Fundamentals to

Analytical Chemistry
Chapter 12
Electrode Potentials and Their
Applications to Oxidation/
Reduction Titrations

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 12A Calculating Potentials Of
Electrochemical Cells

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 Example 12-1
• Calculate the thermodynamic potential of the
following cell and the free energy change
associated with the cell reaction.

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 Example 12-1

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 Example 12-4
• Calculate the cell potential for

• Note that this cell does not require two

compartments (nor a salt bridge) because molecular
H2 has little tendency to react directly with the low
concentration of Ag in the electrolyte solution.

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 Example 12-4

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 Example 12-4
• The negative sign indicates that the cell
reaction as considered,

is nonspontaneous.

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 12B Calculating Redox Equilibrium
Constants

• at chemical equilibrium, we may write

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 12B Calculating Redox Equilibrium
Constants

• Rearrangement of Equation 12-7 gives

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 12B Calculating Redox Equilibrium
Constants

• At 25°C

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 Example 12-5
• Calculate the equilibrium constant for the
reaction shown in Equation 12-4. Substituting
numerical values into Equation 12-8 yields

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 12C-1 Electrode Potentials during
Redox Titrations
• Let us now consider the redox titration of
iron(II) with a standard solution of cerium(IV).

• This reaction is rapid and reversible so that

the system is at equilibrium at all times
throughout the titration.

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 12C-1 Electrode Potentials during
Redox Titrations
• If a redox indicator has been added to this solution,
the ratio of the concentrations of its oxidized and
reduced forms must adjust so that the electrode
potential for the indicator, EIn, is also equal to the
system potential.
• Because
data for a titration curve can be obtained by applying
the Nernst equation for either the cerium(IV) half-
reaction or the iron(III) half-reaction.

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 12C-1 Electrode Potentials during
Redox Titrations
• Equivalence-Point Potentials
• At the equivalence point in the titration of
iron(II) with cerium(IV), the potential of the
system Eeq is controlled by both half reactions:

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 12C-1 Electrode Potentials during
Redox Titrations

• The definition of equivalence point requires

that

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 12C-1 Electrode Potentials during
Redox Titrations

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 Example 12-8
• Obtain an expression for the equivalence-
point potential in the titration of 0.0500 M U⁴⁺
with 0.1000 M Ce⁴⁺. Assume that both
solutions are 1.0 M in H₂SO₄ .

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 Example 12-8

• To combine the log terms, we must multiply

the first equation by 2 to give

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 Example 12-8

• at equivalence

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 Example 12-8

• the equivalence-point potential for this

titration is pH-dependent.

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 12C-2 The Titration Curve
• Let us first consider the titration of 50.00 mL
of 0.0500 M Fe²⁺ with 0.1000 M Ce⁴⁺ in a
medium that is 1.0 M in H₂SO₄ at all times.

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 12C-2 The Titration Curve
• Initial Potential
− we lack sufficient information to calculate an initial
potential.
• Potential after the Addition of 5.00 mL of
Cerium(IV)

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 12C-2 The Titration Curve
• redox reactions used in titrimetry are
sufficiently complete
• Ce⁴⁺ is minuscule with respect to the other
species present in the solution.

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 12C-2 The Titration Curve
• Equivalence-Point Potential
− Substitution of the two formal potentials into
Equation 12-11 yields

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 12C-2 The Titration Curve
• Potential after the Addition of 25.10 mL of
Cerium(IV)

− the iron(II) concentration is negligible

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 Figure 12-3
Figure 12-3 Titration
curves for 0.1000 M Ce4
titration. A: Titration of
50.00 mL of 0.05000 M
Fe2. B: Titration of 50.00
mL of 0.02500 M U4.

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 12C-3 Effect of Variables on Redox
Titration Curves
• Reactant Concentration
− titration curves for oxidation/reduction reactions
are usually independent of analyte and reagent
concentrations.
• Completeness of the Reaction
− The change in the equivalence-point region of an
oxidation/reduction titration becomes larger as
the reaction becomes more complete.

