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Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
Practice Exercise Calculate the pH of a buffer composed of 0.12 M benzoic acid and 0.20 M sodium benzoate. (Refer to Appendix D.) Answer: 4.42
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
Using the quantities of CH3COOH and CH3COO remaining in the buffer, we can determine the pH using the HendersonHasselbalch equation.
Comment Notice that we could have used mole amounts in place of concentrations in the Henderson Hasselbalch equation and gotten the same result. The volumes of the acid and base are equal and cancel. If 0.020 mol of H+ was added to the buffer, we would proceed in a similar way to calculate the resulting pH of the buffer. In this case the pH decreases by 0.06 units, giving pH = 4.68, as shown in the figure in the margin. (b) To determine the pH of a solution made by adding 0.020 mol of NaOH to 1.00 L of pure water, we can first determine pOH using Equation 16.18 and subtracting from 14.
Note that although the small amount of NaOH changes the pH of water significantly, the pH of the buffer changes very little. Practice Exercise Determine (a) the pH of the original buffer described in Sample Exercise 17.5 after the addition of 0.020 mol HCl and (b) the pH of the solution that would result from the addition of 0.020 mol HCl to 1.00 L of pure water Answers: (a) 4.68, (b) 1.70
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
In this case the total volume of the solution is Hence, the concentration of OH(aq) in the solution is Thus, the pOH of the solution equals and the pH equals Practice Exercise Calculate the pH when the following quantities of 0.100 M HNO3 have been added to 25.0 mL of 0.100 M KOH solution: (a) 24.9 mL, (b) 25.1 mL. Answers: (a) 10.30, (b) 3.70
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
The total volume of the solution is The resulting molarities of CH3COOH And CH3COO after the reaction are therefore
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
Comment: We could have solved for pH equally well using the HendersonHasselbalch equation. Practice Exercise (a) Calculate the pH in the solution formed by adding 10.0 mL of 0.050 M NaOH to 40.0 mL of 0.0250 M benzoic acid (C6H5COOH, Ka = 6.3 10-5) . (b) Calculate the pH in the solution formed by adding 10.0 mL of 0.100 M HCl to 20.0 mL of 0.100 M NH3. Answers: (a) 4.20, (b) 9.26
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
The Kb for CH3COO can be calculated from the Ka value of its conjugate acid, Kb = Kw/Ka = (1.0 10-14)/(1.8 10-5) = 5.6 10-10. Using the Kb expression, we have
Making the approximation that 0.0500 x which gives pOH = 5.28 pH = 8.72
Check: The pH is above 7, as expected for the salt of a weak acid and strong base. Practice Exercise Calculate the pH at the equivalence point when (a) 40.0 mL of 0.025 M benzoic acid (C6H5COOH, Ka = 6.3 10-5 ) is titrated with 0.050 M NaOH; (b) 40.0 mL of 0.100 M NH3 is titrated with 0.100 M HCl. Answers: (a) 8.21, (b) 5.28
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
Solve: Following the italicized rule stated previously, the expression for is
In Appendix D we see that this Ksp has a value of 3.9 10-11. Practice Exercise Give the solubility-product-constant expressions and the values of the solubility-product constants (from Appendix D) for the following compounds: (a) barium carbonate, (b) silver sulfate.
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
To calculate Ksp, we need the equilibrium concentrations of Ag+ and CrO42. We know that at equilibrium [Ag+] = 1.3 10-4 M. All the Ag+ and CrO42 ions in the solution come from the Ag2CrO4 that dissolves. Thus, we can use [Ag+] to calculate [CrO42]. Solve: From the chemical formula of silver chromate, we know that there must be 2 Ag+ ions in solution for each CrO42 ion in solution. Consequently, the concentration Of CrO42 is half the concentration of Ag+:
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
The Ksp for CaF2 is 3.9 10-11 at 25 C. Assuming that CaF2 dissociates completely upon dissolving and that there are no other important equilibria affecting its solubility, calculate the solubility of CaF2 in grams per liter. Solution
Analyze: We are given Ksp for CaF2 and are asked to determine solubility. Recall that the solubility of a substance is the quantity that can dissolve in solvent, whereas the solubility-product constant, Ksp, is an equilibrium constant. Plan: We can approach this problem by using our standard techniques for solving equilibrium problems. We write the chemical equation for the dissolution process and set up a table of the initial and equilibrium concentrations. We then use the equilibrium constant expression. In this case we know Ksp, and so we solve for the concentrations of the ions in solution. Solve: Assume initially that none of the salt has dissolved, and then allow x moles/liter of CaF2 to dissociate completely when equilibrium is achieved. The stoichiometry of the equilibrium dictates that 2x moles/liter of F are produced for each x moles/liter of CaF2 that dissolve. We now use the expression for Ksp and substitute the equilibrium concentrations to solve for the value of x:
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
Assuming that 2x is small compared to 0.010 M (that is, 0.010 + 2x 0.010), we have Thus, 3.9 10-7 mol of solid CaF2 should dissolve per liter of 0.010 M NaF solution.
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
The reaction between CO32 and H+ occurs in a stepwise fashion, first forming HCO3. H2CO3 forms in appreciable amounts only when the concentration of H+ is sufficiently high.
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
Solve: If [Ag+] is 0.010 M initially, then [Ag(NH3)2+ will be 0.010 M following addition of the NH3. We now construct a table to solve this equilibrium problem. Note that the NH3 concentration given in the problem is an equilibrium concentration rather than an initial concentration.
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
Solving for x, we obtain x = 1.5 10-8 M = [Ag+] . Thus, formation of the Ag(NH3)2+ complex drastically reduces the concentration of free Ag+ ion in solution. Practice Exercise Calculate [Cr3+] in equilibrium with Cr(OH)4- when 0.010 mol of Cr(NO3)3 is dissolved in a liter of solution buffered at pH 10.0. Answer: 1 10-16 M
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
Any Cl in excess of this very small concentration will cause AgCl to precipitate from solution. Proceeding similarly for PbCl2, we have
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
The number of moles of NH3 in the solution is given by the product of the volume of the solution and its concentration.
The acid HCl and base NH3 react, transferring a proton from HCl to NH3, producing NH4+ and Cl ions.
To determine the pH of the solution, we first calculate the amount of each reactant and each product present at the completion of the reaction.
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
We can calculate the pH using either Kb for NH3 or Ka for NH4+. Using the Kb expression, we have
Hence, pOH = log(9.4 10-6) = 5.03 and pH = 14.00 pOH = 14.00 5.03 = 8.97.
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.