Chemistry 127 Lecture Trans  The net cell reaction that occurs in the cell is the sum of the

ELECTROANALYTICAL CHEMISTRY 2 half-cell reactions

2.1 Electrochemical Cells
Zn(s) ↔ Zn2+ + 2e- (oxidation)
Electroanalytical Chemistry Cu2+ + 2e- ↔ Cu(s) (reduction)
 Group of quantitative analytical methods based upon Zn(s) + Cu2+ ↔ Zn2+ + Cu(s) (overall reaction)
electrical properties of solution of an analyte when part of Ecell = 1.100 V
electrochemical cell
 Study of oxidation-reduction phenomena The potential (Ecell) that develops in the cell is a measure of the
 Advantages: tendency of the reaction to proceed toward equilibrium
o Specific for a particular oxidation state  The 1.100 V reading in the cell shows that the reaction is far
o Exceptionally low detection limits from the equilibrium
o Rich characterization information  As the reaction proceeds, the potential decreases, ultimately
o Instrumentation relatively inexpensive reaching 0.000 V when equilibrium is achieved
o Provide information about activity not
concentration Types of Electrochemical Cells
1. Galvanic (Voltaic) Cells
Electrochemical Cells  Cells that produces electrical energy
 Consists of 2 conductors called electrodes  The reaction in this cell proceeds spontaneously
o Each electrode immersed in a suitable electrolyte  Ex: Zn(s) + Cu2+ ↔ Zn2+ + Cu(s) Ecell = +1.100 V
solution
2. Electrolytic Cells
 Consume electrical energy
 An otherwise nonspontaneous reaction is forced to
take place
 The cell above can be made electrolytic by
reversing the connection of electrodes to the
power supply with an output greater than 1.100 V
Rxn: Zn2+ + Cu(s) ↔ Zn(s) + Cu2+
Ecell = -1.100 V

Chemically reversible cells – a cell in which reversing the direction of

the current simply reverses the reactions of the 2 electrodes

For a current to develop in a cell, Types of Electrodes

1. Electrodes must be connected externally by a metal 1. Cathode
conductor  The electrode at which reduction occurs
2. Two electrolyte solutions must be in contact to permit
 Some cathodic reactions:
movement of ions from one to another
i. Copper is deposited on the electrode
surface
The salt bridge joins the 2 solutions
Cu2+ + 2e- ↔ Cu(s)
 Consists of tube filled with a solution saturated with KCl
 Isolates contents of the 2 halves of the cell while maintaining ii. Only change in oxidation state occurs
electrical contact between them Fe3+ + e- ↔ Fe2+

Conduction in a Cell iii. Occurs if there is no easily reduced

 For the 2 electrode processes: species
Zn(s) ↔ Zn2+ + e- 2H+ + 2e- ↔ H2(g)
Cu + 2e- ↔ Cu(s)
2+

iv. Cathodic reactions can also involve

 Charge is conducted by 3 distinct processes in the cell anionic species
1. Electron conduction IO4- + 2H+ + e- ↔ IO4- + H2O
 In the Cu and Zn electrodes and in the
external conductor, electrons serve as 2. Anode
charge carriers  The electrode at which oxidation occurs
 e-: Zn → external conductor → Cu  Some anodic reactions:
i. Requires copper electrode to supply
2. Ionic conduction Cu2+ ions
 Within the solutions, the flow of Cu(s) ↔ Cu2+ + 2e-
electricity involves migration of both
cations and anions ii. Occurs at an inert electrode; only
change in oxidation state occurs
3. At the 2 electrode surfaces, oxidation and Fe2+ ↔ Fe3+ + e-
reduction reaction provides a mechanism whereby
the ionic conduction of solution is coupled with iii. Hydrogen must be bubbled across the
electron conduction to complete the circuit surface of the electrode
H2(g) ↔ 2H+ + 2e-
 iv. Occurs if there is no easily oxidized
species
H2O ↔ O2(g) + 4H+ + 4e-
Cells Without Liquid Junctions
Pt | H2 (p = 1 atm) | H+ (0.01 M), Cl- (0.01 M), AgCl (sat’d) | Ag
EXERCISE:
Write the half-cell equations and cell reaction equation for the above
cell representation and draw the corresponding electrochemical cell.

Liquid junction – the interface between 2 solutions containing different AgCl(s) + e- ↔ Ag(s) + Cl-(aq) at cathode
electrolytes or different concentrations of the same electrolyte H2(g) ↔ 2H+(aq) + 2e- at anode

Overall: 2AgCl(s) + H2(g) ↔ 2Ag(s) + 2H+(aq) + 2Cl-(aq)

This type of cell has 2 liquid junctions (in red)

1. Zn solution and one end of the salt bridge
2. Cu solution and the other end of the salt bridge

Liquid junctions develop small junction potentials which can affect the
overall measured cell potential

It is possible to prepare cells in which the electrodes share common

analyte and thus eliminate the effect of junction potentials

Zn(s) ↔ Zn2+ + 2e- (anode, oxidation)

O2(g) + 4H+ + 4e- ↔ 2H2O (cathode, reduction)
2Zn(s) + O2(g) + 4H+ ↔ 2Zn2+ + 2H2O (overall reaction)

Schematic Representation of Cells

By convention, the anode and information with respect to the solution

with which it is in contact with are always listed on the left

Rxn: Zn2+ + Cu(s) ↔ Zn(s) + Cu2+

Cell representation: Zn | Zn2+ || Cu2+ | Cu

Rxn: 2Zn(s) + O2(g) + 4H+ ↔ 2Zn2+ + 2H2O

Cell representation: Zn | Zn2+ , H+ | O2 | Pt

 Vertical lines – represent phase boundary

o Between electrode and aqueous ion
o Between aqueous ion and a gas

 Double bar – represents the 2 junctions at either end of the

salt bridge

It is common practice to provide activity or concentration data for the

cell constituents in parentheses

Pt | H2 (p = 1 atm) | H+ (0.01 M), Cl- (0.01 M), AgCl (sat’d) | Ag

 Q is not a constant but changes continuously until equilibrium is
Chemistry 127 Lecture Trans reached, at that point Q = K, and the i subscripts are deleted
ELECTROANALYTICAL CHEMISTRY
2.2 Cell/Electrode Potentials

The Cell
The maximum work obtainable at constant T and P is given by

∆ G=RT ln Q−RT ln K
Where
J
R – gas constant; R=8.3145
mol K
T – temperature in K

