Chapter

14

Principles of Neutralization
Titrations
Neutralization titrations are widely used to determine the amounts of acids and bases
and to monitor the progress of reactions that produce or consume hydrogen ions.

14 A Solutions and indicators for acid/base titrations

Neutralization titrations depend on a chemical reaction of the analyte with a standard

reagent. There are several different types of acid/base titrations.

1. The titration of a strong acid, such as hydrochloric or sulfuric acid, with a strong
base, such as sodium hydroxide.
2. The titration of a weak acid, such as acetic or lactic acid, with a strong base.
3. The titration of a weak base, such as sodium cyanide or sodium salicylate, with a
strong acid.
Standard Solutions

The standard reagents used in acid/base titrations are always strong acids or strong
bases, such as HCl, HClO4, H2SO4, NaOH, and KOH.

Weak acids and bases are never used as standard reagents because they react
incompletely with analytes.

Standard solutions of acids are prepared by diluting concentrated hydrochloric,

perchloric, or sulfuric acid.

Nitric acid is seldom used because its oxidizing properties offer the potential for
undesirable side reactions.

Hot concentrated perchloric and sulfuric acids are potent oxidizing agents and are
very hazardous.
Acid/Base Indicators

An acid/base indicator is a weak organic acid or a weak organic base whose

undissociated form differs in color from its conjugate base or its conjugate acid form.
For example, the behavior of an acid-type indicator, HIn:
HIn + H2O Û In- + H3O+

The equilibrium for a base-type indicator, In:

In + H2O Û InH+ + OH-

The equilibrium-constant expression for the dissociation of an acid-type indicator

takes the form

Ka = [H3O+][In-]
[HIN]
Figure 14-1 Color change and molecular modes for phenolphthalein.
(a) Acidic form after hydrolysis of the lactone form. (b) Basic form.
The human eye is not very sensitive to color differences in a solution containing a
mixture of HIn and In2, particularly when the ratio [HIn]/[In2] is greater than about
10 or smaller than about 0.1.

HIn, exhibits its pure acid color when

[HIn]/[In-] ³ 10/1

and its base color when [HIn]/[In-] £ 1/10

Therefore, the range of hydronium ion concentrations needed for the indicator to
change color can be estimated. For full acid color,
[H3O+] = 10Ka
and for the full base color,
[H3O+] = 0.1Ka
To obtain the indicator pH range, we take the negative
logarithms of the two expressions:

pH (acid color) = -log(10Ka) = pKa + 1

pH (basic color) = -log(0.1Ka) = pKa – 1

Indicator pH range = pKa ± 1

Titration Errors with Acid/Base Indicators

There are two types of titration error in acid/base titrations:

Determinate error that occurs when the pH at which the indicator changes color
differs from the pH at the equivalence point.

It can usually be minimized by choosing the indicator carefully or by making a blank

correction.

Indeterminate error that originates from the limited ability of the human eye to
distinguish reproducibly the intermediate color of the indicator.

The magnitude of this error depends on the change in pH per milliliter of reagent at—
the equivalence point, on the concentration of the indicator, and on the sensitivity of
the eye to the two indicator colors.
Variables That Influence the Behavior of Indicators

The pH interval over which a given indicator exhibits

a color change is influenced by temperature, the
ionic strength of the medium, and the presence of
organic solvents and colloidal particles.

Some of these effects can cause the transition range

to shift by one or more pH units.

Figure 14-2 Indicator color as a function of pH (pKa 5 5.0).

The Common Acid/Base Indicators
14 B Titration of strong acids and bases

The hydronium ions in an aqueous solution of a strong acid have two sources:

(1) the reaction of the acid with water and (2) the dissociation of water itself.

For a solution of HCl with a concentration greater than about 10-6 M:

[H3O+] = cHCL + [OH-] » cHCL

where [OH2] represents the contribution of hydronium ions from the dissociation of
water.

For a solution of a strong base, such as sodium hydroxide:

[OH-] = cNAOH + [H3O+] » cNAOH
Titrating a Strong Acid with a Strong Base

Three types of calculations must be done to construct the hypothetical curve for
titrating a solution of a strong acid with a strong base.

