Determining the Ksp of Calcium Hydroxide Purpose: To use the method of serial dilution to estimate the solubility product constant for the “marginally” insoluble salt calcium hydroxide. The solubility of salts As we have discussed in class, there is no such thing as a truly insoluble salt. When any salt is placed in water, at least a few ions are going to separate from the ionic compound and go into solution. As the concentration of the ions in solution increases, those ions may “find” each other, initiating the reverse reaction in which some solid reforms. When the rates of these two processes are identical, equilibrium has been reached, and the concentration of ions in solution will not increase. The solubility product constant, Ksp , allows us to quantify how much salt will dissolve before equilibrium is reached. For example, consider the insoluble salt iron(III) hydroxide. If we describe the process of dissolving by the equation: Fe(OH)3 (s) Fe3+ (aq) + 3OH− (aq) Then the equilibrium constant, Ksp , will be: Ksp = [Fe3+ ][OH− ] 3 Knowing either the concentration of one of the ions at equilibrium or the Ksp value would allow you the other quantity of interest. In this experiment, we will obtain an estimate for the Ksp of calcium hydroxide. Calcium hydroxide is one of those “annoying” insoluble salts because, as the solubility rules will tell you, it is marginally soluble, meaning that its Ksp is small, but not incredibly small. Typically Ksp values are determined by titration or gravimetric analysis in which one would created a saturated solution of the salt in question and then react or produce a precipitate of one of the ions. One can then use stoichiometry to back calculate the equilibrium constant. However, in this lab we will try to bracket the Ksp value for calcium hydroxide by direct measurement. Essentially we will create 12 different solutions of calcium cations and hydroxide anions in increasing dilute concentrations, observing if a precipitate is formed when each of these concentrations is mixed. At the point we see no precipitate, we will know that the concentrations of cation and anion are too low (and hence Q is less than K), which will result in an estimate for Ksp . Preparing to Experiment You should find the following materials at your station • A 24 well plate • A 12 well micro plate • Several clean and empty Beral micropipets • Distilled water • Solutions of 0.10 M calcium chloride and 0.10 M sodium hydroxide Procedure The procedure here is very simple. We wish to create 12 different solutions of calcium cation and hydroxide anion, each of different concentration. To do so we will use the method of serial dilution, in which you take a little bit of the solution from a previous well, dilute it with a known amount of water, and then add it to the next well. Doing this over 12 wells will create successive solutions of lessening concentration. Specifically you should do the following. 1. Obtain 6 empty beral micropipets 2. Fill one of the pipets with 0.10 M calcium chloride 3. Fill a second pipet with 0.10 M sodium hydroxide 4. Fill a third pipet with distilled water 5. Carefully place 5 drops of 0.10 M calcium chloride into the first well of the 12 well microplate. Make sure before you actually drop into the plate that you can reproduce your drop size. It is extremely important that you hold the pipet vertically while dropping. Practice your dropping technique in the 24 well plate before actually beginning the experiment. 6. Into the second well, add another 5 drops of calcium chloride solution. To wells twotwelve, add an additional 5 drops of distilled water. 7. Using a clean pipet suck up all the solution from well 2. Thoroughly mix this solution by sucking and expelling the solution into the second well several times. When you are certain the solution is thoroughly mixed, drop 5 drops of the diluted solution into well three. Place the remaining solution back into well two. 8. Continue step 7 for all 12 wells. When you complete well 12, remove 5 drops of solution from the well. 9. Add 5 drops of 0.10 M sodium hydroxide to each well. Stir the well with a stir stick, and wait 3-5 minutes to observe if a precipitate forms in each well. 10. Record in the data table below the concentration of each ion in the well and well as if a precipitate formed in the well after mixing the two solutions. 11. Clean your well plate thoroughly with some soap and distilled water. Then reverse the procedure by first adding 5 drops of 0.10 M sodium hydroxide to well 1 and 5 drops of distilled water to wells 2-12. 12. Like in step 8 above, add an additional 5 drops of 0.10 M NaOH to well two. Thoroughly mix the solution with a clean pipet, place 5 drops into well 3, and return the remaining solution to well 2. 13. Continue the previous step for all 12 wells. Again, remove 5 drops from well 12 after mixing. 14. Add 5 drops of 0.10 M calcium chloride to each well. Stir with a clean stir stick and observe any precipitates after 3-5 minutes. Record the concentration of calcium an hydroxide ions in the table below, as well as note in which wells precipitates form. Well # [Ca2+ ] [OH− ] precipitate? 1 2 3 4 5 6 7 8 9 10 11 12 Table 1: Serial dilutions of 0.10 M calcium nitrate solutions Sample calculation of concentrations of calcium cation and hydroxide anion for well Well # [Ca2+ ] [OH− ] precipitate? 1 2 3 4 5 6 7 8 9 10 11 12 Table 2: Serial dilutions of 0.10 M sodium hydroxide solutions Sample calculation of concentrations of calcium cation and hydroxide anion for well Based on the data in tables one and two, what is the best estimate of a range for the Ksp of calcium hydroxide? Explain. Look up the actual value of the Ksp of calcium hydroxide and compare to your best estimate with a percent error calculation. Questions 1. What is the concentration of hydroxide at equilibrium in a solution that contains a mixture of 0.10 M sodium hydroxide and 0.20 M calcium chloride? Justify your answer with a calculation. 2. Would the molar solubility of calcium hydroxide by higher or lower in a solution of calcium chloride? Explain, using Le Chatelier’s principle. 3. When a precipitate of calcium hydroxide is mixed with a sufficient quantity of hydrochloric acid, the solution is seen to clear. Explain, using Le Chatelier’s principle. Conclusion