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Acid-Base Titrations

Introduction

3.) Overview

Titrations are Important tools in providing quantitative and qualitative data for
a sample.

To best understand titrations and the information they provide, it is necessary
to understand what gives rise to the shape of a typical titration curve.

To do this, acid-base equilibria are used to predict titration curve shapes.
Biochemistry, Vol. 41, No. 22, 2002 6945
pK
a
of His in the His-Asp catalytic dyad that catalyzes the oxidation of glucose 6-phosphate
Acid-Base Titrations
Titration of Strong Base with Strong Acid

1.) Graph of How pH changes as Titrant is Added

Assume strong acid and base completely dissociate

Any amount of H
+
added will consume a
stoichiometric amount of OH
-




Reaction Assumed to go to completion

Three regions of the titration curve
- Before the equivalence point, the pH is determined
by excess OH- in the solution

- At the equivalence point, H
+
is just sufficient to
react with all OH
-
to make H
2
O

- After the equivalence point, pH is determined by
excess H
+
in the solution.
14
w
10
K
1
K = =
Acid-Base Titrations
Titration of Strong Base with Strong Acid

1.) Graph of How pH changes as Titrant is
Added

Remember, equivalence point is the
ideal goal

Actually measure End Point
- Marked by a sudden physical
change: color, potential

Different Regions require different kinds
of calculations
- Illustrated examples

The true titration reaction is:
Titrant Analyte
Acid-Base Titrations
Titration of Strong Base with Strong Acid

2.) Volume Needed to Reach the Equivalence Point

Titration curve for 50.00 mL of 0.02000 M KOH with 0.1000 M HBr

At equivalence point, amount of H
+
added will equal initial amount of OH
-
( )( ) ( ) mL 00 . 10 V ) M 02000 . 0 ( mL 00 . 50 M 1000 . 0 ) mL ( V
e e
= =
mmol of HBr
at equivalence point
mmol of OH
-
being titrated
When 10.00 mL of HBr has been added, the titration is complete.
Prior to this point, there is excess OH- present.
After this point there is excess H
+
present.
Acid-Base Titrations
Titration of Strong Base with Strong Acid

3.) Before the Equivalence Point

Titration curve for 50.00 mL of 0.02000 M KOH with 0.1000 M HBr
- Equivalence point (V
e
) when 10.00 mL of HBr has been added
- When 3.00 mL of HBr has been added, reaction is 3/10 complete
( ) M 0132 . 0
00 . 3 00 . 50
00 . 50
M 02000 . 0
00 . 10
00 . 3 00 . 10
OH = |
.
|

\
|
+
|
.
|

\
|

=

] [
Fraction of OH
-

Remaining
Initial concentration
of OH
-
Dilution Factor
Initial volume of OH
-
Total volume
12 . 12 pH M 10 58 . 7
0132 . 0
10 0 . 1
OH
K
H
13
14
-
w
= =

= =

+
] [
] [
Calculate Remaining [OH
-
]:
Calculate [H
+
] and pH:
Acid-Base Titrations
Titration of Strong Base with Strong Acid

4.) At the Equivalence Point

Titration curve for 50.00 mL of 0.02000 M KOH with 0.1000 M HBr
- Just enough H
+
has been added to consume OH
-
- pH determined by dissociation of water








- pH at the equivalence point for any strong acid with strong base is 7.00
- Not true for weak acid-base titration
K
w
K
w
= 1x10
-14
00 . 7 pH M 10 00 . 1 x x K
7 2
w
= = =

x x

Acid-Base Titrations
Titration of Strong Base with Strong Acid

5.) After the Equivalence Point

Titration curve for 50.00 mL of 0.02000 M KOH with 0.1000 M HBr
- Adding excess HBr solution
- When 10.50 mL of HBr is added
( ) M 10 26 . 8
50 . 10 00 . 50
50 . 0
M 1000 . 0 H
4 +
= |
.
|

\
|
+
= ] [
Calculate excess [H
+
]:
Initial
concentration
of H
+
Dilution factor

Volume of excess H
+
Total volume

Calculate volume of excess H
+
:
mL 50 . 0 00 . 10 50 . 10 V V
e equivalenc added
= =
Calculate pH:
08 . 3 ) M 10 26 . 8 log( H
4
= = =
+
] -log[ pH
Acid-Base Titrations
Titration of Strong Base with Strong Acid

