Electrochemistry and

Redox Titration
Dr. Cherrie Pascual
Institute of Chemistry
UP Diliman
IMPORTANT DISCLAIMER: THE MATERIALS HERE ARE
SOLELY FOR THE PURPOSE OF INSTRUCTION FOR CHEM
28 CLASSES OF DR. PASCUAL AT IC-UPD AND NOT
INTENDED TO BE REPRODUCED/COPIED FOR ANY
OTHER PURPOSE.
 ELECTROCHEMISTRY
redox reactions – involve transfer of e-s from 1
reactant to another

oxidation – loss of e-s; reduction-gain of e-s

oxidizing agent or oxidant (OA) – makes possible the

oxidation of the other reactant; e- acceptor
reduced

reducing agent or reductant – makes possible the

reduction of the other substance; e- donor
oxidized
REDOX REACTIONS
Ox1 + Red2 Red1 + Ox2
e.g. Ce4+ + Fe2+ Ce3+ + Fe3+
(OA) (RA)
half-rxns: Ce4+ + e- Ce3+ (redn. of Ce4+)
Fe2+ Fe3+ + e- (oxidn. of Fe2+)

Generalized Eqn. for Redox Rxn:

Ared + Box Aox + Bred
Box + ne Bred
Ared Aox + n2e assume: n1 = n2
Ared + Box Aox + Bred
 REDOX REACTIONS
e.g. rxn. bet. MnO4- & Fe2+
MnO4- + 8 H+ + 5 e- Mn2+ + 4 H2O
5 Fe2+ 5 Fe3+ + 5 e-
MnO4- + 5 Fe2+ + 8 H+ Mn2+ + 5 Fe3+ + 4 H2O

Redox rxns. usually carried out in an electrochemical cell

in w/c reactants (OA & RA) not in direct contact with 1
another

2 half-cells w/ salt bridge for electrical contact

Electrochemical cell – consists of 2 conductors
called electrodes each of which is immersed in an
electrolyte soln.

∙ cathode – electrode where reduction occurs

∙ anode – electrode where oxidation occurs

electrodes can be metal electrodes directly

involved in reaction or an inert electrode like Pt
 REDOX REACTIONS
e.g. cathodic rxns:
Ag+ + e- Ag(s)
NO3- + 10 H+ + 8 e- NH4+ + 3 H2O
2 H+ + 2 e- H2(g) → when aq. soln. w/ no easily
reduced species

e.g. anodic rxns:

Cu(s) Cu2+ + 2 e-
Fe2+ Fe3+ + e-
2 H2O O2(g) + 4 H+ + 4 e- → when aq. soln. w/ no easily
oxidized species
Types of Electrochemical Cells
1) galvanic or voltaic cell – w/ spontaneous redox
rxn.
2) electrolytic cell – w/ nonspontaneous redox
rxn. and requires an external source of electrical
energy for operation
Schematic Representation of Cells:
• short hand notation to describe electrochem. cells
• basic rules:
1) anode listed on the left and cathode on the right
2) single vertical lines – indicates a phase boundary
3) double vertical lines – represents 2 phase boundaries,
one at each end of salt bridge
e.g. Cu | Cu2+ (0.0200 M) || Ag+ (0.0200 M) | Ag
or CuSO4 or AgNO3
cell – a galvanic cell; Ecell = +0.412 V
e-s flow fr. anode to cathode

If some cell connected to a battery (Ebat > 0.412 V)

e- flow reversed; rxns. reversed → electrolytice cell
Write cell notation
Cu | Cu2+ (0.0200 M) || Ag+ (0.0200 M) | Ag
Fig 18-2b, p.495
if some cell connected to a battery (Ebat > 0.412 V)
e- flow reversed; rxns. reversed → electrolytice cell

Rxn. of 1st cell (galvanic): 2 Ag+ + Cu 2 Ag + Cu2+

Rxn. of 2nd cell (electrolytic): 2 Ag + Cu2+ 2 Ag+ + Cu

Reversible cell – cell in w/c direction of electrochem. rxn.

reversed when direction of current (e- flow) reversed

Irreversible cell – cell in w/c reversing the current causes an

entirely diff. half-rxn. to occur at 1 or both of the electrodes
Electrode Potentials
Cell potential – driving force for redox rxn. (diff. bet. 2
half-cell potentials)
∙ no way to det. absolute potentials of electrodes but
can readily det. relative electrode pots.