The relationship implies that the magnitude of the free energy depends
on how far the system is from the equilibrium state
Cell Potentials

The cell potential is related to the free energy of the reaction by

The theoretical aspects of electrode and cell potentials are based on
activities rather than molar concentrations.
∆ G=−nF E cell
The activity of species X is given by: Where
C
α X =γ X [ X ] F – Faraday’s constant; F=96 485
mol e−¿ ¿
Where
n – number of electrons associated with redox process
γ X – the activity coefficient of solute X
Since
For convenience, the activity coefficient is usually assumed to
approach unity so that it is identical with the molar concentration
∆ G=RT ln Q−RT ln K=−nF E cell

For cell reaction: Upon rearrangement,

−RT RT
Ecell = ln Q+ ln K
2AgCl(s) + H2(g) ↔ 2Ag(s) + 2H+(aq) + 2Cl-(aq) nF nF
The equilibrium constant for this reaction is given by Substituting the Q expression,
−RT
K=a ¿ Ecell = ln ¿ ¿ ¿ ¿
H ¿
aCl a ¿ 2
Ag
¿ nF
pH a2AgCl
2

Where The last term is a constant called the standard electrode potential for
a – activities of the various species indicated by the the cell, E°cell
subscripts RT
pH E ° cell= ln K
2
– the partial pressure of hydrogen in atm nF
The activity of a pure solid is unity when it is present in excess, i.e. Substituting E°cell expression yields

a Ag =a AgCl=1.00 RT
Ecell =E ° cell− ln ¿ ¿¿ ¿
nF
The foregoing equation then simplifies to
This is a form of the Nernst equation.
K=a ¿ a Cl
¿
¿
H ¿ Note that the standard potential is equal to the cell potential when the
pH 2

reactants and products are at unit activity and pressure

It is convenient to define a quantity Q such that
Electrode Potentials

Q=¿¿ ¿ The electrochemical cell can be thought of as being made up of 2 half-

cell reactions, each of which has a characteristic electrode potential.
The subscript i indicates that the terms are instantaneous
The electrode potentials measure the driving force for the 2 half
activities and not equilibrium activities reactions when, by convention, they are both written as reductions

For the cell

The 2 electrode reactions are
2AgCl(s) + 2e- ↔ 2Ag(s) + 2Cl-(aq)
2H+(aq) + 2e- ↔ H2(g)
To obtain the cell reaction, the second half is subtracted from the first
The cell illustrates the definition of the electrode potential for a half-
reaction, e.g. Cu2+ reduction:
2AgCl(s) + 2e- ↔ 2Ag(s) + 2Cl-(aq) EAgCl
- 2H+(aq) + 2e- ↔ H2(g) EH+
Cu2+ + 2e- ↔ Cus) E° = +0.337 V (cathode)
2AgCl(s) + H2(g) ↔ 2Ag(s) + 2H+(aq) + 2Cl-(aq) Ecell
- 2H+ + 2e- ↔ H2(g) E° = 0.000 V (anode)
The cell potential is obtained in similar manner: Cu2+ + H2(g) ↔ Cu(s) + 2H+ E° = +0.337 V (cell)

Ecell =E AgCl −EH +¿

¿ From the formula

A more general statement is

Ecell =Ecathode −E anode

Thus
Ecell =Ecathode −E anode
Ecathode =E cell + Eanode
However, no method still exists for determining the absolute value of Ecathode =0.337V + 0.00V
the potential a single electrode (Ecathode or Eanode). All voltage-measuring
devices determine only differences in potential.
Ecathode =0.337V =Ecell
Relative half-cell potentials, measured against a common reference
electrode, are just as useful as the absolute potentials. If Cu is replaced with Zn, the cell potential is observed to be +0.763 V.
In this case Zn acts as the anode of a galvanic cell
The accepted common reference electrode is the standard hydrogen
electrode (SHE) or the normal hydrogen electrode (NHE) 2H+ + 2e- ↔ H2(g) E° = 0.000 V (cathode)
- Zn(s) ↔ Zn2+ + 2e- Eox° = +0.763 V (anode)
2H+ + Zn(s) ↔ Zn2+ + H2(g) E° = +0.763 V (cell)

The composition of hydrogen-gas electrode can be formulated as

Pt , H2 (p atm) | H+ (x M) From the formula

Ecell =Ecathode −E anode
The half cell on the right in the figure illustrates the components of a
typical hydrogen electrode.
Thus
The Standard Hydrogen Electrode Eanode = Ecathode −Ecell
By convention, the potential of the standard hydrogen electrode is
¿ 0.000 V −(+0.763 V )
assigned the value of exactly zero volt at all temperatures when
hydrogen ion activity is unity and partial pressure of hydrogen is 1 atm E Zn 2+ ¿/Zn
=−0.763 V ¿

2H+ + 2e- ↔ H2(g) E° = 0.00 V This is the standard electrode potential for Zn2+/Zn couple, based on
reduction half-reaction.
Electrode potentials are defined as cell potentials for a cell consisting
the electrode in question behaving as the cathode and the SHE acting Thus
as the anode
 Zn(s) ↔ Zn2+ + 2e- Eoxidation° = +0.763 V
Zn2+ + 2e- ↔ Zn(s) Ereduction° = -0.763 V 100Cd2+ + 200e- ↔ 2Cd(s) E° = -0.403 V
(found in table)
To be sure, the Nernst equation must be consistent with the half-
The electrode potentials for the 3 half-cells just described can be reaction as written
arranged in the order
For the first:
Cu2+ + 2e- ↔ Cu(s) E° = +0.337 V 0.0592 1
2H+ + 2e- ↔ H2(g) E° = 0.000 V E=−0.403 V − log ¿
Zn2+ + 2e- ↔ Zn(s) E° = -0.763 V
2 ¿ ¿¿

For the second:

The magnitudes of these standard electrode potentials show the
relative strengths of the 3 ionic species as electron acceptors 0.0592 1
(oxidizing agents)
E=−0.403 V − log ¿
200 ¿ ¿ ¿¿
Order of decreasing strength as oxidizing agents: 0.0592 1
¿−0.403 V − log ¿
2 ¿¿ ¿
Cu2+ > H+ > Zn2+

