Buffer Solutions Buffers contain either a weak acid and its conjugate base or a weak base and its

conjugate acid. Thus, a buffer solution contains both an acid species and a base species in equilibrium. In other words, a buffer solution is a solution of (1) a weak acid or a weak base and (2) its salt; both components must be present. The solution has the ability to resist changes in pH upon the addition of small amounts of either acid or base. Buffers are very important to chemical and biological systems. The pH in the human body varies greatly from one l uid to another; for example, the pH of blood is about 7.4, whereas the gastric juice in our stomachs has a pH of about 1.5. These pH values, which are crucial for the proper functioning of enzymes and the balance of osmotic pressure, are maintained by buffers in most cases. A buffer solution must contain a relatively large concentration of acid to react with any OH2 ions that may be added to it and must contain a similar concentration of base to react with any added H1 ions. Furthermore, the acid and the base components of the buffer must not consume each other in a neutralization reaction. These requirements are satisi ed by an acid-base conjugate pair (a weak acid and its conjugate base or a weak base and its conjugate acid). To understand the action of a buffer, consider one that con-tains approximately equal molar amounts of a weak acid HA and its conjugate base A. When a strong acid is added to the buffer, it supplies hydronium ions that react with the base A.

On the other hand, when a strong base is added to the buffer, it supplies hydroxide ions. These react with the acid HA.

A buffer solution resists changes in pH through its ability to combine with both H3O and OH ions. Figure 16.9 depicts this buffer action.

FIGURE 16.9 Buffer action A buffer is a solution of about equal molar amounts of a weak acid, HA, and its conjugate base, A , in equilibrium (center beaker). When an acid, such as HCI, is added to the buffer, H3Ofrom this acid reacts with A in the buffer to produce HA (left beaker). However, when a base, such as NaOH, is added to the buffer, OH from this base reacts with HA in the buffer to produce A (right beaker). The buffer pH changes only slightly in both cases.

Blood, as a buffer solution, contains H2CO3 and HCO3 , as well as other conju-gate acidbase pairs. A buffer frequently used in the laboratory contains varying pro-portions of the conjugate acidbase pair H2PO4 and HPO42 (Figure 16.10). Buffers also have commercial applications. For example, the label on a pack-age of articial fruit juice mix says that it contains citric acid to provide tartness (acidity) and sodium citrate to regulate tartness. A solution of

citric acid and its conjugate base, citrate ion (provided by sodium citrate), functions as an acidbase buffer, which is what to regulate tartness means. The pH of the buffer is in the acid range. Two important characteristics of a buffer are its pH and its buffer capacity, which is the amount of acid or base the buffer can react with before giving a sig-nicant pH change. Buffer capacity depends on the amount of acid and conjugate base in the solution. Figure 16.11 illustrates the change in pH of a buffer solution containing 1.0 mol of acetic acid and 1.0 mol of acetate ion to which varying amounts of H3Oand OH are added. This buffer changes less than 0.5 pH unit as long as no more than 0.5 mol H3O or OH ion is added. Note that this is one-half (or less than one-half) the amounts of acid and conjugate base in the solution. The ratio of amount of acid to amount of conjugate base is also important. Unless this ratio is close to 1 (between 1:10 and 10:1), the buffer capacity will be too low to be useful. The other important characteristic of a buffer is its pH. Let us now look at how to calculate the pH of a buffer.

FIGURE 16.11 Effect of added acid or base on a buffer solution The buffer contains 1.0 mol of acetic acid and 1.0 mol of acetate ion in 1.00 L of solution. Note that the addition of 0.5 mol or less of strong acid or base gives only a small change of pH.

The pH of a Buffer The solution described in Example 16.10 is a buffer, because it is a solution of a weak acid (0.10 M acetic acid) and its conjugate base (0.20 M acetate ion from sodium acetate). The example described how to calculate the pH of such a buffer (we obtained a pH of 5.07). The next example is similar, except now you are given a recipe for making up a buffer from volumes of solutions and are asked to calculate the pH. In this example, the buffer consists of a molecular base (NH3) and its conjugate acid (NH4). Example 16.11 Calculating the pH of a Buffer from Given Volumes of Solution Instructions for making up a buffer say to mix 60. mL (0.060 L) of 0.100 M NH3 with 40. mL (0.040 L) of 0.100 M NH4Cl. What is the pH of this buffer? Problem Strategy The buffer contains a base and its conjugate acid in equilibrium. The equation is

The problem is to obtain the concentration of H3Oor OH in this equilibrium mixture. To do the equilibrium calculation, you need the starting concentrations in the solution obtained by mixing the NH3 and NH4Cl solutions. For this, you calculate the moles of NH3 and moles of NH4 added to the buffer solution, and divide by the total volume of buffer. Then you are ready to do the equilibrium calculation.

