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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


 Similar to Acid-Base Titrations

 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
- Similar to acid-base indicators that change color with a change in protonation
state
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
Redox Titrations
Finding the End Point

2.) Redox Indicators


 Color Change for a Redox Indicator occurs over a potential range

 Illustration:
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.) Starch
 Commonly used as an indicator in redox titrations involving iodine

 Reacts with iodine to form an intensely blue colored complex

 Starch is not a redox indicator


- Does not undergo a change in redox potential

I6 bound in center of starch helix

Repeating unit
Redox Titrations
Common Redox Reagents

2.) 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

 Examples:
- Preoxidation:
a) Peroxydisulfate or persulfate (S2O82-) with Ag+ catalyst

Powerful oxidants

Oxidizes Mn2+, Ce3+, Cr3+, VO2+


excess S2O82- and Ag+ removed by boiling the solution
Redox Titrations
Common Redox Reagents

2.) Adjustment of Analyte Oxidation State


 Examples:
- Preoxidation:
b) Silver(II) oxide (AgO) in concentrated mineral acids also yields Ag2+
excess removed by boiling
c) Hydrogen peroxide (H2O2) is a good oxidant to use in basic solutions
Oxidizes Co2+, Fe2+, Mn2+
Reduces Cr2O72-, MnO4-
excess removed by boiling

- Prereduction:
a) Stannous chloride (SnCl2) in hot HCl
Reduce Fe3+ to Fe2+
excess removed by adding HgCl2
b) Jones reductor (Zn + Zn amalgam – anything in mercury)
Redox Titrations
Common Redox Reagents

3.) Common Titrants for Oxidation Reactions


 Potassium Permanganate (KMnO4)
- Strong oxidant
- Own indicator

pH ≤ 1
Titration of VO2+ with KMnO4
Eo = 1.507 V
Violet colorless

pH neutral or alkaline
Eo = 1.692 V
Violet brown
Before Near After pH strolngly alkaline
Equivalence point
Eo = 0.56 V
Violet green
Redox Titrations
Common Redox Reagents

3.) Common Titrants for Oxidation Reactions


 Potassium Permanganate (KMnO4)
- Application of KMnO4 in Redox Titrations
Redox Titrations
Common Redox Reagents

3.) Common Titrants for Oxidation Reactions


 Cerium (IV) (Ce4+)
- Commonly used in place of KMnO4
- Works best in acidic solution
- Can be used in most applications in previous table
- Used to analyze some organic compounds
- Color change not distinct to be its own indicator

Yellow colorless

Ce4+ binds anions very strongly results in variation of formal potential

1.70V in 1 F HClO4
Formal potential 1.61V in 1 F HNO3 Measure activity
1.47V in 1 F HCl not concentration
1.44V in 1 F H2SO4
Redox Titrations
Common Redox Reagents

3.) Common Titrants for Oxidation Reactions


 Potassium Dichromate (K2Cr2O7)
- Powerful oxidant in strong acid
- Not as Strong as KMnO4 or Ce4+
- Primarily used for the determination of Fe2+
- Not an oxidant in basic solution
- Color change not distinct to be its own indicator

Eo = 1.36 V
orange green to violet
Redox Titrations
Common Redox Reagents

3.) Common Titrants for Oxidation Reactions


 Iodine (Solution of I2 + I-)
- I3- is actual species used in titrations with iodine

K = 7 x 102

- Either starch of Sodium Thiosulfate (Na2S2O3) are used as indicator

I3- + Starch
I3- I3- + S2O32-

Before Before At
endpoint endpoint endpoint
Redox Titrations
Common Redox Reagents

3.) Common Titrants for Oxidation Reactions


 Iodine (Solution of I2 + I-)
- Application of Iodine in Redox Titrations
Redox Titrations
Common Redox Reagents

3.) Common Titrants for Oxidation Reactions


 Iodine (Solution of I2 + I-)
- Application for Redox Titrations that Produce I3-
Redox Titrations
Common Redox Reagents

3.) Common Titrants for Oxidation Reactions


 Periodic Acid (HIO4)
- Commonly used in titration of organic compounds (especially carbohydrates)

4.) Titrations with Reducing Agents


 Not as common as titrations using oxidizing agents
- Available titrants are not very stable in the presence of atmospheric O2

 Reagents can be generated directly in solution by means of chemical or


electrochemical reactions
Redox Titrations
Common Redox Reagents

5.) 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.

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