Effect of Activity on Electrode Potential

Consider a generalized half-reaction that takes the form

aA + bB + ne- ↔ cC + dD
Standard Electrode Potentials
The Nernst equation is

c d
RT (a C )i (a D )i
E=E °− ln
nF (a A )ai (aB )bi

Substituting the values:

R = 8.314 J/mol K, F = 96 485 C/mol, Troom = 298.15 K and converting
to base 10 logarithms by multiplication by 2.303,

0.0592 (aC )ci (a D )di

E=E °− log
nF (a A )ai (a B )bi Species at the upper left-hand part are most easily reduced (most
potent oxidizing agents) as indicated by the large positive electrode
This is the general statement of the Nernst equation. potential values

The Standard Electrode Potential SOLVED PROBLEM

The Nernst equation is reduced to E = E° when the log term is zero. A cell developed a potential of 0.52053 V. The cell is described by
This happens when Q = 1 (i.e. when the activities of all reactants and
products are unity) Pt , H2 (1.00 atm) | HCl (8.215 × 10-3 M) , AgCl (sat’d) | Ag

Facts regarding standard electrode potential:

Calculate the standard electrode potential for the half-reaction
1. The electrode potential is temperature dependent
2. The electrode potential is a relative quantity (with reference
AgCl(s) + e- ↔ Ag(s) + Cl-
to SHE)
3. The sign of a standard potential is identical with that of the
conductor in contact with the half-cell of interest Use the activity coefficients: γH +¿
=γCl −¿
=0.85 ¿
¿
4. The standard potential is a measure of the driving force for a
half reaction SOLUTION

It is independent of the notation employed to express the half-cell

Ecell =Ecathode −E anode
process
Ecell =¿
Thus the potential for the process,
cathode anode

Cd2+ + 2e- ↔ Cd(s) E° = -0.403 V Combining the 2 log terms

Ecell =E ° AgCl−0.0592 log γ Cl −¿
c Cl ¿ ¿¿
Although dependent upon the concentration of Cd2+ ion, is the same
−¿
γ c ¿
H +¿
H +¿
1/2
p
whether we write the reaction as above or as H
2
 The tendency for the reduction of Ag+ decreases as its concentration
Substitution of values and rearrangement give decreases.

2 The equation
( 8.215 ×10−3 ) ( 0.85)2 aI
E ° AgCl=0.52053+ 0.0592 log −¿

1.00 1/ 2 E=+0.799−0.0592 log ¿

K sp
can also be written as
E ° AgCl=0.26 V
E=+0.799+0.0592 log K sp−0.0592 log a I ¿ −¿

This equation relates the potential of a silver electrode to the iodide ion
activity that is also saturated with silver iodide.

When the iodide ion activity is unity, the potential is the sum of 2
constant; it is the standard electrode potential for the half-reaction

AgI(s) + e- ↔ Ag(s) + I- E° = -0.151 V

Where
E ° AgI =+0.799+0.0592 log K sp
The Nernst relationship for the silver electrode in a solution saturated
with silver iodide can then be written as

E=E °−0.0592 log a I ¿ −¿

Electrode Potentials in the Presence of Precipitation and E=−0.151V −0.0592 log a I ¿ −¿

Complex-Forming Reagents

Reagents that react with the participants of an electrode process have Thus, when in contact with a solution saturated with silver iodide, the
a marked effect on the potential of that process potential of a silver electrode can be described either in terms if Ag+
ion activity (using E°Ag+) or I- ion activity (using E°I-)
Example
Calculate the potential of a silver electrode in a solution that is
saturated with silver iodide and has an iodide ion activity of exactly The potential of a silver electrode in a solution containing an ion that
−17 forms a soluble complex with silver ion can be treated in similar
1.00 ( K sp for AgCl=8.3 ×10 ) manner.

Ag+ + e- ↔ Ag(s) E° = +0.799 V Example

In a solution containing thiosulfate and silver ions, complex formation
occurs:
1
E=+0.799−0.0592 log ¿
a Ag +¿ Ag+ + 2S2O32- ↔ Ag(S2O3)23-
For which
We may calculate a Ag+ ¿ ¿ from the solubility product constant. Thus, a Ag (S O ) 3−¿

Kf = 2 3 2
¿
a +¿ K sp a Ag +¿
aS O ¿
¿
Ag =
¿
¿ 2 3

aI ¿ −¿

Where
Substituting into the Nernst equation gives
Kf – formation constant for the complex
a
E=+0.799−0.0592 log I ¿
−¿

K sp The half-reaction for a silver electrode in such a solution can be written

as
Substituting the values
Ag(S2O2)33- + e- ↔ Ag(s) + 2S2O32--
1.00
E=+0.799−0.0592 log
8.3 ×10−17 The standard electrode potential for this half-reaction will be the
electrode potential when both the complex and the complexing anion
are at unit activity
E=−0.151V
Using the same approach as in the previous example, we find that
This example shows that the half-cell potential for the reduction of
silver ion becomes smaller in the presence of iodide ions. E ° Ag(S O ) 3−¿
2 3 2
=+0.799+0.0592 log¿ ¿¿
E° 3−¿
Ag(S2 O3 )2 =+0.799+0.0592 log
( K1 )¿
f
PbSO4(s) + 2e- ↔ Pb(s) + SO42-
Zn2+ + 2e- ↔ Zn(s)
E° = -0.350 V
E° = -0.763 V

Data for the potential of the silver (and other) electrode systems in the The α values are
presence of selected ions are given in tables
α of SO42- = 4.0
α of Zn2+ = 6.0
Some Limitations to the Use of Standard Electrode Potentials
To obtain activity coefficients for Zn2+ and SO42-, assume
1. Substitution of Concentrations for Activities
Pb2+, H+ and OH- are negligible in calculating the ionic
strength
As a matter of convenience, molar concentrations, rather
than activities, of reactive species are employed in making Use the formulas:
computations with the Nernst equation

The assumption that molar concentrations and activity are

μ=
1
z 2
i 0.509 z 2 √ μ
( ) −log γ=
2∑
identical is valid only in dilute solutions
[ ]
1+0.328 α √ μ
To illustrate, consider a half-reaction a=γ [i]
Fe3+ + e- ↔ Fe2+ E° = +0.771 V M ZnSO4 Ionic Ecell in (a) Ecell in (b) Eexpt’l
Strength
5.00 x 10-4 0.611
One would assume that an inert electrode immersed in a 2.00 x 10-3 0.583
solution containing 1 M of each Fe2+ and Fe3+ ions in HClO4 1.00 x 10-2 0.553
would also exhibit a potential of +0.771 V. 2.00 x 10-2 0.542
5.00 x 10-2 0.529

In fact, the experimentally observed potential in 1 M HClO4 is Which is closer to experimental especially at higher ionic
+0.732 V strengths?

