Analytical Chemistry

Lecture 5
Electrochemistry-Redox Titration

Instructor: Nguyen Thao Trang

Basic concepts of electrochemistry
• Redox reaction : reactions with electron transfer
– oxidized : loses electrons

– reduced : gains electrons

– oxidizing agent (oxidant) : takes electrons from others and becomes

reduced

– reducing agent (reductant) : gives electrons to another substance and

is oxidized

– Example

Fe3+ is an oxidizing agent as: Fe3+ + e- à Fe2+

V2+ is an reducing agent as: V2+ à V3+ + e-

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Basic concepts of electrochemistry
• Redox reaction :
– Half reactions: A common approach for listing species that undergo
REDOX is by using half reactions.

Reduction: Fe3+ + e- à Fe2+

Oxidation: V2+ à V3+ + e-

à Redox reaction is the product of two half reactions

– Each half reaction is associated with a standard reduction potential,
Eo’
Box + e- → Bred , Eo’
Ared → Aox + e-, Eo’

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Basic concepts of electrochemistry
• Redox reaction :
– Listed half reactions with standard reduction potential:

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Basic concepts of electrochemistry
• Redox reaction :
– Example: Determine the balanced equation for the reaction of Fe2+
with Cr2O72- in an acidic solution.
– Solution:
• From the standard reduction potentials, we can get:
Fe3+ + e- = Fe2+ (1)
Cr2O72- + 14H+ + 6e- = 2Cr3+ + 7H2O (2)
• We know that one of the half reactions must be reversed since oxidation
and reduction reactions must both occur
• Based on the question, Fe2+ must undergo oxidation reaction:
à reverse reaction (1): Fe2+ = Fe3+ + e-
– To balance the equation, the number of electrons in both equation must be
the same à multiply (1 ) by 6:
6 x (1): 6Fe2+ = 6Fe3+ + 6e-
+ (2): Cr2O72- + 14H+ + 6e- = 2Cr3+ + 7H2O
6Fe2+ + Cr2O72- + 14H+ = 6Fe3+ + 2Cr3+ + 7H2O

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Basic concepts of electrochemistry
• Electric charge q:
– Is measured in [coulomb] or [C]

– Magnitude of the charge of a single electron = 1.602 x 10-19 C

– A mole of electrons has a charge of (1.602 x 10-19 C) x (6.022 x 1023

mol-1) = 9.649 x 104 C/mol, which is called the Faraday constant (F)

– Relationship between charge and moles:

where n is the number moles of electrons transferred.

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Basic concepts of electrochemistry
• Electric charge q:

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Basic concepts of electrochemistry
• Electric current:
– The quantity of charge flowing each second through a circuit is called
the current.
– The unit of current is the ampere, abbreviated A.
– A current of 1 A represents a charge of 1 C per second flowing past a
point in a circuit.

FIGURE 13-1 Electrons flowing into a

coil of Pt wire at which Sn4+ ions in
solution are reduced to Sn2+.

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Basic concepts of electrochemistry
• Voltage, work, free energy:
– Difference in electric potential, E (measured by volt) between two
points is the work needed when moving an electric charge from one
point to the other:

– Work: Energy in joules

• one joule of energy = one coulomb of charge is moved between points
whose potential differ by one volt.

– Example: How much work is required to move 2.36 mmol of electrons

through a potential difference of 1.05 V ? 2.39 x 102 J
– Free energy change ΔG:
Work done on surroundings = - ΔG
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à ΔG = - E.q = - nEF
Basic concepts of electrochemistry
• Types of electrochemical cell:
1. Galvanic cell (Voltaic):
A cell generates electrical energy from a spontaneous
chemical reaction.

2. Electrolytic cell:
Is where non-spontaneous redox reactions can be made to
occur by the addition of electrical energy (process is termed
electrolysis).

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Basic concepts of electrochemistry
• Common components of a electrochemical cell
– Electrodes: conduct electricity between cell and
surroundings
• Anode: oxidation occurs
• Cathode: reduction occurs

– Electrolytes: mixture of ions involved in reaction or

carrying charge

– Salt bridge: completes circuit (provides charge balance)

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Basic concepts of electrochemistry
• Galvanic cell:
– A simple Galvanic cell: 2 electrodes in a solution of CdCl2:
One electrode is cadmium; the other is metallic silver
coated with solid AgCl.
Anode: Cd (s) ↔ Cd2+(aq) + 2e-
Cathode: 2AgCl (s) + 2e- ↔ 2Ag(s) + 2Cl-(aq)

Cd (s) + 2AgCl (s) ↔ Cd2+(aq) + 2Ag(s) + 2Cl-(aq)

ΔG = -150 kJ/mol Cd

à Oxidation of Cd electrode provides

electrons that flow through the circuit to
the Ag electrode.

