ANALYTICAL CHEMISTRY LEC

(WEEK 11)

Dennis Espineli Salcedo, PhD

CONTENTS
Titrations in Analytical Chemistry
1. Terms used in Volumetric Titrations (Part 1: Week 9)
2. Volumetric Calculations (Part 1: Week 9)
3. Gravimetric Titrations (Part 2: Week 10)
4. Reagents for Neutralization Titrations (Part 3: Week 11)
5. Solving Neutralization Problems (Part: Week 11)
Intended Learning Outcomes (ILOs)
1. Differentiate various titration techniques.
2. Solve gravimetric, volumetric titration and neutralization titration
problems.
 Principles of
Neutralization Titrations
Neutralization Titrations
• Neutralization titrations are widely used to determine the amounts of acids
and bases.
• Neutralization titrations can be used to monitor the progress of reactions
that produce or consume hydrogen ions.

In clinical chemistry, for example, pancreatitis can be diagnosed by measuring

the activity of serum lipase. Lipases hydrolyze the long-chain fatty acid
triglyceride. The reaction liberates two moles of fatty acid and one mole of B-
monoglyceride for each mole of triglyceride present. The reaction is allowed to
proceed for a certain amount of time, and then the liberated fatty acid is
titrated with NaOH using a phenolphthalein indicator or a pH meter. The
amount of fatty acid produced in a fixed time is related to the lipase activity.
Standard Solutions
• The standard solutions used in neutralization titrations are strong acids or
strong bases because these substances react more completely with an
analyte than do weak acids and bases, and as a result, they produce
sharper end points.
• Standard solutions of acids are prepared by diluting concentrated
hydrochloric, perchloric, or sulfuric acid. HCl, HClO4, H2SO4
• 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.
• Standard solutions of bases are usually prepared from solid sodium,
potassium, and occasionally barium hydroxides. NaOH, KOH, BaOH
• Weak acids and bases are never used as standard reagents because they
react incompletely with analytes.
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.
• The pH transition range of most acid type indicators is
roughly pKa ± 1.

• This expression shows that an indicator with an acid

dissociation constant of 1 X 10-5 (pKa = 5) typically shows
a complete color change when the pH of the solution in
which it is dissolved changes from 4 to 6.
• Indicator color as a function of pH (pKa = 5.0) (see right).
Titration Errors with Acid/Base Indicators
1. A determinate error that occurs when the pH at which the indicator
changes color differs from the pH at the equivalence point. This type of
error can usually be minimized by choosing the indicator carefully or by
making a blank correction.
2. An 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.
Some Important Acid/Base Indicators
Some Important Acid/Base Indicators
Titration Curves
Titration Curves
• Titration curves are plots of a
concentration-related variable (y axis)
versus titrant volume (x axis).
• An end point is signaled by an
observable physical change near the
equivalence point of a titration.

The two most widely used signals involve:

1. a changes in color due to the reagent (titrant), the analyte, or an indicator
2. a change in potential of an electrode that responds to the titrant
concentration or the analyte concentration.
Types of Titration Curves
Two general types of titration curves (and thus two
general types of end points) occur in titrimetric
methods.

1. Sigmoidal curve in which the p-function

(concentration of a species, i.e. pH) of analyte
(or sometimes the titrant) is plotted as a
function of titrant volume.

2. Linear segment curve, measurements are

made on both sides of, but well away from, the
equivalence point. Measurements near
equivalence are avoided. In this type of curve,
the vertical axis represents an instrument
reading that is directly proportional to the
concentration of the analyte or the titrant.
1. Titration of a strong acid with a strong base
Suppose our analyte is
hydrochloric acid HCl (strong
acid) and the titrant is sodium
hydroxide NaOH (strong base).

Point 1 No NaOH added yet, so the pH of the analyte is low (it predominantly
contains H3O+).