The reason for discrepancy is seen if the Nernst equation is

written as

E=E °−0.0592 log γ Fe 2+ ¿

¿¿
¿¿

The activity coefficients of the two species are less than one
because of the high ionic strength imparted by perchloric
acid and iron salts

More importantly, the activity coefficient of Fe(III) ion is

smaller than that of Fe(II) 2. Effect of Other Equilibria
 Larger than 1 ratio of activity coefficients = larger
subtrahend The application of standard electrode potentials is further
 Potential of the half-cell smaller than the standard complicated by the occurrence of solvation, dissociation,
potential association, and complex-ion formation reactions involving
the species of interest.
Problem: limited data on activity coefficients for ions
commonly encountered in redox titrations and Electrochem Example:
works In 1 M HClO4: Fe3+ + e- ↔ Fe2+ E° = +0.73 V
 Molar concentrations must be used in many In 1 M HCl: Fe3+ + e- ↔ Fe2+ E° = +0.70 V
calculations In 1 M H3PO4: Fe3+ + e- ↔ Fe2+ E° = +0.60 V
 Appreciable errors may result
This differences arise because iron(III) forms more stable
Exercises complexes with chloride and phosphate ions than does
Calculate potentials for the following cell employing iron(II)
i. Concentrations
ii. Activities Phenomena like this can be taken into account only if the
equilibria involved are known and constants for the
Zn | ZnSO4 (x M), PbSO4 (sat’d) | Pb processes are available

Where x is Formal Potentials

a. 5.00 x 10-4
b. 2.00 x 10-3 Formal Potential, E°’
c. 1.00 x 10-2  Used in place of standard electrode potential
d. 2.00 x 10-2
 To compensate partially for activity effects and errors
e. 5.00 x 10-2
resulting from the side reactions

The half-reactions and potentials are

  The potential of the half-cell with respect to SHE when the
concentrations of reactants and products are 1 M and the
concentrations of any other constituents of the solution are
carefully specified

Examples
E ° ' Fe 3+ ¿/Fe2+¿ (1 M HClO 4 )=+ 0.732V ¿
¿
E ° ' Fe 3+ ¿/Fe2+¿ (1 M HCl)=+0.700 V ¿
¿

Use of these values in place of the standard electrode potential in the

Nernst equation will yield better agreement between calculated and
experimental potentials

Liquid Junction Potential

When 2 electrolyte solutions of different compositions are brought into

contact with one another, a potential develops at the interface

The junction potential, Ej, arises from an unequal distribution of cations

and anions across the boundary due to differences in the rates at
which these species migrate

Consider the liquid junction that exists in the system

HCl (1 M) | HCl (0.01 M)

Both H+ and Cl- ions tend to diffuse across the boundary from the more
concentrated to the more dilute solution

The rate at which various ions move under the influence of a fixed
force (concentration gradient) varies considerably (i.e. the mobilities
are different)

Figure 1. Schematic representation of a liquid junction showing the source of the junction
potential.
 Hydrogen ions are several times more mobile than chloride
ions
 The hydrogen ions would outstrip the chloride ions as
diffusion takes place resulting to charge separation

The more dilute side becomes positively charged owing to the more
rapid migration of hydrogen ions

The concentrated side acquires a negative charge from the excess

slow-moving chloride ions

The charge that develops tends to counter the differences in mobilities

of the two ions and an equilibrium condition soon develops

The junction potential difference resulting from this charge separation

may amount to 30 mV or more

It has been found that the magnitude of junction potential can be

reduced by employing a salt bridge between the two solutions

Example
>4 M KCl solution
 High concentration and almost equal mobility of K+ and Cl-
ions improve the effectiveness

Chemistry 127 Lecture Trans
ELECTROANALYTICAL CHEMISTRY
2.3 Currents in Electrochemical Cells
Electricity is transported within a cell by the migration of ions
With small currents, Ohm’s law is obeyed
E=IR
Where
E – potential difference in volts (V) responsible for
movement of ions
I – current in amperes (A)
R – resistance in ohms (Ω) of the electrolyte to the current
Mass Transport Resulting from Currents
Under a fixed potential, the rate at which various ions move in a
solution differs considerably
Example: mobility of H+ is 7 times the rate of Na+ and 5x of Cl-
To illustrate, consider the cell shown below
The figure illustrates that 6 electrons are forced into the cathode,
resulting in the formation of 3 molecules of H2 at the cathode and 3
molecules of Cl2 at the anode
the resulting charge imbalance brought about by the removals ions is
offset by migration, with positive ions moving forward the negative
electrode and conversely
Because H+ is about 5 times more mobile than the Cl- ions, a
significant difference in concentration develops during electrolysis
In effect, 5/6 of the current has resulted from the movement of the H+
ions and 1/6 from the transport of Cl- ions
However, the current need not result from the transport of electrode
reactants exclusively
Introduction of high concentration of electrolyte (KCl) will offset the
charge imbalance resulting from electrolysis
Essentially all the electricity would be carried within the cell by K+ and
Cl- ions rather than by the reactant ions
Faradaic and Nonfaradaic Currents
Types of processes in the conduction of current across an
electrode/solution interface
Faradaic Processes
 Involves direct transfer of electrons via an oxidation reaction
at the anode and a reduction reaction at the cathode
 Governed by Faraday’s law (the amount of chemical
reaction at an electrode is proportional to the current)
 The resulting currents are called faradaic currents
Nonfaradaic Processes
 Occur under some conditions of a cell even when faradaic
processes are precluded at one or both of the electrodes
Example:
When a DC potential is first impressed across an electrochemical cell,
a momentary surge of current is observed, which rapidly decays to
zero
This current is a charging current that creates an excess (or deficiency)
of negative charge at the surface of the two electrodes
As a consequence of ionic mobility, the layers of solution immediately The departure can be traced to the ff phenomena:
adjacent to the electrode acquire an opposing charge  Ohmic resistance
 Polarization effects
o Charge-transfer overvoltage
o Reaction overvoltage
o Diffusion overvoltage
o Crystallization overvoltage

