Chapter 14

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Analytical Chemistry

Chapter 14. Principles of Neutralization Titrations


Principles of Neutralization Titrations

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


activity of serum lipase. Lipases hydrolyze the long-chain fatty acid triglyceride.
Then the liberated fatty acid is titrated with NaOH.
Neutralization
Titrations
Principles of Neutralization Titrations

➢ Solutions and Indicators for Acid/Base Titrations

➢ Titration of Strong Acids and Bases

➢ Titration of Weak Acids and Bases


Principles of Neutralization Titrations

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.

Eye protection!
Principles of Neutralization Titrations

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 an acid-type indicator

For an base-type indicator


Principles of Neutralization Titrations

Acid/Base Indicators

For an base-type indicator


Principles of Neutralization Titrations

Acid/Base Indicators

For an acid-type indicator


Principles of Neutralization Titrations

Acid/Base Indicators

The human eye is not very sensitive to color differences in a solution


containing a mixture of HIn and In-, particularly when the ratio [HIn]/[In-] is
greater than about 10 or smaller than about 0.1.

pure acid color

pure base color


Principles of Neutralization Titrations

Acid/Base Indicators
Principles of Neutralization Titrations

Titration Errors with Acid/Base Indicators

➢ The first is a determinate error that occurs when the pH at which the
indicator changes color differs from the pH at the equivalence point.
(can usually be minimized by choosing the indicator carefully or by
making a blank correction.)

➢ The second type is an indeterminate error that originates from the


limited ability of the human eye to distinguish reproducibly the
intermediate color of the indicator.
(the visual uncertainty: 0.5 to 1 pH unit and can be decreased to 0.1 pH
unit by matching the color of the solution being titrated with that of a
reference standard containing a similar amount of indicator at the
appropriate pH)
Principles of Neutralization Titrations

The Common Acid/Base Indicators


Principles of Neutralization Titrations

The Common Acid/Base Indicators

Methyl Orange (MO) pKa=3.5


Principles of Neutralization Titrations

The Common Acid/Base Indicators

Methyl Red (MR) pKa=5.0


Principles of Neutralization Titrations

The Common Acid/Base Indicators

Phenolphthalein (PP) pKa=9.1

8.3 9.1 10.0


Titration of Strong Acids and Bases

➢Titrating a Strong Acid with a Strong Base

➢Titrating a Strong Base with a Strong Acid


Titration of Strong Acids and Bases

Titrating a Strong Acid with a Strong Base

➢ Preequivalence
➢ Equivalence
➢ Postequivalence
Titration of Strong Acids and Bases

Titrating a Strong Acid with a Strong Base


Titration of Strong Acids and Bases
Titration of Strong Acids and Bases
Titration of Strong Acids and Bases
Titration of Strong Acids and Bases
Titration of Strong Acids and Bases
Titration of Strong Acids and Bases
Titration of Strong Acids and Bases

Titrating a Strong Acid with a Strong Base

➢ The Effect of Concentration


➢ Choosing an Indicator
Titration of Strong Acids and Bases

Titrating a Strong Base with a Strong Acid

➢ Preequivalence
➢ Equivalence
➢ Postequivalence
Titration of Strong Acids and Bases
Titration of Strong Acids and Bases
Titration of Strong Acids and Bases
Titration of Weak Acids and Bases

Titrating a weak acid with a strong base


Titration of Weak Acids and Bases

Titrating a weak acid with a strong base


Titration of Weak Acids and Bases

Assumption?
pH calculation for buffer solutions

Assuming
Titration of Weak Acids and Bases
Titration of Weak Acids and Bases
Titration of Weak Acids and Bases
Titration of Weak Acids and Bases

Half-titration point: to determine the dissociation constants


Titration of Weak Acids and Bases
Titration of Weak Acids and Bases

The effect of concentration

Assumption
Fails!
Titration of Weak Acids and Bases

The effect of concentration

Assuming
Titration of Weak Acids and Bases

The effect of concentration

Higher

Lower
Titration of Weak Acids and Bases

➢ The effect of reaction completeness


➢ Choosing an indicator
Titration of Weak Acids and Bases
Titration of Weak Acids and Bases
Titration of Weak Acids and Bases

Titrating a weak base with a strong acid


Titration of Weak Acids and Bases
Titration of Weak Acids and Bases
Titration of Weak Acids and Bases

The effect of Kb
Titration of Weak Acids and Bases

The composition of solutions during acid/base titrations

➢ The relative equilibrium concentration of the weak acid: a0


➢ The relative equilibrium concentration of the conjugate base: a1
Titration of Weak Acids and Bases

The composition of solutions during acid/base titrations


Titration of Weak Acids and Bases

Locating titration end points via pH measurement


Titration of Weak Acids and Bases

Locating titration end points via pH measurement


Titration of Weak Acids and Bases

Locating titration end points via the Gran plot


Titration of Weak Acids and Bases
Titration of Weak Acids and Bases

Locating titration end points via the Gran plot


Home work
13-27; 13-28

14-29; 14-30; 14-42; 14-44

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