(1) Preequivalence; compute the concentration of the acid from its starting
concentration and the amount of base added.
(2) Equivalence: the hydronium ion concentration can be calculated directly from
the ion-product constant for water, Kw.
(3) Postequivalence: the analytical concentration of the excess base is computed,
and the hydroxide ion concentration is assumed to be equal to or a multiple of
the analytical concentration.

(1) Kw = [H3O+][OH-]
(2) -log Kw = -log [H3O+][OH-] = -log[H3O+] – log[OH-]
(3) pKw = pH + pOH
The Effect of Concentration

The effects of reagent and analyte

concentration on the neutralization titration
curves for strong acids are shown.

Figure 14-3 Titration curves for HCl with NaOH.

Choosing an Indicator

The selection of an indicator is not critical when the reagent concentration is

approximately 0.1 M.

The volume differences in titrations with the three indicators shown are of the same
magnitude as the uncertainties associated with reading the buret and so are
negligible.

Titrating a Strong Base with a Strong Acid

Titration curves for strong bases are calculated in a similar way to those for strong
acids.
Figure 14- 4 Titration curves for NaOH with HCl.
14 C Titration curves for weak acids

Four distinctly different types of calculations are needed to compute values for a
weak acid (or a weak base) titration curve:

1. At the beginning, the solution contains only a weak acid or a weak base, and the
pH is calculated from the concentration of that solute and its dissociation
constant.

2. After various increments of titrant have been added (up to, but not including, the
equivalence point), the solution consists of a series of buffers.

The pH of each buffer can be calculated from the analytical concentrations of the
conjugate base or acid and the concentrations of the weak acid or base that
remains.
3. At the equivalence point, the solution contains only the conjugate of the weak
acid or base being titrated (that is, a salt), and the pH is calculated from the
concentration of this product.

4. Beyond the equivalence point, the excess of strong acid or base titrant
suppresses the acidic or basic character of the reaction product to such an extent
that the pH is governed largely by the concentration of the excess titrant.
The analytical concentrations of acid and conjugate base are identical when an acid
has been half neutralized.

At the half-titration point in a weak-acid titration,

[H3O+] = Ka and pH = pKa

In the titration of a weak base, the hydroxide ion concentration is numerically equal
to the dissociation constant of the base at the midpoint in the titration curve.

In addition, the buffer capacities of each of the solutions are at a maximum at this
point. These points, often called the half-titration
points.

At the half-titration point in a weak-base titration,

[OH2] = Kb, and pOH = pKb
The Effect of Concentration
Figure 14-5 Curve for the titration
of acetic acid with sodium hydroxide.

The initial pH values are higher and the

equivalence-point pH is lower for the
more dilute solution (Curve B).

At intermediate titrant volumes, however,

the pH values differ only slightly because
of the buffering action of the acetic acid/
sodium acetate system that is present in
this region.
The Effect of Reaction Completeness

Figure 14-6 The effect of acid

strength (dissociation constant) on
titration curves.

Titration curves for 0.1000 M

solutions of acids with different
dissociation constants
are shown.

The pH change in the equivalence

-point region becomes smaller as
the acid becomes weaker.
14D Titration curves for weak bases
Figure 14-7 Hypothetical titration curves for a series of weak bases of different
strengths.

The curves show that indicators with mostly acidic transition ranges must be used for
weak bases.
14 E The composition of solutions during acid/base titrations

The changes in composition that occur while a solution of a weak acid or a weak
base is being titrated can be visualized by plotting the relative equilibrium
concentration a0 of the weak acid as well as the relative equilibrium concentration of
the conjugate base a1 as functions of the pH
of the solution.
Figure 14-8 Plots of relative amounts of acetic acid and acetate ion during a
titration.

The straight lines show the change in relative amounts of HOAc (a0) and OAc2
(a1) during the titration of 50.00 mL of 0.1000 M acetic acid.

The curved line is the titration curve for the system.