Generally, this phenomena

 Reduce the potential of a galvanic cell
 Increase the potential needed to develop a current in an
electrolytic cell

Ohmic Potential or IR Drop

Figure 2. Electric double layer formed at electrode surface as a result of an applied potential.
To develop a current in a cell, a driving force in the form of a potential
The surface of the metal electrode is shown as having an excess of is required to overcome the resistance of the ions to move towards the
positive charge as a consequence of an applied potential electrodes

The parts of charged solution layer:

The potential follows Ohm’s law ( E=IR). This force is generally
1. Compact inner layer
referred to as the ohmic potential, or the IR drop
 The potential decreases linearly with distance from
the electrode surface
The net effect of IR drop is to increase the potential required to operate
2. Diffuse layer
an electrolytic cell and to decrease the measured potential of a
 The decrease in potential is exponential
galvanic cell

The IR drop is always subtracted from the theoretical cell potential:

Ecell =Ecathode −E anode −IR

Electrical Double Layer

SOLVED PROBLEM
 The assemblage of charge at the electrode surface and in
the solution adjacent to the surface
The following cell has a resistance of 4.00 Ω. Calculate its potential
The double layer formed by a DC potential involves a momentary when it is producing a current of 0.100 A.
nonfaradaic current, which then drops to zero (electrode becomes
polarized) unless some faradaic process occurs to cause Cd | Cd2+ (0.01 M) || Cu2+ (0.01 M) | Cu
depolarization
E=ECu −ECd
With continuous AC current in a cell, reversal of charge relationship
occurs with each half-cycle as first negative and then positive ions are
E=0.278 V −(−0.462V )
attracted alternately to the electrode surface E=0.740 V
Each electrode surface behaves as one plate of a capacitor
Ecell =0.740−IR
The capacitance current increases with frequency and which electrode Ecell =0.740−(0.100 × 4.00)
size
Ecell =0.340 V
Effect of Current of Cell Potentials
Note that the potential of the cell drops dramatically in the presence of
When a direct current develops in an electrochemical cell, the a current
measured cell potential normally departs from that derived from
thermodynamic calculations
 The ideal polarized electrode is one in which current remains constant
Calculate the potential required to generate a current of 0.100 A in the and independent of E
reverse direction in the cell described in the preceding example

E=ECd −ECu
E=−0.462V −0.278 V
E=−0.740 V

Ecell =−0.740−IR
In non-polarized electrode, the potential is independent of the current
Ecell =−0.740−(0.100 × 4.00)
Ecell =−1 .1 40 V

An external potential greater than 1.140 V would be needed to cause

Cd2+ to deposit and Cu to dissolve at a rate required for a current of
0.100 A

Figure 3. Current-voltage relationship for a nonpolarized electrode that behaves ideally in the
region between C and D.

This figure shows a current-voltage curve for a cell having electrodes

that exhibit nonpolarized behavior between points A and B

Because of the internal resistance of the cell, the I-E curve has a finite
slope equal to R rather than the infinite slope for the ideal nonpolarized
electrode

Beyond points A and B, polarization occurs resulting in departures

from the ideal straight line

The upper half of the curve describes current-voltage relationship

when the cell is operating as an electrolytic cell
 Note that when polarization arises in an electrolytic cell, a
higher potential is required to achieve a given current

The lower half of the curve describes current-voltage behavior when

Chemistry 127 Lecture Trans the cell is operating as a galvanic cell
ELECTROANALYTICAL CHEMISTRY
 Polarization of a galvanic cell produces a potential that is
2.4 Polarization and Overpotential
lower than expected

The equation
Sources of Polarization
1. Electrode
Ecell =Ecathode −E anode −IR 2. Surface film of solution immediately adjacent to the electrode
3. Bulk of the solution
predicts that at constant electrode potentials, a linear relationship
should exist between the cell voltage and current. Steps in the electrode reaction:

In fact, the relationship is sometimes not linear; the cell is said to be

polarized

Ideal Polarized and Nonpolarized Electrodes and Cell

 A brief current is generated that reduces the surface concentration of
Cd2+ ions to the equilibrium concentration, co

0.0592 1
E=E ° Cd − log
2 co

If no mechanism existed for transport of Cd2+ ions from the bulk of the
solution to the surface film, the current would rapidly decrease to zero

However, several mechanisms do exist that bring Cd2+ ions from the
bulk of the solution into the surface layer at a constant rate

As a consequence, the large initial current decreases rapidly and

Any of the intermediate steps may limit the rate of overall reaction and
thus the magnitude of current
MASS TRANSFER involves movement of Ox from the bulk of the
solution to the surface film (or the reverse movement of Red from
surface film to bulk)
Concentration polarization occurs when mass transfer limits the overall
rate of the reaction
reaches a constant level that is determined by the rate of ion transport
For a rapid and reversible electrode reaction, the concentration of the
surface layer may always be considered to be the equilibrium
concentration which is determined by the instantaneous electrode
potential
The surface concentration co is often far different from that of the bulk
because attainment of equilibrium between the electrode and the bulk
often requires minute or even hours

The Ox’ or Red’ species may form, this intermediate is then the actual For current to be maintained, it is necessary that reactant be brought
participant (active form) in the electron transfer process from the bulk of the solution to the surface layer at a rate dc/dt that is
given by
Reaction polarization is said to exist when the rate of formation or
decomposition of an intermediate limits the current dQ nFdc
I= =
If the rate of physical processes such as adsorption, desorption, or
dt dt
crystallization limits the current, then adsorption, desorption, or
crystallization polarization occurs Where
dQ
– rate of flow of electrons in the electrode (or the
CHARGE-TRANSFER POLARIZATION arises from the slow rate of dt
electron transfer from the electrode to the oxidized species or from the
current I)
reduced species to the electrode
n – number of electrons appearing in the half-reaction
These several types of polarization may occur simultaneously F – the Faraday
Overvoltage or overpotential, η, is a measure of the degree of The rate of concentration change can be written as
polarization; it is the difference bet. the actual electrode potential E and
the thermodynamic or equilibrium potential Eeq
dc
=AJ
η=E−E eq dt
Where
Where
E< E eq A – surface area of the electrode (m )2

Polarization always reduces the electrode potential for a system

J – concentration flux (mol/s)
The two equations can then be combined to give
E is always smaller than Eeq and η is always negative

