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, acidbase equilibria are used to predict titration curve shapes.
Biochemistry, Vol. 41, No. 22, 2002 6945
pK
a
of His in the HisAsp catalytic dyad that catalyzes the oxidation of glucose 6phosphate
AcidBase 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 = =
AcidBase 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
AcidBase 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.
AcidBase 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:
AcidBase 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 acidbase titration
K
w
K
w
= 1x10
14
00 . 7 pH M 10 00 . 1 x x K
7 2
w
= = =
x x
AcidBase 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
AcidBase 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
acidbase
 Not True if a weak baseacid is used
AcidBase 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
AcidBase 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 =
= = =
AcidBase 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
AcidBase 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 weakacid 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
AcidBase 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 HendersonHasselbach 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
AcidBase 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
AcidBase 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
= =
AcidBase 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
AcidBase 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
AcidBase 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
AcidBase 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
AcidBase 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
AcidBase 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
AcidBase Titrations
K
b2
Two equivalence points
K
b1
AcidBase Titrations
End Point Determination
1.) Indicators: compound added in an acidbase 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
AcidBase 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
AcidBase 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
AcidBase 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?