Redox Titrations

Introduction

1.) Redox Titration

 Based on an oxidation-reduction reaction between analyte and titrant
 Many common analytes in chemistry, biology, environmental and materials science
can be measured by redox titrations
Electron path in multi-heme active site of P460

Measurement of redox
potentials permit detailed

analysis of complex
enzyme mechanism

Biochemistry 2005, 44, 1856-1863

 Redox Titrations
Shape of a Redox Titration Curve

1.) Voltage Change as a Function of Added Titrant

 Consider the Titration Reaction (essentially goes to completion):

K ≈ 1016

 Ce4+ is added with a buret to a solution of Fe2+

 Pt electrode responds to relative concentration

of Fe3+/Fe2+ & Ce4+/Ce3+

 Calomel electrode used as reference

Indicator half-reactions at Pt electrode:

Eo = 0.767 V

Eo = 1.70 V
 Redox Titrations
Shape of a Redox Titration Curve

2.) Titration Curve has Three Regions

 Before the Equivalence Point
 At the Equivalence Point
 After the Equivalence Point

3.) Region 1: Before the Equivalence Point

 Each aliquot of Ce4+ creates an equal
number of moles of Ce3+ and Fe3+

 Excess unreacted Fe2+ remains in solution

 Amounts of Fe2+ and Fe3+ are known, use

to determine cell voltage.

 Residual amount of Ce4+ is unknown

 Redox Titrations
Shape of a Redox Titration Curve

3.) Region 1: Before the Equivalence Point

Use iron half-reaction relative to calomel reference electrode:

Eo = 0.767 V

E  E  ( indicator electrode )  E  ( reference electrode )

Potential of
calomel
electrode
 [ Fe 2  ] 
E  0.767  0.05916 log   0.241
3
 [ Fe ] 
Simplify

 [ Fe 2  ] 
E  0.526  0.05916 log  
 [ Fe 3  ] 
 
 Redox Titrations
Shape of a Redox Titration Curve

3.) Region 1: Before the Equivalence Point

 Special point when V = 1/2 Ve

[ Fe 3  ]  [ Fe 2  ]

 [ Fe 2  ] 
E  0.526  0.05916 log  
 [ Fe 3  ] 
 
Log term is zero

E  0.526  E   E o  0.767V

The point at which V= ½ Ve is analogous to the point at

which pH = pKa in an acid base titration
 Redox Titrations
Shape of a Redox Titration Curve

3.) Region 1: Before the Equivalence Point

 Another special point, when [Ce4+]=0

 Voltage can not be calculated

 [Fe3+] is unknown

 If [Fe3+] = 0, Voltage = -∞
- Must be some Fe3+ from impurity
or Fe2+ oxidation

 Voltage can never be lower than value need

to reduce the solvent

Eo = -0.828 V
 Redox Titrations
Shape of a Redox Titration Curve

3.) Region 1: Before the Equivalence Point

 Special point when V = 2Ve

[Ce 3  ]  [Ce 4  ]

 [Ce 3  ] 
E  1.46  0.05916 log  
 [Ce 4  ] 
 
Log term is zero

E  1.46  E   E o  1.70V

The point at which V= 2 Ve is analogous to the point at

which pH = pKa in an acid base titration
 Redox Titrations
Shape of a Redox Titration Curve

4.) Region 2: At the Equivalence Point

 Enough Ce4+ has been added to react with all Fe2+
- Primarily only Ce3+ and Fe3+ present
- Tiny amounts of Ce4+ and Fe2+ from equilibrium

 From Reaction:

- [Ce3+] = [Fe3+]
- [Ce4+] = [Fe2+]

 Both Reactions are in Equilibrium at the

Pt electrode

 [ Fe 2  ] 
E   0.767  0.05916 log  
 [ Fe ] 
3 
 

 [Ce 3  ] 
E   1.70  0.05916 log  
 [Ce 4  ] 
 
 Redox Titrations
Shape of a Redox Titration Curve

4.) Region 2: At the Equivalence Point

 Don’t Know the Concentration of either Fe2+ or Ce4+
 Can’t solve either equation independently to determine E+
 Instead Add both equations together

 [ Fe 2  ]   [Ce 3  ] 
E   0.767  0.05916 log   E   1.70  0.05916 log  
 [ Fe 3  ]   [Ce 4  ] 
   
Add

 [ Fe 2  ]   [Ce 3  ] 
2 E   0.767  1.70  0.05916 log    0.05916 log  
 [ Fe 3  ]   [Ce 4  ] 
   