I =nFAJ
When this demand for reactant cannot be met by the mass transport
DIFFUSION OVERVOLTAGE develops with the onset of concentration process, the IR drop becomes smaller than its theoretical value, and a
polarization diffusion overvoltage appears that just offsets the decrease in IR

Example With the appearance of concentration polarization cell potential

Cd2+ + 2e- ↔ Cd(s) becomes

When a potential is applied to cadmium electrode, the surface layer of Ecell =Ecathode −E anode −IR+ ηcathode
the solution comes to equilibrium with the electrode essentially
instantaneously A more general equation is
 Ecell =Ecathode −E anode + ηcathode + ηanode −IR ELECTROANALYTICAL CHEMISTRY
2.5 Modes of Mass Transport

This is important in preventing or reducing concentration polarization

EXERCISE
Three Mechanisms
The resistance of the galvanic cell 1. Diffusion
 Occurs whenever a concentration difference
Pt | Fe(CN)64- (4.42 x 10-2 M), Fe(CN)63- (8.93 x 10-3 M) || Ag+ (5.75 x 10-2- M) | Ag
develops between two regions of solution (e.g.
when a species is reduced or oxidized at electrode
is 3.85 Ω. Calculate the initial potential when 0.0442 A is drawn from
surface)
this cell.
Ions or molecules move from the more concentrated region
E ° Fe(CN ) 3−¿/Fe (CN)4−¿
6
=+ 0.36V ¿
¿ to more dilute as a result of diffusion
6

E ° Ag +¿/ Ag
=+0.799 V ¿ The rate of diffusion, dc/dt, is given by
dc
=k (c −c o)
Factors Affecting Concentration Polarization dt
Where
1. Reactant concentration c – reactant concentration in the bulk
 Polarization is more probable at low concentration
c o – equilibrium concentration at the electrode
2. Total electrolyte concentration surface
 Polarization is more probable at high k – proportionality constant
concentration
Recall: the value of co is fixed by the potential of the
3. Mechanical agitation electrode and can be calculated from the Nernst equation
 Polarization decreasing in well-stirred solution
The higher the applied potential to the electrode, the smaller
4. Electrode size the co, the greater the rate of diffusion
 Polarization decreases as electrode surface area
increases Ultimately, co becomes negligible with respect to c, the rate
then becomes constant
Charge-transfer Polarization
dc
This arises when the rate of oxidation or reduction reaction at one or When co → 0, =kc
both electrodes is not sufficiently rapid to yield currents of the size dt
demanded by theory
Under this circumstance, concentration polarization is said to
Characteristics of Overvoltage due to CT Polarization be complete, and the electrode operates as an ideal
polarized electrode
1. Overvoltages increase with current density (A/cm2)
Example 2. Migration
Current density (A/cm2) Overvoltage (V) for H2  The process by which ions move under the
formation on Pt electrode influence of electrostatic field
0.001 -0.024
0.01 -0.068 Migration is often the primary process by which mass
1 -0.676 transfer occurs in the bulk of the solution in a cell

2. Overvoltages decrease with increase in temperature
3. Overvoltages vary with chemical composition of the
electrode; most pronounced with soft metals (Pb, Sn, Zn,
Hg)
4. Overvoltages are not marked for electrode processes that
yield gaseous product but negligible in processes that
produce metal deposit and involve change in oxidation state
5. The magnitude of overvoltage cannot be predicted exactly
The electrostatic attraction (or repulsion) bet. a particular
ionic species and the electrode becomes smaller as the total
electrolyte concentration becomes greater
3. Convection
 The process by which particles more upon
application of mechanical force
Forced convection – stirring or agitation
Natural convection – convection resulting from temperature
or density differences

Summary
Concentration polarization is observed when diffusion,
migration and convection are insufficient to transport the
reactant to or from an electrode surface at a rate demanded
by the theoretical current
Chemistry 127 Lecture Trans
 Chemistry 127 Lecture Trans
ELECTROANALYTICAL CHEMISTRY
2.6 Fick’s Law

FICK’S FIRST LAW:

The rate of diffusion (i.e. the flux) is directly proportional to the
concentration gradient

∂C (x ,t)
J ( x , t )=−D
∂x
Figure 4. Three modes of mass transport.
Recall

Nernst-Planck Equation i=nFAJ

FLUX (J) Combination of the 2 equations give
 Measure of mass transport ∂ C (x , t)
 Has 3 components i=nFAD
∂x
∂C ( x , t ) zFDC ∂ ϕ ( x , t ) Thus, the current (at any time) is proportional to the concentration
J ( x , t )=−D − +C ( x ,t ) V (x , t)
∂x RT ∂x gradient

Where Also, the diffusional flux is time-dependent

D – diffusion coefficient (cm /s) 2

FICK’S SECOND LAW:
∂C ( x , t ) Shows the dependence of diffusional flux on time
– concentration gradient (at distance x, time t)
∂x
∂ϕ(x,t) ∂C ( x ,t ) ∂2 C( x , t)
– potential gradient
=D
∂x ∂t ∂ x2
z – charge of electroactive species This equation reflects the rate of change with time of the concentration
C – concentration of electroactive species bet. parallel planes at x (and x + dx) which is equal to the difference in
flux at the 2 planes
V ( x ,t ) – hydrodynamic velocity (in the x direction)
In aqueous media, D usually ranges bet. 10-5 and 10-6 cm2/s

 The situation is complex when 3 modes of transport occur

simultaneously
 It would be difficult to relate the current to the analyte
concentration Figure 5. Linear diffusion.
 The situation is simplified by suppressing the migration and
convection Overall, Fick’s laws describe the flux and the concentration of
o Migration is suppressed by addition of excess inert electroactive species as functions of position and time
salt
o Convection is suppressed by use of a quiescent Potential Step Experiment
solution
 Under these conditions, the analyte ions move by diffusion Consider the reduction of O (oxidized species) to R (reduced)

Conditions: A potential for complete reduction, quiescent solution, and

a planar electrode

Solution to Fick’s laws for these conditions gives the concentration

gradient at the surface:
∂C CO (b)
=
∂ x (π DO t)1/ 2
 C O(b , t) – bulk concentration of O
When substituted to the equation
∂ C (x , t) C O(0 ,t ) – surface concentration of O
i=nFAD
∂x The change in the slope, and hence the resulting current, are due to
changes of both CO(0,t) and δ
gives the Cottrell equation:
nFA DO CO (b) As the potential is scanned negatively and approaches E° of the
i ( t )= 1/ 2 couple, the surface concentration rapidly decreases in accordance with
(π DO t) Nernst equation
Where
( π DO t )1/ 2 – diffusion layer thickness
The current decreases in proportion to the square root of time

