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Analytical Chemistry
Chapter 7
Principles of Neutralization
Titrations: Determining Acids, Bases,
and the pH of Buffer Solutions
7-1
Copyright©2011 Cengage Learning
Titrants
• The titrants, or standard reagents, used in
titrations should be strong acids or bases for a
more complete reaction, in order to produce
sharper end points
• The concentration of titrants must be
established through standardization
5-2
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7A-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.
7-3
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7A-2 Acid/Base Indicators
7-4
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7A-2 Acid/Base Indicators
• 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.
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7A-2 Acid/Base Indicators
• HIn exhibits its pure acid color when
7-6
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7A-2 Acid/Base Indicators
• pH 4-6
5-8
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Sample Problem
• What is the pH range of an indicator that has a
Ka of 4.78x10-5?
• 3.32-5.32
5-9
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7B 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.
7-10
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7B-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.
7-11
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7B-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.
7-12
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Example 7-1
• 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
7-13
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Example 7-1
• After Addition of 10.00 mL of Reagent
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Example 7-1
7-15
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Example 7-1
• Equivalence Point
7-16
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Example 7-1
• After Addition of 25.10 mL of Reagent
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Example 7-1
7-18
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Sample Problem
• A 75.00 mL of 0.0350 M HCl solution was
titrated with 0.2000 M NaOH. What would be
the pH of the analyte after adding the
following volumes of titrant?
• 0 mL 20 mL
• 5 mL
• Volume at pH 7
• 14 mL
5-19
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Answers
• 0 mL, pH=1.46
• 5 mL, pH=1.69
• 13.13 mL, pH=7
• 14 mL, pH=11.29
• 20 mL, pH=12.16
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Table7-2
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Choosing an Indicator
• See Fig 7-4
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Figure 7-4
Figure 7-4 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.
7-23
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7B-2 Titrating a Strong Base with a Strong
Acid
Figure 7-5
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.
7-24
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7B-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.
7-25
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7C Buffer Solutions
7-26
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7C-1 Calculating the pH of Buffer
Solutions
• Buffers Formed from a Weak Acid and Its Conjugate
Base
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Feature 7-3
7-28
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Feature 7-4
7-29
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Henderson-Hasselbalch equation
• pH=pKa +log([A-]/[HA])
• pOH=pKb +log([BH ]/[B])
+
5-30
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Sample Problem
• What is the pH of a solution that is 0.400 M in
formic acid and 1.00 M in sodium formate?
• Ka= 1.80x10-4
• pH=4.14
5-31
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Sample Problem
• What is the pH of a solution that is 0.525 M in
formic acid and 2.47 M in sodium formate?
• Ka= 1.80x10-4
• pH=4.42
5-32
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Sample Problem
• What is the pH of a solution that is 0.200 M in
NH3 and 0.300 M in NH4Cl.
• Ka=5.70x10-10
• pH=9.07
5-33
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Sample Problem
• What is the pH of a solution that is 0.200 M in
NH3 and 1.300 M in NH4Cl.
• Ka=5.70x10-10
• pH=8.43
5-34
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7C-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?
7-35
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Figure 7-6
Figure 7-6 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.
7-36
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7C-2 What Are the Unique Properties of
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.
7-37
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Example 7-5
• 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 a buffer solution
containing 0.200 M NH3 and 0.300 M NH4Cl.
Ka=5.7x10-10
• (a) Addition of NaOH converts part of the in the
buffer to NH₃ :
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Example 7-5
• The analytical concentrations of NH₃ and
NH₄Cl then become
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Example 7-5
• When substituted into the acid-dissociation
constant expression for NH⁴⁺, these values
yield
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Example 7-5
• (b) Addition of HCl converts part of the NH³ to
NH⁴⁺; thus,
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Example 7-5
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Sample Problem
• Calculate the pH change that takes place when a
100-mL portion of (a) 0.0350M NaOH and (b) 0.0700
M HCl is added to 400 mL of a buffer solution
containing 0.200 M NH3 and 0.300 M NH4Cl.
Ka=5.7x10-10
• (a) Addition of NaOH converts part of the NH4+ in the
buffer to NH₃ :
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Answers
• A) 9.10
• B) 9.00
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Figure 7-7
Figure 7-7 Buffer
capacity as a function
of the ratio
cNaA/cHA .
7-45
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7C-2 What Are the Unique Properties of
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.
7-46
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Sample Problem
• What volume of 6.00 M NaOH must be added
to 0.250 L of 0.300 M HNO2 to prepare a
pH=4.00 buffer? Ka=4.0x10-4
• 10 mL NaOH
5-47
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Sample Problem
• If an acetate buffer was going to be prepared
by neutralizing acetic acid with 0.10 M NaOH,
what volume (in mL) of 0.10 M NaOH would
need to be added to 10.0 mL of 0.10 M acetic
acid to prepare a solution of pH=5.50?
Ka=1.78x10-5
• 8.5 mL NaOH
5-48
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7D Calculating pH in Weak Acid Titrations
7-49
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7D Calculating pH in Weak Acid Titrations
7-50
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Figure 7-9
Figure 7-9 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.
7-51
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Figure 7-10
Figure 7-10 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.
7-52
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7E Calculating pH in Titrations
of Weak Bases
• Example 7-7
-A 50.00-mL aliquot of 0.0500 M NaCN is
titrated with 0.1000 M HCl. The reaction is
• Calculate the pH after the addition of (a) 0.00,
(b) 10.00, (c) 25.00, and(d) 26.00 mL of acid.
7-53
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Example 7-7
• (a) 0.00 mL of reagent:
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Example 7-7
• (b) 10.00 mL of reagent:
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Example 7-7
• (c) 25.00 mL of reagent:
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Example 7-7
• (d) 26.00 mL of reagent:
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Figure 7-11
Figure 7-11 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.
7-58
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7F How Do Buffer Solutions Change as A
Function of pH?
7-59
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7F How Do Buffer Solutions Change as A
Function of pH?
7-60
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7F How Do Buffer Solutions Change as A
Function of pH?
7-61
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7F How Do Buffer Solutions Change as A
Function of pH?
7-62
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Figure 7-12
Figure 7-12 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
7-63
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Figure 7-13
Figure 7-13 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.
7-64
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THE END