Additional Aspects of Acid-Base Equilibria NaOH{aq) is slovly added to an aqueous solution containing HCllaq) and the indicator phenolphthalein. The indicator color changes from colorless to red as the pH changes from 8,0 10 10.0. The equivalence point of the neutralization is reached When the solution turns a lasting pink (the pink seen here disappears when the flask is swiried to mix the reactants), The selection ofindicators for acid-base tivations is one of the topics considered in this chapter n our study of acid rain (see Focus On 16-1 on the MasteringChemistry website), we learned that a very small amount of atmospheric COx(g) dissolves in rainwater. Yet this amount is sufficient to lower the pH of rainwater by nearly 2 units. And when acid-forming air pollutants, such as SO2, S03, and NOz, also dissolve in rainwater, it becomes even more acidic. A chemist would say that water has no “buffer capacity”—that is, its pH changes sharply when even small quantities of acids or bases are dissolved in it One of the main topics of this chapter is buffer solutions—solutions that can resist a change in pH when acids or bases are added to them. We will consider how such solutions are prepared, how they maintain a nearly constant pH, and how they are used. At the end of the chapter, we will consider perhaps the most important buffer system to humans: the buffer system that maintains the constant pH of blood. CONTENTS Common-lon Effect in Acid-Base Equilibria Buffer Solutions ‘Acid-Base Indicators Neutralization Reactions and Titration Curves Solutions of Salts of Polyprotic Acids ‘Acid-Base Equilibrium Calculatios ASummary 745746 Chapter 17 Additional Aspects of Acid-Base Equilibria AFIGURE 17-1 ‘A.weak acid-strong acid mixture ‘The solution pictured is 0.100 M CHsCOOH and (0.100. M HCL. The reading on the pH meter (1.0) indicates that essentially ll the Hj0™ comes From the strong acid HCI, The red color of the solution is that of thymol blue indicator. Compare this photo with Figure 16-7, in which the separate acids ave shown, > The common-ion effect is not restricted to weak acids and weak bases, Buffers are the most important examples of the common-ion effect in weak acids and weak bases. A second topic that we will explore is acid-base titrations. Here, our aim will be to calculate how pH changes during a titration. We can use this infor- mation to select an appropriate indicator for a titration and to determine, in general, which acid-base titrations work well and which do not. For the most part, we will find the calculations in this chapter to be extensions of those in Chapter 16. 17-1 Common-lon Effect in Acid-Base Equilibria The questions answered in Chapter 16 were mostly of the type, “What is the pH of 0.10 M HC3H;03, of 0.10 M NE, of 0.10 M HPO, of 0.10 M NH,CI?” In each of these cases, we think of dissolving a single substance in aqueous solution and determining the concentrations of the species present at equilib- rium. In most situations in this chapter, a solution of a weak acid or weak base initially contains 2 second source of one of the ions produced in the ion- ization of the acid or base. The added ions are said to be common to the weak acid or weak base. The presence of a common ion can have some important consequences. Solutions of Weak Acids and Strong Acids Consider a solution that is at the same time 0.100 M CHyCOOH and 0.100 M HCL. We can write separate equations for the ionizations of the acids, one weak and the other strong, and indicate the expected concentrations of molecules and ions in the solution. CH;COOH HO == HO’ + CHCOO K,~18x10% (0100 ~ 2) M xM =M HCl + HO —> HOt + a 100M 100m Of course, there can be only a single concentration of HO” in the solution, and this must be [H3O*] = (0.100 + x) M, Because HO" is formed in both ionization processes, we say that itis a common ion, The weak acid-strong acid mixture described here is pictured in Figure 17-1. Although it might seem that the pH would be lower than 1.0, the figure indicates that this is not the case. Concentrations of the species present in this mixture of a weak acid and a strong acid are calculated in Example 17-1, followed by comments on the significance of the result EXAMPLE 17-1 Demonstrating the Common-lon Effect: A Solution of a Weak Acid and a Strong Acid (2) Determine [30°] and [CHsCOO"] in 0.100 M CHyCOOH. (b) Then determine these same quantities ina solution that is 0.100 M in both CHsCOOH and HCL Analyze In part (a) we must determine the species in a weak acid solution, and in part (b) we investigate the effects of the addition of a strong acid. The two acids have the common ion 150° Solve (@) This calculation was done in Example 16-6 (page 712). We found that in 0.100 M CH,COOH, [Hj0*] = [CHsCOO7 = 1.3 x10°M.17-1 Common-lon Effect in Acid-Base Equilibria 747 (b) Instead of writing two separate ionization equations, as we did just prior to this example, e's write only the ionization equation for CH;COOH and enter information about the common ion, H30", in the following format. CHCOOH + H,O == HOt + CH;COO™ initial conens: weak acid: 100M S - strong acid - 100M = changes: -xM 42M 42M equil conens: (0.100 ~ 2) M (0.100 + x) M xM {As is customary, we begin with the assumption that x is very small compared with 0.100. Thus, 0.100 ~ x ~ 0.100 + x ~ 0.100. _ [HsO'[CH COO] _ (0100 + 2)-x _ 9400-x oe EAST CCCI ULE ace 3 = TCH ;COORT oi00 2 aay 8 X10 x =[CH,COO ] = 18x 105M 0100 +x =[H;0'] = 0.100M Notice that xis only 0.018% of 0:100, and so the assumption that xis small compared with 0.100 is valid Assess In this example the acetate ion concentration goes down after the addition of hydronium ion. In other words, ionization of acetic aid is suppressed by the addition of strong acid. The common-ion effect is not restricted to ‘weak acids and weak bases. Buffers are the most important examples of the common-ion effect in weak acids ‘and weak bases. This shift in equilibrium concentration because of the addition of a common ion is another ilustration of Le Chatelier’s principle PRACTICE EXAMPLE A: Determine [H;0*] and [HF] in 0.500 M HE. Then determine these concentrations in a solution tha i 0.100 M HC! and 0.500 M HE PRACTICE EXAMPLE B: How many drops of 12 M HCI would you add to 1.00 L of 0.100 M CH;COOH to make [CHyCOO™] = 1.0 x 10™ MP Assume that 1 drop = 0.050 mil. and that the volume of solution remains 1.00 L alter the 12 M HCIis diluted, [Hint: What must be the [10°] inthe solution?) Now we see the consequence of adding a strong acid (HCI) to a weak acid (CH;COOH): The concentration of the anion [ CH;COO~ is greatly reduced. Between parts (a) and (b) of Example 17-1, [CH3COO ] is lowered from 10? M to L8 X 10? M—almost a 100-fold decrease. Another way to state this result is through Le Chatelier’s principle (see Chapter 15, page 673). Increasing the concentration of one of the products of a reaction—the common ion—shifts, the equilibrium condition in the reverse direction. The common-ion effect is, the suppression of the ionization of a weak electrolyte caused by adding more of anion that isa product of this ionization. The common-ion effect of H30" on the ionization of acetic acid is suggested as follows. ‘When a strong asi supplies the common ion 1,0", the equlbrim sits to form more CH,COOH, |_ = CH,COOH + 1,0 HO" + CH,COO” K,= 1.8% 10 Equilibrium more CHy¢ =