Redox Titration Curves Oxidation/reduction chemistry can be used to determine the unknown concentrations of many analytes of interest via

titration. As with acid-base titration, the objective is to identify the quantity of a standard solution needed to reach the equivalence point. In acid-base titrations we think of titration curves in terms of pH or pOH versus the concentration of standard. In redox titrations we think of titration curves in terms of cell potential versus the concentration of the standard. The equivalence point in a redox titration can be identified with a redox indicator or via an electrical measurement, such as the potential of the solution. With the Nernst equation, we can predict the shape of a redox titration curve We will use the following reaction to illustrate: Fe2+ + Ce4+ Fe3+ + Ce3+

Fe2+ + Ce4+

Fe3+ + Ce3+

Note: reagent is Ce(NO3)42NH4NO3, a primary standard often used in redox titrations Acidic solutions are used to avoid hydrolysis involving Ce(IV) to yield Ce(OH)x4-x species (which have different reduction potentials). Ce4+ + e- Ce3+ Ce4+ + e- Ce3+ Ce4+ + e- Ce3+ E=1.44 V in 1M H2SO4 E=1.61 V in 1M HNO3 E=1.70 V in 1M HClO4

Why different E values for different acids? They also change with acid concentration. Why different E for different acid concentrations? Ce4+ is actually present in solution associated with the various anions, e.g. Ce(ClO4)3+, Ce(NO3)22+, Ce(SO4)2+, etc. Reduction potential depends upon solvation structure. Furthermore, these anions associate with CeIV more than CeIII. Differential degrees of association are therefore anion and anion concentration dependent.

Fe3+ + e- Fe2+ Fe3+ + e- Fe2+ Fe3+ + e- Fe2+

E=0.68 V in 1M H2SO4 E=0.70 V in 1M HCl E=0.732 V in 1M HClO4

Reduction potentials for iron(III) vary with acid and acid concentration for the same reasons cerium (IV) does. Fe2+ + Ce4+ Fe3+ + Ce3+

How might we write the shorthand notation for a hypothetical cell relevant to this reaction? SHE || Ce4+, Ce3+, Fe3+, Fe2+ | Pt Note that we could actually make this cell by using a standard hydrogen electrode to serve as a reference and a platinum electrode to measure the solution potential relative to the SHE. In fact, this is one way to follow the progress of the titration (potentiometry). However, we do not need to use any electrodes to perform a redox titration provided we have an alternate means for identifying the equivalence point, such as a redox indicator.

Nernst equations for the reduction potentials:

ECe = E
Ce 4+ / Ce 3+

Ce 3+ 0.0592 log n Ce 4 + , n = 1

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0.0592 Ce 3+ ECe = 1.44 log 1 Ce 4 + in 1M H2SO4

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EFe = EFe 3+ / Fe 2+

Fe 2 + 0.0592 log Fe3+ , n=1 1

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Fe 2 + 0.0592 EFe = 0.68 log Fe 3+ , in 1M H2SO4 1

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Which electrode potential reflects the potential of the solution (i.e., the system)? Both are equal to Esystem if equilibrium is established: EFe = ECe = Esystem = EIn (Note that if a redox indicator is present, EIn will also assume the potential of the system. If it is present at very low concentration, it will have a minimal effect on the value of Esystem).

Esystem can be determined by calculating either ECe or EFe. It is more convenient to use one or the other, depending upon conditions. Points in the redox titration: 1. 2. 3. 4. Before titration. Prior to the equivalence point At the equivalence point After the equivalence point

Example: 50.00 mL solution of 0.100 M Fe2+ with 0.100 M Ce4+ in 1 M H2SO4 1. Before titration: no Ce4+ added, very little Fe3+ present and its concentration is likely to be unknown:
Fe 2 + 0.0592 EFe = 0.68 log Fe3+ 1 [ 0.0592 0.1M ] log EFe = 0.68 [??] , insufficient info 1

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If we know [Fe3+], say its 10-8 M, we can determine Esystem: [0.1] 0.0592 EFe = 0.68 log 8 = 0.27V 1 10

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2. Prior to the equivalence point: When Ce4+ is added, it is essentially completely consumed by reaction with Fe2+ and its concentration is not accurately known. Therefore, it is more convenient to calculate Esystem via the Fe2+/Fe3+ couple: 1% reaction addition of 0.5 mL, 0.1 M Ce4+ solution [Fe2+] = (5x10-3 mole 5x10-5 mole)/50.5 mL = 9.8x10-2 M [Fe3+] = 5x10-5 mole/50.5 mL = 9.9x10-4 M
0.0592 9.8 x10 2 EFe = 0.68 log = 0.56V 4 1 9.9 x10

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10% reaction addition of 5.0 mL, 0.1 M Ce4+: [Fe2+] = (4.5x10-3 mole)/55.0 mL = 8.2x10-2 M [Fe3+] = (5x10-4 mole)/55.0 mL = 9.1x10-3 M
0.0592 8.2 x10 2 EFe = 0.68 log = 0.62V 3 1 9.1x10

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50% reaction addition of 25.0 mL of 0.1 M Ce4+: [Fe2+] = (2.5x10-3 mole)/75.0 mL = 3.3x10-3 M [Fe3+] = (2.5x10-3 mole)/75.0 mL = 3.3x10-3 M
0.0592 3.3 x10 3 EFe = 0.68 log = 0.68V 3 3.3 x10 1

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90% reaction addition of 45.0 mL of 0.1 M Ce4+: [Fe2+] = (5x10-4 mole)/95.0 mL = 5.26x10-3 M [Fe3+] = (4.5x10-3 mole)/95.0 mL = 4.7x10-2 M

0.0592 5.26x103 EFe = 0.68 log = 0.74V 2 1 4.7 x10

at 99%, 0.798 V at 99.9%, 0.857 V

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3. At the equivalence point: At the equivalence point, [Ce3+] = [Fe3+] and [Ce4+] = [Fe2+] Esystem = EFe = ECe Add the two Nernst equations (after multiplying by n):
o nCe ECe = nCe ECe

o nFe E Fe = nFe E Fe

[Ce 0.0592 log [Ce [Fe 0.0592 log [Fe

o Ce

3+ 4+ 2+ 3+

] ] ] ] [ Ce ][Fe ] 0.0592 log [Ce ][Fe ]

3+ 2+ 3+ 4+

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(nCe + nFe )E system = nCe E

at the equivalence point,
3+ 2+ 3+ 4+

+ n Fe E

o Fe

[Ce ][Fe ] = log1 = 0 log [Ce ][Fe ]

o o nCe ECe + n Fe E Fe 1x1.44 + 1x0.68 = = = 1.06V (nCe + nFe ) 1+1

Hence,

E system

4. After the equivalence point: Beyond the equivalence point, Fe2+ has been essentially completely converted to Fe3+. Additional Ce4+ has no Fe2+ with which to react, hence it is straightforward to calculate Esystem from the concentrations of Ce3+ and Ce4+. It is much more difficult to attempt to do so with the Fe2+/Fe3+ couple because of the very low and unknown concentration of Fe2+: 1% beyond equivalence point: 5x10-3 mole Ce3+, 5x10-5 mole Ce4+
Ce 3+ 0.0592 ECe = E log n Ce 4 + 0.0592 100 = 1.322V log ECe = 1.44 1 1
Ce 4+ / Ce 3+

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10% beyond equivalence point:

0.0592 10 log = 1.381V ECe = 1.44 1 1 100% beyond equivalence point: 0.0592 1 ECe = 1.44 log = 1.44V 1 1