SHE – ultimate reference or universal reference electrode; a

gas electrode
Rxn: 2 H+ + 2 e- H2(g)
By convention: 0.000 V at all temps.; = 1.00, = 1.00 atm

SHE – reversible; can act either as an anode or cathode

depending upon electrode to w/c it is coupled
Electrode potential – potential of a cell that has SHE as the anode;
electrode in question acts as cathode
Standard electrode potential – electrode potential of a half-cell rxn.
when all the concentrations of reactants and products are unity
e.g. Pt, H2 (p = 1.00 atm) | H+ ( = 1.00) || Cu2+ (a = 1.00) | Cu
or SHE || Cu2+ ( = 1.00) | Cu
anode cathode
Egalvanic cell = + 0.337 V
Rxn: Cu2+ + H2(g) Cu(s) + 2 H+
Cathodic rxn: Cu2+ + 2 e- Cu(s) E° = +0.337 V
Zn electrode paired w/ SHE: E°cell = -0.763 V
Zn2+ + 2 e- Zn(s) = -0.763 V
IUPAC convention: electrode potential is reversed exclusively for
half-rxns. written as reductions (reduction potential)
sign of an electrode potential – actual sign of the half-cell or
electrode of interest when it is coupled w/ SHE
∙ each half-rxn. written as reduction
∙ sign of electrode potential will indicate whether the reduction is
spontaneous wrt SHE
e.g.
Ag+ + e Ag(s) = 0.799 V → rxn. spont. rxn. w/ SHE
2 Ag+ + H2(g) 2 Ag(s) + 2 H+ → rxn. spont.
Cd2+ + 2 e Cd(s) = -0.403 → not spont. rxn. w/ SHE
Cd2+ + H2(g) Cd(s) + 2 H+

reverse rxn. spont. when std. state conds.

The Nernst Equation (Effect of Concn. on Electrode
Potentials)
Consider the reversible half-rxn:
aA + bB + … + ne cC + dD + …

aX – represents activities of various species

E = pot. for given electrode process

E° = std. electrode pot.
R = gas const. = 8.314 JK-1 mol-1
T = absolute temp (K)
n = # moles e- that appear in half-rxn. for electrode process as
it has been written
F = Faraday const. = 96,485 C
at 25 °C:
The Nernst Equation

when species:
• X is a solute, aX ≈ [X]
• X is a gas, aX ≈ PX (atm)
• X is a pure liquid or pure solid or solvent: aX = 1.00 = 1.00
 Nernst Equation
• Effect of Concentration on Electrode Potentials
For the reversible half-reaction
aA + bB + ne  cC + dD

RT [C ] [ D] c d R = 8.314 J/K-mol
EE 
o
ln a b T in Kelvin
nF [ A] [ B] F = 96,485 C mol e-

c d
0.0592 [C ] [ D]
EE  o
log a b
at 25oC
n [ A] [ B]
Application of Nernst Eqn:

( )

+
E° – intensive property (independent of # moles reactant and
product shown in balanced half-rxn)

e.g. Zn2+ + 2 e- Zn(s) E° = -0.763 V

½ Zn2+ + e- ½ Zn(s) E° = -0.763 V

(+) electrode pot. – indicates spontaneous half-rxn. vs. SHE

(-) electode pot. – indicates non-spontaneous half-rxn. vs. SHE
Table of Std. Potentials – usually listed in decreasing numerical
order
w/ large (+) E° values: most effective e- acceptors strongest OAs
bottom list of table: w/ little tendency to take place; opposite rxn.
spontaneous; subst. on right – most effective RA

Limitations to use of E°:

∙ frequently marked diff. exist bet. calcd. & experimentally
measured potentials → due to activity effects and presence of
other equil. like complexation
∙ to compensate for this, formal pot. can be used in place of E°
FORMAL POTENTIAL – electrode pot. when the ratio of
analytical concns. of reactants and products are exactly 1.00
and the molar concn. of any other solutes are specified

e.g. Fe3+ + e- Fe2+ E° = + 0.771 V

E°’ in 1 M HCl = 0.700 V → stal. of Cl- complexes of Fe2+
vs Fe3+
E°’ in 1 M HClO4 = 0.732 V →

w/ use of E°‘ – better agreement bet. calcd. and exptal

potentials

Aox + ne Ared
(anal. concns. used)
Thermodynamic Potential of an Electrochemical Cell (Ecell):
Ecell = Ecathode - Eanode
where Ecathode & Eanode are electrode pots. of the cathode and
anode respectively

Sample problem: Calc. the thermodynamic pot. of ff. cell and

indicate whether it is galvanic or electrolytic:

Pt | UO22+ (0.0150 M), U4+ (0.200 M), H+ (0.0300 M) || Fe2+

(0.0100 M), Fe3+ (0.00250 M) | Pt

Answer: Ec = +0.7946 V; Ea = 0.1204 V

Ecell = Ec – Ea = +0.674 V

Galvanic cell
Calculation of Redox Equil. Constants
from Std. Potentials
∙ Consider 2 reactants Ared & Box producing Aox & Bred
2 electrode rxns: Box + be- Bred
Aox + ae- Ared
Balance # e-s:
cathode: aBox + abe- aBred
anode: bAox + abe- bAred (reverse rxn)
Balanced eqn:
aBox + bAred aBred + bAox
at equil: ΔG = 0; ΔG = -nFE
Ecell = 0 = Ecathode - Eanode
EB = EA
Example:
Given cell: Cu | Cu2+ (xM) || Ag+ (yM) | Ag’
Calc. Keq
Rxn: 2 Ag+ + Cu(s) 2 Ag(s) + Cu2+

Calc. Keq for rxn bet MnO4- & Fe2+

Ans. Keq = 4 × 1062
Redox Titration Curve
Other titration: plot pX vs. Vtitrant
Redox titration: electrode pot. for redox syst.
vs. Vtitrant
Indicators used: OA or RA that responds to changes in pot. of syst.
rather than changes in concn. of any particular reactant or
product

electrode potential for the system – equil. attained after each

addn. of titrant;
system at equil. at all times throughout the titration
Example: Redox titration of Fe(II) w/ std. soln. of Ce(IV)
Ce4+ + Fe2+ Ce3+ + Fe3+
at any pt. in the titration:

if with redox indicator also present:

concns. vary as titration proceeds Esystem also varies

Apply Nernst eqn. for either Ce(IV) or Fe(III) half-rxn.

Hypothetical cell for titration mixture:
SHE || Ce4+, Ce3+, Fe3+, Fe2+ | Pt
Calcn. of Esystem:

before equiv. pt. (w/ x’s analyte):

Esystem most directly evaluated for redox couple involving analyte

after equiv. pt. (w/ x’s titrant):

Esystem evaluated from redox couple involving the titrant
Derive the titration curve for titration of 50.00 ml 0.0500 M Fe2+
with 0.1000 M Ce4+ in 1.0 M H2SO4. Use formal potential data in
1.0 M H2SO4
Ce4+ + e- Ce3+ E°’ = +1.44 V
Fe3+ + e- Fe2+ E°’ = +0.68 V
1) Initial potential (No Ce ions in soln)

[Fe3+] – small but unknown; due to air oxidn. of Fe2+

No sufficient info. to calc. Einitial

2) Before equiv. pt. (e.g. = 5.00 ml)

at equiv. pt.: # mmoles Fe2+ = # mmoles Ce4+

50.00(0.0500) = 0.1000
= 25.00 ml

(2 redox systems mixed; allowed to react and reach equil)

use E°’
3) Equiv. pt. pot. (no x’s titrant nor analyte)

stoich. consideration at equiv. pt:

[Fe3+] = [Ce2+]
[Ce4+] = [Fe2+]

Add 2 eqns:
 For any redox rxn. in w/c # e-s gained by OA
= # e-s lost by RA:

Equil. concns. of reacting species can be readily calcd. fr. Eeq.

4) After equiv. pt. (e.g. V = 25.10 ml) w/x’s Ce4+
equiv. amts. of Fe3+ & Ce3+; [Fe2+] very small

use Ce4+ - Ce3+ pot:

Fig 19-4, p.545
0.1000 M titrant
curve A – symmetrical about equiv. pt. → w/ 1:1 molar ratio of
oxidant to reductant
curve B – not sym.
Curve B: U4+ + 2 Ce4+ UO22+ + 2 Ce3+ + 4 H+
Effect of Completeness of Rxn. on Redox Titrn.
Curves:
∙ the larger the Keq, the larger ΔE at eq. pt.
region

Effect of Concn. on Redox Titrn. Curves:

Titration curves independent of concn. of
reactants
(independent of dilution over considerable
range)
Types of Redox Indicators
1) General redox indicators – respond to pot. of syst.; subst.
that change color upon being oxidized or reduced
Δ color – depend only upon pot. of syst.
Inox + ne Inred

∙ color change when there’s a change in ratio of reactant

concns. of about 100

full color change when:

