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Introduction
Measurement of redox
potentials permit detailed
analysis of complex
enzyme mechanism
K ≈ 1016
Eo = 1.70 V
Redox Titrations
Shape of a Redox Titration Curve
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
[ 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
[Fe3+] is unknown
If [Fe3+] = 0, Voltage = -∞
- Must be some Fe3+ from impurity
or Fe2+ oxidation
Eo = -0.828 V
Redox Titrations
Shape of a Redox Titration Curve
[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
From Reaction:
- [Ce3+] = [Fe3+]
- [Ce4+] = [Fe2+]
[ 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
[ 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
[ 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
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
2/3 height
Redox Titrations
Finding the End Point
0.05916
E Eo volts
n
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
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
1.) Starch
Commonly used as an indicator in redox titrations involving iodine
Repeating unit
Redox Titrations
Common Redox Reagents
Examples:
- Preoxidation:
a) Peroxydisulfate or persulfate (S2O82-) with Ag+ catalyst
Powerful oxidants
- 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
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
Yellow colorless
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
Eo = 1.36 V
orange green to violet
Redox Titrations
Common Redox Reagents
K = 7 x 102
I3- + Starch
I3- I3- + S2O32-
Before Before At
endpoint endpoint endpoint
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.