Solution How many moles of NH3 are added? Recall that

Note that the instructions say to add 60. mL (or 0.060 L) of 0.100 M NH3. So Moles NH3 = molarity NH3 x liters NH3 solution

In the same way, you nd that you have added 0.0040 mol NH 4(from NH4Cl). Assume that the total volume of buffer equals the sum of the volumes of the two solutions. Total volume buffer = 60. mL + 40. mL = 100. mL (0.100 L) Therefore, the concentrations of base and conjugate acid are

Step 1: Fill in the concentration table for the acidbase equilibrium (base ionization of NH3).

2: You substitute the equilibrium concentrations into the equilibrium-constant equation.

3: To solve this equation, you assume that x is small compared with 0.040 and 0.060. So this equation becomes

Therefore, x (1.8 105) 2.7

(0.060/0.040)

105. (Check that x can be neglected in 0.040 x and 0.060 x.) Thus, the hydroxide-ion concentration is 2.7

105 M. The pH of the buffer is pH 105) (If 14.00 pOH 9.43 you have 2.7 14.00 log(2.7

105 in your calculator from the previous calculation, you obtain the pH by pressing the log button, then adding 14.) Answer Check To avoid a very common mistake, prior to setting up the equilibrium problem, always make sure that you rst take into account the total volume of solution and then calculate the concentrations. Exercise 16.12 What is the pH of a buffer prepared by adding 30.0 mL of 0.15 M HC2H3O2 (acetic acid) to 70.0 mL of 0.20 M NaC2H3O2 (sodium acetate)?

HendersonHasselbalch Equation How do you prepare a buffer of given pH? We can show that the buffer must be prepared from a conjugate acid base pair in which the acid-ionization constant is approximately equal to the desired H3O concentration. To illustrate, consider a buffer made up of a weak acid HA and its conjugate base A. The acid-ionization equilibrium is

and the acid-ionization constant is

By rearranging, you get an equation for the H3Oconcentration.

This equation expresses the H3O concentration in terms of the Ka for the acid and the ratio of concentrations of HA and A. This equation was derived from the equi-librium constant, so the concentrations of HA and A should be equilibrium values. But because the presence of A represses the ionization of HA, these concentrations do not differ signicantly from the values used to prepare the buffer. If [HA] and [A] are approximately equal, the hydronium-ion concentration of the buffer is approxi-mately equal to Ka. You can use the preceding equation to derive an equation for the pH of a buffer. Take the negative logarithm of both sides of the equation. That is,

The left side equals the pH. You can also simplify the right side. The pKa of a weak acid is dened in a manner similar to pH and pOH. <

The previous equation can be written

More generally, you can write

This is an equation relating the pH of a buffer for different concentrations of conjugate acid and base; it is known as the HendersonHasselbalch equation. By substituting the value of pKa for the conjugate acid and the ratio [base]/[acid], you obtain the pH of the buffer. The question we asked earlier was how to prepare a buffer of a given pHfor example, pH 4.90. You can see that you need to nd a conjugate acidbase pair in which the pKa of the acid is close to the desired pH. Ka for acetic acid is 1.7 105, and its pKa is log(1.7 105) [base]/[acid]. 4.77. You can get a pH somewhat higher by increasing the ratio

Consider the calculation of the pH of a buffer containing 0.10 M NH3 and 0.20 M NH4Cl. The conjugate acid is NH4, whose Ka you can calculate from Kb for NH3

The solution is basic, as you could have guessed, because the buffer contains the weak base NH3 and the very weak acid NH4.

Concept Check 16.4 You add 1.5 mL of 1 M HCl to each of the following solutions. Which one will show the least change of pH? a. 15 mL of 0.1 M NaOH b. 15 mL of 0.1 M HC2H3O2 c. 30 mL of 0.1 M NaOH and 30 mL of 0.1 M HC2H3O2

d. 30 mL of 0.1 M NaOH and 60 mL of 0.1 M HC2H3O2 Concept Check 16.5 The beaker on the left below represents a buffer solution of a weak acid HA and its conjugate base, A. (Water molecules and spectator ions have been omitted for clarity.) a. Which beaker on the right, X or Y, depicts the solution after the addition of two formula units of NaOH? b. How many HCl molecules can be added to the original buffer solution before the buffer capacity is exceeded? c. Draw a picture of the solution where the buffer capacity has been exceeded by the addition of HCl.