Rearrange

 [ Fe 2  ] [Ce 3  ] 
2 E   2.47  0.05916 log  
 [ Fe 3  ] [Ce 4  ] 
 
 Redox Titrations
Shape of a Redox Titration Curve

4.) Region 2: At the Equivalence Point

 Instead Add both equations together

 [ Fe 2  ] [Ce 3  ] 
2 E   2.47  0.05916 log  
 [ Fe ] [Ce ] 
3  4 
 
[Ce 3  ]  [ Fe 3  ]
Log term is zero
[Ce 4  ]  [ Fe 2  ]

2 E  2.47V  E  1.23V

Cell voltage

E  E  E ( calomel )  1.23  0.241  0.99V

Equivalence-point voltage is independent of the

concentrations and volumes of the reactants
 Redox Titrations
Shape of a Redox Titration Curve

5.) Region 3: After the Equivalence Point

 Opposite Situation Compared to Before the Equivalence Point

 Equal number of moles of Ce3+ and Fe3+

 Excess unreacted Ce4+ remains in solution

 Amounts of Ce3+ and Ce4+ are known, use

to determine cell voltage.

 Residual amount of Fe2+ is unknown

 Redox Titrations
Shape of a Redox Titration Curve

5.) Region 3: After the Equivalence Point

Use iron half-reaction relative to calomel reference electrode:

Eo = 1.70 V

E  E  ( indicator electrode )  E  ( reference electrode )

Potential of
calomel
electrode
 [Ce 3  ] 
E  1.70  0.05916 log   0.241
4
 [Ce ] 
Simplify

 [Ce 3  ] 
E  1.46  0.05916 log  
 [Ce 4  ] 
 
 Redox Titrations
Shape of a Redox Titration Curve

6.) Titration Only Depends on the Ratio of

Reactants
 Independent on concentration and/or
volume

 Same curve if diluted or concentrated by

a factor of 10
 Redox Titrations
Shape of a Redox Titration Curve

7.) Asymmetric Titration Curves

 Reaction Stoichiometry is not 1:1
 Equivalence point is not the center of the steep part of the titration curve

Titration curve for 2:1 Stoichiometry

2/3 height
 Redox Titrations
Finding the End Point

1.) Indicators or Electrodes

 Electrochemical measurements (current or potential) can be used to determine

the endpoint of a redox titration

 Redox Indicator is a chemical compound that undergoes a color change as it

goes from its oxidized form to its reduced form
 Redox Titrations
Finding the End Point

2.) Redox Indicators

 Color Change for a Redox Indicator occurs mostly over the range:

 0.05916 
E   Eo  volts
 n 

where Eo is the standard reduction potential for the indicator

and n is the number of electrons involved in the reduction

For Ferroin with Eo = 1.147V, the range of color change relative to SHE:

 0.05916 
E   1.147  volts  1.088 to 1.206 V
 1 
Relative to SCE is:

 0.05916 
E   1.147    E ( calomel )  1.088 to 1.206 V   ( 0.241 )  0.847 to 0.965V
 1 
 Redox Titrations
Finding the End Point

2.) Redox Indicators

 In order to be useful in endpoint detection, a redox indicator’s range of color
change should match the potential range expected at the end of the titration.

Relative to calomel electrode (-0.241V)

 Redox Titrations
Common Redox Reagents

1.) Adjustment of Analyte Oxidation State

 Before many compounds can be determined by Redox Titrations, must be
converted into a known oxidation state
- This step in the procedure is known as prereduction or preoxidation

 Reagents for prereduction or preoxidation must:

- Totally convert analyte into desired form
- Be easy to remove from the reaction mixture
- Avoid interfering in the titration

 Potassium Permanganate (KMnO4)

- Strong oxidant
- Own indicator
Titration of VO2+ with KMnO4
pH ≤ 1
Eo = 1.507 V
Violet colorless

pH neutral or alkaline
Eo = 1.692 V
Violet brown

pH strolngly alkaline
Eo = 0.56 V
Before Near After
Violet green
Equivalence point
 Redox Titrations
Common Redox Reagents

2.) Example
A 50.00 mL sample containing La3+ was titrated with sodium oxalate to
precipitate La2(C2O4)3, which was washed, dissolved in acid, and titrated
with 18.0 mL of 0.006363 M KMnO4.

Calculate the molarity of La3+ in the unknown.