In chronoamperometry, the working electrode potential is suddenly

stepped from an initial potential to a final potential, and the step usually
crosses the formal potential of the analyte For example, at E = E°, the concentration ratio is 1

The current is quite large at first, but it rapidly decays as the analyte
near the electrode is consumed, and a transient signal is observed 0.0592 C R(0 , t)
E=E °− log
n C O (0 , t)

0.0592
E=E °− log 1
n

E=E °
For potential 59 mV more negative than E°, the CR(0,t) is present at 10-
fold excess, if n=1

0.0592 10
The region within which the solution is depleted of the analyte ion is E=E °− log
known as the diffusion layer, its thickness is given by δ n 1

The concentration gradient is steep at first, and the diffusion layer is E=E °−−0.0592
thin
The decrease in CO(0,t) is coupled with an increase in the diffusion layer
As time goes by, the diffusion layer expands (to δ2 and δ3 at t2 and t3), thickness
and hence the concentration gradient decreases
The change in layer thickness dominates the change in slope after
CO(0,t) approaches zero

The net result is a peak-shaped voltammogram

Potential Sweep Experiment

In voltammetric experiment involving a linear potential scan, the

reduction of O to R is done in quiescent solution

The slope of concentration gradient is given by

CO (b ,t )−C O (0 , t)
In stirred solution, the bulk concentration (CO(b,t)) is maintained at a
δ distance δ by the stirring
Where
The slope of the concentration-distance profile (CO(b,t) – CO(0,t)) / δ is
thus determined solely by the change in the surface concentration
(CO(0,t))

The decrease in CO(0,t) during the potential scan (around E°) results in
sharp rise in the current

When a potential more negative than E° by 118 mV is reached, CO(0,t)

approaches zero, and a limiting current is achieved

nFA DO CO (b ,t )
i l=
δ
The resulting voltammogram thus has a sigmoidal (wave) shape

By increasing the stirring rate (U), the

Chemistry 127 Lecture Trans

ELECTROANALYTICAL CHEMISTRY
2.7 Activated Complex Theory

(32/38) The effect of the operating potential on the rate constants can
be understood in terms of the free energy barrier

Consider the PE curve for the rxn

O + ne ↔ R

Figure Z. Free energy curve for a redox process at a potential more positive than the
equilibrium value.
Chemistry 127 Lecture Trans
ELECTROANALYTICAL CHEMISTRY
2.8 Types of Electroanalytical Methods

Coulometric Methods

Coulometric methods involve quantitative conversion of analyte to a

new oxidation state

1. Electrogravimetry – the mass of electrolysis product is the

basis of analyte determination
2. Constant potential/ current coulometry – the quantity of
electricity serves as a measure of analyte amount

Characteristic of Coulometric Method

 Moderate selectivity, sensitivity, and speed
 Among the most accurate and precise methods
 Require no calibration against standards
o Amount of analyte can be directly obtained from
mass of deposit or charge passed

In electrogravimetry and coulometry, a potential is applied, forcing a

reaction to occur.
1. Polarize the cell
2. Causes unexpected (nonspontaneous) reaction to happen
3. Work is done on the system

Current-Voltage Relationships During an Electrolysis

3 electrolytic methods:
1. Applied cell potential is held constant
2. Electrolysis current is held constant
3. Potential of the working electrode is held constant

For all 3, the behavior of the cell potential is governed by:

Eapplied =E c + E a+ ( ηcc +ηck ) + ( ηac +ηak )−IR

Notes:
1. The 4 overvoltages always carry a negative sign
2. They are the potentials that must be overcome in order for
charge to pass through the cell
3. Of the 7 terms, only Ec and Ea can be obtained from theory
4. The rest can only be evaluated experimentally
  From tables O2 overvoltage is -0.85 V; i.e. ηak = -0.85 V
In electrolytic cells,  Cathodic reaction is fast and reversible, i.e. ηck = 0
 The reaction requiring the smallest applied voltage will occur  Concentration polarization at anode is negligible, because
first reactant water is in excess (will not be depleted); i.e. ηac = 0
 As the reaction proceeds, the applied E increases and other  Initially ηcc = 0; because Cu2+ is initially high
reactions may start
If the cell is operated at initial current of 1.5 A (current density is 0.010
Example that demonstrates quantitative separation of ions through A/cm2), the estimated required potential is
electrolysis:

Starting with 0.1 M each of Pb2+ and Cu2+, can Pb2+ be quantitatively Eapplied =E c + E a+ ( ηcc +ηck ) + ( ηac +ηak )−IR
separated from Cu2+ by electrodeposition?
Eapplied =0.34−1.23+ ( 0+ 0 ) + ( 0−0.85 )−(0.050 ×1.5)
Let us define quantitative as only a part of 10 000 cross contamination ¿−1.8V
(99.99%)
A rough estimate of the potential required to produce an initial current
Cu2+ + 2e- ↔ Cu E° = 0.337 V of 1.5 A is -1.8 V
Pb2+ + 2e- ↔ Pb E° = -0.126 V
Current Changes During an Electrolysis at Constant Applied
Cu deposits first (more positive) Potential

We don’t want any lead to deposit until at least 99.99% of the copper Current decreases with time due to
has been removed, i.e. 10-5 M Cu2+  Depletion of copper ion in solution
The potential required to reduce the remaining 0.01% Cu is  Increase in cathodic concentration polarization

0.0592 1
E=0.337 V − log −5
2 10 The current decrease in exponential in time:
E=0.189 V I t=I o e−kt
Where
Lead would start depositing at
I o – initial current
0.0592 1 I t – current
E=−0.126 V − log
2 0.1 t – time (in minutes) after the onset of polarization
E=−0.156 V
DA
Thus quantitative separation is possible, albeit our calculation neglects
k =25.8
Vδ
any overpotential
Where
Operation of a Cell at a Fixed Applied Potential D – diffusion coefficient (cm /s) 2

A – electrode surface area (cm ) 2

Simplest way:
Applied cell potential is maintained at constant value
V – volume of solution (cm ) 3

δ – diffusion layer thickness (cm)

Cu2+ determination:
Cu2+ + H2O ↔ Cu(s) + ½ O2(g) + 2H+ After application of potential, current decreases exponentially

Cell:
2 Pt electrodes (surface area = 150 cm2) immersed in 200 mL of
solution that is 0.0220 M in Cu2+ and 1.00 in M H+. The cell resistance
is 0.05 Ω

Initial Thermodynamic Potential

Cu2+ + 2e- ↔ Cu E° = 0.34 V

½ O2(g) + 2H+ + 2e- ↔ H2O E° = 1.23 V Changes in current during the electrolytic deposition of Cu2+

Ecell = 0.34 – 1.23 V

Ecell = -0.94 V

Thus, at applied potential less negative (more positive) than -0.94 V,

no electrolysis occurs.