6.) Titration Curve

Rapid Change in pH Near Equivalence Point
- Equivalence point is where slope is greatest
- Second derivative is 0
pH at equivalence point is 7.00, only for strong
acid-base
- Not True if a weak base-acid is used
Acid-Base Titrations
Titration of Weak Acid with Strong Base

1.) Four Regions to Titration Curve

Before any added base, just weak acid (HA) in water
- pH determined by K
a






With addition of strong base buffer
- pH determined by Henderson Hasselbach equation





At equivalence point, all HA is converted into A
-
- Weak base with pH determined by K
b
K
a
|
|
.
|

\
|
+ =

] [
] [
HA
A
log pK pH
a
K
b
Acid-Base Titrations
Titration of Weak Acid with Strong Base

1.) Four Regions to Titration Curve

Beyond equivalence point, excess strong base is added to A
-
solution

- pH is determined by strong base
- Similar to titration of strong acid with strong base


2.) Illustrated Example:
Titration of 50.00 mL of 0.02000 M MES with 0.1000 M NaOH
- MES is a weak acid with pK
a
= 6.27







- Reaction goes to completion with addition of strong base



K

( )
( )
7
27 . 6 14
a w b
10 4 . 5
10 / 10 1
1
K / K
1
K
1
K =

= = =

Acid-Base Titrations
Titration of Weak Acid with Strong Base

3.) Volume Needed to Reach the Equivalence Point
Titration of 50.00 mL of 0.02000 M MES with 0.1000 M NaOH
- Reaction goes to completion with addition of strong base
- Strong plus weak react completely
( )( ) ( ) mL 00 . 10 V ) M 02000 . 0 ( mL 00 . 50 M 1000 . 0 ) mL ( V
e e
= =
mmol of base
mmol of HA
Acid-Base Titrations
Titration of Weak Acid with Strong Base

4.) Region 1: Before Base is Added
Titration of 50.00 mL of 0.02000 M MES with 0.1000 M NaOH
Simply a weak-acid problem
F - x x x
4
a
2 2
10 03 . 1 H x K
x 02000 . 0
x
x F
x
+
= = =

] [
K
a
K
a
= 10
-6.27
Calculate [H
+
]:
Calculate pH:
99 . 3 ) M 10 03 . 1 log( H log - pH
4
= = =
+
] [
10
3
Acid-Base Titrations
Titration of Weak Acid with Strong Base

5.) Region 2: Before the Equivalence Point
Titration of 50.00 mL of 0.02000 M MES with 0.1000 M NaOH
Adding OH
-
creates a mixture of HA and A
-
Buffer
Calculate pH from [A
-
]/[HA] using Henderson-Hasselbach equation

Calculate [A
-
]/HA]:
Relative Initial quantities (HA1) 1 - -
Relative Final quantities -
10
3
10
7
Amount of added NaOH is 3 mL with equivalence point is 10 mL
90 . 5
10
7
10
3
log 27 . 6
HA
A
log pK pH
a
=
|
|
|
.
|

\
|
+ =
|
|
.
|

\
|
+ =

] [
] [
Calculate pH:
Simply ratio of volumes
Simply the difference
of initial quantities
10
3
2
1
Acid-Base Titrations
Titration of Weak Acid with Strong Base

5.) Region 2: Before the Equivalence Point
Titration of 50.00 mL of 0.02000 M MES with 0.1000 M NaOH
pH = pK
a
when the volume of titrant equals V
e
2
1
Relative Initial quantities (HA1) 1 - -
Relative Final quantities -
2
1
a a a
pK
2
1
2
1
log pK
HA
A
log pK pH =
|
|
.
|

\
|
+ =
|
|
.
|

\
|
+ =

] [
] [
2
1
Acid-Base Titrations
Titration of Weak Acid with Strong Base

5.) Region 3: At the Equivalence Point
Titration of 50.00 mL of 0.02000 M MES with 0.1000 M NaOH
Exactly enough NaOH to consume HA








The solution only contains A
-
weak base
Relative Initial quantities (HA1) 1 1 - -
Relative Final quantities - - 1 1
K
b
a
w
b
K
K
K =
F - x x x
a
w
b
2
K
K
K
x F
x
= =

Acid-Base Titrations
Titration of Weak Acid with Strong Base

5.) Region 3: At the Equivalence Point
Titration of 50.00 mL of 0.02000 M MES with 0.1000 M NaOH
Calculate Formal concentration of [A
-
]:
A
-
is no longer 0.02000 M, diluted by the addition of NaOH
( ) M 0167 . 0
00 . 10 00 . 50
00 . 50
M 02000 . 0 ' F = |
.
|

