followed the diverse-ion effect. This experiment can be improved by reducing the systematic errors that could have arised other than those that were discussed in the results and discussion, i.e. the separate preparation of the precipitate of the Ca(OH)2. The error of having prepared and use of a possibly unsaturated solution must also be avoided. The indicator to be used can also be changed to bromthymol blue instead, because phenolphthalein has a pH range that is slightly greater than 7 (about 810).[1] Furthermore, titration techniques must always be observed, such as using half drops when nearing the end point, as well as the practice of patience and care.

Figure 1. Molar Solubility vs. Ionic Strength Based on the graph, it is observed that the solubility of Ca(OH)2 decreased through increasing ionic strength of the solution. This result is rather unprecedented since it is well known that solubility increases through increasing ionic strength of the solution, as explained by the diverse-ion effect[1]. The experiment shows the converse of the diverse-ion effect. Although the experiment yielded a contrary result to the diverse-ion effect, the experiment followed the common-ion effect for the relative solubility of Ca(OH)2 in water compared to a solution with Ca2+. When the Ca(OH)2 was dissolved in water, it had a solubility of 6.4 x 10-3 M, while it was 3.75 x 10-3 M for when it was dissolved in the Ca(NO3)2 solution/medium. This is an application of the Le Chateliers principle on the equilibrium of the solvolysis of Ca(OH)2 shown in Equation 1. Particularly, since the reaction had additional reagents in the product side, the reaction shifted and favored the formation of more of the reactants, effectively decreasing the solubility of the ionic compound. The errors that caused the results could have come mainly from the preparation of the suspension, i.e. the suspension was not saturated enough before an analyte was made out of it. Another cause could have been through over titration. The former would result to concentration values less than that of the equilibrium value and a lower Ksp would be obtained. The latter would yield an erroneous data later in the calculation of the [OH-] and would therefore cause a gross error from the start of the calculations and so on.

REFERENCE Petrucci, P.H., Herring, F.G., Madura, J.D. and Bissonnette C.: General Chemistry, Principles and Modern Application, 10th Ed. Prentice Hall, New Jersey, 2010
[1]

APPENDIX WORKING CALCULATIONS Note: The following equations and sample calculation exhibit the calculations and equations used to solve for the data found in the data table. In the experiment, [OH-] and [Ca2+] are to be solved from the titration data. Here, is the amount of titrant (0.1 M HCl) added to the analyte solution containing the Ca(OH)2 solution. [OH-] = [Ca2+] = (8) (9) Ionic Strength = = Where, ci = [i]; concentration of ion zi = charge of i (10)

Table 1. Solvolysis of Ca(OH)2 Ca(OH)2 Ca2+ + 2OHInitial -Change -+x +2x Equilibrium -+x +2x Molar Solubility of Ca(OH)2 = s = x Keq = Ksp = [Ca2+][OH-]2 = (x)(2x)2 = 4x3 = 4s3 SAMPLE CALCULATION (for deionized water) (1st Trial) [OH-] =
,

(11) (12)

= 0.0136 M

[Ca2+] = = = 6.8 x 10-3 M s = [Ca2+] = 6.8 x 10-3 M (2nd Trial) [OH-] =


,

= 0.012 M

[Ca2+] = = = 6.0 x 10-3 M s = [Ca2+] = 6.0 x 10-3 M Average Solubility = = 6.4 x 10-3 M

Ksp = 4s3 = 4(6.4 x 10-3)3 = 1.048576 x 10-6 1.05 x 10-6 = = = 0.0192 M | x 100 % = | =

%error = |

= 80.93 %

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