Point 2 This is the pH recorded at a time point just before complete

neutralization takes place.
1. Titration of a strong acid with a strong base (cont’d)
Point 3 This is the equivalence point (halfway up the steep curve). At this point,
moles of NaOH added = moles of HCl in the analyte. At this point, H3O+ ions are
completely neutralized by OH- ions. The solution only has salt (NaCl) and water
and therefore the pH is neutral i.e. pH = 7.

Point 4 Addition of NaOH continues, pH starts becoming basic because HCl has
been completely neutralized and now excess of OH- ions are present in the
solution (from dissociation of NaOH).
2. Titration of a weak acid with a strong base
Let’s assume our analyte is
acetic acid CH3COOH (weak
acid) and the titrant is sodium
hydroxide NaOH (strong base).

Point 1 No NaOH added yet, so the pH of the analyte is low (it predominantly
contains H3O+ from dissociation of CH3COOH. But acetic acid is a weak acid, so
the starting pH is higher than what we noticed in case 1 where we had a strong
acid (HCl).
2. Titration of a weak acid with a strong base (cont’d)
Point 2 This is the pH recorded at a time point just before complete
neutralization takes place.

Point 3 This is the equivalence point (halfway up the steep curve). At this point,
moles of NaOH added = moles of CH3COOH in the analyte. The H3O+ ions are
completely neutralized by OH- ions. The solution contains only CH3COONa salt
and H2O.
2. Titration of a weak acid with a strong base (cont’dd)
Point 4 Beyond the equivalence point (when sodium hydroxide is in excess) the
curve is identical to HCl-NaOH titration curve as shown below:
3. Titration of a strong acid with a weak base
Suppose our analyte is
hydrochloric acid HCl (strong
acid) and the titrant is
ammonia NH3 (weak base).

Point 1 No NH3 added yet, so the pH of the analyte is low (it predominantly
contains H3O+ from dissociation of HCl).

As NH3 is added dropwise, H3O+ slowly starts getting consumed by NH3. Analyte
is still acidic due to predominance of H3O+ ions.
3. Titration of a strong acid with a weak base (cont’d)
Point 2 This is the pH recorded at a time point just before complete
neutralization takes place.

Point 3 This is the equivalence point (halfway up the steep curve). At this point,
moles of NH3 added = moles of HCl in the analyte. The H3O+ ions are completely
neutralized by NH3. In the case of a weak base versus a strong acid, the pH is
not neutral at the equivalence point. The solution is in fact acidic (pH ~ 5.5) at
the equivalence point.

So NH4+ is a relatively strong acid (weak base NH3 has a strong conjugate acid),
and thus NH4+ will react with H2O to produce hydronium ions making the
solution acidic.
3. Titration of a strong acid with a weak base (cont’dd)
Point 4 After the equivalence point, NH3 addition continues and is in excess, so
the pH increases. NH3 is a weak base so the pH is above 7, but is lower than
what we saw with a strong base NaOH.
4. Titration of a weak base with a weak acid
Suppose our analyte is NH3 (weak base) and the titrant is acetic acid CH3COOH
(weak acid).

If you notice there isn’t any steep bit in this plot. There is just what we call a
‘point of inflexion’ at the equivalence point. Lack of any steep change in pH
throughout the titration renders titration of a weak base versus a weak acid
difficult, and not much information can be extracted from such a curve
Solving Neutralization Problems
Kw, Water Dissociation Constant
The equilibrium constant, Kw, is called the dissociation constant or ionization
constant of water.

At the equivalence point, the solution is neutral, and pH = pOH. Both pH and
pOH = 7.00, at 25°C.

Kw = [H3O+][OH-] = 1 x 10-14 M
-log Kw = -log[H3O+][OH-] = -log [H3O] -log [OH-]
pKw = pH + pOH

Beyond the equivalence point, we first calculate pOH and then pH. Remember
that pH = pKw - pOH. At 25°C, pH = 14.00 - pOH.

-log 10-14 = 14.00 = pH + pOH

Example 1 (14-1 Titrating Strong Acid with Strong Base)
Generate the hypothetical titration curve for the titration of 50 mL of 0.05 M
HCl with 0.1 M NaOH at 25°C.