\
|
+
=
Initial
concentration
of HA

Dilution factor

Initial volume of HA

Total volume

pH at equivalence
point is not 7.00
Acid-Base Titrations
Titration of Weak Acid with Strong Base

5.) Region 3: At the Equivalence Point
Titration of 50.00 mL of 0.02000 M MES with 0.1000 M NaOH
M 10 76 . 1 OH x 10 86 . 1
x 0167 . 0
x
10 86 . 1
10
10 1
K
K
K
x F
x
5 - - 8
2
8
27 . 6
14
a
w
b
2
= = =

= = =


] [
Calculate [OH
-
]:
Calculate pH:
25 . 9
0167 . 0
10 1
log
x
K
log H log - pH
14
w
=
|
|
.
|

\
|

= |
.
|

\
|
= =

+
] [
pH will always be above 7.00 for titration of a weak acid
because acid is converted into conjugate base at the equivalence point
Acid-Base Titrations
Titration of Weak Acid with Strong Base

5.) Region 4: After the Equivalence Point
Titration of 50.00 mL of 0.02000 M MES with 0.1000 M NaOH
Adding NaOH to a solution of A
-
- NaOH is a much stronger base than A
-
- pH determined by excess of OH
-
( ) M .
. .
.
M .
4
10 66 1
10 10 00 50
10 0
1000 0

= |
.
|

\
|
+
= ] [OH
-
Calculate excess [OH
-
]:
Initial
concentration
of OH
-
Dilution factor

Volume of excess OH
-
Total volume

Calculate volume of excess OH
-
:

mL 10 . 0 00 . 10 10 . 10 V V
e equivalenc added
= =
Calculate pH:
22 . 10
10 66 . 1
10 00 . 1
log
OH
K
log H log
4
14
w
=
|
|
.
|

\
|

=
(
(

= =

+
] [
] [ - pH
Amount of added NaOH is 10.10 mL with equivalence point is 10 mL
Acid-Base Titrations
Titration of Weak Acid with Strong Base

5.) Titration Curve
Titration of 50.00 mL of 0.02000 M MES with 0.1000 M NaOH
Two Important Features of the Titration Curve

Equivalence point: [OH-] = [HA]
Steepest part of curve
Maximum slope
pH=pK
a
V
b
= V
e
Minimum slope
Maximum Buffer
Capacity
Acid-Base Titrations
Titration of Weak Acid with Strong Base

5.) Titration Curve
Depends on pK
a
or acid strength
Inflection point or maximum slope decreases with weaker acid
- Equivalence point becomes more difficult to identify
Strong acid large slope change in
titration curve

Easy to detect equivalence point
weak acid small slope change in
titration curve

Difficult to detect equivalence point
Acid-Base Titrations
Titration of Weak Acid with Strong Base

5.) Titration Curve
Depends on acid concentration
Inflection point or maximum slope decreases with
lower acid concentration
- Equivalence point becomes more difficult to
identify
- Eventually can not titrate acid at very low
concentrations
High concentration large slope change in
titration curve

Easy to detect equivalence point
Low concentration small slope change in
titration curve

Difficult to detect equivalence point
At low enough concentration, can not detect change
Titration in Polyprotic Systems

1.) Principals for Monoprotic Systems Apply to Diprotic and Triprotic Systems
Multiple equivalence points and buffer regions

Multiple Inflection Points in Titration Curve
Acid-Base Titrations
K
b2
Two equivalence points
K
b1
Acid-Base Titrations
End Point Determination

1.) Indicators: compound added in an acid-base titration to allow end
point detection
Common indicators are weak acids or bases
Different protonated species have different colors
pK = 1.7
pK = 8.9
Acid-Base Titrations
End Point Determination

2.) Choosing an Indicator
Want Indicator that changes color in the vicinity of the equivalence point
and corresponding pH
The closer the two match, the more accurate determining the end point will
be
Bromocresol green will change color
Significantly past the equivalence
point resulting in an error.

Bromocresol purple color change
brackets the equivalence point and
is a good indicator choice

Acid-Base Titrations
End Point Determination

2.) Choosing an Indicator
The difference between the end point
(point of detected color change) and the
true equivalence point is the indicator
error

Amount of indicator added should be
negligible
Indicators cover a range of pHs

Acid-Base Titrations
End Point Determination

3.) Example:
a) What is the pH at the equivalence point when 0.100 M hydroxyacetic acid
is titrated with 0.0500 M KOH?

b) What indicator would be a good choice to monitor the endpoint?