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Basic concepts of electrochemistry
• Galvanic cell:
– A simple Galvanic cell: 2 electrodes Cd and Ag in a solution
of Cd(NO3)2 and AgNO3 :

Not really
work!

A little current flows through the circuit as Ag

can react at the Cd electrode.

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Basic concepts of electrochemistry
• Galvanic cell: separation of two half reactions by the
use of a salt bridge

Porous glass disks that allow ions

to diffuse but minimize mixing of
solutions inside and outside the
bridge.

Ions migrate in and out to offset

the charge buildup

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Basic concepts of electrochemistry
• Cell notation: line diagram is used to describe
electrochemical cells

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Standard reduction potential
• Standard reduction potential, Eo’ for each half is measured
using the standard hydrogen electrode (S.H.E.)
• Example: Ag+(aq) + e- ↔ Ag (s); Eo’=0.799 V
à Set the potential of the S.H.E. at 25oC = 0
à A standard reduction potential is really a potential difference between the
potential of the reaction of interest and the potential of S.H.E (set to 0)

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Standard reduction potential
• A positive standard reduction potential means electron flows
from the S.H.E.

– Example: Ag+(aq) + e- ↔ Ag (s); Eo’=0.799 V : e- flow from the Pt

electrode to the Ag electrode

• A negative standard reduction potential means electron flows

to the S.H.E.

– Example: Cd2+(aq) + 2e- ↔ Cd (s); Eo’= -0.402 V : e- flow from the Cd

electrode to the Pt electrode

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Cell potential
• Cell potential Ecell: is the potential difference between two
electrodes of the cell.

• Cell potential is related to free energy of the reaction:

∆𝐺 = −𝑛𝐹𝐸()**

At standard condition:

∆𝐺+ = −𝑛𝐹𝐸+ ()** = −𝑅𝑇𝑙𝑛𝐾)0

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Cell potential
• The signs of the electrodes are assigned as a Galvanic cell is
developed
∆𝐺 = −𝑛𝐹𝐸()** < 0
à 𝐸()** > 0

• Cell potential Ecell: is the potential difference between two

electrodes of the cell.

𝐸()** = 𝐸12345 (8) − 𝐸*):5(;)

à𝐸12345 (8) > 𝐸*):5(;)
(+) cathode: reduction

(-) anode: oxidation

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Cell potential
• Example:

Left (-) Right (+)

Cathode (+): Ag+ (aq) +e- ↔ Ag(s); Eo = 0.799 (V)

Anode (-): Cu (s) ↔ Cu2+ (aq) + 2e- ; Eo = 0.399 (V)

Overall reaction: 2 Ag+ (aq) + Cu (s) ↔ 2 Ag(s) + Cu2+ (aq)

à Measured 𝐸()** = 0.400 V

à Reaction is spontaneous!

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Cell potential
• Example:

Left (-) Right (+)

Cathode (+): Cu2+ (aq) + 2e- ↔ Cu(s); Eo = 0.399 (V)

Anode (-): Ag (s) ↔ Ag+ (aq) + e- ; Eo = 0.799 (V)

Overall reaction: 2 Ag (s) + Cu2+ (aq) ↔ 2 Ag+(aq) + Cu (aq)

à Measured 𝐸()** = - 0.400 V

à Reaction is not spontaneous!

However, 2 Ag+ (aq) + Cu (s) ↔ 2 Ag(s) + Cu2+ (aq) is always

spontaneous no matter how the cell diagram is written!

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Nernst equation for half reaction
• Consider the half reaction:

– The electrode potential:

Solute A à [A] = molar
concentration
At T (K)
Gas Aà [A] = pA partial
pressure
At 298 (K) Pure liquid, solid, or solvent,
no term for A

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Nernst equation for half reaction

• Multiply a half reaction by a number:

– Eo does not change
– n and the log term do change

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Nernst equation for a complete reaction
• For a complete reaction:

𝐸 = 𝐸()** = 𝐸 (8) − 𝐸 (;)

Potential of the electrode Potential of the electrode

attached to the + of the voltmeter attached to the - of the voltmeter

• Procedure for writing a net cell reaction and finding its

potential:
– Write reduction half-reactions for both half-cells, look up for Eo values,
then balance the number of electron in both reactions.
– Write the Nernst equation for the right half cell, E(+), for the left half
cell E(-).
– Calculate Ecell
– Write the net cell reaction by subtracting the left half-reaction from
the right half one. 24
Nernst equation for a complete reaction

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Reference electrode
• Set up a Galvanic cell to measure the relative amount of
Fe2+/Fe3+
Half reactions is written as reductions:

Nernst equations for half reactions:

Cell potential:

The half-cell on the left acts

as a reference electrode à
Depends on [Fe2+]/[Fe3+] fixed
provides a constant
potential to the left side of
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the potentiometer.
Reference electrode
• Set up a Galvanic cell to measure the relative amount of
Fe2+/Fe3+

Indicator
electrode

The Pt wire is the indicator electrode, whose

potential responds to [Fe2+]/[Fe3+].
The half-cell on the left
acts as a reference
à Inert metals used as indicator electrodes
electrode.