Changes in pH during the Titration of a Strong Acid with a Strong Base

Example 1 (14-1 Titrating Strong Acid with Strong Base)
Generate the hypothetical titration curve for the titration of 50 mL of 0.05 M
HCl with 0.1 M NaOH at 25°C.
Example 1 (14-1 Titrating Strong Acid with Strong Base)
Generate the hypothetical titration curve for the titration of 50 mL of 0.05 M
HCl with 0.1 M NaOH at 25°C.
Example 1 (14-1 Titrating Strong Acid with Strong Base)
Generate the hypothetical titration curve for the titration of 50 mL of 0.05 M
HCl with 0.1 M NaOH at 25°C.

Changes in pH during the Titration of a Strong Acid with a Strong Base

Example 2 (14-2 Titrating Strong Base with Strong Acid)
Calculate the pH during the titration of 50 mL of 0.05 M NaOH with 0.1 M HCl at
25°C after the addition of the following volumes of reagent: (a) 24.50 mL, (b)
25.00 mL, (c) 25.50 mL.
Example 2 (14-2 Titrating Strong Base with Strong Acid)
Calculate the pH during the titration of 50 mL of 0.05 M NaOH with 0.1 M HCl at
25°C after the addition of the following volumes of reagent: (a) 24.50 mL, (b)
25.00 mL, (c) 25.50 mL.
Example 3 (14-3 Weak Acids)
Generate a curve for the titration of 50 mL of 0.1 M acetic acid (HOAc) with 0.1
M sodium hydroxide at 25°C.

Changes in pH during the Titration of a Weak Acid with a Strong Base

Example 3 (14-3 Weak Acids)
Generate a curve for the titration of 50 mL of 0.1 M acetic acid (HOAc) with 0.1
M sodium hydroxide at 25°C. (Ka of acetic acid is 1.75 x 10-5)
Example 3 (14-3 Weak Acids)
Generate a curve for the titration of 50 mL of 0.1 M acetic acid (HOAc) with 0.1
M sodium hydroxide at 25°C. (Ka of acetic acid is 1.75 x 10-5)
Example 3 (14-3 Weak Acids)
Generate a curve for the titration of 50 mL of 0.1 M acetic acid (HOAc) with 0.1
M sodium hydroxide at 25°C. (Ka of acetic acid is 1.75 x 10-5)
Example 3 (14-3 Weak Acids)
Generate a curve for the titration of 50 mL of 0.1 M acetic acid (HOAc) with 0.1
M sodium hydroxide at 25°C. (Ka of acetic acid is 1.75 x 10-5)
Example 3 (14-3 Weak Acids)
Generate a curve for the titration of 50 mL of 0.1 M acetic acid (HOAc) with 0.1
M sodium hydroxide at 25°C.

Changes in pH during the Titration of a Weak Acid with a Strong Base

Example 4 (14-4 Weak Bases)
A 50-mL aliquot of 0.05 M NaCN (Ka for HCN = 6.2 x 10-10) is titrated with 0.1 M
HCl. The reaction is
CN- + H3O+ ⇌ HCN + H2O

Calculate the pH after the addition of (a) 0.00, (b) 10.00, (c) 25.00, and (d) 26.00
mL of acid.
Example 4 (14-4 Weak Bases)
A 50-mL aliquot of 0.05 M NaCN (Ka for HCN = 6.2 x 10-10) is titrated with 0.1 M
HCl. The reaction is
CN- + H3O+ ⇌ HCN + H2O

Calculate the pH after the addition of (a) 0.00, (b) 10.00, (c) 25.00, and (d)
26.00 mL of acid.
Example 4 (14-4 Weak Bases)
A 50-mL aliquot of 0.05 M NaCN (Ka for HCN = 6.2 x 10-10) is titrated with 0.1 M
HCl. The reaction is
CN- + H3O+ ⇌ HCN + H2O

