Skoog CH 8 Principles of Neutralization Titrations

Introduction to
Analytical Chemistry
Chapter 8
Principles of Neutralization
Titrations: Determining Acids, Bases,
and the pH of Buffer Solutions
7-1
Copyright©2011 Cengage Learning
8A-2 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 form.
7-2
7-3
• the color imparted to a solution by a typical
indicator appears to the average observer to
change rapidly only within the limited
concentration ratio of approximately 10 to 0.1.
7-4
• HIn exhibits its pure acid color when
and its base color when
7-5
• What Variables Influence the Behavior of

Indicators?
• The pH interval over which a given indicator
exhibits a color change is influenced by
temperature, by the ionic strength of the
medium, and by the presence of organic
solvents and colloidal particles.
7-6
8B Calculating Ph In Titrations Of Strong
Acids And Strong 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.
7-7
8B-1 Titrating a Strong Acid with a Strong
Base
• Each calculation corresponds to a distinct
stage in the titration: (1) preequivalence, (2)
equivalence, and (3) postequivalence.
7-8
8B-1 Titrating a Strong Acid with a
Strong Base
• Before the equivalence point, we calculate the
pH from the molar concentration of unreacted
acid.
• At the equivalence point, the solution is
neutral and pH=7.00.
• Beyond the equivalence point, we first
calculate pOH and then pH. Remember that
pH=pKw - pOH=14.00 - pOH.
7-9
Example 8-1
• Do the calculations needed to generate the
hypothetical titration curve for the titration of
50.00 mL of 0.0500 M HCl with 0.1000 M
NaOH.
• Initial Point
7-10
Example 8-1
• After Addition of 10.00 mL of Reagent
7-11
Example 8-1
7-12
Example 8-1
• Equivalence Point
7-13
Example 8-1
• After Addition of 25.10 mL of Reagent
7-14
Example 8-1
7-15
Table8-2
7-16
Figure 8-4
Figure 8-4 Titration
curves for HCl with
NaOH. Curve A:
50.00 mL of 0.0500
M HCl with 0.1000
M NaOH. Curve B:
50.00 mL of
0.000500 M HCl
with 0.001000 M
NaOH.
7-17
8B-2 Titrating a Strong Base with a Strong
Acid
Figure 8-5
Titration curves
for NaOH with
HCl. Curve A:
50.00 mL of
0.0500 M NaOH
with 0.1000 M
HCl. Curve B:
50.00 mL of
0.00500 M
NaOH with
0.0100 M HCl.
7-18
8B-2 Titrating a Strong Base with a Strong
Acid
• A buffer is a mixture of a weak acid and its
conjugate base or a weak base and its
conjugate acid that resists changes in pH of a
solution.
7-19
8C Buffer Solutions
• By definition, a buffer solution is a solution of

a conjugate acid / base pair that resists
changes in pH.
7-20
8C-1 Calculating the pH of Buffer
Solutions
• Buffers Formed from a Weak Acid and Its Conjugate
Base
• If the first equilibrium lies farther to the right than

the second, the solution is acidic. If the second
equilibrium is more favorable, the solution is basic.
7-21
Feature 8-3
7-22
Feature 8-4
7-23
8C-2 What Are the Unique Properties of
Buffer Solutions?
• Buffers do not maintain pH at an absolutely
constant value, but changes in pH are
relatively small when small amounts of acid or
base are added.
• The Effect of Dilution
• The Effect of Added Acids and Bases
• What Is the Buffer Capacity?
7-24
Figure 8-6
Figure 8-6 The effect of
dilution of the pH of
buffered and unbuffered
solutions. The dissociation
constant for HA is 1.00 
10-4. Initial solute
concentrations are 1.00 M.
7-25
Buffer Solutions?
• The buffer capacity of a buffer is the number
of moles of strong acid or strong base that
causes one liter of the buffer to change pH by
one unit.
• It is related to the total concentration of the
buffering species as well as to their
concentration ratio.
7-26
Example 8-5
• Calculate the pH change that takes place when a
100-mL portion of (a) 0.0500M NaOH and (b) 0.0500
M HCl is added to 400 mL of the buffer solution that
contains 0.200M in NH3 and 0.300 M in NH4Cl.
• (a) Addition of NaOH converts part of the NH4+ in the
buffer to NH₃ :
NH4+ + H2O ↔ NH3 + H3O+ Ka = 5.70 x 10 -10
7-27
Example 8-5
• The analytical concentrations of NH₃ and
NH₄Cl then become
7-28
Example 8-5
• When substituted into the acid-dissociation
constant expression for NH⁴⁺, these values
yield
• and the change in pH is
7-29
Example 8-5
• (b) Addition of HCl converts part of the NH³ to
NH⁴⁺; thus,
7-30
Example 8-5
7-31
Figure 8-7
Figure 8-7 Buffer
capacity as a function
of the ratio
cNaA/cHA .
7-32
Buffer Solutions?
• Preparing Buffers
• we prepare buffers by making up a solution of
approximately the desired pH and then adjust
by adding acid or conjugate base until the
required pH is indicated by a pH meter.
7-33
8D Calculating pH in Weak Acid Titrations
• 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 (in quantities up to, but not including, an
equivalent amount), 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 residual concentrations of the
weak acid or base.
7-34
8D Calculating pH in Weak Acid Titrations
• 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 represses 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.
7-35
Figure 8-9
Figure 8-9 Curve for the
titration of acetic acid
with sodium hydroxide.
Curve A: 0.1000 M acid
with 0.1000 M base.
Curve B: 0.001000 M
acid with 0.001000 M
base.
7-36
Figure 8-10
Figure 8-10 The
effect of acid
strength
(dissociation
constant, Ka ) on
titration curves.
Each
curverepresents
the titration of
50.00 mL of 0.1000
M acid with 0.1000
M base.
7-37
8E Calculating pH in Titrations
of Weak Bases
• Example 8-7
-A 50.00-mL aliquot of 0.0500 M NaCN is
titrated with 0.1000 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.
7-38
Example 8-7
• (a) 0.00 mL of reagent:
7-39
Example 8-7
• (b) 10.00 mL of reagent:
7-40
Example 8-7
• (c) 25.00 mL of reagent:
7-41
Example 8-7
• (d) 26.00 mL of reagent:
7-42
Figure 8-11
Figure 8-11 The
effect of base
strength (Kb) on
titration curves.
Each curve
represents the
titration of
50.00 mL of
0.1000 M base
with 0.1000 M
HCl.
7-43
8F How Do Buffer Solutions Change as A
Function of pH?
7-44
Function of pH?
7-45
Function of pH?
7-46
Function of pH?
7-47
Figure 8-12
Figure 8-12 Plots of relative amounts of acetic acid and acetate ion during a titration. The straight
lines show the change in relative amounts of HOAc (0) and OAc (1) during the titration of 50.00
mL of 0.1000 M acetic acid. The curved line is the titration curve for the system
7-48
Figure 8-13
Figure 8-13 Plots of
relative amounts of
acetic acid and acetate
ion as a function of pH.
The two sigmoid lines
show the change in
relative amounts of
HOAc (0) and OAc— (1)
during the titration of
acetic acid.
7-49
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Introduction to

and its base color when

• What Variables Influence the Behavior of

• By definition, a buffer solution is a solution of

• If the first equilibrium lies farther to the right than

• and the change in pH is

• 1. At the beginning, the solution contains only a

• 3. At the equivalence point, the solution contains

Copyright©2011 Cengage Learning

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