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Reference electrode
• A standard hydrogen electrode is difficult to use because H2
gas and a freshly prepared catalytic Pt surface are required.
• Common reference electrodes:
Ag/AgCl (Silver-silver chloride) Calomel electrode

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Reference electrode
• Voltage conversions between different reference scales
• Example:
– If an electrode (A) has a potential of - 0.461 V with respect to a S.C.E,
what is the potential with respect to S.H.E electrode? If B, whose
potential is 0.033 V from silver-silver chloride

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Redox titration
• A redox titration is based on an oxidation-reduction reaction
between analyte and titrant.

• A titrant is commonly an oxidizing agent.

• This section will focus on:

– Equilibrium and titration calculation.

– Indicators and common titrants.

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Redox titration
• Consider the titration of iron(II) with standard cerium(IV),
monitored potentiometrically with Pt and calomel electrodes:
– Titration reaction:

- At the Pt electrode, 2 half

reactions:
(1)
(2)

(The potentials show above is in 1 M

HClO4 solution)

- How the cell voltage changes as Fe2+ is

titrated with Ce4+. The titration curve has
three regions: before, at and after the
equivalence points
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• Before equivalence point: assuming all added Ce4+
reacts with Fe2+:
– Cell potential E = E+ - E-
• At anode (-), Calomel reference electrode, Eo = 0.241 V
• E = ECe4+/Ce2+ - 0.241; or E = EFe3+/Fe2+ - 0.241

• nFe3+ produced = nCe4+ reacted

• nFe2+ remained = nFe2+ initial – nCe4+ reacted
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Redox titration
• Before equivalence point: when Vtitrant added = 0.5 Vequivalence = 0.5 Ve
– Cell potential is given by: 𝐸 = 𝐸8 − 𝐸;
At anode (-) : calomel reference electrode, Eo = 0.241 V
𝐸 = 𝐸<) => /<) @> − 𝐸(A*+B)*
Or 𝐸 = 𝐸C) D> /C) @> − 𝐸(A*+B)*

𝑛 C) D> E1+FG()F = 𝑛 C)@> 1)BA2H)F

à 𝐸C) D> /C) @> = 𝐸+

– The point at which Vtitrant added = 0.5 Ve is analogous to the point at

which pH = pKa in an acid-base titration.

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Redox titration
• At equivalence point: all added Ce4+ reacts with all Fe2+.
(1)
𝑛 C) D> E1+FG()F = 𝑛 <) D> E1+FG()F
– Fe3+ can react with Ce3+ to produce Fe2+ and Ce4+:
(2)
𝑛 C)@> = 𝑛 <) =>
– At any time, reactions (1) and (2) are both in equilibrium at the Pt
electrode. At the equivalence point, it is convenient to use both
reactions to describe the cell voltage:

– Cell potential:
independent of the concentrations and
volumes of the reactants. 34
Redox titration
• After equivalence point: assuming all Fe2+reacts with added
Ce4+ and Ce4+ is in excess.
– Cell potential is given by: 𝐸 = 𝐸8 − 𝐸;
At anode (-) : calomel reference electrode, Eo = 0.241 V
𝐸 = 𝐸<) => /<) @> − 𝐸(A*+B)*
Or 𝐸 = 𝐸C) D> /C) @> − 𝐸(A*+B)*

Where 𝑛 <) D> E1+FG()F = 𝑛 C) @> 1)A(5)F

𝑛 <) => 1)BA2H)F = 𝑛 <) => 2H252A* − 𝑛 C) @> 1)A(5)F

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Redox titration
• After equivalence point: when Vtitrant added = 2 Ve
– Cell potential is given by: 𝐸 = 𝐸8 − 𝐸;
At anode (-) : calomel reference electrode, Eo = 0.241 V
𝐸 = 𝐸<) => /<) @> − 𝐸(A*+B)*
Or 𝐸 = 𝐸C) D> /C) @> − 𝐸(A*+B)*

𝑛 <) D> E1+FG()F = 𝑛 <) => 1)BA2H)F

à 𝐸<) =>/<)D> = 𝐸 ++

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Shape of a redox titration curve

• Plot of cell potential as a function of volume of

titrant added à titration curve.
• The equivalence point is marked by a steep rise
in voltage.
• The voltage at any point in this titration depends
only on the ratio of reactants à independent on
dilution.
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Shape of a redox titration curve
• The greater the difference in reduction potential between analyte and
titrant, the sharper will be the end point.