Choose indicator w/c would change color at or near eq. pt.
e.g. Ferroin (Phen)3Fe2+
Ph3Fe3+ + e- Ph3Fe2+ E° = +1.06 V
(ferriin) (ferroin)
blue red
2) Specific indicator – reacts in a specific manner with one of
the reactants in titrn. to produce a color
e.g. starch forms a dark blue complex w/ I3- (endpt in titrns. in
w/c I2 is produced or consumed)
or KSCN – complexes w/ Fe3+
REDOX TITRATIONS
∙ redox rxns. widely used in titrimetric analysis
∙ analyte can be present in the sample in more than 1 oxidn.
state and must be converted to a single oxidn. state
prior to its titrn.
∙ auxiliary OA (e.g. H2O2) or RA (metals & amalgams like Zn,
Cd, Hg) added to accomplish this
STANDARD OXIDANTS
Reagent Redn. Product Std. Pot (V) 1° Std. Used
KMnO4 Mn2+ 1.51 Na2C2O4, Fe, As2O3
KBrO3 Br- 1.44 KBrO3
Ce4+ Ce3+ 1.44 Na2C2O4, Fe, As2O3
K2Cr2O7 Cr3+ 1.33 K2Cr2O7, Fe
I2 I- 0.536 BaS2O3∙H2O; Na2S2O3
KMnO4 – most widely used of all std. OAs; readily available,
inexpensive; reqs. no indicator
MnO4- + 8 H+ + 5 e- Mn2+ + 4 H2O E° = +1.51 V
1° std. – Na2C2O4

in acidic soln: H2C2O4 2 CO2(g) + 2 H+ + 2 e- E°ox = +0.48 V

Rxn. w/ KMnO4:
2 MnO4- + 5 H2C2O4 + 6 H+ 2 Mn2+ + 10 CO2(g) + 8 H2O

Ce4+ in H2SO4 – powerful OA; yellow orange

∙ stoich. of rxn. simpler; indefinitely stable but rel.
high cost of Ce4+ cpds.
∙ indic. – ferroin
I2: solns. are weak OA; used for detn. of strong reductants

I3- + 2 e- 3 I- E° = 0.536 V

∙ lack stability; must be restandardized regularly

∙ I2 not very soluble in H2O; dissolved in moderately concd KI
I2(s) + I- I3-

IODIMETRY – I2 used as OA
IODOMETRY – I- used as RA
STANDARD REDUCTANTS:
∙ std. solns of RAs tend to react w/ atm. O2
∙ titrns. carried out in & rgts. stored under an inert atm.
∙ indirect methods used – aliquot contg. x’s reductant added to
sample & x’s quickly back titrated with std. oxidant

Standard Reductants
Rgt. Oxidn. Pot. 1° std. Stability of Soln
unstable unless
Fe(II) -0.77 Fe, K2Cr2O7
protected fr. O2
(Fe2+ → Fe3+ + e-)
Na2S2O3 -0.08 KIO3, I2 freq. stdization reqd.
(2 S2O32- → S4O62- + 2 e-)
indefinitely stable if
As(III) -0.56 As2O3, I2
acidic
(H3AsO3 + H2O → H3AsO4 + 2 H+ + 2 e)
Na2S2O3: moderately strong RA; widely used to determine
OAs by indirect procedure that involves I2 as an intermediate
(IODOMETRY)
∙ std. Na2S2O3 used to titrate I2 liberated by rxn. of analyte w/
unmeasured x’s KI in slightly acidic soln.

Rxn: I2 + 2 S2O32- 2 I- + S4O62-

1° std: KIO3

IO3- + 5 I- + 6 H+ 3 I2 + 3 H2O
3 I2 + 6 e- 6 I-
1 mol IO3- ≡ 3 mol I2 ≡ 6 mol S2O32-
EW KIO3 =

Indicator: starch (specify indicator) – deep blue complex w/ I2

Table 20-2, p.565
Fig 20-5, p.572
Table 20-6, p.577
 Sample Problems
1. Write the Nernst equation for the following reduction reactions.
Balance the reaction first.
a. MnO₄⁻ MnO₂ (s) (acid medium)
b. PbSO₄ (s) Pb (s) + SO₄²⁻
c. HClO Cl₂ (g) (acid medium)
d. O₃ (g) O₂ (g) (acid medium)

2. Given: Titra on of 50.00 ml of 0.0100 M V²⁺ with 0.0500 M Sn⁴⁺.

Calculate the electrode potential after addition of a) 10.00 ml, b)
25.00 ml, c) 50.00 ml and d) 60.00 ml of titrant.

3. Generate equilibrium constant expression for the following

titration reaction and calculate the numerical Keq value:
Fe³⁺ + V²⁺ Fe²⁺ + V³⁺
4. Given the following cell:
Bi / BiO⁺ (0.0175 M), HClO₄ (1.00 × 10-3 M)||KCl (0.0380 M), AgCl (satd)|Ag
a. Following IUPAC convention, write the 2 half-reactions
(reduction reactions) constituting the cell and their
corresponding electrode potentials.
b. Calculate Ecathode.
c. Calculate Eanode.
d. Calculate Ecell.
e. Is the cell galvanic or electrolytic?

5. For the tra on of 50.00 ml of 0.0500 N Fe²⁺ with 0.1000 N

KMnO₄ in acid medium where [H⁺] = 1.00 M, determine the
volume of titrant at the equiv. pt. and the equiv. pt. potential.