As discussed in Chapter 4.4, titrations can be used to quantitatively analyze solutions for their acid or base concentrations. In this section, we will explore the underlying chemical equilibria that make acid-base titrimetry a useful analytical technique.

Titration Curves

A titration curve is a plot of some solution property versus the amount of added titrant (see Chapter 4.4 to review titration vocabulary). For acid-base titrations, solution pH is a useful property to monitor because it varies predictably with the solution composition and, therefore, may be used to monitor the titration’s progress and detect its end point. The following example exercise demonstrates the computation of pH for a titration solution after additions of several specified titrant volumes. The first example involves a strong acid titration that requires only stoichiometric calculations to derive the solution pH. The second example addresses a weak acid titration requiring equilibrium calculations.

Performing additional calculations similar to those in the preceding example permits a more full assessment of titration curves. A summary of pH/volume data pairs for the strong and weak acid titrations is provided in Table 14.2 and plotted as titration curves in Figure 14.20.

A comparison of these two titration curves (strong acid/strong base and weak acid/strong base) demonstrates the four stages of a titration:

• initial state (added titrant volume = 0 mL): pH is determined by the acid being titrated
  • because the two acid samples are equally concentrated, the strong acid exhibits a lower initial pH
• pre-equivalence point (0 mL < V < 25 mL): solution pH increases gradually and the acid is consumed by reaction with added titrant; composition includes unreacted acid and the reaction product, its conjugate base
  • for a weak acid/strong base titration, both the weak acid and its conjugate base are present, creating a buffer. In a weak acid/strong base titration curve, this region is therefore often referred to as the buffer region
• equivalence point (V = 25 mL): occurs when equimolar amounts of acid and base are present; a drastic rise in pH is observed as the solution composition transitions from acidic to either neutral (for the strong acid sample) or basic (for the weak acid sample)
  • for a strong acid/strong base titration, the pH at the equivalence point is 7
  • for a weak acid/strong base titration, the pH at the equivalence point is determined by ionization of the conjugate base of the acid
• postequivalence point (V > 25 mL): pH is determined by the amount of excess strong base titrant added
  • since both samples are titrated with the same titrant, both titration curves appear similar at this stage.

Acid-Base Indicators

Certain organic substances change color in dilute solution when the hydronium ion concentration reaches a particular value. For example, phenolphthalein is a colorless substance in any aqueous solution with a hydronium ion concentration greater than 5.0 × 10⁻⁹ M (pH < 8.3). In more basic solutions where the hydronium ion concentration is less than 5.0 × 10⁻⁹ M (pH > 8.3), it is red or pink. Substances such as phenolphthalein, which can be used to determine the pH of a solution, are called acid-base indicators. Acid-base indicators are either weak organic acids or weak organic bases.

The equilibrium in a solution of the acid-base indicator methyl orange, a weak acid, can be represented by an equation in which we use HIn as a simple representation for the complex methyl orange molecule:

The anion of methyl orange, In⁻, is yellow, and the nonionized form, HIn, is red. When we add acid to a solution of methyl orange, the increased hydronium ion concentration shifts the equilibrium toward the nonionized red form, in accordance with Le Châtelier’s principle. If we add base, we shift the equilibrium towards the yellow form. This behavior is completely analogous to the action of buffers.

The perceived color of an indicator solution is determined by the ratio of the concentrations of the two species In⁻ and HIn. If most of the indicator (typically about 60−90% or more) is present as In⁻, the perceived color of the solution is yellow. If most is present as HIn, then the solution color appears red. The Henderson-Hasselbalch equation is useful for understanding the relationship between the pH of an indicator solution and its composition (thus, perceived color):

In solutions where pH > pK_a, the logarithmic term must be positive, indicating an excess of the conjugate base form of the indicator (yellow solution). When pH < pK_a, the log term must be negative, indicating an excess of the conjugate acid (red solution). When the solution pH is close to the indicator pKa, appreciable amounts of both conjugate partners are present, and the solution color is that of an additive combination of each (yellow and red, yielding orange). The color change interval (or pH interval) for an acid-base indicator is defined as the range of pH values over which a change in color is observed, and for most indicators this range is approximately pK_a ± 1.

There are many different acid-base indicators that cover a wide range of pH values and can be used to determine the approximate pH of an unknown solution by a process of elimination. Universal indicators and pH paper contain a mixture of indicators and exhibit different colors at different pHs. Figure 14.21 presents several indicators, their colors, and their color-change intervals.

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The titration curves shown in Figure 14.22 illustrate the choice of a suitable indicator for specific titrations. In the strong acid titration, use of any of the three indicators should yield reasonably sharp color changes and accurate end point determinations. For this titration, the solution pH reaches the lower limit of the methyl orange color change interval after addition of ~24 mL of titrant, at which point the initially red solution would begin to appear orange. When 25 mL of titrant has been added (the equivalence point), the pH is well above the upper limit and the solution will appear yellow. The titration’s end point may then be estimated as the volume of titrant that yields a distinct orange-to-yellow color change. This color change would be challenging for most human eyes to precisely discern. More-accurate estimates of the titration end point are possible using either litmus or phenolphthalein, both of which exhibit color change intervals that are encompassed by the steep rise in pH that occurs around the 25.00 mL equivalence point.

The weak acid titration curve in Figure 14.22 shows that only one of the three indicators is suitable for end point detection. If methyl orange is used in this titration, the solution will undergo a gradual red-to-orange-to-yellow color change over a relatively large volume interval (0–6 mL), completing the color change well before the equivalence point (25 mL) has been reached. Use of litmus would show a color change that begins after adding 7–8 mL of titrant and ends just before the equivalence point. Phenolphthalein, on the other hand, exhibits a color change interval that nicely brackets the abrupt change in pH occurring at the titration’s equivalence point. A sharp color change from colorless to pink will be observed within a very small volume interval around the equivalence point.