Calculate the pH after the addition of (a) 0.00, (b) 10.00, (c) 25.00, and (d)
26.00 mL of acid.
Example 4 (14-4 Weak Bases)
A 50-mL aliquot of 0.05 M NaCN (Ka for HCN = 6.2 x 10-10) is titrated with 0.1 M
HCl. The reaction is
CN- + H3O+ ⇌ HCN + H2O

Calculate the pH after the addition of (a) 0.00, (b) 10.00, (c) 25.00, and (d)
26.00 mL of acid.
Example 4 (14-4 Weak Bases)
A 50-mL aliquot of 0.05 M NaCN (Ka for HCN = 6.2 x 10-10) is titrated with 0.1 M
HCl. The reaction is
CN- + H3O+ ⇌ HCN + H2O

Calculate the pH after the addition of (a) 0.00, (b) 10.00, (c) 25.00, and (d)
26.00 mL of acid.
Example 4 (14-4 Weak Bases)
A 50-mL aliquot of 0.05 M NaCN (Ka for HCN = 6.2 x 10-10) is titrated with 0.1 M
HCl. The reaction is
CN- + H3O+ ⇌ HCN + H2O

Calculate the pH after the addition of (a) 0.00, (b) 10.00, (c) 25.00, and (d) 26.00
mL of acid.
Example 4 (14-4 Weak Bases)
A 50-mL aliquot of 0.05 M NaCN (Ka for HCN = 6.2 x 10-10) is titrated with 0.1 M
HCl. The reaction is
CN- + H3O+ ⇌ HCN + H2O

Calculate the pH after the addition of (a) 0.00, (b) 10.00, (c) 25.00, and (d) 26.00
mL of acid.
Example 4 (14-4 Weak Bases)
A 50-mL aliquot of 0.05 M NaCN (Ka for HCN = 6.2 x 10-10) is titrated with 0.1 M
HCl. The reaction is
CN- + H3O+ ⇌ HCN + H2O

Calculate the pH after the addition of (a) 0.00, (b) 10.00, (c) 25.00, and (d) 26.00
mL of acid.
Example 4 (14-4 Weak Bases)
A 50-mL aliquot of 0.05 M NaCN (Ka for HCN = 6.2 x 10-10) is titrated with 0.1 M
HCl. The reaction is
CN- + H3O+ ⇌ HCN + H2O

Calculate the pH after the addition of (a) 0.00, (b) 10.00, (c) 25.00, and (d) 26.00
mL of acid.
SUMMARY
Titration Curve
1. In an acid-base titration, a known volume of either the acid or the base (of
unknown concentration) is placed in a conical flask.
2. The second reagent (of known concentration) is placed in a burette.
3. The reagent from is slowly added to the reagent in the conical flask.
4. A titration curve is a plot showing the change in pH of the solution in the
conical flask as the reagent is added from the burette.

A titration curve can be used to determine:

5. The equivalence point of an acid-base reaction (the point at which the
amounts of acid and of base are just sufficient to cause complete
neutralization).
6. The pH of the solution at equivalence point is dependent on the strength of
the acid and strength of the base used in the titration.
For strong acid-strong base titration, pH = 7 at equivalence point
For weak acid-strong base titration, pH > 7 at equivalence point
For strong acid-weak base titration, pH < 7 at equivalence point
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.

In all but the most dilute solutions, however, the contribution from the strong
acid far exceeds that from the solvent.

[H3O+] = cHCl + [OH-] ~ cHCl

An analogous relationship applies for a solution of a strong base, such as

sodium hydroxide.

[OH-] = cNaOH + [H3O+] ~ cNaOH

Titration of Weak Acids and Bases
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.
References:
• Fundamentals of Analytical Chemistry, Skoog, S et al, 9th Edition, 2014.
• https://www.khanacademy.org/test-prep/mcat/chemical-processes/
titrations-and-solubility-equilibria/a/acid-base-titration-curves#:~:text=A
%20titration%20curve%20is%20the,added%20as%20the%20titration
%20progresses.
THANKS FOR LISTENING