Estimation of Required Potential

 Assume kinetic polarization occurs only at the anode, where
O2 is evolved
 Figure X. Changes in potential during electrolytic deposition of Cu 2+.

 Points A and B are potentials at which Pb and Cd (if present)

will start to codeposit
 Point C is the point at which H2 might begin to form at the
cathode

Constant-Current Electrolysis

The current is maintained at constant level

The applied potential is increased periodically as electrolysis proceeds

Figure Y. Changes in cathode potential (Ec + ηcc) during an electrolytic deposition of Cu2+ with a
constant current of 1.5 A.

 Increased Eapplied cause rapid increase in ηcc, and thus the

cathode potential
 At very large Eapplied alternative process of such as reduction
of H+ becomes significant

Chemistry 127 Lecture Trans

ELECTROANALYTICAL CHEMISTRY
2.8.1 Electroanalytical Method: ELECTROGRAVIMETRY

 A quantitative method based on weight gain

 Also referred to as electrodeposition
 A very old method
 When it works, it works well
 Unfortunately, it only works for a limited number of
substances

Steps in the Analysis

1. The electrode is cleaned, dried, and its weight is determined
2. The electrode is then placed in the system and a potential is
applied
3. The analyte deposits on the electrode
4. The electrode is removed and brought to constant weight
5. The method can be conducted either with or without a
controlled potential

No Control of Potential
 Simply set a fixed potential and run
 This is a fixed and inexpensive option
 Unfortunately, it causes problems
 The starting potential must initially be high to ensure a
complete deposition
  Overpotential can cause gas generation
e−¿∈transfer
 The analyte may not be able to diffuse rapidly enough ¿ g ׿ of
 The deposition will slow down as the reaction proceeds formula weight
 As the reaction proceeds, the current decreases, resulting in ¿ of coulombs
the deposition becoming much slower ¿
96 500
It
¿ of equivalents=
96 500
The number of grams deposited then is:

It
Controlled Potential gramsdeposited =
96500
C ( FWn )
 A reference electrode is used in the system mol
 The potential difference between the working and reference Where
electrodes is monitored and held constant I – current in A
o This helps to reduce overpotential and the time for
an analysis t – time in s
 Only a limited number of species work well with FW – formula weight
electrodeposition
n – number of electrons transferred per species
 Only a few metals deposit from an acid solution
quantitatively without hydrogen formation
Example
 Not many metals form a smooth, well-held coating on the
Determine the number of grams of Cu that could be deposited if a
cathode – can lose metal current of 6 A is applied for 5 minutes to a solution of Cu2+

Cathode Electrodeposition
C s g


Copper – done in an acid solution using a Pt cathode
Nickel – conducted in a basic solution gramsdeposited =
( 6 )( 5 min× 60
s min )
( mol )
63. 54
C 2
96 500
Some metals can be determined by deposition of metal complexes mol
(cyanides)
Example: Ag, Cd, Au
gramsdeposited =0.0988 g

Unfortunately, not all of the electrons are used in the reaction – not
100% efficient

Thus
Anode Electrodeposition (eff )It FW
Some metals can be assayed by deposition on the anode. This
gramsdeposited =
96500
C n ( )
requires higher oxidation – deposited as metal oxides mol
Pb2+ ↔ PbO2
Mn2+ ↔ MnO2

Time-Current Requirement for Electrodeposition

 A coulomb is a quantity of electricity

 Current is the rate of electrical flow

96 500 coulombs (C) of electricity are required to reduce 1-gram

equivalent weight of a metal to a lower oxidation state (1 e- charge) Example
How long will it take to remove all copper from one liter of a 1.0 M
96 500 coulombs=1 Faraday ( F ) solution of Cu2+?
I = 0.1 A
current , I = Ampere=C /s 50% efficient

The number of equivalents deposited can be found by: Solution

(eff )It FW
¿ of equivalents=
grams
gram equivalent weight
gramsdeposited =
96500
C n ( )
mol
 C e−¿
t=gdeposited × 96 500 ×2 ¿
mol eff × I × FW

C e−¿
t=63.54 g × 96500 ×2 ¿
mol C g
0.50 × 0.1 ×63.54
s mol

t=3.86 ×10 6 s

t=44.68 days

Chemistry 127 Lecture Trans

ELECTROANALYTICAL CHEMISTRY
2.8.2 Electroanalytical Method: VOLTAMMETRY

A group of analytical methods in which only a small portion of a

material is reduced (or less commonly oxidized) electrolytically

Several types of methods based on:

1. Electrode type
 2. How the potential is applied  The potential is reduced at a known rate and anodic current
3. How the current is measured measured
 The oxidation of the metals from the Hg is monitored in this
Conventional (DC) Polarography step
 Type of voltammetry, discovered in 1920 by Heyrovsky

Polarography
Summary
 Subject to high relative errors (≥ ±1%)
 Works best in the 10-5 to 10-2 M range
 Requires a calibration curve
 Provides both qualitative and quantitative information

The cell current is measured during electrolysis at various potentials

Most common electrode type is a dropping mercury electrode (DME)

A current vs. potential curve is produced

Polarographic Data

2 types of information are obtained

1. Diffusion current (id)
2. Half-wave potential (E1/2)

Diffusion Current

The rate of diffusion current to the electrode is concentration-

dependent based on the Ilkovic equation:

(5/57)

Stripping Voltammetry

Very sensitive method of analysis, 10-6 to 10-9 M

Summary
Step 1: Preconcentration
 A single Hg drop is hung from the electrode
 Go through an electrodeposition step:
5 min for 10-7 M, 60 min for 10-9 M
 This removes all metal from the sample – all will be present
in a single Hg drop

Step 2: Voltammetric/stripping step