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 Figure 12-6
Figure 12-6 Effect of titrant
electrode potential on
reaction completeness.
The standard electrode
potential for the analyte is
0.200 V; starting with curve
A, standard electrode
potentials for the titrant
are 1.20, 1.00, 0.80, 0.60,
and 0.40, respectively. Both
analyte and titrant undergo
a oneelectron change.

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 12D-1 General Redox Indicators
• General oxidation/reduction indicators are
substances that change color upon being
oxidized or reduced.

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 12D-1 General Redox Indicators
• a color change is seen when

• changes to

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 12D-1 General Redox Indicators
• The potential change required to produce the
full color change of a typical general indicator

• a typical general indicator exhibits a

detectable color change when a titrant causes
the system potential to shift from
to or about (0.118/n) V.

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 12D-1 General Redox Indicators
• Starch/Iodine Solutions
− A starch solution containing a little triiodide or
iodide ion can also function as a true redox
indicator.

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 12D-2 Specific Indicators
• the best-known specific indicator is starch,
which forms a dark blue complex with
triiodide ion as discusssed above. This
complex signals the end point in titrations in
which iodine is either produced or consumed.

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 12E Potentiometric End Points
• End points for many oxidiation/reduction
titrations are readily observed by making the
solution of the analyte part of the cell:

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 12F Auxiliary Oxidizing And Reducing
Reagents
• The analyte in an oxidation /reduction
titration must be in a single oxidation state at
the outset.
• when an iron-containing sample is dissolved
usually contains a mixture of iron(II) and
iron(III) ions.

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 12F Auxiliary Oxidizing And Reducing
Reagents
• We must first treat the sample solution with
an auxiliary reducing agent to convert all the
iron to iron(II).
• To be useful as a preoxidant or a
prereductant, a reagent must react
quantitatively with the analyte. In addition,
any reagent excess must be readily removable
because the excess reagent usually interferes
by reacting with the standard solution.

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 12F-1 Auxiliary Reducing Reagents
• A number of metals are good reducing agents
and have been used for the prereduction of
analytes. Included among these are zinc,
aluminum, cadmium, lead, nickel, copper, and
silver.

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 12F-2 Auxiliary Oxidizing Reagents
• Sodium Bismuthate
− Sodium bismuthate is a powerful oxidizing agent;
it is capable, for example, of converting
manganese(II) quantitatively to permanganate
ion.
− The half-reaction for the reduction of sodium
bismuthate can be written as

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 12F-2 Auxiliary Oxidizing Reagents
• Ammonium Peroxydisulfate
• Sodium Peroxide and Hydrogen Peroxide

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 12G-1 Iron(II) Solutions
• Numerous oxidizing agents are conveniently
determined by treatment of the analyte
solution with a measured excess of standard
iron(II) followed by immediate titration of the
excess with a standard solution of potassium
dichromate or cerium(IV)

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 12G-2 Sodium Thiosulfate
• The scheme used to determine oxidizing
agents involves adding an unmeasured excess
of potassium iodide to a slightly acidic solution
of the analyte. Reduction of the analyte
produces a stoichiometrically equivalent
amount of iodine. The liberated iodine is then
titrated with a standard solution of sodium
thiosulfate, Na₂S₂O₃.

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 12G-2 Sodium Thiosulfate

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 12H-1 The Strong Oxidants: Potassium
Permanganate and Cerium(IV)

• The formal potential shown for the reduction of cerium(IV) is

for solutions that are 1 M in sulfuric acid. In 1 M perchloric
acid and 1 M nitric acid, the potentials are 1.70 and 1.61 V,
respectively. Solutions of cerium(IV) in the latter two acids are
not very stable.
• The half-reaction shown for permanganate ion occurs only in
solutions that are 0.1 M or greater in strong acid.

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 12H-5 Determining Water with the
Karl Fischer Reagent
• determination of water in various types of
solids and organic liquids.

• end points are obtained by electroanalytical

measurements.

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 THE END

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