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19.2 Acid-Base Titration Curves
19.2 Acid-Base Titration Curves
19.2 Acid-Base Titration Curves
Therefore,
Figure 19.5 on the next page shows the color changes and their pH ranges for some common
acid-base indicators.
How we perceive colors has a major influence on the use of indicators. Typically, the
experimenter will see the HIn color if the [HIn]/[In-] ratio is 10/1 or greater and the In_ color if
the [HIn]/[In-] ratio is 1/10 or less. Between these extremes, the colors of the two forms merge
into an intermediate hue. Therefore, an indicator has a color range that reflects a 100-fold range
in the [HIn]/[In] ratio, which means that an indicator changes color over a range of about 2 pH
units. For example, as you can see in Figure 19.5, bromthymol blue has a pH range of about 6.0
to 7.6. It is yellow below that range, blue above it, and greenish in between (Figure 19.6).
FIGURE 19.5 Colors and approximate pH range of some common acid-base indicators.
Most have a range of about 2 pH units, in keeping with the useful buffer range of 2 pH units
(pKa ± 1). (The pH range depends to some extent on the solvent used to prepare the indicator.)
FIGURE 19.6 The color change of the indicator bromthymol blue. The acidic form of
bromthymol blue is yellow (left) and the basic form is blue (right). Over the pH range in which
the indicator is changing, both forms are present, so the mixture appears greenish (center).
FIGURE 19.7 Curve for a strong acid-strong base titration. Data obtained from the titration
of 40.00 mL of 0.1000 M HCl with 0.1000 M NaOH are shown at left. The titration curve shows
pH increasing gradually at first and then rapidly near and at the equivalence point, which occurs
when amount (mol) of OH_ added = amount (mol) of H3O+ originally present. In a strong acid–
strong base titration, pH = 7.00 at the equivalence point, and an indicator that changes color on
the steep portion of the curve is used (methyl red and phenolphthalein are shown in the photos).
Beyond this point, added OH- causes a gradual pH increase again. Each blow-up circle depicts
the relative numbers of species present, other than solvent, in a tiny portion of the solution at key
points during the titration. The circles increase in size in proportion to the total volume of the
solution.
Calculating the pH By knowing the chemical species present during the titration, we can
calculate the pH at various points along the way:
1. Original solution of strong HA. In Figure 19.7, 40.00 mL of 0.1000 M HCl is titrated with
0.1000 M NaOH. Because a strong acid is completely dissociated, [HCl] = [H3O+] = 0.1000
M. Therefore, the initial pH is*
2. Before the equivalence point. As soon as we start adding base, two changes occur that affect
the pH calculations: (1) some acid is neutralized, and (2) the volume of solution increases. To
find the pH at various points up to the equivalence point, we find the initial amount (mol) of
H3O+ present, subtract the amount reacted, which equals the amount (mol) of OH- added,
and then use the change in volume to calculate the concentration, [H3O+], and convert to pH.
For example, after adding 20.00 mL of 0.1000 M NaOH:
Find the moles of H3O+ remaining. Subtracting the number of moles of H3O+ reacted
from the number initially present gives the number remaining. Moles of H3O+ reacted
equals moles of OH- added, so
Calculate [H3O_], taking the total volume into account. To find the ion concentrations,
we use the total volume because the water of one solution dilutes the ions of the other:
Given the moles of OH_ added, we are halfway to the equivalence point; but we are still on the
initial slow rise of the curve, so the pH is still very low. Similar calculations give values up to the
equivalence point.
3. At the equivalence point. After 40.00 mL of 0.1000 M NaOH has been added, the
equivalence point is reached. All the H3O+ from the acid has been neutralized, and the
solution contains Na+ and Cl-, neither of which reacts with water. Because of the
autoionization of water, however,
[H3O+] = 1.0x10-7 M pH = 7.00
In this example, 0.004000 mol of OH- reacted with 0.004000 mol of H3O+ to reach the
equivalence point.
4. After the equivalence point. From the equivalence point on, the pH calculation is based on
the moles of excess OH- present. For example, after adding 50.00 mL of NaOH, we have
Features of the Curve When we compare this weak acid–strong base titration curve with the
strong acid–strong base titration curve (dotted curve portion in Figure 19.8 corresponds to
bottom half of curve in Figure 19.7), four key regions appear, and the first three differ from the
strong acid case:
1. The initial pH is higher. Because the weak acid (HPr) dissociates slightly, much less H3O+ is
present than with the strong acid.