• The voltage at any point in this titration depends only on the ratio of
reactants; it will be independent of dilution.

• Prior to the equivalence point, the half-reaction involving analyte is used

to find the voltage because the concentrations of both the oxidized and
the reduced forms of analyte are known.

• After the equivalence point, the half-reaction involving titrant is

employed.

• At the equivalence point, both half-reactions are used simultaneously to

find the voltage.

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Finding the end point
• Gran Plot: uses data from well before the equivalence point
(Ve) to locate Ve.
– For the oxidation of Fe2+ to Fe3+, the potential prior to Ve is

(1)

- If the volume of titrant is V and if the reaction

goes “to completion” with each addition of
titrant:

(2)

- Substitution of (2) into (1):

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Finding the end point
• Redox indicator:
– A redox indicator is a compound that changes color when it goes from
its oxidized to its reduced state.

– Example:

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Finding the end point
• Redox indicator:
– As with acid-base indicators, the color of In(reduced) will be observed
when

– The color of In(oxidized) will be observed when:

– The color change will be observed in the range:

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Finding the end point
• Redox indicator:

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Finding the end point
• Redox indicator:
– Example: Ferroin, with E 1.147 V (Table 15-2) à color change to occur
in the 1.088 V to 1.206 V with respect to the standard hydrogen
electrode (S.H.E.)

– What is the range of voltage for ferroin to change the color with
respect to the standard calomel electrode (S.C.E.)?

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Starch-iodine complex
• Starch is used as an indicator in numerous analytical
procedures are based on redox titrations involving iodine as it
forms an intense blue complex with iodine.

http://iweb.tntech.edu/mcaprio/equipment.htm

• Starch is not a redox indicator

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Oxidation with potassium permanganate
• KMnO4 is a strong oxidant with an intense violet color.
– In strongly acidic solutions (pH < 1), it is reduced to Mn2+.

– In neutral or alkaline solution, it is reduced to brown solid MnO2.

– In strong alkaline solution (2 M NaOH), green manganate ion is

produced.

• Potassium permanganate is not a primary standard.

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Oxidation with potassium permanganate

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Oxidation with Ce4+
• Reduction of Ce4+ to Ce3+ proceeds cleanly in acidic solutions:

yellow colorless

• Color change is not distinct enough for cerium to be its own

indicator. Ferroin and other substituted phenanthroline redox
indicators are well suited to titrations with Ce4+.

• Ce4+ can be used in place of KMnO4 in most procedures:

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Oxidation with potassium dichromate K2Cr2O7
• In acidic solution, orange dichromate ion is a powerful oxidant
that is reduced to chromic ion:

Orange Green-violet

– In 1 M HCl, ECr2O72-|Cr3+ = 1.00 V and in 2 M H2SO4, ECr2O72-|Cr3+ = 1.11 V;

à dichromate is a less powerful oxidizing agent than MnO4- or Ce4+.

• K2Cr2O7 is a primary standard as its solutions are stable, and

cheap.

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Methods involving iodine
• Iodimetry: titration with iodine I2 to produce I-.
• Solubility of iodine in water (1.3× 10-3 M at 20oC) is enhanced
by complexation with iodide:

à When using iodine as a titrant à using a solution of I2 plus

excess I- (standard triiodide I3-).

• Iodine is a weak oxidizing agent used primarily for the

determination of strong reductant.

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Methods involving iodine
• Reducing agents can be titrated directly with standard I3-:

• Determination of the endpoint with starch:

– Starch can be added at the beginning of the titration.
– The first drop of excess I3- after the equivalence point causes the
solution to turn dark blue.

• Example: titration of vitamin C

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Methods involving iodine
• Iodometry: an oxidizing analyte is added to excess I- to
produce iodine, which is then titrated with standard
thiosulfate solution (S2O32-).

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Methods involving iodine
• Reducing agents can be titrated directly with standard I3-:

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Methods involving iodine
• Iodometry:
– In iodometry, triiodide produced by a chemical reaction (strong
oxidizing agent with excess I-) is titrated by standard thiosulfate S2O32-
solution at pH < 9.

(S4O62-)

– Thiosulfate is oxidized to tetrathionate by the half reaction:

– The endpoint is determined by adding starch just right before the

endpoint (fading the deep blue color). If not some iodine tends to
remain bound to starch particles after the equivalence point is
reached.
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