2. A gradually rising portion of the curve, called the buffer region, appears before the steep rise
to the equivalence point. As HPr reacts with the strong base, more and more conjugate base
(Pr-) forms, which creates an HPr-Pr- buffer. At the midpoint of the buffer region, half the
original HPr has reacted, so [HPr] = [Pr-], or [Pr-]/[HPr] = 1. Therefore, the pH equals the
pKa:
Observing the pH at the midpoint of the buffer region is a common method for estimating the
pKa of an unknown acid.
3. The pH at the equivalence point is greater than 7.00. The solution contains the strong-base
cation Na+, which does not react with water, and the weakacid anion Pr-, which acts as a
weak base to accept a proton from H2O and yield OH-.
4. Beyond the equivalence point, the pH increases slowly as excess OH- is added.
Our choice of indicator is more limited here than for a strong acid–strong base titration
because the steep rise occurs over a smaller pH range. Phenolphthalein is suitable because its
color change lies within this range (Figure 19.8). However, the figure shows that methyl red, our
other choice for the strong acid–strong base titration, changes color earlier and slowly over a
large volume (~10 mL) of titrant, thereby giving a vague and false indication of the equivalence
point.
Calculating the pH The calculation procedure for the weak acid–strong base titration is different
from that for the strong acid–strong base titration because we have to consider the partial
dissociation of the weak acid and the reaction of the conjugate base with water. There are four
key regions of the titration curve, each of which requires a different type of calculation to find
[H3O+]:
1. Solution of HA. Before base is added, the [H3O_] is that of a weak-acid solution, so we find
[H3O+] as in Section 18.4: we set up a reaction table with x = [HPr]dissoc, assume [H3O+] =
[HPr]dissoc << [HPr]init, and solve for x:
2. Solution of HA and added base. As soon as we add NaOH, it reacts with HPr to form Pr-. This
means that up to the equivalence point, we have a mixture of acid and conjugate base, and an
HPr-Pr- buffer solution exists over much of that interval. Therefore, we find [H3O+] from the
relationship
(Of course, we can find pH directly with the Henderson-Hasselbalch equation, which is just an
alternative form of this relationship.) Note that in this calculation we do not have to consider the
new total volume because the volumes cancel in the ratio of concentrations. That is, [HPr]/[Pr-]
= moles of HPr/moles of Pr-, so we need not calculate concentrations.
3. Equivalent amounts of HA and added base. At the equivalence point, the original amount of
HPr has reacted, so the flask contains a solution of Pr-, a weak base that reacts with water to form
OH-:
Therefore, as mentioned previously, in a weak acid–strong base titration, the solution at the
equivalence point is slightly basic, pH > 7.00. We calculate [H3O+] as in Section 18.5: we first
find Kb of Pr- from Ka of HPr, set up a reaction table (assume [Pr-] >> [Pr-]reacting), and solve
for [OH-]. We need a single concentration, [Pr-], to solve for [OH-], so we do need the total
volume. Then, we convert to [H3O+]. These two steps are
Combining them into one step gives
4. Solution of excess added base. Beyond the equivalence point, we are just adding excess OH_
ion, so the calculation is the same as for the strong acid–strong base titration:
4. Beyond the equivalence point, the pH decreases slowly as excess H3O+ is added. For this
titration also, we must be more careful in choosing the indicator than we would be for a
strong acid–strong base titration. Phenolphthalein changes color too soon and too slowly
to indicate the equivalence point; methyl red, however, lies on the steep portion of the
curve and straddles the equivalence point, so it is a perfect choice.
FIGURE 19.9 Curve for a weak base–strong acid titration. Titrating 40.00 mL of 0.1000 M
NH3 with a solution of 0.1000 M HCl leads to a curve whose shape is the same as that of the
weak acid–strong base curve in Figure 19.8 but inverted. The midpoint of the buffer region
occurs when [NH3] = [NH4+]; the pH at this point equals the pKa of the acid, NH4+. Methyl red
(photo) is a suitable indicator here. The blow-up circles depict the relative numbers of species
present at key points during the titration.